JPH032171B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polyamino acid urethane copolymer resin. More specifically, the present invention relates to a method for producing a polyamino acid urethane copolymer resin in a mixed solvent of dimethylformamide and dioxane. Conventional polyamino acid-urethane copolymer resin (hereinafter referred to as
(abbreviated as PAu) was developed for the purpose of improving the elastic adhesion of polyamino acid resin, and is used in the field of textile processing.
It is especially used as a resin for artificial leather. Artificial leather coated with PAu has a texture closer to that of natural leather than those coated with other resins (mainly urethane resin), and has excellent moisture permeability, dyeability, cold resistance, and heat resistance. However, since the resin solvent is halogen-based,
When coating with resin in the industrial production of artificial leather, there are problems such as trace amounts of hydrochloric acid generated from the solvent corroding the coating equipment and wet processing being impossible because the solvent is water-insoluble. Therefore, it is impossible to use it as a general-purpose product. The purpose of the present invention is to solve these problems by using water-soluble solvents other than halogen-based solvents.
As a result of various studies on the synthesis method of PAu, we found a mixed solvent of dimethylformamide and dioxane as a solvent, which has good fluidity.
The inventors discovered that a PAu solution could be obtained and that the problems described above using conventional halogenated solvents could be solved, and the present invention was achieved. The gist of the present invention is to provide an α-amino acid-N-containing compound containing optically active γ-alkyl-glutamate-N-carboxylic acid anhydride as a main component in a mixed solvent of dimethylformamide and dioxane in a weight ratio of 95:5 to 30:70. A method for producing a polyamino acid-urethane resin, which is characterized by mixing a carboxylic acid anhydride and a urethane prepolymer having an isocyanate group at the end, and then adding an amine to react the mixture, and the weight ratio of dimethylformamide and dioxane.
A urethane prepolymer having terminal isocyanate groups is reacted with water or amines in a mixed solvent of 95:5 to 30:70, and a mixture containing optically active γ-alkylglutamate-N-carboxylic acid anhydride as a main component is added. A method for producing a polyamino acid-urethane resin characterized by adding and reacting α-amino acid-N-carboxylic acid anhydride, and weight ratio of dimethylformamide and dioxane.
A urethane prepolymer having an isocyanate group at the end is reacted with water or amines in a mixed solvent of 95:5 to 30:70, and the resulting product is made mainly of optically active γ-alkylglutamate-N-carboxylic acid anhydride. The present invention relates to a method for producing a polyamino acid urethane resin, which comprises reacting an α-amino acid-N-carboxylic acid anhydride and then reacting a urethane prepolymer having an isocyanate group at its terminal end. The present invention will be explained in detail below. The solvent composition for PAu production in the present invention, that is, the composition of the mixed solvent of dimethylformamide and dioxane, is in a weight ratio of dimethylformamide/dioxane = 95/5 to 30/70, preferably 80/20 to 50/ 50 more preferably 80/20~60/
It is 40. Here, when dimethylformamide is used alone, that is, at a weight ratio of 100/0, the resulting resin solution is in the form of a transparent gel and is not practical. On the other hand, when dioxane is used alone, i.e., at a weight ratio of 0/100, it becomes a cloudy gel and cannot be used for practical purposes. Optically active γ-alkyl-glutamate-N-carboxylic acid anhydride used in the present invention (hereinafter,
N-carboxylic acid anhydride (abbreviated as NCA) is:
γ-alkyl- such as γ-methyl-L-glutamate NCA, γ-ethyl-L-glutamate NCA, etc.
L-glutamate NCA and γ-methyl-D-
γ-alkyl-D-glutamates such as glutamate NCA, γ-ethyl-D-glutamate NCA, etc.
NCAs are used alone or in mixtures. In addition, α-amino acid NCA mainly composed of γ-alkyl-glutamate NCA refers to the optically active γ
-Alkyl-glutamate NCAs and other amino acid NCAs such as glycine NCA, L-aspartic acid-β-methyl ester NCA, L-alanine
It means a mixture of NCA and D-alanine NCA, etc. Considering physical properties and price, γ-methyl-L
It is often industrially more advantageous to use -glutamate NCA or γ-methyl-D-glutamate NCA alone. The urethane prepolymer having isocyanate groups at the terminals is obtained by reacting isocyanate and polyol under the conditions of equivalent ratio NCO/OH>1, but the isocyanate component is aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate. Diisocyanates alone or mixtures thereof may be used. For example, toluene-2,
4-diisocyanate, 4,4'-diphenylmethane diisocyanate, metaphenylene diisocyanate, 1,6-hexane diisocyanate,
1,10-decane methylene diisocyanate, 1,
Examples include 4-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and the like. As polyol components, polyether glycols and polyester glycols used in ordinary urethane products can be used. Polyether glycols include polyethylene glycol, polypropylene ether glycol, polytetramethylene glycol, bisphenol A and ethylene oxide or propylene. Polyaddition reaction products with oxides etc. are suitable. Polyester glycols include polycaprolactone glycol or ethylene glycol,
Those obtained by reacting diols such as 1,4-butanediol with dibasic acids such as adipic acid, sebacic acid, and succinic acid are used. The number average molecular weight of these polyethers and polyesters is 200-300
The above compounds are preferably used alone or in combination. As the amines used in the copolymerization method of the present invention described later, those represented by the following general formula are suitable.

【formula】

【formula】

[Measurement method: Film: 0.005cm (thickness) x 1.0cm (width) x 12cm (length), chuck spacing 5cm. Tensile strength 5cm/min〕

On the other hand, when dimethylformamide or dioxane alone was used instead of the mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, it gelled and became impossible to stir during the synthesis. Example 2 Polytetramethylene ether glycol (OH
985 g of 1,6-hexamethylene diisocyanate (value 56.9) and 168 g of 1,6-hexamethylene diisocyanate were reacted at 90° C. for 4 hours to obtain a urethane prepolymer having isocyanate groups at the terminals (NCO equivalent weight: 1179). 85 g of the urethane prepolymer and γ-methyl-L-glutamate
Dissolve 85g of NCA in 644g of a mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, add 81.1g of a 2% hydrated hydrazine solution while stirring, and react at 30°C for 2 hours, resulting in an emulsion with a viscosity of 8000cps. A solution with good fluidity was obtained. When this solution was made into a film by a dry method, a colorless and transparent film was obtained. The physical properties of the film are shown below. [Measurement method is the method of Example 1] 20% elongation recovery rate, 73%, Young's modulus, 480 Kg/cm ² .
100% modulus 45Kg/ ^cm2 . Cutting strength 320Kg/
^cm2 . Cutting elongation: 550% On the other hand, when dimethylformamide or dioxane alone was used instead of a mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, it gelled and became impossible to stir during synthesis. Example 3 Polytetramethylene ether glycol (OH
56.9) and 504 g of 1,6-hexamethylene diisocyanate were reacted at 90°C for 5 hours to obtain a urethane prepolymer having isocyanate groups at the terminals (NCO equivalent: 2340). 85 g of the urethane prepolymer and γ-methyl-L-glutamate
When 85g of NCA was dissolved in 666g of a mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, 50g of 2% triethylamine solution was added while stirring, and the reaction was performed at 30°C for 5 hours, resulting in a viscosity of 25000 cps.
(30°C) An emulsion-like solution with good fluidity was obtained. When this solution was made into a film by a dry method, a colorless and transparent film was obtained. On the other hand, when dimethylformamide or dioxane was used alone instead of a mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, the mixture became gel-like during synthesis and became impossible to stir. Example 4 Polytetramethylene ether glycol 1930
g, 348 g of tolylene diisocyanate at 70℃
A urethane prepolymer (NCO equivalent weight: 1163) having an isocyanate group at the end was obtained by reacting for a period of time. 85g of the urethane prepolymer and γ-methyl-L
- Glutamate NCA 85g in dimethylformamide/dioxane (weight ratio) = 7/3 mixed solvent 644
82.2 g of a 2% aqueous hydrazine solution was added with stirring, and the reaction was carried out at 30°C for 2 hours to obtain an emulsified solution with a viscosity of 3500 cps (at 25°C) and good fluidity. When this resin solution was cast onto a glass plate and immersed in water, a microporous white film was obtained. Example 5 57.1g of urethane prepolymer used in Example 3
and 75.6 g of γ-methyl-L-glutamate NCA in dimethylformamide/dioxane (weight ratio) =
The mixture was dissolved in 644 g of a 7/3 mixed solvent, and while stirring, 91 g of a 2% hydrous hydrazine solution was added and the reaction was carried out at 30°C for 2 hours to obtain an emulsified solution with a viscosity of 18,000 cps (at 25°C) and good fluidity. When this resin solution was cast onto a glass plate and immersed in water, a microporous white film was obtained. On the other hand, when dimethylformamide or dioxane was used alone instead of the mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, it became gel-like during synthesis and became impossible to stir. Example 6 85 g of the urethane prepolymer used in Example 3 and 85 g of γ-methyl-L-glutamate NCA were mixed in dimethylformamide/dioxane (weight ratio) = 45/
Dissolve 2% in 644g of mixed solvent of 55 and stir.
91 g of hydrous hydrazine was added and reacted at 30°C for 2 hours to obtain an emulsion-like solution with good fluidity and a viscosity of 12,000 cps (25°C). This resin solution was poured onto a glass plate, immersed in water, and air-dried to obtain a microporous white film. Example 7 85 g of the urethane prepolymer used in Example 3 and 85 g of γ-methyl-D glutamate NCA were mixed in dimethylformamide/dioxane (weight ratio) = 7/3.
644 g of the mixed solvent was dissolved, and while stirring, 91 g of 2% hydrazine was added and reacted at 30°C for 2 hours to obtain an emulsion-like solution with good fluidity and a viscosity of 13,000 cps (at 25°C). This resin solution was poured onto a glass plate, immersed in water, and air-dried to obtain a microporous white film. Example 8 85 g of the urethane prepolymer used in Example 3 and 85 g of γ-ethyl-L-glutamate NCA were mixed in dimethylformamide/dioxane (weight ratio) = 7/
In addition to the mixed solvent of No. 3, 91 g of a 2% hydrous hydrazine solution was added with stirring, and the mixture was reacted at 35°C for 2 hours to obtain an emulsion-like solution with good fluidity and a viscosity of 11,000 cps (at 25°C). This resin solution was poured onto a glass plate, immersed in water, and air-dried to obtain a microporous white film. On the other hand, when dimethylformamide or dioxane was used alone instead of the mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, the mixture became gelatinous during synthesis and became impossible to stir. Example 9 Polytetramethylene ether glycol (OH
985 and 200 g of 4,4'-diphenylmethane diisocyanate were reacted at 70°C for 5 hours to obtain a urethane prepolymer (NCO equivalent: 1850) having isocyanate groups at the ends. 85g of the urethane prepolymer and γ-methyl-L
- 85g of glutamate NCA was dissolved in 550g of dimethylformamide/dioxane (weight ratio) = 60/40, while stirring, 4.6g of triethylamine was dissolved in dimethylformamide/dioxane (weight ratio) =
Add 45g of 60/40 and heat at 30℃ for 5 minutes.
After a time reaction, a fluid emulsion solution with a viscosity of 15,000 cps (30°C) was obtained. Here, if dimethylformamide alone, dioxane alone, or dimethylformamide/dioxane (weight ratio) = 10/90 is used instead of the mixed solvent of dimethylformamide/dioxane (weight ratio) 60/40, a cloudy gel will form during synthesis. It became. In addition, when dimethylformamide/dimethyl ether (weight ratio) = 60/40 and dimethylformamide/diethyl ether (weight ratio) = 60/40 were used as solvents, a cloudy gel was formed. Example 10 Polytetramethylene ether glycol (OH
985 g of 4,4'-diphenylmethane diisocyanate were reacted at 70°C for 5 hours to obtain a urethane prepolymer (NCO equivalent weight: 1255) having an isocyanate group at the end. Next, hydrazine hydrate (H ₂ N−NH ₂
While dissolving _2.03 g of dimethylformamide/dioxane (weight ratio) in 638 g of a mixed solvent of dimethylformamide/dioxane (weight ratio) = 70/30 and stirring, 85 g of the urethane prepolymer was dissolved in dimethylformamide/dioxane (weight ratio) = 70/30.
A solution dissolved in 85 g of a 70/30 mixed solvent was added dropwise to the solution to obtain a urethane solution having an amino group at the end. 85 g of γ-methyl-L-glutamate-NCA was added to the urethane solution and reacted for 4 hours to determine the viscosity.
A PAU solution of 8000 cps/25°C was obtained. Example 11 Hydrazine hydrate (H ₂ N−NH ₂ .H ₂ O)
A mixture of 2.9 g of dimethylformamide/dioxane (weight ratio) = 70/30 was stirred, and 85 g of the urethane prepolymer (NCO equivalent: 1255) used in Example 10 was dissolved in dimethylformamide/dioxane (weight ratio). A solution dissolved in 85 g of a mixed solvent (weight ratio) = 70/30 was reacted dropwise to obtain a urethane solution having an amino group at the end. After adding 85 g of γ-methyl-L-glutamate-NCA to the urethane solution and carrying out a reaction for 2 hours,
To this, 56 g of the urethane prepolymer dissolved in the same weight of dimethylformamide/dioxane = 70/30 mixed solvent was added and reacted.
A PAU solution of 12000 cps/250°C was obtained.

