CN102505170A - Method for preparing silk protein composite cellulose fibers - Google Patents
Method for preparing silk protein composite cellulose fibers Download PDFInfo
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- CN102505170A CN102505170A CN2011103294573A CN201110329457A CN102505170A CN 102505170 A CN102505170 A CN 102505170A CN 2011103294573 A CN2011103294573 A CN 2011103294573A CN 201110329457 A CN201110329457 A CN 201110329457A CN 102505170 A CN102505170 A CN 102505170A
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Abstract
The invention discloses a method for preparing silk protein composite cellulose fibers, which includes steps: firstly, adding degummed waste silk into LiBr solution, dissolving the waste silk to prepare silk protein solution in which silk protein accounts for 3-15%, by weight; secondly, adding the silk protein solution into sodium hydroxide solution with cellulose sulfonate to obtain blended solution of silk protein and cellulose, wherein blended silk protein solution accounts for 5-50% of that of the sodium hydroxide with cellulose sulfonate by weight; and thirdly, spinning the blended solution by coagulating bath and obtaining the silk protein composite cellulose fibers by post-processing. By the method, recovery value of the waste silk is improved greatly, special effects of whitening and skin caring of the silk protein composite cellulose fibers can be realized, and the fibers are smooth and soft to touch as silk, and have the skin caring and whitening effects that the effects of protein powder fibers or blended fibers of protein powder and cellulose solution cannot match.
Description
Technical field
The present invention relates to the cellulose fibre preparing technical field, relate in particular to a kind of preparation of fibroin composite fibre cellulose fiber.
Background technology
Silk is the concretionary continuous fiber of silk liquid of time secretion of being cocoond by matured silkworm, is protein fibre, genus polyporus property material, and the fabric breathability of processing is good, and hygroscopicity is splendid, and comfortable top grade is taken in dress, is described as " fiber queen " by common people.Silk generally is used to knit the various silks and satins of system, knitted fabric, industry, national defence and medical supplies, is one of important textile raw material.But because the cost of breeding silkworms is higher and silk output is lower, cause it to cost an arm and a leg, the restriction in current consumption is bigger.And waste and old silk and silk offcut generally are processed to articles for use such as cocoon silk quilt, and it is much lower that the price of cocoon silk quilt is compared silk fiber, and value is lower.
Though also there is the protein composite fiber of a lot of azelons or viscose to come out at present; But all be that albumen powder dissolving back spinning is prepared into wire protein fiber; Perhaps with albumen powder dissolving back and cellulose solution co-blended spinning; Through cellulose fibre is carried out modification, be prepared into the fibroin composite fiber cellulose fiber.Fibroin study on the modification about viscose with nano-grade silk albumen powder and cellulose blending, makes fibroin blending regeneration cellulose fiber like domestic patent CN200910153053.6, belongs to physical blending.
Cellulose fibre is as a kind of regenerated fiber, has smooth nice and cool, ventilative, advantage such as dyeing is gorgeous, is widely used.And cellulose fibre is easy to and the functional component blending, develops the product with new function, satisfies the many-sided requirement of people to fiber with this.Especially the fine count fiber cellulose fiber has the performance similar with real silk; Therefore if utilize waste and old silk that cellulose fibre is carried out modification; Not only can give as the cellulose fibre silk along sliding, soft hand feeling; Promote the class of cellulose fibre, also made full use of discarded protein material simultaneously, improve its value.
Summary of the invention
Technical problem to be solved by this invention is: to the deficiency of prior art existence; Provide a kind of and utilize waste and old silk that cellulose fibre is carried out modification, preparation has the fibroin compound cellulose fiber preparation method of texture as skin care, beauty functions, the real silk.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of fibroin compound cellulose fiber preparation method may further comprise the steps:
(1) waste and old silk is joined in the LiBr solution after the processing of coming unstuck, heated 2～5 hours down at 45～75 ℃, dissolving is prepared into fibroin solution, and the concentration of fibroin is 3～15wt% in the said fibroin solution.
(2) said fibroin solution is joined in the sodium hydroxide solution of cellulose sulfonate; Through fully mixing, dissolving, filtration, deaeration; Make fibroin and cellulosic blend solution, the addition of said fibroin is cellulosic 5～50wt% by silk-fibroin.
