KR790001402B1 - Heat resistant rubbery polymer composition - Google Patents

Abstract

Degradation-resisting compds. were manufd. by adding antidegradating agent(I) having functional radical which could be reacted with rubbery polymer to the 1.3 diazole compds. (II; R1,R2,R3 = hydrogen, fluorine, chloride, Brom or hydrocarbon radical of carbon no. 1-12, M=metal of II or group in periodic table, n = 2-3) or their derivatives. The thermal and mechanical properties of rubbery polymer, which have good heat and oil resistance were greatly improved by using these compds.

Description

Heat resistant rubbery polymer composition

The present invention relates to a rubbery polymer composition having good heat resistance. In more detail, the compound (I) represented by the following general formula

And 1,3 diazole or a salt derivative thereof represented by the following general formula (II)

It relates to a rubbery polymer composition having good heat resistance by blending.

를 받아 특성이 현저히 저하되는 것이 알려져 있다.Conventional rubbery polymers are degraded by the action of heat, light, oxygen, ozone, etc.

It is known that a characteristic will fall remarkably on receiving.

In order to prevent these characteristics from falling, various well-known deterioration inhibitors are used.

However, these deterioration inhibitors are almost all organic compounds or salts thereof, and when the rubber products containing them come into contact with lipophilic compounds, the deterioration inhibitors are often extracted to be of no use.

This example is sometimes experienced as acrylonitrile-butadiene rubber (NBR) with good oil resistance.

The present inventors have studied diligently to improve these defects, and as a result of using a deterioration inhibitor having a functional group reacting with a polymer in the vulcanization reaction of rubber, and again using a complex deterioration agent containing a 1,3 diazole-based compound It has been found that the heat resistance can be remarkably improved, and that the oil and heat resistances are remarkably improved.

That is, the present invention provides a rubbery polymer to a general formula (I) phenylene diamine-based compound and mercaptobenzo 1,3 diazole or a salt thereof of the general formula (II) shown below. It is the heat-resistant rubber-like composition mix | blended.

Wherein R ¹ and R ² R ⁴ are hydrogen, fluorine, chlorine, a clear or hydrocarbon group of 1-12 carbon atoms, R ³ is hydrogen or a hydrocarbon group of 1-4 carbon atoms, M is a Group II metal or a periodic table Ie metal, where n represents 2 or 3.

As the compound of (I) used in the present invention, β-hydroxy-r- (n'phenyl-p-phenylenediamino) -propyl acrylate ),

β-hydroxy-r- (n'phenyl-P-phenylene diamino) -propyl methacrylate, β-hydroxy-r- (n'-tolyl) -P-phenylene dia Mino) propyl acrylate,

β-hydroxy-r- (n'tolyl-P-phenylene diamino) propyl methacrylate, and the like. As the compound of (II), mercaptobenzo-1,3-diazole, 2-mercapto-4-methylbenzo-1,3-diazole and 2-mercapto-5-ethylbenzo (ethylbenzo) -1,3-diazole, mercaptobenzo-1,3-diazolezinc, mercapto-1,3-diazolemagnesium, mercaptobenzo-1,3-diazolnickel, 2-mercapto-4- Methylbenzo-1,3-diazolecalcium, 2-mercapto-4-methylbenzo-1,3-diazolezinc, 2-mercapto-4-methylbenzo, -1,3-diazolezinc, 2- Mercapto-4-methylbenzo, -1,3-diazolnickel, 2-mercapto-5-ethylbenzo-1,3-diazole nickel and the like can be listed as preferred examples.

The amount of these compounds is not particularly limited as in general formulas (I) and (II), but is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the rubbery polymer. If the effect is lowered and a large amount is included, there is no problem in terms of the effect. However, the effect is not preferable because it promotes scorching or exhibits a plasticizing effect.

There is no particular limitation on the amount relationship between (I) and (II), but many of (II) are preferred.

There are no particular restrictions on the polymers to which the anti-degradation agent of the present invention can be used, but diene-based polymers susceptible to thermal degradation, such as polybutadiene styrene-butadiene copolymers, It is most suitable to use for acrylonitrile butadiene copolymer, polyisoprene, polychloroprene, etc.

In addition, the method of adding the present composite deterioration inhibitor is not particularly limited. For example, a method of dry blending with a roll or banbury, a dispersion of a composite deterioration inhibitor, and a liquid mixture such as rubber latex can be employed. Can be.

When the present invention is described in detail with reference to the following examples, the present invention is not limited by the examples.

Example 1

As (I) of the composite deterioration prevention agent which became this invention

And (I) and (II) as a sample containing mercaptobenzo-1,3-diazole zinc and 2-mercapto-4-methylbenzo-1,3 diazole zinc as (II), or a comparative example. The sampled rubber which contained the sample which did not contain the deterioration inhibitor used alone was used, and the compounding rubber shown in Table 1 was used.

