CN1103387C - Preparation and product of mixed material of modified chitin-chitosan and viscose fiber spinning dope - Google Patents
Preparation and product of mixed material of modified chitin-chitosan and viscose fiber spinning dope Download PDFInfo
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- CN1103387C CN1103387C CN00115071A CN00115071A CN1103387C CN 1103387 C CN1103387 C CN 1103387C CN 00115071 A CN00115071 A CN 00115071A CN 00115071 A CN00115071 A CN 00115071A CN 1103387 C CN1103387 C CN 1103387C
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- chitin
- shitosan
- spinning dope
- intermingling material
- viscose spinning
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Abstract
The present invention relates to the field of the modification and the application of polymers, particularly to making technology of a blending material of a modified viscous chitin-chitosan solution and an adhesive spinning stock solution. The blending material is made into fibers, films, foam materials and various other products by adopting different kinds of solidification forming technology. The blending material and the products not only have low cost, but also have the characteristics of favorable chromaticity, biocompatibility, antibacterial deodorization performance, easy degradation, etc., and can be widely used in spinning industry, medical and pharmaceutical industry and food industry.
Description
The present invention relates to modification processing and Application Areas to polymer.
Viscose though have good hygroscopicity, is worn characteristics such as comparatively suitable as the common chemical fiber product, and this type of textiles can not satisfy people in many-sided requirements such as antibiotic property, biocompatibilities.On the other hand, though chitin-chitosan material has biocompatibility, antibacterial and deodouring and is easy to multifrequency natures such as degraded, but the manufacturing technology that pure chitin-chitin fiber is only arranged at present, or chitin-shitosan used as fabric finishing agent, and about with chitin-chitin modified and and the viscose spinning dope blend do not find with research and the product giving the good dyeability of intermingling material, biocompatibility, antibacterial and deodouring and be easy to multifrequency natures such as degrading.
The object of the present invention is to provide the manufacturing technique and the goods of a kind of modified chitin-shitosan and viscose spinning dope intermingling material, and various products such as fiber that intermingling material is adopted different cure process to produce to have superperformance, film, expanded material is applied to multiple field.
The present invention is achieved in that the manufacturing technique of this intermingling material is:
(1) caustic dip takes off acetyl technology: comprise (1). pre-caustic dip technology: with particle diameter less than 4mm, content of ashes is lower than 0.2%, under 30 ℃, N, in N-dimethylacetylamide/Licl (96/4) mixed solvent concentration expressed in percentage by weight be 0.4% solution viscosity be the chitin raw material of 20 to 250 centipoises under 40-95 ℃, in the NaOH of the 30-50% aqueous solution, soaked 10-120 minute; (2). double alkalisation technology: will in the NaOH of the same concentrations aqueous solution, soak 10-60 minute down through the product of preimpregnation alkali treatment in 30-70 ℃.The ratio of chitin molecule and chitosan molecule is 0.15-0.75.
(2) axnthation reaction: will taking off product that acetyl handles through caustic dip, to be compressed to proportion be that the 3-5 of raw material doubly pulverizes the back, again with it and account for the CS of system gross weight 30-80%
2Carry out the axnthation modified-reaction under 20-35 ℃, the time is 2-5 hour.Then, in system, add and be equivalent to deacetylated chitin-shitosan product weight 2.5-30 trash ice doubly, stirs and it was dissolved in 2-30 hour, acquisition can with the viscosity solution of the modified chitin-shitosan of the even blend of viscose spinning dope.
(3) blend: the viscosity solution of modified chitin-shitosan mixes mutually with viscose spinning dope.
Advantage of the present invention is, after will being arranged, the viscosity solution dope blending of chitin-shitosan can be applicable to blended fiber, film, expanded material, and can use in fields such as knitted fabric, woven fabric, nonwoven fabric, medicine, food, and make relevant product 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, greatly reduce production costs, make the ratio of performance to price more highlight.
Below further specify manufacturing technique of the present invention.
At first be that caustic dip takes off acetyl technology; just have biological natures such as antibacterial and deodouring owing to only contain amino chitosan molecule; its purpose is to make the chitin molecule of acetamide-containing that partly deacetylated reaction modifying takes place; generate and contain amino chitose molecule in the chitin molecule; thereby regulate the ratio of chitin molecule and shell dimeric molecule; both proportion control help the carrying out of blending technology simultaneously in certain limit the most at last.Secondly, for obtain can with the mucus solution of the chitin-shitosan of the even blend of viscose spinning dope, need to take off chitin-shitosan that acetyl handles and carry out the axnthation reaction through caustic dip.
Then, the viscosity solution of above-mentioned modified chitin-shitosan with after viscose spinning dope mixes mutually, is adopted different cure process, can produce the intermingling material of different shape.
