JPH0220629B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to general formula (I) (In the formula, R represents a methyl group or an ethyl group, and A
represents -S( _CH2 )nS-. Here, n is an integer of 2 to 9) The present invention relates to a bisphenol derivative represented by: Conventionally, synthetic resins such as polyolefin, ABS resin, polystyrene, high impact polystyrene, acrylonitrile-styrene copolymer, polyamide, polyacetal and ethylene-propylene copolymer, natural rubber and butadiene rubber, isoprene rubber, isoprene-isobutylene copolymer rubber , styrene-butadiene copolymer rubber,
Synthetic rubbers such as 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 oils are susceptible to deterioration due to heat, light, and oxygen. It is also a well-known fact that various deterioration inhibitors are added in order 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 includes bisphenol derivatives represented by the general formula (I) of the present invention. 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 (I) 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 alkanedithiol. Here, the bisphenol monoacrylate represented by the general formula () is, for example, 2,2'-thiobis(6-t-butyl-4-methylphenol) or 2,2'-thiobis(6-t-butyl-4-methylphenol).
-ethylphenol) and acryloyl chloride in an inert solvent in the presence of a dehydrochlorinating agent. In this production method, the inert solvent is n-
Aliphatic hydrocarbons such as hexane and n-heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclopentane and cyclohexane, halogenated hydrocarbons such as dichloromethane and chloroform, and diethyl ether and tetrahydrofuran. Examples include ethers such as In addition, as the dehydrochlorination agent, tertiary amines such as triethylamine, pyridines, or N,N-dialkylanilines are used, and the amount used is as follows:
The amount ranges from 0.9 to 1.3 mol per mol of bisphenol. The reaction temperature is in the range of -5 to 60°C,
The reaction molar ratio of bisphenol and acryloyl chloride is in the range of 1:0.9 to 1.3. In addition, as compounds of general formula (), 1,2-ethanedithiol, 1,3-propanedithiol,
Examples include 1,4-butanedithiol, 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 alcohols such as methanol, ethanol and t-butanol, dichloromethane, chloroform, etc. are used as such solvents, but the most preferred are It's chloroform. 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. Specifically, the bisphenol derivative represented by the general formula (I) produced in this way includes 4,
7-, dithiadecanoic acid, bis[2-t-butyl-6-(3-t-butyl-2-hydroxy-5
-methyl(or ethyl)phenylthio)-4-
methyl (or ethyl) phenyl] ester,
Bis[2-t-butyl-6-(3-t-butyl-2-hydroxy-) 4,8-dithiaundecanoic acid
5-methyl(or ethyl)phenylthio)-4
- methyl (or ethyl) phenyl] ester,
4,9-dithiadodecanoic acid bis[2-t-butyl-6-(3-t-butyl-2-hydroxy-5
-methyl(or ethyl)phenylthio)-4-
methyl (or ethyl) phenyl] ester,
4,11-dithiatetradecanioic acid bis[2-t-
Butyl-6-(3-t-butyl-2-hydroxy-5-methyl (or ethyl)phenylthio)-
4-methyl (or ethyl) phenyl] ester and 4,14-dithiaheptadecanioic acid bis[2
Examples include -t-butyl-6-(3-t-butyl-2-hydroxy-5-methyl (or ethyl) phenylthio)-4-methyl (or ethyl) phenyl] ester. The thus obtained bisphenol represented by the general formula (I) of the present invention is useful as a deterioration inhibitor for derivatives and organic substances, but is particularly useful for preventing thermal and oxidative deterioration of natural and synthetic polymers. Useful. The bisphenol derivative represented by the general formula (I) 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 production example 1 100ml equipped with thermometer, stirring device, and dropping funnel
2,2'-thiobis(6-t-butyl-
10.75 g (0.030 mol) of 4-methylphenol), 3.34 g (0.033 mol) of triethylamine, and 42 g of toluene were charged, and after replacing the air in the container with nitrogen, it was cooled to 0 to 2°C, and 2.79 g of acryloyl chloride was added from the dropping funnel. g (0.0303 mol) and toluene 12 g
Add the mixture dropwise over an hour. After the addition, excess triethylamine was removed with concentrated hydrochloric acid, triethylamine hydrochloride was filtered off, the filtrate was washed with water, separated, and the toluene layer was distilled under reduced pressure to remove the solvent, yielding 12.1 g (yield 98%) of 2,2 '-thiobis(6-t-butyl-
4-methylphenol) monoacrylate was obtained. This crude product was recrystallized from 25 ml of n-hexane to obtain 10.9 g (yield: 88%) of white crystals (melting point: 157-159°C). Elemental analysis C ₂₅ H ₃₂ O ₃ Calculated values in parentheses C: 72.6% (72.8%) H: 8.0% (7.8%) S: 7.4% (7.8%) Infrared absorption spectrum (liquid paraffin method) (Unit cm ^-1 ) 3420 (νO−H), 1735 (νC=O), 1632 (νC=
C), 1570 (ν ^arom _C=C ), 1170, 1150 (νC−O), 98
Five
(δ out-of-plane _CH ), 850 (δ out-of-plane _arpn , C-H), 790, 780
, 760
(νC-S) Example 1 2.2'-thiobis(6-t-butyl-4-
Methylphenol) monoacrylate 8.37g (0.02
mol), 1,6-hexanedithiol 1.53g (0.01
After charging 50 g of chloroform and replacing the air in the container with nitrogen, 0.15 g (0.0008 mol) of a 28% by weight methanol solution of sodium methoxide was charged, the temperature was raised, and the temperature was kept at 60 to 62°C for 5 hours. Thereafter, it was cooled to 25°C, neutralized with dilute hydrochloric acid, the chloroform layer was washed with water, separated, and the chloroform was distilled off from the organic layer under reduced pressure to obtain 9.6 g of crude product (yield:
97%). Add this crude product to 20 ml of n-hexane.
