JPH0649019A - Phenolic compound and its production - Google Patents

Abstract

PURPOSE: To provide new compds. having good extraction resistance and volatility resistance, and useful for active antioxidant obtained by partly esterifying polyphenol antioxydant to more active form and combinating two of the molecules with a sulfer atom.

CONSTITUTION: These new compds. are expressed by the formula I [where Z is a phenoxy group derived from the polyphenol compds. of the formula II (R¹ and R² are H, alkyl, cycloalkyl, aralkyl or aryl; X is cyclic diene, S, O, NH₂, SS or C=O; n is 0-5); R³ is alkyl; R⁴ is alkyl, aralkyl or aryl; Y is H, alkyl, cycloalkyl, aralkyl or aryl] such as 2-(2-hydroxy-3-tert.-butyl-5- methylbenzyl)-4-methyl-6-tert.-butylphenyl]thiodi-propionate. The compds. of the formula I are obtained by reacting the polyphenol compds. of the formula II with the ester forming compds. of the formula III (V is Cl, I or Br), then combinating the obtained compds. through a sulfer atom.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel compounds useful as antioxidants for organic materials and a process for preparing the novel compounds from standard antioxidant compounds.

Many organic materials are subject to oxidative degradation. This problem is especially acute in the rubber and plastics industry. Antioxidants must be incorporated into these products as they undergo a rapid loss of usefulness upon oxidative degradation.

[0003]

Many compounds have been proposed and used as antioxidants. These, alone or in combination with other compounds, exert the necessary antioxidant effect. It is known to those skilled in the art that high oxidative stability can be obtained by using these compounds in combination. It is also well known to the person skilled in the art that certain combinations of antioxidants lead to even higher antioxidant properties than the sum of the antioxidant effects of these compounds when they are used separately. This fact is French patent No. 12
No. 45606, British Patent 851,670 and US Pat. No. 3,535,277.

[0004]

However, it is difficult to uniformly blend two or more separate components into a polymer. The effectiveness of multi-component systems in polymers depends on the intimate mixing of the components, resulting in a polymer composition containing the specified components in specific proportions. For example, in order to obtain the optimum effect of the phenol / sulfide combination, the ratio of the two separate components incorporated into the polymer must be tightly controlled. The non-uniform distribution of the two antioxidants leads to an undesired and variable antioxidant property in each production batch of the polymer. Also, the proportions of the various antioxidants are perturbed by the respective volatilization rate and / or extraction rate of each individual antioxidant.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for increasing the antioxidant properties of various antioxidants known in the art by combining them by chemical reaction.

[0006] Another object of the present invention is to provide an antioxidant having excellent extraction resistance and volatility resistance.

Other objects of the invention will be apparent to those skilled in the art as the following description proceeds.

The above objective is accomplished by chemically coupling the underlying antioxidants to produce a single high molecular weight molecule with excellent antioxidant properties.

The antioxidants of the present invention partially esterify the polyphenolic antioxidants to a more active form and then bind two molecules of the esterified polyphenolic compound by sulfur atoms to form active high molecular weight antioxidants. Obtained by manufacturing.

The antioxidant of the present invention is a series of reaction products. In most cases, a resinous product is obtained. Many polyphenol starting compounds are well known to those skilled in the art. The antioxidant of the present invention can be prepared from a partial ester of polyphenol. The term "partial ester" means esterified polyphenols in which some of the phenolic hydroxy groups of the polyphenol have been esterified.

The above compounds are (A) a polyphenol compound having two or more aromatic rings each containing a phenolic hydroxy group, and (B) a similar derivative capable of forming an acid halide or an unsaturated ester. It is manufactured by reacting. These products are reacted with thiols such as hydrogen sulfide or 3-mercaptopropionic acid to produce the antioxidant compounds of this invention. The polyphenol starting material can first be prepared by methods well known to those skilled in the art. Alternatively, a commercially available polyphenol can be used. Production examples of these polyphenol compounds are described in US Pat. Nos. 3,036,138 and 3,305,52.
No. 2 specification.

The polyphenolic compounds that can be used to make the antioxidants of the present invention have the following structural formula:

[0013] [R ¹ and R ² are the same or different groups and are hydrogen, C _{1 to} C ₁₆ alkyl group, C _{5 to} C ₈ cycloalkyl group, C _{7 to} C ₁₂ aralkyl group, and C _{6 to} C ₁₂ substituted aryl. A group and an unsubstituted C ₆ -C ₁₂ aryl group; when R ¹ is para to the hydroxy group, R ¹ preferably has 1 or 2 carbon atoms; X is The same or different groups, and (i) C _{5 to} C ₂₀
A divalent group formed from a cyclic diene having non-adjacent carbon double bonds in the ring structure of (ii) -S-, -O-,-
CH _2- , -S-S- and A divalent group selected from the group consisting of: selected from the group consisting of; n is selected from the group consisting of 0 and an integer from 1 to 5. ].

