Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Neoalkoxy Titanate and Zirconate Coupling Agent Additives in

Thermoplastics

Salvatore J. Monte
Kenrich Petrochemicals, Inc.
140 East 22nd Street
Bayonne, NJ 07002-0032 USA
Tel: 201-823-9000 Fax: 201-823-0691
Email: sjmonte@4kenrich.com Web: www.4kenrich.com

SUMMARY
Ti or Zr coupling agents chemically bridge two dissimilar species such as an inorganic
filler/particulate and organic polymer via proton coordination on non-silane reactive
substrates such as CaCO3 and carbon black without the need of water of condensation as
with silanes. Minor amounts of thermally stable neoalkoxy titanate and zirconate
additives provide a means for post reactor, in-situ metallocene-like repolymerization
catalysis of a filled or unfilled polymer during the plastication phase resulting in:
significantly faster thermoplastic processing at lower temperatures; lower polymer
recrystallization time; and the copolymerization of dissimilar polymers. Examples: both
40% CaCO3 filled and unfilled PP compounds experienced respective reductions of
35.5% and 42% in injection mold cycle time and 22% and 11% in process temperature;
17% “pyrophosphato titanate coupled conductive carbon black (CB)” in LDPE provides
the same Positive Temperature Coefficient effect as 25% untreated CB; a 39.7% reduction
in the recrystallization time of PPS; a ten-fold increase in the elongation of a PET/PC
regrind alloy; and the regeneration of recycled blends of LDPE and PP regrinds. The
catalysis effect is shown to be permanent and recyclable. Coupling agent liquid, powder
and pellet forms; dosage; data and applications methodology in compounding, injection
and blow molding are discussed. New and novel transparent and permanent antistatic
agents based on the formation of bipolar layers of dissimilar trineoalkoxy zirconates are
shown to be non-blooming, non-moisture dependent providing volume as well as surface
ESD effects.

INTRODUCTION Figure 1 New thinking – not just filler coupling, but

filler coupling and polymer catalysis
It will be the focus of this paper to establish new
thinking in thermoplastic additives art based on
organometallic “Coupling” and “Catalysis” as taught
through the “Six Functions” of the titanate (zirconate)
molecule (see Figure 1). Titanates will be compared to
Silanes because there is a deep-rooted mindset in the
plastics additives industry as to what silanes can do
and what their limitations are as it relates to reactable
substrates such as CaCO3, carbon black and organic
substrates. Titanate reactability with these substrates
and others that are non-reactable with silanes will be
demonstrated. Superiority of titanates over silanes on
silane reactable substrates will also be shown.

This paper was written for the Addcon World 2001

Conference

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 121

 Salvatore J. Monte
“Coupling” (Function 1) creates a shift in the CPVC
(Critical Pigment Concentration Point) of filled liquid
and solid polymer thermoplastic and thermoset
systems. Figure 2 shows a typical shift in the CPVC of
CaCO3 and ATH in mineral oil using subject titanates.
Mineral oil makes an excellent organic vehicle for
testing additive dispersability effects on fillers because
of its non-polarity and minimum wettability effects.
Figure 3 shows a similar CPVC shift for calcined clay
in mineral oil.
“Coupling” with titanate to form atomic monolayers
on the filler surface will be shown to:
• Eliminate air voids and moisture to create a true
continuous filler/polymer phase thus improving
adhesion, strength, aging and anti-corrosion.
• Shift the CPVC to reduce plasticizer needs and
Figure 2 Shift in critical pigment volume concentration
point of CaCO3 and ATH in mineral oil
Figure 3 Effect of titanate on viscosity of 30% calcined
clay in mineral oil
122
other additives used to induce “flexibility” and
“stretch” in a polymer and to increase filler
functionality such as thermal conductivity,
electron conductivity and flame retardance.
• Make inorganics hydrophobic and organophilic.
• React with all fillers, pigments and fibers that
are silane non-reactive such as CaCO3, Boron
Nitride, and Carbon Black; organic pigments
and dyes; and fibers such as graphite, polyester
and aramid.
• React more completely than silanes on fiberglass,
silica and other silane reactive substrates to
improve visual appearance, profile smoothness
and resistance to delamination under pressure.
• Couple to most substrates in situ in the water,
solvent, liquid polymer or thermoplastic
polymer melt without the need of water of
condensation, drying or pretreatment.
• Provide atomic monolayer phosphato/titanium
intumescent capability to both the inorganic
and organic so as to control burn rate and burn
rate exponent of flame retardant compositions
such as FR thermoplastics and energetics such
as ammunition propellant, solid rocket fuel and
pyrotechnics.
“Catalysis” (Function 2) with titanates will be shown to
create new and novel “Repolymerization” and
“Copolymerization” of polymers independent of
thermoset crosslink mechanisms (Function 5). The
metallocene-like catalysis analogy of “titanate/
titanocene” and “zirconate/zirconocene” (see Figure 1)
will be explored in various polymeric disciplines and
extrapolated to thermoplastic art. The “Catalysis” aspect
of organometallics as coupling agents adds a new
dimension of capability to un-cured – un-crosslinked
thermoplastics such as:
• Increase the toughness (defined as the area
under the plot of stress vs. strain) of the polymer
due to increased elongation per unit length
(strain) maintaining or increasing tensile
strength.
• Create finer more uniform foamed polymers
since open cell formation is reduced because
increased polymer strain strength at elevated
temperatures induced by the additive prevents
the polymer bubbles from breaking during the
elevated temperature where blow occurs.
• Repolymerization of the macromolecule in the
melt allows regrind to be regenerated to virgin
properties.
• Copolymerization in the melt improves the
properties of polymer blends such as curbside
recycled plastics.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
• Reduce the recrystallization time and increase
the polymer flow at lower temperatures resulting
in faster extrusion, blow and injection mold
cycle times and better quality parts as measured
by strength, impact, aging, acid and salt spray
resistance, appearance, weld line elimination
and clearance tolerances.
Recent results from ACS CAS Searches, literature
references and data are provided herein to establish
subject organometallic coupling agents as efficacious
additives in thermoplastic compositions. An ACS
CAS survey for the period from December 22, 1998 to
July 31, 2000 providing 125 condensed abstracts of
thermoplastic compositions containing subject
organometallics is also available from the author.
A discussion outline is useful to understand the
applications scope of titanate, zirconate and aluminate
additives and the considerations necessary for their
successful application. Whenever possible, the most
current work by the author and documentation from
the literature is used to teach. Even more detailed
historical documentation with 500+ figures and
tables is provided in Reference [1] and others by
Monte. References [2] to [20] provide some of the
technical papers written by the author. Table 1
provides an alpha-numeric code for the titanates,
zirconates and silanes discussed in the paper.
OUTLINE
Coupling
• The Six Functions of the Titanate Molecule –
Comparison to Silanes.
• Solubility Parameters, In-situ Coupling,
Localization and Physiabsorption.
• Two Application Principles: Uniform
Distribution and Specific Energy Input.
• Amount of Coupling Agent Based on: Organic
Polymer, Inorganic Pigment, Combinations of
Organic and Inorganic, Treatment Techniques
– Mg(OH)2.
• CaCO3 Substrate Reactivity/Titanate Solubility
Relationship.
• Effect of Atmospheric Moisture.
• Hydrophobicity – CaCO3, Silica, Lithium Nickel
and Lithium Cobalt Oxide.
• The Effect of Substrate Polarity.
• CaCO3 Dispersed in the Organic Phase.
• Comparison of Titanate and Various Lubricants
in CaCO3 Filled LDPE.
• CaCO3 Dispersed in the Water Phase and Mineral
Oil.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
• Acrylic Adhesion to EPDM in the Water Phase.
• Carbon Black Reactivity – Carbon Black
Conductivity in Polyolefins.
• Carbon Black Dispersion in Water.
• Thermally Conductive Graphite Filled Neoprene.
• Other Functional Inorganics – TiO2 Filled Epoxy
– Titanate v. Silane.
• Preparation of Ultrafine TiO2.
• Fe2O3/Styrene/n-Butylmethacrylate Copier
Toner.
• Barium Ferrite Filled Thermoplastic.
• ATH and Mg(OH)2 Non-Toxic Flame Retarded
Thermoplastics.
Catalysis
Crosslinking
Metallocene Catalysis
Repolymerization
• Talc Filled PP.
• Nanoclay Filled SBS.
• BaSO4 filled Polybutadiene.
• Improved Shear and Impact of Elastomers and
Ionomers.
• Increased Strength of Polymers – Virgin and
Regrind Repolymerization.
• Processing Plastics and Elastomers at Lower
Temperatures Without Plasticizers.
• Shorter Recrystallization Time of FG/PPS.
• Carbon Black Filled Polyurethane and SBR.
• Injection Molded Fibreglass/Polycarbonate.
• Increased Impact Strength and Ductility of
Polycarbonate – Engineering Plastics.
• Carbon Black, Cu-Phthalocyanine Blue, AZO
Yellow Dye, Magenta Dye, Silicone Oil/Acrylic
Inks.
• Synergize Blowing Agent Performance –
Exothermic AZO Foamed/PE and PVC and
Endothermic NaHCO3 Foamed SBR.
Copolymerization
• PET Regrind/PC Regrind LDPE.
• LDPE/PP Regrind.
• PP and HDPE/LCP.
• Consumer Waste Recycled Olefins and Natural
Fiber Reinforcement.
Extrusion, Injection and Blow Molding
• Plant Trials, Processing Tips, Faster Cycles,
Lower Process Temperatures, Increased
Strength, Thinner Walls, Weld-line Elimination,
and Greater Part Definition.
123
 Salvatore J. Monte

Table 1 Nomenclature
Code Nomenclature
Silanes
A-187 3-Glycidoxypropyl, trimethoxy silane
A-1100 3-Aminopropyl, trimethoxy silane
Titanates
KR TTS Titanium IV 2-propanolato, tris isooctadecanoato-O
KR 9S Titanium IV 2-propanolato, tris(dodecyl)benzenesulfonato-O
KR 26S Titanium IV 2-propanolato, (4-amino)benzene sulfanoto-O,
bis(dodecyl)benzenesulfonato-O
KR 34S Titanium IV 2-propanolato, tris[4-(2-phenyl)2-propyl-2]phenolato
KR 38S Titanium IV 2-propanolato, tris(dioctyl)pyrophosphato-O
KR 41B Titanium IV tetrakis 2-propanolato, adduct 2 moles (dioctyl) hydrogen phosphite KR 55
Titanium IV tetrakis (bis 2-propenolato methyl)-1-butanolato adduct 2 moles (ditridecyl)
hydrogen phosphite
KR 101 Titanium IV oxoethylene-diolato, bis isooctadecanoato-O
KR 112 Titanium IV oxoethylene-diolato, bis (dioctyl) phosphato-O
KR 134SP Titanium IV oxoethylene-diolato, bis[4-(2-phenyl)2-propyl-2]phenolato
KR 138S Titanium IV oxoethylene-diolato, bis(dioctyl)pyrophosphato-O
KR 138T Titanium IV oxoethylene-diolato, bis(dioctyl)pyrophosphato-O, bis(triethyl) amine salt
KR 201 Titanium IV ethylenediolato, bis isooctadecanoato-O
KR 238S Titanium IV ethylenediolato, bis(dioctyl)pyrophosphato-O
KR 238M Titanium IV ethylenediolato, bis (dioctyl)pyrophosphato-O, bis(dialkyl)amino alkyl-2-
methyl propenoate
LICA 01 Titanium IV 2, 2(bis 2-propenolatomethyl) butanolato, tris neodecanoato-O
LICA 09 Titanium IV 2, 2(bis 2-propenolatomethyl) butanolato, tris (dodecyl) benzenesulfonato-O
LICA 12 Titanium IV 2,2(bis 2-propenolatomethyl) butanolato, tris (dioctyl) phosphato-O
LICA 12WE33 33% Active LICA 12 containing Water Emulsifiers
LICA 38 Titanium IV 2,2(bis 2-propenolatomethyl) butanolato, tris (dioctyl) pyrophosphato-O
LICA 38ENP Titanium IV 2,2(bis 2-propenolatomethyl) butanolato, tris (dioctyl) pyrophosphato –
O:Ethoxylated Nonyl Phenol – 1:1
LICA 38J Titanium IV (bis-2-propenolato-methyl)-1-butanolato, bis(dioctyl) pyrophosphato-O,
(adduct) 3 moles N,N-dimethylamino-alkyl propenoamide
LICA 44 Titanium IV 2,2(bis 2-propenolatomethyl), tris 2-ethylenediamino) ethylato
LICA 97 Titanium IV 2,2(bis 2-propenolatomethyl) butanolato, tris (3-amino) phenylato
KS N100 Combined Mononeoalkoxy Titanates
KS N60WE 60% Active Combined Mononeoalkoxy Titanates containing Water Emulsifiers

124 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 1 Continued
Code Nomenclature
Zirconates
KZ 55 Zirconium IV tetrakis (2, 2-bis propenolato methyl) butanolato, adduct 2 moles bis
tridecyl hydrogen phosphite
NZ 12 Zirconium IV 2,2(bis-2-propenolatomethyl) butanolato, tris (dioctyl)phosphato-O
NZ 37 Zirconium IV bis 2,2(bis-2 propenolato methyl) butanolato, bis (para amino benzoato-O)
NZ 38 Zirconium IV 2,2(bis-2-propenolatomethyl) butanolato, tris (dioctyl)pyrophosphato-O
NZ 38J Zirconium IV 2,2-dimethyl 1,3 propanediolato, bis (dioctyl) pyrophosphato-O (adduct) 2
moles N,N-dimethylamino-alkyl propenoamide
NZ 44 Zirconium IV 2,2(bis-2-propenolatomethyl), tris (2-ethylenediamino) ethylato
NZ 97 Zirconium IV (2,2-bis propenolatomethyl), tris (3-amino) phenylato
KS MZ100 Combined Trineoalkoxy Zirconates
KS MZ60WE 60% Active Combined Trineoalkoxy Zirconates containing Water Emulsifiers
Liquid Form
LICA # = LIquid Coupling Agent, 100% Active Neoalkoxy Titanate
NZ # = Liquid Coupling Agent, 100% Active Neoalkoxy Zirconate
Example: LICA 12 = 100% liquid neoalkoxy titanate
Powder Masterbatch Form
CAPOW L #/Carrier = Coupling Agent POWder,
Example: CAPOW L12/H = 65% LICA 12/35% PPG Hi Sil 233 Silica Carrier
Pellet Masterbatch Form
CAPS L #/Binder = Coupling Agent Pellet System, 20% Active Neoalkoxy Titanate/Binder.
Example: CAPS L12/L = 20% LICA 12/10% Silica/70% LLDPE Binder
Water Soluble Quat Form Quat Blend (QB) Part Ratio
Designation KR 238M :LICA 38J :NZ 38J
QB 012 0 : 1 : 2
QB 521 5 : 2 : 1

Transparent Antistats – Permanent, Transparent, patents filed – many of which are U.S., EP or WO
Non-Blooming and Non-Hygroscopic. (World) based.

Summary – Thermally Conductive Boron Nitride Coupling

Injection Molded Engineering Plastics.
DISCUSSION
ACS CAS Searches for “Ti or Zr coupling agents”
conducted from 1974 to December 31, 2000 provided
abstracted results from 18 primary, non sub-divisional
US Patents and 66 technical papers by the author and
1302 patents and 299 technical papers by others for
the period. The Japanese dominate with 83% of the
Organosilanes have long been used to enhance the
chemical bonding of a variety of thermoset resins
with siliceous surfaces. However organosilanes are
essentially non-functional as bonding agents when
employing carbon black, CaCO3, boron nitride,
graphite, aramid or other organic derived fibers21.
Plueddemann stated21: “It is fairly well established
that silane coupling agents form oxane bonds (M-O-
Si) with mineral surfaces where M = Si, Ti, Al, Fe, etc.
…mechanical properties of filled polymer castings