By recrystallizing from 6.5 g (yield: 65%) of enylthithio-4-methylphenyl]ester were obtained. This is designated as compound (I)-1. Elemental analysis C ₅₆ H ₇₈ O ₆ S ₄ Calculated values in parentheses C: 69.0% (69.0%) H: 8.4% (8.1%) S: 13.0% (13.2%) Infrared absorption spectrum (liquid paraffin method) Unit cm ^{- 1} 3425 (νO−H), 1738 (νC=O), 1595, 1575
(νarom C=C), 1186, 1135 (νC-O), 860
(δ out-of-plane _arpn C-H), 786, 766 (νC-S) Example 2 2,2'-thiobis(6-t-butyl-4-ethylphenol) monoacrylate and 1,6-
By reacting under the same conditions as in Example 1 except for using hexanedithiol, bis[2-t-butyl-6-4,11-dithiatetradecanioate] was prepared.
(3-t-butyl-2-hydroxy-5-ethylphenylthio)-4-ethylphenyl] ester is obtained. This is designated as compound (I)-2. Example 3 2,2'-thiobis(6-t-butyl-
4-methylphenol) monoacrylate 8.37g
(0.02 mol), 1,2-ethanedithiol 0.92 g
After preparing (0.01 mol) and 50 g of chloroform and replacing the air in the container with nitrogen, 0.15 g (0.0008 mol) of a 28% by weight sodium methoxide methanol solution was prepared.
Prepare the ingredients, raise the temperature, and keep at 60-62℃ for 5 hours.
Thereafter, it was cooled to 25°C, neutralized with dilute hydrochloric acid, the chloroform layer was washed with water, separated, and chloroform was distilled off from the organic layer under reduced pressure to obtain 8.83 g of a crude product.
(yield 92%). By recrystallizing this crude product from 20 ml of n-hexane, the melting point was 63-66℃.
6.2 g of 4,7-dithiadecanoic acid bis[2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylphenylthio)-4-methylphenyl] ester as white crystals (yield 67%) obtained. This is designated as compound (I)-3. Elemental analysis C ₅₂ H ₇₀ O ₆ S ₄ Calculated values in parentheses C: 67.7% (67.9%) H: 7.9% (7.7%) S: 14.1% (14.0%) Infrared absorption spectrum (liquid paraffin method) (Unit: cm) ^-1 ) 3430 (νO−H), 1740 (νC=O), 1590, 1575
(νarom C=C), 1190, 1140 (νC-O), 863
(δ out-of-plane _arpn C-H), 790, 770 (νC-S) Reference example 1 After kneading the following composition in a mixer for 5 minutes, the cylinder temperature was 230-240℃, the head die temperature was 250℃,
The mixture was melt-kneaded and granulated using an extruder with a rotational speed of 20 rpm. The pellets thus obtained were formed into a 1 mm thick sheet using a heat press at 210°C, and the sheet size was 40 x 40 x 1 mm.
A test piece was prepared. 30% of the specimen area in a gear oven at 160℃
The time until embrittlement was measured and the thermal and oxidative stability was evaluated. The results are shown in Table-1. <Formulation> Unstabilized polypropylene resin 100 parts by weight Calcium stearate 0.1 Test compound Variables In Table 1, the symbols of the test compounds indicate the following compounds. AO-1 Pentaerythritol Tetrakis [3-(3,5-di-t-butyl-4
-Hydroxyphenyl)propionate] AO-2 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate AO-3 Dilauryl 3,3'-thiodipropionate 【table】

Claims (1)

[Claims] 1. General formula (In the formula, R represents a methyl group or an ethyl group, and A
represents -S( _CH2 )nS-. (wherein n represents an integer of 2 to 9) A bisphenol derivative represented by: 2 General formula (In the formula, R represents a methyl group or an ethyl group.) A bisphenol monoacrylate compound represented by the general formula HS( _CH2 )nSH (wherein, n represents an integer from 2 to 9). General formula characterized by reacting dithiol (In the formula, R has the same meaning as above, A is -S
( _CH2 )nS-, n has the same meaning as above) A method for producing a bisphenol derivative represented by: