Background technology
Chitin is that N-ethanoyl D-glucose passes through the straight-chain polysaccharide that β (1 → 4) glycosidic link links to each other, extensively is present in crustacean and the arthropods heart bacteria cell wall, and be one of organic compound that is only second on the earth cellulosic most abundant.Chitin is through taking off product---the chitosan that acetyl is handled, owing to contain the higher free amine group of a large amount of activity in the molecular structure, therefore have some unique physico-chemical property and physiological functions, have broad application prospects at medicine, food, makeup, agricultural and environmental protection aspects, particularly have many effects to the human body beneficial with this chitosan biological health-care product of making, by European and American countries be described as dewater, the sixth-largest vital principle of needed by human body outside protein, carbohydrate, Mierocrystalline cellulose and the mineral substance.
Chitin fiber can be used as operating sutures, fabric, non-woven fabrics raw material, and the chitosan film material can be used as Freshkeeping Packaging, permeable membrane etc., and chitosan multi-porous material can be used as bone repair tissue engineered vector material.Though chitosan self has good film-forming properties, but still need carry out cross-linking modifiedly, improve performances such as its tensile strength, water resisting property, to satisfy user demand to chitosan material.Oyrton A.C.Monteiro Jr., Claudio A. is at " Somestudies of crosslinking chitosan-glutaraldehyde interaction in a homogeneoussystem " (International Journal of Biological Macromolecules, 1999,26,119-128) (" research of chitosan and glutaraldehyde cross-linking reaction in the homogeneous system ", international biomacromolecule magazine) points out in the literary composition that the traditional cross-linking method of chitosan material is to use glutaraldehyde as linking agent, but product S chiff (Schiff) alkali that chitosan and glutaraldehyde reaction generate is unstable and certain toxicity is arranged, and generally needs further with sodium borohydride its reduction to be changed into stable keys.Simultaneously, discover that glutaraldehyde has certain cytotoxicity,, its application is restricted even also cell growth is inhibited for lower concentration.
Summary of the invention
The objective of the invention is at above shortcomings in the prior art, the preparation method of the cross-linking modified chitosan material of a kind of polysuccinimide is proposed, make it select for use polysuccinimide to make linking agent, polysuccinimide can make the crosslinked bond material of amido linkage of stability and safety with the chitosan single step reaction, and solvent can reuse, save cost, technology is simple, and is easy to operate.
The present invention is achieved by the following technical solutions, chitin fiber, mould material or porous material are suspended in the polysuccinimide organic solvent system, in system, add the amine organism as surface-modifying agent, stir, reaction back filtering out materials under the room temperature, with the distilled water immersion washing for several times, vacuum-drying obtains cross-linking modified chitosan material.
Below the present invention is done further concrete the qualification:
The different polysuccinimide product of molecular weight that reaction was made in 5~30 minutes is dissolved in N, dinethylformamide or N, make the clear solution system of 5~10% weight percents in the N-N,N-DIMETHYLACETAMIDE, chitin fiber with 10% weight percent, film or porous material are suspended in the polysuccinimide solution system, stir, react 12h under the room temperature, add 2~5% weight percent amine organism such as thanomins then, urea, butanediamine, hexanediamine, gelatin, collagen, amino acid and polypeptide, chitosan material is carried out surface modification, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan material.
Described polysuccinimide product, its preparation method is: the 12.5gDL-aspartic acid is placed the 250ml round-bottomed flask, add 6.5g85% phosphoric acid,, abundant mixing, 180 ℃ of decompressions were reacted 5~30 minutes, add 50ml N while hot, dinethylformamide, treat product dissolving after, join in the 300ml water, filter out precipitation, through being washed to neutrality, products therefrom is dissolved in 50ml N, dinethylformamide, reprecipitation, twice, 100 ℃ of vacuum-drying makes the polysuccinimide product repeatedly.