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 125

 Salvatore J. Monte
were improved by addition of appropriate silane
coupling agents with a wide range of mineral fillers.
Greatest improvement was observed with silica,
alumina, glass, silicon carbide, and aluminum
needles. A good but somewhat lesser response was
observed with talc, wollastonite, iron powder, clay,
and hydrated aluminum oxide. Only slight
improvement was imparted to asbestine,
hydroxyapatite (Ca10(OH)2(PO4)6), titanium dioxide,
and zinc oxide. Surfaces that showed little or no
apparent response to silane coupling agents include
calcium carbonate, graphite, and boron”.
The Six Functions of the Titanate Molecule
A discussion of the six functional sites of a titanate (or
zirconate) as compared to a silane [cf. Table 1] to
explain their performance differences may be
represented as follows:
Titanate Silane
(1) (2)(3)(4)(5)(6) (1) (5)
(RO-)-nTi-(-O X R' Y)4-n (RO-)-3Si-(-R' Y)
Where,
(1) RO = hydrolyzable group or substrate reactive
group with surface hydroxyl or protons.
(2) Ti, Si = tetravalent titanium, zirconium or silicon.
The Ti-O (or Zr-O) bond is capable of
disassociation allowing transesterification,
transalkylation and other catalysis mechanisms
such as Repolymerization while the Si-C bond
is more stable and thus unreactive.
(3) X = Binder functional groups such as phosphato,
pyrophosphato, sulfonyl, carboxyl, etc. impart
intumescence, burn rate control, anticorrosion,
quaternization sites, disassociation rate/electron
transfer control, etc.
(4) R’ = thermoplastic functional groups such as:
aliphatic and non-polar isopropyl, butyl, octyl,
isostearoyl groups; naphthenic and mildly polar
dodecylbenzyl groups; or aromatic benzyl,
cumyl phenyl groups.
(5) Y = thermoset functional groups such as acryl,
methacryl, mercapto, amino, etc.
(6) 4-n = mono, di or triorganofunctionality. Hybrid
titanate (zirconate) coupling agents such as
those containing 1 mole of a (function 3) carboxyl
and (function 4) aliphatic isostearoyl ligand
and 2 moles of (function 3) carboxyl and
(function 5) acryl ligands are possible.
126
The function (1) concerns itself with filler/fiber
substrate reaction mechanisms, while functions (2)
to (6) are polymer/curative reactive. In its simplest
terms, the titanate function (1) mechanism may be
termed proton (H + ) reactive via solvolysis
(monoalkoxy) or coordination (neoalkoxy) without
the need of water of condensation while the silane
function (1) mechanism may be termed hydroxyl
(OH-) reactive via a silanol-siloxane mechanism
requiring water of condensation. The silane’s silanol-
siloxane water of condensation mechanism limits its
reactions to temperature environments below 100°C
thereby eliminating the possibility of in situ reaction
in the thermoplastic or elastomer melt above 100°C as
is possible with titanates as invented by the author.
This aspect of in situ coupling will be discussed in
further detail in the Application Methodology section
of the paper. Also, carbonates, sulfur, sulfur donors,
sulphates, nitrides, nitrates, carbon, boron, metal
powders, azodicarbonamide and many other
particulates used in thermoplastics, thermosets and
thermoset elastomers do not have surface silane
reactive hydroxyl groups while almost all three-
dimensional particulates and species have surface
protons thereby apparently making titanates more
universally reactive.
The coupling of the titanate to the inorganic/organic
substrate in atomic monolayers allows for elimination
of air voids, hydrophobicity, and a complete
continuous phase for stress/strain transfer. The
aforementioned shift in CPVC results in an exponential
increase in functional pigment performance for
conductance of: electrons, heat, cold, light and
magnetic forces.
A. Voelkel et al22 provide the most recent reference
relative to function (1) titanate monomolecular layer
formation in their technical paper, “The Use of
Solubility Parameters in Characterization of Titanate
Modified Silica Gel by Inverse Gas Chromatography”.
Their work using IGC characterizes the surface
modification of five titanates on silica and provides a
benchmark for comparison to earlier IGC work on
pyrogenic and precipitated silica using silanes.
Voelkel concluded: It was shown that the corrected
solubility parameter δT and its increments could be
successfully used for the characterization of the
monolayer covering of silica gel. These parameters
are sensitive enough to reflect changes of the
monolayer character caused by a different structure
of the titanium compounds used as the modifiers and
the modification temperature.”
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
In-situ Coupling in the Melt Phase without
the Need for Water of Condensation
The neopositioned quaternary carbon structure of the
neoalkoxy groups permits in-situ coupling at
temperatures above 200°C in the absence of water. No
water of condensation is required in the monoalkoxy
and neoalkoxy titanate or zirconate coupling
mechanisms thus allowing more flexible in-situ
coupling in the polymer phase at ambient and
temperatures above 200°C. However, in-situ coupling
requires careful consideration of good compounding
principles to avoid localization, inconsistent and
incomplete coupling, and subsequent incomplete
catalysis because of inadequate specific energy input
(low shear) caused by reduced polymer viscosity.
Localization and Physiabsorption Creates
Poor Results – Forms of Coupling Agent
The concern with localization and physiabsorption of
the coupling agent on the filler or fiber which results
in whole segments of uncoupled particulate surfaces,
as well as over and under catalysis of the polymer, is
largely overcome by using masterbatches of the
coupling agent. A simple rule is to use like coupling
agent form to like polymer physical form, i.e. liquid to
liquid, powder to powder and pellet to pellet. Therefore,
an organosoluble liquid coupling agent (hence, LICA
neoalkoxy titanate = LIquid Coupling Agent) should
be used for solvent or high solids liquid polymers, a
quaternized or emulsifiable grade of coupling agent for
water based emulsion polymers, a 65% active coupling
agent masterbatch (hence, CAPOW titanate = Coupling
Agent POWder) for powder polymer systems such as
thermoset epoxy powder coatings, rigid PVC
composites and elastomers, and a 20% active coupling
agent masterbatch (hence, CAPS titanate = Coupling
Agent Pellet System) for pelleted polymer systems (cf.
Table 1).
Solubilization and Mixing Shear
Considerations
Coupling in atomic monolayers may take place on the
surface of a particulate in both the organic and water
phase. In order to effect atomic monomolecular level
coupling, the titanate or zirconate must be solubilized
in the organic (solvent, plasticizer, polymer) phase or
finely emulsified into the water followed by addition
of the particulate or reinforcing fiber. If the organic
phase has a high molecular weight, then sufficient
shear and high mixing torque is needed to assure
titanate distribution.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
The hydroxyl groups on the pyrophosphato titanate
or zirconate (i.e. KR 38S, KR 138S, KR 238S, LICA 38,
NZ 38, KR TPP, KZ TPP, KZ OPPR – cf. Reference [1])
ligand may be used to render the hydrolytically stable
titanate or zirconate (no TiO2 or ZrO2 precipitation
after one-year immersion in water) water soluble for
use in latex or emulsion systems via quaternization
with amines such as N, N-dimethylamino-alkyl
propenoamide. Also, suitable surfactants and
cosolvents may be used to emulsify the water insoluble
titanates and zirconates.
Two Application Principles for
Thermoplastics Melt Mixing
The physics of mixing is as important as the chemistry
of coupling. Two principles govern the applications
art of coupling agents: uniform distribution before the
polymer melt phase for uniform coupling/catalysis
and high specific energy input during the polymer
melt phase for maximum shear/work energy for
dispersion so that coupling at the filler interface and
catalysis in the polymer interphase are made complete.
Often times, poor mixing methodology can defeat the
best polymer-filler-reinforcement-additive compound
design.
1. Uniform Distribution – Before the
Polymer Melt Phase or Before Filler
Contact for Uniform Coupling and
Catalysis
Subject organometallics work on a catalytic principle
at stoichiometric levels of 0.1 to 2.0 parts additive per
thousand parts polymer and 0.5 to 0.7% by weight of
most fillers. As stated, in room temperature liquid
waterbased or high solids polymer systems, it is best
practice to add the coupling agent into the liquid
phase just prior to addition of the filler or particulate
to be coupled. The titanate must be soluble directly
into the organic or water phase or able to be cosolvated
or emulsified. The Quat forms such as LICA 38J or
Water Emulsifiable grades such as LICA 38WE50
work well in waterborne systems. KR 44 is the only
directly water soluble titanate under high shear and
LICA 09 is the only directly water emulsifiable titanate.
The pyrophosphato titanates can be quaternized and
most titanates can be made water emulsifiable with
various oxygen and amine bearing surfactants. The
zirconates as a class are more difficult to emulsify
than the analogous titanates. The emulsified titanate
at 5% concentration in water should not precipitate
or settle out on standing.
127
 Salvatore J. Monte
In thermoplastic and thermoset melt systems, the
coupling agent must be dispersed as thoroughly as
possible throughout the unmelted polymer or polymer
composite materials before the onset of melting.
During melting, catalysis is initiated as the titanate or
zirconate solvates into the polymer organic phase for
reaction with polymer ligands and coupling to the
filler/fiber interface. The pellet (CAPS) form is the
simplest and best for the typical thermoplastic
injection, blow molding or extrusion-processing set-
up. Powder forms of the coupling agent work best in
batch mixers such as double sigma blade or internal
mixers or 2-roll mills because they are easier to weigh
out and avoid localization caused by poor mixing
techniques, sticking to the ram or mixer walls.
2. Specific Energy Input During the
Polymer Melt Phase
Once the polymer begins to melt, work energy through
mechanical shear creates the required intimate
polymer/catalyst (coupling agent) mixing. The area
under the power curve formed by a plot of torque vs.
time is a measurement of the work energy or shear on
the polymer/catalyst matrix. The most efficient
polymer mix cycles generate peak torque (AMPS) in
a short time. Torque is controlled by temperature,
rpm’s and backpressure or plasticizer/solvent/water
letdown. High torque creates high polymer shear
rates. Polymers are non-Newtonian in flow and their
melt viscosity decreases asymptotically with
increasing shear. Under high shear rates, polymers
exhibit the lowest viscosity with the least amount of
rheological variation as compared to greater polymer
viscosity variation at lower shear rates - i.e. high shear
rates give reproducible results. Most polymers (except
for heat sensitive PVC) are not damaged by higher
shear. Low shear rate melt indexers are not the way to
measure the effect of subject additives. Use torque
readout instrumentation that plots rheological effects
over a wide shear rate range.
Successful use of titanates and zirconates, or any very
active additive used at low levels, therefore requires
the optimum specific energy input. Lower
temperatures, increased back pressure, higher rpm’s
and other changes in the compounding conditions
are necessary to compensate for the rheological
changes the coupling agent induces into the
compound. Remember, the compounding device –
whether it’s a single or twin screw, intensive or
continuous mixer, a two-roll mill, a Cowles dissolver
or high shear mixer – becomes in effect a Reactor for
coupling and catalysis mechanisms. It’s the interfacial
128
shear that is controlled by the system’s viscosity that
does the work — and the geometry of the compounding
machine just facilitates achieving the necessary work
energy. You can’t just let the Banbury or twin screw
rip away without monitoring torque or amps. You
can bet on this – if you are running control compounds
and titanate containing compounds at the same
conditions – you are not practicing good science, but
simply comparing “apples to oranges”. Mixing the
control and titanate containing compounds to
equivalent work energy is good science.
Much of the information in the literature reporting
the efficacy or lack of efficacy of my invention products
is often not completely accepted by me unless I know
that the investigator has paid careful attention to the
two mixing principles just discussed. Most qualified
polymer compounders know that the best formulation
can produce poor results because of poor mixing.
Rubber and plastic custom compounders and also
paint chemists are alert to mixing art techniques such
as two passes, solvent let downs, solubility parameters,
upside down mixing, predispersion of critical
ingredients, ram pressures, back pressures, increased
rpms, blade and screw designs, mixing element inserts
and all other manner of approaches that seek to
impart the optimum amount of mechanical shear
work energy to the interface of all the ingredients in
the matrix.
Many processors of thermoplastics and thermoplastic
elastomers are not polymer engineers or chemists
and are not aware of the nuances in the art of mixing
polymer formulations containing more than one
primary ingredient. So when they say to me that
additive A or additive B did not work, I first ask them
how they brought the two materials together – first
before the melt and then during the melt.
If they tell me that they mixed the ingredients in a plastic
bag, dumped the liquid coupling agent on top of the
other ingredients in a static bowl, added the liquid
coupling agent in a ribbon blender or a Banbury, then I
know they can’t possibly succeed or obtain the optimum
results. On the other hand, if they spray applied the
liquid titanate or diluted it first and then dropwise
added the liquid blend to a fluidized bed of the powder
ingredients before the melt in a high shear mixer such
as a Henschel, Papenmeier, Littleford Lodige, Patterson
Kelley V Blender with intensifier bar and other such
blenders typically used by PVC compounders, I know
that they have a good chance to succeed according to the
first principle of uniform distribution.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
They can even succeed if they add the coupling agent
into the other ingredients in a plastic bag and shake
if the coupling agent is in a masterbatch CAPOW
powder form or CAPS pellet form (cf. Table 1). I
repeat, a simple rule of thumb is: “liquid additives
into liquid polymer systems, powdered additives
into powdered systems and pelleted additives into
pellet systems.”
New thinking is required because some polymer
vendors will erroneously advise processors that it
isn’t possible to process a polymer 10% or more
lower in temperature than what their non-coupling
agent experience tells them. I have had customers
succeed in injection molding polycarbonate at 100°C
lower than recommended by the polymer vendor.
Not only was the titanate containing polycarbonate
product easier to mold eliminating problems such as
poor weld lines and blotchy color from poorly
dispersed red iron oxide – the titanate (LICA 12) parts
were stronger and aged better! The polymer vendor,
rather than supporting the new additive technology,
threatened that they would not be responsible for any
liability claims if the part failed in service because,
“Polycarbonate processed at 100C lower can not
possibly be polycarbonate any longer.” There is much
work yet to be done on the characterization of polymers
with subject additives.
The discussion by Yeh Wang et al23 in their work
entitled “Single Screw Extrusion Compounding of
Particle Filled Thermoplastics: State of Dispersion
and its influence on Impact Properties” makes the
point on the importance of specific energy input.
The abstract reads: “The compounding of calcium
carbonate filled polypropylene (PP) is discussed
with reference to a single-screw extruder and variants
of mixing sections. The mixing section on the screw
is exchangeable, and two dispersive mixing elements,
namely the Zorro and the Maddock elements, were
used. The calcium carbonate was surface treated
with a liquid titanate coupling agent (LICA 12). The
impact strength was measured by a notched Izod
impact tester with specimens having a U-shaped
sharp notch. The fracture toughness for the PP
homopolymer and the filled composites was
determined using fracture mechanics principles.
The results were correlated with the state of
dispersion of the calcium carbonate filler. The effects
of filler concentration and surface treatment were
examined as well. Correlation between state of
dispersion and impact properties for calcium
carbonate filled PP was obtained. We also
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
investigated the effect of various mixing elements
on the state of dispersion. The experimental results
indicate that good dispersion would improve the
impact properties of the polymer matrix, but only at
moderate filler loading.”
Of course, what Wang is referring to is that the level
of filler – even when coupled – cannot exceed the
CPVC of the matrix. Impact strength typically falls off
when increasing filler content in thermoplastics.
However, the impact strength with coupled filler will
actually increase with increased filler loading up to
slightly below the CPVC, at which point it will begin
dropping in value past virgin to below virgin impact
strength. The optimal amount of amount mineral
filler in uncured thermoplastics is usually 30% by
weight, but can vary depending on fineness of particle
size, particle size distribution, surface area, pore
velocity, particle shape, aspect ratio, bimodal
micropacking, moisture conditions, and a host of
other variables in the art.
Wang continued: “The fracture surfaces of the
specimens filled with LICA 12 treated CaCO3
compounded from the Zorro element, the Maddock
element, and the screw element are presented in
Figure 4(a-c). The filler concentrations are also 12%
by volume. It can be clearly seen that there are fewer
large particles or agglomerates in these composites
when compared with the micrographs of untreated
CaCO3 shown in Figure 3(b-d). As expected, there are
also more large particles and agglomerates in the
composites compounded from the screw element. In
general, better dispersion with a low degree of
agglomeration of the filler was observed with surface
treated CaCO3 filled compounds. Phase 23 separation
between the filler particles and the matrix seems less
distinct due to effective modification of the filler
surface with LICA 12, resulting in fewer agglomerated
particles present on the fracture surface.”
Wang further observes for maximum coupling agent
improvement: “This study clearly demonstrates that
incorporation of treated CaCO3 fillers greatly modifies
the impact strength of PP, but only at a moderate
loading of filler. SEM micrographs with image analysis
reveal better dispersion and decreased agglomeration
of filler particles upon treatment of LICA 12, which is
well known as an effective coupling agent.
Furthermore, proper choice of a mixing device plus
effective surface treatment would give rise to the
maximum improvement.”
129
 Salvatore J. Monte

Amount of Coupling Agent to Use optimum dosage when added early in the grind
before addition of the nanoclay in a 50% Nanocor®
The idealized amount of coupling agent to use is that CWC filled mineral oil. The viscosity of the mix will
amount that will form an atomic monolayer on the be reduced from 416,000 to 4,800 cps – while 0.3%
surface of the pigment to produce optimal pigment LICA 38 yields 89,600 cps – and 1 and 2% LICA 38 do
dispersion effects plus the amount that will have an not reduce the viscosity any lower than 4,800 cps. See
optimal repolymerization catalysis effect on the Table 2. Note the LICA 97 in Table 2 had no effect
polymer. Pigment dispersion being defined as the because it is insoluble in mineral oil.
complete deagglomeration of the pigment as attritted
or precipitated so as to allow all moisture and air in
the interstices of the pigment to be replaced with a Although surface area is an obvious dosage determinant,
continuous organic polymer phase. “Optimal the way the pigment is produced can determine dosage.
repolymerization effect” is defined as being the best For example, a pigment with a surface area of 3m2/g
balance of mechanical properties and systems required 0.35% titanate, while the same pigment
rheology. For example, although 0.2% additive by having a surface area of 1m2/g required 3.2% titanate.
weight of unfilled polymer is usually an optimum The different dosage requirement was not all surface
titanate dosage, ladder plots of effects of varying area dependent, but mostly caused by the different
dosages of 0.4 and 0.6% can be parabolic as well as surfactant chemistries used in the water slurries of the
asymptotic. Of course, benefits have also been noted pigment before drying.
at 2.0% of a polymer, underscoring the systems
specific nature of coupling agent applications art. The amount of coupling agent will even vary with
Most times it is beneficial to develop a three-point time with vast differences in viscosities depending
matrix plot effect with different dosages, i.e. a ladder on whether the viscosity was measured at room
study. A single dosage test at 0.2 wt% of the composite temperature immediately after mixing, or 1-hour, or
is just a data point place in space. Two data points 1-day or 28-days later [cf. Ref. 1]. This variability is
form a line in a plane. Three data points usually due to the pore velocity (the speed or time it takes for
provide a three-dimensional view of effects. a fluid to penetrate and wet the additional internal
inorganic surface area created by its capillary pores as
Amount Based on Organic Polymer determined by the geometric three-dimensional nature
A simple test devised by the author to demonstrate of the pigment) and other long-term interactions with
the repolymerization effect on low molecular the polymer interphase.
polyethylene wax (AC 617A – Allied Signal) was to
dilute one part of the PE wax with three parts of Amount Based on Combined Inorganic and
mineral oil. Mineral oil is a convenient C20 aliphatic Organic
low molecular weight room temperature model for
polyethylene [cf. ref. 1 – page ADD-7, Figure 1]. The A good dosage/data evaluation point would be that
resultant 1:3 blend had a viscosity of 22,400 cps. The which is obtained by the calculation of the combined
addition of 0.1 wt. % to the blend of NZ 12 increased amount of coupling agent needed to form an atomic
the viscosity to 5,000,000 cps, 0.2 wt.% to
7,000,000 cps, and 0.4 wt. % to 1,800,000 cps thereby Table 2 In situ effect of varying amounts of LICA
indicating 0.2 wt. % was optimum for this system. 38 and LICA 97 on viscosity of 50% NANOCOR
Most polymers give balanced property effects at 0.2 to CWC clay dispersed in mineral oil
0.6% titanate dosage.
Additive, % by Nano Mineral Viscosity
Weight of Clay Clay Oil Cps
Amount Based on Inorganic Pigment Control 50 50 416,000
The amount needed to form an atomic monolayer of LICA 38, 0.3% 50 50 89,600
coupling agent is pigment surface area dependent
and generally lies between 0.2 to 0.5 to 0.7% by LICA 38, 0.5% 50 50 4,800
weight of pigment. Figure 3 shows a “booklet” of LICA 38, 1.0% 50 50 4,800
calcined clay and the before and after coupling effect
of titanate to shift CPVC. Even nanoclays and fine LICA 2.0% 50 50 4,800
surface area silicas and blacks show some significant LICA 97, 0.5%* 50 50 416,000
dispersion improvement at 0.5% dosage. For example,
*LICA 97 incompletely soluble
0.5% LICA 38 by weight of nanoclay appears to be the

130 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
monolayer on the filler/reinforcement surface and
the amount needed for optimum repolymerization
effects on the polymer interphase. For example, the
optimum dosage for a 30-40% wollastonite filled PP
may well be that obtained by the combined weight of
0.5 wt% of the wollastonite portion and 0.2 wt% of
the PP portion – or 0.32 wt % additive for 40% filler
and 60% polymer. If Henschel pretreatment is
employed, dilution of 1 part coupling agent in three
parts mineral oil will enhance significantly the
uniformity of coupling agent distribution. Mineral
oil will have a somewhat negative effect on the tensile
strength of most uncured olefinic-based polymers.
Airless pray gun application to a dry fluidized bed of
compound ingredients will minimize diluent
requirements. A discussion follows on the necessity
to dilute titanate when pretreating Mg(OH)2. Similar
tests with ATH showed that dilution with mineral oil
was not necessary.
Amount Based on Treatment Techniques
and The Physics of Mixing – Tests with
LICA 38 for treatment of Mg(OH)2
The following discussion on treatment of Mg(OH)2
emphasizes the point that the “The Physics of Mixing
is as important as The Chemistry of Coupling”. You
may have the right titanate and the right % of titanate
dosage – but how you put it on the dry powder or
shear it into the polymer will affect the results. It
appears that dilution of one part of LICA 38 into three
parts of a compatible (i.e. soluble) liquid plasticizer,
where allowable, gives the best results for Pretreating
Mg(OH)2 to get comparable In Situ results.
In Situ Test Procedure:
Wash mixing vessels numbered 2 - 5 with a “0.25%
LICA 38/99.75% IPA” solution to neutralize surface of
each vessel (see Table 3). Then, add 40 parts mineral
oil to each of vessels 1 – 5, insert a mechanical stirrer
blade into the mineral oil and turn on electrical power
to create a mineral oil vortex of high shear. Then add
LICA 38 to the vortex slowly in the amount (see
column 3 for actual LICA 38 amount) as indicated for
vessels 2 – 5 and post mix for one minute under high
shear to assure complete solubilization and distribution
of the LICA 38 in the mineral oil. Then add 60 parts of
Mg(OH)2 powder slowly to vortex and post mix for one
minute under high shear. Measure Brookfield Viscosity
within 1 or 2 hours after adding metal powder as
viscosity changes with time depending on the “pore
velocity” of the particulate being coated. Then plot
Viscosity (y-axis) vs. % LICA 38 (x-axis). When the
tangent of the slope of the inverse log curve becomes
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
horizontal to the x-axis – that is the amount of LICA 38
needed for the Mg(OH)2 powder. Six in situ and eight
pretreated tests in Table 3 show that 0.7% LICA 38 is
the optimum dosage.
Pretreatment Test Procedure:
Use a high shear mixer typically used in PVC
compounding such as a Henschel. Add the Mg(OH)2
powder to the Henschel mixing bowl and turn on to
low speed at 1800 rpms. Then add neat or diluted
LICA 38 (1:3) dropwise over a one-minute period to
the vortex between the Henschel outer wall and
mixing blade axis followed by a one-minute post mix.
An airless spray gun would of course be better than
dropwise addition and probably result in needing
less diluent plasticizer than the 1:3 ratio dictated by
the dropwise approach. As indicated below, the in
situ tests show 0.7% gives an atomic monolayer and
the pretreatment tests show that 2.8% of a blend of
LICA 38:Plasticizer – 1:3 works to match the in situ
results. We chose two plasticizers – Kenplast ES-2HP
(a cumyl phenyl acetate – acetate compatible with
EVA) and KP-140 (C.P.Hall – FMC – an aliphatic
phosphate) since the Mg(OH)2 is intended for use in
flame retarded systems. The LICA 38 is soluble in
both plasticizers. The Kenplast ES-2HP may give
better mechanicals, but has the disadvantage of color
body formation as a result of the reaction of the
titanate with the phenol (see [Reference 1 – page 7].
KP 140 has a higher flash point and is an aliphatic
phosphato FR plasticizer and is probably the better
choice for this application.
In Table 3, Test 4 (12,800 cps), Test 6 (800,000 cps)
and Test 11 (12,800 cps) – all have the same amount
of Mg(OH)2 and LICA 38 (see Figure 4). The physics
of mixing, as well as the chemistry of the interface,
dictate the uniformity of coupling results. The
dispersion of 60% Mg(OH)2 into 20-melt, non-polar
LLDPE on a two-roll mill is quite difficult and produces
a poor sheet as shown in Figure 5. The smooth sheet
on the right in Figure 5 contains 60% of the 0.7% the
LICA 38 pretreated Mg(OH)2 as pretreated in Test 11.
CaCO3 Substrate Reactivity/Titanate
Solubility Relationship
The reaction of titanate with the intended substrate or
polymer phase is optimized when it is solubilized
into the organic solvent or polymer phase or finely
emulsified into the water dispersion phase where the
substrate to be coupled is next added. CaCO3 is the
most widely used filler in thermoplastics and will be
our discussion model here for coupling most
131
 Salvatore J. Monte

Table 3 The effect of in situ and pretreatment techniques for determining the optimum dosage of LICA 38 on
Mg(OH)2
(1) (2) (3) (4) (5) (6)
Test Mixing LICA 38 Amount (by Actual LICA Mineral Oil Mg(OH)2 Powder Brookfield
Vessel Number % weight of Metal 38 Amount Amount Amount Viscosity, cps @
Powder) 25C
In Situ 1 0.0 0.00 40.00 60 Untr. 1,120,000
In Situ 2 0.2 0.12 40.00 60 Untr. 400,000
In Situ 3 0.5 0.30 40.00 60 Untr. 32,000
In Situ 4 0.7 0.42 40.00 60 Untr. 12,800
In Situ 5 1.0 0.60 40.00 60 Untr. 8,000
In Situ 5a 2.8 1.68 40.00 60 Untr. 12,800
Pretreated 6 0.7% Neat LICA 38. 0.42 40.00 60 Pretr. 800,000
Pretreated 6a Let 6 sit for 24 hrs.
Pretreated 6b Use a Hobart Mixer 800,000
560,000
Pretreated 7 0.7%: 2.1% 0.42 + 1.26 38.74 60 Pretr. 64,000
LICA 38: Mineral Oil
Pretreated 8 0.7%: 2.1% 0.42 + 1.26 38.74 60 Pretr. LICA 38
LICA 38: Et.Glycol insoluble
Pretreated 9 2.8% Neat LICA 38 1.68 38.74 60 Pretr. 96,000
Pretreated 10 0.7%: 2.1% 0.42 + 1.26 38.74 60 Pretr. 12,800
LICA 38: ES-2HP
Pretreated 11 0.7%: 2.1% 0.42 + 1.26 38.74 60 Pretr. 12,800
LICA 38: KP 140

Figure 4 All three jars contain 60% Mg(OH)2 (0.7%
LICA 38 treated) filled mineral oil - in situ Test #4 (see
Table 3) – jar on left; pretreated neat Test #6 (see
Table 3) – jar in center; pretreated diluted Test #11 (see
Table 3) – jar on right
Figure 5 60% Mg(OH)2 untreated filled LDPE (20 M.I.)
(left) and 60% Mg(OH)2 pretreated with 0.7% alkyl
pyrophosphato LICA 38/1.2% alkyl phosphato
plasticizer (right)

particulate and fiber substrates to most polymers. I

would like to discuss some filler-organic-water phase
considerations: atmospheric moisture, organic phase
polarity, and degree of solubilization of the titanate in
the organic and water phases so that one can optimize

