CN102505170B - Method for preparing silk protein composite cellulose fibers - Google Patents
Method for preparing silk protein composite cellulose fibers Download PDFInfo
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- CN102505170B CN102505170B CN 201110329457 CN201110329457A CN102505170B CN 102505170 B CN102505170 B CN 102505170B CN 201110329457 CN201110329457 CN 201110329457 CN 201110329457 A CN201110329457 A CN 201110329457A CN 102505170 B CN102505170 B CN 102505170B
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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 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, the genus polyporus material, and the fabric breathability of making is good, and hygroscopicity is splendid, and comfortable top grade is taken in dress, is described as " fiber queen " by common people.Silk is generally used for knits 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 yield is lower, cause it expensive, the restriction in current consumption is larger.And waste and old silk and silk offcut generally are processed to the articles for use such as cocoon silk quilt, it is much lower that the price of cocoon silk quilt is compared silk fiber, and value is lower.
Although also there is the protein composite fiber of a lot of azelons or viscose to come out at present, but be all that after albumen powder is dissolved, spinning is prepared into wire protein fiber, perhaps albumen powder is dissolved to rear and cellulose solution co-blended spinning, by cellulose fibre is carried out to modification, be prepared into the fibroin composite fiber cellulose fiber.About the fibroin study on the modification of viscose, by nano-grade silk albumen powder and cellulose blending, make fibroin blending regeneration cellulose fiber as domestic patent CN200910153053.6, belong to physical blending.
Cellulose fibre is as a kind of regenerated fiber, has the smooth advantage such as gorgeous of feeling nice and cool, breathe freely, dye, and is widely used.And cellulose fibre is easy to and the functional component blending, develops the product with new function, with this, meet the many-sided requirement of people to fiber.Especially the fine count fiber cellulose fiber has the performance similar to real silk, if therefore utilize waste and old silk to carry out modification to cellulose fibre, not only can give smooth, soft feel as cellulose fibre silk, promote the class of cellulose fibre, also take full advantage of discarded protein material, improve its value simultaneously.
Summary of the invention
Technical problem to be solved by this invention is: the deficiency existed for prior art, provide a kind of and utilize waste and old silk to carry out modification to cellulose fibre, preparation has the preparation method of the fibroin composite cellulose fiber of texture as skin care, beauty functions, real silk.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of preparation method of fibroin composite cellulose fiber comprises the following steps:
(1) waste and old silk is joined in LiBr solution after degumming process, heat under 45～75 ℃ 2～5 hours, dissolve and be prepared into fibroin solution, in described fibroin solution, the concentration of fibroin is 3～15wt%.
(2) described 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 described fibroin, by silk-fibroin, is cellulosic 5～50wt%.
(3) the coagulating bath spinning moulding through sulfur acid, zinc sulfate and sodium sulphate by described blend solution, then through washing, desulfurization, oil, drying, obtain the fibroin composite cellulose fiber.
Wherein, when described waste and old natural silk degumming is processed, use the NaHCO of 0.5～3wt%
3or Na
2cO
3solution, process 30～60 minutes at 70～90 ℃.
As a kind of improvement, in step (1), the fibroin solution made is cooled to normal temperature, after filtering, with the polyglycol solution that molecular weight is 6000～15000, concentration is 5～40wt%, dialysed.
Preferably, described dialysis adopts repeatedly dialysis, and the described repeatedly number of times of dialysis is 2～5 times, and the described repeatedly time of dialysis is 10～40 hours.
Preferably, described filtration adopts the filter screen of 15～25um to be filtered.
Preferably, the molar concentration of described LiBr solution is 5～15mol/L.
Preferably, desulfurizing agent during described desulfurization is sodium sulfite.
Wherein, sulfur acid 100～150g/L, zinc sulfate 5～15g/L, sodium sulphate 300～400g/L in described coagulating bath, the temperature of described coagulating bath is 45～70 ℃.
