JPS6353181B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polymerizable amino acid compounds. When ionic functional groups are introduced into polymer compounds,
Even in small amounts, it has a large effect on the physical and chemical properties of the polymer compound. In addition, the properties of ionic functional groups become more accentuated or compounded in the polymer state. For this reason, research on ion-containing polymer compounds has been actively conducted in recent years. In particular, there is growing interest in compounds in which a cation and an anion forming a counterion are bonded through a covalent bond, that is, they have an internal salt structure and have reactivity, surface activity, electrochemical properties, and biochemical properties. ing. For example, US Pat. No. 2,840,603 states:
CH ₂ =CH—C ₆ H ₄ —CH(NH ₂ )—CO ₂ M′ [wherein M′ is H, NH ₄ or a metal. ] There is a description of the compound. This compound is
It has a zwitterion structure. By the way, it is known that zwitterionic compounds generally have low solubility at their isoelectric point (for example, Takehiko Fujimoto, "Introduction to New Surfactants" (84-85)
page, Sanyo Chemical Industries Publishing)). Therefore, in order to use these compounds as a solution, it is necessary to coexist a basic substance or an acidic substance to improve the dissolving power, making it difficult to use them in the free acid form. The use of such basic or acidic substances causes, for example, the following problems. In a system in which a basic or acidic compound is added to dissolve in water, the opposite liquid conditions cannot be adopted, and for example, the Tweeter monomer may precipitate and polymerization or copolymerization may not be possible. Furthermore, the selection range of initiators and other additives during polymerization is limited. Polymer compositions obtained by polymerization in the coexistence of basic or acidic substances may have lower pigment dispersibility and coating performance (water resistance, chemical resistance, etc.) than those that do not contain the substances. There is. An object of the present invention is to provide a compound that has an internal salt structure and can be used as a polymerizable monomer in order to exhibit such structural characteristics as a polymer compound. Furthermore, another object of the present invention is to provide a compound having a polymerizable internal salt structure that can be dissolved in water, an organic solvent, a copolymer monomer, etc. even without the coexistence of a basic substance or an acidic substance. . The above object is achieved by a novel polymerizable amino acid compound. More specifically, this is achieved by a compound that has a polymerization-reactive functional group, an ammonium group, and a sulfonic acid or carboxylic acid residue in one molecule, and also has a hydroxyl group in the N-substituent of the ammonium group. . This compound has the formula: [In the formula, R ₁ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, and R ₂ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group.
~20 alkyl group or H or carbon number 1-20
alkyl group, A is _CO2 or _SO3 , and n is 1-6. ] It is a polymerizable amino acid compound shown as follows. Such a compound of the present invention can be produced by reacting a benzyl halide compound and a hydroxyalkyl amino acid compound. The reaction is preferably carried out under basic conditions. Specifically, the above benzyl halide compound is prepared under normal pressure or increased pressure, using one or a mixed solvent of two or more of solvents such as alcohol, ethylene glycol monoalkyl ether, dimethyl formamide, dimethyl sulfoxide, and water, if necessary. , a hydroxyalkyl amino acid compound, and a basic substance (alkali metal hydroxide, alkali metal alkoxy, ammonia, organic amine, etc.) are placed in a reaction vessel and mixed with stirring at a temperature of 0 to 150°C for 10 minutes to 48 hours. . The benzyl halide compound has the formula: CH ₂ =CH--C ₆ H ₄ --CH ₂ X [] [wherein X is Cl or Br]. ] Specific examples thereof include (vinylbenzyl) chloride and (vinylbenzyl) bromide. The above hydroxyalkyl amino acid compound has the formula, [In the formula, R ₁ , R ₂ , A, and n have the same meanings as above. ] Specifically, N-hydroxymethylglycine, N-hydroxyethylglycine, N,N-bis-(hydroxyethyl)glycine, N-{2-hydroxy-1,1-bis ―
(Hydroxymethyl)} Glycine type compounds such as ethylglycine, N-hydroxyethyl-N-dodecylglycine, N-hydroxymethyl-β-alanine, N-hydroxyethyl-β-alanine,
N,N-bis-(hydroxyethyl)-β-alanine, N-{2-hydroxy-1,1-bis-
(hydroxymethyl)}ethyl-β-alanine, N
-β-alanine type compounds such as hydroxyethyl-N-dodecyl-β-alanine, N-hydroxymethyl-ε-aminohexanoic acid, N-hydroxyethyl-ε-aminohexanoic acid, N,N-bis-
(hydroxyethyl)-ε-aminohexanoic acid,
N-{2-hydroxy-1,1-bis-(hydroxymethyl)}ethyl-ε-aminohexanoic acid,
ε-aminohexanoic acid type compounds such as N-hydroxyethyl-N-dodecyl-ε-aminohexanoic acid, N-hydroxymethyltaurine, N-hydroxyethyltaurine, N,N-bis-(hydroxyethyl)taurine, N- {2-hydroxy-
Examples include taurine-type compounds such as 1,1-bis-(hydroxymethyl)}ethyltaurine and N-hydroxyethyl-N-dodecyltaurine. In addition, among such hydroxyalkyl amino acid compounds, the formula: [In the formula, R ₁ and R ₂ have the same meanings as above. ] can also be obtained by a novel method independently developed by the present inventors (see Japanese Patent Application No. 54-170624 and Japanese Patent Publication No. 57-47184).
