CN1587282A - Process for preparing poly succinimide crosslinking modified chitosan material - Google Patents

Abstract

A preparation method of polysuccinimide cross-linked modified chitosan material, the invention dissolves polysuccinimide products with different molecular weights prepared by reacting for 5 to 30 minutes in N,N-dimethylformaldehyde 5-10% by weight of a transparent solution system made from methyl formamide or N,N-dimethylacetamide, and 10% by weight of chitosan fibers, membranes or porous materials are suspended in polysuccinimide In the solution system, stir evenly, react at room temperature for 12 hours, then add 2 to 5% by weight of amine organic matter to modify the surface of the chitosan material, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water Three times, vacuum drying at 40°C to obtain a cross-linked modified chitosan material. The invention has simple process, convenient operation and short production period, and is applied in the technical field of chitosan surface treatment.

Description

Preparation method of polysuccinimide cross-linked modified chitosan material

technical field

The invention relates to a preparation method of a cross-linked modified chitosan material, in particular to a preparation method of a polysuccinimide cross-linked modified chitosan material. It is used in the technical field of material surface treatment.

Background technique

Chitin is a straight-chain polysaccharide in which N-acetyl D-glucose is connected by β(1→4) glycosidic bonds. It is widely found in the cell walls of crustacean and arthropod heart bacteria, and is second only to cellulose on the earth. one of the organic compounds. Chitosan, the product of deacetylation treatment of chitin, has some unique physical and chemical properties and physiological functions due to the large number of free amino groups with high activity in its molecular structure. It is widely used in medicine, food, cosmetics, agriculture and environmental protection. It has broad application prospects, especially the chitosan biological health care products made of it have many beneficial effects on the human body, and has been praised by European and American countries as the human body except water, protein, sugar, cellulose and minerals. The sixth major life element needed.

Chitosan fibers can be used as raw materials for surgical sutures, fiber fabrics, and non-woven fabrics. Chitosan membrane materials can be used as fresh-keeping packaging, permeable membranes, etc. Chitosan porous materials can be used as carrier materials for bone repair tissue engineering. Although chitosan itself has good film-forming properties, it is still necessary to cross-link the chitosan material to improve its tensile strength, water resistance and other properties to meet the needs of use. Oyrton A.C.Monteiro Jr., Claudio A. in "Somestudies of crosslinking chitosan-glutaraldehyde interaction in a homogeneous system" (International Journal of Biological Macromolecules, 1999, 26, 119-128) ("Chitosan and glutaraldehyde in homogeneous system Research on Crosslinking Reaction", International Journal of Biomacromolecules) points out that the traditional crosslinking method of chitosan materials is to use glutaraldehyde as a crosslinking agent, but the product Schiff (Xi Fu) alkali is unstable and has certain toxicity, and generally needs to further use sodium borohydride to reduce it into a stable bond. At the same time, studies have found that glutaraldehyde has certain cytotoxicity, and even at low concentrations, it can inhibit cell growth, which limits its application.

Contents of the invention

The purpose of the present invention is to address the above-mentioned deficiencies that exist in the prior art, propose a kind of preparation method of polysuccinimide crosslinking modified chitosan material, make it select polysuccinimide for use as crosslinking agent, The polysuccinimide can be reacted with chitosan in one step to prepare a stable and safe amide bond cross-linked material, and the solvent can be reused, saving cost, simple process and convenient operation.

The present invention is achieved through the following technical scheme, suspending chitosan fiber, membrane material or porous material in the polysuccinimide organic solvent system, adding amine organic matter in the system as a surface modifier, stirring evenly, After reacting at room temperature, the material was filtered out, soaked and washed with distilled water for several times, and vacuum-dried to obtain a cross-linked modified chitosan material.

The present invention is further specifically defined below:

The polysuccinimide products with different molecular weights prepared by reacting for 5-30 minutes are dissolved in N,N-dimethylformamide or N,N-dimethylacetamide to make 5-10% by weight transparent solution system, suspending 10% by weight chitosan fibers, membranes or porous materials in the polysuccinimide solution system, stirring evenly, reacting at room temperature for 12 hours, and then adding 2-5% by weight amines Organic substances such as ethanolamine, urea, butylenediamine, hexamethylenediamine, gelatin, collagen, amino acids and polypeptides are used to modify the surface of the chitosan material. After reacting at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash it with distilled water three times, The cross-linked modified chitosan material was obtained by vacuum drying at 40°C.

