11.02.

2014

Crosslinking of fluoroelastomers
and the influence on final
properties
Matthias Lückmann, Wolfgang Steinhoff

February, 13, 2014

Overview

‰ basics on curing of rubber and fluoroelastomers

‰ ionic cure with bisphenol
ƒ requirements
ƒ crosslinking mechanism
ƒ effect of cross linker to accelerator ratio
ƒ role of metal oxides and influences of level change
ƒ LRQLFFXUHZLWKRXW³VWDQGDUG´FXUHactivators
‰ radical cure with peroxides
ƒ requirements
ƒ crosslinking mechanism
ƒ effect of cross linker and accelerator level
on cure speed and mechanical properties
ƒ different coagents
ƒ Influence of peroxide level
‰ conclusions
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 11.02.2014

Some Basics on Curing of Rubber

ƒ hydrocarbon rubbers are mainly cross-linked with systems

based on sulfur or peroxides
ƒ chemical crosslinking minimizes viscous flow and leads to
material with high elasticity
chemical crosslinks

entanglements entanglements

ƒ the occurring chemical bonds have following energy:

C-S-C: 285 kJ/mol C-S-S-C: 268 kJ/mol
ƒ with increasing bond energy the thermal stability is increasing
ƒ special rubbers like FKM are used in demanding environments and the cross-linked
materials have to withstand high temperatures and should have high chemical
resistance
ƒ crosslinking with bisphenol forms C-O-C bonds; bond energy C-O: 358 kJ/mol
ƒ crosslinking of FKM with peroxides forms C-C bonds; C-C: 352 kJ/mol

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Ionic Cure vs. Peroxide Cure

ionic cure:
¾ Bisphenol AF most common cross linker; phosphonium and ammonium salts most
common accelerator
¾ curative Masterbatches support dispersion
¾ best scorch safety, low mould fouling and good mould release
¾ lowest compression set
¾ excellent heat resistance

crosslinking of
fluoroelastomers

radical cure:
¾ cure sites are incorporated into the polymer 'X3RQWŒ9LWRQ® G types)
¾ peroxide controls the rate of cure, DBPH most common peroxide
¾ coagent controls the number of crosslinks, TAIC most common coagent
¾ best resistance to hot water (or other aqueous fluids like coolants)
¾ improved chemical resistance (e.g. high and low pH)
¾ metal oxides not necessary but lead to higher heat resistance and more efficient cure

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Requirements for Curing with Bisphenol

- CH2 between two carbon (or longer) perfluorinated monomer units

- easy dehydrofluorination (as for HFP:VF2:HFP or TFE:VF2:TFE)

¾ CF3 group aids cross link formation later in the process

Viton® A;
F-content 66%

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Requirements for Curing with Bisphenol

B and F types also cured via C=C, formed at isolated VF2 sequences
but less efficiently because curatives are less soluble in the polymer -
they cannot find the cure sites easily

Viton® B, F;
F-content 66-70%

HFP:VF2:HFP easy formation of C=C, crosslink very efficiently

TFE:VF2:TFE HDV\IRUPDWLRQRI& &GRQ¶WFURVVOLQNDVHDVLO\EHFDXVHQR&) 3
- H and F combine with acid acceptors to form water and metal fluorides

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Bisphenol Cure System ± Curing Mechanism

1. Formation of the soluble bisphenol monophosphoniumsalt,

for nucleophilic reaction with the polymer

[adapted from Schmiegel, Kautschuk Gummi Kunststoffe, 1978, 31, 137 ]

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Bisphenol Cure System ± Curing Mechanism

2. Creation of diene functionality in the polymer chain, through reaction of the
soluble base (bisphenol monophosphoniumsalt) with the FKM (dehydrofluorination)

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Bisphenol Cure System ± Curing Mechanism

3. Crosslinking of two polymer chains

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Influence of Polymer Type on Cure Rate

‡ A types cure very quickly
‡ B types are slower
‡ F types need very high levels of accelerator
‡ Ratios for reasonable cure rates
± A type about 4 : 1 (BP-AF to Accelerator ratio)
± B type about 3 : 1
± F type about 2 : 1
Test at 180 C, 0.5 , 3 mins

F type with 2.85 : 1 (BpAF : Accel)

