JPS6353988B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to 2-substituted phenyl-5-(3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivatives (hereinafter referred to as
It is abbreviated as "tetrazole derivative." ) and its derivatives. Polymers made of natural rubber (NR) or synthetic rubber such as butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), or acrylonitrile-butadiene-styrene resin (ABS), polyacrylonitrile, etc. Products undergo air oxidation deterioration at room temperature, thermal deterioration during heating, and oxidative deterioration in the presence of high oxygen levels. It is well known that polymer products are adversely affected by these deterioration phenomena, such as softening, hardening, or cracking. Conventionally, amine-based or phenol-based anti-aging agents have been developed as a countermeasure against this problem, but most of them have relatively small molecular weights, so they volatilize during use of polymer products. Alternatively, when it is immersed in an organic solvent such as gasoline, it is easily extracted, which has the disadvantage that its anti-aging effect is extremely diminished. Various countermeasures have been proposed in the past to compensate for these shortcomings, but all of them have advantages and disadvantages and have not yet been fully satisfactory. In view of the shortcomings of the prior art, it is an object of the present invention to improve known anti-aging agents and create a new anti-aging agent that has excellent anti-aging properties and is not extracted from polymeric products by organic solvents. The goal is to develop and provide new drugs. As a result of intensive research to achieve the above object, the inventors discovered a novel tetrazole derivative having a 3,5-di-alkyl-4-hydroxyphenyl group as a substituent, which was completely unknown until now. The present inventors have discovered that the present invention is an anti-aging agent with excellent anti-aging effects and non-extractability from polymeric products by organic solvents, and based on this knowledge, they have completed the present invention. The gist of this invention is as follows: 1. General formula [However, in the formula, R ¹ and R ² have 1 to 4 carbon atoms.
alkyl group, R ³ is hydrogen or has 1 to 4 carbon atoms
represents an alkyl group, a methoxy group, an ethoxy group, or a halogen. ] 2-substituted phenyl-5-(3',5'-
Di-alkyl-4'-hydroxyphenyl)tetrazole derivatives. 2 General formula [However, in the formula, R ¹ and R ² have 1 to 4 carbon atoms.
alkyl group, R ³ is hydrogen or has 1 to 4 carbon atoms
represents an alkyl group, a methoxy group, an ethoxy group, or a halogen. ] 2-substituted phenyl-5-(3',5'-
This is a polymer anti-aging agent consisting of a di-alkyl-4'-hydroxyphenyl)tetrazole derivative. The tetrazole derivative according to the present invention is a new compound, and representative examples thereof include 2-phenyl-5-(3',5'-di-methyl-4'-hydroxyphenyl)tetrazole, 2-phenyl-5- −(3′−
Methyl-4'-hydroxy-5'-tert-butylphenyl)tetrazole, 2-phenyl-5-(3',
5′-di-tert-butyl-4′-hydroxyphenyl)
Tetrazole, 2-p-tolyl-5-(3',5'-
di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-p-methoxyphenyl-5-(3',
5′-di-tert-butyl-4′-hydroxyphenyl)
Tetrazole, 2-p-ethoxyphenyl-5-
(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-p-chlorophenyl-5
-(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-p-n butylphenyl-5-(3',5'-di-tert-butyl-4'-hydroxyphenyl) enyl)tetrazole, 2-m-tolyl-5-
(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-m-chlorophenyl-5
Examples include -(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, but the present invention is not limited thereto. Next, the constituent elements of this invention will be specifically explained in detail. The tetrazole derivative according to this invention (1) is 3,
3, which is synthesized by reacting an allylsulfonylhydrazone of 5-di-alkyl-4-hydroxybenzaldehyde and a diazonium salt of an aniline derivative in a basic atmosphere;
As the allylsulfonylhydrazone of 5-di-alkyl-4-hydroxybenzaldehyde, for example, p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde, 3-methyl-4-hydroxy-5-tertiary p-toluenesulfonylhydrazone of butylbenzaldehyde, benzenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, etc. These include, but are not limited to. Examples of diazonium salts of aniline derivatives include aniline, p-toluidine, m-toluidine, p-ethylaniline, m
-ethylaniline, p-propylaniline, m-
Propylaniline, p-butylaniline, m-butylaniline, p-anisidine, m-anisidine, p-phenetidine, m-phenetidine, p-
Examples include diazonium salts of various aniline derivatives such as chloroaniline, m-chloroaniline, p-bromoaniline, and m-bromoaniline, but are not limited thereto. In addition, examples of the basic atmosphere include, but are not limited to, organic bases such as pyridine, dimethylaniline, and diethylaniline, and alcoholic aqueous solutions of inorganic bases such as sodium hydroxide and potassium hydroxide. isn't it. The polymeric anti-aging agent comprising a tetrazole derivative according to (2) of this invention is obtained by (a) kneading into a target polymeric material, and then (b) subjecting it to heat treatment. There is no particular restriction on the polymeric material to be used in (a), and a wide variety of materials can be mentioned. For example, telekirik liquid type synthetic rubber with an average molecular weight of 500 to 8,000, or regular solid natural rubber (NR) with an average molecular weight of 8,000 or more.