That is, the expression [In the formula, R ₁ and R ₂ have the same meanings as above. ] The hydroxyalkylamine compound represented by
Formula, CH ₂ =CH-SO ₃ M [z] [wherein M is an alkali metal. ] An alkali metal salt of an α,β-unsaturated sulfonic acid represented by the following may be reacted, and then a dealkali metal treatment may be performed. The compound of the present invention can also be produced by subjecting a benzylamine compound and a haromethylene acid or its ester to a mensyutkin reaction in a conventional manner, followed by hydrolysis if necessary in the presence of an alkali catalyst. can. The above benzylamine compound has the formula, [In the formula, R ₁ and R ₂ have the same meanings as above. ] Specifically, hydroxymethyl(vinylbenzyl)amine, (hydroxyethyl)(vinylbenzyl)amine, bis-
(hydroxyethyl)(vinylbenzyl)amine,
N-{2-hydroxy-1,1-bis-(hydroxymethyl)}ethyl-N-(vinylbenzyl)
Examples include amine, N-(hydroxyethyl)-N-(vinylbenzyl)dodecylamine, and the like. The above haromethylene acid _{or its} ester has _the formula: _R3 is H
Or it is a residue mainly composed of hydrocarbons having 1 to 12 carbon atoms. ] Specific examples thereof include chloroacetic acid, bromoacetic acid, and ethyl chloroacetate. Specific examples of the compounds of the present invention obtained as described above include N-hydroxymethyl-N-(vinylbenzyl)glycine, N-hydroxyethyl-N-(vinylbenzyl)glycine, N,N-bis-( hydroxyethyl)-N-
(vinylbenzyl)ammonioacetic acid betaine, N-{2-hydroxy-1,1-bis-(hydroxymethyl)}ethyl-N-(vinylbenzyl)
Glycine, N-hydroxyethyl-N-dodecyl-N-
(vinylbenzyl)ammonioacetic acid betaine, N-hydroxymethyl-N-(vinylbenzyl)-β-alanine, N-hydroxyethyl-N-(vinylbenzyl)-β-alanine, N,N-bis-(hydroxyethyl) -N-
(vinylbenzyl)ammoniopropionic acid-2
Betaine, N-{2-hydroxy-1,1-bis-(hydroxymethyl)}ethyl-N-(vinylbenzyl)
-β-alanine, N-hydroxyethyl-N-dodecyl-N-
(vinylbenzyl)ammoniopropionic acid-2
Betaine, N-hydroxymethyl-N-(vinylbenzyl)-ε-aminohexanoic acid, N-hydroxyethyl-N-(vinylbenzyl)-ε-aminohexanoic acid, N,N-bis-(hydroxyethyl)-N ―
(vinylbenzyl)ammoniocaproic acid-5betaine, N-{2-hydroxy-1,1-bis-(hydroxymethyl)}ethyl-N-(vinylbenzyl)
-ε-aminohexanoic acid, N-hydroxyethyl-N-dodecyl-N-
(vinylbenzyl)ammoniocaproic acid-5betaine, N-hydroxymethyl-N-(vinylbenzyl)taurine, N-hydroxyethyl-N-(vinylbenzyl)taurine, N,N-bis(hydroxyethyl)-N- (vinylbenzyl)ammonioethanesulfonic acid-2
Betaine, N-{2-hydroxy-1,1-bis-(hydroxymethyl)}ethyl-N-(vinylbenzyl)
Taurine, N-hydroxyethyl-N-dodecyl-N-
(vinylbenzyl)ammonioethanesulfonic acid-2betaine, etc. Among the compounds of the present invention, the formula: [In the formula, R ₁ , R ₂ and A have the same meanings as above. ] For those represented by the above formula [], the benzylamine compound of the above formula [] is subjected to an addition reaction with an α,β-unsaturated acid or its ester, and then, if necessary, hydrolysis is performed in the presence of an alkali catalyst. It can also be manufactured. In the above addition reaction, the above-described addition reaction is carried out under normal pressure or increased pressure, using one or a mixed solvent of two or more of solvents such as alcohol, ethylene glycol monoalkyl ether, dimethyl formamide, dimethyl sulfoxide, water, etc., if necessary. Benzylamine compounds and α, β-
The unsaturated acid or its ester may be charged into a reaction vessel and mixed with stirring at a temperature of 0 to 150°C for 10 minutes to 48 hours. The above α,β-unsaturated acid or ester thereof has the formula, CH ₂ =CH-A-R ₄ [] [wherein A has the same meaning as above]. R ₄ is H or a residue mainly consisting of a hydrocarbon having 1 to 12 carbon atoms. ], specifically vinylsulfonic acid, vinylcarboxylic acid, methyl vinylsulfonate, ethyl vinylsulfonate, n-butyl vinylsulfonate, 2-ethylhexyl vinylsulfonate, dodecyl vinylsulfonate, Examples include methyl acrylate, ethyl acrylate, butyl acrylate, and dodecyl acrylate. Note that α,
When using a β-unsaturated acid, it is preferably used as a salt of an alkali metal, ammonia, or an organic amine in order to increase the reactivity. The compound of the present invention having the above structure has good reaction properties, interfacial properties, and