30
F type with 1.9 : 1 (BpAF : Accel)
B type with 3.3 : 1 (BpAF : Accel)
25
A type with 4.2 : 1 (BpAF : Accel)

20
Torque (dNm)

15

10

0
0 0.5 1 1.5 2 2.5 3
Time (mins)
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Ratio of Bisphenol to Accelerator ± Impact on Properties

Higher curative level results in : Lower BP-AF : Accelerator ratio results in :

- higher modulus - faster cure
- higher hardness - increases scorch
- lower elongation - poorer compression set
- better compression set - more mould fouling
- poorer TR-10
- better flow Higher BP-AF : Accelerator ratio results in :
- better mould release - slower cure
- less scorch
- better compression set

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BPAF / BTPPC Ratio ± Impact on Curing

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BPAF / BTPPC Ratio ± Impact on Properties

Contour  Plot  of  CS  70  200  vs  BTPPC;;  BPAF

0,6
C S  70  200
<     16,5
16,5 ±     18,0
18,0 ±     19,5
0,5 19,5 ±     21,0
21,0 ±     22,5
22,5 ±     24,0
24,0 ±     25,5
25,5 ±     27,0
BTPPC

0,4 27,0 ±     28,5

28,5 ±     30,0
>     30,0

0,3

0,2
1,2 1,4 1,6 1,8 2,0 2,2
BPAF

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Effect of Metal Oxides During Bisphenol Cure

‰ cure site creation and acid acceptors
¾ usual metal oxides are Ca(OH)2 and MgO : 6 phr Ca(OH)2 and 3 phr MgO

‰ effects of metal oxide levels

¾ higher Ca(OH)2 results in faster curing but poorer compression set and properties
¾ higher MgO results in better heat resistance and better bonding
¾ high metal oxide levels adversely affect for flow (injection)
¾ metal oxides promote mould sticking and fouling

‰ types of MgO
¾ usual levels are 3 phr high activity or 15 of low activity MgO (processing!!!)

Metal oxides are hygroscopic and are often the cause of scorch problems

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Effect of Metal Oxides During Bisphenol Cure

using Calcium Hydroxide to control cure rate
MDR, 180C, 0.5 deg, 12 mins

25

20
Torque (dNm)

15

10 6 CaOH2
4 CaOH2
6 CaOH2, 0.5 VC-30

5 6 CaOH2, 1.0 VC-30

0
0 2 4 6 8 10 12 14
Time (mins)
General Trends:
‡ reducing calcium hydroxide level from 6 to 4 phr reduces cure rate
‡ similar reduction in cure rate by adding 0.5 phr VC-30 but increasing the modulus
‡ adding 1.0 phr VC 30 significantly reduces cure rate but increases modulus
‡ adding VC-30 gives a reduced cure rate because of a higher curative to accelerator ratio
2/11/2014 15

New Bisphenol Curable Grade

¾ standard bisphenol compounds provide poor resistance to organic
acids due to MO
¾ development with new cure activator and good acid resistance
Ÿ Viton® VTR 9307 new bisphenol curable precompound

test conditions: acetic acid, 504h @ 100 C VTR 9307 vs Viton® A331C

ƒ Viton® VTR 9307

ƒ FKM Copolymer
ƒ FKM Terpolymer

X X X X

16
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Requirements for Curing with Peroxides

Viton® GAL-S,
GBL-S, GF-S
65.5-70%F

‡ peroxide cured fluoroelastomers for best hot water resistance, improved

acid and base resistance and low post cure capability
‡ bromine or iodine containing cure site monomers have to be incorporated
‡ no need of metal oxides but could be incorporated for improved
cure efficiency and heat resistance

Viton® GLT-S,
GBLT-S, GFLT-S
64.5-67%F

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Peroxide Cure System ± Curing Mechanism

1. t-butoxy radical generation and beta scission to the

methyl radical and acetone

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Peroxide Cure System ± Curing Mechanism

2. Adding methyl radical to TAIC and abstracting bromine

from polymer chain

more likely the TAIC radical

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polymerizes 19

Peroxide Cure System ± Curing Mechanism

1. polymer radical is formed by reaction of methyl radical with CSM

2. polymer radical reacts with the (poly)coagent

Reality: TAIC Oligomer with some FKM crosslinks

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Peroxide Cure System ± Idealized Mechanism