and synthetic rubbers such as isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), ethylene-propylene rubber (EPDM or EPM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), or These blend rubbers, as well as diene compounds, modified polyolefins, acrylonitrile resins, maleic acid ester resins, acrylonitrile-butadiene-
These include synthetic resins such as styrene resin (ABS). The heat treatment step (b) can be carried out during heating work before normal polymer processing, during kneading or melt mixing using an internal mixer or kneading roll machine in the processing process, or during heat vulcanization. Examples include during injection molding. The characteristic values of typical tetrazole derivatives according to the present invention are shown in Table 1, and the identification values are shown in Table 2. Next, embodiments of the present invention will be described. (1) Production of tetrazole derivatives Allylsulfonium hydrazone (hereinafter referred to as "[H 〕”
It is abbreviated as. ) 1 mole and 1 mole of [H]
~10 preferably 3 to 5 organic bases, or 1 to 10 moles per mole of [H], preferably 3
0.5 to 10, preferably 1 to 4, per mole of [H] is added to an alcoholic aqueous solution in which ~6 mol of an inorganic base is dissolved, and the mixture is heated at a temperature range of -72 to 50°C, preferably -30 to 10°C. Separately prepared diazonium salt of aniline derivative* is added in an amount of 0.5 to 5 moles per mole of [H], preferably 1 to 5 moles.
A 2 molar alcoholic aqueous solution is added dropwise with stirring for a predetermined period of time, and the mixture is further stirred at the same temperature for a predetermined period of time to obtain a tetrazole derivative as crystals. *Preparation of diazonium salt of alinine derivative Per mol of specified aniline derivative [H]
0.5 to 10 moles, preferably 1 to 5 moles, in a solution dissolved in an aqueous solution of hydrochloric acid at a predetermined concentration and a predetermined amount of ethanol, add 0.5 to 5 moles of sodium nitrite per mole of [H], preferably 1 to 2 moles, in a predetermined amount of water. An aqueous solution of the diazonium salt of the aniline derivative is prepared by dropping the mixture into an aqueous solution with stirring at a temperature of 0 to 10° C. to obtain an alcoholic aqueous solution of the diazonium salt of the aniline derivative. (2) Production of a polymeric composition containing a polymeric anti-aging agent A tetrazole derivative is added to the desired polymeric material by mixing with a kneading roll machine or an internal mixer or by melt-mixing according to conventional known techniques. do. The amount added may be determined as appropriate depending on various conditions such as the type of polymer material used and the desired degree of anti-aging effect, and cannot be determined unambiguously. The proportion may be 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight. If necessary, commonly used vulcanization accelerators, sulfur, antioxidants, plasticizers, flame retardants, fillers,
A filler and other additives can be mixed as appropriate. Next, heat treatment is performed using a predetermined heating means. The tetrazole derivative according to the present invention is converted into a nitrile imine derivative having a 3,5-di-alkyl-4-hydroxyphenyl group as a substituent, which has an anti-aging function, by heat treatment in a polymeric material. Then, the converted nitrile imine derivative can be used as C=C, -C≡N,
-OH, -CHO,

[Formula] It was developed based on the technical idea that it can be an excellent reactive anti-aging agent because it binds to active methylene.