(3) with the coagulating bath spinning moulding of said blend solution through sulfur acid, zinc sulfate and sodium sulphate, again through washing, desulfurization, oil, drying, obtain fibroin composite fibre cellulose fiber.
Wherein, said waste and old silk comes unstuck when handling, and uses the NaHCO of 0.5～3wt%
3Or Na
2CO
3Solution was handled 30～60 minutes at 70～90 ℃.
As a kind of improvement, in the step (1), the fibroin solution that makes is cooled to normal temperature, filter the back and use the polyglycol solution that molecular weight is 6000～15000, concentration is 5～40wt% to dialyse.
Preferably, repeatedly dialysis is adopted in said dialysis, and the said repeatedly number of times of dialysis is 2～5 times, and the said repeatedly time of dialysis is 10～40 hours.
Preferably, said filtration adopts the filter screen of 15～25um to filter.
Preferably, the molar concentration of said LiBr solution is 5～15mol/L.
Preferably, the desulfurizing agent during said desulfurization is a sodium sulfite.
Wherein, sulfur acid 100～150g/L, zinc sulfate 5～15g/L, sodium sulphate 300～400g/L in the said coagulating bath, the temperature of said coagulating bath is 45～70 ℃.
Prepare in the process at fibroin and cellulosic blend solution, the composition of blend solution may be controlled to alpha-cellulose content 7～10wt%, alkali content (in NaOH) 4～7wt%, and viscose riscosity may be controlled to 30～80s (falling ball method).
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention is dissolved after waste and old silk is come unstuck again, and silk gum removes and totally helps the stable of fiber production process and fibrous physics mechanical index, with LiBr solution dissolving silk; It is fast to have dissolution velocity; The silk-fibroin less degradation is produced the advantage that is easy to control, and can make stable, even; The white fibroin solution of certain viscosity is arranged, and can control the viscosity of the fibroin solution of gained.In addition, adopt LiBr solution to dissolve waste and old silk, fibroin is in the process of dissolving; Can the part degraded form peptide material; Effects such as research shows, contains 18 seed amino acids in these peptide materials, and Pear Power, skin moisten, isolation ultraviolet ray, delaying skin are aging; Therefore utilize the fibroin of LiBr solution dissolving that viscose is carried out modification; The recycling that has not only improved waste and old silk greatly is worth, and the fibroin composite fibre cellulose fiber of preparation has good sucting wet air permeability, dyeability that cellulose fibre itself has; And can give that the composite fibre cellulose fiber is whitened, the special efficacy of skin care; Fiber is had as the silk along sliding, soft hand feeling, promoted the quality of cellulose fibre greatly, have albumen powder fiber or albumen powder and albumen powder blended fiber incomparable skin care, white-skinned face function.
2, with the fibroin solution of LiBr solution dissolving preparation, be a kind of colloidal solution of homogeneous stability, under salt effects such as sodium sulphate, ammonium sulfate; Can produce and solidify palingenesis, and the viscose solution of cellulose sulfonate uses the coagulating bath of sulfur acid, zinc sulfate, sodium sulphate to solidify regeneration usually, so there is certain intercommunity in the coagulating agent of the two; Be the coagulating agent of sulfur acid, zinc sulfate, sodium sulphate, can solidify the regenerated cellulose sulphonic acid ester, can solidify regenerated silk albumen again; In same coagulating bath; The two media two-phase is regenerated simultaneously, forms two kinds of macromolecular interpenetrating networks shape structures, and the filament albumen that makes combines with cellulose firmly; Silk-fibroin runs off few behind fiber in the process; Production control is comparatively stable, and the fibroin compound cellulose fibrous physics mechanical index that makes is higher relatively, and the follow-up weaving that helps fiber is processed and applied.This is that the present invention adopts silk and cellulose blending to prepare the mechanism place of fibroin composite fibre cellulose fiber.Since silk-fibroin in coagulating bath to solidify reproduction speed slow than cellulose; Event needs higher coagulating bath component concentration, temperature, is that spinning is carried out in 45～70 ℃ coagulating bath so the present invention adopts sulfur acid 100～150g/L, zinc sulfate 5～15g/L, sodium sulphate 300～400g/L, temperature.