Claims (1)

[Scope of Claims] 1. α-Amino acid-N mainly composed of optically active γ-alkyl-glutamate-N-carboxylic acid anhydride in a mixed solvent of dimethylformamide and dioxane in a weight ratio of 95:5 to 30:70. - A method for producing a polyamino acid urethane resin, which comprises mixing a carboxylic acid anhydride and a urethane prepolymer having an isocyanate group at the terminal, and then adding an amine to react the mixture. 2 Optically active γ-alkyl-glutamate is reacted with water or amines and a urethane prepolymer having an isocyanate group at the end in a mixed solvent of dimethylformamide and dioxane in a weight ratio of 95:5 to 30:70. A method for producing a polyamino acid urethane resin, which comprises adding and reacting an α-amino acid-N-carboxylic anhydride mainly consisting of -N-carboxylic anhydride. 3 Optically active γ-alkyl-glutamate is reacted with water or amines and a urethane prepolymer having an isocyanate group at the end in a mixed solvent of dimethylformamide and dioxane in a weight ratio of 95:5 to 30:70. Production of polyamino acid urethane resin characterized by reacting α-amino acid-N-carboxylic acid anhydride mainly composed of N-carboxylic acid anhydride, and then reacting with a urethane prepolymer having isocyanate groups at the terminals. Law.