Therefore, when the anti-aging agent-containing polymer composition comprising the tetrazole derivative according to the present invention is used as a polymer product, the derivative having an anti-aging function does not volatilize, or the anti-aging agent does not volatilize. Since the derivative is not extracted from the composition even when it is in contact with a solvent, it has a higher It exhibits an extremely excellent feature of being able to exhibit a high degree of aging resistance as a molecular product. EXAMPLES Hereinafter, the effects of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 3,5-
0.1 mol [31.8 g] of p-toluenesulfonylhydrazone of di-methyl-4-hydroxybenzaldehyde and 400 ml of pyridine are charged and kept at a temperature of -15 to -10°C while stirring. Separately, add 0.1 mole [7.1 g] of sodium nitrite (97%) to a solution of 0.1 mole [9.3 g] of aniline dissolved in 26 ml of 35% aqueous hydrochloric acid solution and 160 ml of 50% ethanol.
An alcoholic aqueous solution of diazonium salt of aniline prepared by dissolving 40 ml of water in 40 ml of water was added dropwise while stirring at a temperature of 0 to 10°C. Add it dropwise into the flask over 3 hours while stirring. After the dropwise addition was completed, the mixture was further stirred at the same temperature for 3 hours. The precipitated crystals were separated, washed with pyridine, and dried under vacuum to obtain the desired product, 2-phenyl-5-(3',5'-di-methyl-4'-hydroxyphenyl)tetrazole. The yield and characteristic values of the obtained target product are shown in Table 1, and the identified values are shown in Table 2. Example 2 0.1 mol of p-toluenesulfonylhydrazone of 3-methyl-4-hydroxy-5-tert-butylbenzaldehyde was used instead of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1. [36.0g]
2-phenyl-5-(3'-methyl-4'-hydroxy-5'-tert-butylphenyl)tetrazole was obtained in exactly the same manner as in Example 1, except that The yield and characteristic values of the obtained tetrazole derivative are shown in Table 1, and the identification values are shown in Table 2. Examples 3 to 9 p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde in place of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1 0.1 mole [40.2 g],
In addition, instead of aniline, a specified aniline derivative [in the case of aniline (Example 3), in the case of p-toluidine (Example 4), in the case of p-phenetidine (Example 5), in the case of p-chloroaniline (Example 6),
In the case of m-toluidine (Example 7), in the case of m-chloroaniline (Example 8), in the case of p-n butylaniline (Example 9)] Exactly the same as Example 1 except that 0.1 mol was used. Each tetrazole derivative was obtained. The yield and characteristic values of these obtained tetrazole derivatives are shown in Table-1, and the identification values are shown in Table-2. Example 10 In place of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1, 0.1 mol of benzenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde [38.8 g] was carried out in exactly the same manner as in Example 1, to obtain 16.0 g of 2-phenyl-5-(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole (yield: 45.7
%) was obtained. Example 11 0.1 mol of p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde was used instead of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1. (40.2g),
In addition, the procedure was carried out in exactly the same manner as in Example 1, except that 0.15 mol [14.0 g] of aniline, 39 ml of 35% aqueous hydrochloric acid solution, and 0.15 mol [10.7 g] of sodium nitrite (97%) were used. 19.1 g (yield 54.6%) of 5-(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole was obtained. Example 12 0.1 mol of p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde was used instead of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1. [40.2g]
Also, instead of 400 ml of pyridine, add 0.4 mol [17.2 g] of sodium hydroxide (93%) to 160 ml of 90% ethanol.
