JPS58121254A - Preparation of unsaturated quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for flocculants, antistatic agents, etc. in high purity, by reacting a specific unsaturated compound with a tertiary amine. CONSTITUTION:An unsaturated compound of formulaI[R1 is H or CH3; A is -(CH2)n- (n is 2-4), etc.; X is Cl, Br or I], e.g. 2-chloroethyl (meth)acrylate or 2-bromoethyl (meth)acrylate, is reacted with a tertiary amine of formula II (R2- R4 are 1-8C alkyl, hydroxyalkyl and/or benzyl), e.g.trimethylamine, triethylamine or tripropylamine, to give an unsaturated quaternary ammonium salt of formula III. The reaction is preferably carried out in the presence of an organic solvent, e.g. acetonitrile or propionitrile.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for preparing unsaturated quaternary ammonium salts. More specifically, the unsaturated compound I CH-COOAX (1) represented by the general formula [,1] (wherein R8 is H or CH, A is -(Cat)n-Cl).

(However, n = 2 to 4) or -CH, -CH-.

X represents CJ, Br or I. ) and the tertiary amino acid/No. 9 represented by the general formula [1] (however, in the formula 1, u, l R1v R4 have a carbon number of 1 to 8
an alkyl group, a hydroxyalkyl group and/or
Or represents a benzyl group. ) to produce an unsaturated quaternary ammonium salt represented by the general formula [1].

(However, RII R@#"me R41A and X in formula 1 are the same as defined in formulas [1] and [1].) General formula [
The compound represented by 1] is a useful monomer that can be used as a raw material for producing flocculants, antistatic agents, soil conditioners, paper strength enhancers, dye improvers, and the like.

Conventionally, the (meth)acryloyloxyethyl trialkylammonium salt represented by the general formula (13) has been prepared by the reaction formula (1).
) is known to be obtained by the method.

R1 (However, in formula 1, R8 is H or αll*R11"l and R4 is -CH, or -C,H,, X is (-13e B
r or! represents. ) However, in the synthesis of unsaturated quaternary ammonium salts using reaction formula (1) K, it is difficult to obtain a product that completely avoids the contamination of side reactants, and therefore it is difficult to obtain the product polymer with good reproducibility. It is difficult to do this, and improvements in this respect have been strongly desired.

As a result of intensive study to solve this problem, the inventors found that
This is a new production method that is completely different from the conventional method based on reaction formula (1).

The present invention was achieved by discovering that a highly pure unsaturated quaternary ammonium salt represented by the general formula (1) can be produced.

The unsaturated compound 0) as the starting material used in the present invention is 1
For example, 2-chloroethyl (meth)acrylate, 2-bromoethyl (meth)acrylate (v-), 2-iodoethyl (
meth) acrylate t 3-10 logropyr (meth)
Examples of the tertiary amine El) include ac I) V-) t4-chlorobutyl (meth)acrylate and 2-chloro-2-methyl-ethyl (meth)acrylate.

For example, trimethylamine/triethylamine.

Tripropylamine, tributylamine, triethanolamine, tributanolamine, N.

Examples include N-dimethylbenzylamine, dimethylethylamine, diethylmethylamine, and methylethylbutylamine.

The charging ratio of the tertiary amine [13 and the unsaturated compound (1)] can be reacted in a wide range, for example from 0.1 to 10, but preferably from 0.6 to 4.

The present invention is preferably carried out in the presence of an organic solvent.

Solvents used in the reaction are 9, for example, acetonitrile, propionitrile, acetone, methyl ethyl ketone, dimethylformamide, sulfolane, tetrahydrofuran,
Examples include methanol, ethanol, globanol, butanol, hexa/cyclohexane, and the like.

The reaction pressure can be from normal pressure to 100 kflCIA''G-, but depending on the starting material, the reaction may be carried out under reduced pressure. Preferably it is from normal pressure to 20 kflCIA''G.

The reaction is generally carried out at elevated temperatures, preferably between room temperature and 150°C or between 40°C and 100°C. Although the reaction proceeds at temperatures lower than room temperature, the reaction rate is slow (not economical (ゝO Compound (1) and [I''l are polymerizable substances, so a polymerization inhibitor must be present in the reaction system. ◎ As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-ditertiary-butyl para-cresol, urea, thiourea,
2.4.6-) Literary butylphenol, N-phenyl-N'-ingloby-paraphenile/
Diamine etc. are used.

The tertiary amine [111], the unsaturated compound [1], and the polymerization inhibitor may each 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 carried out either batchwise or continuously. For example, in a pressurized batch reaction operation, if necessary, the empty volume of the reactor is replaced with an inert gas, one reactor is sealed, the reaction raw materials and a polymerization inhibitor are added, and after a predetermined time has elapsed at a predetermined temperature, If necessary, cool the reactor and contents to the specified temperature, filter, and crystallize.

