Technical Information

DI-CUP and VUL-CUP® Peroxides

Vulcanizing Nitrile Rubber

DI-CUP® dicumyl peroxide and VUL-CUP® peroxide [a,a'-bis(tert-butylperoxy) diisopropylbenzene] are
effective vulcanizing agents for all types of NBR (nitrile rubber). These peroxides produce vulcanizates
with better heat-aging and lower compression set than sulfur-accelerator systems.

The vulcanizates in this bulletin were compounded with Di-Cup® 40KE dicumyl peroxide and Vul-Cup®
40KE peroxide. Other forms of Di-Cup® and Vul-Cup® can be used with similar results.

Peroxide vs. Sulfur Cure

NBR compounds cured with Di-Cup® dicumyl peroxide and Vul-Cup® peroxide exhibit better heat resistance and
lower compression set than the same compounds cured with a sulfur-accelerator system. Table I on page 2
shows a comparison of the performance of sulfur-cured NBR with that of Di-Cup® and Vul-Cup®. The peroxide
levels were chosen to yield vulcanizates with elongation and modulus values equivalent to those of the sulfur-
cured stock.

The most significant differences between the stocks are the better heat resistance, lower compression set, and
improved low-temperature flexibility of those cured with peroxides.

Basic Formulation
The following basic formulation is suggested as a starting point in developing a new compound. If an existing
formulation is to be modified to include a peroxide, remove all ingredients associated with the previous cure
system and add Di-Cup® dicumyl peroxide or Vul-Cup® peroxide as indicated.

Formulation Parts by Weight

NBR 100
Filler Variable
Zinc oxide 5.0
Antioxidant 0.5
Peroxide Di-Cup® 40KE 2.5-5.0 phr
Vul-Cup® 40KE 1.5-3.0 phr

Typical results using this formulation are shown in Table II. All compounds contain 50 phr HAF black and can be
cured as follows:

Cure Conditions
Peroxide Peroxide, phr Time, min. Temperature, °F (°C)
Di-Cup® 40KE peroxide 3.4 25 330 (166)
Vul-Cup® 40KE peroxide 2.1 25 340 (171)

ORC-105H
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 Technical Information
DI-CUP and VUL-CUP® Peroxides

Table I - Performance of Peroxide vs. Sulfur-Cured Nitrile Rubber

Formulation Sulfur Cure Vul-Cup® Peroxide Cure Di-Cup® Peroxide Cure

Nipol® 1032 100 100 100
HAF black 50 50 50
ZnO 5.0 5.0 5.0
Antioxidant 1 1 1
Stearic acid 1 -- --
MBTS 1.5 -- --
Sulfur 1.5 -- --
Vul-Cup® 40KE -- 1.6 --
Di-Cup® 40KE -- -- 2.5

Cure temperature,°F (°C) 310 (154) 240 (171) 330 (166)

Cure time, min. 30 25 25

Original Properties
100% modulus, psi (MPa) 460 (3.1) 440 (3.0) 460 (3.2)
200% modulus, psi (MPa) 1,150 (7.9) 1,250 (8.6) 1,435 (9.9)
Tensile strength, psi (MPa) 2,800 (19.3) 3,100 (21.4) 3,080 (21.2)
Elongation, % 380 395 345
Shore A hardness, points 65 64 65
T10,000, °C -18 -22 -22

Compression Set, %
70 hrs at 212°F (100°C) 66 20 20
70 hrs at 257°F (125°C) 82 30 30

Air-Oven Aging,
70 hrs at 257°F (125°C)
100% modulus, psi (MPa) -- 1,260 (8.7) 1,215 (8.4)
200% modulus, psi (MPa) -- 3,060 (21.1) --
Tensile strength, psi (MPa) 1,980 (13.7) 3,350 (23.1) 3,000 (20.7)
Elongation, % 80 215 195
Shore A hardness, points 70 77 75

ASTM No. 3 Oil-Aging,

70 hrs at 257°F (125°C)
100% modulus, psi (MPa) 700 (4.8) 520 (3.6) 485 (3.3)
200% modulus, psi (MPa) -- 1,680 (11.7) 1,650 (11.4)
Tensile strength, psi (MPa) 870 (6.0) 2,400 (16.6) 2,620 (18.1)
Elongation, % 107 240 285
Shore A hardness, points 60 53 56
Volume swell, % 10.8 16.6 16.6

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 Technical Information
DI-CUP and VUL-CUP® Peroxides
Table II - Performance of Peroxide-Cured Nitrile Rubber
Acrylonitrile Content
Low Medium Medium High High Very High
Krynac® 2750 Nipol® 1053 Nipol® 1032 Paracril® C Chemigum® Krynac®
N-3 5075
Original Properties
100% modulus, psi (MPa) 595 (4.1) 600 (4.0) 580 (4.7) 680 (5.1) 740 (5.6) 815 (5.6)
200% modulus, psi (MPa) 2045 (14.1) 1960 (13.5) 1810 (12.5) 2520 (17.4) 2270 (15.7) 1845 (12.7)
Tensile strength, psi (MPa) 3060 (21.1) 3150 (21.7) 3120 (21.5) 3420 (23.6) 3160 (21.7) 3255 (22.4)
Elongation, % 260 280 280 250 250 400
Shore A hardness, points 70 75 76 75 77 79