Reacting a polyphenolic compound with a compound of the general formula which is capable of forming an ester; [R ³ is selected from the group consisting of hydrogen and C ₁ -C ₂ alkyl groups; R ⁴ is hydrogen, C ₁ -C ₄ alkyl, C ₇ -C ₉ aralkyl groups, C ₆ -C ₈ substituted aryl and C ₆ Selected from the group consisting of ˜C ₈ substituted aryl; and V is selected from the group consisting of chlorine, iodine and bromine. ] The amount of esterification naturally depends on the molar ratio of the compounds used and the steric hindrance. Preferably, the polyphenol compound is treated with 1 mole to 0.1 mole of ester forming compound for each hydroxy functional group. More preferably, at least one hydroxy functional group is esterified per polyphenol molecule.

When the polyphenol and the ester-forming compound are reacted in a 1: 1 molar ratio, a nearly theoretical reaction occurs. For example, in the formula (A), X is -S-, -CH.
_A divalent group selected from the group consisting of _2- , and R ² is a hydrocarbon (preferably a tertiary group) having a carbon number of C ₄ or higher and is in the ortho position to the hydroxy group (A The compound of 1) has only one easily reactive hydroxy group. Esterification of this unique hydroxy group acts as a steric hindrance to suppress the reaction at the secondary hydroxy group moiety.
For example, if 1 mol of methacryloyl chloride is reacted with 1 mol of 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), a theoretical amount of 2- (2-hydroxy-3-t-butyl) is obtained. -5-methylbenzyl) -4
-Methylphenyl methacrylate is obtained.

A polyphenol compound represented by the structural formula (A) (wherein R ² (preferably a tertiary group) is in the ortho position with respect to the hydroxy group) is added to the ester-forming compound (n + 2 mol) of the structural formula (B). When reacted with, less than n + 2 mol of compound (B) reacts. Generally, the number of ester groups that react with the polyphenol reaction mixture is less than n + 1.5 or less than n-0.75. When n is 0, the number of ester groups that react with the polyphenol compound is usually 1.
It is 5 or less or less than 0.25.

The esterification reaction can be readily carried out at atmospheric pressure and temperatures in the range of 0 ° C. to the boiling point of the reaction compound.
Preferably, temperatures of 0 ° C to 60 ° C are used. The ester-forming compound is usually added to the phenolic compound in the presence of a base such as triethylamine, sodium carbonate, pyridine or potassium carbonate.

Once the esterification has taken place, the unsaturated ester formed is bound by a sulfur atom by reacting the resulting unsaturated ester with hydrogen sulfide gas in the presence of a solvent such as methanol or toluene.

The binding of the esterified phenol molecule with the sulfur atom can be carried out in an organic solvent at a temperature in the range of 0 ° C. to the boiling point of the solvent. The preferred temperature is 25 ° C to 65 ° C. Hydrogen sulfide gas is passed through the solution at a slow rate such that gas evolution is minimal until the reaction is complete. Thus, a compound having the general structural formula II is produced. This reaction can be catalyzed by a base such as potassium hydroxide, sodium acetate or sodium methoxide. When preparing the compound of general structural formula (II), hydrogen sulfide can be replaced by a thiol such as 3-mercaptopropionic acid or a thiol derivative such as 2-mercaptopropionic acid or methyl 3-mercaptopropionate.

The compounds of the present invention have the general structural formula selected from the group consisting of formulas (I) and (II): [Wherein Z is a phenoxy group derived from a phenol compound represented by the structural formula (A); Y is hydrogen, C ₁ -C
₂₀ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₇ -C ₁₂
Aralkyl groups, C ₆ -C ₁₆ substituted aryl group and C ₆ -C
Selected from the group consisting of ₁₆ unsubstituted aryl groups; R ³ and R ⁴ are groups as defined above. ].

Representative examples of groups of the above formula are methyl, ethyl,
Alkyl groups such as butyl, pentyl, hexyl and decyl; cycloalkyl groups such as cyclopentyl, cyclohexyl; alkylaryl groups such as methylphenyl and hexylphenyl; aryl groups such as phenyl and naphthyl; benzyl and 4-methylbenzyl Aralkyl groups such as; and halogens such as bromine, iodine and chlorine.

Representative examples of cyclic dienes useful in the present invention are:
1,5-cyclooctadiene; cyclopentadiene; bicyclo [2.2.1] -2,5-heptadiene; dicyclopentadiene; And 1,5,9-cyclododecadien.

