CN1920129A - Hydroxyethyl chitosan modified viscose fiber and preparation method thereof - Google Patents
Hydroxyethyl chitosan modified viscose fiber and preparation method thereof Download PDFInfo
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- CN1920129A CN1920129A CN 200610015705 CN200610015705A CN1920129A CN 1920129 A CN1920129 A CN 1920129A CN 200610015705 CN200610015705 CN 200610015705 CN 200610015705 A CN200610015705 A CN 200610015705A CN 1920129 A CN1920129 A CN 1920129A
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- hydroxyethyl chitosan
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- chitose
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Abstract
The invention relates to an ethoxylated chitose modified cellulose viscose and relative preparation, wherein it comprises: ethoxylated chitose at 0.5-20%; cellulose at 80-99.5%; the molecular weight of ethoxylated chitose is 20-500 thousand; the replace degree of hydroethyl is 10-90%; and its preparation comprises: 1, alkalization that immerging the ethoxylated chitose whose diameter is lower than 4mm into caustic soda water solution at 10-50% for 30-600min under 10-40Deg. C, while the bath ration is 1:5-30; 2, xanthic acid esterification that putting the product of step 1 into the sealed reaction kettle, adding carbon bisulphide at 20-80% of the quantity of ethoxylated chitose, to react for 1-8hour, at -10-22Deg. C, to obtain the adhesive solution of ethoxylated chitose xanthate; 3, mixing and spinning, that mixing the adhesive solution and the viscose, to be filtered, defoamed, and aged, to obtain the spinning original liquid of ethoxylated chitose modified cellulose viscose, then treating it with general cellulose viscose spinning method.
Description
Technical field
The present invention relates to a kind of chemical fibre manufacturing technology, be specially a kind of hydroxyethyl chitosan modified viscose fiber and manufacture method thereof, international Patent classificating number intends being Int.Cl D01F2/08 (2006.01).
Background technology
Viscose has advantages such as sucting wet air permeability is good, snugness of fit is good as a kind of regenerated fiber, is widely used.In order to satisfy the many-sided requirement of people to fiber, can be by in the spinning process of viscose, adding the exploitation that some functional components realize functional viscose fiber, as Fire resistant viscose fiber, anion viscose fibre, antibacterial viscose fiber etc.
Shitosan is the very abundant natural macromolecular materials of a kind of natural resources, has many-sided advantages such as broad spectrum antibacterial, biocompatibility, biological degradability, utilizes chitin modified other fiber to become fiber functionalization research focus to obtain anti-microbial property.Simultaneously, because shitosan and cellulosic molecule structural similarity, therefore chitin modified cellulose fibre has more feasibility.The industrial production of cellulose fibre especially also mainly depends on viscose in China at present.The main way of utilizing chitosan modified viscose fiber is by certain form the appropriate format and the viscose glue blending of shitosan to be made spinning solution, as U.S. Pat P Re.35151 disclose a kind of with shitosan pulverize for particle diameter less than the particulate of 5 μ m and sneak into the method for carrying out spinning in the viscose glue; Chinese patent 02160199.2 and U.S. Pat P5756111 then disclose shitosan have been carried out after the xanthic acid esterification method with the viscose glue blending spinning.This method has improved shitosan and cellulosic dispersiveness, has improved the performance of fiber.But because the reactivity worth of the xanthic acid esterification of shitosan is poor, the content of ash impurities is very big to its reactivity worth influence in the raw material, content of ashes that need to point out shitosan among the U.S. Pat P5756111 is less than the 0.2% shitosan xanthate that just can make the performance homogeneous, promptly the purity to shitosan has proposed very harsh requirement, need carry out very strict making with extra care to the shitosan raw material.This method efficient is low, the cost height, and difficult quality guarantee not too is suitable for large-scale industrial production.
Summary of the invention
At the deficiencies in the prior art, the technical problem to be solved in the present invention is, design a kind of hydroxyethyl chitosan modified viscose fiber and manufacture method thereof, the antibiotic property of this viscose, biocompatibility, dyeability and biological degradability etc. are good, have actual application value; This manufacturing approach craft is simple, and condition control easily, and is with low cost, is suitable for industrial applications.
