JP2924357B2 - Phosphite compounds, their production and use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphite compound, a process for producing the same, and a use thereof as a stabilizer for organic materials.

[0002]

2. Description of the Related Art Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubbers, mineral oils, lubricating oils, adhesives, paints, etc. act upon heat, oxygen and the like during production, processing, and further use. It is known that the product value is significantly impaired, accompanied by phenomena such as molecular cleavage and molecular crosslinking, and the commercial value is significantly impaired. For the purpose of solving such problems as thermal and thermal oxidative degradation, by adding various phenolic antioxidants and phosphorus-based antioxidants,
It is known to stabilize organic materials.

[0003]

However, these conventionally known antioxidants do not yet have a sufficient effect of stabilizing against thermal degradation or thermal oxidation degradation, and there has been a demand for the development of more excellent antioxidants. .

[0004] It is an object of the present invention to provide compounds which exhibit a higher stabilizing effect on thermal and thermal oxidative degradation of organic materials. Another object of the present invention is to provide a process for preparing such compounds. Yet another object of the present invention is to provide the use of such compounds as stabilizers for organic materials.

[0005]

Means for Solving the Problems The inventors of the present invention conducted research to develop a stabilizer exhibiting a more excellent stabilizing effect on thermal degradation and thermal oxidation degradation of organic materials than conventionally known stabilizers. Has been continued. As a result, a phosphite compound having a specific structure was found, and the present invention was completed.

That is, the present invention provides the following general formula (I)

[0007]

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Wherein R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms,
^{One of 4} and R ⁵ represents an alkyl group having 1 to 8 carbon atoms, the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 2 to 8). A phosphoric acid ester compound is provided.

The phosphite compound represented by the formula (I) is, for example, represented by the following general formula (II)

[0010]

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(Wherein R ¹ , R ² and R ³ have the same meanings as described above) and phosphorus trihalide are reacted in the presence of a dehydrohalogenating agent such as triethylamine. And the following general formula (II
I)

[0012]

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(Wherein R ⁴ , R ⁵ and n have the same meaning as described above).

Accordingly, the present invention also provides a reaction between the bisphenol compound represented by the formula (II) and phosphorus trihalide in the presence of a dehydrohalogenating agent, and further comprising the alcohol compound represented by the formula (III) To provide a method for producing the phosphite compound represented by the formula (I).

The phosphite compound is useful as a stabilizer for organic materials, particularly organic materials which are susceptible to deterioration by the action of heat or oxygen. Accordingly, the present invention further provides a stabilizer for an organic material containing the phosphite compound represented by the formula (I) as an active ingredient, and further comprises a stabilizing effective amount of the phosphite compound in the organic material. Accordingly, a method for stabilizing the organic material is provided, and further, an organic material composition including the phosphite compound in the organic material is provided.

In the phosphite compound represented by the formula (I) of the present invention, the substituents R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, Examples include isopropyl, n-butyl, sec-butyl, t-butyl, t-pentyl, t-octyl, isooctyl and the like. R ¹ is preferably an alkyl group bonded to a benzene ring at a quaternary carbon, for example, t-butyl, t-pentyl, t-octyl and the like, and particularly preferably t-butyl. R ² is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, t-butyl,
-Pentyl and the like are preferred.

The substituent R ³ is a hydrogen atom or a group having 1 carbon atom.
To 11 alkyl groups, and examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, octyl, isooctyl, nonyl, decyl, undecyl and the like. R ³ is preferably a hydrogen atom or an alkyl group having a relatively small number of carbon atoms, particularly preferably a hydrogen atom.

One of the substituents R ⁴ and R ⁵ is an alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ or R
Examples of the alkyl group represented by ⁵ include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, t-pentyl, t-octyl, isooctyl and the like. R ⁴ and R ⁵ are preferably both alkyl groups. More preferably, R ⁴
And one of R ⁵ is a quaternary carbon bonded to a benzene ring, such as t-butyl, t-pentyl or t-butyl.
Octyl, especially t-butyl, the other of which has 1 carbon atom
To 5 alkyl groups, especially methyl or t-butyl.

Further, n is an integer of 2 to 8. Therefore, the alkylene group represented by C _n H _2n includes, for example, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl- 1,
3-propylene and the like.