3,, during with the cellulose solution co-blended spinning, the stability of blend solution there is certain influence because LiBr is an electrolyte; LiBr gets into the coagulating bath meeting simultaneously increases cost recovery; The present invention is to the fibroin solution after the LiBr dissolving, dialyse with polyglycol solution and remove the LiBr in the fibroin solution, and dialysis is adopted, and molecular weight is 6000～15000, concentration is the polyglycol solution of 5～40wt%; Having LiBr separates fast; Be easy to realize industrial advantage, simultaneously, remove the fibroin composite fibre mechanical index that makes behind the LiBr and also increase.
4, the present invention's desulfurizing agent when desulfurization preferably uses sodium sulfite, has effectively avoided the loss of silk-fibroin, has improved the retention of silk-fibroin and the performance of composite fibre in the composite fibre.
5, raw material of the present invention are taken from native cellulose and waste and old silk, and its raw material all has stronger reproducibility.Production process equipment can be used existing cellulose fibre device fabrication fully, makes product be convenient to carry out mass production, and the recycling of waste and old silk has improved its added value greatly simultaneously, makes product have good economic benefit.
The specific embodiment
Below in conjunction with concrete embodiment, further set forth the present invention.
Embodiment 1
After waste and old silk shredded, add the NaHCO of 1.0wt%
3Dissolving is soaked, and is heated to 80 ℃ and continues 30 minutes, dries after the taking-up.The silk that will dry joins in the LiBr solution of 10mol/L, 55 ℃ of dissolvings 5 hours, is prepared into the fibroin solution of 13wt%.After the fibroin solution that makes is cooled to normal temperature; Use the strainer filtering of aperture as 20um; Remove impurity wherein, the fibroin solution after filtering is used molecular weight is 8000, concentration is dialysed as the polyglycol solution of 15wt%, the dialysis membrane molecular cut off is 3000; The dialysis number of times is 3, amounts to dialysis 20 hours.
Fibroin solution with after the dialysis mixes with cellulose fibre solution, through fully mix, dissolving, filtration, deaeration; Make fibroin and cellulosic blend solution; The addition of said fibroin is cellulosic 8wt% by silk-fibroin, with blend solution through sulfur acid 125g/L, zinc sulfate 8g/L, sodium sulphate 360g/L; Temperature is 55 ℃ a coagulating bath spinning moulding; Again through washing, desulfurization, oil, drying, obtain fibroin composite fibre cellulose fiber, the desulfurizing agent of said desulfurization is a sodium sulfite.
Embodiment 2
After waste and old silk shredded, add the Na of 0.5wt%
2CO
3Dissolving is soaked, and is heated to 90 ℃ and continues 40 minutes, dries after the taking-up.The silk that will dry joins in the LiBr solution of 9mol/L, 60 ℃ of dissolvings 4 hours, is prepared into the fibroin solution of 7wt%.After the fibroin solution that makes is cooled to normal temperature, use the strainer filtering of aperture, remove impurity wherein as 15um.
Fibroin solution with after filtering mixes with cellulose fibre solution, through fully mix, dissolving, filtration, deaeration; Make fibroin and cellulosic blend solution, the addition of said fibroin is cellulosic 25wt% by silk-fibroin; With blend solution through sulfur acid 135g/L, zinc sulfate 10g/L, sodium sulphate 335g/L; Temperature is 53 ℃ a coagulating bath spinning moulding, again through washing, desulfurization, oil, drying, obtain fibroin composite fibre cellulose fiber.
Embodiment 3
After waste and old silk shredded, add the NaHCO of 2.5wt%
3Dissolving is soaked, and is heated to 75 ℃ and continues 50 minutes, dries after the taking-up.The silk that will dry joins in the LiBr solution of 7mol/L, 70 ℃ of dissolvings 3 hours, is prepared into the fibroin solution of 10wt%.After the fibroin solution that makes is cooled to normal temperature; Use the strainer filtering of aperture as 25um; Remove impurity wherein, the fibroin solution after filtering is used molecular weight is 9000, concentration is dialysed as the polyglycol solution of 13wt%, the dialysis membrane molecular cut off is 4000; The dialysis number of times is 2, amounts to dialysis 32 hours.
Fibroin solution with after the dialysis mixes with cellulose fibre solution, through fully mix, dissolving, filtration, deaeration; Make fibroin and cellulosic blend solution; The addition of said fibroin is cellulosic 35wt% by silk-fibroin, with blend solution through sulfur acid 120g/L, zinc sulfate 11g/L, sodium sulphate 330g/L; Temperature is 65 ℃ a coagulating bath spinning moulding; Again through washing, desulfurization, oil, drying, obtain fibroin composite fibre cellulose fiber, the desulfurizing agent of said desulfurization is a sodium sulfite.
