JPS63238047A - Polyoxyalkylene polyol derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (n is 2-8; R is n-functional group obtained by removing OH from n-functional polyoxyalkylene polyol). USE:Useful as a raw material for polyurea RIM and elastomer, a polymerization initiator, an epoxy resin curing agent and a raw material for plastics such as heat-resistant and rapidly curing coating compound. PREPARATION:A polyoxyalkylene polyol having 400-10,000 average molecular weight is reacted with a benzyl halide by the use of a caustic alkali (e.g. NaOH, KOH or Na2CO3) to give a compound shown by formula II. Then this compound is chloromethylated to give a compound shown by formula III, which is then reacted with NH3 by the use of a catalyst to give a compound shown by formula I. NH3 in an amount larger than a theoretical amount is used for the reaction in high yield.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides polyoxyalkylene polyol derivatives,
and its manufacturing method. More specifically, the general formula (I
) (n represents an integer of 2 to 8, R represents an n-valent group such as that which can be obtained by removing the hydroxyl group from an n-valent polyoxyalkylene polyol). A polyoxyalkylene polyol derivative having the formula (II) and a polyoxyalkylene polyol having an average molecular weight of 400 to 10,000 are reacted with benzyl halide using caustic alkali, and the resulting general formula (II)
(n in the formula is CI) (same as n in the formula, R is the same as R in the formula (I)) is subjected to a chloromethylation reaction, and the general formula (I[[) (n in the formula is (I) ), and R is the same as n in formula N), and then reacted with ammonia using a catalyst to form a benzylamine-type amino group at the terminal of claim 1. The present invention relates to a method for producing polyoxyalkylene polyol derivatives.

A polyether having an amino group at the terminal provides polyurea through a polyaddition reaction with a polyisocyanate, and is used as a raw material for polyurea RIM and elastomer.

It is also used as an initiator for ring-opening polymerization of epoxy compounds, and is used as epoxy resin curing agents, heat-resistant, fast-curing paints, etc.
It is a compound useful as a raw material for plastics.

[Prior Art] Many attempts have been made to develop polyoxyalkylene polyol derivatives having amino groups at their terminals, and unique ones have been provided.

■Manufactured by reacting the terminal hydroxyl group of polyoxyalkylene polyol with ammonia at high temperature and pressure using a hydrogenation-dehydrogenation catalyst (for example, Belky Patent No. 677124).
No.), (1) those produced by reacting polyoxyalkylene polyol and acrylonitrile to cyanoethylate the terminals and then catalytically reducing them (for example, Japanese Patent Publication No. 53-95906
No.), ■ Aminobenzoic acid ester derivatives of polyether polyols obtained by transesterification reaction between aminobenzoic acid esters and polyoxyalkylene polyols (for example, Japanese Patent Publication No. 60-38412), ■ Paranitrobenzoic acid chloride and polyoxyalkylene polyols (U.S. Pat. No. 4,328,322), isatoic anhydride, which is obtained by reacting polyol with para-aminobenzoic acid ester (U.S. Pat. No. 4,328,322), and then reducing the nitro group. anthranyl ester of polyether obtained by reacting with an ether polyol (JP-A-46-5245); (2) reacting with a polyoxyalkylene polyol and an excess amount of isocyanate to form a compound having an isocyanate end group; Polyamines produced by hydrolyzing polyketimines, polyaldimines, or polyenamines obtained by reacting hydroxylamide with ketimines, aldimines, or enamines having a hydroxyl group formed by the reaction of hydroxyl amines with aldehydes or ketones (Tokuko Showa) 57-570.51) etc. are known.

[Problem that the invention seeks to solve]

The object of the present invention is to obtain the general formula (I) (n represents an integer of 2 to 8, and R represents an n-valent group such as can be obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol) The purpose of the present invention is to provide a novel polyoxyalkylene polyol derivative having a benzylamine type amino group at the terminal represented by the formula, and a method for producing the same.

Conventionally known polyoxyalkylene polyol derivatives having an amino group at the terminal end are those in which the terminal amino group is composed of an aliphatic amine (sections 1 and 2 of the prior art).
The terminal amino group is an aromatic amine composed of an ester bond (sections ■, ■, and ■ of the conventional technology), and the aromatic amine is composed of a urethane bond (section of the conventional technique). It has a different structure from the polyoxyalkylene polyol derivative having a benzylamine type amino group at the terminal of the present invention.

[Means for solving problems]

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 has the following features: 1. General formula (I) (in the formula, n represents an integer of 2 to 8, and R is an A polyoxyalkylene polyol derivative represented by (representing a valent group).

