48 s i l ic o n e c he m i s try
Source: wichientep - Fotolia.com
Non-tin catalysts for
alkoxy silane polymers
Organometallic catalysts developed for moisture cured silane-terminated polymer systems.
By John Florio, Ravi Ravichandran, David Switala and Bing Hsieh, King Industries, Inc.
Regulatory restrictions on the use of tin
catalysts create considerable difficulties
for formulators of crosslinkable silane-
terminated polymer systems. A tin-free
organometallic catalyst can give good
mechanical properties with similar cure
times, and even cure one system where
tin compounds are ineffective.
O rganosilane polymers are used in ad-
hesives, sealants and coatings as either
coupling agents or crosslinkers. As coupling
agents, their role is to promote adhesion
between organic and inorganic substrates.
As crosslinkers, organosilane polymers react
with other functional groups to form covalent
bonds that can generate products with struc-
tural properties.
Crosslinkable organosilane polymers consist
of functionalised backbones with alkoxysilane
terminal groups. The main silane terminated
polymer backbone chemistries are polyether
e u r o p e an co at i ngs J OURNAL 03 – 2016
(Figure 1), polysiloxane and polyurethane.
Cured properties such as Tg and flexibility
are dependent on the backbone chemistry.
Organosilane polymers can promote adhe-
sion, weatherability and reinforcement of
coatings, adhesives, sealants and fillers. Or-
ganosilanes are monomeric compounds with
at least one silicon atom bonded to a carbon.
Siloxane compounds (-Si-O-Si-) are polymeric
organosilane compounds, and silanol groups
(-Si-OH) are hydrolysed silane groups.
Since their development in the late 1970s,
modified silane polymer products have be-
come widely used in DIY and construction seal-
ants and adhesives for a variety of indoor and
outdoor applications on a variety of substrates.
Organosilane crosslinking in-
volves two reactions
The fundamental organosilane crosslinking
process involves two key reactions: hydroly-
sis of an alkoxysilane functional group to
generate silanol groups (Figure 2) and con-
densation of the silanol group with other
functional groups. The silanol groups will
undergo a condensation reaction with other
silanol groups (Figure 3) or with alkoxysilane
groups (Figure 4), each producing crosslinked
siloxane bonds.
The condensation of two silanol groups will
generate water and, as shown in Figures 2
and 4, hydrolysis and condensation of alkox-
ysilane groups will generate an alcohol by-
product.
For the purpose of this discussion, it is con-
venient to assume that the hydrolysis reac-
tion occurs initially, followed by the con-
densation reactions. However, in practice
hydrolysis and condensation occur concur-
rently unless special efforts are made to sep-
arate the steps [1].
Alkoxysilane polymers are used in single-com-
ponent moisture cure applications. For exam-
 s i li c o ne chem i s t ry 49

Results at a glance
űű A new tin-free organometallic
compound has been developed for
the catalysis of crosslinkable silane-
terminated polymer systems. The
catalyst can accelerate the reaction
of alkoxy-silane terminated resins
based on polyether and polyure-
thane backbone chemistries.
űű It can provide a range of me-
chanical properties for various
caulk, sealant and adhesive appli-
cations while providing cure times
similar to tin catalysed systems.
extensively studied and tin compounds sug-
gested as being the most active. However,
the tin catalysts must initially hydrolyse to
form the active species [2].
Tin compounds are commonly used to cata-
lyse the crosslinking of alkoxysilane systems,
particularly systems based on methoxysilane
polymers. Compounds that efficiently cata-
lyse many of these crosslinking reactions in-
clude dioctyltin diacetyl acetonate and dibu-
tyltin dilaurate.
However, concerns about toxicity of tin com-
pounds have driven formulators to explore
other catalyst options. Although these op-
tions can include acids, bases and other
organometallics, finding a catalyst that can
provide sufficient reaction acceleration has
been elusive.
Along with reaction acceleration, physical
properties of the cured product can also
be dependent on the catalyst. For example,
some acids might provide good accelera-
tion of the crosslinking reaction, but the acid
might also accelerate rearrangement of the
formed polysiloxane backbone, causing prod-
uct degradation. Some tertiary amines could
accelerate the crosslinking reaction, but they
might also contribute colour and odour. 