Claims (8)
1. fibroin compound cellulose fiber preparation method is characterized in that may further comprise the steps:
(1) waste and old silk is joined in the LiBr solution after the processing of coming unstuck, heated 2～5 hours down at 45～75 ℃, dissolving is prepared into fibroin solution, and the concentration of fibroin is 3～15wt% in the said fibroin solution;
(2) said fibroin solution is joined in the sodium hydroxide solution of cellulose sulfonate; Through fully mixing, dissolving, filtration, deaeration; Make fibroin and cellulosic blend solution, the addition of said fibroin is cellulosic 5～50wt% by silk-fibroin;
(3) with the coagulating bath spinning moulding of said blend solution through sulfur acid, zinc sulfate and sodium sulphate, again through washing, desulfurization, oil, drying, obtain fibroin composite fibre cellulose fiber.
2. fibroin compound cellulose fiber preparation method as claimed in claim 1 is characterized in that: said waste and old silk comes unstuck when handling, and uses the NaHCO of 0.5～3wt%
3Or Na
2CO
3Solution was handled 30～60 minutes at 70～90 ℃.
3. fibroin compound cellulose fiber preparation method as claimed in claim 1; It is characterized in that: in the step (1); The fibroin solution that makes is cooled to normal temperature, filters the back and use the polyglycol solution that molecular weight is 6000～15000, concentration is 5～40wt% to dialyse.
4. fibroin compound cellulose fiber preparation method as claimed in claim 3 is characterized in that: repeatedly dialysis is adopted in said dialysis, and the said repeatedly number of times of dialysis is 2～5 times.
5. fibroin compound cellulose fiber preparation method as claimed in claim 3 is characterized in that: said filtration adopts the filter screen of 15～25um to filter.
6. fibroin compound cellulose fiber preparation method as claimed in claim 1 is characterized in that: the molar concentration of said LiBr solution is 5～15mol/L.
7. fibroin compound cellulose fiber preparation method according to claim 1 is characterized in that: the desulfurizing agent during said desulfurization is a sodium sulfite.
8. like described any fibroin compound cellulose fiber preparation method of claim 1 to 7; It is characterized in that: sulfur acid 100～150g/L, zinc sulfate 5～15g/L, sodium sulphate 300～400g/L in the said coagulating bath, the temperature of said coagulating bath is 45～70 ℃.
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| CN 201110329457 CN102505170B (en) | 2011-10-26 | 2011-10-26 | Method for preparing silk protein composite cellulose fibers |
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| CN 201110329457 CN102505170B (en) | 2011-10-26 | 2011-10-26 | Method for preparing silk protein composite cellulose fibers |
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| CN104562281A (en) * | 2015-01-22 | 2015-04-29 | 罗莱家纺股份有限公司 | Preparation method of nano silk protein bamboo pulp fibers |
| CN105821518A (en) * | 2016-05-13 | 2016-08-03 | 东莞市联洲知识产权运营管理有限公司 | Silkworm pupa protein/lotus cellulose composite fibers and preparing method thereof |
| CN107604668A (en) * | 2017-09-13 | 2018-01-19 | 苏州贝彩纳米科技有限公司 | The preparation method and schemochrome fabric of structure color fibre based on fibroin |
| CN108589293A (en) * | 2018-04-10 | 2018-09-28 | 湖州金玺丝绸有限公司 | a kind of silk regeneration method |
| CN108708060A (en) * | 2018-06-08 | 2018-10-26 | 苏州印丝特纺织数码科技有限公司 | A kind of preparation method of low-cost and high-performance antibiotic fabric |
| CN113476330A (en) * | 2021-05-28 | 2021-10-08 | 苏州大学 | Silk powder for cosmetics and preparation method thereof |
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| CN113476330B (en) * | 2021-05-28 | 2024-01-30 | 苏州大学 | Silk powder for cosmetics and preparation method thereof |
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| CN102505170B (en) | 2013-12-18 |
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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 No. 1, Aoyang Avenue, Aoyang Industrial Park, Funing County, Yancheng City, Jiangsu Province Patentee before: FUNING AOYANG TECHNOLOGY CO.,LTD. |
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