3. Reaction of the polymer radical with TAIC

4. The coagent provides three potential network points

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Peroxide Cure System

Peroxide / Coagent Ratio ± Impact on Curing
Basic recipe = 100 phr Viton® GLT-600S, 30 phr N-990, 3 phr ZnO, 0.5 phr VPA #2,
Peroxide and Coagent are variables
Ts1  mins  vs  Diak  7,  Luperox  101XL45 MH  dNm  vs  Diak  7,  Luperox  101XL45

ts1 5.0
0.414
MH 5.0
0.390 0.366 28.01
4.5 4.5
27.38
4.0 4.0
26.75
0.342
Diak  7  phr

Diak  7  phr

3.5 3.5
26.12

3.0 0.402 3.0 25.49

2.5 2.5 24.86

24.23
2.0 2.0
0.378 0.354
23.60
1.5 1.5
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Luperox  101XL45  phr Luperox  101XL45  phr

Tc-­50  mins  vs  Diak  7,  Luperox  101XL45 Tc-­90  mins  vs  Diak  7,  Luperox  101XL45
tc50 5.0
0.64
tc90 5.0
0.72 1.3
1.5 1.1 0.9
4.5 0.56
4.5

4.0 0.76 4.0

1.4
Diak  7  phr

Diak  7  phr

3.5 3.5

3.0 3.0

2.5 2.5

2.0 0.68 2.0

0.60 0.52 1.2 0.8
1.0
1.5 1.5
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
2/11/2014 Luperox  101XL45  phr PRESENTATION
Luperox  101XL45  phr TITLE 22

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Peroxide Cure System

Peroxide / Coagent Ratio ± Impact on Properties
Basic recipe = 100 phr Viton® GLT-600S, 30 phr N-990, 3 phr ZnO, 0.5 phr VPA #2,
Peroxide and Coagent are variables
Tensile  Strength  vs  Diak  7,  Luperox  101XL45 Elongation  @  Break  vs  Diak  7,  Luperox  101XL45  
5.0 5.0
Tensile 22.1 Elongation 296 280

4.5 22.9 4.5

4.0 4.0
20.5

Diak  7  phr
Diak  7  phr

3.5 3.5
21.3
312 288

3.0 3.0

2.5 2.5
18.9 19.7

2.0 2.0
304
328 320
1.5 1.5
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Luperox  101XL45  phr Luperox  101XL45  phr

Shore  A  pts  vs  Diak  7,  Luperox  101XL45 Comp  Set  %  vs  Diak  7,  Luperox  101XL45  (70hrs  @  200C)
5.0 5.0
Duro 70.8 Comp 20.0 20.6

21.8
4.5 4.5
69.6
Set
70.2
4.0 4.0
21.2
Diak  7  phr

Diak  7  phr
3.5 3.5
68.4 23.0

3.0 69.0 3.0

22.4

2.5 2.5

67.2
2.0 2.0 23.6 24.2
67.8

1.5 1.5
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
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Luperox  101XL45  phr Luperox  101XL45  phr

Influence of Different Coagents on Cure Speed

- Coagent controls the number of cross links - the most common coagents are
- Triallylisocyanurate (TAIC) ± should be used with Viton® APA polymers
- Trimethallylisocyanurate (TMAIC) ± not recommended for Viton® APA polymers
- Triallylcyanurate (TAC) sometimes used
- TMAIC and TAC
- will give slow and inefficient curing with Viton® APA polymers

30
TAIC - 3
25
Torque (dNm)

TMAIC - 1
20

15 TMAIC - 1.5

10
TMAIC - 2
5
TAC 3
0
0 1 2 3 4
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Time (mins)

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Conclusions
¾ two relevant curing mechanisms ± ionic and radical

¾ Ionic Mechanism ± Bisphenol AF cure

¾ for high efficiency,VF2 units surrounded by HFP units
¾ BTPPC and BPAF commonly used for ionic cure
¾ ratio of BPAF and BTPPC influences cure rate, cure state
and mechanical properties
¾ Novel BPAF cure system overcomes deficiencies in dilute acids

¾ radical cure
¾ requires cure site monomer that contains bromine or iodine
¾ most common peroxide and coagent are DBPH and TAIC
¾ cure rate depends mainly on peroxide level
¾ cure state depends mainly on coagent level
¾ properties influenced by ratio of peroxide and coagent
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2/11/2014

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