In fibroin and cellulosic blend solution preparation process, 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 having adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention will be dissolved after waste and old natural silk degumming again, silk gum removes and totally is conducive to the stable of fiber preparation process and fibrous physics mechanical index, dissolve silk with LiBr solution, there is dissolution velocity fast, the silk-fibroin less degradation, produce and be easy to the advantage of controlling, 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 form peptide material by Partial digestion, research shows, contain 18 seed amino acids in these peptide materials, there is whitening, moisturizing, the isolation ultraviolet ray, the effects such as delaying skin is aging, therefore utilize the fibroin that LiBr solution dissolves to carry out modification to viscose, the recycling that has not only greatly improved waste and old silk is worth, the fibroin composite cellulose fiber of preparation, there is the good sucting wet air permeability that cellulose fibre itself has, dyeability, and can give the composite cellulose fiber whitening, the special efficacy of skin care, make fiber have as silk smooth simultaneously, soft feel, greatly promoted the quality of cellulose fibre, there is the incomparable skin care of albumen powder fiber or albumen powder and albumen powder blended fiber, white-skinned face function.
2, dissolve the fibroin solution of preparation with LiBr solution, a kind of colloidal solution of homogeneous stability, at sodium sulphate, under the salt effects such as ammonium sulfate, can produce and solidify palingenesis, and the viscose solution of cellulose sulfonate is used sulfur acid usually, zinc sulfate, regeneration is solidified in the coagulating bath of sodium sulphate, therefore there is certain intercommunity in the coagulating agent of the two, it is sulfur acid, zinc sulfate, the coagulating agent of 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, form two kinds of macromolecular interpenetrating networks shape structures, the filament albumen made is combined with cellulose firmly, silk-fibroin runs off few after fiber in process, production control is comparatively stable, and the fibroin composite cellulose fiber mechanics index of physics made is relatively high, be conducive to the follow-up textile process of fiber and apply.This is that the present invention adopts silk and cellulose blending to prepare the mechanism place of fibroin composite cellulose fiber.Due to silk-fibroin in coagulating bath to solidify reproduction speed slow than cellulose, therefore need higher coagulating bath component concentration, temperature, therefore the present invention adopts the coagulating bath that sulfur acid 100～150g/L, zinc sulfate 5～15g/L, sodium sulphate 300～400g/L, temperature are 45～70 ℃ to carry out spinning.
3, because LiBr is electrolyte, during with the cellulose solution co-blended spinning, stability to blend solution has certain influence, LiBr enters the coagulating bath meeting simultaneously increases cost recovery, fibroin solution after the present invention is dissolved LiBr, dialyse and remove the LiBr in fibroin solution with polyglycol solution, and it is 6000～15000 that dialysis adopts molecular weight, the polyglycol solution that concentration is 5～40wt%, having LiBr separates fast, be easy to realize industrial advantage, simultaneously, removing the fibroin composite fibre mechanical index made after LiBr also increases.
4, the present invention's desulfurizing agent when desulfurization is preferably used 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, improved its added value greatly simultaneously, makes product have good economic benefit.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
embodiment 1
After waste and old silk is shredded, add the NaHCO of 1.0wt%
3dissolve and soak, be heated to 80 ℃ and continue 30 minutes, dry after taking-up.The silk dried is joined in the LiBr solution of 10mol/L, dissolve 5 hours at 55 ℃, be prepared into the fibroin solution of 13wt%.After the fibroin solution made is cooled to normal temperature, use the strainer filtering that aperture is 20um, remove impurity wherein, fibroin solution after filtering is dialysed with the polyglycol solution that molecular weight is 8000, concentration is 15wt%, the dialysis membrane molecular cut off is 3000, the dialysis number of times is 3, amounts to dialysis 20 hours.
By the fibroin solution after dialysis, with cellulose fibre solution, mixed, through fully mixing, dissolving, filtration, deaeration, make fibroin and cellulosic blend solution, the addition of described fibroin is by silk-fibroin, for cellulosic 8wt%, by blend solution through sulfur acid 125g/L, zinc sulfate 8g/L, sodium sulphate 360g/L, the coagulating bath spinning moulding that temperature is 55 ℃, again through washing, desulfurization, oil, drying, obtain the fibroin composite cellulose fiber, the desulfurizing agent of described desulfurization is sodium sulfite.
embodiment 2
After waste and old silk is shredded, add the Na of 0.5wt%
2cO
3dissolve and soak, be heated to 90 ℃ and continue 40 minutes, dry after taking-up.The silk dried is joined in the LiBr solution of 9mol/L, dissolve 4 hours at 60 ℃, be prepared into the fibroin solution of 7wt%.After the fibroin solution made is cooled to normal temperature, use the strainer filtering that aperture is 15um, remove impurity wherein.
By the fibroin solution after filtering, with cellulose fibre solution, mixed, through fully mixing, dissolving, filtration, deaeration, make fibroin and cellulosic blend solution, the addition of described fibroin, by silk-fibroin, is cellulosic 25wt%, by blend solution through sulfur acid 135g/L, zinc sulfate 10g/L, sodium sulphate 335g/L, the coagulating bath spinning moulding that temperature is 53 ℃, then through washing, desulfurization, oil, drying, obtain the fibroin composite cellulose fiber.
embodiment 3
After waste and old silk is shredded, add the NaHCO of 2.5wt%
3dissolve and soak, be heated to 75 ℃ and continue 50 minutes, dry after taking-up.The silk dried is joined in the LiBr solution of 7mol/L, dissolve 3 hours at 70 ℃, be prepared into the fibroin solution of 10wt%.After the fibroin solution made is cooled to normal temperature, use the strainer filtering that aperture is 25um, remove impurity wherein, fibroin solution after filtering is dialysed with the polyglycol solution that molecular weight is 9000, concentration is 13wt%, the dialysis membrane molecular cut off is 4000, the dialysis number of times is 2, amounts to dialysis 32 hours.
By the fibroin solution after dialysis, with cellulose fibre solution, mixed, through fully mixing, dissolving, filtration, deaeration, make fibroin and cellulosic blend solution, the addition of described fibroin is by silk-fibroin, for cellulosic 35wt%, by blend solution through sulfur acid 120g/L, zinc sulfate 11g/L, sodium sulphate 330g/L, the coagulating bath spinning moulding that temperature is 65 ℃, again through washing, desulfurization, oil, drying, obtain the fibroin composite cellulose fiber, the desulfurizing agent of described desulfurization is sodium sulfite.
Claims (5)
1. the preparation method of a fibroin composite cellulose fiber is characterized in that comprising the following steps:
(1) waste and old silk is joined in LiBr solution after degumming process, under 45～75 ℃, heat 2～5 hours, dissolving is prepared into fibroin solution, in described fibroin solution, the concentration of fibroin is 3～15wt%, the fibroin solution made is cooled to normal temperature, after filtering, with the polyglycol solution that molecular weight is 6000～15000, concentration is 5～40wt%, dialysed, described dialysis adopts repeatedly dialysis, the described repeatedly number of times of dialysis is 2～5 times, and the described repeatedly time of dialysis is 10～40 hours;
(2) described 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 described fibroin, by silk-fibroin, is cellulosic 5～50wt%;
(3) the coagulating bath spinning moulding through sulfur acid, zinc sulfate and sodium sulphate by described blend solution, again through washing, desulfurization, oil, drying, obtain the fibroin composite cellulose fiber, sulfur acid 135～150g/L, zinc sulfate 5～10g/L, sodium sulphate 335～400g/L in described coagulating bath, the temperature of described coagulating bath is 53～70 ℃.
2. the preparation method of fibroin composite cellulose fiber as claimed in claim 1, is characterized in that: when described waste and old natural silk degumming is processed, use the NaHCO of 0.5～3wt%
3or Na
2cO
3solution, process 30～60 minutes at 70～90 ℃.
3. the preparation method of fibroin composite cellulose fiber as claimed in claim 1 is characterized in that: described filtration adopts the filter screen of 15～25um to be filtered.
4. the preparation method of fibroin composite cellulose fiber as claimed in claim 1, it is characterized in that: the molar concentration of described LiBr solution is 5～15mol/L.
5. the preparation method of fibroin composite cellulose fiber as described as claim 1 to 4 any one, it is characterized in that: desulfurizing agent during described desulfurization is sodium sulfite.
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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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| CN102505170B true CN102505170B (en) | 2013-12-18 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562281B (en) * | 2015-01-22 | 2016-08-24 | 罗莱家纺股份有限公司 | A kind of preparation method of nanometer fibroin bamboo pulp fiber |
| CN105821518B (en) * | 2016-05-13 | 2018-02-06 | 广东艺森地毯顾问实业有限公司 | A kind of preparation method of pupa albumen/lotus cellulose composite fiber |
| 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 |
| CN113476330B (en) * | 2021-05-28 | 2024-01-30 | 苏州大学 | Silk powder for cosmetics and preparation method thereof |
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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. |