Highly saturated nitrile copolymer rubber, process for the production thereof, heat-resistant rubber compositions comprising the rubber and composites comprising the rubber and fibers

• US 6,489,385 B1
• Filed: 05/20/1999
• Issued: 12/03/2002
• Est. Priority Date: 03/29/1996
• Status: Expired due to Term

• Current Assignee: Nippon Zeon Co., Ltd. (BASF SE)
• Original Assignee: Nippon Zeon Co., Ltd. (BASF SE)
• Inventors: Fujii, Yoshinori, Ikeda, Atsumi
• Primary Examiner(s): Mulcahy, Peter D.
• Application Number:
  US09/147,067
• Time in Patent Office: 1,293 Days
• Field of Search: 524/186, 524/92, 524/243, 524/257, 524/565, 524/566
• US Class Current: 524/186
• CPC Class Codes: C08K 5/005 Stabilisers against oxidation, heat, light, ozone
• CPC Class Codes: C08K 5/18 with aromatically bound amino groups
• CPC Class Codes: C08L 15/005 Hydrogenated nitrile rubber

Abstract

A highly saturated nitrile group-containing copolymer rubber having a Mooney viscosity lowered by 15 points or more by applying a high shearing force thereto in the presence of an aging inhibitor, which has a Mooney viscosity of 5-35 and a weight average molecular weight/number average molecular weight ratio of 3-5, and exhibits an increase in Mooney viscosity of 10 points or fewer while the rubber is allowed to stand in the air at room temperature for 30 days. The viscosity of the copolymer rubber changes only to a minor extent with the lapse of time, and the copolymer rubber has excellent processability and storage stability. The copolymer rubber can be used as a heat-resistant rubber composition comprising the copolymer rubber and other heat-resistant rubber. The copolymer rubber can be used as a composite thereof with a fiber, which has good mechanical strength.

Claims

1. A highly saturated nitrile group-containing copolymer rubber having a Mooney viscosity lowered by 15 points or more by applying a shearing force at a shearing rate of from 500 to 5,000 S⁻

1 thereto in the presence of 1 to 10 parts by weight, based on 100 parts by weight of the highly saturated nitrile group-containing copolymer rubber, of an aging inhibitor at a temperature of from 180°

C. to 380°

C., which has a Mooney viscosity of from 5 to 135 and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of 3 to 5, and exhibits an increase in Mooney viscosity of 10 points or fewer while the rubber is allowed to stand in the air at room temperature for 30 days after the above-lowering of Mooney viscosity, said copolymer rubber being a hydrogenation product of a copolymer comprising ethylenically unsaturated nitrile monomer units, diene monomer units and optional copolymerizable monomer units wherein the content of the ethylenically unsaturated nitrile monomer units in the copolymer is in the range of 10 to 60% by weight, said copolymer rubber having an iodine value of not larger than 120 as measured before applying the high shearing force, and said aging inhibitor being at least one member selected from the group consisting of aromatic secondary amine-containing, amine-ketone-containing, mercaptobenzoimidazole-containing, bisphenol-containing, monophenol-containing, thiobisphenol-containing, hydroquinone-containing, nickel salt-containing, thiourea-containing, thioether-containing and phosphorus-containing aging inhibitors.

2. The highly saturated nitrile group-containing copolymer rubber according to claim 1, wherein the highly saturated nitrile group-containing copolymer rubber has a Mooney viscosity of from 20 to 90.

3. The highly saturated nitrile group-containing copolymer rubber according to claim 1, wherein the highly saturated nitrile group-containing copolymer rubber exhibits an increase in Mooney viscosity of 5 points or fewer while the rubber is allowed to stand in the air at room temperature for 30 days after the above-lowering of Mooney viscosity.

11. A heat-resistant rubber composition comprising the highly saturated nitrile group-containing copolymer rubber as claimed in claim 1, and a heat-resistant rubber, characterized in that the amount of the highly saturated nitrile group-containing copolymer rubber is at least 5% by weight.

