JPS6228199B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antioxidant, and more particularly to a novel antioxidant for organic synthetic polymer materials, oils and fats, and petroleum. Organic synthetic polymer materials such as polyolefins and polyesters are subject to oxidative deterioration due to oxygen, resulting in a decrease in physical properties such as tensile strength and elasticity, and the generation of odors due to decomposition.Especially in fibers, films, etc.
Discoloration due to deterioration significantly reduces its commercial value. For this purpose, it has been proposed to use many antioxidants such as phosphorus compounds, amine compounds, and phenolic aromatic compounds. however,
The effects of these antioxidants vary, and some are effective in preventing discoloration but cannot prevent decomposition itself, while others prevent decomposition but are themselves unstable to heat etc. However, it has the drawbacks that it can be used only in a limited number of applications due to its poor compatibility.
Therefore, it has been desired to develop an antioxidant that has a high antioxidant effect, does not color products, and has good solubility. As a result of intensive studies, the present inventors have found that the above object has been achieved by using an antioxidant represented by the following general formula [] (hereinafter referred to as the compound of the present invention) in organic synthetic polymers, oils and fats, and petroleum. I discovered that. General formula [] In the formula, R ₁ and R ₂ each have 4 to 4 carbon atoms.
18 alkyl group or cycloalkyl group, and R ₃ and R ₄ each represent an alkyl group or morpholinomethyl group having 1 to 18 carbon atoms. In the general formula [], the alkyl group may be linear or branched, and R ₁
and R ₂ for example n-butyl, t-butyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, 2,2-dimethylpentyl, n-octyl, n-dodecyl, sec-dodecyl, n-hexadecyl or n - octadecyl, etc., for example, as R ₃ and R ₄ , in addition to the alkyl groups listed for R ₁ and R ₂ , methyl, ethyl, propyl, etc., cycloalkyl groups are preferably 5- to 7-membered, such as cyclopentyl, cyclohexyl or cycloheptyl, etc. Furthermore, each of these groups may have a substituent. In the general formula [], each of R ₁ and R ₂ is preferably a linear or branched alkyl group. Further, R ₃ and R ₄ are each preferably a linear or branched alkyl group, and these alkyl groups may be substituted with a hydroxy group, an aryl group, or an alkoxycarbonyl group. Particularly preferred is the case where R ₁ and R ₂ are the same alkyl group, and the case where at least one of R ₃ and R ₄ is a branched alkyl group. Typical specific examples of the compounds of the present invention are shown below, but the compounds used in the present invention are not limited thereto. The compounds of the present invention can be prepared by reacting a hydroquinone compound with an alkylating agent such as an organic halide or sulfuric acid ester in the presence of an alkali, or by reacting a hydroquinone diether compound with an organic halide, alcohol, or olefin in the presence of a Friedel-Crafts catalyst. The desired product can be easily synthesized by condensing the following compounds.
-It is described in specification No. 110363. There are already many documents regarding the antioxidant mechanism of organic materials by phenolic antioxidants. However, the oxidation prevention by a compound having no phenolic hydroxyl group and having an ether bond, such as the compound of the present invention, is new, and the mechanism of its prevention has not yet been determined. In addition, by forming an ether bond in the structure, the melting point is relatively lower than that of hydroquinone compounds, making it more oil-soluble, increasing its compatibility with various building materials, and making it suitable for organic synthetic polymer materials, oils and fats. A major advantage of the compounds of the present invention is that they can be easily added to petroleum products and petroleum products. The compound of the present invention may be added to the organic synthetic polymer material during the polymerization reaction, at the end of the reaction, or to the produced pellets, and it can also be added to oils, fats, and petroleum. The method is not limited. Examples of the organic synthetic polymer materials stabilized in the present invention include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, Chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer Polymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer , vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-
Halogen-containing synthetic resins such as methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, polyethylene,
α-olefin polymers such as polypropylene, polybutyne, poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and these copolymers, polystyrene, acrylic resin, styrene and other Copolymers with monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers,
Acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer, polyesters, polyamides,
Examples include polyurethanes, mixtures of these resins, block copolymers, graft copolymers, etc., which have excellent heat resistance, transparency, and are particularly useful in polyester films or polyolefin-coated papers used as photographic supports. Suitable for products that require high quality performance such as colorless properties. The oils and fats include lubricating oils such as di-(2-ethylhexyl) azelate and pentaerythritol tetracaproate, linseed oil, fat, beef fat, lard, peanut oil, cod liver oil, castor oil, palm oil, Examples of oils include animal and vegetable oils such as corn oil and cottonseed oil, and hydrocarbon substances such as gasoline, natural and synthetic diesel oil, mineral oil, fuel oil, and solid paraffin. Generally, the antioxidant of the present invention is added in an amount of 0.001 to 30% by weight based on the material to be stabilized. These compounds may be the same alone or may be used in combination of two or more. Since the use of other antioxidants in the present invention further increases the oxidative deterioration inhibitor of the present invention, they can be used as appropriate depending on the purpose of use. These antioxidants include other phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, and the like. Typical monovalent phenols include Guaialcohol, resorcinol monoacetate, Vanillin, butyl succilate, 2,6-di-tert-butyl-4-methylphenol, and 2-tert-butyl- 4-methoxyphenol, 2,4-dinonylphenol, 2.
