JPH0730207B2 - Liquid stabilizer composition for organic substances - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel stabilizer composition for an organic substance, and more specifically, for an organic substance formed by condensing dinonylphenol, 4-alkylphenol and formaldehydes. Liquid stabilizer composition.

[Conventional technology and its problems]

Alkylated phenols such as 2,6-di-tert-butylphenol are used as stabilizers that have excellent ability to stabilize organic substances such as rubber, lubricating oils, polyolefins and the like against oxidative deterioration, and are non-polluting. Is generally known.

However, these stabilizers are not only volatile at the temperature at which they are used, but in the case of the production of general-purpose synthetic rubber, since they are solid at room temperature, they must be used after being finely pulverized and then emulsified. Since it requires complicated work when it is used, it is a very big problem from the viewpoint of streamlining the work process.

Also, as a non-polluting, non-volatile liquid stabilizer,
Although aralkylated phenols and methylenebisnonylated cresols are known, these stabilizers are stable against oxidative deterioration of organic substances even if the problems such as when handling the above solid stabilizers are improved. It was still inadequate in terms of the chemical effect.

Further, a stabilizer composed of a polymer obtained by condensing a 2-alkylated phenol and a 2,6-dialkylated phenol with formaldehyde has been proposed, but its effect is still insufficient.

Therefore, an object of the present invention is to have an excellent ability to stabilize an organic substance against oxidative deterioration, yet to be non-polluting and non-volatile.
Another object of the present invention is to provide a liquid stabilizer composition for organic substances, which is extremely advantageous in terms of workability.

[Means for solving problems]

As a result of intensive studies, the present inventors have found that a stabilizer composition that achieves the above object can be obtained by reacting dinonylphenol, monoalkylphenol and formaldehydes.

The present invention was made based on the above findings, and was obtained by reacting (1) dinonylphenol, (2) 4-alkylphenol, and (3) formaldehydes with each other, methylenebis (dinonylphenol) and 2,6-bis (diphenyl). The present invention provides a liquid stabilizer composition for organic substances, which comprises a nonylhydroxybenzyl) -4-alkylphenol as a main component and is a liquid substance at room temperature.

Hereinafter, the liquid stabilizer composition for organic substances of the present invention will be described in detail.

The dinonylphenol used in the present invention includes 2,4
-Dinonylphenol, 2,6-dinonylphenol, 2,5
-Dinonylphenol and a mixture thereof are mentioned, and particularly, 2,4-dinonylphenol or a mixture containing it as a main component is preferable.

The 4-alkylphenol used in the present invention includes 4-alkyl (for example, methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl,
Amino, tertiary amyl, hexyl, octyl, tertiary octyl, nonyl, cyclohexyl) phenol and the like can be mentioned. These phenol compounds may be used alone or in combination of two or more. The 4-alkylphenol may contain a small amount (usually 20 mol% or less) of 2-alkylphenol.

Examples of formaldehyde used in the present invention include formaldehyde, formalin, and paraformaldehyde.

The dinonylphenol / 4-alkylphenol molar ratio is preferably 60 to 90/40 to 10, more preferably 70 to 85/30 to 15, and the amount of the formaldehydes used should correspond to the above molar ratio. Selected.

In the production of the liquid stabilizer composition of the present invention, the above-mentioned three kinds of raw material compounds are usually used in the presence or absence of a solvent in the presence of a catalyst (for example, sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, boron trifluoride). , Stannous halide, stannic halide, ferrous halide, ferric halide, aluminum halide, etc.). Generally, a solvent is often used when the raw material compound is a solid, and as the solvent at this time, a hydrocarbon inert to the reaction, for example, benzene, toluene, xylene and the like is used.

The reaction product thus obtained is a substance that is liquid at room temperature and contains methylenebis (dinonylphenol) and 2,6-bis (dinonylhydroxybenzyl) -4-alkylphenol as main components. Not only is it extremely effective for stabilizing organic substances that are susceptible to deterioration, but it is also non-polluting and hardly volatile.

In addition, it is effective to carry out the reaction of the above-mentioned three kinds of raw material compounds in an atmosphere of an inert gas such as nitrogen because the degree of coloring of the product (the composition of the present invention) is further lowered. If the product has a high viscosity and is inconvenient to use, it may be diluted with a suitable hydrocarbon oil.