It can be used as a polymerizable monomer with electrochemical and biochemical properties, and because it contains a hydroxyl group in the N-substitution, it has excellent solubility in water and organic solvents. There is no need to add any substances, and the degree of freedom in designing polymerization reactions using such Tweeter monomers is increased, and the resulting polymer compounds have a wide range of properties. The hydroxyl group of the compound of the present invention also functions as a reactive functional group when performing a three-dimensional reaction in designing a polymer compound. Furthermore, when A is SO ₃ in the compound of the present invention, the compound has an internal salt structure and has properties as a strong acid. A polymer compound using the compound of the present invention is useful, for example, as a resin for pigment dispersion. Next, the present invention will be specifically explained with reference to Examples and Reference Examples. Example 1 287 parts of N-(2-hydroxyethyl)-4-octyl-ε-aminohexanoic acid (parts by weight,
), 300 parts of water, 200 parts of ethylene glycol monomethyl ether, and 40 parts of caustic soda.
Increase temperature to 80°C while stirring. After the system becomes homogeneously dissolved, vinylbenzyl chloride 153
100 parts and ethylene glycol monomethyl ether
20 parts of caustic soda was added dropwise over 2 hours (at this time, 20 parts of caustic soda was added in each of the 1st and 2nd hours after the start of dropping). Further, heating and stirring was continued for 6 hours to complete the reaction. The resulting reaction product is neutralized with dilute hydrochloric acid, and twice the amount of acetone is added to precipitate a white honey-like substance. The separated precipitate is dissolved in hot water, allowed to cool, and acetone is added to cause reprecipitation, and the resulting precipitate is dried under reduced pressure to obtain 304 parts of a white viscous compound. NMR of this compound shows that this compound has the formula: It is identified as N-(2-hydroxyethyl)-N-octyl-N-(vinylbenzyl)ammoniocaproic acid-5betaine. This is also supported by the results of elemental analysis and molecular weight measurement. <Elemental analysis value> C H N O Calculated value (%) 76.50 9.40 3.19 10.92 Actual value (%) 76.38 9.47 3.25 10.90 Example 2 N-(2 Add 117 parts of -hydroxyethyl)-β-alanine, 68 parts of sodium ethylate, 300 parts of ethylene glycol, and 150 parts of ethylene glycol monomethyl ether, and heat to 100°C with stirring. A solution consisting of 152 parts of vinylbenzyl chloride and 100 parts of ethylene glycol monomethyl ether was added dropwise to this over 2 hours. Further, stirring was continued for 6 hours to complete the reaction. The resulting reaction product is neutralized with hydrochloric acid, and twice the amount of acetone is added to precipitate a white solid substance. The separated precipitate was dried under reduced pressure, and the formula: 191 parts of N-(2-hydroxyethyl)-N-(vinylbenzyl)-β-alanine were obtained. The NMR chart of this product is shown in Figure 1. The results of elemental analysis and molecular weight measurements also agree with this structure. Example 3 Into two flasks equipped with a stirrer, a temperature controller, and a condenser, (hydroxyethyl)(vinylbenzyl) was added.
Prepare 177 parts of amine and 100 parts of ethyl acrylate,
Stir at 80°C for 3 hours. 200 parts of deionized water and 40 parts of caustic soda are added to this, hydrolyzed at 100°C, neutralized with hydrochloric acid, and the precipitate is separated and dried under reduced pressure. The yield of the white solid compound obtained was 204 parts, and the structural analysis results were the same as the compound of Example 2. Example 4 In Example 2, N-(2
The formula, N,N-bis-(2-hydroxyethyl)-N
-(vinylbenzyl)ammoniopropionic acid-
Obtain 220 parts of 2 betaine. The NMR chart of this compound is shown in Figure 2. Example 5 The formula: 180 parts of N-(2-hydroxyethyl)-N-(vinylbenzyl)glycine were obtained. of this compound
The NMR chart is shown in Figure 3. Example 6 The formula, 229 parts of N-(2-hydroxyethyl)-N-(vinylbenzyl)taurine are obtained. of this compound
The NMR chart is shown in Figure 4. Example 7 Example 2 except that 203 parts of N,N-bis-(2-hydroxyethyl)taurine was used as the raw material.
