Processing Aids

Theory & Application

Struktol Singapore
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History
Pelroleum Cls Pelroleum Cls Pelroleum Cls Pelroleum Cls
Eslers Eslers Eslers Eslers
Slearc Acd Slearc Acd Slearc Acd Slearc Acd 'Tradlonal Process Ads 'Tradlonal Process Ads 'Tradlonal Process Ads 'Tradlonal Process Ads' '' '
Faclce Faclce Faclce Faclce
Pubber Crumbs Pubber Crumbs Pubber Crumbs Pubber Crumbs
Waxes Waxes Waxes Waxes
Modern (Fast) Equipment
Tougher Specifications
Product Appearance
Production Efficiency
Tough Synthetics
Created the demand
for sophisticated
Processing Aids
/DD-// //Do-SS /DS /DD-// //Do-SS /DS /DD-// //Do-SS /DS /DD-// //Do-SS /DS
Chemical Peptisers
Physical Peptisers
Dispersing Agents
Homogenising Resins
Plasticisers
Mold Release Agents
Activators
Metal Oxide Preparations
Modified Sulphurs
Modified Accelerators
/-D//S-/S /-D//S-/S /-D//S-/S /-D//S-/S
Required to "soften" tough polymers
To allow Filler to be mixed
To allow Extrusion / Calendering
To allow Molding
TWO Mechanisms Used -- MASTICATION
(CHEMICAL)
-- LUBRICATION
(PHYSICAL)

Chemical Peptisers
"Mastication" is the breaking of rubber chains by
tearing them apart with shear in a mixer or on a mill
Chains break at double bond sites
Heat accelerates chain breaking
Oxygen blocks broken chains from recombining
Chemical Peptisers are catalyst for mastication
so very small amounts are needed
Chemical Peptisers
(cont.)
R
R
R
R
R
R
R
R
R
R
R
R
Oxygen
Heat
Shear
Polymers with low unsaturation (Butyl ; EPDM) cannot be masticated
- not enough double bonds
Because OXYGEN stops broken chains from recombining
ANTIOXIDANTS stop the mastication reaction
CARBON BLACK is a strong antioxidant
Physical Peptisers
Physical peptisers soften polymers by lubrication
between polymer chains
(Lubricant)
Nol allecled by unsaluralon or anloxdanls Nol allecled by unsaluralon or anloxdanls Nol allecled by unsaluralon or anloxdanls Nol allecled by unsaluralon or anloxdanls
so can be used lor synlhelcs so can be used lor synlhelcs so can be used lor synlhelcs so can be used lor synlhelcs
can be used wlh carbon black can be used wlh carbon black can be used wlh carbon black can be used wlh carbon black
Peptisers
Which is BES1 ? Chemical or Physical ?
Chemical
- "Premastication" mixing step required for efficiency
- Not very efficient on mill (not enough heat)
- Breaks chains so lowers physical properties
- Very low levels used (0.15 ~ 0.25 phr)
Physical
- OK to mix with black/fillers present
- Effective on mills
- Highest physical properties
- More effective with synthetics than Chemical
- Higher levels used (2 ~ 3 phr)
Mixture of BOTH becoming common (mainly with black NR compounds)
Peptiser 1esting
Chemical / Physical Combination
Historically Mooney Viscosity
used to measure effectiveness
BUT - it's a low torque test
Higher torque required to represent
mixing / calendering and extrusion
In our lab, Capilliary Flow used
A ram force of
2.03 MPa - Mixing
2.81 MPa - Extrusion
Peptiser 1esting
Compounds
ControI R-11 A86/A50
SIR 20 100.00
Renacit 11


