CN1286856C - Process for preparing poly saccuinimide crosslinking modified chitin material - Google Patents
Process for preparing poly saccuinimide crosslinking modified chitin material Download PDFInfo
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- CN1286856C CN1286856C CN 200410053262 CN200410053262A CN1286856C CN 1286856 C CN1286856 C CN 1286856C CN 200410053262 CN200410053262 CN 200410053262 CN 200410053262 A CN200410053262 A CN 200410053262A CN 1286856 C CN1286856 C CN 1286856C
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Abstract
The present invention relates to a method for preparing poly succuinimide crosslinking modified chitin material. Poly succuinimide products which are prepared through reaction of 5 to 30 minutes and have different molecular weight are dissolved in N, N-dimethylformamide or N, N-dimethyl acetamide, which generates transparent solution whose weight percentage is from 5 to 10% for use; chitin is added to a lithium chloride/N, N-dimethyl acetamide solvent system whose weight percentage is 5%, the lithium chloride/N, N-dimethyl acetamide solvent system is stirred, the chitin is melted, and transparent solution which contains 4% of chitin according to the weight percentage is prepared; poly succuinimide solution is added to the chitin solution, and amine organic matter of 2 to 5% is added according to the weight percentage; crosslinking operation is carried out, and simultaneously, surface modification is carried out; uniform stirring operation is carried out, mixed solution reacts for 12h at the room temperature, ethanol is used as solidification liquid, and fiber or thin film material is prepared in a wet spinning mode; through dryness at the room temperature, the fiber or the thin film material is soaked and washed with distilled water for three times; through vacuum dryness at the temperature of 40 DEG C, crosslinking modified chitin fiber and film material can be respectively obtained. The present invention has the advantages of simple technology and convenient operation. The present invention is applied to the technical field of modified processing of chitin material.
Description
Technical field
The present invention relates to a kind of cross-linking modified chitin preparation methods, the cross-linking modified chitin preparation methods of particularly a kind of polysuccinimide.Be used for the material modification processing technology field.
Background technology
Chitin has another name called chitin or chitin; it is the straight-chain polysaccharide that N-ethanoyl-D-glucose links to each other by β (1 → 4) glycosidic link; be the main body of the shell of ocean arthropods such as shrimp, crab, also be present in simultaneously in the cell walls of the shell of many lower animals such as insect and lower plant such as bacterium, algae.The biosynthesizing amount in nature every year is estimated as 10,000,000,000 tons, is to be only second to one of cellulosic most abundant renewable resource on the earth, can be widely used in environmental protection, food, medicine, biotechnology, daily-use chemical industry, textile printing and dyeing, papermaking and agricultural etc.Utilize good fiberizability of chitin and film-forming properties, can make chitin fiber and mould material etc.Because chitin is a natural polymer, biologically active, biocompatibility and biodegradability, its fiber can be used as the self-absorption surgical sewing thread; Also can be woven into gauze, bandage or make the dressing as wound such as tNonwovens, can be antibiotic, deodorization, analgesia, hemostasis, have the effect that promotes wound healing.
In " chitin " (Chemical Industry Press that Jiang Tingda writes, 2003, the 86th～88 page) in the chitin molecule recorded and narrated owing to there is stronger hydrogen bond, be only soluble in the minority solvent system, cross-linking modified difficulty, generally be to spend the night in the high alkali liquid that earlier chitin is immersed under-20 ℃～-10 ℃ to make the alkali chitin, carry out modified-reaction then.The reaction process of alkali chitin is that micromolecular alkali enters in the macromolecular chitin solid granule and goes, and significant swollen takes place, and swollen continues to carry out, and especially under the lower situation of temperature, has generated the addition compound of alkali and chitin.This preparation method's time is longer, and for avoiding the deacetylated of chitin and degraded, the preparation of alkali chitin and preservation all will be controlled under the lower temperature, because the concentration of lye of handling is higher, product will be with massive laundering to neutral.Preparation technology is relatively complicated thus.
Summary of the invention
The objective of the invention is at above shortcomings in the prior art, the cross-linking modified chitin preparation methods of a kind of polysuccinimide is proposed, can make chitin dissolved lithium chloride/N, carry out in the N-dimethylacetamide solvent system, it is simple to make it have technology, easy to operate advantage, thus remedied the deficiency that exists in the above-mentioned background technology.
