CN102199810B - Method for preparing chitosan fibers - Google Patents

Method for preparing chitosan fibers Download PDF

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Publication number
CN102199810B
CN102199810B CN2011100991744A CN201110099174A CN102199810B CN 102199810 B CN102199810 B CN 102199810B CN 2011100991744 A CN2011100991744 A CN 2011100991744A CN 201110099174 A CN201110099174 A CN 201110099174A CN 102199810 B CN102199810 B CN 102199810B
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chitosan
shitosan
solution
mass fraction
swelling
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CN102199810A (en
Inventor
胡巧玲
李友良
艾锋
张雨菲
邓海琴
张珂
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing chitosan fibers, which comprises the following steps: mixing 2.0 to 6.0 weight percent of chitosan, 4.0 to 6.0 weight percent of lithium hydroxide, 0.5 to 4.0 weight percent of urea, 0.1 to 3.0 weight percent of glycerol and the balance of water, and swelling to prepare chitosan spinning solution; and spinning by a wet-process spinning method, coagulating and precipitating in a coagulating bath to form protofilaments, washing, drawing, and drying to obtain the chitosan fibers. In the invention, the spinning solution is prepared by dissolving chitosan in an alkaline solvent, the chitosan macromolecular chains exist in a high-swelling state, the arrangement of the chitosan macromolecular chains is more compact, the high instability of the chitosan in acidic solution is overcome, the hydrolysis of the chitosan macromolecular chains and the breakage of the glucosidic bonds are avoided, the oriented arrangement of the macromolecular chains is promoted, and the mechanical properties of the chitosan fibers are improved.