2-phenyl-5-(3',5'-
4.0 g (yield: 11.5%) of di-tert-butyl-4'-hydroxyphenyl)tetrazole was obtained. Examples 13-18 In a 50 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer with a mercury seal, liquid polybutadiene [trade name: Polybd R-45HT (molecular weight approximately 2500): manufactured by Alco Chemical Co., Ltd.] 10.8 g [0.2
Mol unit], 3 ml of xylene, and Example 3~
0.01 mol of the corresponding tetrazole derivative obtained in step 8 was added to each, stirred at 160 to 170°C for 30 minutes, and then cooled to 120 to 130°C. After diluting and dissolving the resulting solution by adding 40 ml of xylene, add it little by little into 500 ml of methanol while stirring at room temperature. After stirring for another 30 minutes at room temperature, let it stand and it will settle at the bottom. Liquid rubber was obtained by decanting method. The liquid rubber obtained here was reacted with a tetrazole derivative. Furthermore, the obtained liquid rubber was dissolved in 40 ml of benzene based on the same method as above, and then reprecipitation purification was performed twice by adding it to 500 ml of methanol while stirring and precipitating it. The liquid rubber obtained here was dissolved in 40 ml of benzene, and the benzene was distilled off under reduced pressure to obtain a sticky brown liquid rubber that had reacted with the tetrazole derivative. Regarding the obtained liquid rubber, the identification value derived from the reacted corresponding tetrazole derivative and the reaction rate of each tetrazole derivative with respect to the liquid rubber were measured. The results are shown in Table-3. Comparative Example 1 Examples 13 to 18, except that 2.2 g (0.01 mol) of 2,6-di-tert-butyl-4-methylphenol was used in place of the corresponding tetrazole derivatives used in Examples 13 to 18 above. It was carried out in exactly the same manner as in 18. The results are shown in Table-3. As can be seen from Table 3, the novel tetrazole derivative according to the present invention can be chemically bonded to liquid rubber at a reaction rate of 61 to 85%, and can also be chemically bonded to liquid rubber by reprecipitation using a benzene-methanol system. In contrast, the 2,6-di-tert-butyl-4-methylphenol of the comparative example is not chemically bound to the liquid rubber and therefore cannot be extracted in the benzene-methanol system. It was confirmed that it had been completely extracted by the reprecipitation operation. Examples 19-27 Isoprene rubber [Product name: CALIFLEX IR
-307: manufactured by Ciel Chemical Co., Ltd.] To 100 parts by weight, 0.03 mol of the tetrazole derivative obtained in Examples 1 to 9, 4 parts by weight of tetramethylthiuram disulfide, and 4 parts by weight of zinc oxide were mixed using a kneading roll machine. The mixture was added and kneaded, and the kneaded product was press-vulcanized at 170°C for 15 minutes. For the obtained vulcanized rubber, acetone
The maximum oxygen absorption rate at 130°C was measured before Soxhlet extraction using a mixed solvent of 80 ml + methanol 120 ml and after extraction (24 hours under reflux) using an oxygen absorption measuring device [manufactured by Shibayama Kagaku Kikai] to determine the anti-aging effect. I looked into it. The results are shown in Table 4. Comparative Examples 2 to 3 In place of the respective corresponding tetrazole derivatives used in Examples 19 to 27 above, nothing (Comparative Example 2) or 2,6-di-tert-butyl-
The same procedure as in Examples 19 to 27 was carried out except that 6.6 g (0.03 mol) of 4-methylphenol was used (Comparative Example 3). The results are shown in Table 4. As can be seen from Table 4, the novel tetrazole derivative according to the present invention maintains its anti-aging effect even after solvent extraction of the vulcanizate to which it is added, whereas the anti-aging effect of Comparative Example 2, 6- Di-tert-butyl-4
- It is observed that the anti-aging effect of methylphenol is significantly reduced after solvent extraction of the vulcanizate to which it is added. Example 28 2-phenyl-5-(3',
5′-di-tert-butyl-4′-hydroxyphenyl)
3.5 g [0.01 mol] of tetrazole in nitrogen at 170
After heating and mixing at ~180°C for 30 minutes, a 0.1 mm sheet was produced using a pressure molding machine. The obtained sheet was subjected to Soxhlet extraction using acetone (under reflux).
After 72 hours), the infrared absorption spectrum of hydroxyl groups derived from the added tetrazole derivative and the reaction rate of the tetrazole derivative with this synthetic resin were measured. The results are shown in Table-5. Comparative Example 4 In place of the tetrazole derivative used in Example 28 above, 3.4 g [0.01 mol] of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) was used.
The procedure was carried out in exactly the same manner as in Example 28, except that . The results are shown in Table-5. As can be seen from Table 5, the novel tetrazole derivative according to the present invention was chemically bonded to ABS resin with a reaction rate of 51.2% and could not be extracted by acetone, whereas the novel tetrazole derivative of the comparative example , 2'-methylenebis(4-methyl-6-tert-butylphenol) is not chemically bonded to the ABS resin and is therefore found to be completely extracted by acetone. Ta. As described above, 2-substituted phenyl-5-
The (3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivative is a new compound, and as can be seen from the examples, this compound has been used as an anti-aging agent in polymeric materials. It has been revealed that when heat treated, it becomes non-extractable to organic solvents and provides excellent anti-aging effects.

【table】

【table】 \
*1 In the structural formula

Claims (1)

[Claims] 1. General formula [However, in the formula, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a halogen. ] A 2-substituted phenyl-5-(3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivative represented by: 2 General formula [However, in the formula, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a halogen. ] A polymer anti-aging agent comprising a 2-substituted phenyl-5-(3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivative represented by the following.