JPS6050214B2 - Anti-deterioration agent for rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel anti-degradation agent for rubber.

In general, rubber-like polymeric substances, especially substances with unsaturated bonds in their molecular chains, undergo deterioration such as softening or hardening when exposed to the effects of ozone, oxygen, light, heat, etc., resulting in a significant decline in various properties, making them difficult to use in practice. Very often it becomes a problem. In order to prevent such deterioration, it has been conventional practice to add various deterioration inhibitors such as phenols and amines to synthetic resins or rubber, and under relatively moderate temperature conditions, the It is proving effective. However, recently the conditions for using rubber products have become even more strict.
As seen in automobile exhaust gas countermeasures, engine improvements have resulted in temperatures around the engine becoming higher than before, making it difficult to apply conventional deterioration prevention methods to rubber products that can withstand practical use. Provision is becoming extremely difficult. The present invention is the result of intensive research to develop a deterioration inhibitor with even better deterioration prevention effects, and as a result of the present invention, a novel and excellent deterioration inhibitor has been discovered.

That is, an object of the present invention is to provide a novel anti-aging agent that has an excellent effect on preventing the deterioration of rubbery polymers. This object of the invention is achieved by using diphenylamine derivatives having the following general formula as antidegradants.

R, R.

R-(CONH--AT, NH1-l-i)n\6-
' \■1 / (in the formula, R is an aromatic residue or C, ~, 0
hydrocarbon group, R,,R.

, represents hydrogen, chlorine, bromine, or C, ~, 2 hydrocarbon group, and n represents 2 or 3) Specific examples of the compounds of the present invention include jN-'-di-4-anilinophenyl oxalamide. N,N'-di-4-anilinophenyladipic acid amide N-N'-di-4-anilinophenylmalein 7
Acid amide N,N'-di-4-anilinophenylsebacic acid amide N-N'-di-4-(4-methylanilino)
Phenylsebacic acid amide N●N″◆N″″-4 Anilinophenyltricarballylic acid amide N-N″-G4-
Anilinophenyl terephthalic acid amide N-N''-G4
-(4-Methylanilino)phenyl terephthalic acid amide N●N''-Di-4-anilinophenyl isophthalic acid amide N●N''-Di-4-anilinophenylnaphthalic acid amide N-N''・N''''1 tree 4 -Includes anilinophenyl trimellitic acid amide and the like.

These compounds include an amine represented by the structural formula (R1 and R2 represent hydrogen, chlorine, bromine, or a C1-1. alkyl group) and an aliphatic or aromatic di- or tricarboxylic acid chloride such as oxalic acid chloride or terephthalic acid chloride. Obtained by reaction with acid chloride.

There is no particular restriction on the amount used when the anti-degradation agent of the present invention is blended into a rubbery polymer, but it is 0.01 to 1 part by volume, preferably 0.1 part by weight, per 100 parts by weight of the rubbery polymer. ~5
Parts by weight.

When the deterioration inhibitor of the present invention is blended and used, there are no particular restrictions on the rubber-like polymer that can be used, but diene polymers that are susceptible to thermal deterioration, such as polybutadiene, styrene-butadiene copolymer, acrylonitrile- It is effective when used with butadiene copolymers, polyisoprene, polychloroprene, etc., or mixtures thereof.

Furthermore, there are no particular restrictions on the method of blending the anti-deterioration agent of the present invention.
The rubber-like polymer may be added to the latex or mixed in solution, and for solid rubbers it may be mixed in a commonly used mixer, such as on mixing rolls or in an internal Panbury mixer. May be added. The rubbery polymer blended with the anti-deterioration agent obtained in the present invention can be used alone or as needed! Commonly compounded chemicals such as reinforcing agents,
Fillers, plasticizers, softeners, vulcanizing agents, stabilizers, anti-aging agents, etc. are blended and then vulcanized or without vulcanization, it is suitable for general use as well as heat resistance, weather resistance, It can be widely used in fields that require ozone resistance, oil resistance, etc.

The present invention will be specifically explained below using Examples.

Synthesis example p-aminodiphenylamine 36.8y(4).
2 mol) and anhydrous sodium carbonate 16y in benzene 3
00ml, 23.9g (0.1 mol) of sebacyl chloride was added dropwise at 30°C with stirring.

After the completion of the dropwise addition, the mixture was stirred for 2 hours at 40°C or lower, and the solvent was removed by evaporation, followed by washing with water to obtain 48.2y of N-N''-di-4-alinophenyl sebacic acid amide (1). By reacting p-aminodiphenylamine with terephthalic acid chloride and trimellitic acid chloride, respectively, N-N″-di-4-anilinophenyl terephthalic acid amide (2), N-N″・N″″-tri-4-anilinof Enyl trimellitic acid amide (3) was obtained.Example N-N''-di-4-anilinophenyl sebacic acid amide of the present invention, NIN''-di-4-anilinophenyl terephthalic acid amide and NeN''.N ``'' Samples containing one-trily 4-anilinophenyl trimellitic acid amide, and as comparative examples, samples containing no deterioration inhibitor, samples containing P-P'-dioctyl diphenylamine, and diphenyl-p-phenylene diamine, respectively. A compounded comb was obtained using the compounding recipe shown in Table 1.

Claims (1)

[Claims] 1 The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ A deterioration inhibitor for rubber comprising a diphenylamine derivative represented by a hydrocarbon group of C_1_ to_1_2, where n represents 2 or 3.