JP2549073B2 - Process for producing alkylene oxide adduct of halogenated phenols - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an alkylene oxide adduct of a halogenated phenol, and particularly to an alkylene oxide adduct of a monovalent halogenated phenol or an alkylene oxide on a halogenated bisphenol. The present invention relates to a method for producing an alkylene oxide adduct by reacting

[Prior Art] Conventionally, for producing an alkylene oxide adduct of a monovalent halogenated phenol or an alkylene oxide adduct of a halogenated bisphenol by reacting with an alkylene oxide of a monovalent halogenated phenol or a halogenated bisphenol. The catalyst used in the addition reaction of alkylene oxide with sodium is generally sodium hydroxide,
Although a method using an alkali metal hydroxide such as potassium hydroxide or an alkali metal alcoholate such as sodium methoxide or sodium ethoxide is known,
The method using the alkali metal hydroxide or alcoholate has a problem that the reaction mixture is colored during the reaction.

In addition to the above-mentioned method, JP-A-50-105638 discloses a method for producing a dioxyalkylene ether of tetrabromobisphenol A using trimethylamine as a catalyst in the presence of a polar solvent having no active hydrogen. Kaisho 58
-46034 discloses a method of using N, N-dihydroxy-N-n-alkylamine as a catalyst for adding alkylene oxide to a melt of tetrabromobisphenol A, further disclosed in JP-A-61-148135. In JP-A No. 1993-242, an alkylene oxide of a brominated bisphenol is prepared by slurrying a brominated bisphenol with an alkylene oxide and using as a catalyst a tertiary amine (an alkylene oxide added to an amine, especially ditanolbutylamine). Although a method for producing an adduct is disclosed, all of these methods have a problem that the reaction mixture is colored during the reaction.

[Problems to be Solved by the Invention] Alkylene oxide adducts of halogenated phenols are often useful as additives for synthetic resins and synthetic fibers, particularly addition-type or reaction-type flame retardants, and for that purpose, coloring It is desirable to have as few as possible. However, the method using an alkali metal hydroxide or alcoholate as described above, or the method using trimethylamine, N, N-dihydroxy-Nn-alkylamine or diethanolbutylamine as a catalyst is not preferable during the reaction. In order to color and purify the colored reaction mixture by decolorization, a separately provided purification step is required, resulting in a problem of high product cost.

[Means for Solving the Problems] The present invention has been made in view of the above problems, that is, an alkylene oxide adduct is produced by reacting a monovalent halogenated phenol or halogenated bisphenol with an alkylene oxide. In the method (However, at least one of the alkyl groups of R ¹ , R ² and R ^{3 is} an alkyl group having 5 to 28 carbon atoms, and the other alkyl group is an alkyl group having 1 to 28 carbon atoms.) An alkylene oxide adduct of halogenated phenols, characterized in that the aliphatic tertiary amine represented is reacted in the presence of 0.05 to 3% by weight with respect to the monovalent halogenated phenol and / or halogenated bisphenol. It is a manufacturing method.

[Detailed Description of the Invention] (1) Raw material component Monovalent halogenated phenol and halogenated bisphenol component The monovalent halogenated phenol or halogenated bisphenol used in the present invention has the following general formula: as well as [Wherein, X ^{1 to} X ⁴ each represent an atom selected from chlorine, bromine, iodine or fluorine, and Y represents (R ⁴ and R ⁵ are alkyl groups having 1 to 3 carbon atoms) or Represents ] Monovalent halogenated phenols or halogenated bisphenols represented by the following are used.

In the above formula, a monovalent halogenated phenol
Particularly, X ^{1 to} X ³ are preferably chlorine or bromine.

Alkylene oxide component As the alkylene oxide added to the monovalent halogenated phenol or halogenated bisphenol component, ethylene oxide (hereinafter simply abbreviated as EO), propylene oxide (hereinafter simply abbreviated as PO), butylene oxide (hereinafter simply referred to as (Abbreviated as BuO) and the like, but EO and PO are particularly preferable.

Catalyst As the aliphatic tertiary amine used as a catalyst in the present invention, those represented by the following general formula are used.