The present invention realizes by following technical scheme, the present invention will react the different polysuccinimide product of molecular weight that made in 5～30 minutes and be dissolved in N, the clear solution of making 5～10% weight percents in dinethylformamide or the N,N-dimethylacetamide is stand-by;
Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent;
Polysuccinimide solution is added in the above-mentioned chitin solution, add 2～5% weight percent amine organism then, in the crosslinked surface modification of carrying out simultaneously, stirring, behind the reaction 12h, is solidification liquid with ethanol under the mixing solutions room temperature, wet spinning makes fiber, perhaps make thin-film material, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitin fiber and mould material respectively after drying at room temperature.
Described amine organism comprises: thanomin, urea, butanediamine, hexanediamine, gelatin, collagen, amino acid and polypeptide.
Described polysuccinimide product, the 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, added 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 repeatedly, 100 ℃ of vacuum-dryings make the polysuccinimide product.
The present invention selects for use polysuccinimide to make linking agent, utilizes in polysuccinimide and the chitin a small amount of amino reaction, makes with amido linkage and carries out crosslinked bonded material, and this crosslinking method stability and safety can further improve the mechanical strength of material.The present invention carries out cross-linking modified in lithium chloride/N,N-dimethylacetamide solvent system, and chitin molecule is dissolvable in water in this solvent system, and certain stability is arranged, and helps the carrying out of cross-linking modified reaction, and product is easy to spinning and system film.Select for use polysuccinimide to make linking agent, utilize a small amount of amino reaction in polysuccinimide and the chitin, make with amido linkage and carry out crosslinked bonded material, the different reaction times of control can make the polysuccinimide product of different molecular weight among the present invention, can be by the molecular weight of change polysuccinimide and the crosslinking degree of consumption control chitin material.Utilize among the present invention the amine organism can with polysuccinimide room temperature reaction characteristic, the part polysuccinimide of failing with chitin generation crosslinking reaction is further reacted completely with the amine organism, the amine organism is introduced the chitin material, realize the modification of chitin is handled.The chitin material that filters out can directly be used distilled water wash, removes remaining solvent of material surface and unreacting substance.
The cross-linking modified of chitin material carries out in room temperature among the present invention, and technology is simple, and cross-linking modified chitin fiber that obtains or mould material can be made into the dressing as wound such as gauze, bandage or tNonwovens.
Embodiment
Content below in conjunction with the inventive method provides following examples:
Embodiment 1:
The enforcement of 5% polysuccinimide/crosslinked chitin fiber of N,N-dimethylacetamide.
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.
It is stand-by that the polysuccinimide product is dissolved in the clear solution of making 5% weight percent in the N,N-dimethylacetamide.Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent.Polysuccinimide solution is added in the above-mentioned chitin solution, add 2% weight percent amine organism such as thanomin then, stir, after reacting 12h under the room temperature, with ethanol is solidification liquid, wet spinning makes fiber, and with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain crosslinked chitin fiber material after drying at room temperature.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitin.
Embodiment 2:
The enforcement of the crosslinked chitin film material of 5% polysuccinimide/N,N-dimethylacetamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
It is stand-by that the polysuccinimide product is dissolved in the clear solution of making 5% weight percent in the N,N-dimethylacetamide.Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent.Polysuccinimide solution is added in the above-mentioned chitin solution, add 2% weight percent amine organism such as thanomin then, stir, after reacting 12h under the room temperature, mixing solutions is spread out film at glass surface, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain crosslinked chitin film material after drying at room temperature.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitin, hygrometric state film breaking tenacity is brought up to 2.6MPa by 1.3MPa before crosslinked.
Embodiment 3:
5% polysuccinimide/N, the enforcement of the crosslinked chitin film material of dinethylformamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
The polysuccinimide product is dissolved in N, and the clear solution of making 5% weight percent in the dinethylformamide is stand-by.Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent.Polysuccinimide solution is added in the above-mentioned chitin solution, add 2% weight percent amine organism such as thanomin then, stir, after reacting 12h under the room temperature, mixing solutions is spread out film at glass surface, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain crosslinked chitin film material after drying at room temperature.
Implementation result: the amino generation crosslinking reaction in polysuccinimide and the chitin, hygrometric state film tensile break strength is brought up to 2.5MPa by 1.3MPa before crosslinked.
Embodiment 4:
The enforcement of the 5% low crosslinked chitin film material of polysuccinimide/N,N-dimethylacetamide.
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 50mlN 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 50mlN, dinethylformamide, reprecipitation, twice, 100 ℃ of vacuum-drying makes the polysuccinimide product repeatedly.