The liquid stabilizer composition of the present invention exerts a remarkable stabilizing effect by adding 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight to 100 parts by weight of an organic substance.

Furthermore, since the stabilizer composition for organic substances of the present invention is liquid at room temperature, for example, in the production of general-purpose synthetic rubber,
It is very convenient and effective from the viewpoint of preparation of the dispersion, and there is no deterioration in performance due to aging as seen in usual alkylated polyphenol type antioxidants.

The liquid stabilizer composition of the present invention contains other additives such as ultraviolet absorbers, light stabilizers, sulfur-based and / or phosphorus-based antioxidants, metal soaps, pigments, dyes, fillers, and metal inerts. It can be used in combination with agents and the like.

Examples of the organic substance stabilized by the liquid stabilizer composition of the present invention include natural rubber, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, ethylene / propylene terpolymer, butadiene rubber, isoprene. Rubber, isoprene / isobutylene copolymer rubber, ABS resin (including so-called heat-resistant ABS resin in which a part of styrene component is replaced with α-methylstyrene and so-called super heat-resistant ABS resin in which maleimides are copolymerized), high-impact polystyrene resin, Examples thereof include polyethylene, polypropylene, polystyrene, vinyl chloride resin, polyurethane, polyamide, polyester, polycarbonate, polyacetal, cellulose resin, lubricating oil, animal or vegetable oil, drying oil, wax and fatty acid.

〔Example〕

Next, the present invention will be described in detail with reference to production examples of the liquid stabilizer composition of the present invention and examples showing effects of the liquid stabilizer composition of the present invention, but the present invention is not limited thereto. Absent.

Production Example 1 88.3 g (0.255 mol) of dinonylphenol, 9.9 g (0.045 mol) of 4-nonylphenol, and paraformaldehyde 5.9
5 g (0.173 mol), p-toluenesulfonic acid 0.52 g, and xylene 50 g were charged into a 4-necked flask, and the mixture was stirred at 80 to 85 ° C for 3 hours under a nitrogen stream. The reaction was completed by dehydration under reduced pressure under xylene reflux. After the reaction, sodium carbonate 0.16
g and 30 g of water were added to neutralize the p-toluenesulfonic acid and deactivate the catalyst.

After separation of oil and water, 30 g of water was further added and washed with water. After dehydration and dexylene, 96.3 g (yield 96.0%) of a highly viscous brown liquid product (liquid stabilizer composition of the present invention) was obtained.

When this product was analyzed by liquid chromatography, it contained 55.6% bisphenol compound, 34.6% trisphenol compound, and 9.8% other.

Hydrocarbon solvent for this product (IP2028 made by Idemitsu Petrochemical Co., Ltd.)
When 13% by weight was added, the viscosity (25 ° C) was 16000cp, the refractive index (25 ° C) was 1.5190, and the specific gravity (25 ° C) was 0.954.

Production Example 2 88.3 g (0.255 mol) of dinonylphenol, 4.86 g (0.045 mol) of 4-methylphenol, and paraformaldehyde 5.
95 g (0.173 mol), p-toluenesulfonic acid 0.50 g, and xylene 50 g were charged into a 4-necked flask, and the mixture was stirred at 80 to 85 ° C. under a nitrogen stream for 3 hours. The reaction was completed by dehydration under reduced pressure under xylene reflux. Thereafter, the same operation as in Production Example 1 was carried out to obtain 90.7 g (yield 95.2%) of a highly viscous brown liquid product (the liquid stabilizer composition of the present invention).

When this product was analyzed by liquid chromatography, it contained 52.4% bisphenol compound, 32.7% trisphenol compound, and 14.9% other.

Production Example 3 138.5 g (0.40 mol) of dinonylphenol, 22.0 g (0.10 mol) of 4-nonylphenol, and paraformaldehyde 10.
3 g (0.30 mol), p-toluenesulfonic acid 0.85 g, and xylene 100 g were charged into a 4-neck flask, and 158.0 g (yield 95.5%) of a highly viscous brown liquid product was prepared in the same manner as in Production Example 2. (Liquid stabilizer composition of the present invention) was obtained.

