JPH09143189A - Phosphorous acid ester, its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new phosphorous acid ester produced by reacting a specific bisphenol with a phosphorus trihalide in the presence of a dehydrohalogenation agent and reacting the product with a bisphenol and useful, e.g. as a deterioration preventing agent for olefin polymers. SOLUTION: This new phosphorous acid ester is expressed by the formula I (R<1> , R<2> , R<4> and R<5> are each H, a 1-8C alkyl, a 5-8C cycloalkyl, phenyl, etc.; R<3> and R<6> are each H or a 1-8C alkyl; either one of X1 and X2 is methylene; X2 is single bond when X1 is methylene and X1 is S or a substituted methylene when X2 is methylene; each of R<1> and R<4> , R<2> and R<5> , R<3> and R<6> , and X<1> and X<2> are not H at the same time) and is useful as a deterioration preventing agent for olefin polymers. The compound can be produced by reacting a bisphenol expressed by the formula II with a phosphorus trihalide and reacting the product with a bisphenol expressed by the formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phosphite ester, a method for producing the same, and use thereof as a stabilizer for an olefin polymer.

[0002]

2. Description of the Related Art Olefin-based polymers represented by polyethylene, polypropylene and the like are deteriorated by the action of heat and oxygen during production, processing and use, resulting in molecular cutting and It is known that the product value is significantly impaired due to such phenomena as molecular crosslinking. For the purpose of solving the problems such as heat and oxidative deterioration, it has been conventionally known to stabilize various olefinic polymers by incorporating various phenolic antioxidants and phosphorus antioxidants. There is. For example, as a stabilizer for olefin polymers, Tris
(2,4-di-t-butylphenyl) phosphite, bis (2,4
Phosphorus antioxidants such as -di-t-butylphenyl) pentaerythritol diphosphite are used.

[0003] However, these known phosphorus-based antioxidants have a problem in that the effect of stabilizing against thermal deterioration and oxidative deterioration is insufficient. Also, for example, bis (2,4-
Di-t-butylphenyl) pentaerythritol diphosphite and the like are susceptible to hydrolysis, so they are hydrolyzed during storage and the stability effect varies, and in addition to the problem that stable quality organic materials cannot be obtained, There is also a problem that the metal in the processing machine is corroded by phosphorous acid or the like generated as a result of the decomposition.

On the other hand, as the storage stabilizer for organic isocyanate, two identical bisphenols are bonded to phosphorus.
2- [2- (4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3
-t-Butyl-5-methylbenzyl] -6-t-butyl-4-methylphenol, 2,2'-methylenebis (4-t-butyl-6-methylphenyl) with bisphenols and monophenols bound to phosphorus ) Cyclic phosphites such as phenyl phosphite have been proposed, and it has been shown that their stabilizing effects are substantially equivalent (JP-A-6-321957).

The present inventors have made various studies on various cyclic phosphites in order to find out a more excellent phosphorus-based antioxidant for olefin polymers, and as a result, have conducted intensive studies, and as a result, two bisphenols have been bonded to phosphorus. Specific cyclic phosphite
In addition to being excellent in hydrolysis resistance, it was found that, compared with cyclic phosphite in which bisphenols and monophenols are bound to phosphorus, it shows a particularly excellent stabilizing effect, and further studies of the present invention have been made. completed.

[0006]

That is, the present invention provides a compound represented by the general formula (I)

[0007]

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl group having 6 to 12 carbon atoms Represents an alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbons, and X ₁ and X ₂ are either Represents a methylene group, and when X ₁ is a methylene group, X ₂ is a methylene which may be substituted with a mere bond, a sulfur atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. Represents a group, and when X ₂ is a methylene group, X ₁ represents a sulfur atom, an alkyl group having 1 to 8 carbon atoms or a methylene group substituted by a cycloalkyl group having 5 to 8 carbon atoms, and at the same time, R ¹ and R ⁴ , R ² and R
⁵ , R ³ and R ⁶ and X ₁ and X ₂ are not the same. And a method for producing the same and a use thereof.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the phosphite ester represented by the formula (I) of the present invention, the substituents R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon number of 5
Represents a cycloalkyl group having 8 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group. Here, as typical examples of the alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl,
t-pentyl, i-octyl, t-octyl, 2-ethylhexyl and the like. Further, as typical examples of the cycloalkyl group having 5 to 8 carbon atoms, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, and as typical examples of the alkylcycloalkyl group having 6 to 12 carbon atoms,
For example, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-i-propylcyclohexyl and the like can be mentioned. Representative examples of the aralkyl group having 7 to 12 carbon atoms include:
For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like can be mentioned.