Kneading is carried out in a BR type Banbury mixer, and the vulcanization system is added to an open mill for rubber. The compound is pressed and vulcanized at 155 ° C. for 20 minutes and subjected to heat or oil resistance test.

The results are shown in the second table.

[Table 1] Formulation

[Table 2] Degradation test results (一)

[Table 2] Degradation Test Results (二)

(1) Oil resistance test: Soaked in JIS No. 3 oil at 120 ° C. for 168 hours.

Heat resistance test: 96 hours deterioration at 130 ℃ by test tube method after oil resistance test (same as below)

The results of Table 2 include mercaptobenzo 1,3 diazole or 2-mercapto-4-methylbenzo 1,3 diazole zinc of (I) a phenyldiamine compound and II), which are complex deterioration inhibitors of the present invention. The heat resistant composition to be made is more remarkably improved in heat deterioration resistance and oil resistance deterioration resistance than the compound of (I) having a functional group reacting with a polymer during rubber vulcanization.

Example 2

Degradation test results when mercapto benzo-1,3-diazole was used as (II) in the same manner as in Example 1 are shown in Table 3.

As a result of Table 3, the heat resistant composition comprising the composite antideterioration agent of the present invention is remarkably improved in heat resistance and oil resistance.

[Table 3] Degradation test results (一)

[Table 3] Degradation test results (二)

Example 3

A gear oven was used as a deterioration test in the same manner as in Example 1, and 2-mercapto-4-methylbenzo-1,3-diazole calcium and 2-mercapto-4-methyl were used as (II). Degradation test results when using benzo-1,3-diazole nickel are shown in Table 4.

As a result of Table 4, the heat-resistant composition comprising the composite anti-degradation agent of the present invention is remarkably improved in heat deterioration resistance and oil heat resistance than the compound (I).

[Table 4] (一)

[Table 4] (二)

Comparative Example 1

A phenylene diamine-based compound was used instead of the compound of Example 1 (I), and the compound of (II) was used in the same manner except that mercaptobenzo-1,3-diazole zinc was used. Was carried out.

Degradation test results are shown in Table 5.

As a result of Table 5, in the case of this comparative example, heat resistance in oil resistance is particularly remarkable as compared with the composition containing the composite deterioration agent as the present invention.

[Table 5] (一)

[Table 5] (二)

[Comparative Examples 2 and 3]

As the compound of (II) of Example 1, except that tri (nonylated phenyl) phosphite or ditearyl thio dipropionate was used, It was tested by the method.

From the results in Table 6, it can be seen that excellent effects similar to those of the present invention can be obtained when a compound other than the mercaptobenzo-1,3-diazole or salt thereof specified in the present invention is used as the compound (II).

[Table 6] (一)

[Table 6] (二)

Claims (1)

As described in the text, the general formula (I) is used for at least one rubbery polymer selected from polybutadiene, styrene-butadiene polymer, acrylonitrile butadiene copolymer, polyisoprene, polychloroprene, and the group.

Β-hydroxy, in which R ¹ and R ² represent hydrogen, fluorine, chlorine, a clear or hydrocarbon group having 1 to 12 carbon atoms, and R ³ represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. -r- (n'phenyl-P-phenylenediamino) propyl acrylate, β-hydroxy-r- (n'phenyl-P-phenylenediamino) propyl methacrylate, β-hydroxy-r- at least 1 selected from the group consisting of (n'tolyl-P-phenylenediamino) propyl acrylate, β-hydroxy-r- (n 'tolyl-P-phenylenediamino) propyl methacrylate, Species and general formula (Ⅱ)

Mercapto benzo-1,3, wherein R ⁴ represents hydrogen, fluorine, chlorine, a cancelled or hydrocarbon group of 1-12 carbon atoms, M represents a Group II metal or n-group metal n of the periodic table -Diazole, 2-mercapto-4-methylbenzo, -1,3-diazole, 2-mercapto-4-methylbenzo, -1,3-diazole, 2-mercapto-4-methylbenzo- Group of 1,3-diazole, 2-mercapto-5-ethylbenzo-1,3-diazole, or mercaptobenzo-1,3-diazole zinc, mercaptobenzo-1,3-diazole Magnesium, mercaptobenzo-1,3-diazolnickel, 2-mercapto-4-methylbenzo-1,3-diazolecalcium, 2-mercapto-4-methylbenzo-1,3-diazolezinc, At least one selected from the group consisting of 2-mercapto-4-methylbenzo-1,3-diazolnickel and 2-mercapto-5-ethylbenzo-1,3-diazole nickel, or acrylonitrile butadiene To the copolymer,

Mercaptobenzo-1,3-diazole, 2-mercapto-4-methylbenzo-1,3-diazole, mercaptobenzo-1,3-diazolezinc, 2-mercapto-4-methylbenzo- At least one selected from the group of 1,3-diazolzinc, 2-mercapto-4-methylbenzo-1,3-diazolcalcium and 2-mercapto-4-methylbenzo-1,3-diazolnickel Heat-resistant rubber-like polymer composition which mix | blends.