CN101597818B - Preparation method of chitin viscose spinning dope - Google Patents
Preparation method of chitin viscose spinning dope Download PDFInfo
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- CN101597818B CN101597818B CN2009100162452A CN200910016245A CN101597818B CN 101597818 B CN101597818 B CN 101597818B CN 2009100162452 A CN2009100162452 A CN 2009100162452A CN 200910016245 A CN200910016245 A CN 200910016245A CN 101597818 B CN101597818 B CN 101597818B
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Abstract
The invention discloses a preparation method of chitin viscose spinning dope, comprising the following steps: adopting chitin for three-stage quaternization under different process conditions to obtain chitin-Na and sodium chitosan which are fully alkalized, adding the obtained chitin-Na and sodium chitosan into trash ice to perform glaciation reaction to obtain transparent and uniform chitin colloidal solution, mixing the obtained colloidal solution with viscose cellulose to obtain the spinning dope of chitin viscose, processing the spinning dope which is evenly mixed by ripening, defoaming, filtrating and the like and spinning. The invention avoids the damage of carbon disulfide on the environment, has simpler manufacturing process and is easy to realize the industrialized production.
Description
Technical field
The present invention relates to chemical fibre functional modification technical field, specifically is a kind of chitin viscose spinning dope manufacturing technology.
Background technology
Chitin (Chitin) be by 2-acetamido-2-deoxy-D-glucose with the polysaccharide that β-1,4 glycosidic bond form is formed by connecting, extensively be present in the shell of shrimp, crab, insects, and in the cell membrane of mushroom and algae, be a kind of reproducible natural resources.Chitin has into fibroid, can and do the wet-formed fiber that is spun into by wet method, and its fiber has premium properties such as good adsorption, bactericidal properties and gas permeability, but chitin fiber discarded object natural degradation can not pollute environment.The textiles of making can be resisted bacterial infection and can prevent and treat skin disease as the antibiotic medical materials such as fiber or operation suture thread, bandage of taking, can also deodorization, absorbing sweat preserves moisture, and wears also very comfortable.Medical dressing with chitin fiber is made can make granulation new life, promotes wound healing, has the effect of analgesia, hemostasis clinically.Present various forms of crust rope fiber product is just obtaining more and more widely application in weaving and garment industry.The shortcoming that exists is the processing and fabricating difficulty, causes to cost an arm and a leg, and is difficult to popularize, at present only for batch process.
Prior art all adopts the process route of alkalization, xanthogenation to prepare the chitin spinning solution, must use carbon disulfide as xanthogenating agent in the xanthogenation operation process, reaction is normally carried out, and poisonous, the inflammable and explosive chemicals of carbon disulfide, be discharged in the environment in process of production and go, contaminated environment, harm operator health, cause the increase of side reaction in addition, increase raw materials consumption and accessory substance.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of chitin viscose spinning dope, it has not only been eliminated and has adopted carbon disulfide to carry out the harm that yellow produces environment, and its manufacturing technique is more simple and convenient, is easy to realize suitability for industrialized production.
For achieving the above object, the technical solution used in the present invention is earlier chitin to be carried out three grades of quaternizations under different technology conditions, sufficient sodium chitin and sodium shitosan obtain alkalizing, again sodium chitin and the sodium shitosan that obtains added directly ice reaction of trash ice, promptly make transparent and uniform chitin colloidal solution, with the cellulose viscose glue blending, obtain chitin viscose spinning dope then, this spinning solution that mixes can spinning after operations such as maturation, deaeration, filtration.
