JPH07118280A - Quaternary ammonium phosphite compound and its synthesis - Google Patents

Abstract

PURPOSE:To obtain the compound effective for improving the hydrolysis resistance of a resin and useful as a resin stabilizer, flame-retardant, etc., by reacting a specific phosphite compound with an ammonium compound in the presence of an alkali. CONSTITUTION:The compound of the formula Ican be produced by reacting a secondary phosphite compound of the formula II (R is 1-18C alkyl, phenyl or methylphenyl) with a quaternary ammonium compound of the formula III (R1 to R4 are 1-18C alkyl or benzyl; X is halogen) in the presence of an alkali. The reaction is preferably carried out at room temperature to 100 deg.C for 30min to 3hr using sodium hydroxide, etc., as the alkali.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The compound obtained according to the present invention has the drawback that the secondary phosphite compound, which is a raw material of the compound, is extremely susceptible to hydrolysis.
The present invention relates to an extremely stable and useful substance such as a resin stabilizer and a flame retardant, and a method for producing the substance.

[0002]

2. Description of the Related Art The effects of secondary phosphite compounds have been recognized as resin stabilizers and flame retardants, but they are hydrolyzable and are difficult to handle. Therefore, a very small amount of water contamination is extremely limited, or the mono-substituted phosphite produced by hydrolysis is strongly acidic, so that the amines may be added from the beginning to neutralize it. The method has been used for various purposes, and no definitive solution for hydrolysis resistance of secondary phosphite compounds has been found so far.

[0003]

[Problems to be Solved by the Invention] While maintaining good properties of a secondary phosphite compound, it is possible to improve hydrolysis resistance, and at the same time, search for a substance in which the resulting compound is soluble in an organic solvent, and a method for producing the same. The purpose is to establish.

[0004]

The method for synthesizing a quaternary ammonium phosphite compound is obtained by intermolecular dehydrohalogenation of a quaternary ammonium halide and a secondary phosphite compound, that is, a detailed reaction. Is formula 4
It is synthesized by the reaction shown in.

[0005]

[Chemical 4]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ independently of each other represent a saturated or unsaturated alkyl group having 1 to 18 carbon atoms or Verdyl group, and X represents a halogen atom.
Represents a saturated or unsaturated alkyl group having 1 to 18 carbon atoms, a phenyl group, or a methylphenyl group. )

Next, the outline of the implementation of the synthesis method will be described. That is, an intermolecular dehydrohalogenate is prepared by mixing a quaternary ammonium compound in an equimolar amount or more with a corresponding secondary phosphite compound in the presence of an alkali at room temperature to 100 ° C. for 5 minutes to 5 hours, preferably 30 minutes to 3 hours. To obtain the desired product.

The amount of alkali used is preferably 1.0 to 2.0 times the molar amount of the secondary phosphite. The reaction may be carried out in an aqueous solution or in an organic solvent, but is preferably carried out in an aqueous solution to separate reaction products from n-hexane, benzene,
Extraction using a hydrocarbon solvent such as toluene or xylene or a halogenated hydrocarbon solvent such as dichloromethylene or chloroform, an ester such as ethyl acetate or methyl isobutyl ketone, a ketone solvent, or an alcohol solvent is preferable. . After extraction, the by-product inorganic salt is removed by washing with water, and then the solvent is distilled off to obtain the desired product.

The alkali to be used includes hydroxides and carbonates of alkali and alkaline earth, such as sodium hydroxide, potassium hydroxide, calcium hydroxide,
Magnesium hydroxide, sodium carbonate, potassium carbonate, etc. are suitable.

The quaternary ammonium phosphite compound group obtained by the present invention is a novel substance, and is different from the general concept of the quaternary ammonium compound and the secondary phosphite compound. It is an extremely industrially useful compound which comprises

That is, the compound is used as a cation component in the fourth
It has a secondary phosphite anion as a primary ammonium cation and anion component instead of a halogen ion of a strong electrolytic substance, and therefore has unique properties.

The characteristics of the compound will be described below. 1. It is sparingly soluble in water as compared with general quaternary ammonium halides, and is extremely soluble in organic solvents. 2. It is decomposed by an acid and divided into constituent quaternary ammonium compounds and secondary phosphite compounds. 3. It is noteworthy that it is stable to water and heat, and in particular the hydrolyzability of the secondary phosphite compound disappears. Next, Table 1 shows the characteristics of the quaternary ammonium phosphite compound according to the present invention.

[0013]

[Table 1]

However, in the table, R, R ₁ , R ₂ , R ₃ and R ₄ are of the chemical formula 3.

