KR19980067325A - Deterioration inhibitor and rubber composition with improved aging - Google Patents

Abstract

Deterioration inhibitors for elastomers, plastomers, plastics and other petroleum related products and rubber compositions using the same are disclosed. The deterioration inhibitor has the following structural formula.

RNHC ₆ H ₄ NHC ₆ H ₄ NHR '(wherein R and R' independently represent an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group, and may be the same as or different from each other). Physical properties can be maintained.

Description

Deterioration inhibitor and rubber composition with improved aging

The present invention relates to a novel anti-deterioration agent and an improved aging rubber composition comprising the same. The deterioration inhibitor according to the present invention includes a diamino diphenylamine derivative, which prevents oxidation or ozone deterioration of a rubber or plastic susceptible to oxidation deterioration or ozone deterioration, and which is required to prevent oxidation deterioration with petroleum-related products. Used in the field.

Polymers such as elastomers, plastomers, or plastics are degraded by light, heat, oxygen, ozone, and the like to degrade their physical properties. These deteriorations occur not only in the processed products in these polymers, but also in the production of the polymers, and preventing such deterioration is an important problem in this field. As a chemical | medical agent which prevents oxidation or ozone deterioration of these polymers, a phenolic anti-aging agent or an amine anti-aging agent is mentioned. Amine-based deterioration inhibitors that are particularly effective against phenolic deterioration inhibitors include quinoline derivatives, diphenylamine derivatives and p-phenylenediamine derivatives, and p-phenylenediamine derivatives include 4,4'-dialkyl p-phenylenes. Diamine, 4, 4'-diaryl-p-phenylenediamine, 4-alkyl-4'-aryl p-phenylenediamine. Recently, the most balanced deterioration inhibitor is 4-alkyl 4'-aryl p-phenylenediamine, for example N-isopropyl-N'-phenyl p-phenylenediamine [3C], or N-1,3-dimethyl. Butyl-N'-phenyl p-phenylenediamine [6C] was most used, but the effect was not sufficient. In addition, petroleum-related products are also susceptible to deterioration, and N-phenyl α-naphthylamine, N, N'-disecondary butyl-p-phenylenediamine, and the like have been used.

It is therefore an object of the present invention to provide antidegradants and rubber compositions using them for elastomers, plastomers, plastics and other petroleum related products.

In order to achieve the above object of the present invention, the present invention provides a deterioration inhibitor represented by the following structural formula.

RNHC ₆ H ₄ NHC ₆ H ₄ NHR '(wherein R and R' independently represent an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group, and may be the same as or different from each other)

It is preferable that carbon number of R or R 'is a 3-8 alkyl group or a cycloalkyl group, respectively.

The present invention also provides a rubber composition comprising the deterioration inhibitor in an amount of 0.1 parts by weight to 5.0 parts by weight per 100 parts by weight of the raw rubber.

The diamino diphenylamine derivatives related to the present invention are represented by the following general formula RNHC ₆ H ₄ NHC ₆ H ₄ NHR '(wherein R and R' independently represent an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group, and may be the same as each other. And may be different).

Specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a branched isomer, and the cycloalkyl group includes a cyclohexyl group or methyl cyclohex. Practical skills are included. These compounds can be obtained by subjecting dinitro diphenylamine or diamino diphenyl amine and ketones to reduction alkylation with hydrogen in the presence of a catalyst for hydrogenation, or reacting diamino diphenyl amine with a halogenated compound.

It was confirmed that the diamino diphenylamine derivative according to the present invention had a higher effect even if the amount of use of the diamino diphenylamine derivative was reduced compared to conventionally used (6C) for rubber which is a typical polymer.

Hereinafter, the effect of the diamino diphenylamine derivative | guide_body by this invention is demonstrated about a 6C blend as a comparative sample by an Example.

Example 1

The properties of the diamino diphenylamine derivatives used in this test are shown in Table 1 below. In this test, derivatives in which R and R 'are the same substituents were used.

TABLE 1

Properties of Anti Aging Agent According to the Present Invention

The substituent and molecular weight were confirmed using GC-MS and GPC.

In addition, the mixing | blending of the rubber composition which is this test sample is shown in following Table 2.

TABLE 2

Formula

The physical properties of the vulcanized rubber composition of this test are shown in Table 3 below. In addition, the sample of the rubber composition was subjected to masterbatch dough in a closed kneader, final kneading, and then vulcanized at 145 ° C for 30 minutes to obtain a vulcanized rubber composition in accordance with ASTM D 3182. The vulcanized rubber composition was subjected to a tensile test and a furnace test in accordance with JIS K 6301. The numerical value regarding the physical property is shown by the numerical value which made Comparative Example 2 (6C, 2.0 phr) 100, and shows the favorable physical property especially as the tensile strength (TB) after aging is large.

TABLE 3

Physical properties of vulcanized rubber

(HD: hardness (hardness), EB: elongation at break, TB: strength at break, M100: modulus at 100% elongation, M300: modulus at 300% elongation)

Example 2

Table 4 shows the results of the examples in which the amount of the anti-aging agent was compared based on 6C 0.074 mol based on 0.074 mol × 2/3 of the test sample according to the present invention. The compounding table is the same as in Example 1.

The physical properties of the vulcanized rubber composition of this test are shown in Table 5 below. In addition, the kneading method is a rotation speed: 20rpm. Rotation Ratio 1: 1.22DML Using a 6 × 16 inch roll, the roll temperature was performed at 75 ± 5 ° C. As for vulcanization conditions, the comparative example 1 and Examples 1-5 are 145 degreeC x 15 minutes, the comparative example 2 are 145 degreeC x 20 minutes, and the aging test is 100 +/- 1 degreeC using gear type using the JIS No. 3 type test piece. Physical properties after 24 hours were measured.

TABLE 4

Physical properties of vulcanized rubber

As a result, the diamino diphenylamine derivative according to the present invention has high heat aging resistance even when the amount is 1/2 or the molar ratio is 2/3 molar ratio, compared to 6C, which is currently the best deterioration inhibitor. It was confirmed that can be maintained.

Claims (3)

A deterioration inhibitor having the following structural formula. RNHC ₆ H ₄ NHC ₆ H ₄ NHR ' (In formula, R and R 'independently represent a C1-C8 alkyl group or a cycloalkyl group, and may mutually be same or different.) The deterioration preventing material according to claim 1, wherein each of R or R 'has 3 to 8 alkyl or cycloalkyl groups. A rubber composition comprising from 0.1 part by weight to 5.0 parts by weight per 100 parts by weight of raw rubber having a deterioration preventing material having the following structural formula. RNHC ₆ H ₄ NHC ₆ H ₄ NHR ' (In formula, R and R 'independently represent a C1-C8 alkyl group or a cycloalkyl group, and may mutually be same or different.)