JPH0572412B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a deterioration inhibitor for rubber-like polymers containing a novel reactive anilinophenyl butadiene and its derivatives as active ingredients. (Problems to be solved by the prior art and the invention) In general, rubber-like polymeric substances, especially substances with unsaturated bonds in their molecular chains, soften or harden when exposed to ozone, oxygen, light, heat, etc. etc., resulting in significant deterioration of various properties, which is very often a problem in practice. 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 they are quite effective under relatively moderate temperature conditions. is demonstrated. However, in recent years, the conditions for using rubber products have become even more severe, and improvements in engines, as seen in automobile exhaust gas countermeasures, have resulted in temperatures around the engine becoming higher than before. By applying this method, it has become extremely difficult to provide rubber products that can withstand practical use. The present inventors have conducted intensive research to find compounds that have even better anti-deterioration effects on rubber-like polymers, and as a result, the present invention has developed a novel reactive anilinophenyl butadiene with anti-deterioration properties and its We were able to find a derivative. (Means for solving the problem) That is, the purpose of the present invention is to solve the general formula

【formula】 Or

[Formula] (In the formula, R and R' are hydrogen or a substituent, m is 0
or an integer of 1 to 3, n is 0 or an integer of 1 to 2, and R ₁ to _{R 7} each represent hydrogen or a substituent. An object of the present invention is to provide a deterioration inhibitor for rubber-like polymers, which contains as an active ingredient anilinophenylbutadiene and its derivatives having the reactivity shown in (). Since the oxidative deterioration inhibitor of the present invention has radical polymerizability, it can be directly bonded into the rubbery polymer chain by copolymerization, or it can be added to the rubbery polymer and added to it during the processing or vulcanization process. can be bonded to molecular chains through thermal history. As a result, extraction by solvents and volatilization at high temperatures are suppressed, making it possible to maintain the ability to prevent oxidative deterioration under severe usage conditions. The anilinophenyl butadiene and its derivatives of the present invention have the general formula

