CN101240454A - Solvent method for preparing cellulose mixing fibre and application thereof - Google Patents
Solvent method for preparing cellulose mixing fibre and application thereof Download PDFInfo
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- CN101240454A CN101240454A CNA2008100346803A CN200810034680A CN101240454A CN 101240454 A CN101240454 A CN 101240454A CN A2008100346803 A CNA2008100346803 A CN A2008100346803A CN 200810034680 A CN200810034680 A CN 200810034680A CN 101240454 A CN101240454 A CN 101240454A
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Abstract
The invention relates to a method of cellulose blend fiber solvent and an application of the same, the method is: 1) evenly mixing the cellulose, the polyvinyl polymer and the ionic liquid, dissolved 1 to 80 hours in the 25-160[deg.] C, to form a uniform stability spinning dope of 3-40% of total solid content, the quality mixing ratio of the cellulose, the polyvinyl polymer and the ionic liquid is 99.5:0.5 to 60:40; 2) filtering and deaerating for 3-120 hours, the dope thread gushing from spinneret hole by coagulation bath is solidified to form primary cellulose; 3) drawing, washing, bleaching, finish application and drying to obtain the cellulose blend fiber. The invention prepares a blend cellulose fiber by ionic liquid, the method is high efficiency, green and environmental protection, the prepared fiber has satisfactory mechanical behaviors, and that underwear and handkerchief can be made by blend fiber, the spinning may be pure or blended into all kinds of clothing material, and also into the membrane for artificial organs, water processor, etc.
Description
Technical field
The invention belongs to the blended fiber field, particularly relate to the solvent method for preparing and the application thereof of cellulose blending fibre.
Background technology
Not only storage level is big for cellulose in all substances of occurring in nature, and huge amount of recovery is arranged.Have only the cellulose of minute quantity to be made into fiber at present.Be used to make the cellulose amount of fiber and film, 4% of the cellulose output of producing no more than world industry.Along with the mankind to the deepening continuously and the worsening shortages of resources such as oil, coal, natural gas of nature understanding, cellulosic utilization will enlarge gradually.
Cellulose fibre is because raw cellulose can be changed into steam and carbon dioxide by biological decomposition or safe combustion, and the destruction environmental problem that is caused by discarded object is few.Therefore it is very necessary developing cellulose fibre.
The viscose that suitability for industrialized production makes is as a kind of regenerated celulose fibre, comfortable and easy to wear because of it, good wearability is favored by consumers in general to skin is non-stimulated etc., but unsatisfactory one side is arranged also, for example be easy to generate fold, not well-pressed etc. in the wearing process, energy consumption and water consumption are very big in process of production simultaneously, and have serious " three wastes " problem.Therefore adopt novel dissolvent that cellulose is directly dissolved, to improve some natural defects of viscose and to avoid environmental pollution just to become the task of top priority.
Ionic liquid exists with liquid state in the scope of broad as a kind of novel cellulose solvent, and has good heat endurance, and nontoxic, non-volatility helps environmental protection and operator ' s health.Can pass through to select suitable yin, yang ion population, and change its physicochemical properties to a certain extent, be the good solvent of many organic matters, inorganic matter and macromolecular material.Many ionic liquids are very big to cellulosic solubility, some in addition reach 25%; Be no more than 10% and adopt cellulose yellow method to produce the cellulose concentration that viscose adopted, therefore adopt the ionic liquid produce cellulose fibers obviously to enhance productivity.