The preparation method of the polysuccinimide product is as follows: put 12.5g of DL-aspartic acid in a 250ml round bottom flask, add 6.5g of 85% phosphoric acid, mix well, and react under reduced pressure at 180°C for 5～ For 30 minutes, add 50ml of N,N-dimethylformamide while it is hot. After the product is dissolved, add it to 300ml of water, filter out the precipitate, wash it with water until neutral, and dissolve the obtained product in 50ml of N,N-dimethylformamide Amide, reprecipitation, repeated twice, vacuum drying at 100°C to obtain polysuccinimide product.

Compared with the traditional method, the invention avoids the use of glutaraldehyde, and the polysuccinimide can react with the amino group in the chitosan to directly prepare a stable and safe amide bond cross-linked material. According to the room temperature reaction characteristics of amine organic substances and polysuccinimide, the part of polysuccinimide that has not cross-linked with chitosan can be further reacted with amine organic substances completely, and the specific amines The organic matter is introduced into the surface of the material to realize the surface modification of the chitosan material. The present invention selects polysuccinimide as the crosslinking agent, and polysuccinimide products with different molecular weights can be obtained by controlling different reaction times, and chitosan can be controlled by changing the molecular weight and dosage of polysuccinimide. The degree of cross-linking of the sugar material. The cross-linking modification of the chitosan material in the present invention is carried out at room temperature, and the filtered chitosan material is washed with distilled water, which can remove the remaining solvent and unreacted substances on the surface of the material, and the process is simple. The amide and N,N-dimethylacetamide solvent systems can be reused to save costs.

Detailed ways

The following examples are provided below in conjunction with the content of the method of the present invention:

Example 1:

Implementation of chitosan fibers with 5% polysuccinimide/N,N-dimethylformamide.

Put 12.5g of DL-aspartic acid in a 250ml round bottom flask, add 6.5g of 85% phosphoric acid, mix thoroughly, and react under reduced pressure at 180°C for 10 minutes, add 50ml of N,N-dimethylformamide while it is hot, and prepare the product After dissolving, add it to 300ml of water, filter out the precipitate, wash with water to neutrality, dissolve the obtained product in 50ml of N,N-dimethylformamide, reprecipitate, repeat twice, and vacuum dry at 100°C to obtain polybutylene imide products.

The polysuccinimide product is dissolved in N,N-dimethylformamide to make a transparent solution of 5% by weight, and the chitosan fiber of 10% by weight is suspended in the polysuccinimide solution , stir evenly, react at room temperature for 12 hours, then add 2% by weight of amine organic matter such as ethanolamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain cross-linked modified chitosan sugar fiber.

Implementation effect: cross-linking reaction occurs between polysuccinimide and amino groups in chitosan.

Example 2:

Implementation of chitosan membrane material with 5% polysuccinimide/N,N-dimethylformamide.

Adopt the same method of embodiment 1 to make polysuccinimide product.

The polysuccinimide product is dissolved in N,N-dimethylformamide to make a transparent solution of 5% by weight, and the chitosan film material of 10% by weight is suspended in the polysuccinimide solution , stir evenly, react at room temperature for 12 hours, then add 2% by weight of amine organic matter such as ethanolamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain a cross-linked modified shell Polysaccharide membrane material.

Implementation effect: cross-linking reaction occurs between polysuccinimide and amino groups in chitosan.

Example 3:

Implementation of chitosan porous materials with 5% polysuccinimide/N,N-dimethylformamide.

Adopt the same method of embodiment 1 to make polysuccinimide product.

The polysuccinimide product is dissolved in N,N-dimethylformamide to make a transparent solution of 5% by weight, and the chitosan porous material of 10% by weight is suspended in the polysuccinimide solution , stir evenly, react at room temperature for 12 hours, then add 2% by weight of amine organic matter such as ethanolamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain a cross-linked modified shell Polysaccharide porous materials.

Implementation effect: cross-linking reaction occurs between polysuccinimide and amino groups in chitosan.

Example 4:

Implementation of chitosan membrane material with 5% polysuccinimide/N,N-dimethylacetamide.

Adopt the same method of embodiment 1 to make polysuccinimide product.