Representative examples of phenolic compounds useful in the practice of this invention are 2,6-bis- (2-hydroxy-3).
-T-butyl-5-methylbenzyl) -4-methylphenol; 2,2'-methylene-bis- (4-methyl-6)
-T-butylphenol); 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol); 2,
2'-thio-bis- (4-methyl-6-t-butylphenol); 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenol; 4- (3,5
-Di-t-butyl-4-hydroxybenzyl) phenol; 2- (3,5-di-t-butyl-4-hydroxybenzyl) phenol; 2- (3,5-di-t-butyl-
4-hydroxybenzyl) -5-methylphenol;
2,6-bis- (2-hydroxy-3-t-butyl-5
-Ethylbenzyl) -4-ethylphenol; and 2
-(3,5-di-t-butyl-4-hydroxybenzyl)
-4-Isopropylphenol and U.S. Pat. No. 3,6
25,874, 3,036,138 and 3,
Compounds similar to those produced in 305,522.

Representative examples of ester-forming compounds that can be used in the practice of this invention are acryloyl chloride, methacryloyl chloride, cinnamoyl chloride, acryloyl bromide, ethacryloyl chloride and β- (4-
Methylcyclohexyl) acryloyl chloride.

Representative examples of phenolic ester compounds useful in the practice of this invention are 2- (2-hydroxy-3).
-T-butyl-5-methylbenzyl) -4-methyl-6
2-t-butylphenyl acrylate; 2- (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methyl-6-t-butylphenyl methacrylate; 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
-4-Methylphenyl methacrylate; 2- (3,5-
Di-t-butyl-4-hydroxybenzyl) -4-methylphenyl acrylate; 4- (3,5-di-t-butyl-4-hydroxybenzyl) phenyl acrylate;
2- (2-hydroxy-3-t-butyl-5-methylphenylthio) -4-methyl-6-t-butylphenylmethacrylate; 2- (3,5-di-t-butyl-4-hydroxybenzyl) Phenyl methacrylate; 2,6-
Bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenylmethacrylate.

A typical example of the compounds represented by the structural formula (I) produced by carrying out the present invention is bis [2-
(2-Hydroxy-3-t-butyl-5-methylbenzyl) -4-isopropyl-6-t-butylphenyl] thiodipropionate; bis [2- (2-hydroxy-3)
-T-butyl-5-methylbenzyl) -4-methyl-6
-T-butylphenyl] thiodipropionate; bis [2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenyl] thiodipropionate;
Bis [4- (3,5-di-t-butyl-4-hydroxybenzyl) phenyl] thiodipropionate; Bis [2
-(3,5-di-t-butyl-4-hydroxybenzyl) phenyl] thiodipropionate.

A typical example of the compounds represented by the structural formula (II) produced by carrying out the present invention is 2- (3,
5-di-t-butyl-4-hydroxybenzyl) -4-
Methylphenylphenylthiodipropionate; 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
-4-Methylphenyl-4-decylphenylthiodipropionate; 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenylbenzylthiodipropionate; 2- (2-hydroxy -3-t-butyl-5-methylbenzyl) -4-methyl-6-t-butylphenylcyclohexylthiodipropionate; 4-
(3,5-di-t-butyl-4-hydroxybenzyl)
Phenylcyclooctyl thiodipropionate; 2-
(3,5-Di-t-hexyl-4-hydroxybenzyl) -4-methylphenyl-6-phenylhexylthiodipropionate; 2- (3,5-di-t-butyl-4
-Hydroxybenzyl) -4-methylphenyl-6-phenylhexylthiodipropionate; 2- (3,5-
Di-t-butyl-4-hydroxybenzyl) -4-methylphenyl-2-hexylphenylthiodipropionate; 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenylei It is cosylthiodipropionate.

Representative examples of solvents useful in reacting polyphenol compounds with ester-forming compounds are benzene, toluene, xylene, tetrahydrofuran, dioxane, ethanol, and 2-B-ethanol.
Representative examples of solvents useful for reacting the phenolic esters of the present invention with hydrogen sulfide are methanol, ethanol, isopropanol, benzene, toluene, xylene and tetrahydrofuran.

Representative examples of catalysts useful in reacting the phenolic esters of the present invention with hydrogen sulfide are sodium hydroxide, sodium methoxide, sodium acetate and potassium hydroxide.

The polyphenol compounds disclosed herein can be reacted with the ester-forming compounds in the ratios described above. Preferably, the ester-forming compound 1
More than one mole is reacted with 1 mole of polyphenol compound.
The two esterified polyphenol compounds are combined by reacting with hydrogen sulfide to form a compound of structural formula (I). The esterification can be carried out partially or can be varied depending on the steric hindrance of each molecule. All such compounds are effective in the present invention.

Polymers that can be effectively protected by the compounds disclosed herein include natural rubber, balata,
It is a vulcanized and unvulcanized rubber that is susceptible to oxidative deterioration, such as a rubbery synthetic polymer containing gutta-percha and carbon-carbon double bond.