132 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
the titanate’s reactivity with CaCO3. Of course, most
of the effects can be translated to most any inorganic
or organic particulate.
The Effect of the Filler’s Atmospheric
Moisture on the Viscosity Reduction Effect
of a Fixed Amount of Coupling Agent
Table 4 shows that 50% CaCO3 (CaCO3 in bag exposed
to atmospheric moisture as provided by the relative
humidity) filled mineral oil will yield a 200,000 cps
viscosity. If the same CaCO3 is oven dried above
100°C for 24-hours to remove atmospheric moisture
and then added to the mineral oil in the same ratio,
the viscosity will read 20,000 cps. Of course, it is not
practical to keep inorganics moisture-free in this
manner. However, when 0.5% LICA 12 is added in
situ to the mineral oil, the CaCO3 is rendered
hydrophobic yielding a viscosity of 12,000 cps. It
would appear that there may be some advantages to
drying the filler prior to coupling.
Table 4 The effect of moisture and coupling
agent on viscosity of CaCO3 in mineral oil
Ingredients 1 2 3 and elastomer fillers. Thus, hydrated silica was
CaCO3, 2.5µ 50a 50b 50a
Mineral Oil 50a 50b 50a
LICA 12, 0.5% - - 0.4
Viscosity (cps) 200,000 20,000 12,000
a = CaCO3 - out of bag - subjected to
atmospheric moisture
b = CaCO3 - forced air oven dried at 225°F
for 24 hours
Hydrophobicity – CaCO3, Silica and Metal
Oxide (Lithium Nickel and Lithium Cobalt
Oxide Examples
Water and oxygen are necessary in inorganic filled
organic composites to initiate corrosion and aging
mechanisms. Hydrophobicity is a desirable property
to impart to filler and other functional particulates and
fibers to provide long term aged mechanical properties.
CaCO3, Silica and Metal Oxides will be discussed:
1. CaCO3: Figure 6 details the obvious hydrophobicity
effect of an isostearoyl titanate on CaCO3. The water
emulsifiable 25% active neoalkoxy triisostearoyl
titanate (LICA 01WE25) will provide parallel effects
for CaCO3 in the water phase.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
Figure 6 Effect of titanate on contact angle of a water
droplet on pure CaCO3 compressed slabs
2. Silica: The abstract of a technical paper by A.
Krysztafkiewicz et al24 entitled “The effect of surface
modification on physicochemical properties of
precipitated silica” stated: “The main goal of this
study was to obtain hydrophobic silica whose
properties would allow their application as plasto-
modified by silane and titanate coupling agents. The
modification procedure and appropriate modification
apparatus were developed. The degree of silica surface
modification was evaluated by different methods. As
grounds for this evaluation, changes in the
physicochemical properties, brought about by the
condensation reaction of surface silanol groups with
alkoxyl or hydroxyl groups of the molecules of
coupling agents, were used. The degree of
hydrophobicity of the silica surface was determined
on the basis of the heat of immersion of this surface,
and silanol groups were identified by the infrared
spectroscopy. Moreover, changes in the tendency to
form agglomerates and aggregates of molecules were
studied by microscopy. It was found that modification
with silane and titanate coupling agents leads to an
increase in silica activity. Application of these agents
results in the change of the hydrophilic character to
the hydrophobic one.”
In the discussion, Krysztafkiewicz stated: “The highest
degree of hydrophobicity was observed for silicas
modified with KR TTS (isopropoxy triisostearoyl)
and KR 33CS (isopropoxy trimethacrylic) titanates,
while it was a little lower after modification with 3 wt/
wt aminosilane and methacryloxysilane.” In fact, the
data in Krysztafkiewicz’s Table II of the paper showed
1 wt/wt of the titanate had greater hydrophobicity
than 3 wt/wt of the two silanes mentioned.
133
 Salvatore J. Monte
It was also observed in the Krysztafkiewicz paper that
water was necessary for the silane to couple to silica
while it was not needed for titanate. The absence of
the need of water of condensation to affect titanate
coupling opens up all sorts of possibilities for in situ
coupling in the thermoplastic or thermoset elastomer
melt that is not possible with silanes. It also liberates
the compounder from the constraints of a fixed dosage
of coupling agent on the pretreated filler and permits
tailoring compound performance by varying coupling
agent dosage to effect optimum properties in the final
compound. An application such as extremely flexible
“green” tires comes to my mind.
The Krysztafkiewicz paper concluded:
“Conclusions:
1. Modification of the surface of precipitated silica
results in an increase in its activity. Application
of both silane and titanate coupling agents
leads to an increase in the chemical affinity of
silica to polymer and, in the first place, to a
change of its character from hydrophilic to
hydrophobic.
2. Modification of the silica surface is performed
in a device ensuring a minimum usage of the
solution of modifying agent, i.e. both the solvent
and the coupling agent; modification involves
surface wetting of silica.
3. Modification by silane and titanate coupling
agents is a reaction involving substitution of
these compounds on silanol groups present on
the silica surface, according to a mechanism of
electrophilic proton substitution (SE)
4. The efficiency of the modification can be
estimated with high accuracy by using the
following methods.
a) NIR studies of changes in the intensity of bands
of silanol groups bound to the silica surface;
b) Measurement of the heat of immersion of the
surfaces of modified silicas, which indicates the
degree of hydrophobicity of these surfaces;
c) Electron microscopy studies that permit
interpretation of the effect of modification of
silica on agglomeration of its particles.”
A good example of how hydrophobic silica with
titanate provides long term aging performance as
compared to silanes was shown in Hitachi Chemical
Co., Ltd.’s JP 54, 149, 923 for powdered fused silica
glass, glass fiber filled epoxy novalac resin comparing
titanate and silane [cf. Ref. 1 – Table 4, Page Add-24].
The initial Flexural Strength, kg/cm2 @ 25C and 200C
were similar using both additives, with the silane
having about a 5% higher degree of mechanical strength.
134
But, after aging the composites @ 250C for 3000 hours,
the silane composite’s “Aged Property Retention of
Flexural Strength, %” was <20 while the titanate was
>70” as compared to the original properties.”
3. Lithium Nickel and Lithium Cobalt Oxide: Akihisa
Kajiyama et al25 of TODA KOGYO CORP. (a leading
producer of titanate treated γ-ferric oxide used in
magnetic recording media and copier toner) expressed
the criticality of hydrophobicity in their EP 1 041 041
A1 entitled “Layered rock salt-type oxide particle
powder and process for producing the same”, the
abstract of which read: “The present invention
provides a lithium nickel-layered rock salt-type oxide
particle powder, a lithium cobalt-layered rock salt-
type oxide particle powder or a particle powder of a
solid solution of these layered rock salt-type oxides,
wherein the surface of the particle is rendered
hydrophobic by coating it with a coupling agent
having both a hydrophobic group and a hydrophilic
group. The layered rock salt-type oxide particle
powder is free of an adverse effect caused by absorbed
water because of less amount of water absorbed on
the surface of the particle powder, high in
electrochemical charging and discharging capacities,
low in cycle deterioration, so that it is especially
useful as a positive electrode active material in a
lithium battery.
Kajiyama’s patent discussion of hydrophobicity is
instructive wherein he stated: “ As a measure of
surface hydrophobicity, the amount of adsorbed water
in a powder was determined by a Karl Fischer moisture
meter after the powder was left in an atmosphere at
a temperature of 25°C under 65% relative humidity
for 20 hours.
Example 1
(Production of lithium nickel-layered rock salt-type
oxide particle powder)
(0040) 1.5 equivalents of an aqueous solution of
oxalic acid (concentration = 10% by weight) were
added dropwise to an aqueous solution of nickel
sulfate (concentration = 10% by weight), to form
precipitates of nickel oxalate, which were then filtered
off, washed with water and dried, and the resulting
dried powder was pyrolyzed at 400°C in the air, to
prepare a nickel oxide particle powder. This nickel
oxide particle powder and lithium hydroxide
monohydrate (Li (OH) H2 O) were weighed at a molar
ratio (Li/M) of 1.03 and mechanically mixed, and the
resulting mixed powder was sprayed with 5% by
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
weight of water. This mixed powder was compression-
molded by a roller compactor to prepare a molded
body having a molding density of 2.2 g/cm3. This
molded body was placed in an electric furnace and
heated at 700 oC in an oxygen stream and calcinated
for 10 hours. The resulting molded body was ground
again in a mortar to give a black powder.
(0041) The resulting black powder was a lithium
nickel-layered rock salt-type oxide particle powder
and had good crystallinity, and as a result of
observation under a scanning electron microscope,
its particle size was well-regulated.
(0042) 10g of this lithium nickel-layered rock salt-
type oxide particle powder was dispersed in 100 cm3
toluene, and to this dispersion was added
isopropyltriisostearoyl titanate as a titanium coupling
agent in an amount of 1.0% by weight to the particle
powder, whereby the surface of the particle was
uniformly coated therewith, and this product was
filtered off and air-dried. As a result of x-ray diffraction,
the resulting black powder was a lithium nickel-
layered rock salt-type oxide particle powder and had
good crystallinity, and as a result of observation
under a scanning electron microscope, the particle
diameter and distribution of particle sizes thereof did
not change from those before heat treatment. Further,
the amount of adsorbed water was 0.12% by weight,
indicating that the surface of the particle had been
rendered sufficiently hydrophobic.
(Evaluation of electrochemical characteristics)
(0043) Then, the lithium nickel-layered rock salt-type
oxide particle powder thus obtained was examined
for its electrochemical characteristics as an electrode
active material. To prepare a positive electrode for
measurement, polytetrafluoroethylene as a binder in
an amount of 5% by weight and Acetylene Black as
an electrically conductive material in an amount of
20% by weight were mixed respectively in said layered
rock salt-type oxide particle powder, and 0.1 g of the
resulting mixture was weighed and loaded into a
mesh of titanium as a current collector to prepare a
work electrode. As a negative electrode, a metal foil
of lithium was loaded into a stainless steel mesh. As
a reference electrode, a lithium metal was used. A
solution of 1 M LiBG4 in a mixed solvent consisting of
propylene carbonate and dimethoxyethane at a ratio
of 1:1 by volume was used as an electrolyte.
(0044) The positive work electrode for measurement,
the negative electrode, the reference electrode and
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
the electrolyte which were prepared above were used
to construct an electrochemical cell for measurement.
This electrochemical cell was used to examine a
curve of charging and discharging in the potential
range of 3.0 to 4.5V with the metal lithium electrode
as the reference, at a current of 0.5 mA/cm2 at a
temperature of 30°C. The electrochemical charging
and discharging capacities were determined as an
indicator of the electrochemical activity of this lithium
nickel-layered salt-type oxide particle powder, and
the result indicated that its initial capacity was high
as 190 mAh/g and its capacity after 10 cycles was
189 mAh/g, indicating almost no cycle deterioration.”
The observed “almost no cycle deteriation” is directly
related to titanate complete dispersion and the
resultant true continuous inorganic/organic phase
absent air and moisture, both of which detract from
long-term functional performance of the formulated
polymeric composite.
Similarly, a titanate (KR 138S) provides resistance to
ozone attack for a Cadmium Sulfide/Epoxy
photosensitive plates [(cf. Ref. [1] – Table 34)]. The
untreated and TOT (tetraoctyl titanate) treated
Cadmium Sulfide lost 69% of initial functionality
while the KR 138S lost only 3.5%. The point is that
subject titanates are just as reactive with a metal
sulfide as they are with a metal oxide or barium
sulfate or boron nitride.
The Effect of Polarity of the Organic Phase
on the Viscosity Reduction Effect of a Fixed
Amount of Coupling Agent
Table 5 shows that 60% of a CaCO3 in non-polar
mineral oil will yield a viscosity of 400,000 cps while
the viscosity will be 9,600 cps in a polar aromatic oil
such as Sundex® 790 (Sun Oil Co.). Note that 0.5% KR
38S produces an initial viscosity effect of 2,075 cps in
the non-polar mineral oil and 4,998 cps in the polar
aromatic oil. It is fair to say that use of the titanate (or
zirconate) renders polar-like pigment wetting
characteristics to non-polar organics. This is important
to long term polymer composite color and appearance
because many polar organics contain unsaturated
cyclic chemical structures, which have inherent poor
long term UV stability. It also enables the processor of
EPR, EPDM, butyl, polybutadiene and other non-polar
polymers to use saturated aliphatic process oils as if
they were aromatic in their function without the
negative side effects of odor and free radical absorption
caused by polycylic unsaturation that detracts from
peroxide and free-radical cure efficiency.
135
 Salvatore J. Monte

Table 5 Viscosity effects of KR TTS and KR 38 titanates on CaCO3 initial and aged 7 days in various oils
(plasticizers)
Formulation Brookfield Viscosity, cps @ 25 °C
Oil (As Shown) - 40.00g Control KR TTS KR 38S
CaCO3 (Atomite) -60.00g No
Titanate, 0.35% - 0.21g Titanate
Aged Aged Aged Aged
Oils (Plasticizers) Initial Initial 7 Days 28 Days Initial 7 Days 28 Days
Ester (DOP 432,000 7,326 6,650 11,655 3,499 4,165 3,749
Mineral Oil (Prorex 907) 400,000 3,332 1,992 2,988 2,075 3,519 2,749
Paraffinic Oil (Sunpar 2150) 560,000 11,988 17,490 26,660 46,100 59,400 69,972
Paraffinic Oil (Sunpar 2280) 576,000 16,650 17,985 24,990 79,680 47,481 33,320
Naphthenic Oil (Circosol 415) 480,000 1,665 2,310 7,462 2,249 4,165 2,832
Aromatic Oil (Sundex 790) 9,600 9,628 15,770 9,960 4,998 6,560 6,240

CaCO3 Dispersed in the Organic Phase
The reactivity of subject titanates with CaCO3 has been
established1. SEM’s show [(cf. Ref. [1] - Figures 7A &
7B)] significant dispersion effects of CaCO3 in non-
polar (poor wetting) mineral oil. Transparent polyolefin
films containing titanate and 40% 0.9 micron CaCO3
have been produced1. The author has compounded
70% 2.5 micron untreated and titanate treated CaCO3
filled PP homopolymer and then injection molded the
compounds into dumbbell shaped test specimens.
The untreated specimens would snap at the slightest
attempt at bending whilst the titanate containing
specimens can be bent 180° with no cracking or white
stress formation at the bend. I usually carry these
dumbbells in my shirt pocket at trade meetings and I
am always at the ready to show you the amazing
flexibility that my invention titanates can impart to a
heavily filled plastic. Similar 180° flexibility using the
phosphato titanate in 30% CaCO3 filled polystyrene
has been achieved (cf. Ref. [1] – Figure 177) thereby
predicting similar flexibility in CaCO3 styrenated
polymers such as Acrylics and SBR.
The dispersion effects of subject titanates on CaCO3
in C20 aliphatic mineral oil has been translated into
use in many commercial non-polar olefinic
macromolecular disciplines. For example, M. N.
Ichazo et al 26 in a Technical Paper entitled “Study of
the CaCO3 Filled PP/HDPE Composites Using Different
Surface Modifiers” stated: “This study clearly
demonstrated that the incorporation of the coupling
agent to CaCO3 modifies the mechanical properties of
PP/HDPE/CaCO3 composites. The best coupling agent
concentration resulting is 0.7 wt% for all coupling
agents studied and the best enhancement in
mechanical properties was obtained with LICA 12.”
Comparison of the Wetting of Monoalkoxy
Titanate KR TTS and Various Other
Lubricants in the Dispersion of CaCO3 in
LDPE
Effects on torque reduction and dispersion were
ascertained in a study comparing a titanate with
conventional wetting agents in CaCO3 - filled LDPE
blown film. The samples were prepared in an
electrically heated Brabender, wherein the LDPE,
pigment, and wetting agents and the titanate (KR
TTS) were charged as one blend into the mixing
chamber having the following conditions: rotor speed
82 rpm; temperature 93°C; 0.5 kg. weight on the ram.
Torque readings in grams per square meter were
performed every 30 sec. for 3 min., starting with an
initial reading at 30 sec. elapsed time.
The resulting compounds were cooled and ground in
a Wiley mill, employing a 60-mesh screen. The dry
compound was dry-blended with a 2 melt index, high
clarity, film grade LDPE in a ratio of 9 to 1. Blown film
of 1.5 mil thickness was produced from the dry blend
on a 1.5 in. extruder at a 2.5 to 1 blowup ratio and
temperature profile of 143 to 160°C. The resulting
1.5-mil film was examined for the number of
undispersed pigment particles in 720 sq. in. of film.
The results of this examination are summarized in
Table 6.

136 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 6 Effects of KR TTS and conventional wetting agents on the brabender mixing torque of CaCO3
filled LDPEa,b

Torque (g/m2) Melt Particles

Index per 144
Additive 30 s 60 s 90 s 120 s 150 s 180 s (g/10 min) in.2
None 2,000 2,000 1,900 1,750 1,750 1,750 0.27 312
c
Emcol H31-A 2,150 1,400 1,150 1,000 1,000 1,000 2.30 006
Emcol 117c 1,900 1,400 1,300 1,250 1,100 1,000 1.90 016
Glycerol Monostearate 2,150 1,400 1,300 1,250 1,250 1,150 3.87 044
Emcol 116c 1,900 1,400 1,300 1,150 1,150 1,100 1.69 020
Aluminum Oleate 1,650 1,600 1,400 1,300 1,250 1,250 1.80 044
Aluminum Stearate 1,900 1,400 1,300 1,250 1,250 1,250 1.60 032
Tween G5d 2,500 1,500 1,250 1,000 0,900 0,900 1.25 007
Zinc Stearate 1,900 1,650 1,400 1,150 1,150 1,050 2.30 044
e
Paricin 220 1,900 1,400 1,250 1,150 1,100 1,100 0.95 016
Ken-React KR TTS 1,250 0,900 0,900 0,900 0,750 0,750 4.17 016
a Formulation: 9 parts of LDPE and 1 part of dry blend consisting of 70% CaCO3 (Camel-Tex), 28% LD 501 and
2% Additive
b LDPE 501, Exxon Chemical Co
c Witco Chemical Co
d Imperial Chemical Industries Ltd. (ICI)
e Baker Castor Oil Co

The KR TTS treated CaCO3/LDPE system reflects Table 7 Effect of degree of emulsion of LICA 38
almost instantaneous torque reduction and short with ENP (IGEPAL CO-660) on the viscosity
mixing cycles for optimization. Dispersion is excellent response of 80% CaCO3 in water
with only 33% of normal power requirements when Formulation
compared to conventional systems. The dispersion
of CaCO3 treated with KR TTS in the LDPE would CaCO3 (2.5m) - 80.0
most likely have been improved if the temperature of Water - 20.0
the Brabender had been lowered to increase the
torque and therefore the resultant area under the Additive (Ratio as Shown) - 0.5
power curve, which is a measure of the work energy. Observed
See the “Early Historical” discussion for references Degree of Viscosity, cps
Ratio
on the above work. In retrospect, it is now obvious to LICA 38 @ 25°C
me that 0.2% KR TTS is having a catalytic effect of the Emulsion*
LDPE and changing its intrinsic morphology 0.0 : 0.0 - 3,600,000
independent of CaCO3 content.
0.0 : 1.0 - 1,600,000

CaCO3 Dispersed in the Water Phase 1.0 : 0.125 Poor 240,000

1.0 : 0.25 Very Cloudy 232,000
The importance of solubilizing or finely emulsifying
the titanate in the organic/water dispersion phase 1.0 : 0.5 Less Cloudy 160,000
before the addition of filler is demonstrated in Table 7.
1.0 : 1.0 Clear 3,000
LICA 38 was preblended with varying amounts of
ethoxylated nonyl phenol (ENP – Rhodia Igepal® CO * Ratio blends of LICA 38 and Igepal CO-660
660) emulsifying agent to render the water insoluble added to water at 5% concentration and degree of
LICA 38 water emulsifiable. Blends of LICA 38:ENP emulsion observed

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 137

 Salvatore J. Monte

were varied in ratio from 1:0.125 to 1:1 and then
stirred vigorously into water at the 5% level to
observe the degree of emulsion from ‘poor’ (1:0.125)
to ‘clear’ (1:1). Next the LICA 38:ENP blends were
emulsified into the 20% of water at 0.5% by anticipated
weight of the next added 80% 2.5 micron CaCO3. The
effective amount of finely emulsified (‘clear’ – Table 7)
titanate (LICA 38:ENP-1:1) was 0.25% by weight of
CaCO3 to produce the 3,000 cps effect. The much less
effective amount of poorly emulsified (‘poor’-Table 7)
titanate (LICA 38:ENP-1:0.125) was the greater amount
of 0.4% by weight of CaCO3 to produce the 240,000 cps
lesser effect. More titanate is not better. Better-
dispersed titanate is better. The viscosity reduction
achieved in the water phase from 3,600,000 to
3,000 cps, absent any organic phase, is significant.
1-Micron and 5-Micron CaCO3 Dispersed
in the Water and Organic Phase (Mineral
Oil) – The Effects of In Situ and
Pretreatment with LICA 12WE33
Table 8 studies the effect of a water emulsifiable LICA
12WE33 on CaCO3 in the water and organic phase. It
demonstrates that the Water Emulsifiable titanate
grades are efficacious in the water phase as its analogs
are in the organic phase. Of course, the CaCO3
pretreated with LICA 12 will be more hydrophobic
than the CaCO3 pretreated with like amount of LICA
12WE33 because the surfactants used to make LICA
12 are hydrophilic.

Table 8 LICA 12 WE33 pretreatment and in situ treatment of CaCO3 (1µ and 5µ ) in H2O and mineral oil
Viscosity Viscosity
1% CaCO3 H2O % C.A.b 5% CaCO3 H2O % C.A.b
(cps) (cps)
IN SITUa
Control 82 18 0.00 224,000 80 20 0.00 1,280,000
LICA 12 WE33 82 18 0.35 64,000 80 20 0.35 128,000
LICA 12 WE33 82 18 0.50 64,000 80 20 0.50 44,800

LICA 12 WE33 82 18 0.70 51,200 80 20 0.70 38,400
HENSCHEL PRE-TREATEDc
LICA 12 WE33 82 18 0.50 51,200 80 20 0.50 32,000
Mineral Mineral
IN SITUd
Oil Oil
Control 60 40 0.00 1,120,000 60 40 0.00 240,000
LICA 12 WE33 60 40 0.35 640,000 60 40 0.35 1,720

LICA 12 WE33 60 40 0.50 400,000 60 40 0.50 1,520
LICA 12 WE33 60 40 0.70 208,000 60 40 0.70 1,800
HENSCHEL PRE-TREATEDc
LICA 12 WE33 60 40 0.50 192,000 60 40 0.50 1,400
WATER SLURRY PRE-TREATEDe
LICA 12 WE33 60 40 0.50 80,000 60 40 0.50 2,600
a LICA 12 WE33 (33% active LICA 12 rendered Water Emulsifiable) added to water followed by addition of
untreated CaCO3
b % LICA 12 WE33 by weight of CaCO3
c CaCO3 pretreated in Henschel mixer by dropwise addition over 2.5 min. @ 1,800 RPM and postmixed 30
seconds
d LICA 12 WE33 added to mineral oil followed by addition of untreated CaCO3
e CaCO3/Water slurry - 0.5% of LICA 12 WE33 added to 18 parts of water followed by 82 parts of CaCO3 then
forced air oven dried @ 110°C for 1 hour then added to mineral oil

138 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
EPDM Rubber As A Suitable Substrate for
Coupling in a Water Based Acrylic Using
LICA 12WE33
Since the titanate or zirconate coupling mechanism
works on a proton reactive basis, not only are inorganic
substrates reactable with them, but so are organic
substrates as created by polymers such as EPDM or
fillers such as carbon black or fibers such as polyester2.
Most of the water insoluble titanates can be rendered
water emulsifiable and reactable with inorganic/
organic substrates. For example, Luis M. Calvo et al27
in U.S. Patent 6,036,998 dated March 14, 2000 entitled
“Process for Coloring EPDM Rubber to Produce
Granules for Blending with Polyurethane Resins or to
Use by Themselves to Create Safety and Athletic
Surfaces” stated in their patent Example 1:
“Approximately two tons of 1-3 mm in diameter
EPDM rubber granules were added into a ribbon
blender of approximately 60 to 90 cubic feet in
capacity. The ribbon blender was manufactured by
Ross Inc., of Hauppauge, N.Y. Ten percent (10) Ken
React LICA 12 WE 33 titanate water surface treatment,
available from Kenrich Chemical located in Bayonne,
N. J. was added to the blender at a proportion of 1 part
per weight titanate water surface treatment to EDPM
rubber for the purpose of preparing the EDPM rubber
granules for coating. The titanate water surface
treatment improves the adhesion of the coating to the
EPDM rubber surface. The EPDM rubber and titanate
water surface treatment were mixed in the ribbon
blender for approximately 2 minutes until a
homogenous mixture was obtained.
PolyFlo Green acrylic coating available Polymer
Plastics located in Hauppauge, N.Y. was added to the
blender at 10 parts per weight of coating per weight of
EPDM rubber. The PolyFlor Green coating and EPDM
rubber were blended for approximately 10 minutes
until the EPDM rubber was sufficiently coated.
After the EPDM rubber was coated, the coated granules
were conveyed to a tunnel oven by a conveyor and
heated at 425oF for approximately one hour to dry the
paint thereby providing a permanent coated surface
for the EPDM granules.
The coated granules coated of this Example showed
much better adhesion of the acrylic paint to the outer
surface of the EPDM rubber granules than coated
EPDM rubber granules untreated with titanate.”
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
Carbon Black Substrate Reactivity
Carbon black is the largest filler used in elastomers.
One good way to measure carbon black dispersion is
through changes in its conductivity as measured by
reductions in resistivity in insulating polymer
matrices. Carbon black conducts electrons and thus
lowers the resistivity of conductive composites by
virtue of creating a conductive network of three-
dimensional particulate surface contact. As the
amount of carbon black is increased the resistivity is
decreased as the degree of conductance is increased.
Additionally, the efficiency of a fixed amount of
carbon black is increased because of the increased
dispersion experienced using titanate. Table 9 shows
the volume resistivity reduction effect (7.8 x 1014 to
3.7 x 107) of a neoalkoxy tridodecylbenzene titanate
on a 3.75% XC-72 conductive carbon black in a SBS
Block Copolymer/PS Blend.
Table 9 Resistivity of 3.75% XC-72R conductive
black in styrene-butadiene block copolymer/ps
10mm thick test slab
Percent LICA 09 Resistivity, Ω·cm
3.75% XC-72R Surface Volume
Control > 1016 7.8 x 1014
0.67 1.7 x 1012 3.0 x 1012
1.00 2.1 x 108 4.3 x 107
2.00 5.7 x 107 3.7 x 107
Carbon Black Conductivity in Polyolefins
Gang Yu et al 28 measured carbon black filled
polyolefin as a positive temperature coefficient
material studying the effect of coupling agent
treatment, composition and processing conditions.
Yu stated, “It has been known that carbon-black (CB)-
filled semicrystalline polymers exhibit both
percolation phenomenon and specific temperature
dependence of resistivity. The former makes the
materials have a wide range of conductivity from
insulator to semiconductor, depending on CB
concentration. The latter is characterized by either
positive temperature coefficient (PTC) effect or
negative temperature coefficient…. …For a polymer-
based PTC material of practical value, its volume
resistivity increases remarkably by several orders of
magnitude when temperature approaches to the
139
 Salvatore J. Monte

melting point of matrix resin. …a composite of this Figure 7A, 7B, 7C Initial, during and final – conductive
kind …serves as self-regulating heaters, self-resetting Carbon Black (Cabot XC-72R) placed on water with no
overcurrent protection elements, microswitches, coupling agent (left) and same amount of same Carbon
sensors, etc., with the advantages of excellent Black placed on water containing directly emulsifiable
neoalkoxy tridodecylbenzenesulfonyl titanate and
formability, moldability, light weight, and flexibility
having no mechanical stirring of the ingredients at any
over the conventional inorganic PTC materials. Yu’s time
data shows that an 18-wt% CB (22-24 nm, 150 m2/g,
and DBP 125 mL/100g) loading in LDPE (MFI 2.0 g/
10 min., MP 90-95°C) using titanate creates a composite
with a stable PTC intensity.