űű In the specific case of diethoxy-

silane polymers, which have the
advantage of not emitting toxic
methanol during cure, tin is a very
poor catalyst but the organometallic
product tested produced an effec-
tive cured product within a reason-
able cure time.

ple, formulated alkoxysilane products can Innovative solutions

be stored in sealed cartridges for caulk
and sealant applications. Commercial
through Technical
moisture cure caulks and sealants based Progress
on alkoxysilanes are typically advertised
Binders and Additives for the Paint
to have a shelf life of nine months.
and Coatings Industry
The product becomes activated when
Modern production facilities
it is applied to a substrate and exposed and management systems
to atmospheric moisture. Since the cure Customer-oriented R&D-Team with
involves two concurrent reaction pro- its own application technology
Constantly growing range of products
cesses, accelerating the overall curing
made from renewable raw materials
reaction will require a catalyst that con- High-quality commercial products
tributes to both processes. from well-known partners
There are several variables that play key Market experience since 1851
roles in determining the reaction rates of
moisture cure alkoxysilane systems. The
hydrolysis and condensation reaction
rates are dependent on the pH of the
system and on the alkyl substituents on
the silicon [1]. The other key component
in determining the overall reaction rate is
the catalyst.

Tin and other catalysts:

current situation summarised

The hydrolysis and condensation reac-

tions can be accelerated by acids, bases
and organometallics. Specific mecha- Visit us at the

nisms have been described for each of Eurocoat 2016

the acid and base catalysed reactions at booth B 60.

[1]. The activity of organometallic com-

pounds in organosilane systems was

Worlée-Chemie GmbH Söllerstraße 14 – 16 D-21481 Lauenburg e+49 41 535

u r op 96 coat
e an 0 service@worlee.de
i ngs JOURNA Lwww.worlee.de
03 – 2016
 50 s i l ic o n e c he m i s try

 Implications of EU regulations
limiting tin content
European Commission Decision 2009/425/
EC, which includes restrictions on the use of
dibutyltin, dioctyltin and tri-substituted or-
ganotin compounds, was incorporated into
ANNEX XVII of REACH through regulation (EU)
276/2010 [3]. A summary of these restric-
tions is in Table 1 [4].
With the stigma of being environmentally regu-
lated, tin compounds are more often avoided,
regardless of the dosage required to sufficient-
ly accelerate the reaction. For example, suffi-
cient acceleration of the reaction of polyols
with polyisocyanates for many 2-component
coating applications usually requires levels of
tin metal that are well below the ≤ 0.1% limi-
tation. Coatings formulators still often strive
to formulate completely tin-free systems. The
level of tin metal required to achieve sufficient
cure of moisture cured organosilane polymer
systems is typically very close to the ≤ 0.1%
limit established in REACH Annex XVII, Entry
20. Therefore, while tin replacement is an is-
sue for the polyurethane coatings industry, it is
a greater issue for industries that use moisture
cured organosilane polymer coatings, adhe-
sives and sealants.
Methanol levels in curing may
exceed safety limits
If the R groups in Figures 2 and 4 are methyl,
then the by-product generated in the hydrol-
ysis and condensation reactions would be
methanol. The European Agency for Safety and
Health at Work (EU-OSHA) directive 67/548/
EEC, and the 25th updating of this directive
(98/98/EC), have defined methanol as harmful
with danger of very serious irreversible effects
by inhalation, skin contact and ingestion.
According to Commission Directive 2006/15/
EC of February 7, 2006, the maximum allow-
able methanol exposure for an eight-hour
workday is 260 mg/m3. Methanol exposure
studies of a methoxysilane floor adhesive
based on a NIOSH method [5] have been
conducted that report 5400 mg/m3 emission
of methanol during an eight hour period [6].
An approach to completely eliminating meth-
anol from the alkoxysilane curing process is
to use ethoxylated silane polymers. However,
catalysis of the ethoxysilane crosslinking re-
action is challenging. Tin compounds have
proved to be inefficient for these reactions.
Organometallic catalyst
is studied in three systems
The main motivation for replacing tin in mois-
ture curing organosilane systems is that of
regulatory issues, not performance issues.
An extensive study was conducted to identify
compounds that could be considered as alter-
natives. Included in the study were a range of

Figure 1: Structure of alkoxysilane polymer.

Figure 2: Silanol formation, hydrolysis of alkoxysilanes.

Figure 3: Formation of siloxane crosslinks by condensation of silanols.