Concrete manufacturing technique:
(1) caustic dip takes off acetyl technology
Select for use particle diameter less than the chitin particle of 4mm with being raw material, its content of ashes should be lower than 0.2%, under 30 ℃, in N,N-dimethylacetamide/Licl (96/4) mixed solvent, the raw material weight percentage concentration is that 0.4% solution viscosity is 20 to 250 centipoises.
(1) pre-caustic dip technology: above-mentioned chitin raw material under 40-95 ℃, was soaked 10-120 minute in the NaOH of the 30-50% aqueous solution; (2) double alkalisation technology: will in the NaOH of the same concentrations aqueous solution, soak 10-60 minute down through the product of preimpregnation alkali treatment in 30-70 ℃.The ratio of chitin molecule and chitosan molecule is adjusted between the 0.15-0.75.
(2) axnthation reaction
To take off product that acetyl handles through caustic dip, to be compressed to proportion be that the 3-5 of raw material doubly pulverizes the back, again with it and account for the CS of system gross weight 30-80%
2Carry out the axnthation modified-reaction under in 20 to 35 ℃, the time is 2-5 hour.Then, in system, add and be equivalent to deacetylated chitin-shitosan product weight 2.5-30 trash ice doubly, stirs and it was dissolved in 2-30 hour, acquisition can with the viscosity solution of the modified chitin-shitosan of the even blend of viscose spinning dope.
(3) blend
The viscosity solution of above-mentioned modified chitin-shitosan with after viscose spinning dope mixes mutually, is adopted different cure process (as mixing method spinning technique, polymer solution film-forming process etc.), can produce the intermingling material of different shape.
Above-mentioned intermingling material is widely used, as can be by the technology manufacturing of traditional viscose wet spinning
Go out blended fiber; Adopt conventional polymer solution film-forming process the viscosity solution of above-mentioned chitin-shitosan can be made film; Or adopt conventional polymer foaming technology can make the expanded material that contains chitin-shitosan after in the viscosity solution of above-mentioned chitin-shitosan, adding blowing agent; By that analogy, above-mentioned chitin-chitosan material can obtain in fields such as knitted fabric, woven fabric, nonwoven fabric medicine, food to use equally.Thus obtained have good dyeability, biocompatibility, antibacterial and deodouring and be easy to multifrequency natures such as degraded about product.
Embodiment 1:
Chitin raw material under 40 ℃, was soaked 120 minutes in 50% the NaOH aqueous solution, and product soaked 60 minutes down in 30 ℃ in the NaOH of the same concentrations aqueous solution; Product adds the CS that is equivalent to system gross weight 70% after press filtration
2, reaction is 5 hours about 20 ℃, adds 15 times of trash ices to chitin-shitosan weight again, stirs dissolved in 12 hours make can with the chitin-shitosan viscosity solution of the even blend of viscose spinning dope; Test case is as follows: the above-mentioned viscosity solution that makes 23 grams are added the molten (content of cellulose: 9%) of 240 gram viscose spinning, mix, adopt conventional wet spinning process to make the blended fiber of chitin-shitosan and viscose glue, the character of gained fiber is as shown in table 1.Table 1
| Dry strength | 2.6g/d | The dry state elongation | 17.0％ | |
| Wet strength | 1.6g/d | The hygrometric state elongation | 23.7％ | |
| Antibiotic property | The golden staphylococci kill ratio | 53％ | ||
| Lung bacillus kill ratio | 88％ | |||
| Bluish-green bacterium kill ratio | 45％ | |||
Embodiment 2:
Chitin raw material under 85 ℃, was soaked 60 minutes in 30% the NaOH aqueous solution, and product soaked 30 minutes down in 60 ℃ in the NaOH of the same concentrations aqueous solution; Product adds the CS that is equivalent to system gross weight 30% after press filtration
2, reaction is 2 hours about 35 ℃, adds 30 times of trash ices to chitin-shitosan weight again, stirs dissolved in 2 hours make can with the chitin-shitosan viscosity solution of the even blend of viscose spinning dope.
