JPH07258202A - Polymerizable betaine compound - Google Patents

Abstract

PURPOSE:To obtain a new polymerizable betaine compound useful as a raw material monomer capable of giving a hydrophilic property to various kinds of polymer compounds and a raw material of various kinds of fine chemicals. CONSTITUTION:This compound is expressed by formula I [R<1> and R<2> are methyl, ethyl; (m) is 0 to 2; (n) is 2 to 4], e.g. N-(p-vinylbenzyl)-N,N-dimethyl-N-(3- phosphopropyl)ammonium betaine of formula II. This compound can be synthesized by reacting an amine with vinylsulfonic acid, 1,3-propane sultone or 1,4-butane sultone in a ratio of 1:0.5 to 1:10, preferably 1:0.8 to 1:1.5 on molar base. For example, the above exemplified compound can be synthesized from N,N- dimethyl-p-vinylbenzylamine and 1,3-propane sultone.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polymerizable betaine compound. Since this compound has polymerizability, it is useful as a raw material monomer for various polymer compounds,
It is used in the fields of general-purpose molding polymers, adhesives, coatings, and medical polymers. It is also used as a raw material for fine chemicals such as pharmaceuticals, agricultural chemicals, and pigments.

[0002]

2. Description of the Related Art As a polymerizable betaine compound, US Pat. No. 2,744,130 describes a method for producing carboxybetaine and sulfobetaine having a radically polymerizable acryloyl group or acrylamide group.
Further, U.S. Pat.No. 3,473,998 and U.S. Pat.No. 3,478,001 describe copolymers of these polymerizable betaine compounds with acrylonitrile, and U.S. Pat.No. 3,671,502 describes copolymers with polyalkylene glycol monoacrylate. It is described that the polymer is useful as an adhesive for glass, leather, plastic, steel, wood, etc., respectively. However, since these compounds have a highly hydrolyzable ester bond or amide bond in the molecule, there is a problem that the stability is low in long-term use.

[0003]

An object of the present invention is to provide a novel polymerizable betaine compound having excellent polymerizability, hydrophilicity and hydrolysis resistance.

[0004]

As a result of intensive studies, the present inventors have found that a sulfobetaine compound having a styryl group as a polymerizable group is suitable for solving the above problems, and completed the present invention. Came to do.

The present invention is a polymerizable betaine compound represented by the following general formula (1).

[Chemical 2] (In the formula, R1 and R2 are methyl groups or ethyl groups, and m is 0 to
The integer of 2 and n show the integer of 2-4. )

Hereinafter, in the present invention, "p, m-" is p-
Or represents m-. Examples of the polymerizable betaine compound represented by the general formula (1) of the present invention include N- (p,
m-Vinylphenyl) -N, N-dimethyl-N- (2-
Sulfoethyl) ammonium betaine, N- (p, m-
Vinylphenyl) -N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine, N- (p, m-vinylphenyl) -N, N-dimethyl-N- (4-sulfobutyl) ammonium betaine, N- (P, m-Vinylphenyl) -N, N-diethyl-N- (2-sulfoethyl) ammonium betaine, N- (p, m-vinylphenyl) -N, N-diethyl-N- (3-sulfopropyl) Ammonium betaine, N- (p, m-vinylphenyl) -N, N-diethyl-N- (4-sulfobutyl)
Ammonium betaine, N- (p, m-vinylbenzyl) -N, N-dimethyl-N- (2-sulfoethyl) ammonium betaine, N- (p, m-vinylbenzyl)
-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine, N- (p, m-vinylbenzyl)-
N, N-dimethyl-N- (4-sulfobutyl) ammonium betaine, N- (p, m-vinylbenzyl) -N,
N-diethyl-N- (2-sulfoethyl) ammonium betaine, N- (p, m-vinylbenzyl) -N, N-
Diethyl-N- (3-sulfopropyl) ammonium betaine, N- (p, m-vinylbenzyl) -N, N-diethyl-N- (4-sulfobutyl) ammonium betaine, N- (p, m-vinylphenethyl) -N, N-dimethyl-N- (2-sulfoethyl) ammonium betaine, N- (p, m-vinylphenethyl) -N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine, N- (p, m-Vinylphenethyl) -N, N-dimethyl-N- (4-sulfobutyl) ammonium betaine, N- (p, m-vinylphenethyl) -N, N-diethyl-N- (2-sulfoethyl) ammonium betaine, N -(P, m-vinylphenethyl) -N, N-diethyl-N- (3-sulfopropyl) ammonium betaine, N- (p, m-vinyl Phenethyl) -N, N-diethyl -N- (4- sulfobutyl) ammonium betaine, and the like.