Representative examples of synthetic polymers used in the practice of this invention are polychloroprene; of isoprene and butadiene containing up to 40% by weight of at least one copolymerizable monomer such as styrene and acrylonitrile. Copolymers with conjugated 1,3-dienes such as; Butyl rubber, which is the polymerization product of a majority of mono-olefins with minor amounts of multi-olefins such as butadiene or isoprene; containing carbon-carbon double bonds Polyurethanes; polyethylene, polypropylene, ethylene-propylene copolymers and ethylene-
Polymers and copolymers of monoolefins containing little or no unsaturated bonds such as propylene-non-conjugated diene terpolymers. The exact amount of antiaging agent to be used depends somewhat on the nature of the polymer and the severity of the aging conditions to which the polymer is exposed. For unsaturated polymers such as those made from conjugated dienes, the requirement for aging resistance is higher than that required for saturated polymers such as polyethylene.

Generally, the stabilizers of this invention are used in amounts of about 0.0005% to about 10%, based on the weight of the composition to be stabilized. However, this amount will vary with the particular polymer. A particularly preferred range is about 0.25% to about 1.5%. The compounds of the present invention are particularly useful in stabilizing polyethylene and polypropylene. The antioxidants of the present invention are of high molecular weight. Therefore, the antioxidant of the present invention has a low volatility as compared with the low molecular weight antioxidant and is hard to be extracted from the polymer.

The polymer composition usually contains other compounding ingredients such as additives and reinforcing agents as used for vulcanized rubber products. Typical examples of such additives are metal oxidizers, reinforcing agents, pigments, fillers, softeners, other antioxidants, plasticizers, hardeners and the like.

The equipment necessary to synthesize the compounds of the present invention is well known to those skilled in the art. Hereinafter, representative examples carried out for producing the antioxidant of the present invention will be described. Unless stated otherwise, all parts and percentages given in the examples are by weight.

Example 1 illustrates the preparation of a representative polyphenol antioxidant. Examples 2, 3 and 4 illustrate various degrees of esterification of polyphenolic compounds. Other examples illustrate the preparation of substituted thiodipropionates by coupling unsaturated esters with hydrogen sulfide.

[0037]

【Example】

[0038]

Example 1 324 g of p-cresol and 5.5 g of boron trifluoride etherate were added to a 1 liter three-necked flask equipped with a thermometer, a water-cooled condenser and a stirrer,
And it heated to 90 degreeC. 132 g of dicyclopentadiene was added dropwise over 20 minutes. The solution was stirred for an additional 15 minutes. Reaction vessel temperature 190 ° C and 1
Unreacted cresol was distilled off under the condition of 5 mmHg. The obtained resin was dissolved in 300 ml of toluene. 25 g of toluene sulfuric acid were added, followed by as much isobutylene as possible at 60-70 ° C. The aqueous layer was decanted off and 2 g of dry sodium carbonate was added. Volatile components were distilled off under the conditions of a reaction vessel temperature of 180 ° C. and 15 mmHg. The weight of the residue was 360 g and the hydroxyl number was 347. The physical properties of this compound are shown in US Pat.
No. 305,522.

[0039]

Example 2 Using the same equipment as described in Example 1, 150 g of resin produced as described in Example 1.
With 30 g of triethylamine in tetrahydrofuran 1
Melted to 50 ml. 19 g of acryloyl chloride was added over 7 minutes at a temperature of 35 ° C. or lower. After stirring for 30 minutes, 150 ml of toluene was added. The reaction product was washed with warm water. The volatile components were removed under the conditions of a reaction vessel temperature of 180 ° C. and a vacuum in the presence of 1 g of dry sodium carbonate. The hydroxyl number of this product is 3
It was 13.

[0040]

Example 3 150 g of the product prepared as described in Example 1 was dissolved in a tetrahydrofuran (150 ml) / triethylamine (55 g) mixture. 25 ℃ ~ 33
Acryloyl chloride 3 over 15 minutes at a temperature of ℃
9 g was added. The reaction product was stirred for 50 minutes and diluted with 150 ml of toluene. The mixture was washed with warm water. 2 g of dry sodium carbonate was added, and volatile components were removed from the reaction product under the conditions of a reaction vessel temperature of 170 ° C. and a vacuum. The hydroxyl number of this product was 262.

[0041]

Example 4 150 g of the product prepared as described in Example 1 was dissolved in a tetrahydrofuran (150 ml) / triethylamine (75 g) mixture. 22 ° C-32 ° C
Acryloyl chloride 58 over 25 minutes at
g was added. The reaction product was stirred at 50 ° C. for 45 minutes and then diluted with 200 ml of toluene. After reacting for another 2 hours, the reaction product was washed with water. 2 g of sodium carbonate was added and the volatile components were removed from the reaction product at a reaction vessel temperature of 180 ° C. and under vacuum. The hydroxyl number of this product was 215.

