CN102926015B - Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method - Google Patents
Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method Download PDFInfo
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- CN102926015B CN102926015B CN201210473521.XA CN201210473521A CN102926015B CN 102926015 B CN102926015 B CN 102926015B CN 201210473521 A CN201210473521 A CN 201210473521A CN 102926015 B CN102926015 B CN 102926015B
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Abstract
The invention discloses a method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method. The method comprises the following steps: dissolving hydroxyethyl celluloses with low degree of substitution in uniform mixed aqueous solution containing 4-12 wt% of sodium hydroxide, 1-10 wt% of thiourea and 1-15 wt% of urea at negative 15 to 10 degrees centigrade, filtering and defoaming to obtain spinning solution with solid content of 2-20%; making the spinning solution stand at negative 5-0 degrees centigrade for 10-30 min to perform pre-gel treatment, then spinning by a wet spinning machine, solidifying, regenerating and performing stretching orientation to obtain the hydroxyethyl cellulose fibers. The method performs the pre-gel treatment to the spinning solution, part of molecular chains of the solution are wound with each other at low temperature, and a light cross-linking network structure still exists when the temperature is increased to the spinning temperature so as to effectively reduce swelling of silks generated in the washing process and increase spinning property and spinning speed of the spinning solution. Therefore, the obtained novel fibers have the advantages of compact structure and excellent mechanical property.
Description
Technical field
The present invention relates to a kind of method adopting pre-gel to prepare hydroxyethyl cellulose, belong to field of material technology.
Background technology
Cellulose is the abundantest renewable resource of occurring in nature, and be the natural carbohydrate that distribution is the widest at present, whole world annual production is about 1,500 hundred million tons.Its source mainly comprises cotton, fiber crops, timber, bamboo, and other higher plants, as reed, stalk, bagasse etc.At present, cellulose is mainly for the production of regrown material (fiber, film etc.) and processing synthetic cellulose derivative.And day by day in short supply current of cotton resource, wearability is similar to cotton because having for regenerated celulose fibre, environmental friendliness and the advantage such as raw material (cellulose) is renewable, has caused the great attention of people.But due in the crystal structure of cellulose densification and the molecule of complexity thereof and intermolecular hydrogen bonding, make it be difficult to be dissolved in common solvent or carry out melt-processed, directly hinder development and the application of material of regenerated cellulose.Present most regenerated celulose fibre still adopts traditional viscose process to produce, but this technique discharges a large amount of poisonous H in process of production
2s and CS
2, while serious environment pollution, also compromise health.Current, many scholars have done a large amount of work in exploitation cellulose solvent, and have found many cellulosic novel dissolvents, as LiCl/DMAc, NH
3/ NH
4the SCN aqueous solution, PF/DMSO, Ca (SCN)
2/ NaSCN the aqueous solution, ZnCl
2the aqueous solution, ionic liquid system etc., but these solvents cannot realize industrialization so far due to shortcomings such as solvent are expensive, reclaim difficulty, dissolution conditions is harsh.Alkali/urea solvent is because having low price, and toxicity is lower, direct dissolving cellulos, and generate without derivative, cellulose is seldom degraded, and dissolves rapidly, the advantages such as technique is simple, in the traditional adhering process of replacement, have good application prospect.Wuhan University professor Zhang Lina adopts NaOH and urea mixed aqueous solution, NaOH and thiocarbamide mixed aqueous solution dissolving cellulos also successfully to prepare regenerated cellulose film and fiber, but because dissolution with solvents is limited in one's ability, be only applicable to the cellulose that the degree of polymerization is not high, the solid content of solution is lower, causes the material of regenerated cellulose mechanical property of preparation poor.Donghua University turns round and look at sharp rosy clouds etc. with NaOH, thiocarbamide, urea mixed aqueous solution for solvent, to cellulose, there is stronger solvability, and successfully obtain regenerated cellulose film and fiber, but do not solve cellulosic degree of polymerization equally and the problem such as solid content is on the low side, gained regrown material mechanical property still has to be hoisted.Meanwhile, the cellulose solution character using alkali/urea solvent to prepare is unstable, easily forms irreversible gel, for follow-up spinning process adds difficulty, is unfavorable for suitability for industrialized production.