The method for synthesizing the polymerizable betaine compound represented by the general formula (1) is not particularly limited, but for example,
N, N-dimethyl-p, m-vinylaniline, N, N-
Diethyl-p, m-vinylaniline, N, N-dimethyl-p, m-vinylbenzylamine, N, N-diethyl-
p, m-vinylbenzylamine, N, N-dimethyl-
An amine such as p, m-vinylphenethylamine or N, N-diethyl-p, m-vinylphenethylamine and vinylsulfonic acid, 1,3-propanesultone, or 1,4-butanesultone are mixed at 1: 0.5. From 1:
Charged in a molar ratio of 10 mols, preferably 1: 0.8 to 1: 1.5, without solvent or with water, acetonitrile,
In a solvent such as chloroform, tetrahydrofuran, dioxane, benzene, and toluene, -100 to 120 ° C,
It is possible to synthesize by reacting at 0 to 60 ° C. for 30 minutes to 48 hours, preferably 1 hour to 12 hours.

The polymerizable betaine compound obtained is purified by
The crystals precipitated in the reaction solution can be collected by filtration to obtain a product with sufficient purity, but when further purification is required, recrystallization, reprecipitation, thin layer chromatography, column chromatography- And the like.

Since the betaine compound of the present invention has a styryl group as a polymerizable group, a homopolymer and a copolymer with another copolymerizable monomer can be easily obtained.

Here, other copolymerizable monomers include
Styrene, p-, m- or o-chlorostyrene, p
-, M- or o-bromostyrene, styrene derivatives such as methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate
(Meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl methyl ether,
Allyl ether such as allyl ethyl ether, allyl butyl ether, vinyl acetate such as vinyl acetate, vinyl cinnamate, vinyl stearate, vinyl ether such as ethyl vinyl ether, γ-chloropropyl vinyl ether, (meth) acrylic Examples thereof include acids, carboxylic acids such as maleic acid and itaconic acid, acid anhydrides such as itaconic anhydride and maleic anhydride, and water-soluble monomers such as vinylbenzenesulfonic acid, acrylonitrile and N-vinylpyrrolidone.

The homopolymer or copolymer can be easily prepared by using a well-known method such as a radical polymerization method, an anionic polymerization method or a cationic polymerization method.

[0012]

The present invention is a novel polymerizable betaine compound. Since this polymerizable betaine compound has a styryl group having high polymerizability and reactivity and a sulfobetaine group having high hydrophilicity, it is useful as a raw material monomer for imparting hydrophilicity to various polymer compounds. And can be used as a raw material for various fine chemicals.

[0013]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 N, N-dimethyl-p-vinylbenzylamine 10.
After dissolving 0 g (62 mmol) in 50 ml of chloroform, 7.6 g of 1,3-propane sultone (62 m)
(mol) dissolved in 50 ml of chloroform was added dropwise at 30 ° C. over 1 hour. After stirring for an additional 5 hours, the precipitate was collected by filtration, dried at 40 ° C. under reduced pressure,
N- (p-vinylbenzyl) -N represented by the following formula (2):
N-dimethyl-N- (3-sulfopropyl) ammonium betaine was obtained as a white powder.