Figure 4: Formation of siloxane crosslinks by condensation of silanol and alkoxysilane.

e u r o p e an co at i ngs J OURNAL 03 – 2016


metal compounds, acids, amines, acid/amine
salts and combinations of each.
From this list, one catalyst provided perfor-
mance comparable to tin catalysts in dimethoxy
and trimethoxy silane systems and superior
performance in a diethoxysilane system.This
catalyst, referred to as “K-KAT 670”, is a non-tin
organometallic compound designed to provide
activity that is comparable to tin catalysts for
crosslinking moisture cure organosilane sys-
tems. This catalyst can potentially accelerate the
curing process by all three of the catalytic mech-
anisms reviewed and will not accelerate rear-
rangement of the polysiloxane backbone. This
product was compared to tin catalysts in sev-
eral different formulated alkoxysilane systems.
Experiment I is based on a dimethoxymethylsilyl
(DMS) polyether polymer and Experiment II on
a triethoxysilyl (TMS) polyether polymer system.
Experiment III addresses the issue of methanol
generation by using an organosilane based on a
diethoxysilyl (DES) polyether polymer.
Production and test procedures
Fully formulated single component moisture
cure alkoxysilane systems were used in the
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experiments. The uncatalysed formulations
were stored in dispensing cartridges. Approx-
imately 30 grams of uncatalysed material was
dispensed into a container with a caulk gun
before addition of the catalyst.
The material in the container was mixed on
a “SpeedMixer” rotary mixer for 30 seconds
at 1500 rpm then 2 minutes at 2200 rpm. An
adjustable doctor blade was used to apply 3
mm thickness of the blend onto a paper sub-
strate. The degree of dryness was determined
by using a Model 415 Drying Time Tester [7]
in accordance with DIN 53 150.
The dryness test involved applying a force
onto a paper disk that covered a test area on
the casting for 60 seconds. The results are
based on the amount of tack and on visual
impressions that develop from the applied
force. The dryness testing was done at ap-
proximately 25 °C and 50% relative humidity.
Degree 1 of the DIN 53 150 method was sub-
stituted by a glove test to determine touch
dry. Table 2 defines the rating system used.
Hardness of the castings was determined
with a Shore A [8] hardness tester after the
castings were allowed to cure under ambient
conditions for two weeks. Other mechanical
Colorants & Pigment dispersions
s i li c o ne chem i s t ry 51
properties were measured on an Instron [9]
tester using dog-bone shaped samples cut
from the fully cured 3 mm thick castings.
Performance matched
on dimethoxymethylsilane…
The organometallic catalyst was compared
to dioctyltin diacetylacetonate (DOTDAA) in a
fully formulated system based on a polyether
backbone DMS polymer. Catalyst levels were
derived from ladder studies. Levels of orga-
nometallic were adjusted to produce cast-
ings that dried at rates similar to the system
catalysed with 0.6% DOTDAA.
The tin content of DOTDAA is approximately
21%. At 0.6%, the tin content in the formu-
lated control system is approximately 0.12%,
which would not comply with EU regulations.
The general formulation is in Table 3.
Dryness ratings of 3 mm thick castings ac-
cording to DIN 53 150 are in Table 4. The
systems dried similarly, with each achieving
the highest degree of dryness (paper does
not adhere to 20 kg load, no visible change to
coated surface) in six hours.
Differences in the performance of the two 
e u r op e an coat i ngs JOURNA L 03 – 2016
 52 s i l ic o n e c he m i s try