3,4,5-tetradecylphenol, tetrahydro-α-naphthol, ortho-, meta- and para-cresol, ortho-, meta- and paraphenyl-
Phenols, ortho, meta and para-xylenol, The Garvenols Symmetrical xylenol, ortho, meta and para-decyl phenol, ortho, meta and para-nonylphenol, and ortho, meta and para-octylphenol, ortho- and meta- 3-butyl-
para-cresol, para-n-decyloxyphenol, para-n-decyloxycresol, nonyl-
n-Desyloxycresol, eugenol (Engenol), isoeugenol, thymol, glyceryl monosuccilate, methyl-para-hydroxybenzoate, ethyl-para-hydroxycinnamate, 4-benzyloxyphenol, para-acetylaminophenol, para-stearylamino Examples include phenol, para-di-chlorobenzoylaminophenol, para-hydroxysuccilanilide, α-naphthol, β-naphthol, and the like. Examples of polyhydric phenols include Orcinol, propyl gallate, catechol, resorcinol, 4-octylresorcinol, 4-
Dodecylresorcinol, 4-octadecylcatechol, 4-isooctylphloroglucinol, pyrogallol, hexahydroxybenzene,
4-Isohexylcatechol, 2,6-di-tert
-butylresorcinol, 2,6-diisopropylphloroglucinol, and the like. Examples of polyvalent bis, tris and tetrakisphenols include methylene bis (2,6-di-tert
-butylphenol), 2,2-bis(4-hydroxyphenyl)propane, methylenebis(p-
cresol), 4,4-oxobis(3-methyl-6-isopropylphenol), 2,2'-oxobis(4-dodecylphenol), 4,4'-n
-butylidene bis(2-tert-butyl-5-methylphenol), 4,4′-benzylidene bis(2
-tert-5-methylphenol), 4,4'-cyclohexylidenebis(2-tert-butylphenol), 4,4'-thiobisphenol, 4,4'-thiobis(3-methyl-6-tert -butylphenol), 2,2'-thiobis(4-methyl-6-tert
-butylphenol), 2,2'-methylenebis(4-methyl-6-(1'-methylcyclohexyl)
-phenol), 2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-
Methylphenol, 1,1,3-tris(2'-tris-4'-hydroxy-5'-tert-butylphenyl)butane, tetrakis[(4-hydroxy-
3,5-di-tert-butylphenyl)propionyloxymethyl]methane, 4-octadecyloxycarbonylethyl-2,6-di-tert-butylphenol, 2,4,6-tris(4-hydroxy-3,5- di-tert-butylbenzyl)-1.
Examples include 3,5-trimethylbenzene tris((4-hydroxy-3,5-tert-butylphenyl)propionyl)oxyethyl)isocyanurate. Typical phosphites include triphenyl phosphite, tricresyl phosphite, triisooctyl phosphite, tridecyl phosphite, tri-2-ethylhexyl phosphite, tri(dimethylphenyl) phosphite, triotadecyl phosphite, tri- (tert-octylphenyl) phosphite, tri(tert-nonylphenyl) phosphite, tri(2-cyclohexylphenyl) phosphite, tri-α-naphthyl phosphite, tri(phenylphenyl) phosphite, tri(2-phenylethyl) phosphite, Decyl thiophosphite, tri-p-
tert-butylphenyl thiophosphite, phenyl diethyl phosphite, phenyl di(2-ethylhexyl) phosphite, diphenyl mono(2-ethylhexyl) phosphite, diisooctyl monotolyl phosphite, monophenyl di-cyclohexyl phosphite, isooctyl diphenyl phosphite, diisooctyl monophenyl phosphite, monobutyl dicresyl phosphite, isooctyl di(octylphenyl) phosphite), di(2-ethylhexyl) mono(isooctylphenyl) phosphite, didecyl thio Diphenyl phosphite, ethylene phenyl phosphite, ethylene-
Examples include tert-butyl phosphite, ethylene isooctyl phosphite, ethylene cyclohexyl phosphite, and ethylene isohexyl phosphite. Di(phenyl) phosphite, monophenyl phosphite, mono(diphenyl) phosphite, dicresyl phosphite, monocresyl phosphite, di(o-isooctylphenyl) phosphite, di(p-ethylhexyl phenyl) phosphite, di (p-tert-butylphenyl) phosphite, di(p-tert-octyl phenyl) phosphite, di-2-ethylhexyl phosphite, mono-2-ethylhexyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, mono -dodecyl phosphite, 2-ethylhexyl phenyl phosphite, 2-ethylhexyl n-octylphenyl phosphite, dicyclohexyl phosphite,
Monocyclohexyl phosphite, di(2-cyclohexyl phenyl) phosphite, di-α-naphthyl phosphite, diphenylphenyl phosphite, di(2-phenylethyl) phosphite, dibenzyl phosphite, monobenzyl phosphite, n- butyl cresyl phosphite,
Didodecyl phosphite, decyl phenyl phosphite, tert-octyl phenyl phosphite, tert-butyl phenyl phosphite, ethylene phosphite, phenylcyclohexyl phosphite, isooctyl, tolyl phosphite, ditetrahydrofurfuryl phosphite phosphite, difuryl phosphite, etc. are used. Typical bisallyl phosphites include bis(4,4'thiobis(2-tert-butyl-5
-methylphenol)) isooctyl phosphite, mono(4,4'-thiobis(2-tert-butyl-5-methylphenol))) diphenyl phosphite, tri(4,4'-n-butylidene bis(2-
tert-butyl-5-methylphenol)) phosphite, (4,4'-benzylidene bis(2-tert
-butyl-5-methylphenol)) diphenyl phosphite, isooctyl-2,2'-bis(parahydroxyphenyl)propane phosphite,
Tridecyl-4,4'-n-butyldenbis(2-
tert-butyl-5-methylphenol), phosphite, 4,4'-thiobis(2-tert-butyl-
5-methylphenol) phosphite, 2-ethylhexyl-2,2'-methylenebis(4-methyl-6,1'-methylcyclohexyl)phenol phosphite, tri(2,2'-bis(parahydroxyphenyl)propane) Phosphite, tri(4,4'-thiobis(2-tert-butyl-5-methylphenol)phosphite, isooctyl(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonylphenyl) ) phosphite, tetratridecyl-4·4′-n-butylidenebis(2-tert-butyl-5-methylphenyl) diphosphite, tetraisooctyl-4·
4'-tribis(2-tert-butyl-5-methylphenyl) diphosphite, 2,2'-methylenebis(4-methyl-6,1'-methylcyclohexylphenyl) polyphosphite, isooctyl-4.
4'-isopropylidene-bisphenyl-polyphosphite, 2-ethylhexyl-2,2'-methylenebis(4-methyl-6,1'-methylcyclohexyl)phenyltriphosphite, tetratridecyl-4,4'-oxydiphenyl Diphosphite, tetra-n-dodecyl-4.4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, tetratridecyl-4.
4'-isopropylidene bisphenyl diphosphite, tri-tridecylbutane-1,1,3-tris(2'-methyl-5'-tertbutylphenyl-4')
