JPH05331180A - Organic phosphite compound and use thereof - Google Patents

Abstract

PURPOSE:To provide a new compound excellent in resistance to hydrolysis, easy to purify and handle, useful as a stabilizer for organic materials, thus capable of giving organic materials with excellent processing stability, thermal stability, and oxidative deterioration preventiveness. CONSTITUTION:The compound of formula I [n is 1-6; when n is l, R is H, alkyl, etc.; when n is 2, R is alkylene, alkenylene, group of formula II (A is alkylene, O, S, etc.; R<1> to R<4> are each H or 1-8C alkyl), etc.; when n is 3, R is 2-6C alkane-tolyl; when n is 4, R is 2-6C alkane-tetrayl; when n is 5, R is 2-6C alkane- hexayl; X is l-6C alkylene, O, S, etc.], e.g. 2,2'-methylenebis(4,6-ditertiary butyl-3- methylphenyl)methyl phosphite. The compound of the formula I can be obtained, for example, by reaction of 2,2'-methylenebis(4,6-ditertiary butyl-3-methylphenyl) with a phosphorus halide in the presence of a proton acceptor for tertiary amines in a solvent under reflux while heating followed by reaction with a compound of formula R(OH)n is the presence of an amine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel organic phosphite compound useful as a stabilizer for organic materials and its use.

[0002]

2. Description of the Related Art Organic materials such as natural polymers, synthetic polymers, oils and fats, lubricating oils and hydraulic oils are oxidized to reduce their usefulness. Therefore, various antioxidants have been devised and added to these organic materials. Has been done. For example, it is known that stabilizing agents such as hindered phenol compounds, thioalkanoic acid ester compounds, organic phosphorus compounds, and aromatic amines are used alone or in a combination of two or more. In particular, synthetic resins such as polyethylene, polypropylene, acrylonitrile-butadiene-styrene resin, and polyvinyl chloride resin deteriorate due to the action of heat, oxygen, light, etc.,
It is known that the service life becomes extremely short due to discoloration or deterioration of mechanical strength. Many types of antioxidants have been developed to prevent such deterioration, and among them, phosphorus-based antioxidants have been used extensively to prevent discoloration of resins and to increase heat resistance and weather resistance. Recently, due to high temperatures for high-speed molding and high-temperature molding by alloying with engineering plastics, etc., there is an increasing demand for antioxidants with excellent heat resistance and process stability that are difficult to volatilize at high temperatures. Therefore, phosphite and phosphonite compounds have been developed and commercialized as phosphorus-based antioxidants.

JP-A-58-103537 discloses bis [2,2'-methylenebis (6-tertiary butyl-4-).
Methylphenyl)] 2,2-dimethyltrimethylene phosphite and other stabilized synthetic resin compositions are disclosed, and JP-A-2-284939.
In the publication, 2,2'-methylenebis (4,6-ditertiary
Disclosed is a stabilized polyolefin resin composition obtained by adding a phosphite compound such as secondary butylphenyl) 2-ethylhexyl phosphite.

[0004]

However, even in the commonly used phosphite and phosphonite compounds, the hydrolysis resistance of the compound itself, the thermal stability, and the non-coloring property and the thermal resistance of the resin composition containing the active ingredient. Stability is still unsatisfactory.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such circumstances, and as a result, added a specific organic phosphite compound excellent in hydrolysis resistance and thermal stability to an organic material. By doing so, it was found that a well-balanced organic material having improved processing stability and heat resistance, and improved coloring degree after initial heating and after heating was completed, and the present invention has been completed. That is, the present invention has the general formula

[Chemical 7] [In the formula, n = represents an integer of 1 to 6, and when n = 1, R
Is hydrogen, alkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl, 2,2,6,6 -Tetraalkyl-4-piperidyl is shown, and when n = 2, R is alkylene, alkenylene, alkynylene, optionally substituted cycloalkylene, optionally substituted arylene, formula (a )

[Chemical 8] (In the formula, A is alkylene, -O-, -S-, -SO.
-, -SO ₂ - shows ^{a, R 1, R 2, R} 3, R 4 represents hydrogen, a 1-8 alkyl carbon atoms the same or different. ), A group represented by formula (b)