As described above, the phosphite compound represented by the formula (I) is obtained by reacting the bisphenol compound represented by the formula (II) with phosphorus trihalide in the presence of a dehydrohalogenating agent. And further reacted with an alcohol compound represented by the formula (III).

Examples of the phosphorus trihalide used here include phosphorus trichloride, phosphorus tribromide and the like. In particular, phosphorus trichloride is preferably used.

In the reaction of the bisphenol compound with the phosphorus trihalide in the first step, it is generally preferable to use about 1 to 1.1 mol, more preferably, about 1 mol of phosphorus trihalide per 1 mol of the bisphenol compound of the formula (II). Uses about 1 to 1.05 mol of phosphorus trihalide.

Examples of the dehydrohalogenating agent that can be used in this reaction include tertiary amines.
Specific examples of the tertiary amines include pyridine, trimethylamine, triethylamine, N, N-dimethylaniline,
N, N-diethylaniline and the like, among which triethylamine is preferably used. The dehydrohalogenating agent is preferably used in an amount of about 2 to 3 mol, more preferably about 2.1 to 2.4 mol, per 1 mol of phosphorus trihalide.

This reaction is generally performed in an organic solvent. Examples of the organic solvent that can be used include aromatic hydrocarbons, aliphatic hydrocarbons, oxygen-containing hydrocarbons, and halogenated hydrocarbons. Specific examples of the aromatic hydrocarbon include:
Benzene, toluene, xylene and the like, specific examples of the aliphatic hydrocarbon are n-hexane, n-heptane, n-octane and the like, specific examples of the oxygen-containing hydrocarbon are diethyl ether, tetrahydrofuran and the like. Specific examples of the halogenated hydrocarbon include chloroform and carbon tetrachloride. Among these, toluene is preferably used.

The reaction proceeds at a temperature of about 80 to 120 ° C. and is carried out for about 2 to 3 hours. This reaction proceeds under normal pressure, but may be performed under pressure.

By reacting the bisphenol compound of the formula (II) with phosphorus trihalide, the following general formula (IV)

[0027]

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(Wherein R ¹ , R ² and R ³ have the same meaning as described above, and X represents a halogen atom), and it is considered that a halogenophosphite is formed. The reaction mixture is usually subjected to the reaction with the alcohol compound represented by the above formula (III) in the second step as it is.

The product obtained by the reaction of the bisphenol compound of the formula (II) with phosphorus trihalide has the formula (II)
In reacting the alcohol compound of the formula (I), the compound of the formula (III) is added per mole of the bisphenol compound of the formula (II).
It is preferable to use about 1 to 1.1 mol of the alcohol compound of formula

In this reaction, the organic solvent usually used in the first-stage reaction can be used as it is, and 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 per 1 mol of the alcohol compound of the formula (III).
When the amount of the dehydrohalogenating agent to be added is excessively used in the first step, it is practical to calculate the amount including the remaining dehalogenating agent.

The reaction proceeds at a temperature of about 100 to 120 ° C. and is carried out for about 6 to 7 hours. Usually, this reaction is preferably performed under reflux.

After the completion of the reaction, the hydrohalide salt of the dehydrohalogenating agent formed by the reaction is removed, and after the solvent is removed, an appropriate post-treatment such as crystallization or column chromatography is performed. Thereby, the phosphite compound represented by the formula (I) can be obtained.

The bisphenol compound represented by the formula (II) is known, and a commercially available bisphenol compound can be used as it is. This compound can be produced by reacting a 2,4-dialkylphenol with an aldehyde according to a known method, for example, a method described in JP-A-52-122350 or U.S. Pat. No. 2,538,355. You can also.

The alcohol compound represented by the formula (III) is
The following general formula (V)

[0035]

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Wherein R ⁴ and R ⁵ have the same meanings as described above, and Q represents, for example, a lower alkyl group having about 1 to 4 carbon atoms, and HOC _n H It can be produced by a transesterification reaction with a diol represented by _2n OH.