Examples include triphosphite. Representative aromatic amines include: i.e. isopropoxyphenylamine,
Aniline, N-methylaniline, phenyl-β-
Naphthylamine, N-benzylaniline, diphenylamine, phenyl-α-naphthylamine, dioctyldiphenylamine and acetone, butyraldehyde-aniline condensation product, p-(p-tolyl-sulfonylamide)-diphenylamine,
Di-p-methoxy-diphenylamine, p-phenylenediamine, N.N'-diphenyl-p-phenylenediamine, di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenylenediamine, Dioctyl-p-phenylenediamine, N・N′-diphenylethylenediamine, N・N′-dilso-tolylethylenediamine, diphenylpropylenediamine, N・N′-
Di-sec-butyl-p-phenylenediamine, diaminophenylmethane, N-isopropyl-
N'-phenyl-p-phenylenediamine, m-
Toluenediamine, 6-phenyl-2,2,4-
Trimethyldihydroquinoline, 6-ethoxy-
2,2,4-trimethyldihydroquinoline, 2.
6-diethyl-2,3,4-trimethylhydroquinoline-2,2,4-trimethyldihydroquinoline (monomer or polymer), p-aminophenol, o-hydroxy-p-phenylenediamine,
p-hydroxy-o-phenylenediamine, o-
These include aminophenol, o-hydroxy-p-toluidine, p-hydroxy-o-toluidine, and the like. The organic mono- or polysulfide can be any sulfur compound containing one or more sulfur atoms bonded to the polysulfide unit. Representative compounds include n-dodecyl trisulfide, dioctyl sulfide, didodecyl sulfide, diamyl sulfide, and tertiary-dodecyl sulfide.
Dodecyl disulfide, tetramethylthiuram disulfide, tertiary-octylthiuram tetrasulfide, dimethylthiuram hexasulfide, tetraethylthiuram trisulfide,
Benzothiazyl disulfide, para-tert-butylphenyl trisulfide, dioctyl dithiodiacetate, dibenzyl disulfide, dibenzyl tetrasulfide, dipendyl trisulfide, dioctadecyl sulfide, bis( 2-oxynaphthyl) sulfide, didodecylcetyl sulfide, di-n-eicosyl sulfide, dicetyl sulfide, didodecyl octadecyl thiosuccinate, didodecyl dodecyl thiosuccinate, dioctadecyl dodecyl thiosuccinate, dioctadecyl Examples thereof include octadecyl thiosuccinate, didodecyl octadecyl thiomethyl succinate, didodecyl dodecyl thiomethyl succinate, dioctadecyl dodemyl thiomethyl succinate, dioctadecyl octadecyl thiomethyl succinate, and the like. Thiodialkanoic acid esters that can be used include, for example, monolaurylthiodipropionate, dilaurylthiodipropionate, butylstearylthiodipropionate, 2-ethylhexyllaurylthiodipropionate, di-2-ethylhexylthiodipropionate. , diisodecyl thiodipropionate, isodecyl phenyl thiodipropionate, benzyl lauryl thiodipropionate, benzyl phenyl thiodipropionate, mixed coconut oil alcohol and diesters of thiodipropionic acid, mixed cottonseed alcohol and thiodipropionate. Acidic esters of propionic acid, diesters of mixed tallow fatty alcohol and thiodipropionic acid, acidic esters of mixed soybean oil alcohol and thiodipropionic acid, cyclohexylnonylthiodipropionate, monoolethiodipropionate, hydroxyethyllaurylthiodipropionate Pionate, monoglyceryl thiodipropionate, glyceryl monostearate, monothiodipropionate, sorbityl isodecyl thiopropionate, polyester of diethylene glycol and thiodipropionic acid, polyester of triethylene glycol and thiodipropionic acid, hexamethylene Polyester of glycol and thiodipropionic acid, polyester of pentaerythritol and thiodipropionic acid, polyester of octamethylene glycol and thiodipropionic acid, polyester of p-dibenzyl alcohol and thiodipropionic acid, ethylbenzyl lauryl thiodipropionate , strontium stearyl thiodipropionate, magnesium oleyl thiodipropionate, calcium dodecylbenzyl thiodipropionate, mono(dodecylbenzyl)thiopropionic acid, thiodistearyl butyrate, dilauryl thiodiisobutyrate, 2-ethylhexyl lauryl thio Examples include dibutyrate and lauryl stearyl thiodiisobutyrate. By adding an ultraviolet absorber together with the antioxidant of the present invention to an organic material that is susceptible to oxidative deterioration,
Since the photostability of the organic material is improved, it is possible to appropriately select and use these materials depending on the purpose of use. These include benzophenone, benzotriazole, succilate, substituted acrylonitrile, various metal salts or metal chelates,
Particularly included are nickel or chromium salts or chelates, triazines, and the like. Furthermore, in order to improve the stiffness and dimensional stability of molded synthetic resins such as polyolefin, fillers, especially talc asbestos, calcium carbonate, etc., are added, or when they are not added, melamine, dicyandiamide compounds, etc. Effects can be seen by adding . Others as necessary, such as plasticizers, metal soaps, epoxy stabilizers, organic chelators, pigments, fillers, foaming agents, antistatic agents, antifogging agents, anti-brate-out agents, surface treatment agents, lubricants, flame release agents, light Stabilizers, fluorescent agents, antifungal agents, bactericides, metal deactivators,
Photodegradants, nonmetallic stabilizers, epoxy resins, borate esters, thiourea derivatives, processing aids, mold release agents, and the like can be included. Next, in order to clarify the effects of the present invention, examples of compositions containing the antioxidant of the present invention will be shown together with comparative examples. Example 1 In order to examine the stabilizing effect of the composition of the present invention using polypropylene resin, a composition having the following formulation was mixed for 10 minutes using a strainer. Using a 30 mm extruder (rotating machine 30 rpm),
A compound was created by extrusion at 230°C. This compound was compression molded for 5 minutes at 180° C. and 200 kg/cm ³ to form a sheet with a thickness of 1 mm. The obtained sheets were cut into pieces of 40 x 150 mm, each hung in an independent cylinder, and the oxidative deterioration onset time was measured. The inside of the cylinder was set at 1 atm and 150°C in an oxygen atmosphere. The results are shown in Table 1 below. (Composition) Unstabilized polypropylene resin 100 parts Diraryl thiodipropionate 0.15 Antioxidant 0.05