Air-Oven Aging,
70 hrs at 257°F (125°C)
100% modulus, psi (MPa) 1015 (7.0) 1530 (10.6) 1460 (10.1) 1520 (10.5) 1730 (11.9) 1660 (11.4)
Tensile strength, psi (MPa) 2845 (19.6) 2070 (14.3) 2070 (14.3) 2780 (19.2) 3100 (21.4) 3020 (20.8)
Elongation, % 190 130 130 160 150 200
Shore A hardness, points 76 84 85 81 85 78

ASTM No. 3 Oil-Aging,

70 hrs at 257°F (125°C)
100% modulus, psi (MPa) 465 (3.2) 610 (4.2) 520 (3.6) 650 (4.5) 900 (6.2) 855 (5.9)
200% modulus, psi (MPa) 1925 (13.3) 2190 (15.1) 1920 (13.2) 2600 (17.9) 2570 (17.7) 1865 (12.9)
Tensile strength, psi (MPa) 1925 (13.3) 2340 (16.1) 2350 (16.2) 2630 (18.1) 2730 (18.8) 2435 (16.8)
Elongation, % 200 210 220 205 190 260
Shore A hardness, points 57 63 64 67 73 82
Volume swell, % 22.6 30.2 24.7 17.2 9.0 5.4

Compression Set, %
70 hrs at 257°F (125°C) 16.0 22.7 29.6 18.0 24.6 34.0

Cure Time
The cure curves for Vul-Cup® peroxide in Hycar® 1032 polymer NBR are shown in Figure 1. Physical property data
were determined from vulcanizates cured at 330°F (165°C) for varying lengths of time. The time to 95% cure (t95)
is shown.

The data presented in Figure 1 show that very little curing occurs after the first 20 min., but that the cure does not
become flat until 40 min. Results of postcuring the press-cured samples in Figure 1 are shown in Figure 2. All
compounds were post-cured 4 hours at 300°F (149°C) after an initial press cure for the indicated time. The
response of tensile strength and compression set to post-cure demonstrates the effect of the high post-cure
temperature. All samples were degraded by post-curing.

These results are not thought to be generic for all types of NBR. The experiments were carried out on a medium-
high- acrylonitrile-content polymer. Higher- or lower-nitrile-content products will perform differently. It is suggested
that the compounder carry out similar experiments if postcuring is considered.

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 Technical Information
DI-CUP and VUL-CUP® Peroxides

Figure 1 - Cure Curves -- Vul-Cup®

Peroxide in NBR

Tensile
3,000 Strength
(20.7)

70 hours at 257° F (125° C)

Tensile Strength or 200% Modulus , psi (MPa)

2,500 80

Compression Set, %
(17.2)
60
2,000 Compression
(13.8) Set
40

1,500
(10.3) 20

1,000 200% Modulus

(6.9)

500
(3.4)
20 40 60

90
ODR Torque (lb-in)

70

50

t90 t95
20 40 60
Cure Time, minutes at 330° F (166° C)

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 Technical Information
DI-CUP and VUL-CUP® Peroxides

Figure 2
Effect of Postcure, 4 hrs at 300°F (149°C),
on NBR Cured With Vul-Cup® Peroxide

Tensile Strength

2,500
(17.2)

Key
60

70 hours at 302°F (150°C)

Tensile Strength, psi (MPa)

Property after Press

Compression Set (%)

2,000
(13.8) Property after Press
Cure
40

1,500
(10.3)
Compression Set
20

t95
1,000
(6.9) 0
20 40 60 80
Press-Cure Time at 330°F (166°C), minutes)

For additional information, or to place an order or sample request, call 1.800.331.7654.

IMPORTANT: The statements, technical information and recommendations contained herein are believed to be accurate as of the date hereof.
Since the conditions and methods of use of the product and of the information referred to herein are beyond our control, Arkema expressly
disclaims any and all liability as to any results obtained or arising from any use of the product or reliance on such information; NO WARRANTY
OF FITNESS FOR ANY PARTICULAR PURPOSE, WARRANTY OF MERCHANTABILITY OR ANY OTHER WARRANTY, EXPRESS OR
IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMATION PROVIDED HEREIN. The information provided herein
relates only to the specific product designated and may not be applicable when such product is used in combination with other materials or in any
process. The user should thoroughly test any application before commercialization. Nothing contained herein constitutes a license to practice
under any patent and it should not be construed as an inducement to infringe any patent and the user is advised to take appropriate steps to be
sure that any proposed use of the product will not result in patent infringement.

Before handling this material, read and understand the MSDS (Material Safety Data Sheet) for additional information on personal
protective equipment and for safety, health and environmental information. For environmental, safety and toxicological information,
contact our Customer Service Department at 1.800.331.7654 to request a Material Safety Data Sheet or visit our website at
www.arkemainc.com/crosslinking.
® ®
Di-Cup and Vul-Cup are registered trademarks of Arkema Inc.
® ®
Nipol is a registered trademark of Zeon Corporation; Krynac is a registered of Lanxess Deutschland GmbH; Paracril is a registered trademark
® ® ®
of Paratec Elastomers LLC; Chemigum is a registered trademark of Goodyear Tire & Rubber Company; Hycar is a registered trademark of
Lubrizol Advanced Materials Inc.
© April 2009 Arkema Inc. All rights reserved.

ORC-105H
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Arkema Inc. * Functional Additives * 2000 Market Street * Philadelphia, PA 19103-3222 * 1.800.331.7654 * Fax: 215.419.5455