Utilize oxirane to carry out etherification modified to cellulose, the hydroxyethylcellulose of low molar substitution can be obtained, strengthening the accessibility of solvent molecule to hydroxyl by weakening hydrogen bond action between cellulose macromolecule, the object improving solution solid content can be realized.The hydroxyethylcellulose of low molar substitution has unique alkali solubility, and solution has good film forming, fibre forming property.NaOH described in patent CN101412815A, thiocarbamide, urea mixed aqueous solution, to hydroxyethylcellulose, there is stronger solvability, the hydroxyethyl cellulose solution of high-dissolvability (solubility can reach 100%), high solids content can be obtained, and solution property is stable, modest viscosity, strainability are excellent, the gel thermal reversion formed, is with a wide range of applications.But when being applied to wet spinning, strand water-washing process easily produces swollen, affects the stability of spinning process, reduces spinning speed, is unfavorable for industrialization steady production.
Summary of the invention
The object of this invention is to provide a kind of method adopting pre-gel to prepare hydroxyethyl cellulose, with solve cause because of swollen excessive when strand is washed in existing spinning technique spinnability difference etc. problem.
For achieving the above object, the invention provides a kind of method adopting pre-gel to prepare hydroxyethyl cellulose, it is characterized in that, concrete steps are as follows:
1): preparation contains 4 ~ 12wt% NaOH by weight percentage, 1 ~ 10wt% thiocarbamide, the aqueous solution (i.e. alkali/urea solvent) of 1 ~ 15wt% urea, and is chilled to-15 ~ 10 DEG C in advance; Be 300 ~ 2000 by the degree of polymerization, molar substitution is that the alkali/urea solvent of hydroxyethylcellulose and the precooling of 0.15 ~ 0.85 to mix in mass ratio at 5: 95 ~ 20: 80, stir at-10 ~ 20 DEG C, until dissolve the hydroxyethyl cellulose solution forming homogeneous transparent completely;
2): the filtration step 1) hydroxyethyl cellulose solution of gained, at room temperature utilizes supercentrifuge to the centrifugal 10-60min of filtrate, sloughs bubble;
3) the centrifugal rear spinning solution: by step 2) obtained leaves standstill 10 ~ 30min and carries out pregel process at-5 ~ 0 DEG C, is then warming up to 25 DEG C; Spinning solution is transferred to vacuum defoamation 30 ~ 200min in spinning machine;
4): pressurize to spinning solution with nitrogen, make it, by metering pump of spinning machine, gooseneck and spinneret cap, to enter in coagulating bath and be solidified into strand;
5): the strand after solidification drawing-off, through twice water-bath washing, then enters in the baking oven with coiler device dry at 50 ~ 80 DEG C, finally by winder winding around obtaining white, softness, glossiness fiber.
Preferably, described step 4) in coagulating bath be mixed aqueous solution or 3 ~ 15wt% aqueous hydrochloric acid solution of the aqueous acetic acid of 8 ~ 25wt%, 3 ~ 25wt% sulfuric acid and 3 ~ 25wt% sodium sulphate; Coagulation bath temperature controls at 10 ~ 30 DEG C.
Spinning solution is placed certain hour by the present invention at low temperatures, carries out pregel process.Because intermolecular distance under low temperature reduces, cellulose macromolecule is easily assembled, moieties chain entanglement, when solution temperature rises to spinning temperature, still there is certain Gel baits, there is lightly crosslinked network structure, spinning solution viscosity rises 5% ~ 15%, but still has mobility; Extruded by spinning head by this solution, effectively can reduce the swollen that strand produces in water-washing process, improve spinnability and the spinning speed of spinning solution, obtained fibre structure is fine and close, good mechanical performance.The method is simple to operate, and cost is low, environmentally friendly, is applicable to suitability for industrialized production.The present invention effectively can reduce the swollen that strand produces in water-washing process, and improve spinnability and the spinning speed of spinning solution, the cellulosic fibrous structure obtained is fine and close, and good mechanical performance, has higher TENSILE STRENGTH.