[0042]

Example 5 100 g of the product prepared as described in Example 2 and 6 g of sodium acetate catalyst are charged with a thermometer,
Capacity with stirring blade, water-cooled condenser and gas inlet pipe 1
It was slurried in 500 ml of methanol and 100 ml of toluene in a 1 liter flask. Hydrogen sulfide gas was added at a temperature of 50 ° C. to 55 ° C. at a rate such that no gas was generated for 3.5 hours. The reaction product of Example 1 and the acryloyl chloride / H ₂ S adduct (molar ratio 1: 1) were separated from the volatile components under the conditions of a reaction vessel temperature of 180 ° C. and 35 mmHg. The sulfur content of this product was 2.24%.

Preferably, the sodium acetate catalyst is removed from the product while in solution by washing with water or filtration. A solvent such as benzene or toluene can be used.

[0044]

Example 6 100 g of the product prepared in Example 3
-B-alcohol 400 ml and toluene 100 ml
It was melted and then 6 g of sodium acetate was melted. 55
Hydrogen sulfide gas was added at a temperature of from 65 ° C to 65 ° C at a rate such that hydrogen sulfide was not generated for 6 hours. Then, the volatile components were removed by distillation under the conditions of a reaction vessel temperature of 150 ° C. and vacuum. The sulfur content of the reaction product of Example 1 and the H ₂ S adduct of acryloyl chloride (molar ratio 1: 2) was 2.64%. The catalyst is preferably removed as described in Example 5.

[0045]

Example 7 Using the same equipment as described in Example 5 above, 100 g of the resin prepared in Example 4 was dissolved with 400 g of sodium acetate in 400 ml of 2-B-alcohol and 150 ml of toluene. Hydrogen sulfide gas was added at a temperature of 60 ° C. to 70 ° C. at a rate such that hydrogen sulfide gas was not generated for 5.25 hours. The reaction product was heated under the conditions of a reaction vessel temperature of 75 ° C. and vacuum in order to remove methanol. 500 ml of toluene was added. This resin is 7
It did not completely dissolve at 0 ° C. Therefore, sodium acetate was not removed. Toluene was distilled off under the conditions of a reaction vessel temperature of 160 ° C. and a vacuum. The product reacted with H ₂ S, the molar ratio of reaction product of Example 1 and acryloyl chloride was 1: 3. The sulfur content is 2.
It was 98%.

[0046]

Example 8 116 g of 2,2'-methylene-bis- (4-methyl-6-t-butylphenol) was dissolved in 100 ml of tetrahydrofuran and 42 g of triethylamine. Over a period of 45 minutes, 33.7 g of acryloyl chloride was added at 30 ° C. Stir the contents of the flask for 1.5 hours,
Then, it was diluted with 150 ml of toluene. The contents of the flask were washed with water. After the final decantation, the traces of water which remained were distilled off and the reaction product was filtered. Volatile components were removed from the filtrate at a reaction vessel temperature of 65 ° C. During the distillation, the product started to crystallize out. Petroleum ether containing a small amount of methanol was added and the product was recrystallized. The melting point of the product, 2- (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methyl-6-t-butylphenyl acrylate, is 128 ° C to 131 ° C.
Met.

[0047]

Example 9 Using the same equipment as described in Example 5 above, the 2- (2-hydroxy-3-t-
Butyl-5-methylbenzyl) -4-methyl-6-t-
60 g of butylphenyl acrylate and 5.2 g of sodium acetate were dissolved in 400 ml of methanol. The reaction vessel was heated to 60 ° C. Hydrogen sulfide gas was added at such a rate that hydrogen sulfide gas was not generated for 8.5 hours. Analysis by thin layer chromatography confirmed that all the products of Example 8 had reacted. 65 contents of the flask under vacuum
Heated to ℃ and removed methanol. Benzene was added and the product washed with warm water. Volatile components were removed by distillation under vacuum at 60 ° C. to give a white waxy product. This product is bis [2- (2-hydroxy-3-t-butyl-5-methylbenzyl) -4.
-Methyl-6-t-butylphenyl] thiodipropionate. The sulfur content was 4.1%.

[0048]

Example 10 110 g of 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenol was dissolved in 150 ml of tetrahydrofuran and 45 g of triethylamine. 43.4 g of acryloyl chloride were added over 20 minutes at a temperature below 35 ° C. The reaction product was stirred for 2.5 hours and then diluted with 250 ml of toluene. Subsequently, it was washed with warm water. Volatile components were distilled off from the product under vacuum at a reactor temperature of 75 ° C. 1 product
46 g were obtained. This product is 2- (3,5-di-t-
It was butyl-4-hydroxybenzyl) -4-methylphenyl acrylate.