The technical scheme that the present invention solves described modified viscose fiber technical problem is: design a kind of hydroxyethyl chitosan modified viscose fiber, its percentage by weight prescription is: hydroxyethyl chitosan is 0.5-20%; Cellulose is 80-99.5%, and the viscosity average molecular weigh of described hydroxyethyl chitosan is 2～500,000, and the ethoxy substitution value is 10～90%.
The technical scheme that the present invention solves described modified viscose fiber manufacture method technical problem is: design a kind of manufacture method of hydroxyethyl chitosan modified viscose fiber, this manufacture method comprises following processing step:
(1) basification: under 10～40 ℃, the sodium hydrate aqueous solution kind 10～50% is soaked 30～600min with the hydroxyethyl chitosan of particle diameter≤4mm, and bath raio is 5～30, can get hydroxyethyl chitosan alkalization product;
(2) xanthic acid esterification reaction: gained hydroxyethyl chitosan alkalization product in (1) is placed closed reactor, add carbon disulfide according to 20～80% of hydroxyethyl chitosan quality, in temperature-10～22 ℃ following reaction 1～8 hour, can obtain the viscosity solution of hydroxyethyl chitosan xanthate;
(3) co-blended spinning: the hydroxyethyl chitosan xanthate viscosity solution and the viscose glue that obtain in (2) is even according to formula rate blend of the present invention, through filtration, deaeration, maturing process, obtain the spinning solution of hydroxyethyl chitosan modified viscose fiber, utilize the spinning of conventional viscose spinning technique more promptly.
Compare with present existing chitosan modified viscose fiber technology, the difference of modified viscose fiber of the present invention is to have adopted hydroxyethyl chitosan to make hydroxyethyl chitosan modified viscose fiber as antibacterial modified dose, has good antibacterial property, biocompatibility, dyeability and biological degradability etc.Owing to introduced-CH on the strand of hydroxyethyl chitosan
2CH
2The OH group, its reactivity worth improves greatly, and manufacture method of the present invention is reduced greatly to the purity of raw material, the requirement of reaction condition, and hydroxyethyl chitosan xanthate solubility property, strainability are better, have the favorable industrial application prospect.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment.The present invention is not subjected to the restriction of embodiment.
The present invention designs a kind of hydroxyethyl chitosan modified viscose fiber (the following viscose that is called for short), and its percentage by weight prescription is: hydroxyethyl chitosan is 0.5-20%; Cellulose is 80-99.5%, and the viscosity average molecular weigh of described hydroxyethyl chitosan is 2～500,000, and the ethoxy substitution value is 10%～90%.
Hydroxyethyl chitosan of the present invention and preparation method thereof is a prior art, then is first but adopt hydroxyethyl chitosan as antibacterial modified dose of viscose.Compared with prior art, the antibiotic property of hydroxyethyl chitosan and reactivity worth are better than shitosan.The hydroxyethyl chitosan viscosity average molecular weigh especially at 4～150,000 o'clock, shows very strong anti-microbial property in 2～500,000 scopes.The viscosity average molecular weigh of hydroxyethyl chitosan of the present invention preferred 4～150,000.The substitution value of hydroxyethyl chitosan has certain influence to its reactivity worth, and hydroxyethyl chitosan used in the present invention is characterised in that its substitution value is 10～90%.
The present invention has designed a kind of manufacture method of hydroxyethyl chitosan modified viscose fiber simultaneously, and this manufacture method comprises following processing step:
(1) alkalization process: under 10～40 ℃, the sodium hydrate aqueous solution kind 10～50% is soaked 30～600min with the hydroxyethyl chitosan of particle diameter≤4mm, and bath raio is 1: 5～30, can get hydroxyethyl chitosan alkalization product;
(2) xanthic acid esterification reaction: gained hydroxyethyl chitosan alkalization product in (1) is placed closed reactor, add carbon disulfide according to 20～80% of hydroxyethyl chitosan quality, be-10～22 ℃ in temperature and reacted 1～8 hour down, can obtain the viscosity solution of hydroxyethyl chitosan xanthate;
(3) co-blended spinning: the hydroxyethyl chitosan xanthate viscosity solution and the viscose glue that obtain in (2) is even according to formula rate blend of the present invention, through filtration, deaeration, maturing process, obtain the spinning solution of hydroxyethyl chitosan modified viscose fiber, utilize the spinning of conventional viscose spinning technique more promptly.