Of these, R ¹ and R ⁴ are preferably t-alkyl groups such as t-butyl, t-pentyl and t-octyl. R ² and R ⁵ are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl,
It is preferably an alkyl group having 1 to 5 carbon atoms such as t-pentyl.

The substituents R ³ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Examples of the alkyl group of to 8 include the same alkyl groups as described above. Preferably hydrogen atom or carbon number 1
To 5 alkyl groups, particularly preferably a hydrogen atom or a methyl group.

Also X₁, X_TwoIs either methylene
X represents a group₁Is a methylene group, X_TwoIs just a conclusion
, Sulfur atom, alkyl group having 1 to 8 carbon atoms or carbon
It may be substituted with a cycloalkyl group having a prime number of 5 to 8.
Represents a methylene group, X_TwoIs a methylene group, X₁Is
Sulfur atom or alkyl group having 1 to 8 carbon atoms or carbon number
A methylene group substituted with a cycloalkyl group of 5 to 8
Represent. Here, the number of carbon atoms as a substituent of the methylene group is 1 to
8 alkyl groups and 5 to 8 carbon cycloalkyl groups
Are the same alkyl groups and cycloalkyl groups as described above.
Group. These substituents are simultaneously R¹And R
^Four, R^TwoAnd R^Five, R^ThreeAnd R⁶And X₁And X _TwoIs each
It is never the same.

The phosphite represented by the above formula (I) can be obtained, for example, by the formula (II) in the presence of a dehydrohalogenating agent.

[0014]

The bisphenols represented by the formula (wherein R ¹ , R ² , R ³ and X ₁ have the same meanings as described above) are reacted with phosphorus trihalide, and then the general formula (III) is used.

[0016]

It can be produced by reacting a bisphenol compound represented by the formula (wherein R ⁴ , R ⁵ , R ⁶ and X ₂ have the same meanings as described above). Examples of the phosphorus trihalide used here include phosphorus trichloride and phosphorus tribromide. In particular, phosphorus trichloride is preferably used.

Further, examples of the dehydrohalogenating agent include amines, pyridines and pyrrolidines. The amines may be any of primary amines, secondary amines and tertiary amines, such as t-butylamine, t-pentylamine, t-hexylamine, t-octylamine, di-t-butylamine, di-t-pentyl. Examples thereof include amine, di-t-hexylamine, di-t-octylamine, trimethylamine, triethylamine, N, N-dimethylaniline and N, N-diethylaniline, with preference given to triethylamine. Examples of pyridines include pyridine and picoline, with pyridine being preferred. Examples of pyrrolidines include 1-methyl-2-pyrrolidine. Among these dehydrohalogenating agents,
Triethylamine and pyridine are preferably used.

The reaction is usually performed in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbons, aliphatic hydrocarbons, oxygen-containing hydrocarbons, and halogenated hydrocarbons. Examples of aromatic hydrocarbons include benzene, toluene, xylene, etc., examples of aliphatic hydrocarbons include n-hexane, n-heptane, n-octane, etc., and examples of oxygen-containing hydrocarbons include diethyl ether, Examples of the halogenated hydrocarbon such as tetrahydrofuran include chloroform, carbon tetrachloride, monochlorobenzene, dichloromethane, 1,2-dichloroethane, dichlorobenzene and the like. Among these, toluene, xylene,
Diethyl ether, tetrahydrofuran, dichloromethane and the like are preferably used.

As a reaction method, usually, in the presence of a dehydrohalogenating agent, first, bisphenol (II) is reacted with phosphorus trihalide to form an intermediate, and then bisphenol (III) is reacted. The two-step reaction method of letting it be adopted. In this method, phosphorus trihalide is preferably used in an amount of about 1 to 1.1 mole times, more preferably about 1 to 1.05 mole times, relative to the bisphenol (II). The dehydrohalogenating agent is preferably used in an amount of about 2 to 2.4 mol times, more preferably about 2 to 2.1 mol times with respect to phosphorus trihalide. The reaction between bisphenols (II) and phosphorus trihalide is usually 0 to 150.
It is carried out at about ℃. It is considered that this reaction produces an intermediate halogenophosphite, which may be isolated before being subjected to the next reaction, but is usually subjected to the reaction with the bisphenol (III) as it is as a reaction mixture. .

Then, in reacting the bisphenols (III), the bisphenols (II) are
It is usually used in an amount of 1 to 1.1 mole times. In this reaction, it is preferable to further add a dehydrohalogenating agent. The amount of the dehydrohalogenating agent to be added is preferably about 1 to 1.2 mol times with respect to the bisphenol (III). When the dehydrohalogenating agent is used in excess in the first reaction, the amount of the additional dehydrohalogenating agent is usually calculated including the remaining dehydrohalogenating agent. The reaction is usually carried out at a temperature of about 0 to 150 ° C. This reaction is preferably performed under reflux.

After completion of the reaction, the hydrohalide salt of the dehydrohalogenating agent produced by the reaction is removed, the solvent is further removed, and then an appropriate post-treatment such as crystallization or column chromatography is performed. Thus, the phosphite ester (I) of the present invention can be obtained.

Here, in the bisphenols (II) which are the raw materials of the phosphite esters (I), X ₁ has ₁ to 8 carbon atoms.
In the case of a methylene group substituted by an alkyl group, a cycloalkyl group having 5 to 8 carbon atoms, etc.
It can be produced by reacting an alkylphenol with an aldehyde according to a known method described in 22350 and US Pat. No. 2,538,355. When it is a sulfur atom, it can be produced by reacting an alkylphenol with sulfur chloride according to, for example, a known method.

In the other raw material, bisphenol (III), X ₂ is an alkyl group having 1 to 8 carbon atoms and 5 carbon atoms.
When the cycloalkyl group of -8 is a methylene group which may be substituted or a sulfur atom, it can be produced, for example, by the same method as described above, while when X ₂ is a simple bond, It can also be produced by condensing an alkylphenol in accordance with a known method described in Japanese Patent Publication No. 2-47451. Further, as the bisphenols (II) and (III), if they are commercially available, they can be used.

Thus, the phosphite ester (I) of the present invention is obtained, and typical compounds include, for example, the compounds shown below. 2- [2- (4,8-di-t-butyl-
2,10-Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylbenzyl] -4,6-di- t-butylphenol, 2- [2- (4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) Oxy-3,5-di-t-pentylbenzyl] -4,6-di-t-pentylphenol, 2- [1- (2- (4,8
-Di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,
3,2] Dioxaphosphocin-6-yl) oxy-3-t-butyl
-5-Methylphenyl) ethyl] -6-t-butyl-4-methylphenol, 2- [1- (2- (4,8-di-t-butyl-2,10-dimethyl
-12H-Dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylphenyl) ethyl] -4,6-
Di-t-butylphenol, 2- [1- (2- (4,8-di-t-butyl
-2,10-Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-pentylphenyl) ethyl] -4,6 -Di-t-pentylphenol, 2- [2- (4,
8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,
3,2] Dioxaphosphocin-6-yl) oxy-3-t-butyl
-5-Methylphenyl] -6-t-butyl-4-methylphenol,

2- [2- (4,8-di-t-butyl-2,10-dimethyl-1
2H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylphenyl] -4,6-di-t-butylphenol, 2- [2- (4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-
Yl) oxy-3,5-di-t-pentylphenyl] -4,6-di-t
-Pentylphenol, 2- [1- (2- (4,8-di-t-butyl-
2,10-Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3-t-butyl-5-methylphenyl) thio] -6-t- Butyl-4-methylphenol, 2- [2-
(2,4,8,10- Tetra-t-butyl-12H-dibenzo [d, g] [1,
3,2] Dioxaphosphocin-6-yl) oxy-3-t-butyl
-5-Methylbenzyl] -6-t-butyl-4-methylphenol, 2- [2- (2,4,8,10-tetra-t-butyl-12H-dibenzo
[d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5
-Di-t-pentylbenzyl] -4,6-di-t-pentylphenol, 2- [1- (2- (2,4,8,10-tetra-t-butyl-12H-dibenzo [d, g ] [1,3,2] Dioxaphosphocin-6-yl) oxy
-3-t-Butyl-5-methylphenyl) ethyl] -6-t-butyl
-4-methylphenol