It is stand-by that the polysuccinimide product is dissolved in the clear solution of making 5% weight percent in the N,N-dimethylacetamide.Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent.Polysuccinimide solution is added in the above-mentioned chitin solution, add 2% weight percent amine organism such as thanomin then, stir, after reacting 12h under the room temperature, mixing solutions is spread out film at glass surface, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain crosslinked chitin film material after drying at room temperature.
Implementation result: the polysuccinimide of lower molecular weight and the amino generation crosslinking reaction in the chitin, hygrometric state film tensile break strength is brought up to 2.9MPa by 1.3MPa before crosslinked.
Embodiment 5:
The enforcement of the crosslinked chitin film material of 10% polysuccinimide/N,N-dimethylacetamide.
Adopt embodiment 1 same method to make the polysuccinimide product.
It is stand-by that the polysuccinimide product is dissolved in the clear solution of making 10% weight percent in the N,N-dimethylacetamide respectively.Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent.Polysuccinimide solution is added in the above-mentioned chitin solution, add 4% weight percent amine organism such as thanomin then, stir, after reacting 12h under the room temperature, mixing solutions is spread out film at glass surface, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain crosslinked chitin film material after drying at room temperature.
Implementation result: polysuccinimide respectively with chitin and thanomin in amino generation crosslinking reaction, hygrometric state film tensile break strength is brought up to 2.8MPa by 1.3MPa before crosslinked.
Embodiment 6:
The enforcement of crosslinked thanomin of 10% polysuccinimide/N,N-dimethylacetamide and butanediamine modified chitin mould material.
Adopt embodiment 1 same method to make the polysuccinimide product.
It is stand-by that the polysuccinimide product is dissolved in the clear solution system of making 10% weight percent in the N,N-dimethylacetamide.Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, making chitin is the clear solution system of 4% weight percent.In polysuccinimide solution adding system, add 5% weight percent amine organism such as thanomin and butanediamine then, stir, after reacting 12h under the room temperature, mixing solutions is spread out film at glass surface, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitin film material after drying at room temperature.
Implementation result: polysuccinimide respectively with chitin, thanomin and butanediamine in amino generation crosslinking reaction.
Claims (2)
1, the cross-linking modified chitin preparation methods of a kind of polysuccinimide, it is characterized in that, the polysuccinimide product, the 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, 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 repeatedly, 100 ℃ of vacuum-dryings make the polysuccinimide product;
The polysuccinimide product is dissolved in N, and the clear solution of making 5～10% weight percents in dinethylformamide or the N,N-dimethylacetamide is stand-by;
Chitin is added in 5% weight percent lithium chloride/N,N-dimethylacetamide solvent system, stir and make dissolving, make the clear solution that chitin is 4% weight percent;
Polysuccinimide solution is added in the above-mentioned chitin solution, add a kind of in the thanomin, urea, butanediamine, hexanediamine, amino acid, polypeptide, gelatin, collagen of 2～5% weight percents then, in the crosslinked surface modification of carrying out simultaneously, stir, reaction is after 12 hours under the mixing solutions room temperature, with ethanol is solidification liquid, wet spinning makes fiber, perhaps make thin-film material, with distilled water immersion washing three times, 40 ℃ of vacuum-dryings obtain cross-linking modified chitin fiber or thin-film material respectively after drying at room temperature.
2, the cross-linking modified chitin preparation methods of polysuccinimide as claimed in claim 1 is characterized in that, by the molecular weight of change polysuccinimide or the crosslinking degree of consumption control chitin material.
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| CN 200410053262 CN1286856C (en) | 2004-07-29 | 2004-07-29 | Process for preparing poly saccuinimide crosslinking modified chitin material |
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| CN 200410053262 CN1286856C (en) | 2004-07-29 | 2004-07-29 | Process for preparing poly saccuinimide crosslinking modified chitin material |
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| CA2848648C (en) | 2006-06-02 | 2017-10-10 | Synedgen, Inc. | Chitosan-derivative compounds and methods of controlling microbial populations |
| CN103061043B (en) * | 2013-01-11 | 2015-07-08 | 东华大学 | Method for manufacturing polysuccinimide nano-fiber mat by electrostatic spinning |
| CN107955185A (en) * | 2017-10-27 | 2018-04-24 | 扬州日兴生物科技股份有限公司 | A kind of high-efficiency dissolution method for the chitin that ferments |
| CN110452316A (en) * | 2019-09-26 | 2019-11-15 | 浙江海洋大学 | A method of extracting β-chitin from squid cartilage |
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Granted publication date: 20061129 Termination date: 20110729 |