Use of Acrylate and Polybutadiene Coagents as Reactive Plasticizers

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5714 01/10

ABSTRACT Liquid acrylate coagents are low viscosity, low molecular weight functionalized materials that enhance crosslinking in peroxide-based cure systems. Because of their low viscosity, these coagents also dramatically reduce the Mooney viscosity during the mixing stages. Polybutadiene coagents, although higher in viscosity at room temperature, also have a significant plasticicizing effect. These two coagent products can also be used as crosslinkers. The solid acrylates are shown to improve dynamic and flex properties. This paper describes the various types of coagents in use today, and shows the effect of each type on the properties of commonly used elastomers. INTRODUCTION - PEROXIDE-COAGENT CURE MECHANISMS Cross-linking with peroxide alone results in the formation of a covalent bond. This carbon-carbon bond is quite rigid and stable (343.2 kJ bond energy), compared to the carbon-sulfur and sulfursulfur bonds in sulfur cured systems (C-S, 276.2 kJ bond energy; S-S, 205.1 kJ bond energy). The excellent heat stability of this carbon-carbon covalent bond explains the superior heat aging characteristics of peroxide cured systems(1).
Table 1
Saret (SR) 516 Saret (SR) 517 Saret (SR) 519 Saret (SR) 521 Saret (SR) 522 Saret (SR) 633 Saret (SR) 634 Ricon 100 Ricon 150 Ricon 153 Ricon 154 Ricobond 1756

Coagents function with the peroxide-cured system to modify this C-C network. It has been stated that the coagent either homopolymerizes and/or grafts onto the polymer backbone(2). This results in several property improvements such as higher tensile and tear strength, modulus, and lower compression set than curing with peroxide-alone. These property enhancements will be discussed in greater detail later in this paper. Like sulfur-cure systems, concentration level and ratio of the peroxide-coagent system should be optimized. When converting the peroxide-only system to a peroxide-coagent cure, the peroxide level is usually reduced such that the total concentration of curatives rarely exceeds the original peroxide level. The peroxide-coagent cure system offers greater flexibility in cure over the sulfur-accelerator system. Many peroxides can be selected which have cure ranges from room temperature to 200 A C. wide range of coagents can be selected to compliment the peroxide. Coagents which serve as adhesion-promoters are also available. The coagents focused on in this paper are listed below (by trade name for reference purposes):

Difunctional Methacrylate Trifunctional Methacrylate Trifunctional Acrylate Difunctional Methacrylate Difunctional Acrylate Solid Difunctional Acrylate Solid Difunctional Methacrylate Styrene/Butadiene Copolymer (70% vinyl) 70% Vinyl Liquid Polybutadiene 85% Vinyl Liquid Polybutadiene 90% Vinyl Liquid Polybutadiene 70% Vinyl Liquid Polybutadiene with Maleic Anhydride Adduct

The Saret coagents contain a non-nitroso scorch retarder to prevent premature curing during processing and/or vulcanization.

EXPERIMENTAL Materials A masterbatch containing 100 phr Natsyn 2200, 50 phr N660 carbon black, 5 phr zinc oxide, 1 phr stearic acid, and 1 phr agerite resin D was used in
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all experiments related to natural rubber (synthetic polyisoprene). Natsyn 2200 was obtained from Goodyear chemical. Unless otherwise noted, a masterbatch containing 100 phr Nordel IP4640, 100 phr N660 carbon black, 50 phr Sunpar 2280, 5 phr zinc oxide, and 1 phr stearic acid was used in all experiments related to EPDM rubbers. Nordel IP4640 was obtained from the DuPont Dow Elastomer Company. All Saret and Ricon coagents were supplied by the Cray Valley company. TAC was supplied by Akzo-Nobel. HVA-2 was supplied by Dupont. Peroxides were obtained from Atochem and Hercules.