-- 0.30
StruktoI A86 -- 0.10
StruktoI A50 -- 2.00
N299 50.00
ZnO 3.00
Stearic acid 2.00
TMQ 1.00
SantofIex 13 1.25
SuIphur 2.00
TBBS 1.00
Mixing : Add rubber and peptisers
45 sec Add black, etc
4.25 min Drop
Peptiser 1esting
Mooney Viscosity (3 Tests)
Control
R-11
A86/A50
0
10
20
30
40
50
60
70
80
ML 1+4 @ 100 C
After 24 hr
After 72 hr
Peptiser 1esting
Capiliary Flow at 105 deg C
Force=2.03 MPa
Force=2.81 MPa
0
10
20
30
40
50
60
% improvement over Control
R-11
A86/A50
Peptiser 1esting
Scorch / Reversion
Control
R-11
A86/A50
0
5
10
15
minutes
Scorch 125 C
Reversion (T -2)
Peptiser 1esting
Tensile Strength
Control
R-11
A86/A50
0
5
10
15
20
25
30
MPa
Peptiser 1esting
Heat Buildup
Control
R-11
A86/A50
0
50
100
150
200
degree C
Peptiser 1esting
Conclusion
A combination of Chemical / Physical peptisers gives -
Longer Scorch Safety
Less Reversion
Lower Mooney after storage
Better Flow (at mixing torque)
Higher Tensile Strength
Lower Heat Buildup
than Chemical peptiser alone
Does not need premastication step
At the SAME COST
S1RUK1OL PEP1ISERS
CHEMICAL
A82 - Speciality - for better dispersion (2 phr)
A86 - General purpose (0.15 ~ 0.25 phr)
A88 / A89 - More powerful (0.1 ~ 0.2 phr)
PHYSICAL
A50 - General purpose (2 ~ 3 phr)
A60 - For lower temperature mixing (2 ~3 phr)
EF44 - Most effective in both NR & synthetics (2 ~ 4 phr)
Dispersing Aids
Powders do not mix with rubber easily
-particularly "white" fillers
Certain chemicals assist mixing and powder dispersion
by "wetting" the surface of the powder to make it more
compatible with the rubber
The result is EVEN, complete DISPERSION,
SMOOTH surfaces on Extrusion / Calendering,
improved PHYSICAL properties, enhanced mold FLOW,
SMOOTH cured surfaces
Often used with sulphur / accelerators / ZnO
in Soft compounds
S1RUK1OL DISPERSINC AIDS
WB 212 - General Purpose (2 ~ 3 phr)
WB 42 - Better mold flow (2 ~ 3 phr)
FL - Most effective with high mineral filler levels (2 ~ 4 phr)
WB 222 - For NBR, XNBR, HNBR and Butyls as well as Hypalon (2 phr)
D5 - Inexpensive, for dark colored compounds (2 ~ 3 phr)
Homogenising Agents
These are blends of low molecular weight polymeric resins
Their main function is to enable different types of polymers
to blend together correctly
Typical polymer differences are
POLARITY
UNSATURATION LEVELS
HIGH and LOW MOONEY
A secondary function is "wetting" of fillers, so act
as dispersing aids
Homogenising Agents
Rubbers have a wide range of solubility parameters
Hi-ACN NBR has a solubility parameter of 11
NR is 9.5 and EPDM is 8.6
While polar ether plasticisers mix well in NBR
they are totally incompatible with EPDM
Similarly paraffinic oil mixes well with EPDM
but not with Nitrile
Homogenising agents mix well with all polymers
so allow different rubbers to blend by "bridging"
the solubility parameter gap
Homogenising Agents
Example
For an ozone resistant oil hose
- EPDM gives ozone resistance
while Nitrile gives oil resistance
When mixed together one of the polymers forms
the "continuous phase" with the other "non-continuous"
("pools" of polymer)
If the EPDM is the continuous phase
the mix has poor oil resistance,
and if the Nitrile is the continuous phase
the mix has poor ozone resistance
Only Homogenising Agents can give the mix BOTH
Properties
S1RUK1OL HOMOCENISINC ACEN1S
40MS - General Purpose (black) - 4 ~ 7 phr
60NS - General Purpose (white) - 4 ~ 7 phr
TH 20 - Homogeniser / Tackifier (black) - 4 ~ 7 phr
Higher levels are used, but modulus tends to drop slightly
depending on the cure system
Activators
Sulphur alone cures rubber very slowly
Accelerators speed up curing
Activators form intermediates between sulphur and
accelerators to make curing much faster
Type & level of accelerator(s) and activators
determine the type & number of X-links formed
Activators are normally
Metal Fatty Acid Salts
( e.g. ZnO + Stearic acid Zinc Stearate )
Activators
Zinc is a transition element - behaves as a
normal divalent element or can form complexes
Zinc's electron structure is 3d10 4s2
Full d shell allows co-ordinated complexes -