12. The heat-resistant rubber composition according to claim 11, wherein the heat-resistant rubber is at least one rubber selected from nitrile group-containing unsaturated copolymer rubbers and hydrogenation products thereof, ethylenically saturated copolymer rubbers, polyacrylate ester rubbers, polyether rubbers and fluororubbers.

13. A rubber/fiber composite comprised of the highly saturated nitrile group-containing copolymer rubber as claimed in claim 1 with a fiber.

14. The rubber/fiber composite according to claim 13, which is prepared by incorporating a fiber, which has been treated with a mixture of an aqueous solution of a precondensate of resocinol with formaldehyde, and a rubber latex, in the highly saturated nitrile group-containing copolymer rubber, and vulcanizing the copolymer rubber having incorporated therein the fiber.

4. A process for producing a highly saturated nitrile group-containing copolymer rubber having a low Mooney viscosity, wherein a shearing force at a shearing rate of from 500 to 5,000 S⁻

1 is applied to a highly saturated nitrile group-containing copolymer rubber having an iodine value of not larger than 120 to lower the Mooney viscosity thereof, said copolymer rubber being a hydrogenation product of a copolymer comprising ethylenically unsaturated nitrile monomer units, diene monomer units and optional copolymerizable monomer units wherein the content of the ethylenically unsaturated nitrile monomer units in the copolymer is in the range of 10 to 60% by weight, characterized in that the application of shearing force is carried out in the presence of 1 to 10 parts by weight, based on 100 parts by weight of the highly saturated nitrile group-containing copolymer rubber, of an aging inhibitor at a temperature of from 180°

C. to 380°

C., wherein said aging inhibitor is at least one member selected from the group consisting of aromatic secondary amine-containing, amine-ketone-containing, mercaptobenzoimidazole-containing, bisphenol-containing, monophenol-containing, thiobisphenol-containing, hydroquinone-containing, nickel salt-containing, thiourea-containing, thioether-containing and phosphorus-containing aging inhibitors.

5. The process for producing a highly saturated nitrile group-containing copolymer rubber according to claim 4, wherein the high shearing force is applied in the presence of from 1 to 10 parts by weight, based on 100 parts by weight of the highly saturated nitrile group-containing copolymer rubber, of at least one aging inhibitor selected from the group consisting of aromatic secondary amine-containing aging inhibitors, amine-ketone-containing aging inhibitors which are a condensation product of an aromatic amine with a ketone, mercaptobenzoimidazole-containing aging inhibitors and bisphenol-containing aging inhibitors.

6. The process for producing a highly saturated nitrile group-containing copolymer rubber according to claim 4, wherein the shearing force is applied to a highly saturated nitrile group-containing copolymer rubber having a Mooney viscosity of from 60 to 150 to lower the Mooney viscosity by 15 points or more whereby a highly saturated nitrile group-containing copolymer rubber having a Mooney viscosity of from 5 to 135 is obtained.

7. The process for producing a highly saturated nitrile group-containing coppolymer ruvver according to claim 4, wherein the shearing force is applied to a highly saturated nitrile group-containing copolymer rubber having a Mooney viscosity of from 60 to 150 to lower the Mooney viscosity by 30 points or more whereby a highly saturated nitrile group-containing copolymer rubber having a Mooney viscosity of from 20 to 90 is obtained.

8. The process for producing a highly saturated nitrile group-containing copolymer rubber according to claim 4, wherein the application of a shearing force is carried out substantially in the absence of an oxygen donor.

9. The process for producing a highly saturated nitrile group-containing copolymer rubber according to claim 4, wherein the highly saturated nitrile group-containing copolymer rubber produced by the application of a shearing force has a ratio of weight average molecular weight (Mw) oto number average molecular weight (Mn) of 3 to 5, and exhibits an increase in Mooney viscosity of 10 points or fewer while the rubber is allowed to stand in the air at room temperature for 30 days after the above-lowering of Mooney viscosity.

10. The process for producing a highly saturated nitrile group-containing copolymer rubber according to claim 4, wherein the application of a shearing force is carried out at a temperature of from 240 to 320°

C. by using an extruder having a plurality of barrels.