method D-624 using a die-C template. All hot tear measurements were taken after pre-heating each die-C specimen for 10 minutes at 150C. Compression set was determined by compressing samples at 25% deflection for 70 hours at 212 F. Each sample was then removed and the permanent set measured as a percentage of original height according to ASTM standard D-395B. Flexibility testing was measured according to deMattia flexibility ASTM D-813-95. In this test, each specimen was pierced 0.08 inches and tested at 300 cycles per minute. Cycles to failure were reported when the 0.08 piercing grew to 0.5 inches. Samples were cured 30-32 minutes at 320F for the peroxide-based samples and 20 minutes for the sulfur-based samples. RESULTS AND DISCUSSION General Coagent Description The Saret salts of acrylic and methacrylic acid as peroxide cure coagents vary in effectiveness in controlling cured rubber properties. These coagents also vary in speed of cure. Acrylate coagents are generally faster curing than methacrylate coagents. Also, curing speed generally increases with increasing functionality. The solid coagents offer certain unique properties due to both ionic and covalent bonding during crosslinking. The Ricon coagents function by state addition only, and normally do not offer cure speeds as fast as acrylates. This can be an advantage or a disadvantage depending on the desired physical properties. No single coagent has been found to produce optimum properties for all applications. Hence, it is necessary to pick the right coagent for the application(3). Scorch As mentioned in the previous paragraph, the chemical nature of methacrylate and acrylate coagents results in an increase in cure rate compared to peroxide alone. Even though the Saret line of coagents includes a scorch retardant package, scorch times are still shorter than peroxide alone. This is evidenced in figure 1 below.
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Formulations Rubber compounds were mixed in a Brabender prep mixer model R.E.E.-6. In all cases, the order of addition was as follows: masterbatch, antioxidant, coagent, and peroxide. All samples were compression molded for 40 minutes at 320F unless otherwise indicated. Measurement Processability was determined by measuring Mooney Viscosity at 100C for 4 minutes according to ASTM standard D-1646-64. An Alpha Technologies MV-2000 was used for all viscosity measurements. Cure characteristics which include scorch time, cure rate and torque values were measured over a sixty-minute period at 160C and 3 arc using a Tech Pro oscillating-disk rheometer according to ASTM method D-2084-95. Original physical properties were measured using die D dumbbells tested at 20 in/min. All samples were tested according to ASTM standard D 41297, method A; 2240-97. Shore A hardness values were determined for samples after molding using a hand-held Shore A durometer according to ASTM standard D-224091. Tear strength was determined according to ASTM

Figure 1 Scorch Time Comparison in EPDM at 320F

3.5 3 2.5 2 1.5 1 0.5 0

Ts2 (min)

5 PHR coagent

Peroxide Control

SR 519

SR 522

SR 521

SR 517

Ricobond 1756

Ricon 153

Ricon 154

7.5 PHR 40% DiCumyl peroxide in all formulations

By following the above graph it becomes apparent that by careful coagent selection, potential scorch problems (particularly during high-temperature curing) can be eliminated. Alteration of cure temperature and coagent level can also be used to overcome scorch.

Processability Liquid acrylate and polybutadiene coagents can be classified using the term reactive plasticizers. Their function is two-fold: 1) Reduce the viscosity in the mixing/processing stages. 2) Promote crosslinking upon vulcanization. A previous publication (4) has used the following general graph to explain this trend:

Figure 2

Durometer (Shore A)

90 80 70 25 20 15 10 5

Hardness

Ricon 100

Saret 633

Saret 634

Saret 517 (PHR) 15 20

10

Mooney Viscosity (250F)

Mooney Viscosity

In addition to the benefits listed above, these materials act as non-extractable processing aids since they crosslink into the elastomer matrix. Many sulfur-cured systems require the use of a plasticizer that does not cure into the elastomer matrix. This could cause migration in some cases, as well as volitalization and embrittlement of the elastomer upon heat aging.

To show the plasticizing effects of liquid acrylate and polybutadiene coagents in peroxide-cured systems, figure 3 focuses on a black-filled natural rubber system. In this case, coagents are substituted in place of traditional extractable plasticizers.

Figure 3 Mooney Viscosity (100 C 4 min.) 80 70 60 50 40 30 0 2 5 10 Coagent Level (PHR) SR 517 Ricon 153

Modulus Modulus at 100% elongation was measured for samples containing 2, 5, and 10 PHR additions of methacrylate, acrylate, or polybutadiene coagents.

Modulus response graphs are shown in figures 4, 5, and 6. These graphs indicate that in most cases, using acrylate and methacrylate coagents over polybutadiene coagents (on a part-by-part basis) results in a greater modulus response in EPDM.

Figure 4 -Modulus Response in EPDM at 2 PHR Coagent Addition

350 300

PSI

250 200 150

R 1756 R 153 R 100 R 154 SR 516 SR 634 SR 522 SR 517 SR 521 SR 633 SR 519 perox.

100

7.5 PHR 40% DiCumyl peroxide in all formulations

Coagent

Figure 5 - Modulus Response in EPDM at 5 PHR Coagent Addition

PSI

perox.