Yu’s data in Table III of his paper demonstrated that

the untreated CB control at 18-wt% in LDPE had a
PTC Intensity of 2838 while a pyrophosphato titanate
(KR 38S) treated CB was 115.6. This twenty-four fold
increase in PTC performance means that, based on
PTC Intensity vs. CB content [wt%] values as plotted
in Yu et al’s Figure 2, it would take about 7%
additional untreated CB to reach the KR 38S treated
CB performance level. KR 38S imparts a very
significant amount of efficiency to the performance of
the conductive carbon black and allows the production Figure 7A - Initial
of novel “smart” polymeric composites and more
uniform conductivity control.

Carbon Black Dispersion in Water – Figures 7A, 7B

and 7C are photos of a time lapse of the effect of a
neoalkoxy tridodecylbenzenesulfonyl titanate (LICA
09) on the dispersion of conductive carbon black in
water. This particular titanate (LICA 09) is directly
water emulsifiable. The complete dispersion of the
carbon black as shown in the figures was accomplished
without any mechanical stirring.

Figure 8 shows 1.2% LICA 38ENP by weight of 7.4 %

oxygenated carbon black dispersed in water at a 35%
loading eliminates completely the phase separation Figure 7B - During
between carbon black and water. When a Brookfield
viscometer is inserted into the CB/H2O-25/75 control
mixture without titanate, the spindle reading produces
a viscosity at 25°C equal to 12,800 cps since the
spindle slides past the phase separated and
uncompatibilized carbon black/water mixture. The
addition of the LICA 38ENP to water followed by
carbon black addition increases the viscosity from
12,800 to 192,600 cps as the carbon black becomes
completely compatibilized with the water phase and
no phase separation is noted – even after 1-week
standing. Similarly, 0.8% LICA 38ENP by weight of
2.3% oxygenated carbon black increases the viscosity
from 32,000 cps without titanate to 96,000 cps with
titanate. Again, phase separation of the carbon black
in the water phase is eliminated. Figure 7C - Final

140 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
Figure 8 Compatibilization of 35% Carbon Black in
water. Untreated (left) shows phase separation of Carbon
Black from water. 1.2% LICA 38ENP (by weight of 7.4 %
oxygenated Carbon Black) dispersed in water followed
by CB addition shows no separation
When the 2.3% oxygenated carbon black is dry
powder pretreated with 0.5% KR 134SP, the viscosity
at 35% carbon black loading in an aromatic oil
(dimethyl naphthalene-Kenplast G) is 640,000 cps as
compared to 800,000 cps for the control. When the
KR 134SP is added directly to the aromatic oil at 0.5%
by weight of the carbon black, which is then added at
the same 35% loading, the resultant viscosity is
400,000 cps.
Thermally Conductive Graphite Filled
Neoprene GRT
There is a correlation between electrical and thermal
conductivity of particulates added to polymers. Any
thermally conductive composition can be made more
efficient by increasing the loading of the thermal or
electron conductive material. The trick is to load up
the polymer compound without losing the ability to
process the compound and then to form a part that
has suitable mechanical properties. That’s why a
shift in CPVC induced by titanate is usually predictive
of an increase in a functional particulate’s
performance. A good example of the benefits of the
teachings of this paper are in Ogino Masaaki’s JP
Patent 0307075429 entitled “Rubber compositions
with high heat-conductivity” the abstract of which
states: “Title compns. useful for electronic parts
contain rubbers and expanded graphite flakes (I)
treated with titanate couplers. Thus, 72.6 g I (EXP-P)
was treated with 300 mL MEK contg. 1% bis
(dioctylpyrophosphate) ethylene titanate for 5 days.
The obtained graphite (20% vs. total compn.) was
roll-kneaded with Neoprene GRT (chloroprene rubber)
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
100, Mg0 4, ZnO 5, and stearic acid 1 part to obtain
a sheet showing heat cond. 0.53 kcal/m-h-, degree. C,
modulus M100 33 kg/cm2, elongation 871%, and
hardness 75, vs. 0.41, 21, 637, and 73, resp., for the
compn. Contg. untreated I.”
Other Functional Inorganics Used in
Thermoplastics and Thermoset Elastomers
We will offer a brief discussion on coupling agent
effects on some other widely used inorganics in
various polymer systems to compare titanate to silane
performance.
TiO2 Filled Epoxy–Monoalkoxy
Pyrophosphato Titanate v. Trisalkoxy
Aliphatic Amino Silane
Investigators from Osaka University concluded30:
“The effects of different coupling agents on the
mechanical properties of the TiO2 coated with a
silane coupling agent were compared with composites
prepared by dispersing titanate coupling agent-coated
TiO2 in epoxy, Young’s modulus and flexural strength
of the titanate coupling agent-treated composites
were significantly better than those of the silane
coupling agent-treated composites. Apparently a
strong interfacial bonding between the filler and the
matrix existed when the titanate coupling agent was
used.”
Preparation of Ultrafine TiO2
Tadahiro Murakata et al31 synthesized TiO2 from
tetraalkoxy titanate and introduced the pyrophosphato
titanate directly into the manufacturing process to
create a highly functional metal oxide. The abstract of
their technical paper entitled “Preparation of Ultra
Fine TiO2 Particles Dispersible in Organic Solvents
and Their Photocatalytic Properties” reads: “Ultra
fine TiO2 particles which dispersed in various organic
solvents were synthesized through hydrolysis of a
titanium alkoxide to form colloidal TiO2 particles
followed by modification of the colloidal particles
with a hydrophobic coupling agent. The organic
solvent solutions of the synthesized TiO2 particles
were transparent and had high colloidal stability.
Photochemical properties of the TiO2 particles in
organic solvents were studied: namely how Ti3+ species
were formed in the particles and accumulated in
them; and how the particles were photocatalyticly
active for oxidation of I- and reduction of methylene
blue and Ag+. From comparative studies of the
photocatalytic reactions, the TiO2 particles are found
141
 Salvatore J. Monte
to have higher photocatalytic activity than
commercially available anatase and rutile powders.”
Fe2O3/Styrene/n-Butylmethacrylate Copier
Toner
Increased iron oxide functionality using titanate is
demonstrated in Xerox’s US Patent 5,489,497 dated
Feb. 6, 1996 entitled, “Magnetic Toner Compositions
with Surface Additives” wherein Eugene F. Young
and Dennis J. O’Keefe stated: “The invention is
generally directed to toner and developer
compositions…wherein there is selected as the toner
pigment a magnetite, especially a spherical magnetite
treated with a phosphate titanium coupling agent….
The toner compositions of the present
invention…possess rapid charging or admix
characteristics for an extended number of imaging
cycles. Furthermore, the toner compositions of the
present invention are substantially insensitive to
relative humidity and enable developed images with
excellent optical densities. …Moreover, the toners of
the present invention enable developed images with
excellent solid area densities (SAD)….
In the aforementioned U.S. Pat. No. 5,278,018 there
is illustrated a negatively charged toner with
crosslinked resin particles, silane treated magnetite
particles, wax particles, and a negative chromate
charged additive. …The SAD of the developed images
of the ‘018 patent is inferior in some instances when
compared to the SADs of the present invention as
illustrated herein.
…One preferred toner contains 60 weight percent of
resin, especially a styrene, 51 weight percent; n-
butylmethacrylate, 49 weight percent; and which
resin has been crosslinked with divinylbenzene,
0.05 weight percent, and benzoyl peroxide, 3 weight
percent; 32 percent plus or minus 2 percent by weight
of the treated or coated magnetite; 5 weight percent of
wax like polypropylene, such as 550PTM available
from Sanyo Chemicals of Japan; 3 weight percent
plus or minus 1 percent of charge additive, and as
external additives 0.4 weight percent, plus or minus
0.1, of the colloidal silica AEROSIL R812®, available
from Degussa Chemicals, and 2.5 weight, plus or
minus 0.5, percent of strontium titanate
…A SAD density below 1.3 was readable, but was not
anesthetically acceptable. It tended to be nonuniform.
It fell below the benchmark of about equal to or
greater than 1.3. For densities above 1.5, there was a
142
tendency for the machine to produce black streaks or
background on the copy due to excess toner present
in the development zone or excess toner charge
causing over development. It also stressed the cleaning
system and caused cleaning failures.
The performance essence of the patent shows that
0.23 micron Spherical Fe2O3 treated with 0.5% γ-
Glycidoxypropyltrimethoxy silane produced an
Unacceptably low SAD (1.19) at 80 ºF/10 percent
Relative Humidity while 0.5% (KR 38S) titanate
produced a Good SAD (1.4) at 70 ºF/20 percent
Relative Humidity. The Xerox data pointed to the
importance of doing a ladder study because, whilst
0.5% KR 38S was the best performer, 1% of the same
titanate was the worst. Toda Kogyo Corp., Japan uses
the KR 38S titanate as produced by Ajinomoto, Tokyo
under license from Kenrich Petrochemicals, Inc.
Barium Ferrite Filled Thermoplastic
Natural Rubber (TPNR) – Electrical and
Magnetic Properties
In their technical paper entitled, “Electrical and
Magnetic Properties of Barium Ferrite Thermoplastic
Natural Rubber (TPNR) Composites” Sahrim Ahmad
et al32 concluded: “Electrical resistivity, magnetic
and mechanical properties of thermoplastic natural
filled with barium ferrite powder have been
investigated. Barium ferrite indicated a suitable
additive to make a magnetic thermoplastic natural
rubber with good magnetic, conductive and better
mechanical properties after treatment with LICA 38.
Barium ferrite TPNR composite is useful as a lighter
magnetic material for some applications.”
ATH and Mg(OH)2 Non-Toxic Flame
Retarded Thermoplastics
Non-toxic Flame Retardance - Phosphato and
pyrophosphato functionality provides phosphato and
pyrophosphato intumescent synergism and high
loadings of non-toxic ATH [1] or Mg(OH)233. Typically,
greater than 60% ATH loading by weight is needed in
PP to obtain a UL94 Vo rating. For example, Robert
Andy stated [ref. 1 – page Add-9] in U.S. 4,525,494
concerning the use of a phosphato titanate (KR 12)
treated ATH: “The present invention provides a
polypropylene composition containing (64%)
hydrated alumina which has high izod impact
strength, increased flow, increased elongation,
increased deflection and increased Gardner impact
values compared with the original polypropylene,
without loss of tensile strength. The practice of this
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
invention will give flame retardance to any
polypropylene system while enhancing the strength
of the product. For example, the practice of this
invention has produced polypropylene products that
have impact strengths which are increased four times
and flow rates increased seven times over the starting
material without loss of tensile or any other critical
property”.
Further documentation of the application of titanate
and zirconate coupling agents in non-toxic flame
retardant thermoplastic and elastomer polymers with
ATH and Mg(OH) 2 is embodied in Alusuisse
Martinswerk GMBH’s WO 00/15710 Patent dated
14 September 199934 entitled “Surface-Modified Filling
Material Composition”, the abstract of which reads:
“The invention relates to surface modified filling material
compositions for thermoplastic, duroplastic or
elastomeric materials which comprise a halogen-free,
flame-retardant filling material. Said filling material is
surface-treated with organotitanates and/or with
organozirconates and with a siloxane derivative.”
Masaharu Kato et al35 made similar observations as to
which additives produced new and novel non-toxic
flame retardant compositions in their EP 0 708 143
A1 entitled, “Polyvinyl chloride based resin
composition and products derived therefrom” the
abstract of which reads: “A blended polyvinyl chloride
based resin composition consisting essentially of
100 parts by weight of a vinyl chloride resin has a
chlorine content of from about 50 to about 73 percent
by weight, from about 5 to about 12 parts by weight of
a flame-retarding agent and from about 1 to about
30 parts by weight of a graft polymer. The blended
vinyl chloride based resin composition and products
derived therefrom exhibit improved flame-retarding
and heat tolerance properties. The blended resin
composition and its products also exhibit improved
vacuum moldability and increased impact resistance.
In particular, the blended resin composition and its
products emit substantially less smoke and less toxic
fumes containing hydrogen chloride. A method to
produce the blended vinyl chloride based resin
composition including a method of processing
moldings by thermoforming is also disclosed.”
Their discussion of possible additives included:
“Titanium Coupling Agent, Thermal Stabilizers,
Lubricant, Inorganic Fillers, UV Absorbers and Anti-
oxidants, Vinyl Chloride Based Resins, Flame-
retarding Agents, Impact Modifiers, Graft Polymers,
HCl Inhibitors, Miscellaneous Additives”. The
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
compound designed for thermoforming also contained
rubber modifiers consisting of Polyorganosiloxane,
n-Butyl Acrylate and Allyl Acrylate.
Kato’s patent discussion under Titanium Coupling
Agent read: “The blended resin composition may
further include a titanium coupling agent. Its inclusion
is optional, however, the presence of this compound
substantially improves the overall impact resistance
of the blended resin composition and products derived
therefrom. The amount of the titanium coupling
agent preferably ranges from about 0.1 to about
8 parts by weight.” Actually, all of the 47 compounds
cited in the patent tables contained LICA 38, LICA 44,
KR TTS or KZ 55 (cf. Table 1).
CATALYSIS
Organic titanates (and zirconates) are well known
catalysts used in the manufacture of: polyolefins,
polyesters, polybutylene terephthalate,
polyurethanes, polycarbonates, and
polysiloxanes1,12,36,37,38. The coordinate titanates are
shown to improve the color and appearance of the
base polymer such as PET and PBT. For example,
Reference [37] discloses the use of a complex catalyst
consisting of antimony and titanium (tetraisopropyl
di(dioctyl)phosphito coordinate titanate – KR 41B,
cf. Table 1) compounds to produce a PBT polymer
“…having excellent color, a small amount of side-
product and a high degree of polymerization within
a short time”.
A patent38 using KR 41B titanate in a method to
produce a PET polyester resin states: “The method
can considerably reduce both the esterification end
time and the polycondensation time and provides a
good color, reduced content of diethylene glycol and
reduced concentration of terminal carboxyl groups
in the prepared polyesters.”
A patent demonstrates [cf. Ref. 1 – Table 76] that KR
41B titanate performed better as a conventional
transesterification catalyst than TIPT (tetraisopropyl
titanate) and ferrous lactate. See Table 10. Specifically,
0.5 ppm (as Ti) of KR 41B compared to 1.0 ppm (as Ti)
TIPT provided: a decrease in esterification reaction
time (99.8% conversion) from 9 to 7 hours; a decrease
in Acid value (mg-KOH/g) from 0.70 to 0.21; a decrease
in OH value (mg-KOH/g) 54.1 to 52.4; an increase in
molecular weight as measured by viscosity (cps,
30ºC) increase from 7300 to 7700; improved color
(APHA) from 50 to 40 (see Table 2).
143
 Salvatore J. Monte

Table 10 Comparison of KR 41B, TIPT and ferrous lactate as catalysts in the manufacture of an aliphatic
polyester
Example 1 Example 2 Example 3
Catalyst Type KR 41B TIPT Ferrous Lactate
Catalyst Conc. (ppm)
0.5 1.0 1.0
(as Ti)
Catalyst Volume (g)
0.032 0.021 0.017
(as Ti)
Esterification Acid Value Esterification Acid Value Esterification Acid Value
(%) (mg-KOH/g) (%) (mg-KOH/g) (%) (mg-KOH/g)
Reaction Time 5 96.44 13.4 94.76 19.7 94.58 20.4

6 99.33 2.5 98.27 6.5 97.32 10.1

7 99.88 0.45 99.31 2.6 98.59 5.3

8 99.65 1.3 99.15 3.2
9 99.81 0.7 99.44 2.1
11 99.73 1.0
13 99.84 0.6
Acid Value
0.21 0.70 0.61
(mg-KOH/g)
OH Value (mg-KOH/g) 52.4 54.1 52.6
Viscosity, cps @ 30°C 7700 7300 7400
Color (APHA) 40 50 100
Example 1 – To make the polyester, the mixture of adipic acid 1634.25g, ethylene-glycol 694g and 1,4-butanediol
1007.4g, in the presence of 0.5ppm (as Ti) KR 41B, was heated to 240°C in 5hrs. under N2 gas, in reaction
equipment with rectification tower (the percentage of reaction was 93-97% at this point) and heated
continuously at 240°C reducing the pressure from 760mm Hg to 100mm Hg in 1hr, and continued for 1-2hrs
under 100mm Hg.
Example 2 – The mixture was the same as Example 1 except tetraisopropyl titanate (TIPT) 1.0ppm, 0.021g was
used in place of KR 41B
Example 3 – The mixture was the same as example 1 except ferrous lactate 1.0 ppm, 0.017g was used in place of
KR 41B

Subject organometallics can accelerate or slow down
the gel time of 2-component polyurethanes [cf. Ref. 1
– Tables 270, 271]. For example, a typical 2-component
polyurethane can have a gel time of 7’12” using dibutyl
tin dilaurate as the catalyst, while the substitution of
the aliphatic amino titanate (KR 44) as the catalyst will
reduce the gel time to a very short 0’20” and the
isopropoxy pyrophosphato titanate (KR 38S) will
increase the pot life to 10’00”. For example, for one-
component, moisture curable sealant compositions,
Baghdachi stated in US Patent 4,889,903 entitled,
“Fast-cure Polyurethane Sealant Composition
Containing Titanium Ester Accelerators”: “It has been
found in accordance with the present invention that
the inclusion of such titanate accelerators (subject
titanates) in the sealant compositions significantly
increases the cure rates over the cure rates for similar
sealant compositions which lack the titanate ester
accelerator compounds…”.
M.C. Barker in ICI’s EP 0 361 764 A2 Patent uses the
neoalkoxy pyrophosphato titanate (LICA 38) as a
“degellant” additive to produce new and novel
polyurethane foams: “Flexible foams prepared from
such novel compositions showed improved cell-
opening characteristics, making such foams more
readily crushable or even avoiding the need of
crushing. Rigid foams prepared from such
compositions appeared to exhibit lower density.”

