CN1424441A - Production of modified chitin and viscose fiber dope mixture and its product - Google Patents
Production of modified chitin and viscose fiber dope mixture and its product Download PDFInfo
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- CN1424441A CN1424441A CN 02160199 CN02160199A CN1424441A CN 1424441 A CN1424441 A CN 1424441A CN 02160199 CN02160199 CN 02160199 CN 02160199 A CN02160199 A CN 02160199A CN 1424441 A CN1424441 A CN 1424441A
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- chitin
- chitosan
- spinning dope
- intermingling material
- viscose
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Abstract
A mixture used for preparing fibres, film, or foam material is prepared through controlling the deacetylated level of chitin-chitosan to 10-85% of -20-40 deg.c in alkalizing procedure, baretting reacting to prepare chitin-chitosan xanthogenate, and mixing it with the dope of viscose fibre. Its advantages are low cost, high colourability, biocompatibility and degradability and good antibacterial deodouring action.
Description
Technical field
The manufacturing technique of modified chitin-chitosan of the present invention and viscose spinning dope intermingling material and goods relate to be handled and uses the modification of polymer.
Background technology
Viscose is as the common chemical fiber product, though have the comparatively suitable characteristics of good hygroscopicity, dress, but this type of textiles can not satisfy many-sided requirements such as people's antibiotic property, biocompatibility, on the other hand, chitin-chitosan has biocompatibility, antibacterial and deodouring and is easy to multifrequency natures such as degraded.Therefore, people have dropped into great enthusiasm with the research and development and the product of viscose spinning dope blend after to the chitin-chitosan modification, to give the good dyeability of intermingling material, biocompatibility, antibacterial and deodouring and to be easy to multifrequency natures such as degraded.As number of patent application 00115071.5 and 01126469.1.In addition, the difference of chitin and shitosan is: the former is the product of chitin N-deacetylation, and generally speaking, the N-acetyl group is sloughed more than 55%, just can be described as shitosan, in the present invention, as does not particularly point out, and should be referred to as chitin-chitosan.
Summary of the invention
The object of the present invention is to provide a kind of good uniformity, the modified chitin-chitosan of the easy control of the extent of reaction and the manufacturing technique and goods thereof of viscose spinning dope intermingling material of reacting.
Purpose of the present invention is achieved through the following technical solutions: the manufacturing technique of a kind of modified chitin-chitosan and viscose spinning dope intermingling material: (one) alkalization process: with particle diameter less than 4mm, content of ashes is lower than 0.2%, under 30 ℃, N, concentration expressed in percentage by weight is that 0.4% solution viscosity is chitin, the shitosan raw material of 20 to 250 centipoises in N-dimethylacetylamide/Licl (96/4) mixed solvent, at-20 ℃--under 40 ℃, in the NaOH of the 16-50% aqueous solution, soaked 10-600 minute bath raio 2--30.The deacetylation of control chitin or shitosan is that 10-85% is advisable; This technical process control deacetylation is more stable, and it is more even to alkalize.(2) carry out the axnthation reaction, preparation chitin-chitosan xanthate; (3) carry out blending reaction, be about to the modified chitin-chitosan and the viscose spinning dope blend of gained in (two).
On above-mentioned technology basis, described axnthation reaction, be that chitin-chitosan xanthate preparation method can be: the alkalization product of chitin-chitosan is compressed to the doubly back pulverizing of 2-7 of raw material weight, add then and be equivalent to chitin-chitosan weight 2.5-30 trash ice doubly, stir 10-100 minute to becoming transparent dispersion liquid, the carbon disulfide that in this dispersion liquid, adds the 1/4-1/2 that is equivalent to chitin-chitosan weight, at-10 ℃--under 40 ℃, reaction obtained the viscosity solution of chitin-chitosan xanthate in 1-20 hour in sealed reactor.Yellow when reaction reactant is a liquid phase, and better than the reaction uniformity of the solid phase reaction of original technology, technology is controlled easily.