2- [1- (2- (2,4,8,10-tetra-t-butyl-12H
-Dibenzo [d, g] [1,3,2] dioxaphosphin-6-yl)
Oxy-3,5-di-t-butylphenyl) ethyl] -4,6-di-t
-Butylphenol, 2- [1- (2- (2,4,8,10-tetra-t-butyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6
-Yl) oxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenol, 2- [2- (2,4,8,10-
Tetra-t-butyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3-t-butyl-5-methylphenyl] -6-t-butyl- 4-methylphenol, 2- [2- (2,4,
8,10- Tetra-t-butyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylphenyl] -4, 6-di-t-butylphenol, 2- [2- (2,4,8,
10-Tetra-t-butyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-pentylphenyl] -4,6- Di-t-pentylphenol, 2- [1- (2-
(2,4,8,10-Tetra-t-butyl-12H-dibenzo [d, g] [1,3,
2] Dioxaphosphocin-6-yl) oxy-3-t-butyl-5
-Methylphenyl) thio] -6-t-butyl-4-methylphenol,

2- [2- (2,4,8,10-tetra-t-pentyl-12H
-Dibenzo [d, g] [1,3,2] dioxaphosphin-6-yl)
Oxy-3-t-butyl-5-methylbenzyl] -6-t-butyl-4
-Methylphenol, 2- [2- (2,4,8,10-tetra-t-pentyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6
-Yl) oxy-3,5-di-t-pentylbenzyl] -4,6-di
-t- Pentylphenol, 2- [1- (2- (2,4,8,10-tetra-t
-Pentyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3-t-butyl-5-methylphenyl) ethyl] -6-t-butyl-4 -Methylphenol, 2- [1-
(2- (2,4,8,10-tetra-t-pentyl-12H-dibenzo [d, g]
[1,3,2] Dioxaphosphocin-6-yl) oxy-3,5-di-
t-Butylphenyl) ethyl] -4,6-di-t-butylphenol, 2- [1- (2- (2,4,8,10-tetra-t-pentyl-12H-dibenzo [d, g] [ 1,3,2] Dioxaphosphocin-6-yl) oxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-
Pentylphenol, 2- [2- (2,4,8,10-tetra-t-pentyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6
-Yl) oxy-3-t-butyl-5-methylphenyl] -6-t-
Butyl-4-methylphenol,

2- [2- (2,4,8,10-tetra-t-pentyl-12H
-Dibenzo [d, g] [1,3,2] dioxaphosphin-6-yl)
Oxy-3,5-di-t-butylphenyl] -4,6-di-t-butylphenol, 2- [2- (2,4,8,10-tetra-t-pentyl-12H
-Dibenzo [d, g] [1,3,2] dioxaphosphin-6-yl)
Oxy-3,5-di-t-pentylphenyl] -4,6-di-t-pentylphenol, 2- [1- (2- (2,4,8,10-tetra-t-pentyl-12H- Dibenzo [d, g] [1,3,2] dioxaphosphocin-6-
Yl) oxy-3-t-butyl-5-methylphenyl) thio]-
6-t-butyl-4-methylphenol, 2- [2- (4,8-di-t-butyl-2,10,12-trimethyl-12H-dibenzo [d, g] [1,3,2]
Dioxaphosphocin-6-yl) oxy-3-t-butyl-5-
Methylbenzyl] -6-t-butyl-4-methylphenol, 2-
[2- (4,8-di-t-butyl-2,10,12-trimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy
-3,5-Di-t-butylbenzyl] -4,6-di-t-butylphenol, 2- [2- (4,8-di-t-butyl-2,10,12-trimethyl-1
2H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-pentylbenzyl] -4,6-di-t-
Pentylphenol,

2- [2- (2,4,8,10-tetra-t-butyl-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6
-Yl) oxy-3-t-butyl-5-methylbenzyl] -6-t-
Butyl-4-methylphenol, 2- [2- (2,4,8,10-tetra
-t-Butyl-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylbenzyl] -4,6 -Di-t-butylphenol, 2- [2- (2,4,8,10
-Tetra-t-butyl-12-methyl-12H-dibenzo [d, g] [1,
3,2] dioxaphosphin-6-yl) oxy-3,5-di-t-
Pentylbenzyl] -4,6-di-t-pentylphenol, 2-
[2- (2,4,8,10-Tetra-t-pentyl-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3- t-Butyl-5-methylbenzyl] -6-t-butyl-4-methylphenol, 2- [2- (2,4,8,10-tetra-t-pentyl
-12-Methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylbenzyl] -4,
6-di-t-butylphenol, 2- [2- (2,4,8,10-tetra-t
-Pentyl-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-pentylbenzyl] -4,6-di -t- Pentylphenol etc.

