JPS645014B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to tetrakis[2-(4-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane, a method for producing the same, and a method for producing organic substances containing the same as an active ingredient. Regarding anti-deterioration agents. 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, Synthetic rubbers such as styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, and chloroprene-ethylene-propylene ternary copolymer rubber, petroleum products such as lubricating oil and fuel oil, and various organic substances such as fats and greases are exposed to heat. 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. -Hydroxy-2
-Methylphenyl)acetyloxymethyl]-methane is a new compound that has not been described in any literature, and was first discovered by the present inventors. Tetrakis [2-(4-t-butyl-) of the present invention
5-Hydroxy-2-methylphenyl)acetyloxymethyl]-methane is useful as a deterioration inhibitor for organic materials. Tetrakis [2-(4-t-butyl-) of the present invention
5-Hydroxy-2-methylphenyl)acetyloxymethyl]-methane is 4-t-butyl-5-
It is produced by transesterifying hydroxy-2-methylphenylacetic acid alkyl ester and pentaerythritol in the presence of a basic catalyst. Preferred alkyl esters are esters with lower alcohols. Lower alcohol means branched and straight chain alcohols having 1 to 6 carbon atoms. As the basic catalyst, a lower alkoxide of an alkali metal is used. Generally lithium methoxide, sodium methoxide, sodium ethoxide and potassium t-butoxide are preferred, with sodium methoxide being most preferred. The amount of catalyst used is usually pentaerythritol 1
From about 0.01 to about 0.5 moles per mole. This reaction is usually carried out without solvent, but small amounts of dipolar neutral solvents such as dimethyl sulfoxide or dimethyl formamide can be used. If a solvent is used, approximately 2
Add an amount equal to ~3% by weight. However, if necessary, it can exceed 50% by volume of the total reaction mixture. If necessary, other solvents of dimethylsulfoxide and dimethylformamide can be used in addition, such as tetrahydrofuran, dioxane, pyridine, dimethylacetamide, nitrobenzene, 1,2-dimethoxyethane and 0-nitroanisole. This transesterification reaction is carried out at a temperature range of 80 to 200°C, preferably 120 to 160°C, while removing the lower alcohol produced from the system. In order to effectively remove the produced alcohol, it is preferable to carry out the reaction under reduced pressure. In addition, 4-t, which is a raw material for transesterification of the present invention,
-Butyl-5-hydroxy-2-methylphenylacetic acid alkyl ester is, for example, 2,6-di-
It can be produced in high yield using t-butyl-4-methylphenol as a raw material according to the method of the following formula. Tetrakis [2-(4-t-butyl-) of the present invention
5-Hydroxy-2-methylphenyl)acetyloxymethyl]-methane is useful as an inhibitor for organic materials, but is particularly useful for preventing thermal, photochemical, and oxidative degradation of natural and synthetic polymers. . One of the major advantages of the antidegradants of the present invention is due to their large molecular weight and excellent compatibility with most organic substances. The amount of antidegradant used varies depending on the organic material to be stabilized, and is generally about 0.001 to about 10% by weight of tetrakis[2-(4-
t-Butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane is used,
The range for most applications is from about 0.01 to about 5% by weight. For example, when stabilizing α-monoolefin homopolymers, copolymers, or terpolymers, from about 0.05 to about 2.5
wt% of tetrakis[2-(4-t-butyl-5
-Hydroxy-2-methylphenyl)acetyloxymethyl]-methane is used. Tetrakis[2-(4-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane can be incorporated into an organic substance by a conventional method. Tetrakis[2-(4-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane is effective in stabilizing organic compounds when used alone, but it can also be used with other additives, such as antioxidants. agents, 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, detergents Oil additives such as dispersants and extreme pressure agents, metal chelating agents, and the like may be used in combination depending on their respective purposes. In particular, tetrakis [2-(4-t-butyl-5-
Hydroxy-2-methylphenyl)acetyloxymethyl]-methane is 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole 2-(2'-hydroxy-5'-methylphenyl)
Benzotriazole 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole 2-(2'-hydroxy-3'-t-butyl-5'methylphenyl)-5-chlorobenzotriazole 2-(2'-hydroxy-3'-t-butyl-5'-