 systems were not significant based on the
mechanical property results (Table 5). The two
castings developed similar tensile stress (which
can be associated with toughness), modulus
(elastic modulus) and strain (elongation).
…Almost equalled on trimethox-
ysilane…
DOTDAA was also compared to the organo-
metallic catalyst in a polyether backbone TMS
polymer system. The general uncatalysed
formulation is in Table 3. The dryness ratings
in Table 4 indicate slightly higher reactivity
with the DOTDAA catalysed system.
The DOTDAA system achieved the maximum
dryness rating (passed 20 kg load test) in five
hours while the non-tin catalyst required six
hours to reach the 7 dryness rating. The cast-
ings developed similar mechanical properties
after the two weeks of ambient cure (Table 5).
…While tin performs poorly in
diethoxysilane polymer
Results of the DES polymer study were very
different compared to the DMS and TMS re-
sults. The basic uncatalysed DES formulation
is in Table 3. DOTDAA was essentially not ac-
tive in this system at 0.5% and 1.0% on total
formulation weight.
Higher dosages were not evaluated since the
tin level incorporated with the 1.0% dosage
was more than double the maximum allowed
by EU regulations. The 3 mm thick castings
required more than 120 hours to achieve a
dryness rating of 7. Dryness ratings are in Ta-
ble 4 and mechanical properties in Table 5.
To investigate a tin compound with a different
ligand, dibutyltin dilaurate (DBTDL) was added
to the study. However, as with DOTDAA, activ-
ity of the DBTDL system was poor. Dry times
of the DES system with organometallic catalyst
were significantly faster than the tin catalysed
systems and indeed were comparable to the
DMS and TMS systems. The system also com-
pleted five weeks of storage at 50 °C with no
loss of activity.
The DOTDAA system required a month of am-
bient cure before it was suitable for testing on
the Instron. Even so, the casting had very weak
properties.
Regulatory compliance and a
broader application area
Addressing tin regulatory restrictions, new
tin-free organometallic compounds have
been developed that have demonstrated
activity similar to tin catalysts for accelerat-
ing moisture cure methoxysilane crosslinking
reactions. The test catalyst demonstrated
activity that was similar to tin in dimethoxy-
methylsilane and trimethoxysilane polymer
systems.
Also addressed in this work was the catalysis
of a non-methanol-emitting moisture cure
system based on a diethoxysilane polymer. In
this case, the non-tin product catalysed the
crosslinking reaction while tin catalysts were
essentially not active at double the maximum
tin concentration levels allowable under cur-
rent EU regulations.  
REFERENCES
[1] Osterholtz F.D., Pohl E.R., Kinetics of the
hydrolysis and condensation of organofunc-
tional alkoxysilanes: a review, Jnl. Adhesion
Sci. Technol., 1992, Vol. 6, No. 1, pp 127-
149.
[2] Torry S.A. et al, Kinetic analysis of organosi-
lane hydrolysis and condensation, Internat.
Jnl. Adhesion & Adhesives, 2006, Vol. 26, pp
40-49.
[3] Commission Regulation (EU) No 276/2010
of 31 March 2010, http://eur-lex.europa.eu/
LexUriServ/LexUriServ.do?uri=OJ:L:2010:08
6:0007:0012:EN:PDF
[4] Safeguards SGS Consumer Testing Services,
No. 062/10 April 2010, http://newsletter.
sgs.com/eNewsletterPro/uploadedimag-
es/000006/SGS-Safeguards-06210-Com-
mission-Publishes-Regulation-Amending-
REACH-Restrictions-EN-10.pdf
[5] NIOSH method (National Institute for Occupa-
tional Safety and Health, USA)- method 2000,
Issue 3.

Table 1: Summary of organotin requirements under European Regulation (EU) 276/2010 amending Annex XVII of REACH, REACH
Annex XVII, Entry No 20.

Substance Scope Requirement Date effective

Tri-substituted organostannic compounds Article or part of an article ≤ 0.1% 1 July 2010
such as Tributyltin (TBT) compounds, Triph-
enyltin (TPT) compounds and Dibutyltin (DBT) 1. Mixture
≤ 0.1% 1 January 2012
compounds 2. Article or part of an article (except food contact materials)

1. One-component and t wo-component room temperature vul-

Dioctyltin (DOT) compounds
Dioctyltin (DOT) compounds
canisation sealants (RTV-1 and RTV-2 sealants) and adhe-
sives,
2. Paints and coatings containing DBT compounds as catalysts
when applied on articles,
3. Soft polyvinyl chloride (PVC) profiles whether by themselves or ≤ 0.1% 1 January 2015
coextruded with hard PVC,
4. F abrics coated with PVC-containing DBT compounds as stabi-
lisers when intended for outdoor applications,
5. Outdoor rainwater pipes, gutters and fittings, as well as cover-
ing material for roofing and facades.
1. Textile articles intended to come into contact with the skin,
2. Gloves,
3. F
 oot wear or part of foot wear intended to come into contact with
the skin,
4. Wall and floor coverings,
≤ 0.1% 1 January 2012
5. Childcare articles,
6. Female hygiene products,
7. Nappies,
8. Two-component room temperature vulcanisation moulding kits
(RTV-2 moulding kits).

e u r o p e an co at i ngs J OURNAL 03 – 2016

 s i li c o n e chem i s t ry 53

Table 2: Degree of dryness (DIN 53 150).

1 Touch dry, no visible residue remaining on rubber glove

2 Paper does not adhere, but visible change with 20 g load

3 Paper does not adhere, but visible change with 200 g load

4 Paper does not adhere, but visible change to coated surface

with 2 Kg load

5 Paper does not adhere, no visible change to coated surface

with 2 Kg load

6 Paper does not adhere, but visible change to coated surface

with 20 Kg load

7 Paper does not adhere, no visible change to coated surface

with 20 Kg load

Table 3: Experimental system formulations.