4 co-ordinated
TETRAHEDRAL
5 co-ordinated
BIPYRAMIDAL
6 co-ordinated
OCTAHEDRAL
Activators
Chemical 1heory
If the acid has a benzene ring (aryl)
like AKTIVATOR 73 the intermediate is
S
N
C
Zn
N
S
S
C
S
Which forms mainly Disulphide X-links
Activators
Chemical 1heory
Or co-ordination can occur to give
O
C
C
O
R
R
Zn
S
S
S
SS
S
N
S
R'
1his intermediate would give a
predominance of Di-sulphide X-links
S1RUK1OL AC1IJA1ORS
IB531 - General Purpose - very effective (0.25 ~ 1.0 phr)
Main use non-blooming EPDM (sulphur cured)
ZEH - Main use - NR - very tight cures (0.5 ~ 2.0 phr)
Predominance of monosulphidic
AKTIVATOR 73
- Main use - tires, belting (2.0 ~ 3.0 phr)
Reversion resistant
Low heat buildup
Low rolling resistance
Release Agents
Designed to prevent compound sticking to metal
- Banburies, mills, extruders, calenders and molds
"INTERNAL" - added to the compound
"EXTERNAL" - applied to metal surfaces
- molds, platens, etc
Release Agents
"INTERNAL"
All dispersing aids have this property to a limited degree
Speciality release agents contain complex amides
- "super lubricants"
No negative effect on tack or adhesion
- tested up to 10 phr (overdose)
The mechanisim is simple lubrication between
the rubber and the metal
Release Agents
"EXTERNAL"
Silicone emulsion used in the past
Only effective 1~3 cures
Give delamination defects
Not environmentally friendly
Curable silicone resins in solvent
As above water soluble now developed
Resin cures on the empty mold
Film formed "semi-permanent"
Very smooth finished on cured article
Prevent mold corrosion and fouling
Lasts several shifts
S1RUK1OL RELEASE ACEN1S
"INTERNAL"
WB16 - Very powerful general purpose (1 ~ 3 phr)
TR131 - Mainly used in PVC
"EXTERNAL"
Permalease 10 - Solvent based
Permalease 20 - Solvent based with higher polymer
content -- suitable for complicated
mold
(Both available in spray cans or bulk)
Permalease 70 & 80 - water based
(now replacing solvent based type)
S1RUK1OL RELEASE ACEN1S
(Cont.)
They're silicone free, thermally stable and biodegradable
Does not form resinous coke-like deposits on mandrel
Less contamination (especially with EPDM peroxide cure)
MR 161
Good for Vamac (ACM) & CSM
MR 187
Good for peroxide & sulphur cured EPDM
** both not suited for NBR, CR & ECO
- for Mandrel Release
Plasticisers
Highly polar - designed for use in NBR, ECO, ACM
Lowering Hardness
Improving Low Temperature Performance
Improving Heat Resistance
STRUKTOL PLASTICISERS
WB300 - General Purpose (Low Extractability)
KW400 - For Low Temperature Flexibility
KW500 - Very good Heat Resistance
KW 600 - Super Low Temperature Flexibility
AW1 - Antistatic Property
Other Processing Aids
Many activators / accelerators / curing agents
very difficult to disperse, particularly in soft compounds
Results are variable physicals
intermittent bloom
intermittent scorch
surface discoloration
wasted high cost material
- Two solutions -
Predisperse in low MW polymer
Combine with dispersing agents
Other Processing Aids
WHICH 1O CHOOSE ???
Polymer Bound
Essential if powder is hazardous, e.g ETU
Good in medium hard compounds (high shear in mixer)
Not practical for soft compounds
For soft, must use Dispersant Type

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