Compared with prior art, the advantage that has of the present invention is as follows:
(1) the low degree of substitution hydroxyethyl cellulose solution of the high solids content that the present invention relates to, by carrying out etherification modified to cellulose, the solvability of the etherification product obtained in alkali solvent especially alkali/urea solvent significantly improves, prepared solution has higher solid content, better stability and more excellent strainability, and the gel thermal reversion that solution is formed, have a extensive future.
(2) the present invention adopts pre-gel to make the hydroxyethylcellulose spinning solution of high solids content form slight cross-linked structure, reaches certain Gel baits in advance, but still has mobility.The method effectively can improve the spinnability of spinning solution, reduces the run-inflation effect that strand produces in water-washing process, effectively improves spinning speed, and the fibre structure obtained after spinning is fine and close, good mechanical performance.And the method is simple to operate, cost is low, environmentally friendly, is applicable to suitability for industrialized production.
(3) regenerated celulose fibre that obtains of the present invention, cross section is circular, has bigger difference with existing viscose.Its fibre structure is finer and close, and degree of crystallinity is higher, and mechanical property is more excellent.
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
(1) be 8wt% NaOH by 455g component, the Homogeneous phase mixing aqueous solution of 6.5wt% thiocarbamide, 8wt% urea is chilled to-5 DEG C in advance, add that the 45g degree of polymerization is 1000, molar substitution is the hydroxyethylcellulose of 0.31, at 0 ~ 5 DEG C, stir 2h, hydroxyethylcellulose dissolves the solution forming homogeneous transparent completely.
(2) filter gained hydroxyethyl cellulose solution, utilize supercentrifuge to the centrifugal 10min of filtrate under room temperature, slough bubble.
(3) centrifugal rear spinning solution is left standstill at 0 DEG C 10min and carry out pregel process, be then warming up to 25 DEG C, spinning solution viscosity rises 5%, and solution reaches certain Gel baits, produces lightly crosslinked structure, but still has mobility; Spinning solution is transferred to vacuum defoamation 60min in spinning machine.
(4) nitrogen is utilized to be forced into 0.1Mpa to spinning solution, making it by metering pump of spinning machine, gooseneck and 24 apertures, hole is the spinneret cap of 0.1mm, enter in the long first coagulating tank for 100cm and be solidified into strand, and by the first drawing roller of adjustable speed, preliminary draft is carried out to strand at first coagulating tank tail end, the mixed aqueous solution that the coagulating bath used is 12wt% sulfuric acid and 10wt% sodium sulphate, coagulation bath temperature is 20 DEG C, and the preliminary draft ratio of the first drawing roller to strand is 80%.
(5) after drawing-off, strand, through twice water-bath washing, then enters in the baking oven with coiler device and carry out drying at 70 DEG C, finally by winder winding around obtaining regenerated celulose fibre.
This fiber is white, soft glossy.According to ASTM D2256-80, the intensity being recorded regenerated celulose fibre of the present invention by electronics strength tester is 2.49cN/dtex, and the fibre strength obtained after solidification drawing-off without the spinning solution of pregel process under the same terms is 1.71cN/dtex.
Embodiment 2
(1) be 6wt% NaOH by 450g component, the Homogeneous phase mixing aqueous solution of 4wt% thiocarbamide, 1wt% urea is chilled to-10 DEG C in advance, add that the 50g degree of polymerization is 1200, molar substitution is the hydroxyethylcellulose of 0.49, at-5 ~ 0 DEG C, stir 2h, hydroxyethylcellulose dissolves the solution forming homogeneous transparent completely.
(2) filter gained hydroxyethyl cellulose solution, utilize supercentrifuge to the centrifugal 30min of filtrate under room temperature, slough bubble.
