JPH02135223A - Production of polyoxyalkylene polyketone - Google Patents

Abstract

PURPOSE:To obtain in high yield the title compound useful as a raw material for plastics or as an intermediate for organic synthesis by reaction between a polyoxyalkylene polyol and an alpha-haloketone. CONSTITUTION:The objective compound can be obtained by reaction at room temperature - 150 deg.C and 0-10kg/cm<2>G for 1-20hr between (A) a polyoxyalkylene polyol (pref. of 2-8 functionality and >=400 in average molecular weight) and (B) an alpha-haloketone (pref. monochloroacetone), at pref. 1-3 equivalents of the component B based on the component A, in the presence of normally 1-10 equivalent times (based on the alpha-haloketone) of a hydrogen halide scavenger such as sodium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a polyoxyalkylene polyketone, and more specifically, the present invention is characterized by reacting a polyoxyalkylene polyol with an α-haloketone. The present invention relates to a method for producing polyoxyalkylene polyketone.

Polyethers having a carbonyl group at the end are useful as raw materials for plastics and intermediates in organic synthesis.

[Conventional technology]

The method of obtaining a polyoxyalkylene polyketone having a carbonyl group at the end is known. For example, a method of oxidizing with chromium dioxide in a pyridine solvent (Chemical Society of Japan No. 52
Spring Annual Meeting Lecture Proceedings, PEOT Lecture No. IJ18) However, this method requires a large amount of oxidizing agent;
In addition, the post-treatment process is complicated and the yield is low, making it undesirable as a method for industrially producing polyoxyalkylene polyketones.

[Problem to be solved by the invention]

An object of the present invention is to provide a method for obtaining polyoxyalkylene polyketones in high yield.

[Means to solve the problem]

The present inventors have made extensive studies to achieve the above object, and have finally arrived at the present invention.

That is, the present invention provides a polyoxyalkylene polyol;
This is a method for producing polyoxyalkylene polyketone, which is characterized by reacting with α-haloketone.

The polyoxyalkylene polyol used in the present invention is
Those with 2 to 8 functionalities and an average molecular weight of 400 or more are suitable. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, bisphenol A, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, dipropylene glycol, bisphenol F, dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone , redulucin, naphthalene diol, aminophenol, aminonaphthol, phenol formaldehyde polymerization h, phloroglucin, methyljetanolamine, ethyldiisopropanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, bis(p-aminocyclohexyl)methane, tolylenediamine It is a polyoxyalkylene polyol obtained by adding one or more types of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. to amine, diphenylmethane diamine, naphthalene diamine, etc. In addition to the above, examples include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

Examples of the α-haloketone used in the present invention include monochloroacetone, monobromoacetone, phenacyl chloride, phenacyl bromide, and the like.

α-Haloketone is determined depending on the application, but usually
0.3 to 10 equivalents based on hydroxyl group, preferably 0.5
~5 equivalents are used, most preferably 1 to 3 equivalents.

The α-haloketone may be added as appropriate or may be charged in bulk depending on the progress of the reaction.

The hydrogen halide scavenger used in the present invention includes alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and alkali metal carbonates such as sodium hydroxide and potassium hydroxide. Examples include alkaline earth metal hydroxides such as hydroxide, calcium hydroxide, and magnesium hydroxide, and tertiary amine compounds such as trimethylamine, triethylamine, and tributylamine.

The hydrogen halide scavenger is usually used in an amount equivalent to to 10 times the amount of α-haloketone.

In addition, a method is adopted in which an alkoxide of a polyoxyalkylene polyol is prepared in advance from a polyoxyalkylene polyol and the above-mentioned alkali metal hydroxide, or an alkali metal such as metallic sodium or metallic potassium, and then reacted with an α-haloketone. You can also.

Water and an organic solvent may or may not be present in the reaction system.

The reaction conditions of the present invention vary depending on the raw materials used, especially the boiling point and reactivity of α-haloketone, and are not particularly limited.
1 reaction pressure is 0~10kg/cfflG reaction time 1~2
Do it in 0 hours.

After the reaction is completed, excess base and by-product salts are removed by methods such as neutralization and washing with water, and then the desired polyoxyalkylene polyketone is obtained by appropriately combining methods such as drying and filtration. be able to.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 Polyoxypropylene triol obtained by addition polymerizing propylene oxide to glycerin (hydroxyl value 33.
4mgKOH/g-average molecular weight 5040, hereinafter abbreviated as polyol P. ) 250g, monochloroacetone 13.9g, sodium carbonate 15.9g, water 150g
While stirring in a 500 ml glass autoclave, the temperature was raised to 100''C, and the reaction was carried out for 5 hours.

After the reaction was completed, the mixture was neutralized with phosphoric acid, the aqueous layer was separated by static separation, and washing was repeated with a large amount of water.

The polyoxyalkylene polyketone was purified by dehydration under reduced pressure and filtration. The ketone value of the obtained polyoxyalkylene polyketone was determined using hydroxylamine hydrochloride in accordance with JIS K 1525. Further, absorption of carbonyl group (1720 cm-') was confirmed by IR spectrum. The results are shown in Table 1.

Example 2 A reaction was carried out under the same conditions as in Example 1, except that water was not present in the system and an equivalent amount of sodium hydroxide was used instead of sodium carbonate. The results are shown in Table 1.

Example 3 In Example 1, 1 liter of triethylamine (NEt+) was added instead of sodium carbonate without water being present in the system.
The reaction was carried out using 0 times the equivalent at a reaction temperature of ElO'C. Other conditions are the same as in Example 1.

The results are shown in Table 1.

Example 4 The reaction was carried out under the same conditions as in Example 1, except that monobromoacetone was used instead of monochloroacetone. The results are shown in Table 1.

Example 5 A reaction was carried out under the same conditions as in Example 1, except that phenacyl chloride was used instead of monochloroacetone. The results are shown in Table 1.

Example 6 A reaction was carried out under the same conditions as in Example 1, except that phenacylbromide was used instead of monochloroacetone. The results are shown in Table 1.

Example 7 In Example 1, instead of polyol P, polyoxypropylene polyoxyethylene triol (ethylene oxide content 15-tχ
, hydroxyl value 33.0mgKO1l/g, average molecular weight 151
00, hereinafter abbreviated as polyol Q. ) was used, but the reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example Day In Example 1, polytetramethylene ether glycol (hydroxyl value 112 mgKOH/
g, average molecular weight: 11,000; hereinafter abbreviated as polyol R. ) was used, but the reaction was carried out under the same conditions as in Example 11. The results are shown in Table 1.

Example 9 The reaction was carried out under the same conditions as in Example 1, except that the equivalent ratio of polyol P/monochloroacetone/sodium carbonate was changed to 170.8/4 and the amount of water used was changed to 120 g. The results are shown in Table 1.

〔Effect of the invention〕

By reacting a polyoxyalkylene polyol with an α-haloketone, it becomes possible to obtain a polyoxyalkylene polyketone in a high yield using a slower method than conventional methods.

Claims (1)

[Claims] 1. A method for producing a polyoxyalkylene polyketone, which comprises reacting a polyoxyalkylene polyol and an α-haloketone. 2. The molecular weight of the polyoxyalkylene polyol is 40
The manufacturing method according to claim 1, wherein the number is 0 or more. 3. The manufacturing method according to claim 1, wherein the α-haloketone is monochloroacetone. 4. The manufacturing method according to claim 1, wherein the reaction is carried out in the presence of sodium carbonate as a hydrogen halide scavenger in the reaction system.