2. An n-valent polyoxyalkylene polyol with an average molecular weight of 1,400 to 10,000 is reacted with benzyl halide using caustic alkali, resulting in the general formula % formula % [) (n in the formula is (I) formula 〇〇 (similarly, R is the same as R in formula (I)) is subjected to a chloromethylation reaction, and the general formula (III) (n in the formula is the same as n in (I) 2, R is the same as in formula (I) ) and then reacting with ammonia using a catalyst to produce a polyoxyalkylene poly(1-) derivative having a benzylamine type ψ amino group at the terminal as set forth in claim 1. It is.

The n-valent polyoxyalkylene polyol with an average molecular weight of 1400 to 1000 used in the present invention can be obtained by a known method. alkylene oxide in the presence of a suitable initiator,
It is obtained by ring-opening polymerization using a basic catalyst such as an alkali metal hydroxide.

Initiators include propylene glycol, diethylene glycol, tripropylene glycol, other polypropylene glycols, ethylene glycol, diethylene glycol, triethylene glycol, other polyethylene glycols, glycerin, diglycerin, pentaerythritol, sorbitol, sucrose, and other polypropylene glycols. Examples include hydrohydric alcohols, bisphenol A, bisphenol S luzole, novolak, other polyhydric phenols, triethanolamine, jetanolamine, and other alkanolamines.

Further, as the alkylene oxide, propylene oxide, ethylene oxide, and butylene oxide are usually used alone or in any combination.

A polyoxyalkylene polyol obtained by a known method and a benzyl halide of general industrial grade or higher,
React in the presence of caustic alkali.

Typical examples of the benzyl halide are benzyl chloride and benzyl bromide, and the caustic alkali used includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.

The reaction conditions are not particularly limited, but it is usually preferable to use benzyl halide and caustic alkali in an amount greater than the theoretical amount for the polyoxyalkylene polyol, to add the raw materials all at once, or to add the raw materials in advance to the polyoxyalkylene polyol. It is carried out by a method such as dropping benzyl halide onto an alkali metal salt obtained by reacting a polyol with a caustic alkali, but it may also be carried out in the presence of a solvent such as DMF and water.8 The reaction temperature ranges from room temperature to 200°C. C is preferable; if it is too low, the reaction will be slow; if it is too high, there will be problems of coloring and deterioration of the product, which is undesirable. Remove and purify using conventional methods.

General formula (II) obtained by the above method (n in the formula is the same as n in formula (I), R is the same as R in formula (I)) having a phenyl group at the terminal In the chloromethylation reaction of polyoxyalkylene polyol derivatives, monochloroethyl ether obtained by blowing hydrogen chloride into methanol and formalin is converted into 5nC1a, Fe(:Is
, AlCl5, ZnC1z, BF3・EtOH.

The reaction is carried out by a known method such as a method of reacting in the presence of a Lewis acid catalyst such as ASCI3, or a method of reacting paraformaldehyde and hydrogen chloride in the presence of the Lewis acid using a solvent such as ethylene dichloride or acetic acid. The reaction product after chloromethylation is washed with water, washed with alkali, and dehydrated, and the obtained general formula (I [I) (n in the formula is the same as n in formula (I), R is 0 reaction in which ammonia is reacted with a polyoxyalkylene polyol derivative having a benzyl chloride group at the terminal represented by
O3, NatCOx, Na0CHs or KOC11
The degree of 0 reaction in the presence of 3 etc. is carried out at 200 °C or less considering the quality of the main product. In order to carry out the reaction with good yield, it is preferable to use ammonia in excess of the theoretical amount. The reaction can also be carried out using a solvent such as water or alcohol. After the reaction, the general formula (
I) polyoxyalkylene represented by (in the formula, n represents an integer of 2 to 8, and R represents an n-valent group such as that which can be obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol) Polyol derivatives can be produced.

Representative examples of novel compounds of polyoxyalkylene polyol derivatives having amino groups at the terminals obtained by the method of the present invention include the following.

CI'+3 (Xl,, Xt -, Xs, yt % V, y2
,
or represents a positive integer) [Examples] The present invention will be described below with reference to Examples.

Example 1 300 with stirrer, reflux condenser and thermometer
An average molecular weight of 1500 obtained by addition polymerizing propylene oxide to glycerin in the glass round bottom flask of d.
(0) IV 112.4mgKOH/g) (150g of D polyoxypropylene triol was inserted. 45%
Add 30 g of caustic soda and stir at 100"C for 1 hour, then add 75 g of reagent-grade benzyl chloride while stirring vigorously.
was added dropwise over 1 hour, and stirring was continued for 5 hours while maintaining the temperature at 100'C. After cooling, it was taken out into a separatory funnel, 250 d of methylene chloride was added, and washed three times with 500 ml of water. The mixture was heated to 80°C under reduced pressure, and methylene chloride, water, and unreacted benzyl chloride were distilled off to obtain 168 g of the residue.
7) OHV was 6.5 mgKOH/g, and as a result of spectrum analysis using an infrared spectrophotometer, absorption was observed near 730 c+a-' due to out-of-plane bending vibration of 1CH due to the aromatic monosubstituted product.