[Table] Example 2 Acrylonitrile-butadiene- of the present invention
In order to see the excellent effect of the styrene resin composition, after thoroughly mixing the sample according to the following formulation,
A sheet with a thickness of 2 mm was prepared using a kneading roll. The sheet was then aged at 210° C. for 10 minutes under a load of 50 kg/cm ² and the color tone of the sheet was measured. Regardless of the presence or absence of a stabilizer, the color of the sheet of acrylonitrile-butadiene-styrene resin gradually changes from white to light yellow, yellow, tan, and brown due to thermal deterioration. In this example, this was divided into 10 levels and compared. In other words, white was set as 1 and brown was set as 10. The test results are shown in Table 2 below. (Composition) Unstabilized acrylonitrile-butadiene-styrene 100 parts Calcium stearate 1.0 Trisnonyl phenyl phosphite 0.3 Antioxidant 0.5

[Table] Example 3 In order to examine the stabilizing effect of the composition of the present invention using vinyl chloride resin, the following formulation was kneaded at 170°C for 5 minutes using a mixing roll to create a sheet with a thickness of 1 mm. did. This sheet was subjected to an accelerated heating test in an oven at 190°C in an air atmosphere, and the results are shown in Table 3 below. (Composition) Polyvinyl chloride homopolymer 100 parts Dibutyltin bis(butyl maleate) 2.5 Butyl stearate 0.5 Antioxidant 0.3