Concrete manufacture method of the present invention comprises step: be 25-75 ten thousand with mean molecule quantity at first, the ash mass content is lower than 0.3% chitin, and to be immersed in mass concentration in the ratio of mass ratio 1: 20～30 be in 30～50% the NaOH aqueous solution, reaction 1～3h under 15～25 ℃ (h: hour), subsequently under vacuum 15～25 ℃ the reaction 3～6h, further elevated temperature to 45～65 ℃ of reaction 2～3h again make the mixture of sodium chitin and sodium shitosan;
Above-mentioned reaction under vacuum condition can promote the infiltration of alkali greatly, guarantee the uniformity and the adequacy of quaternization, to guarantee that follow-up sodium chitin and sodium shitosan can sufficient reacting directly and during the reaction of ice ice, obtain transparent and uniform chitin colloidal solution.
The deacetylated reaction of part has taken place in chitin in the above-mentioned quaternization process at 15～25 ℃ of following chitins; the part deacetylate; deacetylation can further take place for 45～65 ℃ in elevated temperature, makes to have better amino of a certain proportion of bacteriostatic activity in the product.
With after alkali lye is removed in squeezing, alkali lye is removed in squeezing, to sodium chitin and sodium chitosan mass be 2.5～3.5 times of raw material chitin quality, pulverize the back and place 6～30h down at 15～35 ℃;
Relative sodium chitin and 3～5 times of trash ices of sodium chitosan mass will be added afterwards in sodium chitin and the sodium shitosan, react 2～5h down at-5～5 ℃, add NaOH and water subsequently and get stereoplasm amount content 3.5～7.5%, NaOH alkali mass content 3.0～5.5% makes chitin colloidal solution; This colloidal solution and viscose have good compatibility.
At last chitin colloidal solution and the cellulose viscose glue blending that obtains obtained chitin viscose spinning dope, spinning after operations such as maturation, deaeration and filtration.And this cellulose viscose glue be fabricated to the known manufacture method of person skilled in art.
The viscosity of considering the chitin colloid is too high sometimes, be unfavorable for carrying, the carrying out of operation such as filtration and deaeration, in the preparation process of chitin colloid, can in the chitin colloidal solution, add urea with the chitin equivalent, again at 20～30 ℃ of maturation 12～20h, in the maturation process after filtration, the degassing, can reduce the viscosity of chitin glue.
Be filtration, deaeration, the conveying that makes things convenient for chitin colloidal solution, the viscosity that also can control chitin glue is 20-100s (falling ball method), conditions such as resting period that can be by the control degree of polymerization of chitin and sodium chitin, temperature.
The present invention has removed the xanthogenation operation that pollutes, and has eliminated the harm of carbon disulfide to environment, its simplified manufacturing process, and technology is more simple and convenient, also is easy to realize suitability for industrialized production.On the other hand since sodium chitin and sodium shitosan without xanthan acidification response, the destruction that its big molecular aggregates attitude structure is subjected to is less, can keep the original structure of the big molecule of chitin preferably, the biologically active that its chitin is intrinsic is able to better maintenance as effects such as antibacterial bacteriostatic, promotion wound healing, analgesia, hemostasis.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment one
Be 260,000 at first with mean molecule quantity, the chitin raw material of ash mass content 0.25% is immersed in the NaOH aqueous solution of mass concentration 48% in 1: 21 ratio of mass ratio, react 3h down at 15 ℃, subsequently under vacuum 25 ℃ the reaction 3h, further elevated temperature to 65 ℃ reaction 2h again makes the mixture of sodium chitin and sodium shitosan; Alkali lye is removed in squeezing afterwards, squeeze to sodium chitin and sodium chitosan mass be 3 times of raw material chitin quality, pulverize the back and place 12h down at 25 ℃; Relative sodium chitin and 3.5 times of trash ices of sodium chitosan mass will be added then in above-mentioned sodium chitin and the sodium shitosan, react 4.5～5h down at-5 ℃, add NaOH and water subsequently and adjust it and consist of stereoplasm amount content 3.5%, alkali mass content 5.5% makes chitin colloidal solution; Can in the chitin colloidal solution, add the urea with the chitin equivalent, at 30 ℃ of maturation 14h, in the maturation process after filtration, the degassing, the viscosity of control chitin colloidal solution is 35s (falling ball method).With above-mentioned chitin colloidal solution that obtains and cellulose viscose glue blending, obtain chitin viscose spinning dope.