144 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
CROSSLINKING
Titanates (and zirconates) are able to cross-link or
cure a variety of polymers: polyolefins,
polybutadienes, styrene-butadiene copolymers,
polystyrene, polysiloxanes, epoxy, fluorocarbon
resins, acrylic and methacrylic resins, and polyvinyl
alcohol [cf. ref. 4, ref. 31-60]. For example, the abstract
of ref. [39] reads: “A neoalkoxy trimethacryl zirconate
CAS # [PMN No. P91-77] crosslinked more effectively
than a silane when used at 3 phr in a 0.5 phr dicumyl
peroxide ethylene-vinyl acetate copolymer when
immersed in 78°F (25°C) water for 72 hours”.
METALLOCENE CATALYSIS
New polymers derived from metallocene (titanocene
or zirconocene) catalysts have been introduced
recently exhibiting superior flow and increased strain
properties as compared to analogous Ziegler-Natta
catalyzed polymers. The author claims13 metallocene-
like benefits can be obtained in situ at the elevated
temperatures of even engineering thermoplastics using
small amounts (0.1 to 2 parts per thousand) of the
thermally stable titanium and zirconium ester forms
as typified by subject titanates and zirconates. We call
this metallocene-like catalysis effect
“Repolymerization”40.
REPOLYMERIZATION
Repolymerization is a patented40 concept by the
author to explain titanate and zirconate new and
novel rheology and stress/strain effects in
thermoplastics and thermosets independent of
crosslink and curative effects. Thermosets are
relatively high molecular weight thermoplastic
macromolecules or lower molecular weight liquid
chemical compounds (i.e. two component systems)
until they are crosslinked. For example, a rubber
compound containing curative is considered a
thermoplastic until the degree of crosslink obtained
during a heat activated cure rises above the 5-point
rise (% degree of cure) as measured on a torque
rheometer. Or a thermoplastic saturated (no C=C)
macromolecule such as polyethylene can be
crosslinked into a thermoset via radiation or a free
radical peroxide.
The aromatic (e.g. phenyl, naphthyl, styrenic) or
aliphatic (e.g. ethyl, propyl, butyl) backbones which
typically make up the thermoplastic macromolecule,
liquid chemical compounds or thermoplastic
elastomer are functions (2) to (4) reactive with titanate
(or zirconate) independent of a function (5) curative
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
reaction mechanisms. Thus, the monolayered,
organometallic-coupled particulate and/or fiber
becomes a catalyst support bed for single site, in-situ,
metallocene-like repolymerization 40 of the
surrounding polymer.
Currently, published efforts in metallocene (titanocene
and zirconocene) chemistry by major polymer
producers appear to be centered on olefin polymers
and copolymers. Metallocene derived HDPE and
engineering plastics appear to be still off in the future
while the titanate and zirconate esters appear to be
efficacious to some degree in virtually all polymers
synthesized via various routes1.
In the “Repolymerization” EP patent (EP Application
No. 87301634.9-2109) peer reviewed by the EPO in
Munich in November, 1996 and accepted in 1998
(eleven years after the U.S. Patent was issued),
examples 6 to 16 showed the physical property
improvement effects of six neoalkoxy titanates (LICA’s
01, 09, 12, 38, 44 and 97) and six neoalkoxy zirconates
(NZ’s 01, 09, 12, 38, 44 and 97) in powder form at 3
to 5 dosage levels in eleven thermoplastics (ABS,
Acetal, Acrylic, CAB, Nylon 6, PC, PP, HDPE, PBT,
PPO, and PS). The “best” titanate or zirconate and
“optimum” dosage for each polymer were reported
[cf. ref.11 - Fig. 4]. Table 11 is extracted from the EP
application shows effects in ABS, PC, PP and PS.
Moreover, the titanocene or zirconocene catalysts
used in synthesis of metallocene-derived polymers
do not remain in the polymer. Now with
“Repolymerization”, thermoplastics may be
regenerated to virgin or recycled more efficiently
since the thermally stable titanate or zirconate ester
forms of subject organometallics “anneal” or
“reconnect” polymer chain lengths that are normally
“scissored” during processing.
Repolymerization appears to effect the isothermal
recrystallization time, chain branching and
morphology of the polymer chains surrounding the
particulate or fiber. The metallocene-like benefits
thus derived such as easier processing and better
mechanical properties (particularly increased strain
properties) are apparent from the examples discussed
in this paper.
Talc Filled PP
In a Technical Paper by Chuah Ai Wah et al41 entitled:
“Effects of titanate coupling agent on rheological
145
 Salvatore J. Monte

Table 11 Repolymerization effect of various neoalkoxy titanates and zirconates on the mechanical properties of
unfilled ABS, PC, PP and PS thermoplastics
Elong. @ Flexural Flexural Notched
Titanate/ Tensile Yield, % H2O, 24
Resin Break, % Strength, Modulus, Izod, ft.lb./in.
Zirconate psi D638 Hr. D570
D638 psi D790 Psi D790 D256
Control 7,100 18 12,000 410,000 3.0 0.30
A BS
L44/H, 0.5 9,400 17 42,000 690,000 4.8 0.08
Control 9,700 65 13,000 330,000 6.0 0.20
PC
NZ 12/H, 0.5 10,200 73 14,000 340,000 7.9 0.14
Control 4,900 120 - 210,000 0.7 -
PP
L12/H, 0.5 5,600 148 - 220,000 1.4 -
Control 5,100 10 9,500 370,000 2.5 -
PS
L12/H, 0.3 5,900 51 9,900 370,000 3.7 -

behaviour dispersion characteristics and mechanical
properties of talc filled polypropylene” the abstract
stated: “A commercially available titanate coupling
agent, LICA 12 from Kenrich Petrochemicals was used
to study its effect on talc filled polypropylene. It was
found that the melt viscosity of the filled PP decreased
and dispersion quality was improved in the presence
of coupling agent. Further investigation on molecular
weight distribution (MWD) shows that polypropylene
(PP) molecules have undergone some chain scission
and coupling reactions resulting in a broader MWD.
Glass transition temperature (T) measurement revealed
the plasticising effect caused by coupling agent which
has imparted changes in morphological character and
mechanical properties. Tensile and flexural properties
were observed to decrease whilst impact and elongation
properties were improved with the incorporation of
coupling agent in the filled system.”
produced 56 abstracts. One of those abstracts is the
result of work by Andrea Galanati, et al42 with my first
titanate molecule invention (KR TTS – cf. Table 1),
which states: A series of composites based on a
block-polystyrene (SBS) copolymer sample and clays
was prepd. using iso-Pr tristearoyl titanate (KR TTS),
a coupling agent. The composites with the
surface-modified clays (Montmorillonitic nanoclays)
present lower temp. of mixing and torque than the
analogous composites prepd. without coupling agent.
No side reactions were obsd. after processing and the
thermoplastic and mech. properties of the unmodified
SBS are retained after compounding with the
surface-modified inorg. fillers. In addn., elongation
at break and heat deflection temp. increase with
respect to the starting SBS. Flexible and efficient
modeling of the material properties for on-demand
tech. requirements is suggested.

The author theorizes that since thermoset elastomer
chemists are able to build tensile and modulus through
the use of curatives, subject organometallics provide an
opportunity to formulate thermoset compounds –
particularly thermoset elastomer compounds that are
both strong and flexible with new and novel strain
performance capabilities. The ability to impart high
strain strength in elastomers with less plasticizer permits
wider latitude for the rubber compounder to increase
levels of curative for higher degrees of crosslinking
without producing inflexible and hard rubber products.
Exploitation in tire compounds is an obvious application.
Nanoclay Filled SBS
An ACS CAS Search from August to December 2000
The effect of titanate on the viscosity and elongation
(while maintaining or improving HDT) is anticipated
based on the work done by the author on nanoclay in
mineral oil as shown in Table 2.
Increased Elongation of BaSO4 Filled Poly-
butadiene (Wilson® TITANIUM Golf Ball)
BaSO4 is another silane non-reactive filler that is
titanate reactive. The Wilson TITANIUM golf ball
takes advantage of the increased strain strength of a
peroxide cured thermoset composite afforded by the
titanate Repolymerization effect. The increased strain
strength (elongation/unit length) and maintained or
increased tensile strength (force/unit area) of the
barytes (BaSO4) filled polymer allows the golf ball to

146 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
compress more so as to have a “fatter” feel on the club
head while the increased energy needed to return to
shape as measured by coefficient of restitution (COR)
provides greater distance and spin control. The
abstract of Frank M. Simonutti’s patent43 reads: “The
cores showing excellent coeff. of recovery (COR)
comprise rubbers 100, crosslinking agents 10-50,
crosslinking initiators 0.2-5.0, and titanate coupling
agents 0.1-2.0 parts. Golf balls consisting of the cores
and covers are also claimed. Thus, a core prepd.
From BR 1207 (butadiene rubber) 100, SR 416D (Zn
diacrylate) 32, ZnO 5, barytes 16.2, Di-Cup 40C
(dicumyl peroxide) 3, an antioxidant (Wingstay L-
Hls) 0.2, and KR TTS (iso-Pr triisostearoyl titanate)
0.1 part showed improved COR compared with a
control not contg. the titanate.”
Improved Rheological and Mechanical
Properties – Improved Shear Resistance
and Durability of Elastomers, Ionomers and
Combinations Thereof for Hitting Golf Balls
Golf balls and their covers, like most elastomer
compounds, require high performance and most
efficient use of the raw materials in its composition to
produce high shear strength and impact resistance.
Hyun Kim et al44, Taylor Made Golf Ball Company, Inc.
state in their WO 00/40306 patent dated 13 July 2000:
(54) Title: IMPROVEMENT OF GOLF BALL COVER
USING ORGANOMETALLIC COMPOUNDS
(57) Abstract
A composition for use in golf balls (1) comprising base
material and 0.01-20phr of at least one organometallic
compound chosen from the group consisting of
titanates, zirconates, aluminates and silicates. Preferred
vase materials are elastomers, ionomers, and
combinations thereof. The compositions of the present
invention have improved rheological and mechanical
properties, which result in improved, shear resistance
and improved durability during repeated hitting of
golf balls having covers (2) and/or mantles (4)
comprising the compositions of the invention.
Table 1
Control Invention
Cover Material Pebax 1205 Pebax 1205 0.5 phr CAPOW LICA 97
Coefficient of Restitution 0.791 0.789
Shear Test Score 5 2.55
Durability First Failure 95 No failure
Durability 50% Failure 195 250+
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
Testing and Results
A composition of the present invention was tested in
the form of a golf ball cover. The composition tested
comprised 0.5 phr CAPOW LICA 97
(neopentyl(diallyl)oxy, tri(amino)phenyl titanate,
Kenrich Petrochemicals) in Pebax 1205
(copolyetheramide, Elf Atochem). Quantities of Pebax
1205 and LICA 97 were weighed according to the
formulation and dry blended in a tumbler mixer for
30 minutes at room temperature. The batch of dry
blended resins were then compounded by a 35 mm
twin screw extruder. The processing conditions were
as follows: from the feeder to die, T1 = 80°C, T2 =
185°C, T3 = 205°C, T4 = 210°C, T5 = 210°C, T6 =
195°C, Tdie = 195°C, and screw speed = speed =
150 rpm. The extruded resins were made into a golf
ball cover by injection molding. Control golf balls
having Pebax 1205 covers (without organometallic)
were also made. The control golf balls and the golf
balls of the present invention were three-piece golf
balls and had the same core and mantle materials.
Two types of commercially available balls, one having
a synthetic balata cover and one having a cover made
of Surlyn ionomer, completed the set of test balls.
To test the cut resistance of the covers, a shear test
was done on the set of test balls above. In the test, two
golf balls of each cover composition were shot twice
at 80 mph with a Taylor Made Tour55 sand wedge
type club having the following physical characteristics:
lie: 64°; loft: 55°; bounce: 8°; club length: 35 inches. A
visual evaluation was made, and each ball was given
a score from 1 to 5, depending on the degree of
damage to the ball. The criteria for the scores were as
follows: 1 = excellent (no paint or cover damage); 2 =
good (paint damage only); 3 = average (minor cover
damage); 4 – fair (moderate cover damage, slight
material removed); 5= poor (major cover damage,
moderate material removed). An average was taken
of the scores for each golf ball cover composition to
get a final score for that composition.
These results appear in Table 1 below.
Comparative 1 Comparative 2
Synthetic Balata Soft Surlyn
0.793 0.793
2.56 3.92
No failure No failure
250+ 250+
147
 Salvatore J. Monte
To test the durability of the golf ball covers, a test
was done to simulate the effect of being struck
repeatedly with a driver. In the durability test, the set
of test golf balls were fired out of the cylinder of a
testing machine of the type used for conventional
coefficient of restitution testing. The set of test golf
balls (12 of each) were conditioned at room
temperature for a period of two weeks prior to the
test. The balls were fired out of the cylinder at 125 ft/
sec onto a stationary steel plate, and periodically
checked for cracks. The test for each set of 12 balls
consisted of up to 5 cycles of 50 hits (firings) for each
ball in the set. The test for a set of balls ceased when
50% of the balls in the set had crack failures (50%
failure). If 50% failure was not reached, the test was
stopped after 5 cycles (250 hits). The number of hits
for the first failure and the number of hits for the
50% failure are recorded for each set of test balls.
The results of this test are shown in Table 1.
It can be seen from the data in Table 1 that the
addition of a small quantity of an organometallic
compound to the elastomeric base material results in
a substantial difference in the durability and shear
resistance of the golf ball cover. Addition of a small
amount of organometallic compound resulted in a
shear resistance that was “good“ compared to “poor”
for the control ball. Additionally, none of the inventive
balls tested experienced a crack failure in the
durability test after as many as 250 hits, compared to
the 50% failure at 195 found for the control balls.
Furthermore, the increase in durability and shear
resistance was not achieved at the expense of the
coefficient of restitution, which translates into good
speed when leaving the club head.
Shorter Recrystallization Time of Unfilled
and Fiberglass Reinforced Polyphenylene
Sulphide
A modified polyphenylene sulphide resin containing
titanium organometallic compound (LICA 09) and
molten polyphenylene sulphide (PPS) resin was
prepared without any particulate or fiber content45.
The isothermal crystallization time (at 250°C) of the
PPS was substantially decreased from 175 secs to
106 secs, and the crystallization temperature was
increased by 8°C, with the addition of titanium
organometallic compound. Similarly, a ram extruded
40% fiberglass PPS using 0.5% CAPOW NZ 97/H
exhibited1 increased flow-eliminating necking, the
doubling of elongation, and the elimination of
embrittlement and cracking.
148
Viscosity Reduction of Carbon Black Filled
Polyurethane and Styrene Butadiene
Elastomer
The viscosity reduction effect of titanates and
zirconates are therefore often a result of
repolymerization as well as a filler dispersion effect
from coupling. When an aliphatic amino titanate
(LICA 44) is used at 0.66 parts, the viscosity of 33 parts
of XC-72R conductive black dispersed in 100 parts of
a TDI based urethane cut with 300 parts of methylene
chloride is reduced from 55,000 to 600 cps.1. Just
0.65 parts a pyrophosphato titanate (KR 38S) will
drop the Mooney viscosity, ML (1 + 4) @ 100°C of a
50 phr HAF Black filled SBR 1500 from 64 to 281.
Increased Strength of Polymers
Repolymerization allows the use less plastic or
thermoplastic elastomer to equivalent strengths. Blow
molded thermoplastics, where outer dimensions are
unaffected by thinner gauging, provides an
opportunity to demonstrate the catalysis effect of
titanates. We will discuss two blow molded HDPE
applications, the first with virgin polymer and the
second with regrind:
1. Virgin Polymer Repolymerization: A blow molded
HDPE marine fuel tank produced by Flambeau
Corporation, Baraboo, Wisconsin, USA uses 1% CAPS
NZ 12/L zirconate to reduce cycle time from 186 to 116
seconds. The tank is formed at a lower process
temperature while reducing part weight from
1745 grams to 1500 grams to equivalent drop weight
impact strength [cf. Figure 9 this paper or ref. 11 - Fig.
Figure 9 Comparison of blow molded virgin HDPE
marine fuel tanks processed without and with 20%
active zirconate coupling agent pellet masterbatch
demonstrating the “repolymerization” catalysis effect
to permit faster cycle times and down gauging of wall
thickness to equivalent drop weight impact strength
CONTROL 1% CAPS NZ 12/L
Cycle Time - 186 secs. Cycle Time - 116 secs.
@ Lower process temp.
Part Weight: 1745 grams Part Weight: 1500 grams
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

14]. The strength tests consisted of 3+-meter drop- Figure 10 Blow molded HDPE toy wheels of equal
weight impact of water filled containers and two-year strength – “repolymerization” by 0.2% zirconate added
Florida Everglades UV exposure of fuel filled containers. to liquicolor permits fourfold increase in HDPE regrind
content and 18% faster processing @ 8% lower melt
temperature
2. Regrind Polymer Repolymerization: Table 12
shows that 0.2% NZ 12 zirconate, when added via a
liquid color concentrate, had the following effects on
a blue blow molded HDPE toy wheel (see Figure 10):

• Reduce part weight to equal strength from 125-

135 to 100-105 grams.
• Increased regrind to virgin ratio from 50:50 to
80:20.
• Reduced Cycle Time from 50.6 to 41.1 seconds.
• Reduced temperature of the process melt from
361 to 332°F (183 to 166°C).
CONTROL 0.2% NZ 12 Zirconate
Process Engineering Plastics and Virgin:Regrind 50:50 20:80
Pat Weight, g 125-135 100-105
Thermoset Elastomers at Lower Melt Temps., °C 184 168
Temperatures and Without Plasticizers Cycle Time, sec. 50.6 41.1
PET, PETG, PBT, PCT, PC and their copolymers are
engineering plastics belonging to a class of
condensation (acid –base reaction with water by-
they buy already formulated from a custom
product) polymers known as polyesters. Apparently,
compounder. Stanley A. Watson, Electroplating
subject organometallics are effective esterification
Manager/Chemist stated in a letter dated May 16,
catalysts in the polyester macromolecular melt.
1994 (cf. Ref. 1 - Fig. 10): “Our application is in
molding 40% Fiberglass filled high molecular weight
For example, Diamond Machinery Technology Inc. polycarbonate resin onto a perforated sheet of
makes whetstones for knife sharpening using 40% 16 gauge cold rolled steel. Our problem has been with
fiberglass reinforced, red iron oxide pigmented shrinkage cracks along weld lines where there really
polycarbonate as a base (cf. Ref. 11 - Fig. 11) which is very little glass content - see enclosed examples. To

Table 12 Blow molded HDPE toy wheels of equal strength – "repolymerization" by 0.2%
zirconate added to liquicolor permits a fourfold increase in HDPE regrind content and 18%
faster processing @ 8% lower melt temperature
Virgin: Regrind 50:50-No NZ 50:50 – NZ 12 20:80 – NZ 12
Part Weight, g 125-135 100-105 100-105
Process Temps., °F Set Act Set Act Set Act
350 372 330 —- 310 339
350 355 330 —- 310 351
350 375 330 —- 310 374
Die I Die II 370/370 370/371 370 —- 370 —- 370 —- 370 —-
350/378 350/350 350 —- 350 —- 350 —- 350 —-
330/331 330/330 330 —- 330 —- 330 —- 330 —-
Melt Temp. 361 350 332
Cycle Time, sec. 50.6 41.1 41.1

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 149

 Salvatore J. Monte

aid our problem we’ve gone through a long process of
mold solutions to change internal radii, hold down
pin size, gate configuration, etc.
In general, we have seen a reduction in the severity of
cracking with the highest degree of success being with
L12/E additive.
We have, as your Reference Manual indicates,
experienced a significant decrease in barrel
temperatures from as high as 580 °F without coupling
agent to as low as 370°F with agent. Our initial tests
had such drastically altered rheology that most of our
testing involved an attempt to regain prior flows and
characteristics.
All our tests were done with coupling agent at 1%
weight of CAPS and with red colored polycarbonate.
We were able to reduce cure time by approximately
4 seconds with most of the agents”.
On March 27, 1996 I met Mr. Watson in person for the
first time when he visited our stand at MASSPLASTIC
’96 in Fitchburg, MA and he confirmed that after two
years of product in the field, they are the best looking
and best performing whetstones DMT has ever
produced. The reduction of the injection mold
temperature requirements of polycarbonate by 116°C
from 304°C (580°F) to 188°C (370°F) reported by
Watson with just 0.2% LICA 12 is significant.
In confirmation of Watson’s work, a Ford 40%
fiberglass/polycarbonate injection mold study of the
effects of 0.2% LICA 12 on a 57 gram F-Series Fuse
Cover (F2TB-15045D64; 4426-2056; PC-WSB-
M4D627) truck part showed: a 60 to 45 sec reduction
in mold cycle time; a 52°C reduction in process
temperature; a 45% SPC (Statistical Process Control)
reduction in out of tolerance measurements (i.e.,
improved dimensional stability); and an increase in
minimum specific property requirements: tensile
strength at yield (54.5 MPa), notched izod (44.6KJ/
m2) and melt flow (22.9 g/10 min.). Table 13 lists the
control conditions for the fully automated injection
molding machinery set-up and then the five (I to V)
trial tests run to establish the new conditions for the
1% CAPS L12/E containing material.
Seven test runs were necessary for a PC electrical
outlet plate cover (cf. Table 14) to achieve a cycle time
reduction of 40% from 47.5 to 28.5 seconds, at half
the injection pressure and at 15% lower temperature
from an average of 267 to 223°C.
Engineering resins such as polycarbonate need to be
dried and are placed in a hopper dryer normally run
at about 120 °C. At these temperatures, CAPS made
with EVA binder softened and created lumping
problems for investigators such as Mr. Watson. A
switch to 20 melt LLDPE binder solved the problem.
The injection molded PC increased melt flow and
concurrent melt increased strength observation made
by Watson as taught by Monte is consistent with Ping
Yuan Liu’s observations in GE European Patent 547809
dated June 23, 1993 [cf. Ref. 16 – Page 5], part of which
was: “…It has also been surprisingly discovered that

Table 13 Effect of 1% CAPS L 12/E on injection molded 40% fiberglass/PC

Conditions Control 1% CAPS L 12/E

I II III IV V
Temp. (°C) Rear 304 274 254 219 227 210

Center 293 288 270 232 238 232

Front 298 288 268 232 238 244
Valve 288 271 257 221 227 238
Cycle Time (sec) 060 - - - 050 045
Observation No Splay Splay Splay Splay Splay No Splay
Injection Pressure (kPa)
High 7590 - - - - -
Low 8625 - - - 11,040 10,695

150 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 14 Injection molded polycarbonate electrical outlet plate cover

Conditions 1% CAPS KR 134S/K
Control #1 #2 #3 #4 #5 #6 #7
Rear (°C) 258 235 229 229 224 218 216 202
Middle (°C) 269 257 254 249 243 238 235 227
Front (°C) 276 265 259 252 252 246 246 241
Injection Pressure (kPa) 10,360 9,300 9,300 6,800 6,800 6,800 5,500 5,500
Injection Time (sec) 11.0 8.0 8.0 8.0 8.0 8.0 7.0 7.0
Injection Full Pressure (sec) 4.5 2.5 1.5 1.5 1.5 1.5 1.5 1.5
Cool (sec) 30 25 23 20 25 22 20 18
Total Cycle 47.5 37.5 34.5 31.5 36.5 33.5 30.5 28.5
Appearance Good Good Good Sinks Better ← No Sinks →

Fita Tight Tight Loose Loose Looser Looser Very Loose

Note: ª Tight fit caused by excessive shrinkage around gates

when the melt viscosity of the resulting composition Ross

was decreased through the use of the neoalkoxy PA General Electric Company, USA
titanate the strand integrity, contrary to general SO Eur. Pat. Appl., 21 pp. CODEN:
experience, is increased to improve the processability EPXXDW
of the final composition. This is very surprising DT Patent
because strand integrity, which is directed to the LA English
integrity of the strand of the entire composition, is a FAN.CNT 1
function of melt strength. It is known that melt PATENT NO. KIND DATE APPLICATION NO.
strength is a component of melt viscosity, therefore, DATE
typically it would be expected that when melt viscosity ——————— —— ———— ——————— ————
is decreased the melt strength will also be decreased. PI EP 926201 A1 19990630 EP 1998-
In the present invention, the opposite occurs, in that 310024 19981208
a decrease in melt viscosity does not bring about a R: AT, BE, CH, DE, DK, ES, FR, GB,
corresponding decrease in strand integrity. This GR, IT, LI, LU, NL, SE, MC, PT, IE,
SI, LT, LV, FI, RO
combination of properties is unexpected.”
US 6221940 B1 20010424 US 1997-997628
19971223 <—
An ACS CAS Search conducted May 22, 2001 JP 11269382 A2 19991005
produced 62 more references of which the following JP 1998-363717 19981222
“L113 ANSWER 47 OF 62 HCA COPYRIGHT 2001 PRAI US 1997-997628 A 19971223
ACS” is further confirmation of the ability of subject AB A thermoplastic resin compn. contg.
organometallics to repolymerize or improve the a polyetherimide resin, a
ductility and impact strength of polymers such as glycidylester impact modifier and an
polycarbonate: organometallic compd. exhibits
improved impact strength and
L113 ANSWER 47 OF 62 HCA COPYRIGHT ductility. A compn. contained 2,2-
2001 ACS Bis[4-(3,4-
AN 131:59550 HCA dicarboxyphenoxy)phenyl]propane
TI Polyetherimide resin compositions dianhydride-m-phenylene diamine
with good impact strength and copolymer, ethylene-glycidyl acrylate
ductility copolymer, and Lica 12, optionally
IN Puyenbroek, Robert; Fishburn, James other polymers such as polycarbonate.

