JPS61136582A - Antioxidant - Google Patents

Abstract

PURPOSE:An antioxidant being liquid at normal temp. and having a sufficient anti-oxidant activity on a wide range of org. materials, which has a structure of a specified formula. CONSTITUTION:An antioxidant having a structure of the formula I [wherein G is dihydric alcohol residue; A is aliph. dibasic acid residue; n is 2-20; R is a group of the formula II (wherein R1 is 4-8C tertiary alkyl; R2 is H or 1-8C alkyl; R3 is a group of the formula III or IV)]. The antioxidant is liquid at normal temp. and has a sufficient anti-oxidant activity on a wide range of org. materials. The subject org. material for the antioxidant includes a variety of synthetic resins, polymeric materials including rubber, synthetic ester-base lube oil, mineral oil, wax, soap, etc. The antioxidant is usually used in a concn. of about 0.001-10wt% for an org. material to be stabilized.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to superior antioxidants for protecting organic materials normally susceptible to oxidative degradation from oxidation.

It is extremely important to prevent oxidation of various organic materials, and today many antioxidants are added to synthetic resins, rubber products, oils and fats, lubricating oils, foods, etc.

However, conventional antioxidants have the disadvantage that they are not sufficiently effective against a wide range of organic materials, and most of them are solids, which is inconvenient in terms of formulation.

The inventors of the present invention have conducted intensive studies to obtain an antioxidant that has a sufficient antioxidant effect on a wide range of organic materials and is liquid at room temperature. As a result, the following compound has been developed. ,
The present invention was achieved by discovering that it has an excellent antioxidant effect on various organic materials and is liquid at room temperature.

That is, the present invention provides an antioxidant for organic materials represented by the following general formula.

[In the formula, G represents a residue of a dihydric alcohol, A represents a residue of an aliphatic dibasic acid, n represents 2 to 20, and R represents a group represented by the following formula.

p.

It represents a trialkyl group, R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R' represents C-4- or -
CHz-, 5-CH2- is shown. )] The antioxidant of the present invention will be explained below.

The dihydric alcohol residue represented by G includes ethylene glycol, propylene glycol, 1°4-butanediol, neopentyl glycol, 1°6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, Examples include residues such as teto-diethylene glycol, dipropylene glycol, tripropylene glycol, and 1,4-cyclohexane dimetatool.

The aliphatic dibasic acid residues represented by A include malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid,
Examples include residues of cepatic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, and the like.

Examples of the tertiary alkyl group having 4 to 8 carbon atoms represented by R1 include tertiary butyl, tertiary amyl 1, and tertiary octyl.

The alkyl group having 1 to 8 carbon atoms represented by R2 includes methyl, ethyl, propyl, butyl, nibutyl, tert-butyl, isobutyl, amyl, tertiary amyl, octinoP2 isooctyl, 2-ethylhexyl, tertiary octyl. etc. can be mentioned.

The above compound used as an antioxidant in the present invention is, for example, a lower alkyl ester of a carboxylic acid or a nucleic acid containing an alkylated phenyl group represented by R-OH or R-0-lower alkyl, I(O-G- It can be easily produced by reacting a dihydric alcohol represented by 01() and an aliphatic dibasic acid represented by HOCO-A-Cool in a desired ratio.

Next, the antioxidant of the present invention will be explained in more detail with reference to a specific synthesis example.

Synthesis Example 1 Propylene glycol 41.8 g (0.55 mol)
, adipic acid 58.5 g (0.4 mol), β-(3
, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate (58.4 g (0.2 mol)) and tetraisopropyl titanate (0.32 g) were taken and stirred at 165 to 170° C. for 2 hours under a nitrogen stream. After that, the pressure of the system was gradually reduced, and the
Stir for hours.

The obtained product was filtered through Celite, and the viscosity was 26,000 centipoise (25°C) and the refractive index was 1.4925 (25°C).
, pale yellow liquid with a molecular weight of approximately 1300 (antioxidant Wllhl)
I got it.

Synthesis Example 2 Dipropylene glycol 36.9 g (0,1375
mol), adipic acid 29.2 g (0.1 mol), β
27.8 g (0.05 mol) of -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and 0.046 g of tetraisopropyl titanate were taken and stirred at 165 to 170°C under a nitrogen stream for 2 hours. . Thereafter, the pressure of the system was gradually reduced, and the mixture was stirred for 11 hours at a maximum volume of 110 mm and 1 L at 185°C.

The obtained product was filtered through Celite, and the viscosity was 20.000 centipoise (25°C) and the refractive index was 1.4859 (25°C).
A pale yellow liquid (antioxidant filtrate 2) with a molecular weight of about 1,600 was obtained.

