JP2001302685A - Method for producing organophosphorus compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple and ready method for producing an organophosphorus compound by which the high-quality compound is obtained in high yield and problems about safety and health or environments are scarcely caused. SOLUTION: This method for producing the organophosphorus compound represented by formula (1) (wherein, X1 to X3 denote each hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; R1 to R5 denote each hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or hydroxyl group; and R denotes an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group) comprises reacting an organophosphorus compound represented by formula (2) with a nuclearly substituted hydroxybenzyl alkyl ether represented by formula (3) in the absence or presence of an acidic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a stabilizer and a flame retardant, and more particularly, to a method for producing an organic phosphorus compound.

[0002]

2. Description of the Related Art Heretofore, as a method for producing an organic phosphorus compound of the general formula (1), 9,10-dihydro-10-oxa-
9-phosphaphenanthrene-9-oxide (hereinafter H
A method of reacting 3,5-di-t-butyl-4-hydroxybenzyl alcohol with no catalyst or an acidic catalyst (Japanese Patent Application Laid-Open No. 47-16479) is known.

However, the method used in this method,
5-Di-t-butyl-4-hydroxybenzyl alcohol is a compound which is inferior in yield, expensive, and unstable in its production. Also, in the reaction with the general formula (2), there were many by-products such as a dimer of a benzyl alcohol compound, and the yield was low, which was economically disadvantageous.

[0004] A method is known in which HCA and 2,6-dimethyl-3-hydroxy-4-t-butyl-benzyl chloride are dehydrochlorinated and condensed (Japanese Patent Application Laid-Open No. 56-115383).

However, this method has a problem that it is difficult to produce the benzyl chloride compound and a toxic gas is generated during the production.

In recent years, polymer compounds such as thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins and melamine resins, ABS resins, AS resins, P resins
As a method for making thermoplastic resins such as ET resin, PBT resin and PMMA resin flame-retardant, organic halogen compounds are mainly used as flame retardants. After the intended use, they are generally incinerated.

However, high molecular compounds containing organic halogen compounds are known to generate highly toxic dioxins which have a bad influence on the environment during the process of pellet molding, heat melting and incineration of objects of use. I have.

On the other hand, a polymer compound obtained by adding an organic phosphorus compound represented by the general formula (1) for the purpose of stabilization and flame retardation does not contain the above-mentioned dioxins even if it is incinerated. It has been found that no toxic gas such as phosgene is generated during the production.

[0009]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in order to overcome these disadvantageous conditions and find more economically advantageous conditions. The use of a nucleus-substituted hydroxybenzyl alkyl ether, which is chemically stable and easily reactive with the general formula (2), improves the yield and obtains a high-quality product. Heading to the present invention.

[0010] An object of the present invention is to provide a simple and easy method for producing an organic phosphorus compound, in which a high-quality compound can be obtained in a high yield with little safety and health or environmental problems. .

[0011]

According to the present invention, there is provided an organic phosphorus compound represented by the general formula (2):

[0012]

Embedded image

In the formula, X ¹ , X ² and X ³ are the same or different and each represent a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

A nucleus-substituted hydroxybenzyl alkyl ether represented by the general formula (3) is

[0015]

Embedded image

In the formula, R ^{1 to} R ⁵ are the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group,
An aralkyl group or a hydroxyl group, and at least one of R ^{1 to} R ⁵ is a hydroxyl group. R is carbon number 1
And 12 alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups.

A process for producing an organophosphorus compound is provided, wherein the reaction is carried out in the absence of a catalyst or in the presence of an acidic catalyst to obtain an organophosphorus compound represented by the general formula (1).

[0018]

Embedded image

In the formula, X ¹ , X ² and X ³ are the same or different and represent a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ^{1 to} R ⁵ are the same or different. A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aralkyl group or a hydroxyl group, and at least one of R ^{1 to} R ⁵ is a hydroxyl group. R represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.

The alkyl group in the present invention includes a methyl group, an ethyl group, a propyl group and a tertiary butyl, and the cycloalkyl group includes a cyclohexyl group and a 3-methyl-cyclopentyl group. Examples thereof include a phenyl group, a tolyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group.

[0021]

Embodiments of the present invention will be described below in detail.

The organophosphorus compound represented by the general formula (1) produced according to the present invention is mixed with an organic polymer compound to modify, improve, stabilize and improve the physical and chemical properties of the substrate. It demonstrates excellent performance in combustion.