The phosphite ester (I) of the present invention is effective in stabilizing the olefin polymer against heat deterioration and oxidative deterioration. Examples of the olefin-based polymer that can be stabilized by the present invention include the followings, which can be used alone or as a mixture of two or more kinds, but are not limited thereto. It is not something that will be done.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-P)
E), linear low density polyethylene (LLDPE), (2)
Polypropylene, (3) Methylpentene polymer, (4) E
EA (ethylene / ethyl acrylate copolymer) resin, (5)
Ethylene / vinyl acetate copolymer resin, (6) ethylene / vinyl alcohol copolymer resin, (7) ethylene / propylene copolymer, etc. Among them, polyethylene, such as HD-P
It is preferably used for polyolefins such as E, LD-PE, LLDPE and polypropylene.

When the phosphite ester (I) of the present invention is contained to stabilize an olefin polymer, the phosphite ester (I) is added in an amount of 0.01 to 100 parts by weight of the olefin polymer. It is preferable to blend in the range of about 2 parts by weight. If the amount used is less than 0.01 parts by weight, the stabilizing effect is not always sufficient, and even if the amount is more than 2 parts by weight, the effect corresponding to that cannot be obtained, which is economically disadvantageous.

The olefin-based polymer containing the phosphite ester (I) of the present invention may further contain other additives, if necessary, such as a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Antioxidant, UV absorber, hindered amine light stabilizer, lubricant, plasticizer, flame retardant, nucleating agent, metal deactivator, antistatic agent, pigment, inorganic filler,
An antiblocking agent, and also a neutralizing agent such as calcium stearate and hydrotalcite may be contained. These additives can, of course, be blended at the same time as the phosphite ester (I), or at a stage different from the phosphite ester (I).

Examples of the phenol-based antioxidants for rice include the following. n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3,5-di-t-butyl-4-hydroxyfell) propionate], 2-t-butyl-6- (3 -t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di -t
-Pentylphenyl acrylate,

3,9-Bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,2'-ethylidenebis (4,6-di-t-butylphenol) , 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6- t-butylphenol), 2,6-
Di-t-butyl-4-methylphenol etc.

Examples of sulfur antioxidants include the following. Dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, pentaethaslithyl Tetrakis (3-lauryl thiopropionate) etc.

Examples of the ultraviolet absorber include the followings. 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone,
Bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone,

2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3-t-butyl-2-hydroxy-5-
Methylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-5-t-octylphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl ) Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl ] -2H- benzotriazole,

2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2,2'-methylenebis [4- t-butyl-6- (2H-
Benzotriazol-2-yl) phenol], poly (3 ~
11) (Ethylene glycol) and methyl 3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate condensate, 2-ethylhexyl
3- [3-t-butyl-5- (5-chloro-2H-benzotriazole
-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl 3- [3-t-Butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t-butyl-5- (5-chloro-2H-benzo Triazol-2-yl) -4-hydroxyphenyl] propionic acid and the like.

Examples of the hindered amine light stabilizer include the followings. Screw (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis
(1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-
Di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acroyl-2,2,6,6-tetramethyl-4-
Piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) decandioate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-t-butyl
-4-Hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2-
(2,2,6,6-Tetramethyl-4-piperidyl) amino-N- (2,
2,6,6-tetramethyl-4-piperidyl) propionamide,

Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate, 1,2,3,4-
Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-
Mixed esterification products with piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-
Mixed esterification product of tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,
4,8,10- Tetraoxaspiro [5.5] undecane mixed esterified product, 1,2,3,4-butanetetracarboxylic acid and 2,
2,6,6-Tetramethyl-4-piperidinol and 3,9-bis
(2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed esterified product,

Poly [(6-morpholino-1,3,5-triazine), a polycondensation product of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine -2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl
-4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl) ((2,2,6 , 6-Tetramethyl-4-piperidyl) imino)
Hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl) hexamethylenediamine and 1,2-dibromoethane polycondensate, N, N ', 4,7-tetrakis [4,6-bis (N
-Butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-
1,10-diamine, N, N ', 4-tris [4,6-bis (N-butyl-
N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,
3,5-Triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ', 4,7-tetrakis [4,6-bis (N-butyl-N-
(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,
5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ', 4-tris [4,6-bis (N-butyl-N- (1,2,2,6 ,
6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