The desired compound can be obtained by conventional methods such as extraction and solvent removal.

As the reactor, an autoclave with a stirring device, a single-pressure pipe, or the like is used. Continuous operation involves a reactor equipped with a stirring device, for example, in which the reaction raw materials and polymerization inhibitor are continuously added to the reactor, and the reactor mixture is kept at a predetermined temperature for a predetermined time; It may be a device such as an autoclave, a pressure tube, or a coil.A detailed description will be given below using examples.

Example 1 74p (2-chloroethyl methacrylate) (0.5 mol) and hydroquinone monomethyl ether 0.15 F, acetonitrile 10 at room temperature in a glass-lined autoclave equipped with a stirrer, a pressure gauge and a thermocouple.
Add 0m of trimethylamine, seal the container, and add trimethylamine 30F.
(0.5 mol) was added into the vessel over approximately 30 minutes.

The mixture was then heated to 75°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 two reactors was returned to normal pressure, the crystals were filtered and dried to yield 100 crystals! I got it.

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-methacryloyloxyethyltrimethylammonium chloride.

Example 2 To the same reactor as in Example 1, 0.13 F of 2-chloroethyl acrylate)67/(0.5 mol) hydroquinone monomethyl ether and 100 Wil of acetonitrile were added at room temperature, the container was sealed, and 30. P(0,
5 mol) was added into the vessel over approximately 30 minutes.

The mixture was then heated to 75°C and reacted at this temperature for 10 hours.

After the reaction completed liquid was cooled to room temperature and the pressure in one reactor was returned to normal pressure, the contents were taken out, filtered and dried to obtain crystal 92/.

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-acryloyloxytyltrimethylammonium chloride.

Example 3 Using the same reaction apparatus as in Example 1, 2-gulo-ethyl methacrylate 7-4 p (0,s-v-nyl), 0.151 ml of hydroquinone monomethyl ether, and 100 ml of acetonitrile were added at room temperature, and the container was sealed. , 89 t (1.5 moles) of trimethylamine were added into the vessel over about 45 minutes.

The mixture was then heated to 75°C and reacted at this temperature for 6 hours.

After the reaction completed liquid was cooled to room temperature and the pressure in one reactor was returned to normal pressure, the contents were taken out, filtered and dried to obtain crystal 97/.

The obtained crystals were analyzed in the same manner as in Example 1. It was confirmed that 2-methacryloyloxyethyltrimethylammonium chloride with a high M degree was obtained.

Example 4 Using the same reactor as in Example 1, 2-chloroethyl methacrylate 74JF (0.5 mol) and hydroquinone 0.1! M, Acetonitrile 10OWLt
was added, the container was sealed, and trimethylamine 23.6P (
0.4 mol) was added into the vessel over about 20 minutes.

The mixture was then heated to 75°C and reacted at this temperature for 12 hours.

The trapping operation was carried out in the same manner as in Example 1 to obtain crystal 38F.

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

Example 5 2-Chloroethyl methacrylate 74JF (0,
5 mol), hydroquinone 0.15! , acetonitrile 100- and triethanolamine 75M (0.5 mol) were added at room temperature, the temperature was raised, and the reaction was carried out at 75°C for 10 hours.

The reaction completed liquid was cooled to room temperature, the contents were taken out, filtered and dried to obtain crystal 1391.

The same analysis as in Example 1 was conducted to obtain methacryloyloxyethyl trihydroxyethylammonium chloride with a purity of 99.9.

Example 6 In a 40 flask equipped with a stirrer, a thermometer and a condenser, 2-chloroethyl methacrylate 74/(0.5 mol), hydroquinone 0.15 t, acetonitrile 10
0d and N,N dimethylbenzylamine 68P (0,
After adding 5 mol) at room temperature, the temperature was raised and the reaction was carried out at 90°C for 8 hours.

The reaction completed liquid was cooled to room temperature, the contents were taken out, filtered and dried to obtain crystals 136J'.

As a result of the same analysis as in Example 1, the purity was 100.01.
It was confirmed that it was 2-methacryloyloxyethyl N,N dimethylbenzylammonium chloride.

Claims (2)

[Claims] (1) General formula [! ] Unsaturated compound 1 cm, = c-coohx (1) (wherein R1 in formula 9 is H or CH, A is -(cHm), -CH. (however, n is 2 to 4) or -〇 H, -CH-. A method for producing an unsaturated quaternary ammonium salt represented by the general formula (1), which comprises reacting the unsaturated quaternary ammonium salt with an alkyl group, a hydroxyalkyl group, and/or a benzyl group. (In the formula R1* R@e R@m g, , A and X
is the same as defined in formula El) and formula CI). ) (2) The manufacturing method according to claim 1, wherein the reaction is carried out in the presence of an organic solvent.