When this product was analyzed by liquid chromatography, it contained 44.0% of bisphenol compound, 43.9% of trisphenol compound and 12.1% of others. Production Example 4 129.8 g (0.375 mol) of dinonylphenol, 27.5 g (0.125 mol) of nonylphenol , Paraformaldehyde 10.8
g (0.3125 mol), p-toluenesulfonic acid 0.85 g, and xylene 100 g were operated in the same manner as in Production Example 2 to give 154.
6 g (yield 95.1%) of a highly viscous yellow liquid product (liquid stabilizer composition of the present invention) was obtained.

When this product was analyzed by liquid chromatography, it contained 35.0% bisphenol compound, 51.6% trisphenol compound, and 13.4% other.

Example 1 Using a strip latex of styrene-butadiene rubber containing 2% of the test sample shown in Table 1 below, a coagulated product obtained by coagulating with saline and sulfuric acid by a conventional method was washed with water, and then vacuum dried. . The dried rubber was aged at 100 ° C. in a test tube heating aging tester according to JIS K-6301. The rubber was cut out at regular intervals, immersed in benzene, filtered through a 100-mesh stainless steel wire net, and the insoluble material was dried to obtain a gel component. The results of the gel formation test are shown in Table 1 below.

Example 2 The test sample shown in Table 2 below was blended into unstabilized polypropylene (Profax 6501 manufactured by Hercules Co., Ltd.) by dry mixing at a concentration of 0.6%, kneaded at 160 ° C to 120 ° C, and then 180 ° C. Was compression molded. The compression molded film was aged in an oven at 150 ° C. The performance of the test sample was measured by the time until the polymer became brittle. The results are shown in Table 2 below.

Example 3 The test sample shown in Table 3 below was added to neutral No. 150 lubricating base oil at a concentration of 0.1%, and the test temperature was measured by a rotary pump oxidation stability test method according to ASTM D 2272-67.
The oxygen absorption induction period was measured in the presence of 140 ° C ± 0.5 ° C, oxygen pressure of 7 kg / cm ² , and copper coil. The results of the lubricating oil oxidation stability test are shown in Table 3 below.

Example 4 Solution Polymerization Method without Stabilizer Stabilizers shown in Table 4 below in an amount of 1 part by weight per 100 parts by weight of solid rubber in a 15% benzene solution of cis-1,4-polybutadiene rubber (BR). Was added, and the mixture was stirred and mixed to form a uniform solution, and then a crumb of BR containing a stabilizer was obtained from a benzene solution by ordinary steam coagulation.

The crumb was allowed to stand in an 80 ° C. Gar type aging tester, and the time until 10% by weight of gel was formed was determined. Also, 196
The gel content was measured when the sample was left for 15 minutes in a tester at ℃.
The results are shown in Table 4 below.

The gel content was measured by placing approximately 0.2 g of rubber after aging in an 80-mesh Harris cage and immersing it in 100 cm ³ of toluene at room temperature for 24 hours to obtain a dry weight of toluene-insoluble matter remaining in the Harris cage. Was calculated and expressed as% by weight with respect to the amount of rubber before immersion in toluene.

Example 5 Stabilizer-free acrylonitrile-butadiene copolymer rubber (NBR, 33% by weight of bound acrylonitrile) was added on a mixing roll with an amount of 1% based on the resin content shown in Table 5 below. After kneading, an NBR sheet (0.5 mm thick) was obtained.

About the obtained NBR sheet, at 2 ℃ at 80 ℃ with a gear aging tester
After aging for 0 days, the change in Mooney viscosity (ML _{1 + 4} , 100 ° C.) was measured according to JIS K-6300. The result is the following fifth
Shown in the table.

Example 6 0.6 part by weight of a stabilizer shown in Table 6 below was added to 100 parts by weight of an unstabilized ABS resin (rubber content 50%), and after kneading, a test piece was prepared by pressing at 170 ° C. for 5 minutes. The test piece was placed in a gear oven at 180 ° C. and the thermal stability was measured. The results are shown in Table 6 below.

[Effect of the invention] The liquid stabilizer composition for an organic substance of the present invention has an excellent ability to stabilize an organic substance against oxidative deterioration, and is non-staining.
It is not volatile and is extremely advantageous in terms of workability.

Claims (1)

[Claims] 1. Methylenebis (dinonylphenol) and 2,6-bis (dinonylhydroxybenzyl) obtained by reacting (1) dinonylphenol, (2) 4-alkylphenol and (3) formaldehyde.
-4-A liquid stabilizer composition for organic substances, which is mainly composed of 4-alkylphenol and which is liquid at room temperature.