On above-mentioned technology basis, described axnthation reaction, be that chitin-chitosan xanthate preparation method also can be: the alkalization product of chitin-chitosan is compressed to the doubly back pulverizing of 2-7 of raw material weight, then in a sealed reactor with the carbon disulfide reaction of the 1/4-1/2 that is equivalent to chitin-chitosan weight 1-10 hour, and then in system, add trash ice, and keep reaction temperature-10 ℃ of-19 ℃ of scopes, react the viscosity solution that obtained chitin-shitosan xanthate in 1-20 hour.This reaction temperature is lower, and course of reaction easy to control has the reaction good uniformity, and quality is the characteristics of control easily.Goods after modified chitin-chitosan of the present invention and the viscose spinning dope blend, can be: with the fiber that this intermingling material is done, described fiber comprises common viscose fiber, richness viscose, koplon and Pori's nosik (polynosic) viscose etc.; The film of making of this intermingling material; Expanded material and the yarn of making of this intermingling material, knitted fabric, woven fabric and the nonwoven fabric etc. made of this intermingling material; Also can be used for fields such as medicine and food.
Principle of the present invention is: at first be alkalization process; just have biological natures such as antibacterial and deodouring owing to only contain amino chitin or chitosan molecule; therefore; must control the amino ratio on chitin or the chitosan molecule; the purpose of alkalization is except alkalizing to the hydroxyl on chitin or the chitosan molecule; also can make the N-acetylamino on chitin or the chitosan molecule that deacetylated reaction takes place; generate amino; further improve its ratio; thereby regulated the deacetylation of chitin or shitosan; simultaneously, also help the carrying out of blending technology.Therefore; the raw material of alkalization process can be lower chitin of deacetylation or shitosan raw material; when controlling alkalization temperature or alkalization time in certain limit, partly deacetylated reaction takes place in alkalization, finally obtain the chitin or the shitosan of certain deacetylation scope.The raw material of alkalization also can be the chitin or the shitosan of certain limit deacetylation, at this moment, can make chitin or shitosan that quaternization mainly takes place by control alkalization temperature or alkalization time, and deacetylated reaction does not take place substantially.Secondly, for obtain can with the viscosity solution of the even blend of viscose spinning dope, need and will carry out xanthan acidification response through chitin or the shitosan that alkalizes.At last, the chitin-chitosan viscosity solution of modification with after viscose spinning dope mixes mutually, is adopted different cure process, can produce the intermingling material of different shape.
Superiority of the present invention is: the goods of the viscosity solution of modified chitin-chitosan and viscose spinning dope intermingling material, have good dyeability, biocompatibility, antibacterial and deodouring and be easy to multifrequency natures such as degraded, in the time of except acquisition excellent product performance, also can greatly reduce production costs, better properties of product price ratio is arranged.
Be described in further detail the present invention below in conjunction with embodiment.
The specific embodiment
Embodiment 1
With 150 gram particles footpaths less than the chitin raw material of 4mm under 25 ℃, in 50% the NaOH aqueous solution, soaked 120 minutes.Product pulverizes through press filtration that to make weight be three times of chitin, trash ice with the 1.5-1.8 kilogram mixes then, the carbon disulfide that adds 50CC again, reaction temperature is not higher than 10 ℃, be reflected in the airtight container and carry out, through a few hours, carbon disulfide reacts completely, and can obtain the chitin-chitosan xanthate.The content of chitin-chitosan is 6.7-7.5% in this viscosity solution, and the content of NaOH is 7.4-8.5%.The above-mentioned viscosity solution that makes 20 grams are added in the 210 gram viscose spinning dopes (content of cellulose 8%), mix and through filtration, deaeration, adopt conventional wet spinning process to make the blended fiber of modified chitin-chitosan and viscose glue.
Embodiment 2
With the shitosan raw material under 25 ℃, in 45% the NaOH aqueous solution, soaked 60 minutes, product pulverizes through press filtration that to make weight be three times of shitosan, add the carbon disulfide that is equivalent to shitosan weight 40% then, reaction is 120 minutes about 15 ℃, add 15 times of trash ices again, stirred 10 hours to shitosan weight, the dissolving make can with the chitin-chitosan viscosity solution of the even blend of viscose spinning dope.
Embodiment 3
Chitin 400 restrains in the NaOH aqueous solution that impregnated in 8 liter 42%, and soaking at room temperature 2 hours vacuumizes during dipping.To remove surplus alkali after the impregnation product squeezing, making weight is 1200 grams, with 4.0--5.0 kilogram trash ice rapid mixing, obtains transparent aqueous dispersions then, after fully mixing, slowly adds 150 gram carbon disulfide again.Initial temperature is reduced to-10 ℃ during beginning, and temperature slowly rises to 0 ℃ then, fully stirs 5 hours, promptly gets the viscosity solution of chitin xanthate, this solution can with the viscose spinning dope co-blended spinning.