Description

A kind of preparation method of chitin fiber
Technical field
The present invention relates to a kind of novel preparation method of chitin fiber.
Background technology
Advantages such as chitin fiber has broad-spectrum antiseptic, antimicrobial efficiency is high and nontoxic; Simultaneously; The ability that has biodegradability, biologically active and adsorbing metal ions again; And through clinical practice; Prove to have to promote new skin to generate, accelerate functions such as healing speed, minimizing pain, can be applicable to suture, fields such as medical adhesive-bonded fabric, hemostatic cotton, artificial skin and organizational project.Along with the expansion of range of application, the demand of chitin fiber is inevitable increasing.But the mechanical property of chitin fiber is also relatively poor at present, and on the acid flux material that one of them major reason just is to use.Solvent commonly used both at home and abroad is various diluted acids, and shitosan is extremely unsettled in acid solution, can cause the partial hydrolysis and the glycosidic bond fracture of shitosan long-chain, the chitosan molecule amount is reduced and polydispersion, thereby cause the chitin fiber performance not enough.
Summary of the invention
The objective of the invention is to provide a kind of preparation method, to expand the range of application of chitin fiber with chitin fiber of good mechanical property, stability and biocompatibility.
The preparation method of chitin fiber of the present invention, step is following:
1) contain by weight percentage and measure each component: shitosan 2.0 ~ 6.0%, lithium hydroxide 4.0 ~ 6.0 %, NaOH 0.5 ~ 4.0 %, urea 6.0 ~ 9.0%, glycerine 0.1 ~ 3.0%, all the other are water; Said components is mixed the back swelling 3 hours, swelling solution at-60 ℃ ~-20 ℃ freezing 1-4h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to solidify precipitating in 30 ℃ the coagulating bath that is frozen into silk to generate protofilament with shitosan spinning solution implantation temperature, through 5 ~ 30 ℃ of following washing stretchings after, 20 ~ 50 ℃ of dryings must chitin fiber.
Above-mentioned coagulating bath can be that mass fraction is the H of 2.0 ~ 18.0 % 2SO 4, or mass fraction is the H of 2.0 ~ 18.0 % 2SO 4With the ethanol mixed liquor of 1:8～8:1 by volume, or mass fraction is the H of 2.0 ~ 18.0 % 2SO 4, ethanol and mass fraction be the NaCl mixed liquor of 3:6:1 by volume of 2.0 ~ 8.0 %.
The invention has the advantages that:
The present invention is a spinning solution with basic solvent dissolving shitosan; Make the shitosan macromolecular chain exist with the height solvent swelling state, it is tightr that the shitosan macromolecular chain is arranged, but not the big molecule of shitosan exists with the form of chitosan salt in acid solution; Having overcome shitosan is utmost point unsure state in acid solution; Guarantee that shitosan not hydrolysis of macromolecular chain and glycosidic bond do not rupture, more help the macromolecular chain orientations, make the mechanical property of chitin fiber be improved.
The specific embodiment
Further specify the present invention below in conjunction with instance.
Embodiment 1:
1) contain by weight percentage and measure each component: with the 9.0g shitosan, 12.0g lithium hydroxide, 1.5g NaOH, 18.0g urea, 0.3g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-60 ℃ of freezing 1h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 18.0 % 2SO 4, obtain the shitosan protofilament;
4) with the shitosan protofilament at 25 ℃ down after the washing, 20 ℃ of pneumatic conveying dryings.Obtain white chitin fiber.
Embodiment 2:
1) contain by weight percentage and measure each component: with the 9.0g shitosan, 15.0g lithium hydroxide, 3.0g NaOH, 18.0g urea, 1.5g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-40 ℃ of freezing 2h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 10.0 % 2SO 4With the ethanol mixed liquor of 2:7 by volume, obtain the shitosan protofilament;
4) with the shitosan protofilament at 5 ℃ down after the washing, 50 ℃ of dryings obtain white chitin fiber.
Embodiment 3:
1) contain by weight percentage and measure each component: with the 9.0g shitosan, 15.0g lithium hydroxide, 1.5g NaOH, 21.0g urea, 1.5g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-30 ℃ of freezing 3h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 8.0 % 2SO 4, ethanol and mass fraction be the NaCl mixed liquor of 3:6:1 by volume of 5.0 %, obtains the shitosan protofilament;
4) with the shitosan protofilament at 10 ℃ down after the washing, 30 ℃ of dryings obtain white chitin fiber.
Embodiment 4:
1) contain by weight percentage and measure each component: with the 12.0g shitosan, 15.0g lithium hydroxide, 4.5g NaOH, 24.0g urea, 6.0g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-20 ℃ of freezing 4h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 4.0 % 2SO 4With the ethanol mixed liquor of 4:5 by volume, obtain the shitosan protofilament;
4) with the shitosan protofilament at 15 ℃ down after the washing, 20 ℃ of dryings obtain white chitin fiber.
Embodiment 5:
1) contain by weight percentage and measure each component: with the 12.0g shitosan, 12.0g lithium hydroxide, 4.5g NaOH, 21.0g urea, 6.0g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-60 ℃ of freezing 1h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 2.0 % 2SO 4, ethanol and mass fraction be the NaCl mixed liquor of 3:6:1 by volume of 2.0 %, obtains the shitosan protofilament;
4) with the shitosan protofilament at 25 ℃ down after the washing, 30 ℃ of dryings obtain white chitin fiber.
Embodiment 6:
1) contain by weight percentage and measure each component: with the 12.0g shitosan, 15.0g lithium hydroxide, 5.0g NaOH, 24.0g urea, 7.5g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-50 ℃ of freezing 1.5h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 2.0 % 2SO 4With the ethanol mixed liquor of 8:1 by volume, obtain the shitosan protofilament;
4) with the shitosan protofilament at 25 ℃ down after the washing, 50 ℃ of dryings obtain white chitin fiber.
Embodiment 7:
1) contain by weight percentage and measure each component: with the 10.5g shitosan, 18.0g lithium hydroxide, 1.5g NaOH, 24.0g urea, 3.0g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-40 ℃ of freezing 2h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 14.0 % 2SO 4, ethanol and mass fraction be the NaCl mixed liquor of 3:6:1 by volume of 7.0 %, obtains the shitosan protofilament;
4) with the shitosan protofilament at 20 ℃ down after the washing, 40 ℃ of dryings obtain white chitin fiber.
Embodiment 8:
1) contain by weight percentage and measure each component: with the 10.5g shitosan, 15.0g lithium hydroxide, 1.5g NaOH, 24.0g urea, 4.5g glycerine, all the other are water, altogether 300g; Said components is mixed the back swelling 3 hours, swelling solution at-30 ℃ of freezing 2h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to become fine in 30 ℃ the coagulating bath that is frozen into silk with shitosan spinning solution implantation temperature, used coagulating bath is that mass fraction is the H of 12.0 % 2SO 4, ethanol and mass fraction be the NaCl mixed liquor of 3:6:1 by volume of 5.0 %, obtains the shitosan protofilament;
4) with the shitosan protofilament at 10 ℃ down after the washing, 50 ℃ of dryings obtain white chitin fiber.