[Chemical 9] A group represented by [hereinafter, the formula (b) may be referred to as an SPG group. ], Formula (c)

[Chemical 10] A group represented by the formula [hereinafter, the formula (c) may be referred to as a CKG group. ], Formula (d)

[Chemical 11] The group represented by the formula [hereinafter, the formula (d) may be referred to as an ETG group. ], Formula (e)

[Chemical formula 12] Represents a group represented by, and when n = 3, R has 2 carbon atoms
~ 6 linear or branched alkane-triyl, when n = 4, R represents a linear or branched alkane-tetrayl having 2 to 6 carbon atoms, n = 5 When,
R is a linear or branched alkane having 2 to 6 carbon atoms
Shows a pentile, and when n = 6, R represents a linear or branched alkane-hexayl having 2 to 6 carbon atoms,
X is alkylene having 1-6 straight or branched chain carbon, -O-, -S -, - SO- , -SO 2 - shows a. ] The organic phosphite compound represented by these, the stabilizer of the organic material which consists of this compound, and the stabilized organic material containing this compound as a stabilizer.

In the above definition, the substituent of R will be explained. Alkyl means methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, tertiary pentyl, hexyl, isohexyl, heptyl, octyl, 2
-Ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,
C1-C22 linear or branched alkyl such as icosyl and docosyl is shown, and alkenyl is vinyl,
1 to 2 carbon atoms such as 1-propenyl, allyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, docosenyl, etc. Or represents a branched alkenyl, and alkynyl is ethynyl, 1-propynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl. , Nonadecynyl, icosinyl, docosynyl and the like, which is a straight chain or branched alkynyl group having 2 to 22 carbon atoms, The cycloalkyl group of cycloalkyl which may be mentioned is a cycloalkyl having 3 to 7 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or other natural or synthetic terpene group, and is substituted. As a group, a linear or branched alkyl group having 1 to 8 carbon atoms (methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
The cycloalkyl may have 1 to 3 secondary butyl, tertiary butyl, heptyl, octyl etc.) or phenyl. The aralkyl group of aralkyl which may have a substituent is benzyl, 2-phenylethyl, 3-
Phenylpropyl, 4-phenylbutyl, 1-naphthylmethyl, 2-naphthylmethyl, 2- (2-naphthyl) ethyl, etc. are shown, and as a substituent, a linear or branched alkyl group having 1 to 8 carbon atoms or The cycloalkyl may have 1 to 3 phenyls and the like. The aryl group of aryl that may have a substituent represents phenyl or naphthyl, and as a substituent, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 24 carbon atoms, or The aryl may have 1 to 3 phenyl, the above alkyl substituted with an alkoxycarbonyl having 2 to 24 carbon atoms, and the like. Where the carbon number is 2
The 24 alkoxycarbonyls are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxy. Examples thereof include carbonyl, tridecyloxycarbonyl, tetradecyloxycarbonyl, pentadecyloxycarbonyl, hexadecyloxycarbonyl, heptadecyloxycarbonyl, octadecyloxycarbonyl, nonadecyloxycarbonyl, icosyloxycarbonyl and docosyloxycarbonyl. Alkylene is methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, methylmethylene, ethylmethylene, dimethylmethylene, diethylmethylene, dimethylethylene, diethylethylene, dimethyltrimethylene, diethyltrimethylene. Methylene, dimethyltetramethylene, diethyltetramethylene, nonamethylene, decamethylene, dodecamethylene and the like represent a straight or branched alkylene having 1 to 12 carbon atoms, alkenylene and vinylene, propenylene, butenylene, pentenylene, hexenylene, Carbon number 2 such as octenylene, nonenylene, desenylene, undecenylene, dodecenylene
Twelve linear or branched alkenylenes are shown, and alkynylene is ethynylene, propynylene, butynylene, pentynylene, hexynylene, heptynylene, octynylene, nonenylene, decynylene, undecynylene,
A cycloalkylene group of a cycloalkylene which may have a substituent and has a carbon number of 2 to 12 such as dodecynylene, or a branched alkynylene is cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene. , A cycloalkylene having 3 to 7 carbon atoms such as cycloheptylene or other natural or synthetic terpene-based group, and the substituent is a linear or branched alkyl group having 1 to 8 carbon atoms or For example, phenyl.
The arylene group of the arylene which may have a substituent represents phenylene, biphenylene or naphthalenediyl, and the substituent is a linear or branched alkyl group having 1 to 8 carbon atoms, for example, 1,4-phenylene, tolylene, 2,4,6-trimethyl-1,3-phenylene,
2,3,5,6-tetramethyl-1,4-phenylene,
2,5-ditertiary butyl-1,4-phenylene and the like. A linear or branched alkane having 2 to 6 carbon atoms-
Triyl refers to ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, etc., and straight-chain or branched alkane-tetrayl having 2 to 6 carbon atoms is ethanetetrayl, propanetetrayl, Butanetetrayl, pentanetetrayl, hexanetetrayl, etc. are shown, and the linear or branched alkane-pentile having 2 to 6 carbon atoms is propane pentile, butane pentile, pentane pentile, hexane pentile. And the linear or branched alkane-hexayl having 2 to 6 carbon atoms means propanehexayl, butanehexayl, pentanehexayl, hexanehexayl and the like. As a specific example of the formula (a),

