JPS5973560A - Polymerizable sulfobetaine compound and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R1 is H, or methyl; R2 is 2-4C alkylene; R3 and R4 are 1-4C alkyl; R5 is 3-4C hydroxyalkylene). USE:Useful a raw material for preparing various kinds of high polymer compounds. For example, providing the high polymer compounds with antistatic properties and surface active effects. PROCESS:An amine compound (e.g., dimethylaminoethylacrylamide, etc.) shown by the formula II is reacted with an alkylene halohydrinsulfonate shown by the formula X-R5-SO3M(X is halogen; M is alkali metal) in an aqueous medium under basic conditions (e.g., in the presence of an alkali metal hydroxide) at 60-100 deg.C, preferably at 80-100 deg.C to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polymerizable sulfobetaine compound and a method for producing the same.

A monomer containing a quaternary ammonium group and a sulfo group in its molecule and capable of forming a polymer by a vinyl addition mechanism, and a polymer obtained by polymerizing this monomer, have cationic and anionic functionalities. It has attracted attention in recent years because it has a group within the same molecule and exhibits unique reactivity, surface activity, electrochemical properties, and biochemical properties.

For example, in Japanese Patent Publication No. 42-11651, an amine represented by the formula % is reacted with a sultone represented by the formula 8-1-0 1 O-S-〇1 (CHz) m-I H / CH2= JP-A-56-78834 discloses that it is possible to obtain a polymerizable intermediate ω-isomer represented by CR- \ I and homopolymerize or copolymerize it to produce a polymer excellent as an antistatic agent. CI-I CON+-1<Cl-12>
It has been shown that a polymer excellent as a photographic antistatic agent can be obtained by copolymerizing a sulfobetaine represented by 3N (C1k)3SO:PH3 with a fluorine-containing monomer.

However, all of these conventionally known polymeric acid sulfobetaine compounds are characterized only by having a polymerizable unsaturated group and amphoteric functional groups such as a quaternary ammonium group and a sulfo group in the molecule. When this was polymerized, there was no intention to utilize the specific surface activity and electrochemical properties of the functional groups incorporated into the polymer. Moreover, the reaction of unsaturated amine compounds and sultones is used to produce yA of these betaine compounds, but sultones have been recognized to be carcinogenic, and research has made remarkable progress to date. The current situation is that we have not seen the current situation.

The present inventors have discovered that a compound represented by the following general formula (1) which further has a hydroxy functional group in the molecule in addition to a polymerizable unsaturated group and amphoteric functional groups such as a quaternary ammonium group and a sulfo group, Because of the hydroxyl group, the properties of the polymer related to hydrophilicity, e.g. The present inventors have completed the present invention by discovering that the compound is extremely useful and that it can be produced industrially advantageously without using sultones, which are toxic substances.

That is, according to the present invention, general formula (1) (wherein R1 is a hydrogen atom or a methyl group; R2 is an alkylene group having 2 to 4 carbon atoms; R3 and R4 are each an alkyl group having 1 to 4 carbon atoms; R5 is a hydroxyalkylene group having 3 to 4 carbon atoms) A polymerizable sulfobetaineite compound is provided.

The compound according to the present invention is a novel compound that has not been described in any literature, and is a compound represented by the general formula (n) 6- (wherein R1, R2, R3 and R4 are as described above) in an aqueous medium, and a compound represented by the general formula (n) 6- (wherein R1, R2, R3 and R4 are as described above) III)X R5SO3M
...(III) (wherein R5 is as described above, x is a halogen atom, M+, and one alkali metal atom) can be easily and advantageously produced by reacting the compound represented by the formula under basic conditions.