The polysuccinimide product is dissolved in N,N-dimethylacetamide to make a transparent solution of 5% by weight, and the chitosan film material of 10% by weight is suspended in the polysuccinimide solution , stir evenly, react at room temperature for 12 hours, then add 2% by weight of amine organic matter such as ethanolamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain a cross-linked modified shell Polysaccharide membrane material.

Implementation effect: cross-linking reaction occurs between polysuccinimide and amino groups in chitosan.

Example 5:

Implementation of chitosan membrane material with S% oligosuccinimide/N,N-dimethylformamide.

Put 12.5g of DL-aspartic acid in a 250ml round bottom flask, add 6.5g of 85% phosphoric acid, mix thoroughly, react under reduced pressure at 180°C for 5 minutes, add 50ml of N,N-dimethylformamide while hot, and prepare the product After dissolving, add it to 300ml of water, filter out the precipitate, wash with water to neutrality, dissolve the obtained product in 50ml of N,N-dimethylformamide, reprecipitate, repeat twice, and vacuum dry at 100°C to obtain polybutylene imide products.

The polysuccinimide product is dissolved in N,N-dimethylformamide to make a transparent solution of 5% by weight, and the chitosan film material of 10% by weight is suspended in the polysuccinimide solution , stir evenly, react at room temperature for 12 hours, then add 2% by weight of amine organic matter such as ethanolamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain a cross-linked modified shell Polysaccharide membrane material.

Implementation effect: the cross-linking reaction occurs between the lower molecular weight polysuccinimide and the amino group in chitosan.

Embodiment 6:

Implementation of chitosan membrane material with 10% polysuccinimide/N,N-dimethylformamide.

Adopt the same method of embodiment 1 to make polysuccinimide product.

The polysuccinimide product is dissolved in N,N-dimethylformamide to make a transparent solution of 10% by weight, and the chitosan film material of 10% by weight is suspended in the polysuccinimide solution , stir well, react at room temperature for 12 hours, then add 4% by weight of amine organic matter such as ethanolamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain a cross-linked modified shell polysaccharide material.

Implementation effect: cross-linking reaction occurs between polysuccinimide and amino groups in chitosan.

Embodiment 7:

Implementation of chitosan porous material with 10% polysuccinimide/N,N-dimethylformamide and surface modification with butanediamine.

Adopt the same method of embodiment 1 to make polysuccinimide product.

The polysuccinimide product is dissolved in N,N-dimethylformamide to make a transparent solution of 10% by weight, and the chitosan porous material of 10% by weight is suspended in the polysuccinimide solution , stir evenly, react at room temperature for 12 hours, then add 5% by weight of amine organic substances such as ethanolamine and butanediamine, react at room temperature for 12 hours, filter out the material with a copper mesh, soak and wash with distilled water three times, and vacuum dry at 40°C to obtain cross-linked Linked modified chitosan material.

Implementation effect: the polysuccinimide reacts with the amino group in the chitosan and butylenediamine molecules to make the chitosan porous material surface bind the butanediamine molecules.

Claims (3)

1, a kind of preparation method of polysuccinimide crosslinking modified chitosan material is characterized in that, the polysuccinimide product that the molecular weight that reacts 5～30 minutes is different is dissolved in N, N-dimethylformamide or N,N-dimethylacetamide is made into a transparent solution system with 5% to 10% by weight, and 10% by weight of chitosan fibers, films or porous materials are suspended in polybutylene In the diimide solution system, stir evenly, react at room temperature for 12 hours, then add 2 to 5% by weight of amine organic matter to modify the surface of the chitosan material, react at room temperature for 12 hours, and filter out the material with a copper mesh. Soak and wash with distilled water for three times, and vacuum dry at 40°C to obtain a cross-linked modified chitosan material. 2, the preparation method of polysuccinimide cross-linking modified chitosan material as claimed in claim 1 is characterized in that, adds amine organic matter in the reaction system, chitosan material is carried out surface modification, so The above-mentioned amine organic substances include: ethanolamine, urea, butylenediamine, hexamethylenediamine, gelatin, collagen, amino acid and polypeptide. 3, the preparation method of polysuccinimide crosslinking modified chitosan material as claimed in claim 1 is characterized in that, by changing the molecular weight of polysuccinimide or consumption control the crosslinking of chitosan material connection degree.