The further feature of the manufacture method of viscose of the present invention is, in described (2) xanthic acid esterification reaction, after earlier the alkalization product of described hydroxyethyl chitosan being squeezed 2～8 times to the hydroxyethyl chitosan raw material weight, insert again in the capping still.The design of squeezing process helps removing part alkali solubility impurity, improves shitosan xanthic acid esterification reaction.Squeezing process is originally as known technology.
Viscose preparation method described in the manufacture method of the present invention is originally as known technology, and the technology adjustment is few.But it is contribution of the present invention that the hydroxyethyl chitosan technology suitably is incorporated in viscose prescription and the manufacture method thereof.Introduced on the strand of hydroxyethyl chitosan of the present invention-CH
2CH
2The OH group, reactivity increases, and reactivity worth improves.
Characteristics such as viscose anti-microbial property of the present invention, dyeability, biocompatibility, biological degradability have raising, are applicable to weaving processing clothes, dormitory articles, medical textile etc.
The present invention does not address part and is applicable to prior art.
Below provide specific embodiments of the invention.
Embodiment 1
Hydroxyethyl chitosan under 20 ℃, is soaked in the 42%NaOH aqueous solution and alkalized in 180 minutes.The alkalization product is 3.5 times of raw material weights through squeezing, transfers in the capping still and adds 0.65 times CS
2Reacted 3 hours down at 18 ℃; Add 6 times of soft water, stir and obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 5: 95 quality than blend, after filtration, utilize traditional adhering process to carry out spinning after the deaeration, slaking, the content that makes hydroxyethyl chitosan in the modified viscose fiber is 6.1%.
Embodiment 2
Under 10 ℃, caustic dip is 60 minutes in the 38%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1: 10.Transfer in the capping still and add 0.5 times CS
2Reacted 4 hours down at 10 ℃, obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 10: 90 quality than blend, carry out spinning (with embodiment 1), obtain hydroxyethyl chitosan content and be 12% modified viscose fiber.
Embodiment 3
Under 15 ℃, caustic dip is 600 minutes in the 15%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1: 30.The alkalization product is 7 times of raw material weights through squeezing, transfers in the capping still and adds 0.7 times CS
2Reacted 6 hours down at 0 ℃, obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 1: 99 quality than blend after spinning, obtain hydroxyethyl chitosan content and be 1.5% modified viscose fiber.
Embodiment 4
Under 30 ℃, caustic dip is 300 minutes in the 25%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1: 25.Transfer in the capping still and add 0.7 times CS
2Reacted 6.5 hours down at 0 ℃, obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 20: 80 quality than co-blended spinning, obtain hydroxyethyl chitosan content and be 10% modified viscose fiber.
Embodiment 5
Under 30 ℃, caustic dip is 120 minutes in the 30%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1: 15.Transfer in the capping still and add 0.55 times CS
2Reacted 8 hours down at-10 ℃, obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 10: 90 quality than co-blended spinning, obtain hydroxyethyl chitosan content and be 7.9% modified viscose fiber.
Embodiment 6
Under 38 ℃, caustic dip is 30 minutes in the 50%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1: 15.Transfer in the capping still and add 0.20 times CS
2Reacted 4 hours down at 12 ℃, obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 25: 75 quality than co-blended spinning, obtain hydroxyethyl chitosan content and be 20% modified viscose fiber.
Embodiment 7
Under 25 ℃, caustic dip is 300 minutes in the 25%NaOH aqueous solution with hydroxyethyl chitosan, and bath raio is 1: 5.Transfer in the capping still and add 0.35 times CS
2Reacted 5 hours down at 15 ℃, obtain hydroxyethyl chitosan xanthate viscosity solution.With this viscosity solution and viscose glue with 5: 95 quality than co-blended spinning, obtain hydroxyethyl chitosan content and be 9.8% modified viscose fiber.