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18] And so on. The linear or branched alkylene having 1 to 6 carbon atoms of X is methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene,
Hexamethylene, methylmethylene, ethylmethylene, dimethylmethylene, diethylmethylene, dimethylethylene, dimethyltrimethylene, etc. are shown.

The organic phosphite compound of the present invention can be produced by the following method known per se. For example, it can be produced by reacting a phosphorus halide, a bisphenol compound having a specific group of the present invention, and an alcohol or a phenol either sequentially or in one step. In addition, instead of phosphorus halide, triphenyl phosphite or trimethyl phosphite can be used for the transesterification reaction. That is, the organic phosphite compound of the present invention is produced by the following method. 2,2'-methylenebis (4,6-ditertiary butyl-3-methylphenyl) and phosphorus halide (phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, etc.) are used as a tertiary amine (triethylamine, In the presence of a proton acceptor such as N-methylmorpholine, pyridine, etc., preferably a solvent (benzene, toluene, hexane, heptane,
(Diethyl ether, tetrahydrofuran, chloroform, carbon tetrachloride, dichloroethane, chlorotoluene, chlorobenzene, etc.) in a cooling or at a temperature from room temperature to the boiling point of the solvent used, preferably with heating under reflux, and then the resulting phosphonate is obtained. Chloride compound and a compound represented by the general formula (II) R- (OH) n (II) (in the formula, each symbol has the same meaning as above) in a stoichiometric amount or more, and dimethylformamide, triethylamine, Tributylamine, morpholine, dimethylaniline, pyridine, quinoline, collidine, aminopyridine, 1,8-
In the presence of amines such as bis (dimethylamino) naphthalene and 1,8-azabicyclo [5.4.0] undec-7-ene, benzene, toluene, hexane, heptane, diethyl ether, tetrahydrofuran, chloroform,
It can be produced by reacting in a solvent such as carbon tetrachloride, dichloroethane, chlorotoluene and chlorobenzene under cooling or at a temperature from room temperature to the boiling point of the solvent used for 30 minutes to 24 hours.

The target compound thus obtained can be purified by a conventional method such as a recrystallization method or a chromatography method.

The novel organic phosphite compound of the present invention is a compound which is particularly excellent in hydrolysis resistance, is easy to purify and is easy to handle, and has almost no hygroscopicity.
It has characteristics such as good storage stability and low volatility at high temperature, and is useful as a stabilizer for preventing oxidative deterioration of organic materials.

