Unsaturated nitrile-conjugated diene copolymer, process for prod

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

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526 79, 526 80, 526 87, 526224, 5262928, 526342, 526917, 525233, 525239, 524424, 524426, 524456, 524565, 524566, 524828, 528485, 528487, 528503, 428 36, C08F23604, C08F 238

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057031894

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

This invention relates to an unsaturated nitrile-conjugated dienes copolymer, a process for producing the same, and a vulcanizable rubber composition comprising the copolymer and a vulcanizer. More particularly, it relates to a nitrile-conjugated dienes copolymer having good mechanical strength and good and balanced oil resistance and cold resistance, a process for producing this copolymer wherein a specific thiol compound as a molecular weight modifier is added in lots in the course of polymerization, and a vulcanizable rubber composition comprising the copolymer and a sulfur-containing vulcanizer.


BACKGROUND ART

In recent years, injection molding has been widely employed for molding an acrylonitrile-butadiene rubber (hereinafter abbreviated to "NBR") in view of productivity and rationality, that is used in applications for which good oil resistance and thermal resistance are required. Recently the range of its use is increasing, which includes vibration insulating rubbers, electrical parts, automobile parts, industrial moldings and footwears.
For injection molding of NBR, a high fluidity and a high crosslinking efficiency, i.e., a high-rate vulcanizability, at a high-temperature and short-time vulcanization are generally required. However, in general, the higher the vulcanization temperature of rubber, the lower the degree of the crosslinking efficiency. Therefore injection molded articles have poor tensile stress and impact resilience as compared with compression molded articles (for example, see Journal of Society of Rubber Industry, Japan, vol. 59, No. 4, p 214-215, 1986).
To impart a high-rate vulcanizability to NBR, many proposals have been made, which include for example a method of introducing a functional group such as a carboxyl group or an amino group, a method of incorporating a suitable vulcanization promotor, and a method of conducting an emulsion polymerization using minimum amounts of an emulsifier and a coagulant and thus minimizing residual catalyst in NBR. However, the high-rate vulcanizability attained by these proposals is not on a high level and in some cases physical properties such as cold resistance and permanent set are deteriorated.
Further, contamination of a mold is conspicuous in the injection molding of NBR wherein vulcanization is carried out at a high temperature. That is, where the molding is repeated, staining materials are gradually deposited on the mold with the result of contamination of moldings and spoiling of the surface appearance. Therefore the mold must be cleaned at regular intervals, but the cleaning is time-consuming and costly and leads to reduction in productivity.
To avoid the contamination of a mold, proposals have been made wherein talc, sodium thiosulfate, carbon wax or silicone oil is incorporated in rubber. However, these proposals are generally not effective for commercially available general purpose NBR. Especially where the vulcanization is effected at a high temperature and a high rate as in injection molding, it is difficult to avoid the mold contamination.
Further, it is required for NBR depending upon the use thereof that MBR has good and balanced oil resistance and cold resistance. To improve the balance between the oil resistance and the cold resistance, for example, a method has been proposed in Japanese Patent Publication No. 62-7943 wherein acrylonitrile is incorporated in a polymerization mixture in lots during polymerization whereby the breadth (.DELTA.AN) of compositional distribution of acrylonitrile in a copolymer is narrowed.
Although the balance between the oil resistance and the cold resistance is improved by narrowing the AN, the strength of the rubber vulcanizate is reduced. Especially, when rubber is subjected to injection molding for which a high-rate and high-temperature vulcanizability is required, the strength and other properties of the rubber vulcanizate are drastically reduced.


DISCLOSURE OF INVENTION

In view of the foregoing, an object of the present invention is to provide an unsaturated nitrile-c

REFERENCES:
patent: 4004072 (1977-01-01), Tamura
patent: 4027090 (1977-05-01), Giddings et al.
patent: 4060680 (1977-11-01), Hendy
patent: 4082818 (1978-04-01), Coffey et al.
patent: 4145494 (1979-03-01), Neubert
patent: 4157319 (1979-06-01), Feeney et al.
patent: 5627250 (1997-05-01), Tsuji et al.

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