(3) centrifugal rear spinning solution is left standstill at 0 DEG C 30min and carry out pregel process, be then warming up to 25 DEG C, spinning solution viscosity rises 7%, and solution reaches certain Gel baits, produces lightly crosslinked structure, but still has mobility; Spinning solution is transferred to vacuum defoamation 90min in spinning machine.
(4) nitrogen is utilized to be forced into 0.1Mpa to spinning solution, making it by metering pump of spinning machine, gooseneck and 24 apertures, hole is the spinneret cap of 0.08mm, enter in the long first coagulating tank for 100cm and be solidified into strand, and by the first drawing roller of adjustable speed, preliminary draft is carried out to strand at first coagulating tank tail end, the mixed aqueous solution that the coagulating bath used is 15wt% sulfuric acid and 10wt% sodium sulphate, coagulation bath temperature is 25 DEG C, and the preliminary draft ratio of the first drawing roller to strand is 110%.
(5) after drawing-off, strand, through twice water-bath washing, then enters in the baking oven with coiler device and carry out drying at 60 DEG C, finally by winder winding around obtaining regenerated celulose fibre.
This fiber is white, soft glossy.According to ASTM D2256-80, the intensity being recorded regenerated celulose fibre of the present invention by electronics strength tester is 2.32cN/dtex, and the fibre strength obtained after solidification drawing-off without the spinning solution of pregel process under the same terms is 1.57cN/dtex.
Embodiment 3
(1) be 9wt% NaOH by 440g component, the Homogeneous phase mixing aqueous solution of 1wt% thiocarbamide, 4wt% urea is chilled to 0 DEG C in advance, add that the 60g degree of polymerization is 800, molar substitution is the hydroxyethylcellulose of 0.51, at-2 ~ 0 DEG C, stir 2h, hydroxyethylcellulose dissolves the solution forming homogeneous transparent completely.
(2) filter gained hydroxyethyl cellulose solution, utilize supercentrifuge to the centrifugal 60min of filtrate under room temperature, slough bubble.
(3) centrifugal rear spinning solution is left standstill at-5 DEG C 10min and carry out pregel process, be then warming up to 25 DEG C, spinning solution viscosity rises 8%, and solution reaches certain Gel baits, produces lightly crosslinked structure, but still has mobility; Spinning solution is transferred to vacuum defoamation 100min in spinning machine.
(4) nitrogen is utilized to be forced into 0.1Mpa to spinning solution, making it by metering pump of spinning machine, gooseneck and 30 apertures, hole is the spinneret cap of 0.1mm, enter in the long first coagulating tank for 100cm and be solidified into strand, and by the first drawing roller of adjustable speed, preliminary draft is carried out to strand at first coagulating tank tail end, the coagulating bath used is 15wt% acetum, coagulation bath temperature is 10 DEG C, and the preliminary draft ratio of the first drawing roller to strand is 90%.
(5) after drawing-off, strand, through twice water-bath washing, then enters in the baking oven with coiler device and carry out drying at 80 DEG C, finally by winder winding around obtaining regenerated celulose fibre.
This fiber is white, soft glossy.According to ASTM D2256-80, the intensity being recorded regenerated celulose fibre of the present invention by electronics strength tester is 2.18cN/dtex, and the fibre strength obtained after solidification drawing-off without the spinning solution of pregel process under the same terms is 1.26cN/dtex.
Embodiment 4
(1) be 9wt% NaOH by 460g component, the Homogeneous phase mixing aqueous solution of 4wt% thiocarbamide, 8wt% urea is chilled to 0 DEG C in advance, add that the 40g degree of polymerization is 1400, molar substitution is the hydroxyethylcellulose of 0.34, at-5 ~ 0 DEG C, stir 2h, hydroxyethylcellulose dissolves the solution forming homogeneous transparent completely.
(2) filter gained hydroxyethyl cellulose solution, utilize supercentrifuge to the centrifugal 20min of filtrate under room temperature, slough bubble.