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 151

 Salvatore J. Monte
The Repolymerization effect of neoalkoxy titanate on
polycarbonate engineering plastic and polypropylene
commodity thermoplastic used in injection molded
toys was further confirmed by Yan Er Ming of CVI
Modern Technology Development, Ltd., Hong Kong
in a private communication to the author dated
21 March 2001. Using the neoalkoxy phosphato
titanate in an injection molded polycarbonate Ken
Griffey (an American professional baseball player)
action model (see Figure 11) Ming stated, “The PC
stick (i.e. baseball bat) of the toy becomes
stronger…before use ‘of the additive’ this part broke
easily. Also attached is another toy sample – the PP
toy becomes stronger and has better impact after
using ‘the additive’.”
Carbon Black, Cu-Phthalocyanine Blue,
AZO Yellow Dye, Magenta Dye, Silicone
Oil/Acrylic Inks
Kensuke Fukae et al, Advance Color Technology,
Inc.46 takes advantage of the proton reactivity of KR
46B to couple silane non-reactive pigments such as
carbon black (Degussa Printex G), Cu-phthalocyanine
blue, AZO Yellow Dye, Magenta Dye – and the
superior coefficient of friction characteristics of
silicone over conventional hydrocarbon vehicles to
produce new and novel high speed printing inks. The
titanate allows for higher solids in the silicone acrylic
to facilitate faster transfer of the pigment in the liquid
developer for electrophotographic printing. The
repolymerization effect appears to affect all polymers
– liquid thermosets and solid thermoplastics, both
filled and unfilled.
Figure 11 1% CAPS L12/L eliminates problem of injection
molded PC baseball bat handle breakage thus
demonstrating “repolymerization” because the PC
engineering plastic is made more ductile and tougher
152
Synergize Blowing Agent Performance
Endothermic and exothermic blowing agents are
made significantly more efficient using subject
organometallics to produce lighter polymers with
more uniform cell structure47. This because, among
other effects, titanates and zirconates at the elevated
temperature where gas generation (blow) occurs
maintain or increase polymer bubble stress (force/
area) properties while strain (elongation/unit length)
properties are doubled or tripled. Thus, polymer
bubbles do not break because of the titanate or zirconate
induced greater stress/strain strength resulting in
smaller and more uniform cell structure. Just a few
examples are cited here. See Reference [47] for more
complete detail.
Azodicarbonamide Foamed PE and PVC
Cell size variation is reduced from 6-48 micron to 9-
15 micron in an exothermic azodicarbonamide-
foamed PE communication cable insulation core
compound, which increases average abrasion
resistance from 260 for the control to 830 with use of
0.03 parts of KR TTS (4.3% on AZO) titanate due to
more uniform expansion ratio and cell size. [cf. JP 58
75,713 Showa Denka Kk, ref. 1 - pgs. 60 to 62 and ref.
18 - Fig. 17]. The density of an azodicarbonamide-
foamed flexible PVC is decreased threefold from
0.408g/cc to 0.129g/cc [cf. ref. 16 - Fig. 3]. Figure 12
shows effects in an AZO PVC plastisol.
NaHCO3 Foamed SBR
The amount of endothermic sodium bicarbonate
needed to foam SBR (Styrene Butadiene Rubber) is
reduced twenty-nine fold from 15 phr of NaHCO3
powder to 0.68 phr of a 75% active NaHCO3 paste
masterbatch containing pyrophosphato titanate in
the aromatic plasticizer phase [cf. ref. 47 - Fig. 7].
COPOLYMERIZATION
Copolymerization is Repolymerization in the presence
of two dissimilar polymers.
Titanate and zirconate coupling agents may act as
compatabilizers via activation of both addition and
condensation polymers20. When the activation occurs
to more than one polymer simultaneously (in the
absence or presence of filler or reinforcement – both
inorganic and organic, or peroxide) repolymerization
manifests itself as copolymerization (i.e.
intermolecular rearrangement), or grafting, or other
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Figure 12 The effect of LICA 38 on PVC foam to give finer and more uniform cell structure via a claimed metallocene-
like catalysis mechanism which increases the stress/strain properties of the polymer at blowing agent activation
temperatures so as to stop bubble breakage

Control 0.8% Titanate

PVC Plastisols foamed a 190°C – 1 hour in forced air oven

Plastisol ingredients Control LICA 38
DOP 50.00 47.00
 
Ken-React ‚ LICA ‚ 38 - 0.34
BaZna 1.50 1.50
Epoxidized Soybean Oilb 2.00 2.00
c
AZO Foaming Agent 3.00 6.06f
CaCO3 (3µ)d 75.00 75.00
e
PVC 100.00 100.00
231.50 231.90
Initial Viscosity (x103 cps) 960 640
Notes: a) Mark 4712, Witco
b) Paraplex G-62, CP Hall
c) AZO 130, Uniroyal
d) OMYA CARB 3, OMYA
e) Geon 124, Geon
f) MIX: DOP - 50.00
LICA 38 - 0.34
AZO - 50.00

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 153

 Salvatore J. Monte
molecular modifications. The result is some form of
superior “chemical alloying” as opposed to inferior
“physical alloying”.
Activation of both addition and condensation polymers
by selected organometallics may result in catalysis and
a wide variety of copolymerization reactions:
• Rapid equilibration of molecular weights to
produce near thermodynamic equilibrium
distribution irrespective of starting
compositions.
• Randomization of most block copolymers except
some aliphatic polyethers.
• Reduction in polydispersity of molecular weight
resulting in a narrower molecular weight
distribution curve.
• Controlled introduction of organofunctional
groups for bonding enhancement.
In-Situ Copolymerization, Alloying or
Compatabilization of Polyblends
Three examples are discussed:
1. PET Regrind/PC Regrind – A. Maupome reported
in an article written by Jan Schut [48] the results with
recycled PET/recycled PC mixtures using 0.2 and
0.5% LICA 12. The PET/PC blends were treated by
dropwise addition of coupling agent to a fluidized
bed (1800 rpm) of the polymer blend over 21/2 minutes
using a Henschel mixer (principle of uniform
distribution). The two blends were compounded,
along with a blank blend in a Werner & Pfleiderer
2SK-30 twin screw extruder. In all the experiments,
the torque was held at a reasonably high constant
torque value so as to maintain equivalent degree of
dispersion (principle of specific energy input). The
use of 0.2% LICA 12 against the control increased
elongation to break almost tenfold (ASTM D638 9.85
to 93.34%) and tensile modulus almost twofold
(ASTM D638 - 189,140 to 348,800 psi).
2. LDPE/PP Regrind – The copolymerization of LDPE/
PP-80/20 with 1% CAPS L12/L creates an apparent
new olefin copolymer. Figure 13 (on page 45)
demonstrates clearly the improvement in the
appearance of pellets made from an 80/20 blend of
LDPE regrind/PP regrind using 1% CAPS L12/L. A
silane does not catalyze an olefin in this way because
of its non-metallocene-like nature and stable Si-C
bond as per the previous discussion of Function 2 of
the titanate molecule.
154
3. PP and HDPE/LCP – Another example of subject
organometallic effects on polymer blends is discussed
in a Neste Oy Patent49. R. Holsti-Miettinen49 overcame
the difficulties of blending a polar liquid crystalline
polymer (LCP) with non-polar polyolefins (PP and
HDPE) using neoalkoxy titanates and zirconates. The
art of recycling polymers often requires the blending
of polar and non-polar ingredients and Example 1
from the patent is herein provided:
“Example 1 (WO 95) 3183):
PP/LCP and HDPE/LCP blends were prepared in a
Berstoff ZE 25 x 33 D twin screw extruder. The melt
temperature was at 240 - 245°C and “Polyblends”
screw configuration was used. Rotation speed was
200 rpm and feeding rate about 9 kg/hr. The LCP
component was predried before melt blending for
5 hours at 50°C. The prepared blends were predried
overnight at 80°C before injection molding. Injection
molded specimen were mechanically tested after
2 days of conditioning.
The materials used were the following:
- HDPE: NCPE 1515 supplied by Neste Oy,
- PP: VB 65 supplied by Neste Oy,
- LCP: Rodrum LC-3000 (a copolyester of p-
hydroxybenzoic acid and poly-
ethyleneterphthalate, supplied by Unitka Ltd.),
- Zirconate: neopentyl (diallyl) oxy, tri
(dioctyl)phosphato zirconate, supplied under
the name CAPS NZ 12/L by Kenrich
Petrochemicals, Inc.,
- Titanate I: neopentyl(diallyl)oxy, tri(dioctyl)
phosphato titanate, supplied under the name
CAPS L12/L by Kenrich Petrochemicals, Inc.,
- Titanate II: neopentyl (diallyl)oxy, tri(N-
ethylenediamino) ethyl titanate, supplied under
the name CAPS L44/E by Kenrich
Petrochemicals, Inc.
- Compatibilizer I: Lotader 8660 supplied by
Norsolor and
- Compatibilizer II: a MAH-grafted PP supplied
under the name Exxelor 1015 by Exxon
Chemicals.
The recipes of the blends are given in Table 1 (Ref. [49]).
Part of the samples were tested for orientation under
drawing. Blends were extruded in a single screw
Brabender extruder and immediately quenched in a
water bath and drawn at different speeds of the take-
up machine to form strands of different diameter. The
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 1. Recipes of polyolefin/LCP blends

Sample # Isotropic polymer/wt-% LCP/wt - % Organometallic Compatibilizer

compound/wt-% wt - %
1 PP/69 30 Zirconate/1 -
2 PP/69 30 Titanate I/1 -
3 PP/69 30 Titanate II/1 -
4 PP/70 30 - -
5 PP/69 30 - Comp. I/1
6 PP/69 30 - Comp. II/1
7 PP/68 30 Titanate I/1 Comp. I/1
8 PP/68 30 Titanate I/1 Comp. II/1
9 HDPE/69 30 Zirconate/1 -
10 HDPE/69 30 Titanate I/1 -
11 HDPE/69 30 Titanate II/1 -
12 HDPE/70 30 - -
13 HDPE/70 30 - Comp. I/1

draw ratio for each strand was determined as the ratio
between the die and strand sections. The dimensions
of the round hole capillary die were: length 30 mm
and diameter 5 mm. The screw speed was kept at
100 rpm for all blends. The strands were tensile
tested. The diameter of the rods was uneven but it was
evaluated as an average of at least five measurements.
Results of mechanical and thermal testing are shown
in Table 2 (ref. [49]).
It is apparent from the results indicated in Table 2
(Ref. [49]) that the addition of neoalkoxy zirconates
improves the tensile modulus of both LCP/HDPE and
LCP/PP blends. The improvement with neoalkoxy

Table 2. Mechanical and thermal properties of LCP/PP blends

Sample Tensile Tensile Stress Tens. Strain at Tensile Flexural
# Modulus (MPa) at Break (MPa) Break (%) Strength (MPa) Modulus (MPa)
1 3260 39.7 2.5 39.8 3230
2 3030 37.7 2.6 37.7 3070
3 2680 34.5 2.4 34.7 2940
4 2900 36.8 2.7 37.0 2860
5 2930 38.0 2.7 38.1 2910
6 3070 37.8 2.4 38.0 2930
7 3010 38.1 2.6 38.5 3020
8 3150 38.6 2.6 39.0 3080
9 2810 38.3 2.8 38.4 2740
10 3060 38.7 2.5 38.8 2990
11 2780 36.9 2.7 36.9 2750
12 2560 36.8 3.1 36.9 2520
13 2350 36.1 3.2 36.2 2460

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 155

 Salvatore J. Monte
titanates was more pronounced in HDPE/LCP blends
that in PP/LCP blends. It is worthwhile noticing that
the mechanical strength of blend sample 8, which
contained both a titanate and a compatabilizer
(Exxelor 1015), was better than that of Reference
Sample No. 4. This combination of modifiers also
gave the best impact strength”.
4. Regeneration of Waste Plastics Reinforced with
Cellulose Fibre – The technical paper by N.A. Miller
et al50 was selected because it confirms my
Repolymerization and Copolymerization teachings
in that the major benefit in this application, just like
the unfilled virgin and regrind HDPE in the discussion
on Increased Strength of Polymers, is more the result
of catalysis and less of coupling. Also, N.A. Miller’s
mixed post-consumer waste plastics from municipal
waste collection by its very nature contains a variety
of thermoplastic and thermoset materials after the
removal of HDPE milk bottles and PET beverage
containers. Typically, what is left is a mixture of PS,
PVC and other assorted styrene and acrylic based
polymers. The reinforcing fibre used was untreated
“Pinus Radiata” medium density fibre (MDF)
produced by thermo-mechanical pulping.
The abstract of Miller’s technical paper is entitled
“Waste Plastics/Cellulose Fibre Composites”, which
reads: “Commingled post-consumer waste plastics,
from municipal recycling collections, have been melt
blended with Pinus Radiata fibre to form composite
materials. Increases in tensile strengths of the order of
30% to 50% over those of the matrix materials have
been achieved in these composite materials with the
use of suitable coupling agents. Five different coupling
agents were trialed but only two, Epolene E-43 (a
maleated propylene wax) and Ken-React CAPS L12/
L (a proprietary neoalkoxy titanium phosphate) gave
significant increases in tensile strength.”
Specifically, Miller states: “The most significant gain
in tensile strength (53%) was achieved with the
Kerbside #2 fraction. Addition of EPO (Epolene E-43)
to the HDPE regrind did not give an increase in tensile
strength but the addition of 1% CAPS (Titanium (IV)
neoalkoxy tris (diisooctyl) phoshate) with both 20%
and 40% MDF fibre gave significant increases in
strength. The 40% fibre addition gave the largest
increase, of the order of 30%.
Miller’s conclusions were:
“1. Composite materials with tensile strengths of
the order of 25 MPa can be made by melt
156
blending commingled post-consumer waste
plastic and “Pinus Radiata” fibre with a
maleated propylene wax as the coupling agent.
This represents an increase in tensile strength
of around 50% over the waste plastic on its own.
2. Composite materials made by melt blending
HDPE regrind and “Pinus Radiata” fibre with a
proprietary coupling agent, Ken-React CAPS
L12/L, gave tensile strengths of the order of
32.5 Mpa, which represents an increase in tensile
strength over the HDPE of approximately 30%.
3. This research demonstrated that composite
materials with useful tensile strengths can be
formed by melt blending commingled post
consumer waste plastic with “Pinus Radiata”
fibre, thus offering a possible method for
utilization of this material.
4. Scanning electron microscopy studies of the
composite materials showed little evidence of
bonding between the fibre and the matrix, despite
the increase in tensile strength measured.”
Note, there is little evidence of bonding or coupling
as stated in 4., and yet the CAPS L12/L gives increased
strength over the control without coupling agent.
Catalysis or Repolymerization, or in this case,
copolymerization is a possible explanation.
EXTRUSION, INJECTION AND BLOW
MOLDING
Discussion to this point has been from the viewpoint
of the polymer chemist, additive compounder,
formulator, and filler pretreater. However, most
plastics additives are consumed in polymers that are
processed by either extrusion (and subsequent
thermoforming), blow and injection molding. The
people who do the processing of plastics are not
always trained in classical polymer chemistry and
may be mechanical or electrical engineers,
entrepreneurs or technicians who treat polymer and
masterbatch pellets as materials that must fit into
their factory mechanical set up that includes silos,
graviometric feed systems, molds and molding
machinery, computer controls and cooling devices.
They do not have Henschels, Banburys, twin-screws
and do not preblend, filler pretreat in the water or
organic phase. For them, discussion must center
around the benefits as they measure them – such as
faster cycle times or extrusion rates. And the additive
must be delivered to them as a pellet masterbatch to
be used like a color concentrate or a liquid that will
be compatible with their liquicolor masterbatch
without effecting the final part’s color. A discussion
from their viewpoint follows.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Benefits to Thermoplastics Processors Quality - Stronger, Better Parts

The plastics processor is looking for lower costs
through faster cycle times, using more regrind where
possible, while improving part quality. They want
plastic products that are produced better, faster and
stronger for less money.
Faster Cycles, Less Energy
1% Ken-React CAPS L12/L (cf. Table 1 for description
of pellet masterbatch form) on average will reduce
injection and blow mold cycle times by 19% and
process temperatures by 9% (cf. Table 15). Up to 40%
cycle time reductions have been achieved1,11,14-17.
Typically, a 4% cycle time reduction for a fully
employed production capital equipment setup pays
the cost of the additive (cf. Table 16).
As a practical matter, most injection molders and
thermoplastic processors handle many different
polymers and prefer to handle pellets over liquids
and powders. Accordingly, the 20% active
masterbatch pellet form of the liquid coupling agent
LICA 12 identified as CAPS L12/L dosed at 1 part
per 100 parts of total polymer weight has become the
general purpose commercially recommended
additive for a wide range of polymers. For those
compounders who cannot tolerate silica or who
want to hold polymer carrier “contamination” to a
minimum, a 60% active pellet form identified as
CAPS L12/MPL-60 and 80% active powder form
using Akzo Nobel’s Accurel® MP series polymers
was introduced in 1997.

Table 15 A summary of the productivity effect (when compared to a control) of various coupling agents in
various thermoplastic plant trials
% Reduction
Plant Molding Part Coupling Cycle
Trial Polymer Process Produced Agent Temp. Time
1* HDPE (PHILLIP S5202) Blow Automotive CAPS NZ 12/L 8.6 32.4
2 HDPE (REGRIND 25053P) Blow Drum NZ 12 9.2 18.9
3 HDPE (0.96M.I.) Blow Container CAPS LZ 12/L 12.2 9.2
4 HDPE (Regrind 25053P) Blow Ski Board CAPS L 12/E 16.1 18.4
6 HDPE (Undisclosed) Inj. Milk Crate CAPS NZ 12/L 10.2 8.2
8 HDPE (Dow 08054) Inj. 14,928 gms. LICA 12 6.6 15.8
10 HDPE (Dow 4052N) Inj. Drum Rim CAPOW NZ 12/H 15.8 16.0
12 MDPE (100% Regrind) Ext. Profile CAPS C.A./B.A. 12.3 14.1
13 LDPE (Undisclosed) Inj. Bumper CAPS NZ 12/L 4.5 17.3
14* PP (Soltex) Inj. Carry Box CAPS L12/E 8.3 8.7
15 PP (Himont SB-787) Inj. Proprietary LICA 12 12.0 28.5
16 PP (8310KO) Inj. Crock Pot CAPS NZ 12/L 14.7 15.0
20* HIPS Inj. Vac. Nozzle CAPS L 12/K 9.8 16.7
21 GPPS Inj. Closure CAPS L 12/E 7.0 21.0
23* ABS (BW KJC 34187) Inj. Computer CAPS L 09/K 11.9 22.1
24* ABS (33838 Regrind) Inj. Carrier Box CAPS L 12/E 3.4 12.8
25 ABS (Undisclosed) Inj. Printer CAPS L 09/K 7.9 16.4
27 ABS (Regrind) Ext. Frames CAPS L 09/K 5.0 13.7
31 PBT (Celanese #2012) Inj. Proprietary CAPOW KZ TPP/H 3.4 31.2
32 PBT (Cel. 2002-2EK) Inj. Proprietary CAPOW L 12/H 1.1 30.5

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 157

 Salvatore J. Monte

Table 16 Injection molding cost analysis using neoalkoxy phosphato titanate in pellet masterbatch form (CAPS
L12/L)
Costs: Machine Time US $60.00/hr.
HDPE US $1.10/kg
CAPS L12/L US $11.00/kg
(CAPS L12/L price based on F.A.S. New York price range of US
9.78/kg for 250 kg quantity to US $8.34/kg for 18,000 kg quantity)
Part Weight: 250g
Cycle Time: 60 sec.
Machine Time Cost: $1.00/60 sec. cycle/250 g part @ 100% utilization
Cycle Time, sec. 60 60 58 54 48
Machine Time, US $ 100 1.00 0.9673 0.90 0.80
HDPE, US $ 0.275 0.275 0.275 0.275 0.275
1% CAPS L12/L, US $ 0.0000 0.0275 0.0275 0.0275 0.0275
Total Part Cost, US $ 1.2750 1.3025 1.2698 1.2025 1.1025

Table 17 compares the mechanical property effects of
0.3% CAPOW® L12/H (equivalent to 1.0% CAPS
L12/L) and 0.3% CAPOW NZ® 12/H on the mechanical
properties of the eleven thermoplastics: ABS, Acetal,
Acrylic, CAB, Nylon 6, PC, PP, HDPE, PBT, PPO and
PS.
Some other reported quality benefits beyond
elimination of weld lines, brighter color and increased
strength (as shown in Table 5) are:
• Flatter surfaces for hot stamping derived from
cooler processing temperatures (cf. Ref. [15] -
Plant Trial #28).
• Better part definition such as sharper holes,
indentations and texture to plastic surfaces
from “complete mirroring” of mold designs due
to improved flow (cf. Ref. [11] – Figure 6).
• Elimination of shrinkage cracks along weld
lines where there is usually little reinforcement
(cf. Ref. [11] - Fig. 10).
zirconate gives better color. We have already discussed
the case histories of the blow molded fuel tank and
increased use of regrind while down gauging from the
chemist’s standpoint of Repolymerization and
Copolymerization. Additional case histories derived
from field plant trials and tests by plastics processors
in various process categories follows.
Blow Molding
Blow Molded Drum
Table 18 shows the use of 1% CAPS L12/L and
alternately 0.3% CAPOW NZ 12/H for a 30 gal.
(112 Liter) blow molded drum to allow the reduction
of: average temperature of all zones 13% from 213 to
184°C; cycle time 21% from 191 to 151 seconds; and
weight 8% from 6.0 to 5.5 kg.
The drum passed proprietary internal pressure and
external stacking tests.

Use Less Plastic Blow Molded Container

Since Repolymerization allows the use of less plastic
to equivalent strengths, blow molding processors can
reduce part weight because outer dimensions are
unaffected by thinner gauging. Blow Molders most
often work with unfilled polymers such as HDPE and
prefer the zirconate CAPS NZ12/L because the
Table 19 shows 1% CAPS NZ 12/L allows a blow
molded HDPE container to have a cycle time reduction
of 18% from 52.50 to 42.94 seconds (extruder speed
increased 44% from 45 to 65 rpm). However, in this
instance, average process temperature was reduced
only 2.6% from 228 to 222°C.