The organic materials stabilized by the compound of the present invention are represented by high molecular weight polymers, fats and oils, mineral oils, and the like themselves, and the high molecular weight polymers include polyethylene, polypropylene and polybutene. , Polypentene, α-olefin polymers such as poly-3-methylbutylene or ethylene-vinyl acetate copolymers, polyolefins such as ethylene-propylene copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinyl chloride Vinylidene, polyvinylidene fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene,
Rubber chloride, 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 terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-
Isobutylene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, chlorinated Vinyl-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resin such as internal plastic polyvinyl chloride, petroleum resin, coumarone resin, polystyrene, styrene and other monomers (maleic anhydride,
Styrene resins such as copolymers with butadiene and acrylonitrile (also referred to as styrene copolymers), acrylonitrile-butadiene-styrene resins, acrylic acid ester-butadiene-styrene resins, methacrylic acid esters-butadiene-styrene resins, etc. , Polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin, polyacrylonitrile, linear polyester, polyphenylene oxide, polyamide, polycarbonate, modified polyphenylene oxide, polyacetal, polyurethane, fibrous resin, unsaturated polyester Resin, phenol resin, urea resin, melamine resin, epoxy resin, silicone resin, polyethylene terephthalate, reinforced polyethylene terephthalate Door, polybutylene terephthalate,
Examples thereof include polysulfone resin, polyether sulfone, polyphenylene sulfide, polyether ketone, polyetherimide, polyoxybenzoyl, polyimide, polymaleimide, and polyamideimide. Further, synthetic rubbers such as natural rubber, isoprene rubber, butadiene rubber, and acrylonitrile-butadiene copolymer rubber, and blended products of these resins may be used. The polyolefin, after polymerization, was subjected to a slight purification treatment including a step of removing the catalyst residue, and those which were purified to a relatively high degree, using a highly active catalyst, whether the catalyst removal step has not been performed, Alternatively, it may be a polyolefin containing a catalyst residue obtained by simplification, particularly a crystalline polyolefin obtained by using a Ziegler type catalyst having a halogen-containing magnesium compound as a catalyst carrier and not yet undergoing a catalyst residue removal step. (Japanese Patent Publication No. 62-4418
(See the official gazette).

More preferably, polyethylene (high density polyethylene, low density polyethylene, linear low density polyethylene, linear medium density polyethylene, etc.), polyolefin such as polypropylene, polyvinyl chloride, acrylonitrile-butadiene-styrene resin, polycarbonate, modified polyphenylene. Examples include oxide.

When the compound of the present invention is used as a stabilizer for organic materials, it is preferably 0.01 to 10 relative to the organic material.
It is preferable to blend in a proportion of wt%, more preferably 0.01 to 5 wt%.

Furthermore, by combining the stabilizer compound of the present invention with a phenol-based antioxidant or a sulfur-based antioxidant, an organic material having excellent thermal stability can be obtained. In the present invention, when one or more of these phenol-based antioxidants or sulfur-based antioxidants are combined and used as a stabilizer for organic materials, these antioxidants are preferably added to the organic material in an amount of 0.01 to It is preferable to add 10% by weight, more preferably 0.01 to 5% by weight. When used in combination, they may be added separately or may be added as a premixed compounding agent. The compounding ratio is 0.1 to the compound of the present invention.
A range of 10 times the amount is preferable.

As a phenolic antioxidant, 2,6-
Ditertiary butyl-4-methylphenol, 4-hydroxymethyl-2,6-ditertiary butylphenol, 2,6
-Ditertiary butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl 3- (4-hydroxy-3,5-ditertiary butylphenyl) propionate, distearyl (4-hydroxy-3) -Methyl-5-tertiary butyl) benzyl malonate, propyl gallate, octyl gallate, dodecyl gallate, tocopherol, 2,2'-methylenebis (4-methyl-6-)
Tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiarybutylphenol), 4,
4'-methylenebis (2,6-ditertiary butylphenol), 4,4'-butylidene bis (6-tertiary butyl-
m-cresol), 4,4′-thiobis (6-tertiary butyl-m-cresol), styrenated phenol, N,
N'-hexamethylene bis (3,5-ditertiary butyl-
4-hydroxyhydrocinnamide), bis (3,5-ditertiary butyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tert. Tertiary butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-ditertiary butyl-4-hydroxybenzyl)
Benzene, tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,6-hexanediol-bis [3-
(3,5-ditertiary butyl-4-hydroxyphenyl)
Propionate], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 1,3,5-tris (4 -Tertiary butyl-
3-Hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3,5-ditertiarybutyl-4-hydroxybenzyl) isocyanuric acid, triethyleneglycol-bis [3- (3 -Tertiary butyl-4-
Hydroxy-5-methylphenyl) propionate],
2,2'-Oxamide bis [ethyl 3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3,5-ditertiary butylanilino) -2, 4-Dioctylthio-1,3,5-triazine, bis [2-tertiary butyl-4-methyl-6-
(2-Hydroxy-3-tertiary butyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis [2-
[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane or 3,9-bis [2- [3-
(3,5-ditertiary butyl-4-hydroxyphenyl)
Propionyloxy] -1,1-dimethylethyl]-
Examples thereof include 2,4,8,10-tetraoxaspiro [5.5] undecane, but are not limited thereto.