(3) centrifugal rear spinning solution is left standstill at-5 DEG C 30min and carry out pregel process, be then warming up to 25 DEG C, spinning solution viscosity rises 15%, and solution reaches certain Gel baits, produces lightly crosslinked structure, but still has mobility; Spinning solution is transferred to vacuum defoamation 120min in spinning machine.
(4) nitrogen is utilized to be forced into 0.1Mpa to spinning solution, making it by metering pump of spinning machine, gooseneck and 12 apertures, hole is the spinneret cap of 0.1mm, enter in the long first coagulating tank for 100cm and be solidified into strand, and by the first drawing roller of adjustable speed, preliminary draft is carried out to strand at first coagulating tank tail end, the coagulating bath used is 15wt% hydrochloric acid solution, coagulation bath temperature is 15 DEG C, and the preliminary draft ratio of the first drawing roller to strand is 90%.
(5) after drawing-off, strand, through twice water-bath washing, then enters in the baking oven with coiler device and carry out drying at 80 DEG C, finally by winder winding around obtaining regenerated celulose fibre.
This fiber is white, soft glossy.According to ASTM D2256-80, the intensity being recorded regenerated celulose fibre of the present invention by electronics strength tester is 2.58cN/dtex, and the fibre strength obtained after solidification drawing-off without the spinning solution of pregel process under the same terms is 1.77cN/dtex.
Embodiment 5
(1) be 9wt% NaOH by 470g component, the Homogeneous phase mixing aqueous solution of 4wt% thiocarbamide, 8wt% urea is chilled to 0 DEG C in advance, add that the 30g degree of polymerization is 600, molar substitution is the hydroxyethylcellulose of 0.41, at-5 ~ 0 DEG C, stir 2h, hydroxyethylcellulose dissolves the solution forming homogeneous transparent completely.
(2) filter gained hydroxyethyl cellulose solution, utilize supercentrifuge to the centrifugal 50min of filtrate under room temperature, slough bubble.
(3) centrifugal rear spinning solution is left standstill at 0 DEG C 20min and carry out pregel process, be then warming up to 25 DEG C, spinning solution viscosity rises 6%, and solution reaches certain Gel baits, produces lightly crosslinked structure, but still has mobility; Spinning solution is transferred to vacuum defoamation 200min in spinning machine.
(4) nitrogen is utilized to be forced into 0.1Mpa to spinning solution, making it by metering pump of spinning machine, gooseneck and 24 apertures, hole is the spinneret cap of 0.1mm, enter in the long first coagulating tank for 100cm and be solidified into strand, and by the first drawing roller of adjustable speed, preliminary draft is carried out to strand at first coagulating tank tail end, the coagulating bath used is 15wt% hydrochloric acid solution, coagulation bath temperature is 20 DEG C, and the preliminary draft ratio of the first drawing roller to strand is 90%.
(5) after drawing-off, strand, through twice water-bath washing, then enters in the baking oven with coiler device and carry out drying at 80 DEG C, finally by winder winding around obtaining regenerated celulose fibre.
This fiber is white, soft glossy.According to ASTM D2256-80, the intensity being recorded regenerated celulose fibre of the present invention by electronics strength tester is 1.88cN/dtex, and the fibre strength obtained after solidification drawing-off without the spinning solution of pregel process under the same terms is 1.16cN/dtex.
