JPH0148893B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and A represents -S(CH ₂ ) nS-. Here, n is 2
(representing an integer of 9 to 9) and a method for producing the same. Conventionally, synthetic resins such as polyolefin, ABS resin, polystyrene, impact polystyrene, acrylonitrile-styrene copolymer, polyamide, polyacetal and ethylene-propylene copolymer, natural rubber and butadiene rubber, isoprene rubber, isoprene-isobutylene copolymer rubber, Various organic substances such as synthetic rubbers such as styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, and chloroprene-ethylene-propylene terpolymer rubber, petroleum products such as lubricating oil and fuel oil, oils and fats, and greases are heated. It is a well-known fact that they are susceptible to deterioration due to light and oxygen, and that various deterioration inhibitors are added to suppress such deterioration. The present invention was completed as a result of research aimed at developing a compound that has excellent performance in preventing the deterioration of organic substances, and the bisphenol derivative represented by the general formula () of the present invention is This is a new compound that has not been described in any literature and has extremely excellent effects as a deterioration inhibitor for organic substances. The bisphenol derivative represented by the general formula () has the general formula () (In the formula, R has the same meaning as above) and a bisphenol monoacrylate compound represented by the general formula () HS (CH ₂ ) nSH () (In the formula, n has the same meaning as above) It can be produced by reacting with an alkanediol. In the above general formula, the substituent R is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group, and the compound of the general formula () is, for example, a 2,2'- methylenebis(6-t-butyl-4-methylphenol),
2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-methylenebis(6-
It can be easily synthesized by reacting t-butyl-4-sec-butylphenol) and 2,2'-methylenebis(4,6-di-t-butylphenol) with acryloyl chloride. In addition, compounds of general formula () include 1,2-ethanediol, 1,3-propanedithiol,
Examples include 1,4-butanediol, 1,6-hexanedithiol, and 1,9-nonanedithiol. In the present invention, the reaction between the bisphenol monoacrylate compound and the alkanedithiol is usually carried out in a solvent, and such solvents include alcohols such as methanol, ethanol, and t-butanol, and ethers such as dichloromethane, chloroform, and dioxane. Most preferred are chloroform and ethanol. The presence of basic catalysts is more effective in this reaction, and such catalysts include alkali metal alkoxides of lower alcohols having 1 to 4 carbon atoms, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, triethylamine, etc. amines, benzyltrimethylammonium hydroxide, etc. are commonly used, and sodium methoxide is particularly preferred. When these basic catalysts are used, the amount used is usually 0.5 to 5% by weight based on the bisphenol monoacrylate compound. The reaction temperature usually ranges from 10°C to the reflux temperature of the solvent used, but in many cases it is carried out at reflux temperature. The reaction molar ratio of both reaction materials is generally 2 to 2.2 times the bisphenol monoacrylate compound to the alkanedithiol. The thus obtained bisphenol derivatives of the present invention represented by the general formula () are useful as deterioration inhibitors for organic substances, but are particularly useful for preventing thermal and oxidative deterioration of natural and synthetic polymers. It is. The bisphenol derivative represented by the general formula () is effective in stabilizing organic substances even when used alone, but other additives such as antioxidants,
Sulfur-containing compounds, phosphorus-containing compounds, ultraviolet absorbers, light stabilizers, plasticizers, metal soaps, pigments, dyes, fillers and corrosion inhibitors, rust inhibitors, pour point depressants, antifoaming agents, cleaning and dispersing agents , oil additives such as extreme pressure agents, metal chelating agents, etc. may be used in combination depending on their respective purposes. The present invention will be explained below using examples. Raw material manufacturing example 1 500ml with thermometer, dropping funnel and stirrer
Add 2,2'-methylene bis(6-t-