For example, a phenylpropionic acid ester of the formula (V) and an approximately equimolar amount of a diol are charged and dissolved by heating, a small amount of a basic catalyst is added, and the mixture is further heated to distill off the formed monohydric alcohol. An operation such as allowing the reaction to proceed can be employed. The reaction proceeds at a temperature of about 100 to 180 ° C. After completion of the reaction, if necessary, by adding a solvent and diluting, neutralizing with an acid such as acetic acid, washing with water, distilling off the solvent, and purifying the residue by, for example, column chromatography or the like. Formula (III)
Can be obtained.

In this reaction, the amount of phenylpropionate and diol to be charged is preferably about 1 to 1.2 moles per 1 mole of phenylpropionate.

Examples of the basic catalyst include organic alkali metal compounds such as sodium methoxide, lithium methoxide and lithium amide; alkali metals such as calcium oxide, sodium hydroxide, lithium hydroxide and potassium hydroxide; Alkaline earth metal hydroxides or oxides are used. The amount of basic catalyst used is
0.1 to 0.1 to 1 mol of phenylpropionate.
About 2 mol is preferred.

As the diluting solvent, aromatic hydrocarbons,
Aliphatic hydrocarbons, alcohols, ethers, and the like are used, but aromatic hydrocarbons are usually preferred, and specific examples include toluene, xylene, and monochlorobenzene.

The compound represented by the formula (I) of the present invention is effective for stabilizing an organic material against thermal deterioration and thermal oxidation deterioration. Examples of the organic materials that can be stabilized by the present invention include the following, each of which can stabilize a single material or a mixture of two or more, but is limited to these organic materials. It is not something to be done.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-P)
E), linear low-density polyethylene, (2) polypropylene, (3) methylpentene polymer, (4) EEA (ethylene / ethyl acrylate copolymer) resin, (5) ethylene / vinyl acetate copolymer resin, (6) ) Polystyrenes such as polystyrene, poly (p-methylstyrene), poly (α-
(7) AS (acrylonitrile / styrene copolymer) resin, (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin, (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin,
(10) ACS (acrylonitrile / chlorinated polyethylene /
Styrene copolymer) resin,

(11) chlorinated polyethylene, polychloroprene, chlorinated rubber, (12) polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14) ethylene / vinyl alcohol copolymer resin, (15) fluorine resin , (16) polyacetal, (17) grafted polyphenylene ether resin and polyphenylene sulfide resin, (18) polyurethane, (19) polyamide, (20) polyethylene terephthalate, polybutylene terephthalate,

(21) polycarbonate, (22) polyacrylate, (23) polysulfone, polyetheretherketone, polyethersulfone, (24) aromatic polyester resin, (25) epoxy resin, (26) diallylphthalate prepolymer, (27) silicone resin, (28) unsaturated polyester resin, (29) acryl-modified benzoguanamine resin, (30) benzoguanamine / melamine resin, (31) urea resin,

(32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymer, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymer Polymer, (38)
Silicone rubber, (39) epichlorohydrin rubber, (40)
Acrylic rubber, (41) natural rubber,

(42) chlorine rubber paint, (43) polyester resin paint, (44) urethane resin paint, (45) epoxy resin paint, (46) acrylic resin paint, (47) vinyl resin paint,
(48) amino alkyd resin paint, (49) alkyd resin paint, (50) nitrocellulose resin paint, (51) oil-based paint,
(52) wax, (53) lubricating oil.

When the phosphite compound of the present invention is blended with an organic material to stabilize the organic material, the phosphite compound represented by the above formula (I) is added to the organic material in an amount of 100 parts by weight. It is preferably used in the range of about 0.01 to 2 parts by weight. The amount of phosphite compound is 0.0
If the amount is less than 1 part by weight, the stabilizing effect is not always sufficient, and if the amount exceeds 2 parts by weight, the effect corresponding to the improvement cannot be obtained, which is economically disadvantageous.

The organic material containing the phosphite compound according to the present invention may further contain other additives, if necessary, such as a phenolic antioxidant, a sulfuric antioxidant, a phosphorus antioxidant, and an ultraviolet absorber. , Hindered amine light stabilizers, lubricants, plasticizers, flame retardants, nucleating agents, metal deactivators, antistatic agents, pigments, inorganic fillers and the like. Of course, these additives can be added simultaneously with the phosphite compound of the formula (I),
Also, it can be blended at a different stage from the phosphite compound.

In incorporating the phosphite compound of formula (I), or other optional additives, into the organic material, any known method and apparatus for obtaining a homogeneous mixture may be used. it can. For example, when the organic material is a solid polymer, a phosphite compound or an optional additive can be dry-blended directly to the solid polymer, or a phosphite compound or an optional additive can be added to the solid polymer. It can also be incorporated into solid polymers in the form of a masterbatch. When the organic material is a polymer, it can also be added to the polymer solution during or immediately after the polymerization in the form of a solution or dispersion of a phosphite compound or an optional additive. On the other hand, when the organic material is a liquid such as oil, the phosphite compound or any other additive can be directly added and dissolved, or the phosphite compound or any other additive can be added. It can also be added in the state of being dissolved or suspended in a liquid medium.

[0050]

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.

Reference Example: 2- [3- (3-t-butyl-4)
Preparation of -Hydroxy-5-methylphenyl) propionyloxy] ethanol 3- (3-t-butyl-4-hydroxy-5-methyl) was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, and a condenser. Phenyl) methyl propionate 100.2
g, and 24.8 g of ethylene glycol, and the inside of the vessel was replaced with nitrogen. Then, the mixture was heated to 120 ° C. with stirring to dissolve both, and kept warm for 30 minutes. 1.5 g of lithium methoxide was added thereto, and the temperature was raised to 150 ° C.
The reaction was completed by keeping the temperature for 2 hours while distilling off the generated methanol.

After cooling to room temperature, 100 g of toluene
Was added and diluted, then acetic acid was added for neutralization, and 100 g of water was added for washing. After the toluene was distilled off from the organic layer, the residue was purified by silica gel column chromatography to give 2- [3- (3-t-butyl-
72.0 g of 4-hydroxy-5-methylphenyl) propionyloxy] ethanol were obtained as a colorless viscous oil.

By performing the same reaction as described above except that the raw materials are changed, R ⁴ and R ⁵ in the general formula (III) can be obtained.
And compounds in which n is varied within the ranges defined above can be prepared.

Example 1 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl 2,2'-methylenebis (6-tert-butyl-4-methylphenyl) Preparation of phosphite (compound 1) In a 200 ml four-necked flask equipped with a thermometer, a stirrer, and a condenser, 6.8 g of 2,2'-methylenebis (6-t-butyl-4-methylphenol), anhydrous toluene 5
0 g and 4.2 g of anhydrous triethylamine were charged, and the atmosphere in the vessel was replaced with nitrogen.
Was added dropwise. After completion of the dropwise addition, the mixture was kept at 80 ° C for 3 hours, and then 2.1 g of anhydrous triethylamine and 20 g of anhydrous toluene
Then, 5.6 g of 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethanol dissolved in g was charged and the mixture was kept under reflux for 6 hours. Next, after cooling to room temperature, 50 g of toluene was added for dilution, and triethylamine hydrochloride generated by the reaction was filtered. After concentrating the filtrate, the residue was purified by silica gel column chromatography to obtain 11.1 g of compound 1 as a colorless viscous oil. Mass spectrometry (FD-MS): m / z 648 Elemental analysis (C ₃₉ H ₅₃ O ₆ P ₁ ): Calculated P 4.77%, Observed P 4.64%

Example 2: 4- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] butyl 2,2'-methylenebis (6-tert-butyl-4-methylphenyl) Production of phosphite (compound 2) 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 1
Instead of ethanol, 4- [3- (3-t-butyl-4
-Hydroxy-5-methylphenyl) propionyloxy] butanol was used in the same manner as in Example 1, except that the filtrate obtained after filtration of triethylamine hydrochloride was concentrated. The residue was concentrated with normal hexane. By crystallization, 11.7 g of Compound 2 was obtained as white crystals having a melting point of 135.0 to 137.0 ° C. Mass spectrometry value (FD-MS): m / z 676 Elemental analysis value (C ₄₁ H ₅₇ O ₆ P ₁ ): Calculated value P 4.58%, Actual value P 4.52%