Specific examples of the organic phosphorus compound represented by the general formula (2) used in the present invention include 9,10-
Dihydro-10-oxa-9-phosphaphenanthrene-9-oxide, 1-methyl-9,10-dihydro-
10-oxa-9-phosphaphenanthrene-9-oxide, 1,3,7-tri-t-butyl-9,10-dihydro-10-oxa-9-phosphaphenanthrene-
9-oxide and 1,3-dicyclohexyl-9,1
Examples include, but are not limited to, 0-dihydro-10-oxa-9-phosphaphenanthrene-9-oxide.

Of these compounds, 9,10-dihydro-10-oxa-9-
Phosphaphenanthrene-9-oxide is preferred.

The nucleus-substituted hydroxybenzyl alkyl ether represented by the general formula (3) used in the present invention is obtained by reacting a corresponding phenol compound and paraformaldehyde with a fatty acid in the presence of a basic catalyst (for example, triethylamine or monomethylamine). By reacting in a group alcohol (for example, methanol or ethanol), it can be easily, inexpensively, and safely produced.

Specific examples of the compound include 3,5-di-t-butyl-4-hydroxybenzyl methyl ether, 3,5-di-t-butyl-4-hydroxybenzyl ethyl ether, -T-butyl-4-hydroxybenzyl-n-butyl ether, 3,5-di-t-
Butyl-4-hydroxybenzyl-n-butyl ether, 3,5-di-t-butyl-4-hydroxybenzyloctyl ether, 3,5-di-t-butyl-4-hydroxybenzylcyclohexyl ether, 3-methyl-
5-isopropyl-4-hydroxybenzyl methyl ether, 3-t-butyl-5-isopropyl-4-hydroxybenzyl methyl ether, 2,6-dimethyl-4-
Examples include, but are not limited to, t-butyl-3-hydroxybenzyl methyl ether and 2,6-diethyl-4-t-butyl-3-hydroxybenzyl ethyl ether.

Among these compounds, 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether and 3,5-di-tert-butyl-4 are generally available because of their availability.
-Hydroxybenzyl-n-butyl ether and 2,6
-Dimethyl-4-t-butyl-3-hydroxybenzyl methyl ether is preferred.

In the present invention, when a catalyst is used,
Although an acidic catalyst is used, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, aluminum trichloride, aluminum chloride, zinc chloride, iron chloride,
Examples include, but are not limited to, boron trifluoride, activated clay, and strongly acidic ion exchange resins.
Further, a mixture of two or more of the above may be used.

Of these compounds, sulfuric acid or p-toluenesulfonic acid is often used in general in terms of availability and price.

The amount used is an amount that is convenient for the reaction operation and post-treatment, but is usually 0.1 to 100% by weight of the amount of the raw material, and the generally preferred range is 1 to 10% by weight. .

The reaction solvent used in the present invention may or may not be used. When used, a solvent inert to the reaction is used.

Examples of the inert organic solvent include aromatic compounds such as benzene, toluene and xylene, hydrocarbon compounds such as hexane, petroleum ether and cyclohexane, and halogen compounds such as carbon tetrachloride, methylene chloride, chloroform, trichloroethane and tetrachloroethane. , Diethyl ether, dimethyl ether, ether compounds such as dioxane, and the reaction-formed hydroxy compound (R-OH) of the compound represented by the general formula (3), but are not limited thereto.

The amount used is an amount that is convenient for the reaction operation and post-treatment, but is usually 0 to 10 times the amount of the raw material, and generally a preferable range is 1 to 5 times the amount.

The reaction temperature may be at least the melting point of the starting compound (mixture with the medium), and is 0 to 300 ° C, preferably 100 to 200 ° C. If necessary, it can be carried out under pressure.

The reaction time varies depending on various reaction conditions, but is completed in about 4 to 10 hours after the start of the reaction.

After completion of the reaction, an appropriate post-treatment is carried out, the reaction mixture is cooled, solidified or crystallized from the target substance, filtered, washed and dried to obtain the product represented by the general formula (1) To obtain an organic phosphorus compound represented by the formula:

[0037]

The present invention will be described below in more detail with reference to specific examples.