Preferred phenolic antioxidants are 2,6-ditertiary butyl-4-methylphenol,
n-octadecyl-3- (4-hydroxy-3,5-ditertiary butylphenyl) propionate, tetrakis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxymethyl] methane, Triethylene glycol-bis [3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate],
4,4'-butylidene bis (6-tertiary butyl-m-cresol), 4,4'-thiobis (6-tertiary butyl-
m-cresol), 1,3,5-tris (3,5-ditertiary butyl-4-hydroxybenzyl) isocyanuric acid, 1,1,3-tris (2-methyl-4-hydroxy-5-tert. Tertiary butylphenyl) butane, 3,9-bis [2- [3- (3-tertiary butyl-4-hydroxy-5
-Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

The sulfur type antioxidants are thioalkanoic acid esters such as dilauryl ester, dimyristyl ester, distearyl ester, didocosyl ester, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Examples thereof include esters with polyhydric alcohols such as trishydroxyethyl isocyanurate.

Preferred are dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate and pentaerythritol-tetrakis (β-lauryl thiopropionate).

Further, in order to further improve the weather resistance of the organic material, an ultraviolet absorber or a light stabilizer may be used in combination with the stabilizer compound of the present invention.

As these ultraviolet absorbers and light stabilizers, phenyl salicylate, p-tertiary butyl phenyl salicylate, p-octyl phenyl salicylate,
2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octyl Oxybenzophenone, 2
-Hydroxy-4-isooctyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-di Sulfobenzophenone disodium, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2-
Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditertiary butylphenyl) benzotriazole, 2- (2-hydroxy-
3-tertiary butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-
Ditertiary butylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-5- (1,1,3,3-
Tetramethylbutyl) phenyl] benzotriazole,
n-Hexadecyl-3,5-ditertiary butyl-4-hydroxybenzoate, 2,4-ditertiary butylphenyl-3,5-ditertiary butyl-4-hydroxybenzoate, ethyl-2-cyano -3,3-diphenyl acrylate, {2,2'-thiobis [4- (1,1,3,3-
Tetramethylbutyl) phenolate]}-n-butylamine nickel, {2,2′-thiobis [4- (1,
1,3,3-Tetramethylbutyl) phenolate]} nickel, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) nickel, bis (2,2
2,6,6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-ditertiary butyl-4 -Hydroxybenzyl) -2-n-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-
4-Piperidyl) bis (3,5-ditertiary butyl-4)
-Hydroxybenzyl) malonate, tetrakis (2,
2,6,6-tetramethyl-4-piperidyl) -1,
2,3,4-butane tetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) imino-s-triazine-2,4-diyl] [(2,2,
6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, poly {(6-morpholino-s-
Triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino]}, 1-hydroxyethyl-2,2,6,6-
Tetramethyl-4-piperidinol / succinic acid condensate,
Cyanuric chloride / tertiary octylamine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate, salicylic acid type, benzophenone type, benzotriazole type, cyano Acrylate type, nickel compound type or 2,2,6,6-
Examples thereof include tetramethylpiperidine compounds.

Preferably, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-)
5-methylphenyl) benzotriazole, 2- (2-
Hydroxy-3-tertiary butyl-5-methylphenyl)
-5-chlorobenzotriazole, 2- (2-hydroxy-3,5-ditertiary butylphenyl) -5-chlorobenzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , Poly {[6- (1,
1,3,3-Tetramethylbutyl) imino-s-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6 , 6-Tetramethyl-4-piperidyl)
Imino]} and the like.

The compound of the present invention may be used in combination with other phosphorus-based antioxidants. Examples of the phosphorus-based antioxidants include tris (2,4-ditertiarybutylphenyl) phosphite and tetrakis. (2,4-ditertiary butylphenyl) -4,4'-biphenylenediphosphonite, bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiary Tertiary butyl-
4-Methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-ditertiary butylphenyl) -2-ethylhexylphosphite and the like can be mentioned.