Component DMS TMS DES

DMS polymer [10] 32.8

TMS polymer [11] 32.8
DES polymer [12] 20.2
Plasticiser 16.4 16.4 23.1
Filler 39.3 39.3 49.1
Titanium dioxide 6.6 6.6 3.3
Thixotrope 1.6 1.6 --
Antioxidant -- -- 0.3
HALS 0.3 0.3 0.3
UVA 0.3 0.3 0.8
Moisture scavenger 0.7 0.7 1.4
Adhesion promoter 2.0 2.0 1.5
Total 100.0 100.0 100.0

Table 4: Degree of dryness (hours).

Catalyst /
1 2 3 4 5 6 7
drying degree
DMS polymer
0.6% DOTDAA 0.8 2.3 3.5 4.0 4.5 5.0 5.5
2.0% 1.5 2.3 3.0 3.5 4.5 5.5 6.0
organometallic
TMS polymer
0.6% DOTDAA 0.3 0.5 1.0 1.3 3.0 3.3 5.0
2.0% 1.0 1.5 2.0 2.3 4.0 4.3 6.0
organometallic
DES polymer
0.5% DOTDAA 120+ 120+ 120+ 120+ 120+ 120+ 120+
2.0% 1.3 3.0 4.5 5.0 6.0 6.5 7.0
organometallic

e u r op e an coat i ngs JOURNA L 03 – 2016

54 s i l ic o n e c he m i s try

“Addition of the tin-free

compounds does not
require extraordinary
incorporation techniques.“

3 questions to Dr Ravi Ravichandran

In short, why is tin seen as critical? While tin is viewed as a versatile catalyst, there are consid-
erable regulatory and toxicological hurdles on the horizon, that is encouraging users to phase out Dr Ravi
these catalysts.The changes in classification and possible labelling changes to account for repro- Ravichandran
ductive and mutagenic toxicity, have led formulators to strive for tin free sytems where possible. In Vice-President, Research &
addition REACH has established limits and restrictions on the use levels of these catalysts, in various Development
applications. King Industries
ravichandran@kingindustries.com
How elaborate is it to incorporate the tin-free compounds into existing formulations? Ad-
dition of the tin-free compounds does not require extraordinary incorporation techniques. Depend-
ing on the system, they are preferably added to the formulation after steps that generate or require
high temperatures.

Are further property improvements feasible with these compounds? Along with the regulato-
ry benefits of being tin-free, an important benefit of using the K-KAT 670 is its activity in ethoxysilane
systems, which do not produce methanol byproduct and are poorly catalysed with tin compounds.
In addition they provide a range of mechanical properties for various caulk, sealant and adhesive
applications while providing cure times similar to tin catalysed systems.

[6] Galbiati Dr. A., Maestroni Dr. F., Silane adhesives: origin, diffusion and
environmental problems, N.P.T. Research Unit, Gropello Cairoli, Pavia,
Italy, 2008, http://www.ecosimpflooring.com/download/adesivi-silani-
ci-origine-diffusione_eng.pdf
[7] “Model 415” Drying Time Tester, Erichsen GmbH & Co. KG.
[8] Instron Corporation, Shore A durometer.
[9] Instron Corporation, Dual column table top model, 30 kN (6700 lbf) load
capacity.
[10] M S Polymer “S303H” dimethoxymethylsilane polymer, Kaneka Corpora-
tion, Osaka, JP.
[11] M S Polymer “SAX520”, trimethoxysilane polymer, Kaneka Corporation,
Osaka, JP.
[12] Diethoxysilane polymer, Easterly Research, Warminster, PA.

Table 5: Mechanical properties (cure: 2 weeks ambient except

where noted otherwise).

Shore A Stress at Strain at Modulus

max psi max % psi
DMS polymer
0.6% DOTDAA 52 378 234 265
2.0% organometallic 52 324 256 243
TMS polymer
0.6% DOTDAA 52 313 320 189
2.0% organometallic 52 359 362 173
DES polymer
0.5% DOTDAA* 22 93 267 85
2.0% organometallic 48 291 608 103

*1 month ambient cure.

e u r o p e an co at i ngs J OURNAL 03 – 2016

 s i li c o ne chem i s t ry 55

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