[Table] Example 4 In order to examine the excellent stabilizing effect of the composition of the present invention using a polyester resin, a polyester was synthesized according to the following formulation, and the intrinsic viscosity at the initial stage of dissolution was measured using o-chlorophenol. Further 280℃
The intrinsic viscosity was measured after heating and deteriorating for 1 hour in a nitrogen stream, and the results of the rate of decrease are shown in Table 4 below. Synthesis method (formulation) Dimethyl terephthalate 100 parts Ethylene glycol 80 Calcium acetate 0.1 Antimony trioxide 0.05 The above mixture was heated at 150 to 220°C for 3 hours, and after distilling off the theoretical amount of methanol, the antioxidant (the amount added was (shown in the table) under reduced pressure of 1 mmHg or less.
Condensation was carried out at 280°C for 2 hours.

【table】

[Table] Example 5 100g of solid paraffin with a melting point of 52 to 4°C was placed in a reaction tube, and 0.05g of the antioxidant shown in Table 5 was added to the reaction tube and uniformly dissolved at 170°C. 170
Dry air was introduced into the molten paraffin at a rate of 2 l/hr while maintaining the temperature at °C, samples were taken at regular intervals, the peroxide value was measured, and the time at which the value suddenly increased (deterioration start time) was measured. The results are shown in Table 5.

[Table] Enol Example 6 Take 20g of cottonseed oil in a reaction tube, add 0.01g of the antioxidant shown in Table 6 into it, place it in a thermostat at 100℃, and blow dry air into the oil at 8l/hr. The peroxide value in the sample was measured, and the time at which the value suddenly increased (deterioration start time) was measured. The results are shown in Table 6 below.

[Table] Measurements were made using di-2-ethylhexyl sebacate or lard instead of cottonseed oil.
Compounds of the invention likewise showed good results.

Claims (1)

[Scope of Claims] 1. An antioxidant for organic synthetic polymer materials, oils and fats, and petroleum, represented by the following general formula []. General formula [] [In the formula, R ₁ and R ₂ each have 4 to 18 carbon atoms.
represents an alkyl group or a cycloalkyl group,
R ₃ and R ₄ each represent an alkyl group having 1 to 18 carbon atoms or a morpholinomethyl group. ]