Example 3 5- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] pentyl 2,2'-methylenebis (6-t-
Preparation of butyl-4-methylphenyl) phosphite (compound 3) 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 1
Instead of ethanol, 5- [3- (3-t-butyl-4-
The same reaction and post-treatment as in Example 1 were carried out except that 6.5 g of [hydroxy-5-methylphenyl) propionyloxy] pentanole was used, to obtain 11.1 g of compound 3 as white crystals having a melting point of 120.5 to 122.0 ° C. . Mass analysis (FD-MS): m / z 690 Elemental analysis _{(C 42 H 59 O 6 P} 1): Calculated P 4.48%, Found P 4.25%

Example 4: 8- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] octyl 2,2'-methylenebis (6-t-
Preparation of butyl-4-methylphenyl) phosphite (compound 4) 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 1
8- [3- (3-t-butyl-4) instead of ethanol
-Hydroxy-5-methylphenyl) propionyloxy] octanol was used in the same manner as in Example 1 except for using 7.3 g, to obtain 12.2 g of compound 4 as a colorless viscous oil. Mass analysis (FD-MS): m / z 732 Elemental analysis _{(C 45 H 65 O 6 P} 1): Calculated P 4.23%, Found P 4.09%

Example 5 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl 2,2'-methylenebis (4,6-di-tert-butylphenyl) Preparation of phosphite (compound 5) In a 200 ml four-necked flask equipped with a thermometer, a stirrer and a condenser, 8.5 g of 2,2'-methylenebis (4,6-di-t-butylphenol) and 50 g of anhydrous toluene were added.
Then, 4.2 g of anhydrous triethylamine was charged, and the inside of the vessel was replaced with nitrogen. Then, 2.7 g of phosphorus trichloride was added dropwise with stirring. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 3 hours, and then 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethanol dissolved in 2.1 g of anhydrous triethylamine and 20 g of anhydrous toluene. 5.6 g was charged and kept under reflux for 6 hours. Next, after cooling to room temperature, 50 g of toluene was added for dilution,
The triethylamine hydrochloride generated by the reaction was filtered.
After concentrating the filtrate, the residue was purified by silica gel column chromatography to obtain 12.7 g of compound 5 as white crystals having a melting point of 144.2 to 146.9 ° C. Mass spectrometry value (FD-MS): m / z 733 (M ⁺ ) Elemental analysis value (C ₄₅ H ₆₅ O ₆ P ₁ ): Calculated value P 4.23%, Observed value P 4.20%

Example 6: 4- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] butyl 2,2'-methylenebis (4,6-di-tert-butylphenyl) Preparation of phosphite (compound 6) 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 5
Instead of ethanol, 4- [3- (3-t-butyl-4
-Hydroxy-5-methylphenyl) propionyloxy] butanol was used, except that 6.2 g of Compound 6 was used. As a result, 12.6 g of Compound 6 was obtained as white crystals having a melting point of 123.2 to 126.0 ° C. Mass spectrometry (FD-MS): m / z 760 Elemental analysis (C ₄₇ H ₆₉ O ₆ P ₁ ): Calculated P 4.07%, Observed P 4.01%

Example 7: 5- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] pentyl 2,2'-methylenebis (4,6-
Di-t-butylphenyl) phosphite (compound 7)
Preparation of 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 5
Instead of ethanol, 5- [3- (3-t-butyl-4-
The same reaction and post-treatment as in Example 5 were carried out except that 6.5 g of [hydroxy-5-methylphenyl) propionyloxy] pentanol was used to obtain 13.0 g of compound 7 as white crystals having a melting point of 147.9 to 149.5 ° C. Mass spectrometry (FD-MS): m / z 774 Elemental analysis (C ₄₈ H ₇₁ O ₆ P ₁ ): Calculated P 4.00%, Observed P 3.95%

Example 8: 8- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] octyl 2,2'-methylenebis (4,6-
Di-t-butylphenyl) phosphite (compound 8)
Preparation of 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 5
8- [3- (3-t-butyl-4) instead of ethanol
-Hydroxy-5-methylphenyl) propionyloxy] octanol was used in the same manner as in Example 5, except that 7.3 g of Compound 8 was obtained as a colorless viscous oil. Mass spectrometry (FD-MS): m / z 816 Elemental analysis (C ₅₁ H ₇₇ O ₆ P ₁ ): Calculated P 3.79%, Observed P 3.53%

