Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
1999-03-03
2001-04-10
Cain, Edward J. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S425000, C524S426000, C524S495000, C524S497000, C524S525000, C524S565000, C525S233000, C525S238000, C525S295000
Reexamination Certificate
active
06214922
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to an improved nitrile polymer vulcanizate and to a process for the production thereof. More particularly, in one of its aspects, the present invention relates to nitrile polymer vulcanizates having improved hot air aging characteristics. In another of its aspects, the present invention relates to a vulcanizable composition useful to produce such vulcanizates. In yet another of its aspects, the present invention relates to a method for improving the hot air aging characteristics of a nitrile polymer vulcanizate.
BACKGROUND OF THE INVENTION
The effects of oxidizing conditions on vulcanizates obtained from polymers having carbon—carbon double bond unsaturation have long been a problem, particularly in applications where the vulcanizates are exposed to elevated temperatures for extended periods of time. A variety of approaches have been developed in the art in an attempt to solve this problem.
It is known that the carbon—carbon double bonds of such polymers activate the vulcanizate to oxidative attack. One solution to the problem of oxidative attack is to use polymers with few or no carbon—carbon double bonds. Examples of such polymers include butyl rubber (copolymers of isobutylene and isoprene) which typically contain from about 0.5 to about 3.0 mole percent of carbon—carbon double bond unsaturation, and ethylene-propylene copolymers which contain no such unsaturation.
Certain applications, such as the various hoses and seals in the engine compartment of automobiles, require vulcanized polymers with a combination of oil resistance, and resistance to oxidative attack in air at elevated temperatures for extended periods of time. Vulcanizates of copolymers of conjugated dienes and &agr;,&bgr;-unsaturated nitrites, such as acrylonitrile-butadiene copolymer, commonly known as nitrile rubber or NBR, are well known for their oil resistance. However, they contain carbon—carbon double bond unsaturation and therefore are susceptible to oxidative attack unless subjected to special compounding procedures for the production of oxidation resistant vulcanizates.
In order to reduce the amount of carbon—carbon double bond unsaturation in NBR and yet retain the copolymer's oil resistance which is thought to be provided by the nitrile functional groups in the copolymer, methods have been developed to selectively hydrogenate the carbon—carbon double bond unsaturation of NBR without hydrogenating the nitrile groups to produce hydrogenated NBR or HNBR. See for example, British patent 1,558,491, the contents of which are hereby incorporated by reference.
While the development of HNBR has been a significant advance in the art, there is still room for improvement. Specifically, there is a continuing need to develop nitrile polymer vulcanizates which are characterized by improved physical properties such as hot air aging and the like.
SUMMARY OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one of the above-mentioned disadvantages of the prior art.
It is another object of the present invention to provide a novel nitrile polymer vulcanizate.
It is yet another object of the present invention to provide a novel process for producing a nitrile polymer vulcanizate.
It is yet another object of the present invention to provide a novel vulcanizable composition for producing a nitrile polmer vulcanizate.
It is yet another object of the present invention to provide a novel method for improving the hot air aging characteristics of a nitrile polymer vulcanizate.
Accordingly, in one of its aspects, the present invention provides a nitrile polymer vulcanizate produced by vulcanizing a composition comprising:
(i) a nitrile polymer;
(ii) a filler;
(iii) an additive selected from the group comprising: a strong base, a salt of strong base and a weak acid, a salt of a weak acid, a carbodiimide, a polycarbodiimide and mixtures thereof; and
(iv) a vulcanization system.
In another of its aspects, the present invention provides a process for producing a nitrile polymer vulcanizate comprising the step of admixing a polymer composition comprising:
(i) a nitrile polymer;
(ii) a filler;
(iii) an additive selected from the group comprising: a strong base, a salt of strong base and a weak acid, a salt of a weak acid, a carbodiimide, a polycarbodiimide and mixtures thereof, and
(iv) a vulcanization system.
In yet another of its aspects, the present invention provides a vulcanizable composition comprising:
(i) a nitrile polymer;
(ii) a filler;
(iii) an additive selected from the group comprising: a strong base, a salt of strong base and a weak acid, a salt of a weak acid, a carbodiimide, a polycarbodiimide and mixtures thereof; and
(iv) a vulcanization system.
In yet another of its aspects, the present invention provides a method for improving the hot air aging characteristics of a nitrile polymer comprising the step of admixing a nitrile polymer with an additive selected from the group comprising: a strong base, a salt of a strong base and a weak acid, a salt of a weak acid, a carbodiimide, a polycarbodiimide and mixtures thereof.
In yet another of its aspects, the present invention provides a hydrogenated nitrile polymer vulcanizate having a hot air aging time to reach 100% elongation at break of at least about 200 hours when measured pursuant to ASTM-D573-88 at 150° C., the vulcanizate derived from a sulfur-based vulcanization system.
Thus, it has been discovered that incorporation of a particular additive in a nitrile polymer vulcanizate results in a surprising and unexpected improvement in the hot air aging characteristics of the vulcanizate (i.e., an improvement in the resistance to oxidative attack in air at elevated temperature aging under oxidizing conditions). The improvement in the hot air aging characteristics of the vulcanizate can manifest itself in a number of ways, including (by way of example only) an increase in: (i) the period of time needed for the vulcanizate to reach 100% elongation at break at 150° C.; and (ii) the maximum service temperature to which the vulcanizate can be exposed for a specified period of time before reaching 100% elongation at break, when compared to a vulcanizate made without the additive. The present vulcanizates may also be characterized by improvement (i.e., in comparison to a vulcanizate produced without the additive) in one or more of the following properties: aged hot fluid aging, aged compression set, aged dynamic elastic modulus (E′), aged dynamic viscous modulus (E″), aged static modulus, aged low temperature properties and aged hardness.
REFERENCES:
patent: 5127973 (1992-07-01), Sengupta et al.
patent: 5312869 (1994-05-01), Nomura et al.
patent: 5362533 (1994-11-01), Fukuda et al.
patent: 5376726 (1994-12-01), Noyama et al.
patent: 5556919 (1996-09-01), Oyama et al.
patent: 5731371 (1998-03-01), Nesbitt et al.
patent: 1558491 (1980-01-01), None
patent: 61-066724 (1986-04-01), None
Bayer Inc.
Cain Edward J.
Cheung Noland J.
Gil Joseph C.
Wyrozebski-Lee Katarzyna I
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