Claims (2)
1. adopt pre-gel to prepare a method for hydroxyethyl cellulose, it is characterized in that, concrete steps are as follows:
1): preparation contains 4 ~ 12wt% NaOH by weight percentage, 1 ~ 10wt% thiocarbamide, the aqueous solution (i.e. alkali/urea solvent) of 1 ~ 15wt% urea, and is chilled to-15 ~ 10 DEG C in advance; Be 300 ~ 2000 by the degree of polymerization, molar substitution is that the alkali/urea solvent of hydroxyethylcellulose and the precooling of 0.15 ~ 0.85 to mix in mass ratio at 5: 95 ~ 20: 80, stir at-10 ~ 20 DEG C, until dissolve the hydroxyethyl cellulose solution forming homogeneous transparent completely;
2): the filtration step 1) hydroxyethyl cellulose solution of gained, at room temperature utilizes supercentrifuge to the centrifugal 10-60min of filtrate, sloughs bubble;
3) the centrifugal rear spinning solution: by step 2) obtained leaves standstill 10 ~ 30min and carries out pregel process at-5 ~ 0 DEG C, is then warming up to 25 DEG C; Spinning solution is transferred to vacuum defoamation 30 ~ 200min in spinning machine;
4): pressurize to spinning solution with nitrogen, make it, by metering pump of spinning machine, gooseneck and spinneret cap, to enter in coagulating bath and be solidified into strand;
5): the strand after solidification drawing-off, through twice water-bath washing, then enters in the baking oven with coiler device dry at 50 ~ 80 DEG C, finally by winder winding around obtaining white, softness, glossiness fiber.
2. a kind of method adopting pre-gel to prepare hydroxyethyl cellulose according to claim 1, it is characterized in that, described step 4) in coagulating bath be mixed aqueous solution or 3 ~ 15wt% aqueous hydrochloric acid solution of the aqueous acetic acid of 8 ~ 25wt%, 3 ~ 25wt% sulfuric acid and 3 ~ 25wt% sodium sulphate; Coagulation bath temperature controls at 10 ~ 30 DEG C.
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| CN105350313B (en) * | 2015-12-24 | 2017-10-03 | 西南大学 | Anti- prodding and itching feeling method for sorting of the sodium hydroxide/urea aqueous systems to ramie fabric |
| CN105926063B (en) * | 2016-05-23 | 2018-08-21 | 东华大学 | A kind of macroscopic fibres and preparation method thereof aligned based on bacteria cellulose nanofiber |
| CN109610024B (en) * | 2018-11-20 | 2020-02-18 | 华南理工大学 | Cellulose-molybdenum disulfide aerogel composite fiber and preparation method and application thereof |
| CN114605664B (en) * | 2020-12-17 | 2023-07-04 | 赣南师范大学 | Hydrogel and preparation method thereof |
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| US6123887A (en) * | 1994-01-26 | 2000-09-26 | Michelin Recherche Et Technique | Process for preparing regenerated cellulose article |
| CN1482159A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | Solvent composite and preparation method and use thereof |
| CN101164676A (en) * | 2007-08-22 | 2008-04-23 | 武汉大学 | Method for preparing cellulose gel film |
| CN101215725A (en) * | 2007-12-27 | 2008-07-09 | 天津工业大学 | Cellulose solvent and method for preparing spinning fluid from the same |
| CN101381479A (en) * | 2007-09-06 | 2009-03-11 | 刘兆峰 | Method for synthesizing alkaline soluble glycol cellulose for spinning/membrane manufacturing |
| CN101429682A (en) * | 2008-11-28 | 2009-05-13 | 东华大学 | Method for producing regenerated cellulose fiber by dual-bath coagulation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6123887A (en) * | 1994-01-26 | 2000-09-26 | Michelin Recherche Et Technique | Process for preparing regenerated cellulose article |
| CN1482159A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | Solvent composite and preparation method and use thereof |
| CN101164676A (en) * | 2007-08-22 | 2008-04-23 | 武汉大学 | Method for preparing cellulose gel film |
| CN101381479A (en) * | 2007-09-06 | 2009-03-11 | 刘兆峰 | Method for synthesizing alkaline soluble glycol cellulose for spinning/membrane manufacturing |
| CN101215725A (en) * | 2007-12-27 | 2008-07-09 | 天津工业大学 | Cellulose solvent and method for preparing spinning fluid from the same |
| CN101429682A (en) * | 2008-11-28 | 2009-05-13 | 东华大学 | Method for producing regenerated cellulose fiber by dual-bath coagulation |
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