Embodiment 4
Chitin 100 gram impregnated in 40% the NaOH aqueous solution of 400ml, soaks 1 hour down at 4 ℃, places 10 hours down in-20 ℃ again.Add 600 grams-700 gram water then, and maintain the temperature at about 0 ℃, simultaneously, being stirred to becomes transparent dispersion liquid, and at this moment, NaOH content is 16--18%, if necessary, can regulate by adding acid.Slowly add 40--50 gram carbon disulfide at above-mentioned transparent dispersion liquid, in airtight container,, promptly get the viscosity solution of chitin xanthate in 15 ℃ of stoichiometric numbers hour, this solution can with the viscose spinning dope co-blended spinning.
Embodiment 5
Chitin 150 gram impregnated in 42% the NaOH aqueous solution of 3000ml, and 4 ℃ of insulations 1 hour down, pulverize press filtration to 450 gram back then.At-20 ℃ down after freezing 10 hours, in airtight container, vacuumize back and 75 gram carbon disulfide 28 ℃ of reactions 14 hours down, and then mixes stirring with trash ice, obtain containing NaOH and chitin after dissolving fully and be respectively 5.9% and 7% solution.This solution was further descended freezing 4 hours at-20 ℃, in 3 hours, be warming up to 0--5 ℃ then, obtain the viscosity solution of the good chitin xanthate of strainability, with this solution and viscose spinning dope co-blended spinning.
Claims (10)
1, the manufacturing technique of a kind of modified chitin-chitosan and viscose spinning dope intermingling material: (one) alkalization process: with particle diameter less than 4mm, content of ashes is lower than 0.2%, under 30 ℃, N, concentration expressed in percentage by weight is that 0.4% solution viscosity is the chitin-chitosan raw material of 20 to 250 centipoises in N-dimethylacetylamide/Licl (96/4) mixed solvent, at-20 ℃--under 40 ℃, soaked 10-600 minute in the NaOH of the 16-50% aqueous solution; bath raio is 2-30, the deacetylation of control chitin-chitosan is 10-85%; (2) carry out the axnthation reaction then, preparation chitin-chitosan xanthate; (3) carry out blending reaction, be about to the modified chitin-chitosan and the viscose spinning dope blend of gained in (two).
2, the manufacturing technique of modified chitin-chitosan according to claim 1 and viscose spinning dope intermingling material, it is characterized in that described axnthation reaction, be that chitin-chitosan xanthate preparation method is: the alkalization product of chitin-chitosan is compressed to doubly back pulverizing of the heavy 2-7 of raw material, add then and be equivalent to chitin-chitosan weight 2.5-30 trash ice doubly, stir 10-100 minute to becoming transparent dispersion liquid, the carbon disulfide that in this dispersion liquid, adds the 1/4-1/2 that is equivalent to chitin-chitosan weight, at-10 ℃--under 40 ℃, reaction obtained the viscosity solution of chitin-chitosan xanthate in 1-20 hour in sealed reactor.
3, the manufacturing technique of modified chitin-chitosan according to claim 1 and viscose spinning dope intermingling material, it is characterized in that described axnthation reaction, be that chitin-chitosan xanthate preparation method is: the alkalization product of chitin-chitosan is compressed to the doubly back pulverizing of 2-7 of raw material weight, then in a sealed reactor with the carbon disulfide reaction of the 1/4-1/2 that is equivalent to chitin-chitosan weight 1-10 hour, and then in system, add trash ice, and keeping reaction temperature at-10 ℃--19 ℃ of scopes, reaction obtained the viscosity solution of chitin-chitosan xanthate in 1-20 hour.
4, the modified chitin-chitosan that obtains according to claim 1 and the intermingling material of viscose spinning dope.
5, the goods of modified chitin-chitosan according to claim 4 and viscose spinning dope intermingling material, it is characterized in that: with the fiber that this intermingling material is done, described fiber comprises common viscose fiber, richness viscose, koplon and Pori's nosik (polynosic) viscose.
6, the goods of modified chitin-chitosan according to claim 4 and viscose spinning dope intermingling material is characterized in that: the film of making of this intermingling material.
7, the goods of modified chitin-chitosan according to claim 4 and viscose spinning dope intermingling material is characterized in that: the expanded material of making of this intermingling material.
8, the goods of modified chitin-chitosan according to claim 4 and viscose spinning dope intermingling material is characterized in that: the yarn of making of this intermingling material.
9, the goods of modified chitin-chitosan according to claim 4 and viscose spinning dope intermingling material is characterized in that: knitted fabric, woven fabric and the nonwoven fabric made of this intermingling material.