Similarly, the expression N,N-bis-(2-hydroxyethyl)-N
-263 parts of (vinylbenzyl)ammonioethanesulfonic acid-2betaine are obtained. of this compound
The NMR chart is shown in Figure 5. Example 8 The formula: 327 parts of N-(2-hydroxydodecyl)-N-(vinylbenzyl)taurine are obtained. Example 9 The formula: N-methyl-N-(2-hydroxyethyl)-
245 parts of N-(vinylbenzyl)ammonioethanesulfonic acid-2betaine are obtained. of this compound
The NMR chart is shown in Figure 6. In addition, the results of elemental analysis and molecular weight measurement of the compounds of Examples 3 to 7 were all consistent with each compound. Reference Example Table 1 shows the solubility of the compounds obtained in Examples 1 to 9 in water at a temperature of 20°C or 80°C (amount (g) of the compound dissolved in 100g of water). In addition, as comparative samples, N-(vinylbenzyl)glycine (Comparative Example 1), N-(vinylbenzyl)-β-alanine (Comparative Example 2), N-(vinylbenzyl)taurine (Comparative Example 3), and N-methyl The results for -N-(vinylbenzyl)taurine (Comparative Example 4) are also shown. 【table】

[Brief explanation of drawings]

1 to 6 are Examples 2, 4, 5, and 5, respectively.
NMR of the compounds of the present invention obtained in 6, 7 or 9
It's a chat.

Claims (1)

[Claims] 1 formula, [In the formula, R ₁ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, and R ₂ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group.
~20 alkyl group or H or carbon number 1-20
alkyl group, A is _CO2 or _SO3 , and n is 1-6. ] A polymerizable amino acid compound represented by: 2. The compound according to item 1 above, wherein R ₁ has a β-hydroxy structure, for example β-hydroxyethyl. 3. The compound according to item 1 above, wherein R ₂ is an alkyl group having 1 to 20 carbon atoms and having at least one hydroxyl group. 4. The compound according to item 1 above, wherein R ₂ is H. 5. The compound according to item 1 above, wherein n is 2. 6 Under basic conditions, _{the formula, CH2=CH-C6H4-CH2X [ ] [} wherein X is Cl or Br]. ] A benzyl halide compound represented by the formula, [In the formula, R ₁ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, and R ₂ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group.
~20 alkyl group or H or carbon number 1-20
alkyl group, A is CO ₂ or SO ₃ , n is 1-6
It is. ] By reacting with a hydroxyalkyl amino acid compound represented by the formula, [In the formula, R ₁ , R ₂ , A, and n have the same meanings as above. ] A method for producing a polymerizable amino acid compound, characterized by obtaining a polymerizable amino acid compound represented by the following. 7 formula, [In the formula, R ₁ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, and
R ₂ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, H or an alkyl group having 1 to 20 carbon atoms. ] _A benzylamine compound represented by the formula, X-(CH ₂ ) _o -A-R ₃ [] [wherein,
SO ₃ and R ₃ are H or a residue mainly composed of a hydrocarbon having 1 to 12 carbon atoms, and n is 1 to 6. ] A mensyutkin reaction is carried out with haromethylene acid or its ester represented by the formula, followed by hydrolysis in the presence of an alkali catalyst if necessary, to obtain the formula, [In the formula, R ₁ , R ₂ , A, and n have the same meanings as above. ] A method for producing a polymerizable amino acid compound, characterized by obtaining a polymerizable amino acid compound represented by the following. 8 formula, [In the formula, R ₁ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, and
R ₂ is an alkyl group having 1 to 20 carbon atoms having at least one hydroxyl group, H or an alkyl group having 1 to 20 carbon atoms. ] A benzylamine compound represented by the formula, CH ₂ = CH-A-R ₄ [] [wherein A is CO ₂ or SO ₃ and R ₄ is mainly H or a hydrocarbon having 1 to 12 carbon atoms] This is the residue. ] with an α,β-unsaturated acid or its ester represented by the formula, followed by hydrolysis in the presence of an alkali catalyst if necessary, to obtain the formula, [In the formula, R ₁ , R ₂ and A have the same meanings as above. ] A method for producing a polymerizable amino acid compound, characterized by obtaining a polymerizable amino acid compound represented by the following.