methylphenyl)benzotriazole 2-(2'-hydroxy-3',5'-di-t-amyl phenyl)-5-chlorobenzotriazole 2-(2'-hydroxy-3',5'-di-t-amyl phenyl) Benzotriazole 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole 2,4-dihydroxybenzophenone 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-octoxybenzophenone 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-benzyloxybenzophenone 2,4,2',4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone Benzoic acid esters UV absorbers such as cyano-acrylic esters, nickel compounds Bis-(2,2,6,6-tetramethyl-4-
sterically hindered amine compounds such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine bis(2,2,6,6-tetramethyl-4-carbonyloxypiperidine)-para-dimethylbenzyl dithio Carbamate, zinc dialkylthiophosphate Tris(mono or/and dinonylphenyl phosphite) Tris(2,4-di-t-butylphenyl)phosphite Tetrakis(2,4-di-t-butylphenyl)-4,4'- Biphenylene phosphite 3,9-bis(octadecyloxy)-2,4,
8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane 3,9-bis(dodecyloxy)-2,4,8,
10-Tetraoxa-3,9-diphosphaspiro[5,5]undecane 3,9-bis(octoxy)-2,4,8,10
-Tetraoxa-3,9-diphosphaspiro[5,5]undecane Tetrakis(2,4-di-t-butylphenyl)[1,1'-biphenyl]-4,4'-diylbisphosphonite such as phosphorus-containing Compounds and dioctyl-3,3'-thiodipropionate dinonyl-3,3'-thiodipropionate didecyl-3,3'-thiodipropionate dicetyl-3,3'-thiodipropionate dilauryl-3, 3'-thiodipropionate Dimyristyl-3,3'-thiodipropionate Distearyl-3,3'-thiodipropionate Dipalmityl-3,3'-thiodipropionate Dicyclohexyl-3,3'-thiodipropionate Pionates Pentaerythritol-tetrakis (β-laurylthiopropionate) Pentaerythritol-tetrakis (β-stearylthiopropionate) Peroxide-degrading compounds such as organic sulfides and similar sulfur-containing compounds such as distearyl disulfide When used in combination with the above, an excellent synergistic deterioration prevention effect can be obtained. Particularly useful among the sulfur-containing compounds is pentaerythritol-tetrakis (β-alkylthiopropionate), and more useful are those in which the alkyl group is lauryl, myristyl, stearyl, etc. When these sulfur-containing compounds are used together, the amount added to the organic substance is tetrakis [2-(4
-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-1 for methane
~10 times by weight is preferred. Furthermore, when used in combination with the above-mentioned ultraviolet absorbers and photostabilizers, a synergistic anti-deterioration effect can be obtained that is superior to that expected from the photodeterioration-preventing effects of the individual ultraviolet absorbers and photostabilizers. There are cases. Of course, the various additives mentioned above may be mixed in advance with tetrakis[2-(4-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane. The present invention will be explained below using examples. Example 1 In a 500ml four-necked flask, add 4-t-butyl-5-
Methyl hydroxy-2-methylphenylacetate
Add 128.6g and 16.5g of pentaerythritol,
The air in the reaction vessel is replaced with dry nitrogen, and 0.5 g of sodium methoxide is added. The reaction is carried out at 130°C for 2 hours, and then at 140-150°C under reduced pressure of 20 mmHg for 10 hours. During this reaction, 1.5 g of sodium methoxide is added in three equal portions as the reaction progresses. After the reaction is completed, the internal temperature is cooled to 80°C and neutralized with glacial acetic acid. Add toluene to this, wash with water, and dehydrate with anhydrous sodium sulfate. Then, removing the solvent under reduced pressure gives 101.4
g (yield 88%) of pale yellow viscous liquid Tetrakis[2-(4-t-butyl-5-hydroxy-2-
Methylphenyl)acetyloxymethyl]-methane is obtained. When this is recrystallized from n-heptane, white crystals with a mp of 89-91°C are obtained. Elemental analysis C ₅₇ H ₇₆ O ₁₂ Calculated values in parentheses C: 71.7% (71.8), H: 8.2% (8.0) ¹ H-NMR (CDCl ₃ ) δ (ppm) 1.33 (36H, s), 2.80 (12H) , s), 3.45 (8H,
s), 3.79 (8H, s), 5.47 (4H, s), 6.25
(4H, s), 6.99 (4H, s) Example 2 After mixing the following formulation with a mixer for 5 minutes,
The compound obtained by melt-kneading with a mixing roll at 180°C was molded into a sheet with a thickness of 1 mm using a hot press at 210°C, and a test piece of 40 x 40 x 1 mm was prepared. 30 of the specimen area in a gear oven at 150 °C
The thermal and oxidative stability was evaluated by measuring the time until % embrittlement. The results are shown in Table-1. <Formulation> Unstabilized polypropylene resin (Sumitomo Noblen FS-200) 100 parts by weight Calcium stearate 0.1 Test compound Variable [Table]

Claims (1)

[Scope of Claims] 1. Tetrakis[2-(4-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane. 2 Tetrakis [2-(4-t
-Butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane production method. 3. A deterioration inhibitor for organic substances containing tetrakis[2(4-t-butyl-5-hydroxy-2-methylphenyl)acetyloxymethyl]-methane as an active ingredient.