In blending the phosphite (I), or other additives used as necessary, with the organic material, any known method and apparatus for obtaining a homogeneous mixture may be used. it can. For example, when the olefin-based polymer is a solid polymer, the phosphite ester (I) or further other additives may be directly dry blended with the solid polymer, or the phosphite compound or further Other additives can also be incorporated into the solid polymer in the form of masterbatches. In the case where the olefin polymer is a polymer, it may be added to the polymer solution during or immediately after the polymerization in the form of a solution or dispersion of the phosphite (I) or further other additives. On the other hand, when the olefin polymer is a liquid such as oil, the phosphite ester (I) or further other additives can be directly added and dissolved,
It is also possible to add the phosphite (I) or other additives in a state of being dissolved or suspended in a liquid medium.

[0045]

The phosphite ester (I) of the present invention is
It has excellent performance as a stabilizer for olefin polymers,
The olefin polymer containing this compound is stable against heat deterioration and oxidative deterioration during production, processing and use, and becomes a high quality product.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1: 2- [2- (4,8-di-t-butyl-2,1
0-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylphenyl] -4,
Production of 6-di-t-butylphenol (Compound 1) 2,2'-methylenebis (6-t-butyl-4-methylphenol) was added to a 1 liter four-necked flask equipped with a thermometer, a stirrer and a condenser. 31 g, toluene 200 ml, triethylamine 1
After charging 9.3 g and replacing the inside of the container with nitrogen, 12.5 g of phosphorus trichloride was added dropwise with stirring. 3 at 80 ° C after completion of dropping
After incubating for an hour, add a solution consisting of 9.6 g of triethylamine, 200 ml of toluene and 37.3 g of 4,4 ', 6,6'-tetra-t-butyl-2,2'-biphenol to this and incubate at 85 ° C for 6 hours. did. Then, after cooling to room temperature, the formed triethylamine hydrochloride was filtered. After the filtrate was concentrated, the residue was recrystallized from hexane to obtain 43.4 g of white crystals.

Mass spectrometric value (FD-MS): m / z 770 Melting point: 212 to 217 ° C. Elemental analytical value (C ₅₁ H ₇₁ O ₄ P): P 4.0% (calculated value 4.0%)

Example 2: 2- [1- (2- (4,8-di-t-butyl-
2,10-Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-butylphenyl) ethyl] -4,6- Di-t-butylphenol (Compound 2)
Production of Example 1 In a 0.5 l flask, 20.9 g of 2,2'-methylenebis (6-t-butyl-4-methylphenol) 30.9 g
, Toluene 250 ml, triethylamine 19.2 g were charged, phosphorus trichloride was added dropwise, and after keeping warm, triethylamine 9.6
g and toluene 100 ml and 2,2'-ethylidene bis (4,6-di-t-
(Butylphenol) was carried out in accordance with Example 1 except that a solution of 39.9 g was charged to obtain 58 g of white crystals.

Mass spectrum (FD-MS): m / z 806 Elemental spectrum (C ₅₃ H ₇₄ O ₄ P): P 3.7% (calculated 3.8%) Melting point: 228 to 231 ° C.

Example 3: 2- [1- (2- (4,8-di-t-butyl-
2,10-Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3,5-di-t-pentylphenyl) ethyl] -4,6- Production of di-t-pentylphenol (Compound 3) In Example 1, 30.9 g of 2,2'-methylenebis (6-t-butyl-4-methylphenol) was used in a 0.5 l flask.
, Toluene 250 ml, triethylamine 19.3 g were charged, phosphorus trichloride was added dropwise, and after incubation, triethylamine 9.6
g and toluene 100 ml and 2,2'-ethylidene bis (4,6-di-t-
(Pentylphenol) was carried out in the same manner as in Example 1 except that a solution of 44.9 g was charged to obtain 58 g of white crystals.

Mass spectrum (FD-MS): m / z 863 Elemental spectrum (C ₅₇ H ₈₃ O ₄ P): P 3.4% (calculated 3.6%) Melting point: 205-207 ° C.