butyl-4-methylphenol) 82.0g (0.24mol), toluene 200g and triethylamide 29.3g
(0.29 mol), replace the air in the container with nitrogen, and cool to 1°C. A mixture of 25 g (0.28 mol) of acryl chloride and 50 g of toluene is dropped into the reaction vessel from a dropping funnel over a period of 2 hours. After the addition is complete, excess triethylamine is neutralized with dilute hydrochloric acid, washed with water, separated, and 180 g of the solvent is distilled from the oil layer to obtain a viscous oil. When about 50 g of n-hexane is added to this and recrystallized, 90.0 g (yield 95
%) of 2,2'-methylenebis(6-t-butyl-
4-methylphenol) monoacrylate is obtained. Melting point 133-134℃ Elemental analysis C ₂₆ H ₃₄ O ₃ Calculated value in parentheses C: 79.34% (79.15%) H: 8.86% (8.69%) Example 1 4,11-dithiatetradecanedioic acid bis(2- t
Production of -butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl) ester 200ml equipped with stirrer, thermometer and cooling tube
In a four-necked flask, add 2,2'-methylene bis(6-
7.93 g (0.020 mole) of t-butyl-4-methylphenol monoacrylate, 1.50 g (0.010 mole) of 1,6-hexadithiol and 50 g of ethanol
After charging g and replacing the air in the container with nitrogen,
28% sodium methoxide methanol solution 0.17g
Prepare. The temperature was raised and the mixture was reacted under reflux for about 8 hours, then cooled to 30°C. 50g of chloroform was charged, neutralized with diluted hydrochloric acid, washed with water, dehydrated, chloroform was distilled off, 20g of n-hexane was charged and recrystallized, yielding 7.47g (80% yield) of white crystals with a melting point of 121-122℃. , 11-dithiatetradecanedioic acid bis(2
-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl) ester is obtained. Elemental analysis ( ) Calculated values C ₅₈ H ₈₂ O ₆ S ₂ C; 74.08% (74.16), H; 8.90% (8.80) S; 6.87% (6.83) Example 2 4,7-dithiadecanedioic acid bis(2 -t-butyl-6-(3-t-butyl-2-hydroxy-
5-methylbenzyl)-4-methylphenyl)
Production of esters 200ml with stirrer, thermometer and cooling tube
In a four-necked flask, add 2,2'-methylene bis(6-
t-butyl-4-methylphenol) monoacrylate 7.95 g (0.02 mol), 1,2-ethanedithiol 0.92 g (0.0098 mol) and ethanol 50
After charging g and replacing the air in the container with nitrogen,
28% sodium methoxide methanol solution 0.17g
Prepare. After raising the temperature and reacting under reflux for about 10 hours, it was cooled to 30°C, charged with 50 g of chloroform, neutralized with diluted hydrochloric acid, washed with water, dehydrated, then distilled off the chloroform, charged with 20 g of n-hexane and recrystallized.
7.51g - (Yield 85%) White crystalline 4,7-dithiadecanedioic acid bis(2-t-butyl-6-(3-t-butyl-2-hydroxy-5-
methylbenzyl)-4-methylphenyl) ester is obtained. Elemental analysis Calculated values in parentheses C ₅₄ H ₇₄ O ₆ S ₂ C; 73.72% (73.43), H; 8.68% (8.44) S; 7.32% (7.26) Reference example 1 Solution polymerized polybutadiene containing no antioxidant The sample rubber was prepared by roll-kneading the test compounds shown in Table 1 into rubber (rubber obtained by extracting the antioxidant from JSR BR-0.1 with acetone).
Thermal and oxidative stability and heat discoloration resistance tests were conducted. The results are shown in Table-1. The thermal and oxidation stability of the sample rubber is 100%.
The gel content (toluene insoluble content) was measured every 15 hours by heat aging in a gear oven at ℃, and the gel content was 10wt.
It was evaluated based on the time taken to reach % (GEl IP). In addition, heat discoloration resistance was evaluated by the rubber hue after heat aging in a gear oven at 100°C for 15 hours, 60 hours, and 120 hours.

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Claims (1)

[Claims] 1. General formula (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and A represents -S(CH ₂ ) nS-. Here, n is 2
(representing an integer of ~9) A bisphenol derivative represented by: 2 General formula (wherein, R represents an alkyl group having 1 to 4 carbon atoms) and a bisphenol monoacrylate compound represented by the general formula HS(CH ₂ )nSH (wherein, n represents an integer from 2 to 9). General formula characterized by reacting alkanedithiols (In the formula, R has the same meaning as above, A is -S
(CH ₂ )nS-, n has the same meaning as above) A method for producing a bisphenol derivative represented by: