CN103819905B - A kind of method that PTMC and polyvinylpyrrolidone improve poly-peptide film wetting ability - Google Patents

Abstract

The invention discloses a method for improving the hydrophilicity of a polypeptide film by using polytrimethylene carbonate and polyvinylpyrrolidone. The following steps are adopted: 1) Synthesis of a graft copolymer of polytrimethylene carbonate-polytrimethylene carbonate: Add polypeptide homopolymer, polytrimethylene carbonate monododecyl ether, solvent and catalyst into the drying reactor, under inert atmosphere, stir and react at 55-58°C for 3-4 days, then filter, dialyze, Drying to obtain the target product; 2) Preparation of polytrimethylene carbonate and polyvinylpyrrolidone modified polypeptide film: add polypeptide-polytrimethylene carbonate graft copolymer, polyvinylpyrrolidone to the drying reactor and a solvent, under an inert atmosphere, stir and mix at 40-50°C for 50-70 minutes, then form a film by casting method and dry to obtain the object of the present invention. The preparation process of the invention is simple and easy to master, and the hydrophilicity of the obtained modified membrane is greatly improved.

Description

A method for improving the hydrophilicity of polypeptide membranes with polytrimethylene carbonate and polyvinylpyrrolidone

technical field

The invention relates to a method for improving the hydrophilicity of a polypeptide film, belonging to the technical field of polymer film preparation.

Background technique

Polypeptide is a biomaterial with good biocompatibility and biodegradability. Polypeptide film can be used as artificial skin, etc., but the lack of good hydrophilicity of polypeptide film limits its application to some extent. application. Polytrimethylene carbonate has better biocompatibility and biodegradability, and has better blendability with polyvinylpyrrolidone. Polyvinylpyrrolidone has good biocompatibility and biodegradability, and has excellent hydrophilicity. Firstly, the polytrimethylene carbonate segment is introduced into the polypeptide segment to form a polypeptide-polytrimethylene carbonate graft copolymer to improve the blendability of the polypeptide, and then the polyvinylpyrrolidone segment is added to the polypeptide- The polytrimethylene carbonate graft copolymer forms a blend to prepare a modified polypeptide film, thereby greatly improving the hydrophilicity of the polypeptide film.

Contents of the invention

The purpose of the present invention is to provide a method for improving the hydrophilicity of the polypeptide membrane with simple operation and good effect. Its technical solution is:

A method for improving the hydrophilicity of a polypeptide film by using polytrimethylene carbonate and polyvinylpyrrolidone, characterized in that: the molecular weight of the polypeptide segment in the modified film is 60,000 to 80,000, and the polytrimethylene carbonate The molecular weight of the segment is 1000-2000, and the molecular weight of the polyvinylpyrrolidone segment is 4000-5000; the modification method adopts the following steps:

1) Synthesis of polypeptide-polytrimethylene carbonate graft copolymer: Add polypeptide homopolymer, polytrimethylene carbonate monolauryl ether, solvent and catalyst in a dry reactor, and under an inert atmosphere , after stirring and reacting at 55-58°C for 3-4 days, the target product was obtained by filtration, dialysis and drying;

2) Preparation of polypeptide film modified by polytrimethylene carbonate and polyvinylpyrrolidone: add polypeptide-polytrimethylenecarbonate graft copolymer, polyvinylpyrrolidone and solvent in a drying reactor, and under an inert atmosphere , Stirring and mixing at 40-50°C for 50-70 minutes, forming a film by casting method and drying to obtain the target product.

In the method for improving the hydrophilicity of a polypeptide film by using polytrimethylene carbonate and polyvinylpyrrolidone, in step 1), the homopolymer of the polypeptide is poly(r-benzyl-L-glutene amino acid ester), poly(r-ethyl-L-glutamate) or poly(r-methyl-L-glutamate), polytrimethylene carbonate monolauryl ether and polypeptide The molar ratio of the homopolymer is 15-25:1.

In the method for improving the hydrophilicity of the polypeptide film with polytrimethylene carbonate and polyvinylpyrrolidone, in step 1), the catalyst uses p-toluenesulfonic acid, and the molar ratio of the catalyst to the homopolymer of the polypeptide is The ratio is 25-45:1, the solvent is dimethyl sulfoxide, and the concentration of the reactant solution is 5-15g:100ml.

In the method for improving the hydrophilicity of a polypeptide film by using polytrimethylene carbonate and polyvinylpyrrolidone, in step 2), the mass percentage of polyvinylpyrrolidone in the modified film is 1-3%, The solvent is dimethyl sulfoxide, and the concentration of the mixture solution is 25-30g:100ml.

Compared with the prior art, the present invention has the advantages of:

1. The method for improving the hydrophilicity of the polypeptide film with polytrimethylene carbonate and polyvinylpyrrolidone adopts two methods of graft copolymerization and blending, which are simple to operate and easy to master;

2. The hydrophilicity of the polypeptide modified membrane has been greatly improved.

detailed description

Example 1

1) Synthesis of polypeptide-polytrimethylene carbonate graft copolymer:

Add 12 grams of poly(r-benzyl-L-glutamate) with a molecular weight of 60,000, 3.1 grams of polytrimethylene carbonate monolauryl ether with a molecular weight of 1000, and 0.9 grams of p-toluene in the dry reactor. Sulfonic acid, then add 260 ml of dimethyl sulfoxide solvent, under inert atmosphere, stir and react at 55°C for 3 days, terminate the reaction, and then obtain the target object by filtration, dialysis, and drying;

2) Preparation of Polytrimethylene Carbonate and Polyvinylpyrrolidone Modified Polypeptide Film:

Add 10 grams of polypeptide-polytrimethylene carbonate graft copolymer and 38 ml of dimethyl sulfoxide solvent into the dry reactor, and add polyvinylpyrrolidone (molecular weight 4000) accounting for 1% of the total weight of the modified membrane , under an inert atmosphere, stirred and mixed at 40°C for 50 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.