Example 9: 2- [3- (3,5-di-t)
-Butyl-4-hydroxyphenyl) propionyloxy] ethyl 2,2'-methylenebis (4,6-di-t
Production of -butylphenyl) phosphite (compound 9) 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 5
Instead of ethanol, 2- [3- (3,5-di-t-
The same reaction and post-treatment as in Example 5 were carried out except that 6.5 g of [butyl-4-hydroxyphenyl) propionyloxy] ethanol was used, to obtain 14.7 g of compound 9 as white crystals having a melting point of 93.1 to 95.2 ° C. Mass spectrometry value (FD-MS): m / z 775 (M ⁺ ) Elemental analysis value (C ₄₈ H ₇₁ O ₆ P ₁ ): Calculated value P 4.00%, measured value P 3.98%

Example 10: 2- [3- (3-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphite (compound Production of 10) 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] in Example 5
Instead of ethanol, 2- [3- (3-t-butyl-4
-Hydroxyphenyl) propionyloxy] ethanol was subjected to the same reaction and post-treatment as in Example 5 except that 5.3 g of ethanol was used, thereby obtaining 13.1 g of compound 10 as white crystals having a melting point of 173.5 to 175.0 ° C. Mass analysis (FD-MS): m / z 718 Elemental analysis _{(C 44 H 63 O 6 P} 1): Calculated P 4.31%, Found P 4.30%

Example 11: 2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl 2,2'-ethylidenebis (4,6
-Di-t-butylphenyl) phosphite (compound 1
Production of 1) Instead of 2,2'-methylenebis (4,6-di-t-butylphenol) in Example 5, 2,2'-ethylidenebis (4,6-di-t-butylphenol) was used.
The same reaction and post-treatment as in Example 5 were carried out except for using 8.8 g, to obtain 13.4 g of compound 11 as white crystals having a melting point of 119.5 to 121.4 ° C. Mass spectrometry (FD-MS): m / z 747 (M ⁺ ) Elemental analysis (C ₄₆ H ₆₇ O ₆ P ₁ ): Calculated P 4.15%, Observed P 4.15%

Example 12: Thermal stability test of polypropylene [Compound] Unstabilized polypropylene 100 parts by weight Calcium stearate 0.05 part by weight Test compound 0.1 part by weight

Using a 30 mmφ single screw extruder, the above compound was melt-kneaded at 230 ° C. and pelletized. The obtained pellets were placed in a melt indexer and flowability (MI value: g / 1) after staying at 270 ° C. for 5 minutes according to JIS K7210.
0 minutes) to evaluate the thermal stability. Polypropylene breaks molecular chains due to heat and increases fluidity, so that a smaller MI value after 5 minutes of residence means better thermal stability. The results are shown in Table 1.

[0067]

[Table 1]

[0068]

The phosphite compound of the present invention has excellent performance as a stabilizer for various organic materials such as thermoplastic resins. For example, a resin containing this compound is stable against thermal deterioration and thermal oxidative deterioration during production, processing, and use, and a high-quality product can be obtained.

Continued on the front page (72) Inventor Tamaki Ishii 3-1-198, Kasuganaka, Konohana-ku, Osaka City Within Sumitomo Chemical Industries Co., Ltd. (72) Inventor Motohiko Sazomi 3-1-198, Kasuganaka, Konohana-ku, Osaka-shi Sumitomo Chemical Co., Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) The following general formula (I): (Wherein, R ¹ and R ² each independently have 1 carbon atom)
And R ³ represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and R ⁴ and R ⁵
One represents an alkyl group having 1 to 8 carbon atoms, the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 2 to 8). . 2. A compound represented by the following general formula (II): (Wherein R ¹ , R ² and R ³ represent the meanings defined in claim 1) with a phosphorus trihalide in the presence of a dehydrohalogenating agent. Of the general formula (III) 2. The method for producing a phosphite compound according to claim 1, wherein an alcoholic compound represented by the formula (1) wherein R ⁴ , R ⁵ and n have the same meaning as defined in claim 1 is reacted. 3. A stabilizer for an organic material, comprising the phosphite compound according to claim 1 as an active ingredient. 4. A method for stabilizing an organic material, comprising adding the stabilizing effective amount of the phosphite compound according to claim 1 to the organic material. 5. A stabilized organic material composition comprising an organic material containing the phosphite compound according to claim 1.