Embodiment two
Be 700,000 at first with mean molecule quantity, the chitin raw material of ash mass content 0.22% is immersed in the NaOH aqueous solution of mass concentration 32% in 1: 29 ratio of mass ratio, react 1.5h down at 25 ℃, subsequently under vacuum 25 ℃ the reaction 6h, further elevated temperature to 46 ℃ reaction 3h again makes the mixture of sodium chitin and sodium shitosan; Alkali lye is removed in squeezing afterwards, to sodium chitin and sodium chitosan mass be 3.5 times of raw material chitin quality, pulverize the back and place 8h down at 35 ℃; Relative sodium chitin and 5 times of trash ices of sodium chitosan mass will be added then in above-mentioned sodium chitin and the sodium shitosan, react 5h down at 5 ℃, add NaOH and water subsequently and adjust it and consist of stereoplasm amount content 6.9%, alkali mass content 5.5% makes chitin colloidal solution; With above-mentioned chitin colloidal solution that obtains and previously prepared cellulose viscose glue blending, obtain chitin viscose spinning dope.
Embodiment three
Be 500,000 at first with mean molecule quantity, the ash mass content is lower than 0.3% chitin raw material and is immersed in the NaOH aqueous solution of mass concentration 41% in 1: 25 ratio of mass ratio, react 2h down at 20 ℃, subsequently under vacuum 20 ℃ the reaction 5h, further elevated temperature to 55 ℃ reaction 2.5h again makes the mixture of sodium chitin and sodium shitosan; Alkali lye is removed in squeezing afterwards, to sodium chitin and sodium chitosan mass be 3 times of raw material chitin quality, pulverize the back and place 18h down at 25 ℃; Relative sodium chitin and 4.5 times of trash ices of sodium chitosan mass will be added in above-mentioned sodium chitin and the sodium shitosan, react 3h down at-3 ℃, add NaOH and water subsequently and adjust it and consist of stereoplasm amount content 4.8%, NaOH alkali mass content 5.2% makes chitin colloidal solution; The urea of adding and chitin equivalent in the chitin colloidal solution, at 25 ℃ of maturation 18h, the viscosity of control chitin colloidal solution is 95s (falling ball method).With above-mentioned chitin colloidal solution that obtains and previously prepared cellulose viscose glue blending, obtain chitin viscose spinning dope, spinning after operations such as maturation, deaeration, filtration.
More than be the application's a specific embodiment, should be understood that these embodiment only be used to the invention is described and be not used in the restriction the invention scope.Should be understood that in addition those skilled in the art can make various changes or modifications the invention after the content of having read the invention instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (3)
1. the preparation method of a chitin viscose spinning dope may further comprise the steps:
(1) be 25-75 ten thousand with mean molecule quantity, the ash mass content is lower than 0.3% chitin, and to be immersed in mass concentration in the ratio of mass ratio 1: 20～30 be in 30～50% the NaOH aqueous solution, react 1～3h down at 15～25 ℃, subsequently under vacuum 15～25 ℃ the reaction 3～6h, further elevated temperature to 45～65 ℃ of reaction 2～3h again make the mixture of sodium chitin and sodium shitosan;
(2) alkali lye is removed in squeezing, to sodium chitin and sodium chitosan mass be 2.5～3.5 times of raw material chitin quality, pulverize the back and place 6～30h down at 15～35 ℃;
(3) relative sodium chitin and 3～5 times of trash ices of sodium chitosan mass will be added in sodium chitin and the sodium shitosan, react 2～5h down at-5～5 ℃, add NaOH and water subsequently and get stereoplasm amount content 3.5～7.5%, NaOH alkali mass content 3.0～5.5% makes chitin colloidal solution;
(4) with the chitin colloidal solution and the cellulose viscose glue blending that obtain, obtain chitin viscose spinning dope.