After testing: the hydrophilic rate of the object of the present invention is increased by 12.8% compared with that before modification.

Example 2

1) Synthesis of polypeptide-polytrimethylene carbonate graft copolymer:

Add 12 grams of poly(r-ethyl-L-glutamate) with a molecular weight of 70,000, 5.3 grams of polytrimethylene carbonate monolauryl ether with a molecular weight of 1500, and 0.91 grams of p-toluenesulfonate in the dry reactor. acid, then add 230 ml of dimethyl sulfoxide solvent, under an inert atmosphere, stir and react at 56 ° C for 4 days, terminate the reaction, and then obtain the target object by filtration, dialysis, and drying;

2) Preparation of Polytrimethylene Carbonate and Polyvinylpyrrolidone Modified Polypeptide Film:

Add 10 grams of polypeptide-polytrimethylene carbonate graft copolymer and 36 ml of dimethyl sulfoxide solvent into the drying reactor, and add polyvinylpyrrolidone (molecular weight 4500) accounting for 2% of the total weight of the modified membrane , under an inert atmosphere, stirred and mixed at 45°C for 60 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.

After testing: the hydrophilic rate of the object of the present invention is increased by 13.9% compared with that before modification.

Example 3

1) Synthesis of polypeptide-polytrimethylene carbonate graft copolymer:

Add 12 grams of poly(r-methyl-L-glutamate) with a molecular weight of 80,000, 7.2 grams of polytrimethylene carbonate monolauryl ether with a molecular weight of 2000, and 1.03 grams of p-toluenesulfonate in the dry reactor acid, then add 177 ml of dimethyl sulfoxide, under an inert atmosphere, stir and react at 58°C for 3 days, terminate the reaction, and then obtain the target product by filtration, dialysis, and drying;

2) Preparation of Polytrimethylene Carbonate and Polyvinylpyrrolidone Modified Polypeptide Film:

Add 10 grams of polypeptide-polytrimethylene carbonate graft copolymer and 35.5 milliliters of dimethyl sulfoxide into the drying reactor, and add polyvinylpyrrolidone (molecular weight is 5000) accounting for 3% of the total weight of the modified membrane, Under an inert atmosphere, after stirring and mixing at 50°C for 70 minutes, a film was formed by casting method, and dried in a vacuum oven at 50°C to obtain the target product.

After testing: the hydrophilic rate of the object of the present invention is increased by 15.8% compared with that before modification.

Claims (4)

1. A method for improving the hydrophilicity of a polypeptide film with polytrimethylene carbonate and polyvinylpyrrolidone, characterized in that: the molecular weight of the polypeptide segment in the modified film is 60000 to 80000, and polytrimethylene The molecular weight of the carbonate segment is 1000-2000, and the molecular weight of the polyvinylpyrrolidone segment is 4000-5000; the modification method adopts the following steps: 1) Synthesis of polypeptide-polytrimethylene carbonate graft copolymer: Add polypeptide homopolymer, polytrimethylene carbonate monolauryl ether, solvent and catalyst in a dry reactor, and under an inert atmosphere , after stirring and reacting at 55-58°C for 3-4 days, the target product was obtained by filtration, dialysis, and drying. Among them, the polypeptide homopolymer was poly(γ-benzyl-L-glutamate), poly( γ-ethyl-L-glutamate) or poly(γ-methyl-L-glutamate); 2) Preparation of polypeptide film modified by polytrimethylene carbonate and polyvinylpyrrolidone: add polypeptide-polytrimethylenecarbonate graft copolymer, polyvinylpyrrolidone and solvent in a drying reactor, and under an inert atmosphere , Stirring and mixing at 40-50°C for 50-70 minutes, forming a film by casting method and drying to obtain the target product. 2. A method for improving the hydrophilicity of a polypeptide film with polytrimethylene carbonate and polyvinylpyrrolidone according to claim 1, characterized in that: in step 1), polytrimethylene carbonate The molar ratio of dodecyl ether to polypeptide homopolymer is 15-25:1. 3. A method for improving the hydrophilicity of a polypeptide film with polytrimethylene carbonate and polyvinylpyrrolidone according to claim 1, characterized in that: in step 1), p-toluenesulfonic acid is used as the catalyst, The molar ratio of the catalyst to the polypeptide homopolymer is 25-45:1, the solvent is dimethyl sulfoxide, and the concentration of the reactant solution is 5-15g:100mL. 4. A method for improving the hydrophilicity of a polypeptide film with polytrimethylene carbonate and polyvinylpyrrolidone according to claim 1, characterized in that: in step 2), polyvinylpyrrolidone is added to the modified film The mass percentage in the mixture is 1-3%, the solvent is dimethyl sulfoxide, and the concentration of the mixture solution is 25-30g:100mL.