JPS5916859A - Preparation of unsaturated quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high purity in high yield, by reacting an unsaturated compound with a tertiary amine in the absence of a solvent. CONSTITUTION:An unsaturated compound shown by the formula I [R1 is H, or CH3; A is -(CH2)n-(n is 2-4), or group shown by the formula II; X is Cl, Br, or I] is reacted with a tertiary amine shown by the formula III (R2-R4 are 1- 8C alkyl, hydroxyalkyl, or benzyl) in the absence of a solvent to give the desired compound shown by the formula IV. Since no solvent is required, the process is economically simplified without needing the recovery of the solvent. The reaction is carried out preferably at 40-80 deg.C at from normal pressure - 100kg/ cm<2>G. Since the compounds shown by the formula I and formula IV are polymerizable substances, preferably a polymerization inhibitor (e.g., hydroquinone, etc.) is present in the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present inventors have developed an unsaturated quaternary compound represented by the general formula [Otori] described below.
Regarding the production of grade ammonium salts, we have previously proposed a new method for producing high quality ammonium salts in the presence of an organic solvent (Japanese Patent Application No. 4433/1983).

The present inventors subsequently made further improvements to the method for producing the same compound, and as a result, it was possible to produce a highly pure unsaturated quaternary ammonium salt represented by the general formula [''] without using an organic solvent. The present invention was arrived at based on this finding.

That is, 1. the present invention is characterized in that an unsaturated compound represented by the following general formula CD is reacted with a tertiary amine represented by the general formula [111] in the absence of a solvent. This is a method for producing a quaternary ammonium salt.

CH, = c-COOA X [
D (in the formula, R1 is H or C13, A is -(CH2) -
(However, n is a number that may be 2 or 4.) What about f? 1.CH2-CI-, X represents Ce, Br or ■.

R, , R, , R, are an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group or a be/zyl group, and 1 is also acceptable. ) generally relating to the production of quaternary ammonium salts.

There is a so-called Menschutkin reaction,
It has been reported that polar solvents are advantageous in this reaction.

The present inventors have investigated the amount of organic solvent and surprisingly found that the reaction proceeds satisfactorily even without a solvent.

In other words, in this production method, by conducting the reaction without a solvent, a highly pure unsaturated quaternary ammonium salt can be obtained at a yield almost the same as that in a solvent-added system, so there is no need for a solvent recovery step, and the process The major feature is that it is a simplified and economically advantageous manufacturing method.

Unsaturated compounds as starting materials used in the present invention (Ill is 2, for example, 2-chloroethyl (meth)acrylate, 2
-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, 3-chloropropyl (meth)acrylate.

Tertiary amines [10 include 2 such as trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, tributanolamine, N,N-dimethylbenzylamine, dimethylethylamine, diethylmethylamine,
Methyl ethylph.

Examples include thylamine and tribenzylamine.

The molar ratio of the tertiary amine [111] to the unsaturated compound [1] can be used within a wide range, for example from 0.1 to 10, but preferably from 0.6 to 4.

The reaction pressure can be from normal pressure to 100 ky/cTL2G, but depending on the starting materials, the reaction may be carried out under reduced pressure. Preferably, the pressure is from normal pressure to 20 ky/crrt"G.

The reaction is generally carried out at elevated temperatures, from room temperature to 150°C, but preferably from 40°C to 80°C.

Although the reaction proceeds at temperatures lower than room temperature, the reaction rate is slow and uneconomical.

Since the compounds [13:t=5 and [■] are polymerizable substances, it is preferable that a polymerization inhibitor be present in the reaction system.

Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and phenothiazine 2,6-di-tert-butyl para-cresol.

Urea, thiourea, 2,4,6-tritertiary-butylphenol, N-phenyl-N'-/l-mprovir-baraphenylenediamine, etc. are used.

The tertiary amine [11], the unsaturated compound [1], and the polymerization inhibitor may be added to the reactor by separate means (or some or all of them may be mixed before the reactor inlet). may be added to the reactor.