In the present invention, an ultraviolet absorber, a light stabilizer,
At least one stabilizer such as phosphorus-based antioxidant
When used in combination as a stabilizer for organic materials, these stabilizers are preferably used in an amount of 0.01 to 1 relative to the organic material.
It is preferable to add 0% by weight, more preferably 0.01 to 5% by weight.

As described above, the organic phosphite compound of the present invention, a phenol-based antioxidant, a sulfur-based antioxidant,
There is provided a stabilizer for an organic material, which comprises at least one selected from an ultraviolet absorber, a light stabilizer and a phosphorus-based antioxidant.

The compound of the present invention alone or in combination with the compound of the present invention together with one or more kinds of stabilizers such as other antioxidants or ultraviolet absorbers and light stabilizers can be used as a method of blending into an organic material. Then, it can be processed in steps such as kneading and extrusion. The compounds of the present invention are further metal soaps, heavy metal deactivators, nucleating agents, organotin stabilizers, plasticizers, epoxy compounds, pigments, fillers, foaming agents, antistatic agents, flame retardants, lubricants, processing aids. It can also be used in combination with.

[0025]

The present invention will be described in detail below with reference to examples and experimental examples, but the present invention is not limited to these.

Example 1

(1) 2,2'-methylenebis (4,6-
Di-tertiary butyl-3-methylphenol) 27.1 g,
After dissolving 100 g of toluene and 9.5 g of pyridine, 9.6 g of phosphorus trichloride was added dropwise at 20 ° C or lower, and after completion of the addition, reaction was carried out at 90 to 100 ° C for 5 hours. After cooling to room temperature, the pyridine hydrochloride formed from the reaction solution was filtered off, washed thoroughly with toluene, the filtrate was concentrated under reduced pressure, and the concentrate was recrystallized from hexane to give 2,2 ′ having a melting point of 197 to 202 ° C.
25 g of white crystals of methylenebis (4,6-ditertiarybutyl-3-methylphenyl) phosphochloride were obtained. (2) 1.2 g of methanol, 50 g of toluene and 3.7 g of triethylamine were mixed, and then 17.1 g of 2,2′-methylenebis (4,6-ditertiarybutyl-3-methylphenyl) phosphochloride was added. Then, the mixture is reacted at room temperature for 30 minutes, and further at 90 to 100 ° C. for 6 hours. After completion of the reaction, the mixture is allowed to cool and triethylamine hydrochloride is filtered off. The filtrate was concentrated under reduced pressure, and the obtained yellow glass was purified by column separation to give 2,2'-methylenebis (4,6-ditertiarybutyl-3-methyl) as pale yellow crystals having a melting point of 190-192 ° C. Phenyl) methyl phosphite 8g
Is obtained. The obtained compound was confirmed to be the target by means of infrared absorption spectrum, nuclear magnetic resonance spectrum, mass spectrum, elemental analysis and the like.

The organic phosphite compounds of the present invention synthesized in the same manner are shown in Table 1 below.

[0029]

[Table 1]

[0030]

[Table 2]

Next, the effects of the present invention will be described with reference to experimental examples.

Experimental Example 1

Product heat volatility: Temperature rising rate 1 in nitrogen atmosphere
Weight reduction start temperature (℃) by thermogravimetric analysis under the condition of 0 ℃ / min
And the temperature (° C) at 10% weight loss was determined.

In the table, Comparative Examples 1 to 4 show the following compounds (the same applies to the following experimental examples). Compound of Comparative Example 1: 2,2'-methylenebis (4,6-
Ditertiary butylphenyl) -2-ethylhexyl phosphite

Compound of Comparative Example 2: Bis (2,4-dithird)
Butylphenyl) pentaerythritol diphosphite

Compound of Comparative Example 3: Tris (2,4-ditertiary butylphenyl) phosphite

Compound of Comparative Example 4: Tetrakis (2,4-
Ditertiary butylphenyl) -4,4'-biphenylenediphosphonite

The results are shown in Table 3.