The present invention compares with traditional method, has avoided the use of glutaraldehyde, and polysuccinimide can react with the amino in the chitosan, directly makes the crosslinked bond material of amido linkage of stability and safety.The present invention by the amine organism can with polysuccinimide room temperature reaction characteristic, the part polysuccinimide of failing chitosan and crosslinking reaction taking place is further reacted completely with the amine organism, and, realize surface modification to chitosan material with certain amines type organic introducing material surface.The present invention selects for use polysuccinimide to make linking agent, because the different reaction times of control can make the polysuccinimide product of different molecular weight, can pass through to change the molecular weight of polysuccinimide and the crosslinking degree of consumption control chitosan material.The cross-linking modified of chitosan material carries out in room temperature among the present invention, and the chitosan material distilled water wash that filters out can be removed remaining solvent of material surface and unreacting substance, technology is simple, N, dinethylformamide, N, N-dimethylacetamide solvent system can reuse, saves cost.
Embodiment
Content below in conjunction with the inventive method provides following examples:
Embodiment 1:
Chitin fiber and 5% polysuccinimide/N, the enforcement of dinethylformamide.
The 12.5gDL-aspartic acid is placed the 250ml round-bottomed flask, add 6.5g85% phosphoric acid, fully mixing, 180 ℃ of decompressions were reacted 10 minutes, added 50ml N while hot, dinethylformamide, after treating the product dissolving, join in the 300ml water, filter out precipitation, through being washed to neutrality, products therefrom is dissolved in 50ml N, dinethylformamide, reprecipitation, twice, 100 ℃ of vacuum-drying makes the polysuccinimide product repeatedly.
The polysuccinimide product is dissolved in N, make the clear solution of 5% weight percent in the dinethylformamide, the chitin fiber of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 2% weight percent amine organism such as thanomin then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitin fiber.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitosan.
Embodiment 2:
Chitosan film material and 5% polysuccinimide/N, the enforcement of dinethylformamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
The polysuccinimide product is dissolved in N, make the clear solution of 5% weight percent in the dinethylformamide, the chitosan film material of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 2% weight percent amine organism such as thanomin then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan film material.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitosan.
Embodiment 3:
Chitosan multi-porous material and 5% polysuccinimide/N, the enforcement of dinethylformamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
The polysuccinimide product is dissolved in N, make the clear solution of 5% weight percent in the dinethylformamide, the chitosan multi-porous material of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 2% weight percent amine organism such as thanomin then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan multi-porous material.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitosan.
Embodiment 4:
The enforcement of chitosan film material and 5% polysuccinimide/N,N-dimethylacetamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
The polysuccinimide product is dissolved in N, make the clear solution of 5% weight percent in the N-N,N-DIMETHYLACETAMIDE, the chitosan film material of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 2% weight percent amine organism such as thanomin then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan film material.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitosan.
Embodiment 5:
Chitosan film material and S% hang down polysuccinimide/N, the enforcement of dinethylformamide.
The 12.5gDL-aspartic acid is placed the 250ml round-bottomed flask, add 6.5g85% phosphoric acid, fully mixing, 180 ℃ of decompressions were reacted 5 minutes, added 50ml N while hot, dinethylformamide, after treating the product dissolving, join in the 300ml water, filter out precipitation, through being washed to neutrality, products therefrom is dissolved in 50ml N, dinethylformamide, reprecipitation, twice, 100 ℃ of vacuum-drying makes the polysuccinimide product repeatedly.
The polysuccinimide product is dissolved in N, make the clear solution of 5% weight percent in the dinethylformamide, the chitosan film material of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 2% weight percent amine organism such as thanomin then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan film material.
Implementation result: the polysuccinimide of lower molecular weight and the amino generation crosslinking reaction in the chitosan.
Embodiment 6:
Chitosan film material and 10% polysuccinimide/N, the enforcement of dinethylformamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
The polysuccinimide product is dissolved in N, make the clear solution of 10% weight percent in the dinethylformamide, the chitosan film material of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 4% weight percent amine organism such as thanomin then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan material.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitosan.
Embodiment 7:
Chitosan multi-porous material and 10% polysuccinimide/N, dinethylformamide also use the enforcement of butanediamine surface modification.
Adopt embodiment 1 same method to make the polysuccinimide product.
The polysuccinimide product is dissolved in N, make the clear solution of 10% weight percent in the dinethylformamide, the chitosan multi-porous material of 10% weight percent is suspended in the polysuccinimide solution, stir, react 12h under the room temperature, add 5% weight percent amine organism such as thanomin and butanediamine then, use the copper mesh filtering out materials behind the reaction 12h under the room temperature, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitosan material.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and chitosan and the butanediamine molecule makes chitosan multi-porous material surface in conjunction with the butanediamine molecule.