[However, at least 1 of the alkyl groups of R ¹ , R ² and R ³
One is an alkyl group having 5 to 28 carbon atoms (preferably 8 to 22 carbon atoms), and the other alkyl group is an alkyl group having 1 to 28 carbon atoms. ] When all the carbon atoms of R ^{1 to} R ³ in the above formula are less than 5, or the carbon number exceeds 28, a sufficient catalytic effect cannot be obtained. That is, if the carbon number is all 4 or less, or if the carbon number is 29 or more,
The reaction product is highly colored.

The amount of the aliphatic tertiary amine as the above catalyst added is 0.05 to 3% by weight, preferably 0.2 to 0.8% by weight, based on the monovalent halogenated phenol or halogenated bisphenol. If the added amount is less than the above range, the effect of the present invention cannot be sufficiently exhibited, and if the added amount is too large, unfavorable results are produced depending on the use of the product.

The catalyst used in the present invention may be used alone, or two or more kinds of these catalysts may be used in combination.

(2) Reaction It is preferable to carry out the reaction under pressure. Specifically, the reaction varies depending on the amount of catalyst, type of catalyst, type of alkylene oxide, halogenated phenols, halogenated bisphenols, etc. The pressure is selected appropriately,
Generally, the pressure is 0 to 3.0 kg / cm ² .

The reaction temperature is generally 80 to 200 ° C., preferably 100.
~ 150 ° C. When the reaction temperature is lower than the above range, the reaction rate becomes slow, and when it is high, decomposition is promoted during the reaction and the yield is deteriorated, which is not preferable.

(3) Addition reaction product The reaction product produced by the addition reaction is an alkylene oxide adduct of a monovalent halogenated phenol and / or an alkylene oxide adduct of a halogenated bisphenol. The reaction product can be used as it is or after being modified and then blended as a flame retardant for synthetic resin or synthetic fiber.

The alkylene oxide component is usually added to the addition reaction product in an amount of about 1 to 6 mol by this addition reaction. The degree of addition is appropriately determined according to the degree of flame retardancy of the addition reaction product or the application such as melting point.

[Examples] Examples 1 to 11 and Comparative Examples 1 to 7 In an autoclave having an inner volume of 2 equipped with a stirrer, a thermometer, and a gas introduction pipe, halogenated phenols and catalysts shown in Table 1 or Table 2 Was added, and after sufficiently substituting with nitrogen, the mixture was heated with stirring, and when the reaction temperature shown in Table-1 or Table-2 was reached, the alkylene oxide shown in Table-1 or Table-2 was gradually introduced. Then, the reaction was performed for the reaction time shown in Table-1 or Table-2.

The reaction was carried out after the introduction of the alkylene oxide was stopped and then aged for 1 hour under stirring while maintaining the same temperature.

After the aging was completed, the reaction product was taken out by cooling to 60 ° C.

The color tone of this reaction mixture is based on the Gardner method color tone standard (Refer to pages 150-151 of the manual for oleochemicals: Showa 38, Nikkan Kogyo Shimbun).
Issued October 30, 2013).

 The results are shown in Table-1 and Table-2.

[Effects of the Invention] Alkylene of the halogenated phenols of the present invention The method for producing an oxide adduct is such that an alkylene oxide adduct of a halogenated phenol and / or a halogenated bisphenol of which the coloring degree of the product is significantly lower than the conventional method for producing an alkylene oxide adduct of halogenated phenols. Since an alkylene oxide adduct can be produced, even if the product is directly blended with a synthetic resin and a synthetic fiber as a flame retardant, a synthetic resin and a synthetic fiber with little coloring can be obtained, which is industrially very useful. It is something.

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Claims (1)

(57) [Claims] 1. A method for producing an alkylene oxide adduct by reacting a monovalent halogenated phenol or a halogenated bisphenol with an alkylene oxide, wherein: (However, at least one of the alkyl groups of R ¹ , R ² and R ^{3 is} an alkyl group having 5 to 28 carbon atoms, and the other alkyl group is an alkyl group having 1 to 28 carbon atoms.) An alkylene oxide adduct of halogenated phenols, characterized in that the aliphatic tertiary amine represented is reacted in the presence of 0.05 to 3% by weight with respect to the monovalent halogenated phenol and / or halogenated bisphenol. Production method.