[0039]

[Table 3]

From Table 3, the compound of the present invention has excellent volatility resistance and stability at high temperature.

Experimental Example 2 A compound of the present invention described in the following compounding examples was added to a polypropylene (homopolymer) resin containing no additive, mixed for 5 minutes with a mixer, and then pelletized with an extruder (20 mmφ). Created (die temperature 280 ℃). The melt index value (melt index: MI value) of this pellet was measured with a melt indexer (230 ° C., load 2.16 Kg), and the coloring degree (yellowness: YI) was determined with a color meter. Further, after mixing for 5 minutes with the above mixer, pellet production (resin temperature 280 ° C., residence time constant) was repeated four times with an extruder (20 mmφ), and the melt index value was measured.

The results are shown in Table 4.

[0043]

[Table 4]

From Table 4, the compounds of the present invention have a small yellowness (YI) and a small coloring property as compared with the comparative examples, and the melt index value of the pellet extruded 4 times repeatedly is small, and the processing stability is excellent. You can see that

[0045]

Industrial Applicability The organic phosphite compound of the present invention is a compound which is particularly excellent in hydrolysis resistance, is easy to purify and is easy to handle, and has almost no hygroscopicity, good storage stability, and high temperature. It has the characteristics of compensating the drawbacks of known phosphorus-based antioxidants, such as low volatility. By using this compound as a stabilizer for organic materials, it has excellent processing stability and thermal stability and prevents oxidative deterioration. The extremely effective organic material can be obtained.

Front page continuation (72) Inventor Tetsuji Ike, 955, Shoji, Yoshitomi-cho, Fukuoka Prefecture, Kazato, Kotomi Pharmaceutical Research Laboratories (72) Inventor, Matsuichi Horie, 2-6, Hirano-cho, Chuo-ku, Osaka No. 9 Yoshitomi Pharmaceutical Co., Ltd.

Claims (8)