Example 4: 2- [2- (2,4,8,10-Tetra-t-butyl-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin Preparation of -6-yl) oxy-3-t-butyl-5-methylbenzyl] -6-t-butyl-4-methylphenol (Compound 4) In Example 1, using a 0.5 l flask, 2, 2'-ethylidene bis (4,6-di-t-butylphenol) 39.9 g,
Toluene 100 ml and triethylamine 19.3 g were charged, phosphorus trichloride was added dropwise, and after incubation, a solution consisting of triethylamine 9.6 g, toluene 100 ml and 2,2'-methylenebis (6-t-butyl-4-methylphenol) 31 g was charged. The procedure of Example 1 was repeated to obtain 51 g of white crystals.

Mass spectrum (FD-MS): m / z 806 Elemental spectrum (C ₅₃ H ₇₄ O ₄ P): P 3.8% (calculated 3.8%) Melting point: 213-215 ° C.

Example 5: 2- [2- (2,4,8,10-tetra-t-pentyl-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin -6-yl) oxy-3-t-butyl-5-methylbenzyl] -6-t-butyl-4-methylphenol (Compound 5)
Production of Example 1 In a 0.5 l flask, 45 g of 2,2'-ethylidene bis (4,6-di-t-pentylphenol),
Toluene (200 ml) and triethylamine (19.3 g) were charged, phosphorus trichloride was added dropwise, and after incubation, a solution consisting of 9.6 g of triethylamine, 100 ml of toluene and 31 g of 2,2'-methylenebis (6-t-butyl-4-methylphenol) was charged. The procedure of Example 1 was repeated to obtain 44 g of white crystals.

Mass spectrum (FD-MS): m / z 863 Elemental spectrum (C ₅₇ H ₈₃ O ₄ P): P 3.4% (calculated 3.6%) Melting point: 162-166 ° C.

Example 6: 2- [1- (2- (4,8-di-t-butyl-
2,10-Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3-t-butyl-5-methylphenyl) propyl] -6-t- Production of butyl-4-methylphenol (Compound 6) In Example 1, using a 0.5 l flask, 23 g of 2,2'-methylenebis (6-t-butyl-4-methylphenol),
Toluene (200 ml) and triethylamine (14.4 g) were charged, phosphorus trichloride (9.3 g) was added dropwise, and after heating, triethylamine (7.2 g) was added.
And 2,2'-propylidene bis (6-t-butyl-4-methylphenol) 25 g were charged in the same manner as in Example 1,
30 g of white crystals were obtained.

Mass spec (FD-MS): m / z 737 Elemental spec (C ₄₈ H ₆₅ O ₄ P): P 3.8% (calculated 4.2%) Melting point: 205-208 ° C.

Example 7: 2- [2- (4,8-di-t-butyl-2,1
0-Dimethyl-12-ethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3-t-butyl-5-methylbenzyl] -6-t- Production of butyl-4-methylphenol (Compound 7) In Example 1, using a 0.5 l flask, 2,2'-propylidenebis (6-t-butyl-4-methylphenol) 25
g, 200 ml of toluene, 14.4 g of triethylamine were added, 9.3 g of phosphorus trichloride was added dropwise, and after heating, triethylamine was added.
The procedure of Example 1 was repeated except that 7.2 g and 23 g of 2,2'-methylenebis (6-t-butyl-4-methylphenol) were charged to obtain 32 g of white crystals.

Mass spectrum (FD-MS): m / z 737 Elemental spectrum (C ₄₈ H ₆₅ O ₄ P): P 4.1% (calculated 4.2%) Melting point: 196 to 198 ° C.

Example 8: 2- [2- (4,8-di-t-butyl-2,1
0-Dimethyl-12-propyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-yl) oxy-3-t-butyl-5-methylbenzyl] -6-t- Production of butyl-4-methylphenol (Compound 8) In Example 1, using a 0.5 L flask, 2,2'-butyritebis (6-t-butyl-4-methylphenol) 25 g,
Charge 250 ml of toluene and 19.3 g of triethylamine, add 9 g of phosphorus trichloride dropwise, and after keeping the temperature warm, add 6.9 g of triethylamine.
The procedure of Example 1 was repeated except that 22.2 g of 2,2'-methylidenebis (6-t-butyl-4-methylphenol) was charged, to obtain 28 g of white crystals.

Mass spectrum (FD-MS): m / z 751 Elemental spectrum (C ₄₉ H ₆₇ O ₄ P): P 3.9% (calculated value 4.1%) Melting point: 181 to 184 ° C.