Furthermore, the method of the present invention may be operated either batchwise or continuously. For example, in a batch-type reaction operation, if necessary, fill the reaction holding volume with an inert gas, add the reaction raw materials and polymerization inhibitor, and react at a predetermined temperature for a predetermined time. The desired compound can be obtained by cooling to a temperature of 100 ml, followed by conventional methods such as filtration and drying.

In continuous operation, 9 for example, a reactor equipped with a stirring device in which the reaction raw materials and polymerization inhibitor are continuously added and the reaction mixture is kept at a predetermined temperature for a predetermined residence time;
Alternatively, a pressurized reaction device such as an autoclave may be used.

This will be explained in detail below using examples.

Example 1 2-chloroethyl methacrylate 74/(0.5 mol) and hydroquinone monomethyl ether 0.15 F were added at room temperature into a glass-lined autoclave equipped with a stirring device, a pressure gauge, and a thermocouple, and the container was sealed. Trimethylamine 35/(0.6 mol) was added into the vessel over about 30 minutes.

The mixture was then heated to 65°C and reacted at this temperature for 10 hours with stirring. After the reaction completed liquid was cooled to room temperature and the pressure in the reactor was returned to normal pressure, the crystals were filtered once, and excess trimethylamine was dried and collected under reduced pressure to obtain crystals 907'.

The obtained crystals were confirmed to be highly pure methacryloyloxyethyltrimethylammonium chloride from IR, NMR, double bond value, quaternary salt, and elemental analysis.

Example 2 To the same reactor as in Example 1, 2-chloroethyl acrylate 67JF (0.5 mol), hydroquinone monomethyl ether o, i3p were added at room temperature, the vessel was sealed, and trimethylamine 35/(0,6 mol) was added into the vessel over approximately 30 minutes.

The mixture was then heated to 65°C and reacted at this temperature for 10 hours. After the reaction completed liquid was cooled to room temperature and the pressure in the two reactors was returned to normal pressure, the contents were taken out, and the crystals were filtered, and excess trimethylamine was recovered under reduced pressure to obtain crystals 76F.

The obtained crystals have IR, NMR, double bond value, acid value,
It was confirmed from grade salt and elemental analysis that it was highly pure 2-acryloyloxyethyltrimethylammonium chloride.

Example 3 Using the same reaction apparatus as in Example 1, 2-chloroethyl methacrylate 74JF (0.5 mol) and hydroquinone monomethyl ether 0.1st were added at room temperature, the container was sealed, and trimethylamine 89/(1.5 mol) was added. was added to the container over about 30 minutes.

The mixture was then heated to 65°C and reacted at this temperature for 12 hours. After the reaction completed liquid was cooled to room temperature and the pressure in the second reactor was returned to normal pressure, the contents were taken out, fl overdried, and crystals 88
I got it.

The obtained crystals were analyzed in the same manner as in Example 1, and it was confirmed that highly pure 2-methacryloyloxyethyltrimethylammonium chloride was obtained.

Example 4 Using the same reactor as in Example 1, 2-chloroethyl methacrylate 89P (0.6 mol) and hydroquinone 0.20 P were added at room temperature, the container was sealed, and trimethylamine 30/(0.5 mol) was added. was added to the container over about 20 minutes.

The mixture was then heated to 65°C and reacted at this temperature for 12 hours.

The same procedure as in Example 1 was carried out to obtain crystal 89P.

As a result of analysis in the same manner as in Example 1, it was confirmed that it was highly pure 2-methacryloyloxyethyltrimethylammonium chloride.

Examples 5 to 14 Reactions were conducted in the same manner as in Example 1 using various reaction raw materials under the conditions shown in Table 1. The results are shown in Table-1.

Claims (1)

[Claims] An unsaturated compound represented by the following general formula CD and the general formula [■]
A method for producing an unsaturated quaternary ammonium salt represented by the general formula [11], which comprises reacting a tertiary amine represented by the formula in the absence of a solvent. R1 (wherein R, is H or CH, A is -(CH2)n-(
However, n is a number of 2 or 4), or CH3 CH, -CH-, and X represents C13, Br or I. R,, Rs, and R may be the same alkyl group, hydroxyalkyl group, or benzyl group having 1 to 8 carbon atoms. )