Example 1 9,10-Dihydro-10-oxa-9-phosphaphenanthrene-9-oxide was placed in a 1-liter reaction flask equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer. : HCA 259.2 g (1.2 mol) manufactured by Sanko Co., Ltd. was charged and heated. After the contents were dissolved at 120 to 140 ° C., stirring was started, and 300 g (1.2 mol) of 3,5-di-t-butyl-4-hydroxybenzyl methyl ether was added little by little.

Thereafter, the temperature was reduced from 150 ° C. to 200 ° C.
The temperature was gradually raised over time to complete the reaction. The methanol produced by the reaction was distilled off under reduced pressure and solidified to obtain 512.2 g of a pale yellow-white product. Yield 98.
The purity was 5% and the purity was 97.9%.

When this product was recrystallized and purified using toluene, white crystals having a melting point of 198 ° C. were obtained.

As a result of IR and GC-MASS analysis, it was confirmed that this product was a compound represented by the structural formula (A).

[0042]

Embedded image

Example 2 Using the same apparatus as in Example 1, 259.2 g of HCA, 3,5-di-t-butyl-4
-Hydroxybenzyl methyl ether (300 g), xylene (1677.6 g) and sulfuric acid (1.25 g) were charged, stirring was started, and the temperature was gradually increased.

After maintaining the reaction temperature at 130 to 140 ° C. for 6 hours, the catalyst was removed by washing twice with 200 ml of hot water and cooled to precipitate crystals. After filtration at room temperature, washing and drying, a white product, 488.8 g of the compound of the structural formula (A), was obtained. 94.0% yield, purity 9
9.1%, and the melting point of the compound of structural formula (A) is 198.
° C.

Example 3 Instead of 300 g of 3,5-di-t-butyl-4-hydroxybenzyl methyl ether in Example 2, 2,6-dimethyl-4-t-butyl-3-hydroxybenzyl methyl ether 267g
By operating in the same manner as in Example 2 except that (1.2 mol) was used, 380 g of a compound of the structural formula (B) as white crystals was obtained. The yield was 93.5%, the purity was 99.2%, and the melting point of the compound of the structural formula (B) was 264 ° C.

[0046]

Embedded image

[0047]

As described above, according to the present invention, an organophosphorus compound useful as a stabilizer and a flame retardant has a high yield and a high quality with almost no problems in safety, health and environment. Thus, a simple and easy method for producing an organic phosphorus compound can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/12 C09K 21/12 (72) Inventor Kenichi Ikemoto 1-10-24 Itikaichi, Ibaraki-shi, Osaka Sanko Sanko F-term (reference) 4F028 AA35 4H039 CA11 CA90 CD10 CD40 4H050 AA02 BA50 BA52 BA66 WA12 WA26 4J002 AA001 CC031 CC101 CC181 CD001 CF211 EW136 FD136

Claims (5)

[Claims] 1. An organic phosphorus compound represented by the general formula (2): (In the formula, X ¹ , X ² and X ³ are the same or different and each represent a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.) A nuclear-substituted hydroxybenzyl represented by the general formula (3) With an alkyl ether Wherein R ^{1 to} R ⁵ are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aralkyl group or a hydroxyl group, and at least one of R ^{1 to} R ⁵ is a hydroxyl group. R represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.) The organic phosphorus compound represented by the general formula (1) is reacted in the absence of a catalyst or an acidic catalyst. A method for producing an organophosphorus compound, comprising: Embedded image (Wherein X ¹ , X ² and X ³ are the same or different and represent a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ^{1 to} R ⁵ are the same or different and represent a hydrogen atom , alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aralkyl group or a hydroxyl group, R ¹ to R ⁵
At least one is a hydroxyl group. R represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group) 2. The organic phosphorus compound according to claim 1, wherein the organic phosphorus compound represented by the general formula (2) is 9,10-dihydro-10-oxa-9-phosphaphenalene-9-oxide. Production method. 3. The organic phosphorus compound according to claim 1, wherein the nucleus-substituted hydroxybenzyl alkyl ether represented by the general formula (3) is 3,5-di-t-butyl-4-hydroxybenzyl methyl ether. Production method. 4. The method according to claim 1, wherein the nucleus-substituted hydroxybenzyl alkyl ether represented by the general formula (3) is 2,6-dimethyl-4-.
The method for producing an organophosphorus compound according to claim 1 or 2, which is t-butyl-3-hydroxybenzyl methyl ether. 5. The method for producing an organic phosphorus compound according to claim 1, wherein the acidic catalyst when a catalyst is used in the reaction is sulfuric acid.