Antioxidants produced by the same procedure as in Synthesis Example 1 or 2 are shown below.

The above antioxidant of the present invention is useful as an antioxidant for various organic materials.

Examples of organic materials stabilized by the antioxidant of the present invention include polyethylene, polypropylene, polybutene-1, polybutadiene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polyvinyl chloride,
Polyvinylidene chloride, polyvinylidene fluoride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-chloride Vinylidene copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-urethane copolymer, petroleum resin, coumaron resin, polystyrene, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) Copolymers of ABS resin, MBS resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polyether polyester, wholly aromatic polyester , polycarbonate, polyphenylene oxide, polyamide, polyurethane, cellulose resin, phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, imprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene Examples include polymer materials including synthetic resins and rubbers such as copolymer rubber, lubricating oils based on synthetic esters, mineral oils, animal and vegetable oils, polyethylene oxide oils, waxes, soaps, and the like.

The antioxidant represented by the above general formula of the present invention is generally used in a concentration of about 0.001 to 10% by weight based on the organic material to be stabilized.

The antioxidants of the present invention may be used alone or in conjunction with other stabilizers. Other stabilizers include thioether antioxidants, organic phosphites or phosphonite compounds, other phenolic antioxidants, light stabilizers, etc. Especially when used in combination with thioether antioxidants, they may act synergistically. can significantly improve the stability of organic materials.

Examples of these thioether antioxidants include dialkyl thiodipropionates such as dilauryl, simiristyl, and distearyl, and butyl and octyl.
Polyhydric alcohol esters such as pentaerythritol of alkylthiopropionic acids such as , lauryl, and stearyl are mentioned, and the amount used is 0.01 to 100% based on the organic material.
5 parts by weight.

If necessary, the antioxidant of the present invention may also contain a heavy metal deactivator, a nucleating agent, a metal soap, an organic tin compound, a plasticizer, a pigment, a filler, an antistatic agent, a flame retardant, a lubricant, etc. be able to.

“Next, the effects of the antioxidant of the present invention will be specifically explained using Examples. However, the present invention is not limited by these Examples.

Example 1 After mixing the following formulation, it was kneaded at 180°C for 5 minutes, and then compression molded at 180°C and 250 Kg/c+w for 5 minutes to create a specimen with a thickness of 0.5 n++w. .

Using this sample, thermal stability in gear oscine at 150°C and 160°C was measured.

The results are shown in Table-1.

Calcium stearate 0.05 Dilaurylthiodipropionate 0.2 Antioxidant (Table 1)
0.1 Table-1 Example 2 ABS resin 100 parts by weight Calcium stearate 1 Antioxidant (Table-2) 0.3 The above formulation was extruded at 200°C to create pellets. Using this pellet, injection molding was performed at 230° C. to prepare a test piece.

After heating this test piece in a gear oven at 135°C for 30 hours, the degree of coloration was measured using a Hunter colorimeter.
The whiteness was determined. In addition, the Izod impact value of the test piece before and after heating was measured to determine its residual rate.

The results are shown in Table-2.

Table-2 Example 3 Intrinsic viscosity 0.56 dl/g (25°C in chloroform)
50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide), 2.5 parts by weight of polycarbonate, 47.5 parts by weight of polystyrene, 3 parts by weight of titanium dioxide and 0.3 parts by weight of an antioxidant, Pellets were prepared using a Henschel mixer and a booster. Using this pellet, a test piece was created by injection molding.

This test piece was heated in a gear oven at 125° C. for 100 hours, and the elongation retention and Izod impact value retention before and after heating were measured. The results are shown in Table-3.

Table 3 Example 4 Cis-1,4-isoprene rubber (average molecular weight 116,800
00), 0.2 parts by weight of an antioxidant, and 250 parts by weight of isooctane were uniformly dissolved and then the solvent was removed. The obtained rubber composition was heated in the open at 100° C. for 3 hours, and the intrinsic viscosity before and after heating was measured.

The results are shown in Table-4.

Table-4 Example 5 Paraffinic mineral oil (kinematic viscosity: 30 centistics/3
Add 1 part by weight of sorbitan monooleate and 0.5 parts by weight of an antioxidant to 100 parts by weight (0°C), JISK251
A test in the presence of an iron catalyst was conducted according to 5. The results are shown in Table-5.

Table-5

Claims (1)

[Claims] An antioxidant for organic materials represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, G represents the residue of dihydric alcohol, A represents the residue of aliphatic dibasic acid, n represents 2 to 20, and R represents the following Indicates a group represented by the formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 represents a tertiary alkyl group having 4 to 8 carbon atoms, R_2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R^1 represents -
Indicates C_2H_4- or -CH_2-S-CH_2-. )〕