Make the semi-products of regenerated celulose fibre---the raw material source of pulp is quite extensive, from the needlebush of high-quality and cotton linter to leaf wood, fast growing wood, bamboo and various herbaceous plant (as bagasse, reed, jute bar etc.).Wherein, bamboo wood is originated as a kind of cellulose, and its growth cycle is short, the felling of can becoming a useful person in general 3～5 years, and the output height, low to the growing environment requirement, make cost lower.And not influencing the ecological balance, therefore is following splendid textile raw material.And the cross section of bamboo fibre has been covered with irregular space, is a kind of super doughnut, can have splendid ventilative, saturating wet capillary effect at transient absorption and transpiring moisture; Therefore, bamboo fibre have that moisture pick-up properties is good, gas permeability is strong, soft, fabric fall good, colouring is easy, bright in colour, series of advantages such as dress is nice and cool.Simultaneously, bamboo fibre also has bacteriostasis property, and the time does not reduce because of dress and washing or disappear.Consider that simultaneously polyethylene base class high polymer and copolymer thereof have some unique character, by with cellulose blending, be dissolved in the cosolvent jointly, make blended fiber and except that having the original characteristic of bamboo cellulose, have some novel characteristics again, as good light resistance, weather fastness, good solvent resistance, chemical stability etc., it is significant therefore to develop cellulose/polyethylene base class blended fiber.
List of references:
1. United States Patent (USP) 20030157351 discloses a kind of cellulose and has dissolved and method for processing in ionic liquid.
2. Chinese patent ZL01126469.1 discloses and has adopted the high wet modulus method to produce the method and the purposes of viscose.
3. Chinese patent CN1596282A discloses the method that adopts ion liquid dissolving and processing of cellulose.
4. the manufacture method of Chinese patent CN03129531.2 solvent method bamboo cellulose fibre.
Summary of the invention
The purpose of this invention is to provide a kind of solvent method for preparing and application thereof of cellulose blending fibre, by being that cosolvent prepares cellulose blending fibre with the ionic liquid, solve the problem of environmental pollution that present employing viscose process production of cellulose blended fiber is brought, satisfied the production demand.
The solvent method for preparing of cellulose blending fibre of the present invention comprises the following steps:
(1) with comminuted fibres element, polyethylene base class high polymer, under mechanical agitation, put in the ionic liquid, mix, under 25～160 ℃ of temperature, dissolved 1～80 hour, the formation total solid content is 3～40% stable homogeneous spinning solution, microwave radiation, apply the dissolving that certain vacuum etc. helps pulp, the mass mixing ratio of its cellulose, polyethylene base class high polymer is 99.5: 0.5～60: 40;
(2) after filtration, deaeration is after 3～120 hours, adopt wet spinning, dry-jet wet spinning or melt and spray wet spinning and carry out spinning, be solidified into the as-spun fibre element from the stoste thread of spinneret orifice ejection through coagulating bath, wherein coagulating bath is the ionic liquid aqueous solution of water or 0～60%, coagulation bath temperature is 0～90 ℃, and spinning speed is 5～150 meters/minute;
(3) drawn, washing, bleaching again, thoroughly to remove the various impurity in the fiber, again through oiling, operation such as drying, obtain cellulose blending fibre.
Described comminuted fibres element is to adopt the degree of polymerization 400～2500, the native cellulose of alpha-cellulose content 90%～100% (can use bamboo pulp, wood pulps, the cotton pulp dregs of rice, reed pulp, bagasse pulp, waste of flax slurry etc. or its to mix uses) passes through mechanical crushing, and pulp passes through activation processing or do not process.
Described polyethylene base class high polymer is homopolymers or multiple copolymer (as PMA, polymethyl methacrylate, polyvinyl acetate, polyacrylonitrile, polymaleic anhydride, polyvinyl alcohol etc.), and molecular weight is 30000～300000.
Described ionic liquid is made up of CATION and anion, and its CATION is that substituting group is hydrogen, C
1～C
6Alkyl, vinyl, propenyl, cyclobutenyl, ethoxy, hydroxypropyl, alkoxyl in one or more quaternary ammonium alkyl ion, alkyl quaternary phosphonium ion, alkyl imidazole ion, alkyl pyridine ion; Its anion is halide ion, BF
4 -, PF
4 -, SCN
-, CN
-, OCN
-, CNO
-, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, (CF
3SO
2)
2Cl
-In one or more.
Described stretching is to stretch through one or more combinations such as anxiety stretching, jet stretch, plasticization drawing, air bath after-drawing or retractions, and total drawing ratio is 1～200%.
Described blended fiber is blend staple fibre or long filament, and fibre strength is 1～5cN/dtex.