The general formula (
The compound represented by IT) is commercially available and can be easily prepared, if necessary, by the method described in US Pat. No. 4,287,363. Typical amine compounds (II) include diethylaminoethyl acrylamide, diethylaminoethyl acrylamide,
Dimethylaminohexyl acrylamide, diethylaminoethyl acrylamide, diethylaminepropylacrylamide, diethylaminohexyl acryl 7-amide, dipropylaminoedyl acrylamide dipropylaminobrobyl acrylamide, dipropylaminobutylacrylamide, di-111-bylaminohexyl acrylamide, dibupur aminoethyl acrylamide,
Examples of dibutylaminopyryl acrylamide, diethylaminoethyl acrylamide, dibutylaminohexyl acrylamide, or their corresponding methacrylamides.
The sulfonic acid salt of cohydrin represented by HA [
Sodium 1-xy-propanesulfonate, 1-methyl-
These include sodium 2-hydroxy-3-halopropanesulfonate and sulfur to lithium 2-hydroxy-4-halobutanesulfonate.

The reaction proceeds easily by simply heating both of the above biocompounds under base f1 conditions in an aqueous medium. Water is preferably used as the reaction medium, but if desired, a mixed solvent of water and a water-miscible organic solvent such as lyacerone can also be used.3 The above reaction is conveniently carried out under basic conditions F. In this case, the base is an alkali metal hydroxide,
Carbonates or alkaline earth metal hydroxides, carbonates, etc. are used appropriately. Further, the amine compound (If) and the halide (I[[), which are reaction raw materials, are used in approximately equimolar proportions, but the latter is used in a slight excess, for example, 0.1 to 0.
It is preferable to use a 4 molar excess because it ensures a rapid reaction. The reaction is usually carried out at 60-100°C under normal pressure.
It is preferably carried out at a temperature of 80 to 100°C, but it is also possible to use higher temperatures or lower temperatures above or below atmospheric pressure, if desired. It is more advantageous to carry out the reaction in the presence of a small amount, for example 300 to 3000 ppm, of a water-soluble radical polymerization inhibitor 1F agent, such as varanitrosophenol, in order to prevent premature polymerization. In this way, the reaction proceeds easily and is completed in about the usual time. After the reaction is completed, the reaction mixture is neutralized with an acid, the solvent is removed under reduced pressure, and then a suitable polar solvent such as methanol or ethanol is added. , methyl cellosolve, etc., and the desired compound represented by the general formula (I>) can be fractionated by ordinary means of solvent removal.The compound represented by the general formula (I) of the present invention thus obtained is It is generally soluble in water, and soluble in polar solvents such as methanol, ethanol, methyl ester, nittylene glycol, and DMSO.
Full. Since these compounds have an internal salt structure, they have the property of being soluble in water and organic solvents without the coexistence of basic substances and acidic substances.

In addition, because of the polymerizable unsaturated group, the structural characteristics of the internal salt can be incorporated into a polymer compound, such as providing antistatic properties with electrical properties, and emulsifying into a polymer compound as a surface active agent. , dispersion, and permeability, and are useful as shield parts made of various polymer compounds.

The present invention will be explained below with reference to Examples. Example sentence 1. Unless otherwise specified, "parts" means "parts by weight."

10- Example 1 Dimethylaminopropyl methacrylamide 1 in a reaction vessel
70 parts of sodium 3-chloro-2-hydroxy-propanesulfonate, 236 parts of deionized water, 5 parts of sodium hydroxide, and 1 part of p-21-rosophenol were mixed to produce 8 parts.
The reaction was completed by stirring at 0°C for 5 hours. The reaction solution is cooled and excess sodium hydroxide is neutralized with hydrochloric acid. Water in the reaction solution is removed under reduced pressure. Further, 500 parts of methanol is added and dissolved to form a suspension containing white crystals. The white crystals were removed by passing through the mouth, methanol was removed from the resulting N solution under reduced pressure, and A was washed with 400 parts of ton.
281 parts of a yellowish white solid was removed by drying under reduced pressure. As a result of NMR and IR analysis, this product was confirmed to be a compound having the following structural formula.

FIG. 1 shows an NMR chart of this compound.

It should be noted that the measurement is to be carried out in D20 solvent (the same applies hereafter).