Example 2 Into the same apparatus used in Example 1, 150 g of the residue obtained in Example 1 and methylene chloride IOM were inserted, and 20 g of reagent special grade zinc chloride was added, stirred, and heated under normal pressure to reflux the reagent. After 61 g of methyl ether was added dropwise over 1 hour, stirring was continued for 8 hours while heating under reflux at normal pressure. After the reaction was completed, methylene chloride and unreacted monochloromethyl ether were distilled off, transferred to a separating funnel, and methylene chloride 25M! was added and washed twice with 500 d of 5% aqueous sodium carbonate solution, and further washed with 500 ml of water. The organic layer obtained was heated to 80° C. under reduced pressure to remove methylene chloride and water. 151g of pot residue was obtained, and the analysis results using oxygen flask combustion method and ion chromatography showed that chlorine was 5.4.
%, and the result of spectrum analysis by infrared spectrophotometer is 730 due to out-of-plane bending vibration of 1CH due to aromatic substitution.
Absorption was observed near cab-' and 800 cea-'.

Example 3 90 g of pot residue obtained in Example 2, NaHCO31
0g1 and liquid ammonia 105g in stainless steel 30
The mixture was placed in a zero-pressure autoclave and stirred at 80°C for 20 hours.

The reaction pressure was 37 arms. After cooling, unreacted 7
7-F-Nia is discharged and the contents are diluted with methylene chloride 1
00d and washed three times with 20oIR1 of water. Yes
methylene chloride and water were distilled off by heating to 80° C. under reduced pressure to obtain 78.5 g of a sticky liquid as a residue.

The elemental analysis values of the liquid are: C65.01%, H9.6
8%, N 2.06% Teatte, calculated value for benzylamine derivative of polyoxypropylene polyol with average molecular weight f1500, C64,51%, H9,73%, N2.
26%. Amine value is 58.9■HCI/
g, and the result of spectrum analysis using an infrared spectrophotometer is 730 due to the out-of-plane bending vibration of one CH due to the aromatic substituent.
cm-', 800 cm-', stretching vibration of -NH and absorption of 34oo cm-1, 3500 cm-' were observed. Based on the analysis results, the product manufactured in the example was as follows:
R in the general formula (I) in claim 1 is an average molecule of 1
1500 residues of polyoxypropylene triol n
It is clear that this is a substance corresponding to 3.

[Effects of the Invention] The present invention provides a new compound of a polyoxyalkylene polyol derivative having a benzylamine type amino group, which has a structure different from conventionally provided polyoxyalkylene polyol derivatives having an amino group at the end. be.

The compound of the present invention does not contain an ester bond or a urethane bond in its molecule, and can be effectively used as a raw material for plastics, such as by reacting with isocyanate to obtain a polyurea resin with urea bonds.

Patent applicant: Mitsui Toatsu Kagaku Co., Ltd. Proceeding Officer (spontaneous) April 1988 Z'-”5 Commissioner of the Patent Office Kunio Ogawa 1, Indication of case: 1988 Patent Application No. 069051 2, Title of the invention: Polyoxyalkylene polyol derivatives and their manufacturing method 3; Relationship with the case of the person making the amendment Patent applicant address: 3-2-5 Kasumigaseki, Chiyoda-ku, East East Name (31
2) Mitsui Toatsu Chemical Co., Ltd. 4. Number of inventions increased by amendment Zero (I) CH on page 13, lines 3-4 of the specification.

There is a certain thing

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, n represents an integer from 2 to 8, and R is an n-valent polyoxyalkylene polyol. A polyoxyalkylene polyol derivative represented by (representing an n-valent group that can be obtained by removing a hydroxyl group). 2. General formula (II) obtained by reacting benzyl halide with a polyoxyalkylene polyol having an average molecular weight of 400 to 10,000 using caustic alkali ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) n is the same as n in formula (I), and R is R in formula (I).
) is subjected to a chloromethylation reaction, and the general formula (III)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (III) (n in the formula is the same as n in formula (I), R is R in formula (I)
) and then reacting with ammonia using a catalyst to produce the polyoxyalkylene polyol derivative having a benzylamine type amino group at the terminal as claimed in claim 1.