10, the goods of modified chitin-chitosan according to claim 5 and viscose spinning dope intermingling material is characterized in that: knitted fabric, woven fabric and the nonwoven fabric made of this fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021601992A CN1182282C (en) | 2002-12-27 | 2002-12-27 | Production of modified chitin and viscose fiber dope mixture and its product |
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| CNB021601992A CN1182282C (en) | 2002-12-27 | 2002-12-27 | Production of modified chitin and viscose fiber dope mixture and its product |
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| CN1424441A true CN1424441A (en) | 2003-06-18 |
| CN1182282C CN1182282C (en) | 2004-12-29 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321947C (en) * | 2004-12-06 | 2007-06-20 | 西南交通大学 | Prepn process of porous spherical granular inorganic material |
| CN101831740A (en) * | 2010-05-21 | 2010-09-15 | 盐城纺织职业技术学院 | Mulberry fiber and viscose-based chitin fiber blended yarn and processing technique thereof |
| CN101597818B (en) * | 2009-06-17 | 2011-06-15 | 阜宁澳洋科技有限责任公司 | Preparation method of chitin viscose spinning dope |
| CN101665589B (en) * | 2009-09-18 | 2011-08-10 | 浙江大学 | Method for enhancing and modifying three-dimensional chitosan bar material by using chitin fibre |
| WO2012142879A1 (en) * | 2011-04-20 | 2012-10-26 | 佛山市优特医疗科技有限公司 | Wound dressing with bacteriostasis and hygroscopicity |
| CN103526319A (en) * | 2013-09-26 | 2014-01-22 | 江苏金太阳纺织科技有限公司 | Preparation method of non-dissolution type durable antibacterial regenerated cellulose fibers |
| CN111250054A (en) * | 2020-01-20 | 2020-06-09 | 中南林业科技大学 | Group functionalized hypha filter membrane and preparation method and application thereof |
| CN112494460A (en) * | 2020-12-10 | 2021-03-16 | 浙江大飞龙动物保健品股份有限公司 | Tilmicosin powder and preparation method thereof |
-
2002
- 2002-12-27 CN CNB021601992A patent/CN1182282C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321947C (en) * | 2004-12-06 | 2007-06-20 | 西南交通大学 | Prepn process of porous spherical granular inorganic material |
| CN101597818B (en) * | 2009-06-17 | 2011-06-15 | 阜宁澳洋科技有限责任公司 | Preparation method of chitin viscose spinning dope |
| CN101665589B (en) * | 2009-09-18 | 2011-08-10 | 浙江大学 | Method for enhancing and modifying three-dimensional chitosan bar material by using chitin fibre |
| CN101831740A (en) * | 2010-05-21 | 2010-09-15 | 盐城纺织职业技术学院 | Mulberry fiber and viscose-based chitin fiber blended yarn and processing technique thereof |
| WO2012142879A1 (en) * | 2011-04-20 | 2012-10-26 | 佛山市优特医疗科技有限公司 | Wound dressing with bacteriostasis and hygroscopicity |
| CN103526319A (en) * | 2013-09-26 | 2014-01-22 | 江苏金太阳纺织科技有限公司 | Preparation method of non-dissolution type durable antibacterial regenerated cellulose fibers |
| CN111250054A (en) * | 2020-01-20 | 2020-06-09 | 中南林业科技大学 | Group functionalized hypha filter membrane and preparation method and application thereof |
| CN111250054B (en) * | 2020-01-20 | 2022-08-16 | 中南林业科技大学 | Group functionalized hypha filter membrane and preparation method and application thereof |
| CN112494460A (en) * | 2020-12-10 | 2021-03-16 | 浙江大飞龙动物保健品股份有限公司 | Tilmicosin powder and preparation method thereof |
| CN112494460B (en) * | 2020-12-10 | 2022-03-11 | 浙江大飞龙动物保健品股份有限公司 | Tilmicosin powder and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1182282C (en) | 2004-12-29 |
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Owner name: SHANGHAI SHIHLIN FIBER MATERIALS CO., LTD. Free format text: FORMER OWNER: SHILIN SPINNING CO., LTD., SHANGHAI Effective date: 20031105 |
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Effective date of registration: 20031105 Address after: 201100 Shanghai City No. 6269 humin road Yinxiao building room 1105 Applicant after: Shanghai Shilin Fiber Material Co., Ltd. Address before: 201100 Shanghai City No. 6269 humin road Yinxiao building room 1105 Applicant before: Shilin Spinning Co., Ltd., Shanghai |
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