[Claims] 1. A compound represented by the general formula (I): [In the formula, n represents an integer of 1 to 6, and when n = 1, R represents hydrogen, alkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, or optionally substituted. Good aralkyl, optionally substituted aryl or 2,2,6,6-tetraalkyl-4-piperidyl, when n = 2, R has alkylene, alkenylene, alkynylene, or a substituent Optionally substituted cycloalkylene, optionally substituted arylene, and a compound of the formula (a): (In the formula, A is alkylene, -O-, -S-, -SO.
-, -SO ₂ - shows ^{a, R 1, R 2, R} 3, R 4 represents hydrogen, a 1-8 alkyl carbon atoms the same or different. A group represented by formula (b): A group represented by the formula (c): A group represented by the formula (d): A group represented by the formula (e): Represents a group represented by, and when n = 3, R has 2 carbon atoms
~ 6 linear or branched alkane-triyl, when n = 4, R represents a linear or branched alkane-tetrayl having 2 to 6 carbon atoms, n = 5 When,
R is a linear or branched alkane having 2 to 6 carbon atoms
Shows a pentile, and when n = 6, R represents a linear or branched alkane-hexayl having 2 to 6 carbon atoms,
X is alkylene having 1-6 straight or branched chain carbon, -O-, -S -, - SO- , -SO 2 - shows a. ] The organic phosphite compound represented by these. 2. A stabilizer for an organic material comprising the organic phosphite compound according to claim 1. 3. A stabilized organic material containing the organic phosphite compound of claim 1 as a stabilizer. 4. The organic material is polyolefin, halogen-containing synthetic resin, petroleum resin, coumarone resin, polystyrene, styrene copolymer, styrene resin, polyvinyl acetate,
Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin,
Polyacrylonitrile, linear polyester, polyphenylene oxide, polyamide, polycarbonate, modified polyphenylene oxide, polyacetal, polyurethane, fibrin resin, unsaturated polyester resin, phenol resin, urea resin, melamine resin, epoxy resin, silicone resin, polyethylene terephthalate, Reinforced polyethylene terephthalate, polybutylene terephthalate, polysulfone resin, polyether sulfone, polyphenylene sulfide, polyetherketone, polyetherimide, polyoxybenzoyl, polyimide, polymaleimide, polyamideimide, natural rubber, synthetic rubber and blends thereof. Stabilizer according to claim 2, selected from the following: 5. The organic material is polyolefin, halogen-containing synthetic resin, petroleum resin, coumarone resin, polystyrene, styrene copolymer, styrene resin, polyvinyl acetate,
Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin,
Polyacrylonitrile, linear polyester, polyphenylene oxide, polyamide, polycarbonate, modified polyphenylene oxide, polyacetal, polyurethane, fibrin resin, unsaturated polyester resin, phenol resin, urea resin, melamine resin, epoxy resin, silicone resin, polyethylene terephthalate, Reinforced polyethylene terephthalate, polybutylene terephthalate, polysulfone resin, polyether sulfone, polyphenylene sulfide, polyetherketone, polyetherimide, polyoxybenzoyl, polyimide, polymaleimide, polyamideimide, natural rubber, synthetic rubber and blends thereof. The organic material according to claim 3, which is selected from products. 6. The organic phosphite compound according to claim 1 is used in combination with at least one selected from a phenol-based antioxidant, a sulfur-based antioxidant, an ultraviolet absorber, a light stabilizer and a phosphorus-based antioxidant. Stabilizer for organic materials. 7. The phenolic antioxidant is 2,6-ditertiary butyl-4-methylphenol, 4-hydroxymethyl-2,6-ditertiary butylphenol, 2,6-ditertiary butyl. -4-ethylphenol, butylated hydroxyanisole, n-octadecyl-3- (4-hydroxy-3,5-ditertiarybutylphenyl) propionate, distearyl. (4-hydroxy-3-methyl-5)
-Tertiary butyl) benzyl malonate, propyl gallate, octyl gallate, dodecyl gallate, tocopherol, 2,2'-methylenebis (4-methyl-6-tertiary
Butylphenol), 2,2'-methylenebis (4-
Ethyl-6-tertiary butylphenol), 4,4′-methylenebis (2,6-ditertiary butylphenol),
4,4'-butylidene bis (6-tertiary butyl-m-cresol), 4,4'-thiobis (6-tertiary butyl-
m-cresol), styrenated phenol, N, N'-
Hexamethylenebis (3,5-ditertiary butyl-4-hydroxyhydrocinnamide), bis (3,5-ditertiary butyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3 -Tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Ditertiary butyl-4-hydroxybenzyl) benzene, tetrakis [3- (3,5-ditertiary butyl-4-
Hydroxyphenyl) propionyloxymethyl] methane, 1,6-hexanediol-bis [3- (3,5-
Ditertiary butyl-4-hydroxyphenyl) propionate], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol ], 1,3,5-Tris (4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-Tris (3,5-ditertiary butyl-4)
-Hydroxybenzyl) isocyanuric acid, triethylene glycol-bis [3- (3-tertiary butyl-4-hydroxy-5-methylphenyl)] propionate, 2,
2'-Oxamide bis [ethyl 3- (3,5-di-third
Butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3,5-ditertiary butylanilino) -2,4-dioctylthio-1,3,5-triazine, bis [2-tertiary] Butyl-4-methyl-6-
(2-Hydroxy-3-tertiary butyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis [2-
[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane or 3,9-bis [2- [3-
(3,5-ditertiary butyl-4-hydroxyphenyl)
Propionyloxy] -1,1-dimethylethyl]-
The stabilizer of claim 6 which is 2,4,8,10-tetraoxaspiro [5.5] undecane. 8. The phenolic antioxidant is 2,6-ditertiary butyl-4-methylphenol, n-octadecyl-3- (4-hydroxy-3,5-ditertiary butylphenyl) propionate, Tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, triethylene glycol-bis [3- (3-tertiary butyl-4-hydroxy-5-methylphenyl] ) Propionate], 4,4′-butylidene bis (6-tertiary butyl-m-cresol), 4,4 ′
-Thiobis (6-tert-butyl-m-cresol),
1,3,5-Tris (3,5-ditertiary butyl-4-hydroxybenzyl) isocyanuric acid, 1,1,3-Tris (2-methyl-4-hydroxy-5-tertiary butylphenyl) Butane or 3,9-bis [2- [3- (3-
Tert-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy] -1,1-dimethylethyl]-
The stabilizer of claim 6 which is 2,4,8,10-tetraoxaspiro [5.5] undecane.