Claims (6)
1, the manufacturing technique of a kind of modified chitin-shitosan and viscose spinning dope intermingling material:
(1) caustic dip takes off acetyl technology: comprise (1) pre-caustic dip technology: 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 raw material of 20 to 250 centipoises in N-dimethylacetylamide/Licl (96/4) mixed solvent, is soaking 10-120 minute in the NaOH of the 30-50% aqueous solution under 40-95 ℃; (2) double alkalisation technology: will soak 10-60 minute down in 30-70 ℃ in the NaOH of the same concentrations aqueous solution through the product of preimpregnation alkali treatment, the ratio of chitin molecule and chitosan molecule is 0.15-0.75,
(2) axnthation reaction: will taking off product that acetyl handles through caustic dip, to be compressed to proportion be that the 3-5 of raw material doubly pulverizes the back, again with it and account for the CS of system gross weight 30-80%
2Carry out the axnthation modified-reaction under in 20 to 35 ℃; time is 2-5 hour; then; in system, add and be equivalent to deacetylated chitin-shitosan product weight 2.5-30 trash ice doubly; stir 2-30 hour with its dissolving; acquisition can with the viscosity solution of the modified chitin-shitosan of the even blend of viscose spinning dope
(3) blend: the viscosity solution of modified chitin-shitosan is mixed mutually with viscose spinning dope.
2, the modified chitin-shitosan and the viscose spinning dope intermingling material that obtain by claim 1.
3, the goods by the described modified chitin-shitosan of claim 2 and viscose spinning dope intermingling material is characterized in that: the fiber of making of this intermingling material.
4, the goods by the described modified chitin-shitosan of claim 2 and viscose spinning dope intermingling material is characterized in that: the film of making of this intermingling material.
5, the goods by the described modified chitin-shitosan of claim 2 and viscose spinning dope intermingling material is characterized in that: the expanded material of making of this intermingling material.
6, the goods by the described modified chitin-shitosan of claim 2 and viscose spinning dope intermingling material is characterized in that: knitted fabric, woven fabric and the nonwoven fabric made of this intermingling material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN00115071A CN1103387C (en) | 2000-03-23 | 2000-03-23 | Preparation and product of mixed material of modified chitin-chitosan and viscose fiber spinning dope |
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| Application Number | Priority Date | Filing Date | Title |
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| CN00115071A CN1103387C (en) | 2000-03-23 | 2000-03-23 | Preparation and product of mixed material of modified chitin-chitosan and viscose fiber spinning dope |
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| Publication Number | Publication Date |
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| CN1265433A CN1265433A (en) | 2000-09-06 |
| CN1103387C true CN1103387C (en) | 2003-03-19 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093189C (en) * | 2000-10-31 | 2002-10-23 | 上海中大科技发展有限公司 | Apocynum fibre, chitin fibre and cotton fibre blended yarn, its preparation method and application |
| CN1093188C (en) * | 2000-10-31 | 2002-10-23 | 上海中大科技发展有限公司 | Bacteriostatic odour-resistant blended yarn, its preparation method and application |
| CN101649505B (en) * | 2009-09-10 | 2011-09-14 | 山东省花生研究所 | Composite fiber of isolated peanut protein and preparation method thereof |
| CN106757459B (en) * | 2016-11-17 | 2019-06-14 | 汕头市珂玲服饰有限公司 | A kind of antibacterial mite-resistant cellulose viscose and preparation method containing sophora alopecuroides extract |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183417A (en) * | 1996-11-25 | 1998-06-03 | 李振生 | Process for extracting chitosan from soluble chitin |
| CN1261111A (en) * | 2000-01-14 | 2000-07-26 | 东华大学 | Antibacterial fibres containing chitin and its derivatives, and preparing process thereof |
| CN1266922A (en) * | 2000-01-25 | 2000-09-20 | 天津大学 | Antibacterial viscose fibre and its making method |
| CN1266855A (en) * | 1999-09-15 | 2000-09-20 | 天津大学 | Process for preparing chitosan |
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- 2000-03-23 CN CN00115071A patent/CN1103387C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183417A (en) * | 1996-11-25 | 1998-06-03 | 李振生 | Process for extracting chitosan from soluble chitin |
| CN1266855A (en) * | 1999-09-15 | 2000-09-20 | 天津大学 | Process for preparing chitosan |
| CN1261111A (en) * | 2000-01-14 | 2000-07-26 | 东华大学 | Antibacterial fibres containing chitin and its derivatives, and preparing process thereof |
| CN1266922A (en) * | 2000-01-25 | 2000-09-20 | 天津大学 | Antibacterial viscose fibre and its making method |
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Owner name: SHANGHAI SHIHLIN FIBER MATERIALS CO., LTD.; HE HA Free format text: FORMER OWNER: SHILIN SPINNING CO., LTD., SHANGHAI; HE HANHONG Effective date: 20040203 |
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Effective date of registration: 20040203 Address after: 201100 Shanghai Min Min Road 6269, Yin Xiao Building, Room 1105 Patentee after: Shanghai Shilin fiber materials Co. ltd. Patentee after: He Hanhong Address before: 201100 Shanghai Min Min Road 6269, Yin Xiao Building, Room 1105 Patentee before: Shilin Spinning Co., Ltd., Shanghai Patentee before: He Hanhong |
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