【formula】 Or

[Formula] (In the formula, R and R' are hydrogen or a substituent, m is 0
or an integer of 1 to 3, n is 0 or an integer of 1 to 2, and R ₁ to R ₇ each represent hydrogen or a substituent such as a lower alkyl group or halogen. ) is a radically polymerizable compound represented by The anilinophenylbutadiene and its derivatives of the present invention are obtained by diazotizing the primary amine of p-aminodiphenylamine or its nuclear-substituted p-aminodiphenylamine derivative, and reacting the diazonium compound with a conjugated diene compound. It can then be obtained by dehalogenating or dehydrohalogenating. Examples of the conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, fluoroprene, chloroprene, and bromoprene. Specific examples of anilinophenylbutadiene and its derivatives include 1-anilinophenyl-1,3-
Butadiene, 1-anilinophenyl-3-methyl-1,3-butadiene, 1-anilinophenyl-
3-chloro-1,3-butadiene, 1-anilinophenyl-2-methyl-1,3-butadiene, 1
-anilinophenyl-2-chloro-1,3-butadiene, 2-anilinophenyl-1,3-butadiene, 2-anilinophenyl-3-methyl-1,
Examples include 3-butadiene, 2-anilinophenyl-3-chloro-1,3-butadiene, and the like. The anti-deterioration agent for rubber-like polymers of the present invention can be added to the rubber-like polymer or mixed with other monomers constituting the polymer as a polymerizable anti-deterioration agent at the stage of producing the rubber-like polymer. Although it is used in a state where it is copolymerized and directly bonded to the polymer molecular chain, there are no particular restrictions on the manner in which it is used. There is no particular restriction on the amount used when the anti-degradation agent of the present invention is blended into a rubbery polymer.
0.01 to 10 parts by weight per 100 parts by weight, preferably
It is 0.1 to 5 parts by weight. 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-butadiene copolymer, polyisoprene, polychloroprene, etc. It exhibits remarkable effects when used in modified polymers by hydrogenation, etc. Furthermore, there are no particular restrictions on the method of blending the anti-aging agent of the present invention, and it may be added and mixed into the latex or solution of the rubbery polymer. , for example on mixing rolls or in an internal Banbury mixer. Furthermore, when copolymerizing the anti-degradation agent of the present invention with other monomers in a free radical polymerization system in order to directly bond it into the molecular chain of a rubbery polymer, anilinophenylbutadiene and its derivatives are all monomers.
0.01 to 20 parts by weight in 100 parts by weight, preferably 0.1 to 10 parts by weight
Used in parts by weight range. The monomer copolymerized with the derivative may be one or more conjugated diene monomers selected from 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, etc. It may also be a mixture of these conjugated diene monomers and monoethylenically unsaturated monomers. Monoethylenically unsaturated monomers include unsaturated nitriles such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; monovinylidene aromatic hydrocarbons such as styrene, alkylstyrenes (o-, m-, or p-chloro Styrene, 2,
unsaturated carboxylic acids or their esters, such as acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid or methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, etc.; unsaturated aldehydes such as acrolein, methacrolein; vinylpyridine; vinyl esters such as vinyl acetate and vinylidene halide. Examples include one or more of vinylidene chloride and vinylidene bromide. Also, examples of free radical initiators used in conventional emulsion polymerization are those known as "redox" initiators, such as ferrous sulfate, sodium formaldehyde sulfoxylate, and e.g. cumene hydroperoxide, paramenthane. A suitable combination of organic peroxides such as hydroperoxide and other initiators such as azobisisobutyronitrile, benzoyl peroxide, hydrogen persulfate, potassium persulfate may also be used depending on the particular polymerization system. It can be used as The antidegradants of the present invention are particularly suitable for other oxidative antidegradants, such as 2-mercaptobenzimidazole,
Or mercaptobenzimidazoles such as nickel and zinc salts; N-alkyl-substituted dithiocarbamic acids such as nickel dibutyldithiocarbamate and zinc dimethyldithiocarbamate;
dilaurylthiodipropionate, ethane-1,
-bis(3-n-dodecylthiopropionate),
When used in combination with thioether compounds such as 3,6,9-trioxaundecene-1,11-bis(3-n-dodecylthiopropionate), its oxidative degradation prevention effect can be synergistically improved. can. The anti-deterioration effect of the anti-deterioration agent of the present invention is particularly applicable to fields where rubber products or rubber-like polymers containing these are required to have a high degree of deterioration resistance for a long period of time, especially when they are in contact with solvents or oil, or are immersed. , for example, when used in fields such as fuel hoses, printing rolls, spinning rolls, apron bands, packing, oil seals, diaphragms, fuel tanks, textile coating agents, and adhesives. Next, the present invention will be specifically explained using examples. Synthesis Example 1 184 gr (1 mol) of p-aminodiphenylamine is dissolved in about 5% hydrochloric acid solution and then cooled to 0°C. While stirring this aqueous solution, add 69 gr of sodium nitrite.
(1 mol) was added dropwise little by little. Stirring was continued for 1 hour after the completion of the dropwise addition. Next, filtration is performed while cooling. While keeping the filtrate below 0°C, acetone, an aqueous solution of 80g of sodium acetate crystals, an aqueous solution of 30g of cupric chloride, and 81g of butadiene (1.5 mol) are slowly added dropwise under strong stirring. After dropping and stirring for a day and night, the generated 1-(p-anilinophenyl)
-4-Chloro-2-butene is extracted with ether. Remove ether by distillation under reduced pressure, dissolve the residue in methanol, and add 112 g (2 moles) of potassium hydroxide.
Add dropwise methanol solution. After dropping, the reaction mixture is poured into cold water, filtered and dried. The product was purified with petroleum ether to give 1-anilinophenyl-1,3
53.1 gr (yield 24.0%) of -butadiene was obtained. The melting point of this product was 89°C. The results of elemental analysis were as follows. Actual value (%) C86.79, H6.80, N6.41 Theoretical value (%) C86.84, H6.83, N6.33 Synthesis example 2 In synthesis example 1, butadiene was replaced with isoprene and chloroprene and the reaction was carried out. , 1-anilinophenyl-3-methyl-1,3-butadiene (yield 20.5
%), 1-anilinophenyl-3-chloro-1,
3-Butadiene (yield 23%) was obtained. Example 1 The formulations shown in Table 1 were prepared for the anilinophenylbutadiene derivatives synthesized in Synthesis Examples 1 and 2 and samples using N-phenyl-N'-isopropyl-p-phenylenediamine as a comparative example.
Heat aging and composite aging tests were conducted on the vulcanized samples obtained by press vulcanization at 160°C for 20 minutes. The results are shown in Table 2.

【table】

【table】

[Table] From the results in Table 2, it can be seen that NBR containing the deterioration inhibitor of the present invention clearly has significantly improved heat aging resistance under extremely severe conditions. Example 2 Using the anilinophenyl butadiene derivatives prepared in Synthesis Examples 1 and 2 as a polymerizable monomer, a copolymer of butadiene and acrylonitrile (NBR) was used as a third polymerizable monomer.
It was made according to the polymerization recipe shown in the table. Raw materials other than butadiene are charged into a glass pressure-resistant bottle with an internal volume of approximately 1. After repeating depressurization and nitrogen replacement to remove dissolved oxygen, butadiene is added and the bottle, which is sealed with a stopper, is placed in a constant temperature water bath at 5°C and rotated. The polymerization reaction was carried out for 15 hours while stirring. The final reaction rate and the Mooney viscosity of the crumb recovered from the latex by salting out are shown in Table 3. As a comparative example, N,
N'-diphenyl-p-phenylenediamine was added and mixed in an amount of 3 parts by weight based on 100 parts by weight of the rubber solid content.

[Table] The obtained copolymer rubber (NBR) was prepared as a vulcanizate sample using the same formulation and vulcanization conditions as in Example 1, and was subjected to heat aging and combined aging tests. The results are shown in Table 4.

【table】

【table】

【table】

[Table] From the results shown in Table 4, NBR copolymerized with the anilinophenyl butadiene derivative of the present invention clearly shows an excellent effect on heat aging resistance, and also has significantly improved composite aging resistance.

Claims (1)

[Claims] 1 General formula [Formula] or [Formula] (wherein R and R' represent hydrogen or a substituent, m represents 0 or an integer of 1 to 3, and n represents 0 or an integer of 1 to 2. an integer,
R ₁ to R ₇ each represent hydrogen or a substituent. ) A deterioration inhibitor for rubber-like polymers containing reactive anilinophenyl butadiene and its derivatives as an active ingredient.