[Chemical 3]

¹ H-NMR, I of the compound obtained below
R, the measurement results of elemental analysis are shown. ¹ H-NMR (270 MHz: D ₂ O / DSS: δ (ppm): J (Hz)) 7.56 (d, e, f, g,: m: 4H) 6.84 (c: dd: 1H: Jb = 10.9, Ja = 17.8) 5.96 (b: d: 1H: Jc = 17.5) 5.45 (a: d: 1H: Jc = 10.9) 4.49 (5: s: 2H) 3.46 ( 1: m: 2H) 3.07 (4: s: 6H) 3.00 (3: t: 2H: J = 7.25) 2.34 (2: m: 2H) IR (KBr; cm ^-1 ) 1484 ( N ⁺ ) 1194 (SO ₃ ) 1044 (aromatic ring) 997, 918 (vinyl) Elemental analysis (H ₂₁ C ₁₄ NO ₃ S) Calculated value H; 7.48, C; 59.34, N; 4.95 Measurement Value H; 7.47, C; 59.35, N; 4.92

Example 2 N, N-dimethyl-p-vinylbenzylamine and N, N
Mixture with dimethyl-m-vinylbenzylamine (3: 7) 10.0 g (62 mmol) was dissolved in 50 ml of chloroform, and then 7.6 g (62 mmol) of 1,3-propanesultone was added to 50 ml of chloroform.
What was melt | dissolved in was dripped at 30 degreeC over 1 hour. After further stirring for 5 hours, the precipitate was collected by filtration, dried under reduced pressure at 40 ° C., and N- (p-vinylbenzyl) -N, N-dimethyl-N- (3-of the formula (2) was used. Sulfopropyl) ammonium betaine and N represented by the following formula (3)
-(M-Vinylbenzyl) -N, N-dimethyl-N-
A mixture of (3-sulfopropyl) ammonium betaine was obtained as a white powder.

[Chemical 4]

¹ H-NMR, I of the compound obtained below
R, the measurement results of elemental analysis are shown. The mixing ratio of the p-form and the m-form is c in the formula (2) and the formula (3) in ¹ H-NMR.
As a result of obtaining from the proton ratio of c ′ and c ′, it was 3: 7 as in the charged molar ratio. ¹ H-NMR (270 MHz: D ₂ O / DSS: δ (ppm): J (Hz)) 7.56 (d, e, f, g, d ', e', f ', g': m: 4H ) 6.84 (c, c ': dd: 1H: Jb = 10.9, Ja = 17.8, Jb' = 10.9, Ja '
= 17.8) 5.96 (b: d: Jc = 17.5) 5.96 and 5.93 at 1H 5.93 (b ': d: Jc' = 17.8) 5.96 and 5.93 at 1H 5.45 (a: d: Jc = 10.9) 5.45 and 5.43 at 1H 5.43 (a ': d: Jc' = 10.9) 5.45 and 5.43 at 1H 4.49 (5,5 ': s: 2H) 3.46 (1,1 ': m: 2H) 3.07 (4,4': s: 6H) 3.00 (3,3 ': t: 2H, J = 7.25) 2.34 (2,2 ': m: 2H) IR (KBr; cm ^-1 ) 1484 (N ⁺ ) 1194 (SO ₃ ) 1044 (aromatic ring) 997,918 (vinyl) Elemental analysis (H ₂₁ C ₁₄ NO ₃ S) Calculated H; 7.48, C; 59.34, N; 4.95 Measured H; 7.46, C; 59.36, N; 4.92

Reference Example Next, a polymerization example of the polymerizable betaine compound of the present invention will be shown.
1 g of the betaine compound according to the invention obtained in Example 1
(3.5 mmol) was dissolved in 10 ml of distilled water, and 100 μl of a 5% ammonium persulfate aqueous solution (22
μmol) was added and the atmosphere was replaced with nitrogen, followed by polymerizing at 80 ° C. for 6 hours, and then dialyzing overnight in running water using a SPECTRUM dialyzer (fraction molecular weight 3,500). further,
By freeze-drying, a white powdery polymer compound (number average molecular weight of about 13,000) was obtained.

Claims (1)

[Claims] 1. A polymerizable betaine compound represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ and R ² are methyl groups or ethyl groups, and m is 0 to
The integer of 2 and n show the integer of 2-4. )