[0049]

Example 11 100 g of 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenyl acrylate prepared in Example 10 and sodium acetate 9
g was dissolved in 550 ml of methanol. Hydrogen sulfide gas
Hydrogen sulfide gas was added at a temperature of 55 ° C. at such a rate that it did not occur for 6.5 hours. Methanol is distilled off, benzene 60
0 ml was added. The flask contents were washed with warm water, and benzene was distilled off from the flask contents at 80 ° C. and 22 mmHg. 108 g of product was obtained.
The sulfur content was 4.45%. The product is bis [2- (3,
5-di-t-butyl-4-hydroxybenzyl) -4-
Methylphenyl] thiodipropionate. According to an alternative method of isolating the product, the product is precipitated by cooling the methanol solution. Wash with water, and
After drying, a white powder was obtained. Melting point 139-142
It was ℃.

[0050]

Example 12 Using the apparatus described in Example 1, 50 g of the resin prepared in Example 2 and 3 g of sodium acetate are added to 2 g of the resin.
% B-alcohol (benzene-alcohol mixture) 300
melted to ml. 15 g of 3-mercaptopropionic acid was added, and the mixture was reacted at 40 ° C to 50 ° C for 12 hours. The solvent was distilled off under vacuum at a reaction vessel temperature of 80 ° C. 200 ml of toluene was added to dissolve the resin. The contents of the flask were washed several times with warm water. 1 g of Na ₂ CO ₃ was added. Volatile components were removed from the product by distillation at a reaction vessel temperature of 80 ° C. under the conditions of 12 mmHg. 56 g of product was obtained. The sulfur content was 4.3%.

Traditionally, the antioxidant effect has been obtained by simply mechanically mixing antioxidants that act by different mechanisms. For example, GB 10782 discloses mixing dilauryl thiodipropionate with di-t-butyl p-cresol. However, such antioxidant systems are much more susceptible to extraction and volatilization than the chemically linked high molecular weight molecules as disclosed herein.

The compounds of the present invention were evaluated by oxygen absorption. The data obtained are shown below. Control compounds are disclosed in US Pat. No. 3,305,522. 1% oxygen
The time until absorption (unit: hr) was measured. The results are shown in Table 1. The test method is Industrial and Engin
eering Chemistry, Vol.43, p.456 (1951)
And ibid., Vol. 45, p. 392 (1953). Examples 2, 3 and 4 are typical examples for Examples 5, 6 and 7. Example 8 is a control example to Example 9.

In Tables 2 and 3, the symbols used represent various coloring properties in polypropylene. Coloring properties were measured as defined below. The symbol "Rd" is Ga based on a MgO standard with a value of 91.1.
It is the reflection speed by the rdner colorimeter. The position of this value along the achromatic axis from black to white is shown. If this value is high, it indicates that the reflection or gloss is strong.

The symbol "a" is predominantly red (when the value is +).
And also indicates that green is dominant (when the value is −). The intensity of either color is indicated by the magnitude of the value, regardless of the symbol. The standard value is the value given for MgO, 0.0.

The symbol "b" is predominantly yellow (when the value is +).
It also indicates that blue is dominant (when the value is −). The intensity of either color is indicated by the magnitude of the value, regardless of the symbol. The standard value is the value given for MgO, 0.0.

The color index is a measure of the overall tinting properties of the polymer and is calculated according to the formula Rd / a + b.

[0057] The compounds of the present invention were further tested according to the prescribed formulation.
The data obtained is shown in Table 4 below.

[0058] Although typical examples and details have been described in order to explain the present invention, those skilled in the art are not limited to these and can make various modifications and improvements within the scope of the spirit of the present invention. it is obvious.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 21/00 23/00 7107-4J C09K 15/12 // C07B 61/00 300

Claims (16)