[0015]

Embodiments will be specifically described below with reference to embodiments. Example 1. 3.8 gr of sodium hydroxide in 100 ml of water
(0.095 mol) was dissolved, and 26.4 gr (0.095 mol) of tetra-n-butylammonium chloride was added thereto. Furthermore, diethyl phosphite 13.1
Gr (0.095 mol) was added, and the mixture was stirred at 40 to 50 ° C for 3 hr. After the reaction, the mixture was extracted with 100 ml of dichloromethane and washed with 50 ml of water 3 times each time. The dichloromethane layer was separated and concentrated under reduced pressure to obtain a colorless transparent liquid substance, tetra-n-butylammonium diethylphosphite 33.5 gr (yield 93.1%). Next, in order to observe the hydrolysis resistance of this substance, a 25 ° C. and 90% humidity exposure test is performed to show the progress of hydrolysis of the secondary phosphite. The acid value was traced. Acid value initial 1 day 7 days later Uninvented substance 1.1 1.1 1.1 Raw material secondary phosphite 3.5 46.9 498

The raw material secondary phosphite (diethylphosphite) is hydrolyzed according to the following formula (5).

[0017]

[Chemical 5]

Chemical formula 4 (i) is a neutral substance, but it reacts with water at room temperature to become the chemical formula 4 (ii) substance, and this monophosphite compound (ii) is strongly acidic. However, it was found that the substance of the present application did not undergo the above-mentioned hydrolysis, and therefore the acid value did not increase with time.

Example 2 5.8 gr (0.10) of sodium hydroxide was added to 200 ml of water.
3 mol) and 34.0 gr (0.100 mol) of dimethyllaurylbenzylammonium chloride.
Was added. 41.8 gr (0.100 mol) of dilauryl phosphite was added dropwise to this at 20 to 25 ° C. with stirring for 1 hour. After stirring for 2 hours at the same temperature, extract with 200 ml of chloroform, 50m each time
It was washed 3 times with 1 l of water. Separate the chloroform layer,
After concentration under reduced pressure, 70.8 g (yield 98.2%) of white waxy dimethyllaurylbenzylammonium dilaurylphosphite was obtained. Next, in order to observe the hydrolysis resistance of this substance, an exposure test was conducted at 25 ° C. and a humidity of 90%, and the acid value showing the progress of hydrolysis was traced. Acid value Initial 1 day 7 days Uninvented substance 1.5 1.5 1.5 Raw material secondary phosphite 2.8 15.1 131.7

Example 3 In 100 ml of water, 3.7 gr of calcium hydroxide (0.05
Mol) trimethylbenzyl ammonium bromide 1
0.2 gr (0.055 mol) was added, and di-2-ethylhexyl phosphite 15.3 gr was added at 20 to 25 ° C.
(0.05 mol) was added dropwise with stirring for 30 minutes. Then, the mixture was stirred at 40 to 50 ° C. for 2 hours, extracted with 50 ml of dichloromethylene, and washed with 20 ml of water 3 times each time. The dichloromethylene layer was concentrated under reduced pressure to obtain a pale yellow oily form of trimethylbenzylammonium-di-2-ethylhexylphosphite 21.1 gr.
(Yield 92.5%) was obtained.

Example 4 3.0 gr (0.053) of potassium hydroxide was added to 100 ml of water.
Mol) and 17 gr (0.05 mol) of dimethyl lauryl benzene ammonium chloride, and 15-20 degreeC
At that time, 29.1 gr (0.05 mol) of dioleyl phosphite was added while stirring for 30 minutes. Then 40-5
After stirring at 0 ° C for 2 hours and 30 minutes, 100 ml of toluene
Was extracted and washed with 50 ml of water three times. The toluene layer was separated, and the toluene was distilled off by concentration under reduced pressure to obtain 43.3 g (yield 97.7%) of pale yellow jelly-like dimethyllaurylbenzylammonium dioleyl phosphite.

Example 5 15.0 gr (0.109 g) of potassium carbonate was added to 300 ml of water.
Mol) and 42.2 g (0.100 mol) of dimethylbenzyl oleyl ammonium chloride, and 2
23.4 gr of diphenyl phosphite at 5-30 ° C
(0.100 mol) was added with stirring for 30 minutes. Then, the mixture was stirred at 40 to 50 ° C. for 2 hours, extracted with chloroform, and washed with 50 ml of water three times. The chloroform layer was concentrated under reduced pressure to give a pale yellow oily form of dimethylbenzylammonium diphenylphosphite 59.6 gr.
(Yield 96.3%) was obtained.

[0023]

The secondary phosphite compound is a very useful substance such as a resin stabilizer and a flame retardant, but it is extremely hydrolyzable and its hydrolysis product exhibits strong acidity. The methods and fields of use were limited. It is considered that the uninvented compound contributes to industrial development by remarkably expanding the range of uses and methods of use by improving the above-mentioned drawbacks.

Claims (2)

[Claims] 1. A general formula: A quaternary ammonium phosphite compound represented by (3). 2. A general formula: (1) A secondary phosphite compound represented by the formula (wherein R represents a saturated or unsaturated alkyl group having 1 to 18 carbon atoms, a phenyl group or a methylphenyl group) and a compound represented by the general formula: (2) (in the formula, R ₁ , R ₂ , R ₃ , and R ₄ independently of each other represent a saturated or unsaturated alkyl or benzyl group having 1 to 18 carbon atoms and X represents a halogen atom). It is characterized by reacting with a quaternary ammonium compound in the presence of an alkali. A method for synthesizing a quaternary ammonium phosphite compound represented by the general formula (3):