Claims (4)
1. hydroxyethyl chitosan modified viscose fiber, its percentage by weight prescription is: hydroxyethyl chitosan is 0.5-20%; Cellulose is 80-99.5%, and the viscosity average molecular weigh of described hydroxyethyl chitosan is 2～500,000, and the ethoxy substitution value is 10～90%.
2. hydroxyethyl chitosan modified viscose fiber according to claim 1, the viscosity average molecular weigh that it is characterized in that described hydroxyethyl chitosan is 4～150,000.
3, a kind of manufacture method of hydroxyethyl chitosan modified viscose fiber, this method comprises following processing step:
(1) basification: under 10～40 ℃, the sodium hydrate aqueous solution kind 10～50% is soaked 30～600min with the hydroxyethyl chitosan of particle diameter≤4mm, and bath raio is 1: 5～30, can get hydroxyethyl chitosan alkalization product;
(2) xanthic acid esterification reaction: gained hydroxyethyl chitosan alkalization product in (1) is placed closed reactor, add carbon disulfide according to 20～80% of hydroxyethyl chitosan quality, in temperature-10～22 ℃ following reaction 1～8 hour, can obtain the viscosity solution of hydroxyethyl chitosan xanthate;
(3) co-blended spinning: the hydroxyethyl chitosan xanthate viscosity solution and the viscose glue that obtain in (2) is even according to the formula rate blend described in claim 1 or 2, through filtration, deaeration, maturing process, obtain the spinning solution of hydroxyethyl chitosan modified viscose fiber, utilize the spinning of conventional viscose spinning technique more promptly.
4. the manufacture method of hydroxyethyl chitosan modified viscose fiber according to claim 3, it is characterized in that in described (2) xanthic acid esterification reaction, after earlier the alkalization product of described hydroxyethyl chitosan being squeezed 2～8 times to the hydroxyethyl chitosan raw material weight, insert again in the capping still.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008138202A1 (en) * | 2007-05-13 | 2008-11-20 | Qingdao Biotemed Biomaterial Co., Ltd | A chitosan based fiber material, preparing method and application thereof |
| CN102277640A (en) * | 2010-06-12 | 2011-12-14 | 罗莱家纺股份有限公司 | Hydroxyethyl chitosan modified viscose and manufacturing method thereof |
| CN105705690A (en) * | 2013-06-17 | 2016-06-22 | 连津格股份公司 | Highly absorbent polysaccharide fiber and use thereof |
| CN106433078A (en) * | 2016-11-18 | 2017-02-22 | 郑州丽福爱生物技术有限公司 | High-performance polycarbonate composite material for automobiles, and preparation method and application thereof |
| CN106496998A (en) * | 2016-11-18 | 2017-03-15 | 郑州丽福爱生物技术有限公司 | A kind of high performance polycarbonate composite and preparation method and application |
-
2006
- 2006-09-20 CN CN 200610015705 patent/CN1920129A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008138202A1 (en) * | 2007-05-13 | 2008-11-20 | Qingdao Biotemed Biomaterial Co., Ltd | A chitosan based fiber material, preparing method and application thereof |
| CN102277640A (en) * | 2010-06-12 | 2011-12-14 | 罗莱家纺股份有限公司 | Hydroxyethyl chitosan modified viscose and manufacturing method thereof |
| CN105705690A (en) * | 2013-06-17 | 2016-06-22 | 连津格股份公司 | Highly absorbent polysaccharide fiber and use thereof |
| CN105705690B (en) * | 2013-06-17 | 2018-12-14 | 连津格股份公司 | High-absorbable polysaccharide fiber and application thereof |
| CN106433078A (en) * | 2016-11-18 | 2017-02-22 | 郑州丽福爱生物技术有限公司 | High-performance polycarbonate composite material for automobiles, and preparation method and application thereof |
| CN106496998A (en) * | 2016-11-18 | 2017-03-15 | 郑州丽福爱生物技术有限公司 | A kind of high performance polycarbonate composite and preparation method and application |
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