[Claims] 1. The following formula (A) The polyphenol compound represented by the following formula (B) By reacting with an ester-forming compound represented by and then binding via a sulfur atom: A compound consisting of a reaction product obtained by producing a compound represented by: [wherein Z is a phenoxy group derived from a polyphenol compound having the structural formula (A); R ¹ and R ² are the same or a different group of hydrogen, C ₁ -C ₁₆ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₇ -C ₁₂ aralkyl group, C ₆ -C ₁₂ substituted aryl and unsubstituted C ₆ -C ₁₂ Selected from the group consisting of aryl groups; X is the same or different and (i) C
_A divalent group formed from a cyclic diene having non-adjacent carbon-carbon double bonds in a _5- C ₂₀ ring structure and (ii)-
S -, - O -, - CH 2 -, - S-S- and A divalent group selected from the group consisting of: selected from the group consisting of: Y is hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₅ -C ₈ cycloalkyl group, a C ₇ -C ₁₂ aralkyl group, C ₆ To C ₁₆ substituted aryl groups and C _{6 to} C ₁₆ unsubstituted aryl groups; n is selected from the group consisting of 0 and integers from 1 to 5; R ³ is hydrogen and C _{1 to} C ₂ alkyl. It is selected from the group consisting of groups; R ⁴ is hydrogen, C ₁ -C ₄ alkyl groups, C ₇ -C ₉ aralkyl group, C ₆ -C ₈ substituted aryl and unsubstituted C ₆ -C ₈ group consisting of an aryl group And V is selected from the group consisting of chlorine, iodine and bromine. ]. 2. A compound according to claim ¹ wherein R ¹ is a C ₁ -C ₂ alkyl group and said R ¹ group is para to the phenolic hydroxyl group. 3. Polyphenol compound (A) in an amount of 1 mol to 0.1 mol of ester-forming compound (B) per hydroxyl functional group, more preferably at least one per molecule of polyphenol molecule to be esterified. The compound of claim 1 which is treated with the hydroxyl functional group of. 4. The polyphenol compound is 2,6-bis-
(2-Hydroxy-3-t-butyl-5-methylbenzyl) -4
-Methylphenol; 2,2'-methylene-bis- (4-
Methyl-6-t-butylphenol); 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol); 2,2'-thio-bis- (4-methyl-6-t-butylphenol) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-methylphenol; 4- (3,5-di-t-
Butyl-4-hydroxybenzyl) phenol; 2- (3,
5-di-t-butyl-4-hydroxybenzyl) phenol; 2- (3,5-di-t-butyl-4-hydroxybenzyl) -5-methylphenol; 2,6-bis- (2-hydroxy-) A compound selected from the group consisting of 3-t-butyl-5-ethylbenzyl) -4-ethylphenol; and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -4-isopropylphenol. The compound according to 1. 5. The cyclic diene is 1,5-cyclooctadiene; cyclopentadiene; bicyclo [2.2.1] -2,5-
Heptadiene; Dicyclopentadiene; And a compound according to claim 1 selected from the group consisting of and 1,5,9-cyclododecadienes. 6. A compound according to claim 1, wherein the ester-forming compound is selected from the group consisting of acryloyl chloride and methacryloyl chloride. 7. The following formula (A) The polyphenol compound represented by the following formula (B) By reacting with an ester-forming compound represented by and then binding via a sulfur atom: A non-vulcanized polymer composition containing a compound consisting of a reaction product obtained by producing a compound represented by: [wherein Z is a phenoxy group derived from a polyphenol compound having a structural formula (A)] R ¹ and R ²
Are the same or different groups and are hydrogen, C ₁ -C ₁₆ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₇ -C ₁₂ aralkyl group, C ₆ -C ₁₂ substituted aryl group and unsubstituted C ₆ ~
Selected from the group consisting of C ₁₂ aryl groups; X is the same or different and is formed from (i) a cyclic diene having non-adjacent carbon-carbon double bonds in the C ₅ -C ₂₀ ring structure. that divalent group and (ii) -S -, - O -, - CH 2 -, - S
-S- and A divalent group selected from the group consisting of: selected from the group consisting of: Y is hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₅ -C ₈ cycloalkyl group, a C ₇ -C ₁₂ aralkyl group, C ₆ To C ₁₆ substituted aryl groups and C _{6 to} C ₁₆ unsubstituted aryl groups; n is selected from the group consisting of 0 and integers from 1 to 5; R ³ is hydrogen and C _{1 to} C ₂ alkyl. It is selected from the group consisting of groups; R ⁴ is hydrogen, C ₁ -C ₄ alkyl groups, C ₇ -C ₉ aralkyl group, C ₆ -C ₈ substituted aryl and unsubstituted C ₆ -C ₈ group consisting of an aryl group And V is selected from the group consisting of chlorine, iodine and bromine. ]. 8. The following formula (A) The polyphenol compound represented by the following formula (B) By reacting with an ester-forming compound represented by and then binding via a sulfur atom: A vulcanized rubber composition containing a compound consisting of a reaction product obtained by producing a compound represented by:
[Wherein Z is a phenoxy group derived from a polyphenol compound having the structural formula (A); R ¹ and R ² are the same or different groups and are hydrogen, C ₁ -C ₁₆ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₇ -C ₁₂ aralkyl group, C ₆ -C ₁₂ substituted aryl and unsubstituted C ₆ -C ₁₂