Example 9: 2- [2- (4,8-di-t-butyl-2,1
0-Dimethyl-12-i-propyl-12H-dibenzo [d, g] [1,3,2]
Dioxaphosphocin-6-yl) oxy-3-t-butyl-5-
Production of Methylbenzyl] -6-t-butyl-4-methylphenol (Compound 9) In Example 1, using a 0.5 l flask, 2,2′-i-
Butylidene bis (6-t-butyl-4-methylphenol) 15
g, toluene 250 ml, triethylamine 8.3 g were charged, phosphorus trichloride 5.4 g was added dropwise, and after heating, triethylamine
The procedure of Example 1 was repeated except that 4.2 g and 2,3'-methylidene bis (6-t-butyl-4-methylphenol) 13.3 g were charged to obtain 20 g of white crystals.

Mass spectrometric value (FD-MS): m / z 751 Elemental analytical value (C ₄₉ H ₆₇ O ₄ P): P 3.8% (calculated value 4.1%) Melting point: 114 to 121 ° C.

Example 10: Thermal stability test of linear low-density polyethylene [composition] Unstabilized linear low-density polyethylene 100 parts by weight Hydrotalcite 0.1 parts by weight n-octadecyl-3- (3,5-di) -t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight Test compound 0.05 part by weight Chemical formula-1: Compound 1 (produced in Example 1) Chemical formula-2: Compound 2 (produced in Example 2) Chemical formula-3: Compound 3 (manufactured in Example 3) Chemical-4: Compound 4 (manufactured in Example 4) Chemical-5: Compound 5 (manufactured in Example 5) P-1: 2,2'-methylenebis (4-t- Butyl-6-methylphenyl) octyl phosphite P-2: 2,2'-methylenebis (4-t-butyl-6-methylphenyl) phenyl phosphite

The above mixture was melt-kneaded at 250 ° C. and pelletized using a 30 mmφ uniaxial extruder. The obtained pellets were prepared using a Labo Plastomill under a nitrogen atmosphere at 240
The mixture was kneaded at 100 ° C. and 100 rpm, and the time (gel build-up time, minutes) at which the torque value due to crosslinking became maximum was measured. The results are shown in Table 1. The longer gel build-up time means that the crosslinking during kneading is suppressed and the processing stability is excellent. Further, the same test was carried out by using the test compound left in a constant temperature and humidity chamber of 40 ° C. and 80% for 7 days, and the hydrolysis resistance of the compound was evaluated. The results are shown in Table 1. A hydrolyzed product has a lower processing stability, and therefore, a product having a better processing stability after the treatment has a higher hydrolysis resistance.

[0067]

TABLE 1 implementation example comparisons Example 10-1 10-2 10-3 10-4 10-5 1 2 test compound of -1 of -2 reduction -3 reduction -3 reduction -3 P-1 P- 2 Processing stability 18 16 12 18 18 14 9 11 Hydrolysis resistance 18 16 12 18 14 8 9

Claims (5)

[Claims] 1. The compound of the general formula (I) (In the formula, R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl having 6 to 12 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, wherein R ³ and R ⁶ are each independently a hydrogen atom or carbon 1
To 8 alkyl groups. Either X ₁ or X ₂ represents a methylene group, and when X ₁ is a methylene group, X ₂ is a mere bond, a sulfur atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. Represents a methylene group which may be substituted, and when X ₂ is a methylene group,
X ₁ represents a methylene group substituted with a sulfur atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and at the same time, R ¹ and R ⁴ , R ² and R ⁵ , R ³ and R
⁶ and X ₁ and X ₂ are not the same
. Phosphites represented by). 2. The formula (I) in the presence of a dehydrohalogenating agent.
I) (In the formula, R ¹ , R ² , R ³ and X ₁ have the same meanings as in claim 1.) A bisphenol represented by the formula (3) is reacted with phosphorus trihalide, and then the general formula (III) (In the formula, R ⁴ , R ⁵ , R ⁶ and X ₂ have the same meaning as in Claim 1.) A bisphenol compound according to claim 1 is produced. how to. 3. A stabilizer for an olefin polymer containing the phosphite ester according to claim 1 as an active ingredient. 4. A method for stabilizing an olefin polymer, characterized in that the phosphite ester according to claim 1 is contained in the olefin polymer. 5. A stabilized olefin polymer composition comprising an olefin polymer containing the phosphorous acid ester according to claim 1.