[R analysis result 10 〇 N L at 1660 cm' and 1550 cm'
Absorption by l- and absorption by SOp at 1040cvl were observed.

Example 2 Diethylaminopropyl methacrylamide 19 was used instead of dimethylaminopropyl methacrylamide in Example 1.
Solid 305 was obtained by the same formulation and operation except that 8 parts were used.
I got the department.

It was confirmed by NMR1IR analysis that this compound has the following structural formula.

NMR analysis CHz Cl-13 - IR analysis 1660cm', 10ON+-1 at 1550ctvl
Absorption due to -SOP was observed at -11040 cm'.

Example 3 Yellow-white solid 31
Got 9 copies.

The structure of this thing is It was confirmed that

13- NMR analysis Cl-120 mountain C ratio C mountain [R analysis 1660 ct', 100 N at 1550 cm-1
Absorption of SOp was observed at +-1- and at 1040 cm-1.

Example 4 A yellowish white solid of 28% was obtained by the same blending procedure as in Example 1 except that 170 parts of dimethylaminopropylmethacrylamide was used instead of dimethylaminopropylmethacrylamide.
I got 8 copies.

The structure of this thing is CH+ It was confirmed that

NMR analysis -L/I- δ=5.7-6.4ppm (C112=CH).

1.8~2.5 (CI'12C1(2C±CH2)C
H3-3,2(-N-) CH3 IR analysis 1660cn+-', 1540cm-' -CONH
Absorption of -SOP was observed in - and also in 1040CIl+'1.

Example 5 Dietylaminoedyl acrylamide 170 in the reaction vessel
part and 4-chloro-2-hydroxybutanesulfonic acid 25
3 parts, 290 parts deionized water, 5 parts sodium hydroxide, p
- Add 1.2 parts of nitrosophenol and stir at 80°C for 8 hours to complete the reaction.

After cooling, excess sodium hydroxide is neutralized with hydrochloric acid. Water was removed from the reaction solution under reduced pressure, dissolved in 600 parts of ethanol, solids were removed from the resulting suspension by filtration, and ethanol was removed from the remaining solution under reduced pressure, followed by washing with 400 parts of acetone. Dry under reduced pressure, yellowish white solid 29
The structure of this product was confirmed to be C11z C1-13.

NMR analysis δ=5.7-6.411r)III (CI-12=
Cl-1).

Cl42 CH3 1 part analysis 1660cm-', 1450cn+-'' -〇 〇
Absorption of NH- and 1040CIIl' (-SOP) was observed.

[Brief Description of the Drawings] Figure 1 shows the compound according to the present invention (general formula ①, R1=CH
3, R2= Ctlz CD□C1-1□-, R3, R
4=Cl-13. 17-

Claims (1)

[Scope of Claims] (1) General formula (wherein R1 is a hydrogen atom or a methyl group; R2 is an alkylene group having 2 to 4 carbon atoms; R3 and R4 are each a carbon number 1
~4 alkyl group; R6 is a hydroxyalkylene group having 3 to 4 carbon atoms) A polymerizable sulfobetaine compound represented by the following. (2) The compound according to claim 1, wherein R5 is -CH2CH(OH)CH2-. A compound according to claim 1. (4) General formula (in the formula, R1 is a hydrogen atom or a methyl group; Rz is an alkylene group having 2 to 4 carbon atoms; R3 and R4 are each a carbon number 1
~4 alkyl group) and a compound represented by the general formula % formula % (1)' (wherein, R5 is a carbon number 3 to 4 dialkylene group, X is a halogen atom, and M is an alkali metal Atom) with the general formula (wherein R+, R2, R3, R4, R6 are as described above), characterized by reacting an alkylene halohydrin sulfone lJi represented by A method for producing a polymerizable sulfobetaine compound as shown. (5) The method according to claim 3, wherein the reaction is carried out in the presence of a base catalyst of an alkali metal hydroxide and/or an alkaline earth metal hydroxide. (6) The method according to claim 3, wherein the reaction is carried out in the presence of a polymerization inhibitor.