SR 516

SR 521

SR 634

SR 517

SR 633

SR 519

7.5 PHR 40% DiCumyl peroxide in all formulations

Coagent

Figure 6 - Modulus Response in EPDM at 10 PHR Coagent Addition

500
PSI

400 300 200

R 1756 R 100 R 153 SR 521 SR 516 R 154 SR 634 SR 517 SR 519 SR 522 SR 633 perox.

100

7.5 PHR 40% DiCumyl peroxide in all formulations

Coagent

Hot Tear Strength Tear strength is usually quoted as a deficiency for peroxide cure versus sulfur cure. Figure 7 illustrates 150C hot tear values in EPDM from several coagents as well as a sulfur-accelerator control. The graphs on the following page indicates that methacrylates as well as polybutadiene coagents are the most suitable choices for improving hot tear
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strength in peroxide cured-formulations. SR 634 is an interesting coagent in that it increases tear-resistance of peroxide cured rubbers, even though it gives a relatively high modulus response as shown in figures 4-6. A similar study was performed in a natural rubber formulation that also included TAC and HVA-2 coagents. The results are shown below in figure 8.

SR 522

R 100

R 154

R 1756

R 153

400 350 300 250 200 150 100

Figure 7 Hot Tear Response in EPDM at 5 PHR Coagent Addition

140 120 100

7.5 PHR 40% DiCumyl peroxide in all formulations except *

Lb/in

80 60 40 20
SR 517 SR 522 SR 633 SR 519 SR 521 Sulfur * Ricon 153 Ricon 100 Ricobond 1756 Ricon 154 SR 634

* Sulfur Control: 2 PHR Sulfur, 1 PHR MBT, 1.5 PHR TMTM

Figure 8- Hot Tear Response in IR at 5 PHR Coagent Addition

140 120 100 80 60 40 20

Ricon 153 Ricon 154 Ricobond 1756 HVA-2 TAC Ricon 100 SR 519 SR 522 SR 517 SR 521 SR 633 SR 634

Lb/in

7.5 PHR 40% DiCumyl peroxide in all formulations

Fast Cure

Table 2 shows a comparison in performance properties between SR 519 and HVA-2. SR 519 is generally the fastest curing liquid acrylate among the coagents listed

in table 1. The solid maleimide HVA-2 reacts similar to acrylate coagents by increasing both the state and rate of reaction.

Table 2
Natsyn 2200 IR N660 Black Zinc Oxide Naugard Q Stearic Acid DiCup 40 KE SR 519 HVA-2 ODR 325F MH-ML (in/lb) Ts 2 (min) Tc 90 (min) Shore A Hardness Tensile Strength (psi) Modulus100 (psi) Total % Elongation Peroxide 100 50 5 1 1 4.0 26.2 2.08 29.4 54 2530 255 500 Peroxide/ SR 519 100 50 5 1 1 4.0 2.0 53.8 1.87 26.1 62 2825 460 355 Peroxide/ HVA-2 100 50 5 1 1 4.0 2.0 49.1 1.85 28.8 63 2825 475 350

Compression Set Figure 9 below shows the effects of both types of coagents on compression set in an EPDM formula-

tion. Acrylates generally give lower compression set values than methacrylates and polybutadienes.

Figure 9 Compression Set in EPDM at 5 PHR Coagent Addition

50 45 40 35 30 25 20 15 10 5 0

7.5 PHR 40% DiCumyl peroxide in all formulations

SR 522 SR 519 Ricon SR 521 SR 516 SR 517 Ricon Ricon SR 633 Ricon SR 634 153 150 154 100

Rubber-to-Metal Adhesion SR 633 is a coagent that produces extremely strong rubber-to-metal adhesion without the use of external adhesives. Previous papers(5) (6) have shown that strong bonding can be obtained with a variety of rubbers such as neoprene, SBR, NBR, and HNBR. Ricobond 1756 is also used as an adhesion promoter in peroxide cured systems. Since Ricobond 1756 is a liquid, it works more as a plasticizer than the solid SR 633. Tables 3 and 4 show adhesion values for SR 633 and Ricobond 1756 in both EPDM and synthetic natural rubbers.

These tables also show that interesting results are obtained by using both coagents in a single system (far right column in both tables). In this case, the flexibility of the polybutadiene (as evidenced by high t-peel adhesion) is combined with the high hardness bond of the solid acrylate (evidenced by high lap shear adhesion). This is a key example of how coagents can sometimes be combined in a single system to create the best of both worlds.