Is selected from the group consisting of aryl groups; X is the same or different groups, the carbon not adjacent to the ring structure of (i) C ₅ ~C ₂₀ - two formed from cyclic dienes having a carbon-carbon double bond valent group and (ii) -S -, - O -, - CH 2 -, - S-S-
and A divalent group selected from the group consisting of: selected from the group consisting of: Y is hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₅ -C ₈ cycloalkyl group, a C ₇ -C ₁₂ aralkyl group, C ₆ To C ₁₆ substituted aryl groups and C _{6 to} C ₁₆ unsubstituted aryl groups; n is selected from the group consisting of 0 and integers from 1 to 5; R ³ is hydrogen and C _{1 to} C ₂ alkyl. It is selected from the group consisting of groups; R ⁴ is hydrogen, C ₁ -C ₄ alkyl groups, C ₇ -C ₉ aralkyl group, C ₆ -C ₈ substituted aryl and unsubstituted C ₆ -C ₈ group consisting of an aryl group And V is selected from the group consisting of chlorine, iodine and bromine. ]. 9. A compound selected from the group consisting of polyethylene and polypropylene and having the formula (A): The polyphenol compound represented by the following formula (B) By reacting with an ester-forming compound represented by and then binding via a sulfur atom: A polymer containing an antioxidant amount of a compound consisting of a reaction product obtained by forming a compound represented by:
[Wherein Z is a phenoxy group derived from a polyphenol compound having the structural formula (A); R ¹ and R ² are the same or different groups and are hydrogen, C ₁ -C ₁₆ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₇ -C ₁₂ aralkyl group, C ₆ -C ₁₂ substituted aryl and unsubstituted C ₆ -C ₁₂
Is selected from the group consisting of aryl groups; X is the same or different groups, the carbon not adjacent to the ring structure of (i) C ₅ ~C ₂₀ - two formed from cyclic dienes having a carbon-carbon double bond valent group and (ii) -S -, - O -, - CH 2 -, - S-S-
and A divalent group selected from the group consisting of: selected from the group consisting of: Y is hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₅ -C ₈ cycloalkyl group, a C ₇ -C ₁₂ aralkyl group, C ₆ To C ₁₆ substituted aryl groups and C _{6 to} C ₁₆ unsubstituted aryl groups; n is selected from the group consisting of 0 and integers from 1 to 5; R ³ is hydrogen and C _{1 to} C ₂ alkyl. It is selected from the group consisting of groups; R ⁴ is hydrogen, C ₁ -C ₄ alkyl groups, C ₇ -C ₉ aralkyl group, C ₆ -C ₈ substituted aryl and unsubstituted C ₆ -C ₈ group consisting of an aryl group And V is selected from the group consisting of chlorine, iodine and bromine. ]. 10. A compound according to claim 1, wherein R ⁴ is selected from the group consisting of C ₁ -C ₂ alkyl groups and phenyl groups. 11. The following formula (A) The polyphenol compound represented by the following formula (B) Reacting with an ester-forming compound of
The product is reacted with a compound selected from the group consisting of hydrogen sulfide, thiols and thio derivatives and has the general formula: A method for producing a phenolic antioxidant comprising producing a compound represented by the formula: [wherein Z is a phenoxy group derived from a polyphenol compound having the structural formula (A); R ¹ and R ² are the same. Or a different group,
Selected from the group consisting of hydrogen, C ₁ -C ₁₆ alkyl groups, C ₅ -C ₈ cycloalkyl groups, C ₇ -C ₁₂ aralkyl groups, C ₆ -C ₁₂ substituted aryl groups and unsubstituted C ₆ -C ₁₂ aryl groups. X are the same or different groups, and (i) C _5-
A divalent group formed from a cyclic diene having non-adjacent carbon-carbon double bonds in the C ₂₀ ring structure and (ii) -S-,
-O-, -CH _2- , -S-S- and A divalent group selected from the group consisting of: selected from the group consisting of: Y is hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₅ -C ₈ cycloalkyl group, a C ₇ -C ₁₂ aralkyl group, C ₆ To C ₁₆ substituted aryl groups and C _{6 to} C ₁₆ unsubstituted aryl groups; n is selected from the group consisting of 0 and integers from 1 to 5; R ³ is hydrogen and C _{1 to} C ₂ alkyl. It is selected from the group consisting of groups; R ⁴ is hydrogen, C ₁ -C ₄ alkyl groups, C ₇ -C ₉ aralkyl group, C ₆ -C ₈ substituted aryl and unsubstituted C ₆ -C ₈ group consisting of an aryl group And V is selected from the group consisting of chlorine, iodine and bromine. ]. 12. The method according to claim 11, which comprises reacting the polyphenol compound and the ester-forming compound in a molar ratio of 1: 1. 13. The method according to claim 11, wherein the esterification reaction to form the unsaturated ester is carried out at a temperature within the range of 0 ° C. to the boiling point of the reaction compound. 14. The unsaturated ester at 0 ° C. in the presence of a solvent selected from the group consisting of toluene or methanol.
14. A method according to claim 13 which comprises binding via sulfur atoms by reacting with hydrogen sulfide gas at a temperature in the range of -65 ° C. 15. The method of claim 11 which comprises catalyzing the esterified phenol linkage with a base selected from the group consisting of potassium hydroxide, sodium acetate and sodium methoxide. 16. The thiol or thiol derivative is 3-
The method of claim 11 selected from the group consisting of mercaptopropionic acid, 2-mercaptopropionic acid and methyl 3-mercaptopropionic acid.