158 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 17 Effect of neoalkoxy titanate (LICA 12) and neoalkoxy zirconate (NZ 12) on the properties of injection
molded unfilled polymers
Coupling Polymer CAPOW Tensile % Flexural Flexural Notched % Water
Agent Type Form Yield Elongation Strength Modulus Izod @ Absorption
Additive Resin Weight % K psi @ Break K psi psi x 104 R.T. @ R.T. 24
of Resin ft.lb./in. Hr. Imm.
None ABS - 7.1 18 12 41 3.0 0.30
LICA 12 ABS 0.3 8.4 39 26 62 4.4 0.19
NZ 12 ABS 0.3 8.2 34 30 70 4.1 0.20
None Acetal - 8.8 40 13 38 1.0 0.22
LICA 12 Acetal 0.3 9.9 64 20 47 2.7 0.17
NZ 12 Acetal 0.3 9.7 61 21 53 2.1 0.14
None Acrylic - 1.2 5 15 26 0.3 0.27
LICA 12 Acrylic 0.3 1.7 31 23 29 0.7 0.15
NZ 12 Acrylic 0.3 1.7 23 24 35 0.7 0.17
None CAB - 5.8 42 8.3 25 1.7 1.8
LICA 12 CAB 0.3 6.5 72 9.4 33 2.6 0.9
NZ 12 CAB 0.3 6.4 67 9.3 32 1.9 1.5
None Nylon 6 - 18 60 16 41 1.0 1.6
LICA 12 Nylon 6 0.3 24 81 25 52 1.8 0.9
NZ 12 Nylon 6 0.3 19 78 22 49 1.7 1.0
None PC - 9. 7 65 13 33 6.0 0.20
LICA 12 PC 0.3 10.5 89 27 41 6.9 0.14
NZ 12 PC 0.3 10.4 69 19 42 7.4 0.16
None PP - 4.9 120 - 21 0.7 -
LICA 12 PP 0.3 5.7 142 - 26 1.1 -
NZ 12 PP 0.3 5.9 157 - 26 1.4 -
None HDPE - 4.5 820 - 19 6.0 -
LICA 12 HDPE 0.3 5.4 1000 - 24 6.7 -
NZ 12 HDPE 0.3 4.9 870 - 20 6.9 -
None PBT - 8.7 200 12 34 1.0 0.08
LICA 12 PBT 0.3 9.6 250 17 49 1.7 0.03
None PPO - 11 48 35 35 10 0.10
LICA 12 PPO 0.3 12 50 38 39 13 0.07
NZ 12 PPO 0.3 14 57 43 35 14 0.06
None PS - 5.1 10 9.5 37 2.5 -
LICA 12 PS 0.3 5.9 51 9.9 37 3.7 -
NZ 12 PS 0.3 5.8 17 10.3 41 2.9 -

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 159

 Salvatore J. Monte

Table 18 Reduced cycle time, temperature and weight using 1% CAPS L12/L and 0.3% CAPOW NZ 12/H in a
30 gal. (112 liter) coextrusion blow molded drum
Temp. (°C)
Control % CAPS L12/L 0.3% CAPOW NZ 12/H
Left Extr.
Zone 1 235 215-215 212-212 212-212
2 235 215-230 212-227 212-227
3 235 215-215 212-217 212-217
Left Elbow 260 240-240 237-237 237-237
Right Extr.
Zone 1 178-188 158-173 155-160 155-160
2 178-183 158-158 155-160 155-160
3 178-193 158-180 155-180 155-180
Right Elbow 255 235-235 235-235 235-235
Accumul. 1 200-200 185-185 150-150 150-150
2 200-200 185-185 150-160 150-160
3 200-190 185-185 150-150 150-150
4 200-200 185-185 150-150 150-150
5 200-200 185-185 150-150 150-150
Amps 65-70 70-75 70 70
rpm's 900 1100 1050 1050
Cycle, sec. 191 166 151 151
a
Weight, kg. 6.0 5.5 5.5 5.5 a
Note: a Lighter weight drum met all proprietary pressure and weight stacking tests

Blow Molded HDPE (Regrind) Ski Boards
(cf. Ref. 18 - Table 10 and Figure 11) Results using 1%
CAPS L12/E in Dow 25053P 100% HDPE regrind to
produce blow molded HDPE ski boards showed the
average temperature for the nine zones to be reduced
16% from 224 to 185°C while the cycle time was
reduced 28% from 176 to 126 seconds. Also warpage
was reduced or eliminated with the coupling agent;
flash was removed easier; and the time needed to
clean the molds was eliminated.
Blow Molding Application Techniques
I will quote some conventional blow molding and
technical tips For Blow Molding Bottles and Other
Containers as presented by Robert Gilbert, Equistar
Chemicals, LP and then interject how the neoalkoxy
zirconate or titanate effects standard practice:
Suggested Start-Up & Shut-down
Procedures for Blow Molding Polyethylene
Resins
Introduction
Optimum start-up and shutdown procedures are
often found through experimentation. For that reason
and because the number of types of blow molding
machinery available is large, the recommendations
presented here have been kept general. Finding and
implementing precise optimum blow molding
procedures is very important especially to minimize
material degradation during processing. If, during
extrusion, polyolefin resins are subjected to very high
heat of long residence times, oxidized material can
build up on the internal surfaces of the extruder and
head tooling. This oxidized material can lead to gels
and black specks in the end product – and

160 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 19 Reduced cycle time of a blow molded HDPE (0.96 Melt Index) container using 1% CAPS NZ 12/L
Compounding Conditions:
1% CAPS NZ 12/L
Item Control Initial Final
Screw speed, rpm 45 56 65
Load, % 30 32 32
Pressure, kPa @ 5 sec
17,950 19,665 20,010
Before Air Blow
Temp. °C Set Actual Set Actual Set Actual
Extruder Barrel 1 221 221 210 210 213 212
Barrel 2 221 221 210 212 207 207
Barrel 3 224 224 210 209 207 208
Barrel 4 227 227 213 214 221 222
Adapter 249 249 235 225a 235 220a
Melt 246 257 246 254 246 253
Mold Zone 1 221 221 221 221 221
Zone 2 221 221 221 221 221 221
Zone 3 227 227 221 221 221 221
Die 238 237 238 238 236 236
Cycle time, sec. 52.50 46.47 42.94
Physical Appearance Good Good Good
Note: a = Heater band became inoperative

unacceptable condition. Even the best antioxidant
additive package cannot protect a polyolefin from
degradation when it is subjected to abnormal
temperature and residence time conditions.
Sometimes purging is enough to clear out the degraded
material but often all equipment must be dismantled
and cleaned – a lengthy and costly process. Author’s
Note: Due to Repolymerization and apparent lower
viscosity of the melt at a given temperature, it is
possible to run at 30-50°F lower temperatures.
Suggested Start-Up Procedure
I. Heating the Extruder
A. Method #1
1. Turn on the power to the die head heater bands.
If applicable, turn on die head preheaters. Set
the die heads heater set points to 27 5°F (135 °C).
2. After the die head temperatures have reached
to set points, turn on power to the extruder
heaters. Set heater set point to 275°F (135°C).
3. After the extruder temperatures reached the set
points, raise all set points to 325°F (163°C).
Author’s note: With neoalkoxy titanate, raise
all set points to 275 to 295°F (135 to 146°C).
4. After the die head and extruder temperatures
have reached the set point, proceed to Set ll.
B. Method #2
1. Turn on power to all extruder and die heater
bands. If applicable, turn on
2. die head preheaters. Set temperature set points
to 325°F (163°C). Author’s note: With neoalkoxy
titanate, raise all set points to 275 to 295°F (135
to 146°C).
3. After the die head and extruder temperatures
have reached the set points, allow 30 minutes
for machine heat to stabilize.
4. Proceed to Step II.

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 161

 Salvatore J. Monte

II. After the Temperatures have reached few minutes to reduce the chance of resin
the Set Points degradation.

A. Turn off the die head preheaters.

B. Start the hydraulic system.
C. Start extruding polymer at minimum screw
speed.
CAUTION: Head pressure and extruder motor
amperage should be watched closely. Make sure
levels do not exceed recommended maximums.
D. Set temperatures at desired operating levels.
III. After temperatures have once again
reached Set Points.
A. Turn on the chiller for mold cooling.
B. Gradually increase extruder speed to the proper
operating level.
CAUTION: Head pressure and extruder motor
amperage should be watched closely. Make sure
levels do not exceed recommended maximums.
C. Open the valve that supplies pressurized air to
the blow molding machine. The air Pressure
range should be 80-120 psi. Pre-blow air should
range from 5-15 psi.
IV. Set timers and die programmers to the
established settings.
V. Start the blow molding machine on its
automatic cycle for continuous operation.
Suggested Shut-down Procedures
I. If the equipment will be down for less
than 60 minutes:
A. Leave the heaters at their operating set points.
B. Periodically, run the extruder at low speed for a
II. If the equipment will be shut down for
more than 60 minutes:
A. Reduce heater set points to 325°F(163°C).
Author’s note: With neoalkoxy titanate, reduce
all heater set points to 275 to 295°F (135 to
146°C).
B. Lower the extruder speed to the minimum.
C. CAUTION : Head pressure and extruder motor
amperage should be watched closely. Make
sure levels do not exceed recommended
maximums.
III. When temperatures reach the set
points:
A. Stop the extruder.
B. Lower heater set points to 275°F (135°C).
Author’s note: With neoalkoxy titanate, reduce
all heater set points to 225 to 255°F (107 to
113°C).
C. Cover the face of the die tooling with plastic
coated aluminum foil with the plastic side
facing the tooling. Covering the tooling with this
material minimizes the amount of oxygen
entering the system and thus, minimizes polymer
degradation.
CAUTION: The equipment should not be left
unattended during this process. An electrical
malfunction can cause damage. Electrically energized
equipment should be checked periodically. If the
equipment must be left unattended, it should be
completely shut down.

Suggested Operating Conditions

No Titanate or Zirconate With Titanate or Zirconate
Setting LDPE LLDPE HDPE PP LDPE LLDPE HDPE PP
Temp. Zones, °F
Rear 310 135 330 370 260-280 265-285 280-300 320-350
Transition 320 325 350 390 270-290 275-295 300-320 330-350
Metering 330 330 360 400 280-300 280-300 310-330 250-280
Head 60 60 60 60 60 60 60 60
Air Pressure
Blow Air 90 90 90 90 90 90 90 90
Pre-Blow 10 10 10 10 10 10 10 10

162 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
Injection Molding
Typically in thermoplastic processing with neoalkoxy
titanates in injection molding, machine rear zone
temperatures are reduced 15% and front zone
temperatures 5%. Generally, the injection molding
plant trial begins by holding the injection molding
machine’s normal running conditions constant except
for the temperature, which we begin lowering in
increments of about 10°C across all zones (front,
middle and rear) until polymer flow is such that the
part is incompletely filled—and then back off by
raising the front and center zones until part quality is
acceptable. But, every machine and every polymer
behaves differently.
In the case of thermoplastic polyesters such as
polycarbonate, the coupling agent’s effect on temperature
is very significant. Besides the bottom line 40% reduction
in cycle times, a close examination of Table 14 shows
the rear zone temperatures were reduced 20% from
258° to 202°C and the front zone by 12% while injection
pressure was dropped 53% from 10360 kPa to 5500 kPa
to achieve the desired part quality.
On occasion, injection pressure can be manipulated
if temperature lowering does not fill the mold properly.
Usually, when 1% CAPS is added to the polymer and
the machine’s conditions are “normal”, injection will
create excessive flash and the pressure will have to be
dropped significantly if the temperature is not
lowered. Since the cooling of the polymer compound
in the mold is often the limiting time factor in
injection molding, because of the low thermal
conductivity of polymers, it makes more sense from
an efficiency and non-Newtonian rheology standpoint
to use the machine’s high pressure capabilities by
maintaining the pressure settings and alternately
dropping process temperatures. High pressure assures
less variability in the apparent melt flow of the shear
dependent polymer.
Table 20 Injection molded unfilled polypropylene syringe cylinder
Temperature (°C) Control
Rear 190 185
Center 1 245 240
Center 2 255 250
Front 265 260
Cycle time (sec) 19.5 - 16.0
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
Generally, rpm’s and temperature are more dominate
control parameters in extrusion processing as
temperature and pressure would be in injection
molding (I.M.). It is often a good idea to increase rpm’s
when using neoalkoxy titanates because a wider
torque window (before reaching limiting Amps) is
made possible. We usually do not adjust the rpm
setting during I.M. plant trials. Of course, with the
proper computer and software attached to an I.M.
machine, the perfect balance of temperature, pressure
and rpm’s could be achieved for maximum efficiency.
But, even with computerization, it is difficult for the
human computer to handle more than two variables
simultaneously so for injection molding the dominant
condition of temperature is dealt with first, followed
by pressure only when necessary and rpm’s rarely.
Other Considerations
Many thermoplastic resins require thorough drying
prior to injection molding or extruding to eliminate
void formation or a degradation of the material at
molding temperatures and continuous hopper dryers
are often used. Our experience with the CAPS
masterbatches has shown that EVA and Kraton/
Styrenic binder systems often “gum-up” while a 20
melt LLDPE appears to work satisfactorily for most
applications. Other considerations such as color
formation with titanate, flow lines and other real
world plant trial adjustments are next discussed
through case histories.
Unfilled PP Syringe Cylinder
Table 20 shows that 1% CAPS L12/L enabled
Pentaforma Manufacturers C.A., Venezuela to reduce
the cycle time by 25% of an unfilled polypropylene
syringe cylinder on a medium sized 250 Ton I.M.
machine from 19.5 to 14.0 sec. while reducing the
front and center zone temperatures by 10%. In this
plant trial, it was not practical to lower the rear zone
1% CAPS L 12/L
165 145 175 185
220 200 190 210
230 210 205 220
240 220 210 235
16.0 15.0 14.0
163
 Salvatore J. Monte
temperature more than 3% because the feed pellets
would not melt sufficiently when lowered below its
normal setting of 185 to 190°C.
The biggest problem with this test run was that there
was a slight yellowing of the part due to an assumed
reaction of the titanate with the unidentified phenolic
antioxidant (not Irganox® 1010 or 1076) used in the
undisclosed grade of PP. Titanates are usually used
over zirconates because they are less expensive.
However, all materials have inherent natural
limitations.
An area of concern in using titanates is the possibility
of undesirable color formation experienced when
they come in contact with additives containing
phenolic functionality such as heat and light stabilizers
(antioxidants) used in thermoplastic vinyl and
polyolefin systems, alkyds and urethanes. Phenolics
are also used as chain stops in polyester systems,
urethanes, alkyds and acrylics. In common with
virtually all Titanium IV derivatives, titanate based
coupling agents (including neoalkoxy and
acetylacetonate) produce colored pigments on contact
with phenolic containing free hydroxyl groups. The
color intensity developed is proportional to the
increasing concentration and conjugation of the
phenolic hydroxyl from yellow through orange to red
and burgundy.
Fortunately, since writing Reference [1] we have
established that the LICA 12 titanate does not form
color bodies with popular antioxidants and thermal
stabilizers such as Irganox 1010 (CIBA-3.5-bis(1,1-
Dimethylethyl)-4-hydroxy- benzenepropanoic acid,
2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-
hydroxyphenyl]-1-oxopropoxy]methyl]1,3-
propanediyl ester) widely used in PP and Irganox
1076 (CIBA-Octadecyl 3,5-bis(1,1-dimethylethyl)-4-
hydroxybenzene-propanoate) widely used in HIPS.
Not only are parts made with plastics using these
antioxidants and LICA 12 neoalkoxy titanate good in
color, but also no discoloration is observed when
LICA 12 is mixed directly with either Irganox 1010 or
Irganox 1076 at 1:1 ratios.
Zirconates in general are not color body producers in
contact with phenols other than nitrophenols. Both
the organotitanate and organozirconate coupling
agents do not interact with hindered amines (light
stabilizers and/or antioxidants - HALS) under
common operating conditions. Zirconates would
164
appear to have greater thermal stability than titanates.
For example, when equal amounts of CAPOW L12/H
and CAPOW NZ 12/H were exposed to 235°C for 1
hour in a forced air oven, the titanate powder turned
from white to black while the zirconate turned from
white to very light tan. However, since the titanate is
used at 2 parts per 1000 parts of heat sink polymer,
thermal tolerance is higher than indicated in the
forced air oven test.
Unfilled PP Syringe Cylinder
In any case, since it was not appropriate to ask Mr.
Ailen Austurias of Pentaforma to disclose the PP
specifications for the material being tested, a plant
trial using the zirconate was run 6 months later. In the
less-than-laboratory perfect world of plant trials, the
inside syringe plunger (and not the cylinder as in
Table 20) was being run on a different machine.
Table 21 shows the effect of the zirconate (CAPS NZ
12/L) on the unfilled PP wherein the cycle time was
reduced by 30% from 23 to 16 sec. while the
temperatures on this machine were reduced 14% in
the rear zone and about 5% in the front zone to get the
proper balance of injection mold part quality for the
polypropylene syringe plunger. The color problem
did not occur with the CAPS NZ 12/L.
Table 21 Injection molded unfilled polypropylene
syringe plunger
Temperature (°C) Control 1% Caps L12/L
Rear 186 170 160
Center 1 215 200 190
Center 2 220 205 200
Front 240 225 215
Cycle Time (sec) 023 - 016
PP Chairs
Grival LTDA did not run into any color problems
when using 1% CAPS L12/L to injection mold PP
toilet seats on an Asian Pacific Machinery Corp.
(Model SM650) and was able to lower cycle times
16% on the first trial run setting (see Table 22).
Leonardo Montano of Multiportes LTDA injection
molded PP chairs on an Ingersoll Rand 500-2135
machine and was able to reduce cycle times 21% on
the second trial (see Table 23). The chairs had good
color also.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 22 Injection molded polypropylene toilet Table 24 Injection molded ABS appliance parts
seat
Temp. (°C) Control 1% CAPS L12/L
Temperature (°C) Control 1% Caps L12/L
Set Actual
Set Actual
Rear 225 210 210
Rear 190 175 186
Zone 2 225 210 210
Zone 2 195 180 192
Zone 3 230 200 226
Zone 3 200 185 198
Zone 4 230 210 216
Zone 4 205 190 208
Nozzle, % 220 210 210
Zone 5 210 195 196
Cooling cycle time (sec) 40 15
Zone 6 215 215 215
Total cycle time (sec) 77 52
Nozzle, % 50 35 40
Notes: Unilemh LTDA Machine: Engel
Cycle time (sec) 145 121
Notes: Grival LTDA Machine: Asian Pacific
Machinery Corp. SM650 Figure 13 Repolymerization effect of 1% CAPS L12/L
(20% neoalkoxy pyrophosphato titanate) on PP regrind/
LDPE regrind-80/20 processed in a twin screw extruder

Table 23 Injection molded polypropylene chair

Temperature (°C) Control 1% Caps L12/L
Set Actual
Rear 195 180 165
Zone 2 190 180 175
Zone 3 185 170 165
AMPS 110/115 130 130
Cycle time (sec) 140 125 110
Notes: Multiparts LTDA Machine: Ingersoll Rand
500-2135

Injection Molded ABS

(cf. Ref. [18] - Table 12 and Figure 13) An ABS Record
Carrier Case made from 60% virgin and 40% regrind
used 1% CAPS L12/E to reduce the average injection
molded cycle 13% from 165 to 144 seconds while
running the zones between 10 to 15°C cooler. In
addition flash was removed much more readily from
the parts containing the coupling agent.
ABS parts run on an Engel injection molding machine
at Unilemh LTDA had flow lines show up at irregular
intervals. The use of 1% CAPS L12/L eliminated the
flow lines and provided a better appearing part with
higher gloss while reducing cycle time by one-third
from 77 to 52 seconds at 5% average lower temperature
(see Table 24).
No Titanate With Titanate
Extruded ABS (Regrind) Picture Frames
Of course, injection and blow molding effects also
apply to extruded parts. For example, 1% CAPS L09/
K allowed for an 8% reduction in zone temperatures
while the line speed was increased 16% from 17.5 to
20 meters per minute (cf. Ref. [18] - Table 13).
Injection Molded HIPS Ladies High Heels
Polytac LTDA injection molds heels for ladies shoes
using HIPS and a trial as shown in Table 25 showed

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 165

 Salvatore J. Monte

a 31% reduction in cycle time by the second trial. and part quality was optimized. The average
This result would have been acceptable to Humberto temperature for all zones and the nozzle (seven
Pinilla if we had not encountered an incompatibility settings) was reduced 20% from 214°C for the control
between the LDPE carrier in the CAPS L12/L and the to 171°C while the cycle time was reduced 19% from
HIPS. This incompatibility resulted in a loose film 86.5 to 70.0 seconds.
forming on the outside of the part. There was a
definite separation of materials, especially when the Blowing Agent (Gas Assisted) Injection
part was cooled in water. Trials will have to be rerun Molding
using the CAPS L12/K to hopefully overcome the
difficulty caused by the CAPS’ LDPE binder. Another benefit for the compounder or thermoplastics
processor would be using a combination of coupling
and blowing agent for the elimination of sink marks
Table 25 Injection molded hips heels for ladies as is shown in Table 27 Controlled blow eliminated
shoes sink marks at 12.9% lower temperature with just 2.5
parts of LICA 12 per 10,000 parts MIPS.
Temperature (°C) Control 1% Caps L12/L
1 2
Transparent, Permanent, Non-Blooming
Rear 200 170 160 and Non-Moisture Dependent Anti-Static
Zone 2 205 170 160 Polymers
Zone 3 206 180 170 Minor amounts of thermally and hydrolytically stable
combined dissimilar polarity type neoalkoxy titanates
Nozzle, % 050 050 040
and/or zirconates can be added directly into the
Total Cycle Time (sec) 19 15 13 polymer during the thermoplastic or thermoset
compounding phase at temperatures in excess of
Notes: Polytac LTDA – Incompatibility noted
between HIPS and CAPS LDPE binder
200°C to form bipolar layers that provide a transparent,
non-blooming organometallic transfer (cf. Figure 11)
circuit resulting in a volume as well as surface antistatic
effect51. A complete discussion is provided in the
Injection Molded HDPE Baby Bath Tub Addcon World 2001 paper on the subject52.