Table 3 Adhesion Data in EPDM at 5 PHR Coagent Addition

1 Nordel IP4640 MB DiCup 40KE Saret 633 Ricobond 1756 T-Peel Adhesion (cold roll steel) lbs Lap Shear Adhesion (cold roll steel) psi

2 257 7.5 5 76 1279

3 257 7.5 2.5 2.5 69 1792

257 7.5 5 44 1720

Table 4 Adhesion Data in IR at 10 PHR Coagent Addition

1 157 4.0 10 13 1286 2 157 4.0 10 43 1103 3 157 4.0 5 5 38 1780

Natsyn 2200 MB DiCup 40KE Saret 633 Ricobond 1756 T-Peel Adhesion (cold roll steel) lbs Lap Shear Adhesion (cold roll steel) psi

SR 634 can also be used as an adhesion promoter in applications where higher elongation properties are required. This coagent normally offers 50-60% of the adhesive strength compared to SR 633.

As shown in figure 10 below, Ricobond 1756 can also be used in applications where adhesion is desired as well as relatively low compression set. Figure 10 illustrates this effect versus SR 633 in synthetic natural rubber.

Figure 10- Compression Set Response in Synthetic Natural Rubber

60 50

3 PHR coagent 5 PHR coagent

2 PHR DiCup 40 KE Peroxide Sulfur Control: 1.6 PHR Sulfur, 1.6 PHR TBBS

40 30 20 10 0

Ricobond 1756

SR 633

Sulfur Control
alone, sulfur, trifunctional methacrylates, and several polybutadiene coagents. Figure 11 highlights these results.

Flex Fatigue DeMattia flexibility testing in natural rubber shows that the solid coagents SR 633 and SR 634 give outstanding flex fatigue resistance versus peroxide

Figure 11 DeMattia Flex Response in IR at 5 PHR Coagent Addition

200 180 160 140 120 100 80 60 40 20 0

Cycles to Failure X 1000

2 PHR DiCup 40 KE Peroxide

Sulfur Control: 1.6 PHR Sulfur, 1.6 PHR TBBS

Sulfur

R 1756

Peroxide

R 153

SR 517

SR 633

SR 634

Coagent

Studies have also been duplicated in EPDM rubber with similar results (7). In these tests, SR 633 and 634 both reached 1 million cycles without failure. The sulfurbased cure system failed at 5000 cycles. SUMMARY It has been shown that liquid (meth)acrylate and polybutadiene coagents are non-extractable materials that provide additional crosslinking in a peroxide-based cure system. This can lead to an improvement in tear strength, compression set, and
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other performance properties. Liquid coagents can be used to replace extractable plasticizers and still have the same effect in process viscosity reduction. Solid acrylate coagents, although usually not as effective in reducing process viscosity of a formulation, deserve special attention because of their high modulus, adhesive, and flex properties. Because no single coagent can produce optimum properties for all applications, dual-coagent systems can also be used in some cases to combine the positive performance properties of each coagent.

References 1. C. B. McElwee and J. E. Lohr. Comparison of Rubber Curing Systems: PeroxideCoagent Versus Sulfur-Accelerator in Polyisoprene. April 24-27, 2001, ACS Spring Rubber Show, Paper No. 34. 2. J. B. Class. Fundamentals of Crosslinking With Peroxides. Oct. 11-14, 1994. ACS Fall Rubber Show, Paper No. 3.

5. R. C. Costin, W. Nagel, and C. B. McElwee. Coagent Selection for Peroxide-Cured Elastomers. Oct. 17-20, 2000, ACS Fall Rubber Show, Paper No. 77. 6. R.C. Costin and W. Nagel. Metallic Coagents for Rubber-to Metal Adhesion. Oct. 11-14 1994, ACS Fall Rubber ShowPittsburgh, PA. 7. R. C. Costin, W. Nagel, and C. B. McElwee. Coagent Selection for Peroxide-Cured Elastomers. Oct. 17-20, 2000, ACS Fall Rubber Show, Paper No. 77.

3. R. C. Costin, W. Nagel, and C. B. McElwee. Coagent Selection for Peroxide-Cured Elastomers. Oct. 17-20, 2000, ACS Fall Rubber Show, Paper No. 77. 4. R. C. Costin, W. Nagel, and C. B. McElwee. Coagent Selection for Peroxide-Cured Elastomers. Oct. 17-20, 2000, ACS Fall Rubber Show, Paper No. 77.

The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond Cray Valley Company's control. The listed properties are illustrative only, and not product specifications. Cray Valley Company disclaims any liability in connection with the use of the information, and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.

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