2. the preparation method of a kind of chitin viscose spinning dope according to claim 1 is characterized in that: can add the urea with the chitin equivalent in the chitin colloidal solution, at 20～30 ℃ of maturation 12～20h.
3. the preparation method of a kind of chitin viscose spinning dope according to claim 1 and 2, it is characterized in that: the falling ball method viscosity of described chitin colloidal solution is 20-100s.
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| CN2009100162452A CN101597818B (en) | 2009-06-17 | 2009-06-17 | Preparation method of chitin viscose spinning dope |
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| CN2009100162452A CN101597818B (en) | 2009-06-17 | 2009-06-17 | Preparation method of chitin viscose spinning dope |
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| CN101597818B true CN101597818B (en) | 2011-06-15 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI477670B (en) * | 2011-01-06 | 2015-03-21 | Taiwan Textile Res Inst | Micro-fibrous hemostatic materials and methods for preparing the same |
| CN104939391A (en) * | 2015-07-14 | 2015-09-30 | 爱谱诗（苏州）服装有限公司 | Production technology of shrimp and crab shell fabric |
| CN107955988B (en) * | 2017-12-21 | 2020-05-22 | 中科纺织研究院（青岛）有限公司 | Preparation method of viscose containing chitin |
| CN111118878A (en) * | 2020-01-15 | 2020-05-08 | 河南驼人贝斯特医疗器械有限公司 | Silver ion alginate wound dressing and preparation method thereof |
Citations (4)
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| CN1424441A (en) * | 2002-12-27 | 2003-06-18 | 上海士林纺织有限公司 | Production of modified chitin and viscose fiber dope mixture and its product |
| WO2003056081A1 (en) * | 2001-12-24 | 2003-07-10 | Ibeks Technologies Co., Ltd. | Chitosan-containing spun yarn and method for producing the same |
| CN101041910A (en) * | 2007-04-18 | 2007-09-26 | 山东海龙股份有限公司 | Chitin element and cellulosic composite fiber and method for manufacturing same |
| CN101210354A (en) * | 2006-12-28 | 2008-07-02 | 山东海龙股份有限公司 | Method for preparing health care fibre and health care fibre produced by the same method |
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- 2009-06-17 CN CN2009100162452A patent/CN101597818B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2003056081A1 (en) * | 2001-12-24 | 2003-07-10 | Ibeks Technologies Co., Ltd. | Chitosan-containing spun yarn and method for producing the same |
| CN1424441A (en) * | 2002-12-27 | 2003-06-18 | 上海士林纺织有限公司 | Production of modified chitin and viscose fiber dope mixture and its product |
| CN101210354A (en) * | 2006-12-28 | 2008-07-02 | 山东海龙股份有限公司 | Method for preparing health care fibre and health care fibre produced by the same method |
| CN101041910A (en) * | 2007-04-18 | 2007-09-26 | 山东海龙股份有限公司 | Chitin element and cellulosic composite fiber and method for manufacturing same |
Non-Patent Citations (4)
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| JP特开2007-197649A 2007.08.09 |
| 张园园等.壳聚糖纺丝原液制备及湿法纺丝工艺初探.《合成纤维工业》.2008,第31卷(第2期),33－36. * |
| 张瑞文等.甲壳素纤维制备工艺研究进展.《化纤与纺织技术》.2007,(第1期),32-35、52. * |
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Effective date of registration: 20211206 Address after: 224400 Jiangsu Yancheng Funing high tech Industrial Development Zone Aoyang Avenue Saideli (Yancheng) Fiber Co., Ltd Patentee after: Saideli (Yancheng) Fiber Co.,Ltd. Address before: 224400 Funing County of Jiangsu province Aoyang Industrial Park Patentee before: FUNING AOYANG TECHNOLOGY CO.,LTD. |