Claims (1)

1. the preparation method of a chitin fiber is characterized in that step is following:
1) contain by weight percentage and measure each component: shitosan 2.0～6.0%, lithium hydroxide 4.0～6.0%, NaOH 0.5～4.0%, urea 6.0～9.0%, glycerine 0.1～3.0%, all the other are water; Said components is mixed the back swelling 3 hours, swelling solution at-60 ℃～-20 ℃ freezing 1-4h, is at room temperature thawed then, get chitosan solution;
2) chitosan solution is through filtering, and uses the centrifuge deaeration, makes the shitosan spinning solution;
3) be to solidify precipitating in 30 ℃ the coagulating bath that is frozen into silk to generate protofilament with shitosan spinning solution implantation temperature, through 5～30 ℃ of following washing stretchings after, 20～50 ℃ of dryings must chitin fiber;
Above-mentioned coagulating bath is that mass fraction is 2.0～18.0% H 2SO 4, or mass fraction is 2.0～18.0% H 2SO 4With 1: 8 by volume～8: 1 mixed liquor of ethanol, or mass fraction is 2.0～18.0% H 2SO 4, ethanol and mass fraction be 2.0～8.0% 3: 6: 1 by volume mixed liquor of NaCl.
CN2011100991744A 2011-04-20 2011-04-20 Method for preparing chitosan fibers Expired - Fee Related CN102199810B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2518199A (en) * 2013-09-13 2015-03-18 Xiros Ltd Method of producing a swellable polymer fibre

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CN102534864B (en) * 2011-11-19 2013-10-16 青岛科技大学 Preparation method of alkylation chitosan fiber
CN102406961B (en) * 2011-11-29 2013-12-18 司忠 Absorbable operating suture line and preparation method thereof
CN103343399B (en) * 2013-07-11 2016-01-27 武汉大学 Buck system dissolution in low temperature chitin prepares the method for chitin regenerated fiber
CN103409849B (en) * 2013-07-15 2015-08-12 东华大学 A kind of take compound ion liquid as the method that chitosan hollow tunica fibrosa prepared by solvent
CN103480038B (en) * 2013-09-09 2015-03-25 浙江大学 Preparation method for chitosan/hydroxyapatite composite hydrogel
CN103463683B (en) * 2013-09-09 2015-01-14 浙江大学 Preparation method of chitosan/calcium phosphate bone tissue healing porous scaffold
CN103463686B (en) * 2013-09-09 2014-12-10 浙江大学 Preparation method of high-strength medical chitosan bone nail
CN105401242A (en) * 2015-10-23 2016-03-16 徐爱军 Medical nonwoven fabric with antibiosis and antiphlogosis efficacy, and preparation method thereof
CN108625172B (en) * 2018-04-26 2019-11-26 东华大学 A kind of processing method of chitin fiber
CN108660741B (en) * 2018-04-26 2020-08-11 海斯摩尔生物科技有限公司 Preparation method of antibacterial chitosan fiber
CN109537096A (en) * 2018-12-09 2019-03-29 合肥英士博户外用品科技有限公司 A kind of fiber spinning solution
CN111519280B (en) * 2019-02-01 2021-07-20 武汉大学 Preparation method of chitosan fiber material
CN111748870B (en) * 2019-03-29 2021-09-14 武汉大学 Fiber material prepared from chitosan solution with pH value of 6-8 and preparation method thereof

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CN101215341A (en) * 2008-01-14 2008-07-09 浙江大学 Basic solvent for dissolving chitosan and using method thereof
KR100912644B1 (en) * 2009-02-13 2009-08-17 김덕례 The preparing method of chemically transformed chitosan fiber

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CN101215389A (en) * 2008-01-14 2008-07-09 浙江大学 Chitosan hydrogel and preparation method thereof
CN101215341A (en) * 2008-01-14 2008-07-09 浙江大学 Basic solvent for dissolving chitosan and using method thereof
KR100912644B1 (en) * 2009-02-13 2009-08-17 김덕례 The preparing method of chemically transformed chitosan fiber

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* Cited by examiner, † Cited by third party
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GB2518199A (en) * 2013-09-13 2015-03-18 Xiros Ltd Method of producing a swellable polymer fibre

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