Table 26 is the result of the use of 1% CAPS L12/L by

Hartmut H. Schlaubitz and German Ramirez while
injection molding a HDPE baby bath tub on a MIR
RMP 675 unit at Prinsel Inyeccion S.A. in Mexico on
May 1, 2000. It shows that six adjustments were
made in the settings before a balance of conditions
SUMMARY
Thermally Conductive Thermoplastic
I picked Ferro Corporation’s PCT patent53 on boron
nitride filled thermoplastics as a summary case history

Table 26 The use of 1% caps L12/L in injection molded HDPE baby bath tub on a MIR RMP 675
M Control 1% Caps L 12/L
T, °C Set Act Set Set Set Set Set Act
Zone 1 205 205 185 175 165 155 160 157
Zone 2 210 210 190 180 170 160 165 163
Zone 3 217 216 197 187 177 167 170 169
Zone 4 218 218 198 188 178 168 175 176
Zone 5 220 220 200 190 180 170 175 176
Zone 6 225 225 205 195 185 175 180 183
Nozzle 205 205 185 175 165 155 175 170
Cycle, Sec. - 86.5 81.5 No read 76.0 68.0 - 70.0

166 Polymers & Polymer Composites, Vol. 10, No. 2, 2002

 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics

Table 27 Use of a coupling and blowing agent combination to eliminate sink marks in a mips injection molded
part
Combination = Ken-React CAPS K-63331*
Conditions Control 1.0% 1.0% 0.50% 0.50% 0.25%
Temp (°C)
Rear Zone 193 193 177 165 154 154
Center Zone 196 196 185 177 165 165
Front Zone 202 199 197 188 177 177
Front Ext. 205 206 205 199 188 188
Nozzle 205 205 205 199 188 188
Cycle Time (sec) 35 35 35 35 35 35
Results
Sink Marks Yes No No No No No
Blow None Too Much Too Much Too Much Too Much Good
Color Change None Yes Yes Yes Yes Yes
Temp. Drop (%) 0 0.2 3.2 7.3 12.9 12.9
*Note: CAPS K-63331 = CAPOW L12/H Coupling Agent - 15.0
LLDPE DNDA 7441 - 50.0
Celogen AZ 130 Blowing Agent - 30.0
Zinc Stearate H - 5.0
- 100.0

out of the 1302 patents because it was fairly recent
(filed 11 January 2000), available in English from
ACS CAS, addresses the stringent material
performance demands of Moore’s Law in
microelectronics — and because it covers so many of
the points I have tried to make in this paper as to:
• Reactivity with non-silane reactive inorganics
such as boron. (To repeat the final part of the
statement by Pluedemann: Surfaces that showed
little or no apparent response to silane coupling
agents include calcium carbonate, graphite,
and boron”.)
• In Situ application of the pellet or powder
masterbatches of the coupling agent can take
place in temperatures in excess of 200°C.
• Dispersion effects and Adhesion effects – or
stated another way – Coupling and Catalysis
effects as it relates to: improved process rheology
of filled polymers; increased flow of the polymer
itself; shift in CPVC of filler to polymer ratio;
increased pigment functionality such as thermal
conductivity; increase in mechanical properties;
and increase in end product performance.
• A host of polymers and processes and equipment
used in thermoplastics and thermoset processes
are discussed.
• It is a patent that Ferro has decided to file on
11 January 2000, not only in the U.S., but also in
ninety countries, thus indicating some
significant commercial value since the
international patent filing language translation
fees alone should be in excess of $US 100,000.
I quote:
“Title: THERMALLY CONDUCTIVE
THERMOPLASTIC
Abstract: The invention relates to a thermally conductive
moldable polymer blend comprising a thermoplastic
polymer having a tensile at yield of at least 10,000 psi;
at least 60% by weight of a mixture of boron nitride
powders having an average particle size of at least
50 microns; and a coupling agent. The composition
displays a thermal conductivity of at least about 15 W/
moK and it is capable of being molded using high speed
molding techniques such as injection molding.

Polymers & Polymer Composites, Vol. 10, No. 2, 2002 167

 Salvatore J. Monte
Summary Of Invention
…Thermoplastic polymers are lightweight materials
having good mechanical and electrical insulating
properties. They can be easily processed into various
forms using low cost, automated, high speed
processing techniques such as injection molding.
Unfortunately, polymers as a class of materials have
low thermal conductivity (typically in the range of
0.2-0.4 W/moK). By adding high K fillers such as metal
powder, carbon fiber or select ceramics to the polymer
matrix, a substantial increase in thermal conductivity
can be realized under heavy filler loading. However,
high filler loading can result in an extremely high
melt viscosity, making the composite difficult to melt
process via injection molding. In the past, this has
generally limited the thermal conducting capability
of thermoplastic composites to below about 10 W/
mOk (typically in the range of 2 to 5 W/moK). A recent
break-through utilizing high thermal conductivity
carbon fibers has allowed an increase in K of injection
moldable polymer composites up to 17-20 W/moK.
Unfortunately, carbon fiber based polymer composite
materials give inconsistent results due to the fact that
carbon fibers often break down under high shear
condition and it is also difficult to control the
orientation of carbon fiber in high speed molding
application. In addition, the inherent electrical
conductivity of carbon fiber, combined with the high
cost of this material have also limited its application.
Consequently, there is a continuing interest in
developing low cost polymer composites with good
processability, high thermal conductivity, low
coefficient of thermal expansion, good electric
insulative property and high mechanical strength…
Description Of The Preferred Embodiments
This invention relates generally to an injection
moldable thermally conductive thermoplastic
composite composition or blend useful where heat
dissipation is required, e.g. heat sinks, electronic
device packaging, bearing applications, etc.
A major drive for development in the electronic
industry is to product components that are lower in
cost, lighter in weight and smaller in size while
having ever increasing performance characteristics.
As a result, more heat per unit is typically generated
in these devices. High-speed chips used in today’s
advanced systems require appropriate heat removal
to ensure optimal system performance. Thus, the
need to develop low cost thermal management
solutions for effective heat dissipation has increased.
168
The ability of a thermal management material to
dissipate heat is determined by its thermal
conductivity. Thermal conductivity (K) is one of the
basic thermophysical properties which determine
the heat flux and the resulting temperature field in a
device configuration, subject to boundary conditions.
Thermal conductivity (K) inW/mOK is defined as:
K= 100 x α x ρ x Cp
It is, therefore an objective of the present invention to
provide thermoplastic molding compositions which
offer the capability to use the high volume, low cost
molding processed such as injection molding,
combined with high thermal conductivity, a low
coefficient thermal expansion, light weight and good
electrical insulative properties (when required).
In accordance with the present invention, it has been
discovered that thermally conductive thermoplastic
polymer compositions may be prepared by mixing a
polymer matrix or base resin, a de-agglomerated
boron nitride powder or a mixture of the
deagglomerates boron nitride powder and a coupling
or dispersing agent to achieve a product with a
thermal conductivity of above 15 W/moK, and a
coefficient of thermal expansion (CTE) of below about
15 ppm/oC, and good electrical insulative properties
with volume resistivity of a least 1016 Ohms.cm.
Preferable, the composition display a thermal
conductivity of at least about 18 W/moK, and more
preferable, a conductivity of at least 20 W/moK. These
new materials can be easily molded into various
forms using normal injection molding techniques.
These new materials provide excellent low cost
alternatives to alumina and other packaging materials
for a myriad of applications from microprocessor
packaging to bearing housings and other heat-
exchanger applications such as heat sinks for
microprocessors and integrated circuit chips, plastic
ball grid array packages, quad flat packs, and other
common surface-mounted integrated circuit
packages. As new thermoplastic composites of the
present invention are electric insulating and exhibit
such a high thermal conductivity which is close to
that of pure alumina (about 25 /W/moK), they may be
used in many microelectronic chip packaging
currently dominated by ceramic packaging materials
which are heavier, higher cost and more difficult to
process. The materials of the present invention may
also be injection molded directly into heat sink and
heat spreader applications with a variety of compact
and complex shapes to provide highly efficient cooling
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
for microprocessors and other heat generating
electronic devices….”
The patent then goes on to explain that the Base Resin
(A) can be polymer such as polyethylene naphthalate,
polyethylene terephthalate, polybutylene
terephthalate, polyamide, polyphthalamide,
polyphenylene sulfide, polycarbonates,
polyetheretherketones, polyphenylene oxide and
liquid crystal polymers with processing temperatures
in the range of 230 to 300°C. The polymer (a), boron
nitride (B) and coupling agent (C) can be processed on
conventional melt equipment such as a mill, Banbury,
A Brabender, a single or twin screw extruder,
continuous mixers, kneaders, etc. In other words, the
equipment used in some instances would be the same
as that used in conventional thermoset elastomers.
The effects of the coupling agent (C) are noted:
“Coupling Agent (C)
The polymer system of the present invention includes
by weight from about 0.1% to about 5% by weight of
the coupling agent (C). The coupling and/or dispersing
agent serves to facilitate a better wetting of the boron
nitride fillers. It also helps to reduce the melt viscosity
of the composition and allows higher loading of the
fillers in the composition. In addition, the coupling
and dispersion agent may also improve the interface
adhesion polymer and the ceramic fillers and thus
provides better physical and mechanical properties.
The coupling and/or dispersion agent must have
high thermal stability to survive the harsh conditions
of common high volume melt processing such as
extrusion, compounding and injection molding, which
usually operate at temperatures above the melting
temperature of the thermoplastic polymer. Any
number of conventional coupling agents may be
employed in the blends of the present invention.
Examples of suitable coupling and dispersion agents
include, for example, a neoalkoxy titanate coupling
agent sold under the trade designation of Ken-React
CAPS L12/L and Ken-React CAPS L38/L, or a
monoalkoxy titanate coupling agent sold under the
trade designation of Ken-React KR 55 or Ken-React
CAPOW KR55/H by the Kenrich Petrochemicals
Company…”
CONCLUSION
For the past quarter of a century, I have been teaching
the use of subject organometallics. The net effect of
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
my efforts before numerous polymer organizations
and societies in plastics, coatings, inks, composites,
defense, adhesive and sealants is not only the
substantial body of information as embodied in
references and data given in this paper, but also the
commercial entities that have been created from that
intellectual property base. We have, for example:
contributed greatly to the solving of the problems of
the U.S. Military’s Insensitive Munitions Program;
China has five plants manufacturing my invention
products; and the licensed Ken-React (Plenact)
assigned by Kenrich Petrochemicals, Inc. to
Ajinomoto, Tokyo in 1980 now has over 1,000
employees connected with the manufacture and
servicing of subject technology.
This paper is then just a continuation of my mission
to teach the more efficient use of raw materials
through titanium. The abbreviated version of abstracts
of technical papers containing mention of my
invention products for the ACS CAS period of
December 22, 1998 to July 31, 2000 is available in the
literature54 or can be requested. Many of the patents
in the literature are based on ideas and suggestions I
made in lectures before Japanese Polymer Societies
in Osaka and Tokyo in 1979 and 1984 – and the many
extensive papers such as this one that have been
offered since the beginning of my mission in 1974. As
a result of the invention process, my papers are
necessarily a mixture of ideas, applications data,
abstracts, extrapolations, observations and review
and do not by their nature follow the usual scientific
experimental methodology – and are often outside of
the box. But my role here is to be a champion of new
ideas for application of subject organometallics in the
materials sciences. I hope this paper inspires
practioners of the plastics additives art to create more
new and novel applications of titanate and zirconate
coupling agents in thermoplastic and thermoset
polymer compositions.
REFERENCES
1. Monte, S.J., Kenrich Petrochemicals, Inc., “Ken-
React® Reference Manual - Titanate, Zirconate
and Aluminate Coupling Agents”, Third Revised
Edition, March 1995, 340 pgs.
2. Monte, S.J. and Sugerman, G., Kenrich
Petrochemicals, Inc.: S.M. Gabayson and W.E.
Chitwood, General Dynamics, “Enhanced
Bonding of Fiber Reinforcements to Thermoset
Resins”, 33rd International SAMPE Symposium,
Anaheim, CA, March 7-10, 1988.
169
 Salvatore J. Monte
3. Monte, S.J. and Sugerman, “Heavy Metal Free,
High Solids Anticorrosive Baked Coatings”,
33rd Int’l SAMPE Symp., Anaheim, CA, March
7-10, 1988 (SAMPE II).
4. Monte, S.J. and G. Sugerman, G., “High
Temperature Inorganic Anti-corrosive Coatings
Using Organometallic Titanate and Zirconate
Quat Blends (QB),” Corrosion ’90, Las Vegas,
NV, April 23-27, 1990, Paper No. 432.
5. Monte, S.J. and Sugerman, G., “Corrosion
Resistant One Hundred Percent Solids,
Environmentally Sound Coatings”, Water-Borne
& Higher Solids Coatings Symposium, New
Orleans, LA Feb. 3-5, 1988.
6. Monte, S.J. and Sugerman, G., “Alkoxy Titanates
and Zirconates as Corrosion Inhibitors in Clear
Coats and Unfilled Polymers”, Corrosion/88,
NACE, St. Louis, MO, March 21-25, 1988.
7. Monte, S. J. and Sugerman, G., “Very High
Solids and Waterborne Anticorrosive Coatings”,
Western Coatings Societies’ 19th Biennial
Symposium and Show, Anaheim, CA. March
14-16, 1989.
8. Monte, S.J. and Sugerman, G., “The Usage of
Organometallic Reagents as Catalysts and
Adhesion Promoters in Reinforced Composites”,
Second International Conference on Composite
Interfaces (ICCI-II), Case Western Reserve
University, Cleveland, Ohio, June 13-17, 1988.
9. Monte, S.J. and Sugerman, G., KPI; A. Damusis
and P. Patel, Polymer Institute, University of
Detroit, Application of Titanate Coupling Agent
in Mineral and Glass Fiber Filled RIM Urethane
Systems,” SPI Urethane Division 26th Annual
Technical Conference, November 1981.
10. Monte, S.J. and Sugerman, G., KPI, “Titanate
Coupling Agents - 1985 Urethane Applications”,
SPI Urethane Division 29th Annual Technical /
Marketing Conference, October 1985.
11. Monte, S.J. “Injection Molding with Neoalkoxy
Titanates and Zirconates’, SPE RETEC, White
Haven, PA, USA October 19, 1995.
12. Monte, S.J., “Titanium and Zirconium Esters
vs. Couplers and Single Site Catalysts for In-
Situ Repolymerization and Copolymerization
Useful for Recycled Polymeric Compositions,”
ACS Rubber Div., Louisville, KY, Oct. 8-11,
1996, Paper No. 57.
170
13. Monte, S.J., “Better Bonding and Metallocene-
like Catalysis Benefits for Elastomers”, Rubber
Technology International ’96, UK & Int’l Press,
a Div. of Auto Intermediates Ltd (1996).
14. Monte, S.J. “Compounding and Molding with
Neoalkoxy Titanates and Zirconates”,
Polyblends ’97 SPE Div./Sect. Conference,
NRCC, Montreal, Canada, Oct. 9, 1997.
15. Monte, S.J., “Increased Productivity of
Thermoplastics Using Organometallic Titanate
and Zirconate Coupling Agents”, SPE ANTEC,
May 1-3, 1989.
16. Monte, S.J., “Coupling Agents Increase PVC
Productivity”, Plastics Compounding Magazine,
November/December 1989.
17. Glaysher, W.A., Haff, D.R., Schlaubitz, H.H.,
and Monte, S. J., “The Use of Organometallic
Coupling Agents as Process Aids in Blow Molded
HDPE”’ SSPE RETEC, High Performance Blow
Molding Conference, Oct. 9-10. 1990.
18. Monte, S.J., “New Opportunities in Recycled
Plastics With Neoalkoxy, Titanate and Zirconate
Coupling Agents”’ SPE Recycle RETEC, October
31, 1989.
19. Monte, S.J., “More Efficient Manufacture of
Better Foamed, Filled and Unfilled Polymer
Compounds With Titanate and Zirconate
Coupling Agents”, Northeast Regional Rubber
& Plastics Exposition, September 21-22, 1994,
Mahwah, NJ.
20. Monte, S.J., Sugerman, G. “The Use of
Organometallic Titanates & Zirconates as
Reactants and Compatabilizers in Polymers”,
Compalloy ’90, Mar. 9, 1990, New Orleans, LA.
21. Plueddemann, Edwin P., “Silane Coupling
Agents”, Pg. 114, 1982 Plenum Press.
22. Voelkel, A. and Grzeskowiak, T., Poznan
University of Technology, Institute of Chemical
Technology and Engineering, “The Use of
Solubility Parameters in Characterization of
Titanate Modified Silica Gel by Inverse Gas
Chromatography”, Chromatographia Vol. 51,
No. 9/10, May 2000.
23. Wang, Yeh and Huang, Jiang-Shen, Dept. of Chem.
Eng’g, Tunghai University, “Single Screw
Extrusion Compounding of Particulate Filled
Thermoplastics: State of Dispersion and Its
Influence on Impact Properties”, Journal of Applied
Polymer Science, Vol. 60, 1779-1791 (1996).
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
 Neoalkoxy Titanate and Zirconate Coupling Agent Additives in Thermoplastics
24. Krysztafkiewicz, A.; Rager, B.; Jesionowski, T.,
Institute of Technology and Chemical
Engineering, Pozna? University of Technology,
“The Effect of Surface Modification on
Physiochemical Properties of Precipitated
Silica”, Journal of Materials Science 32 (1997)
1333-1339.
25. Kajiyama, Aklhisa; Nakamura, Tatsuya, Toda
Kogyo Corp., EP 1 041 041 A1 dated 04.10.2000,
“Layered rock salt-type oxide particle powder
and process for producing same”.
26. Ichazo, M.N.; González, J.; Albano; C.; Diaz, B.;
Departmento De Mecánica, Grupo De Polimeros,
Universidad Simon Bolivar, ANTEC 1999,
“Study of the CaCO3 Filled PP/HDPE Composites
Using Different Surface Modifiers”.
27. Calvo, Luis M.; Noskin, Steve; Kahan,
Sansodeen; McWilliams, Matthew, Polymer
Plastics Co., U.S. 6,036,998 dated Mar. 14, 2000,
“Process For Coloring EPDM Rubber To Produce
Granules For Blending With Polyurethane
Resins Or To Use by Themselves To Create
Safety And Athletic Surfaces”.
28. Yu, G., Zhang, M.Q., Zeng, H.M., “Carbon-
Black-Filled Polyolefine as a Positive
Temperature Coefficient Material: Effect of
Composition, Processing, and Filler Treatment”,
Journal of Applied Polymer Science, Vol. 70,
559-566 (1998).
29. Ogino, Masaaki, Bando Chemical Industries,
Ltd., JP03070754 dated 19910326, “Rubber
Compositions With High Heat-Conductivity”.
30. The Instit. Sc. & Ind. Res., Osaka University,
“Effects of coupling agents on the mechanical
properties improvement of the TiO2 reinforced
epoxy system”, Mater. Lett.(1996), 26(6), 299-
303 Coden:MLETDJ;ISSN:0167-577X.
31. Murakata, Tadahiro; Yamamoto, Ryoich;
Yoshida, Yuichi; Hinohara, Masanobu; Ogata,
Tateaki; and Sato, Shimo, Dept. of Materials
Science and Eng’g, Yamagata University,
“Preparation of Ultra Fine TiO2 Particles
Dispersible in Organic Solvents and Their
Photocatalytic Properties”, Journal of Chemical
Engineering of Japan, Vol. 31, No.1, pp. 21-28,
1998.
32. Ahmad, Sahrim; Abdullah, Ibrahim; Abdullah,
Mustfa; and Wai, Wong Chuan, Faculty of
Applied and Physical Sciences, Universiti
Kebangsaan Malaysia, “Electrical and Magnetic
Polymers & Polymer Composites, Vol. 10, No. 2, 2002
Properties of Barium Ferrite Thermoplastic
Natural Rubber (TPNR) Composites”, Sci. Int.
(Lahore), 10(4), 375-377, 1998, ISSN 1023-5316;
CODEN; INTE 8.
33. Mitsubishi Cable Ind., US 4,769,179 - 9/6/88.
34. Eichler, Hans-Jürgen; Palmer Michael; Herbiet,
René, ALUSUISSE MARTINSWERK GMBH,
WO 00015710 dated 14. September 1999,
“Surface-Modified Filling Material
Composition”.
35. Kato, Masaharu; Omoto, Masanobu; Ishimatsu,
Hirofumi; Madalle, James; Kratzer, Jeff A.; EP
0 708 143 A1 dated 24.04.1996, “Polyvinyl
Chloride Based Resin Composition and Products
Derived Therefrom”.
36. Field, R. and Cowe, P.L., “The Organic
Chemistry of Titanium”, Butterworth & Co.,
Washington, D.C., 1965 (213 pp. 791 references).
37. Korea Institute of Science and Technology, U.S.
5,237,042, Aug. 17, 1993.
38. Kim, C.Y., Cho, H.N., Yoo, H.W., Kim, H.J.,
Korea Institute of Science and Technology,
“Method for the Preparation of Polyester by Use
of Composite Catalyst”, U.S. 5,714,570 dated
Feb. 3, 1998.
39. Donald W. Kelley, U.S. Patent 4,837,272, June
6, 1989.
40. Monte, S.J., Sugarman, G., Kenrich
Petrochemicals, Inc., “Repolymerization”, U.S.
Patent 4,657,988 dated April 14, 1987.
41. Waha, Chuah Ai; Choongb, Leong Yub; Neonb,
Gan Seng, a Petronas Research and Scientific
Services, b Dept. Chem. Eng’g., U. of Malaysia,
European Polymer Journal 36 (2000) 789-801.
42. Galanti, Andrea; Laus, Michele; Fiorini,
Maurizio, CS Mixer S.r.l., Ravenna, Italy,
“Reinforcement of SBS by organophilic clay
fillers”, Kautsch. Gummi Kunstst. (1999), 52(1),
21-25, CODEN: KGUKAC; ISSN: 0022-9520, PB
Huethig GmbH, cc 39-9 (Synthetic Elastomers
and Natural Rubber).
43. Simonutti, F.M., Wilson Sporting Goods Co.,
Japan, “Golf ball cores containing titanate
coupling agents”, JP 10108925 dated 28 April
1998.
44. Kim, Hyun; Snell, Dean A., Taylor Made Golf
Company, Inc.. WO 00/40306 dated 13 July
2000, “Improvement of Golf Ball Cover Using
Organometallic Compounds”.
171
 Salvatore J. Monte
45. Industrial Technology Res. Inst., Hsinchu,
Taiwan, US 5,340,861, Aug. 23, 1994.
46. Fukae, Kensuke and Yoshida, Ichiro, Advance
Color Technology, Inc., U.S. 6,132,922 dated
Oct. 17, 2000, “Liquid Developer for
Electrophotographic Printing Apparatus”.
47. Monte, S.J., Kenrich Petrochemicals, Inc.,
“Titanate and Zirconate Coupling Agents in
Foamed Polymers”, RAPRA Foams Conference,
March 13, 2001, Frankfurt, Germany.
48. Schut, J. “Organometallic Esters Enhance
Recycled PET/PC Blends,” Plastics Formulating
and Compounding, Sept./Oct., 1996.
49. Neste Oy, WO 95/23183, Feb. 28, 1995.
50. Miller, N. A.; Jones, M.S.; and Stirling, C.D.,
Industrial Research Limited, “Waste Plastics/
Cellulose Fibre Composites”, Polymers &
Polymer Composites, Vol.6, No. 2, 1998.
172
51. U.S. Patent 5,659,058 dated August 19, 1997,
“Thermally Stable Antistatic Agents” – Monte, S.J.
52. S. J. Monte, “Permanent, Transparent, Non-
Blooming and Non-Hygroscopic Antistatic
Agents Based On Combined Neoalkoxy
Organometallics”, Addcon World 2001
Conference, 9 October 2001, Berlin, Germany.
53. Zhuo, Qizhuo; Skovran, Dennis C.; Lightner,
Leo F.; Randall, Michael S.: Stygaer, Vernon E.,
Ferro Corporation, WO 00/42098 dated 20 July
2000, “Themally Conductive Plastic”.
54. Monte, S.J., Paper No. 16, “Applications of
Titanate and Zirconate Coupling Agents in
Thermoplastics and Thermoset Elastomers-
2001”, ACS Rubber Division, April 25, 2001.
Polymers & Polymer Composites, Vol. 10, No. 2, 2002