The application of cellulose blending fibre of the present invention: the spinning solution of being made up of cellulose, polyethylene kind high polymer can be spun into hollow-fibre membrane, be used for the film of using of manufacture of intraocular internal organs and water purifier.
Beneficial effect of the present invention:
(1) the preparation-obtained cellulose blending fibre of the present invention has excellent mechanical intensity, the conventional viscose that its mechanical performance is produced apparently higher than corresponding employing viscose process;
(2) adopt ionic liquid to prepare the blended fiber cellulose fiber, avoided the tediously long and complicated production process of viscose process, production process obviously shortens, process energy consumption and operating cost are low, and ionic liquid is as a kind of novel cellulose solvent, nontoxic, non-volatility, help environmental protection and operator ' s health, the ion liquid aqueous solution also can be used as coagulating bath, and ionic liquid is easy to reclaim, and meets the requirement of green production;
(3) blended fiber can be made underwear, handkerchief, can be made into various garment materials through blending or pure spinning, and also can be made into film and is used for many-sided purposes such as artificial organ, hydrotreater.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
9.95 parts of bamboo celluloses pulverizing, 0.05 part of polyethylene base class high polymer are mixed, mix, stirred 24 hours down, obtain spinning solution at 45 ℃ with 100 parts of [BMIM] Cl (1-butyl-3-methylimidazole hydrochloride) ionic liquid.
Spinning solution after filtration, deaeration is after 30 hours, enters into through the porous spinnerets to contain 5% ion liquid coagulating bath, and coagulation bath temperature is 25 ℃.Behind 10% plasticization drawing, again through wash, bleach, oil, dry supervisor, spinning speed is 5 meters/minute, obtains the fiber that intensity is 3.2cN/dtex.
Embodiment 2
9.5 parts of gossypins pulverizing, 0.5 part of polyethylene base class high polymer are mixed, with 200 parts of [BMIM] Cl/[BMIM] BF
4(1-butyl-3-methylimidazole hydrochloride/1-butyl-3-methyl imidazolium tetrafluoroborate, proportioning is 10: 0.1～4: 6) ionic liquid mixture mixes, and stirs 24 hours down at 100 ℃, obtains spinning solution.
Spinning solution after filtration, deaeration is after 120 hours, enters into the water coagulating bath through the porous spinnerets, and coagulation bath temperature is 15 ℃.Behind 1% plasticization drawing, again through wash, bleach, oil, dry supervisor, spinning speed is 20 meters/minute, obtains the fiber that intensity is 3.5cN/dtex.
Embodiment 3
9 parts of lignoses pulverizing, 1 part of polyethylene base class high polymer are mixed, mix, stirred 80 hours down, obtain spinning solution at 60 ℃ with 40 parts of [AMIM] Br (bromination 1-allyl-3-methylimidazole salt) ionic liquid.
Spinning solution after filtration, deaeration is after 80 hours, enters into through the porous spinnerets to contain 25% ion liquid coagulating bath, and coagulation bath temperature is 55 ℃.Behind 8% plasticization drawing, again through wash, bleach, oil, dry supervisor, spinning speed is 30 meters/minute, obtains the fiber that intensity is 4.0cN/dtex.
Embodiment 4
9 parts of bamboo celluloses pulverizing, 1 part of polyethylene kind based high-polymer are mixed, mix, stirred 50 hours down, obtain spinning solution at 150 ℃ with 90 parts of [AMIM] Cl (1-allyl-3-methylimidazole hydrochloride) ionic liquid.
Spinning solution after filtration, deaeration is after 60 hours, enters into through the porous spinnerets to contain 45% ion liquid coagulating bath, and coagulation bath temperature is 85 ℃.Behind 5% plasticization drawing, again through wash, bleach, oil, dry supervisor, spinning speed is 40 meters/minute, obtains the fiber that intensity is 2.3cN/dtex.
Claims (8)
1. the solvent method for preparing of a cellulose blending fibre comprises the following steps:
(1) with comminuted fibres element, polyethylene base class high polymer, under mechanical agitation, mix with ionic liquid, under 25～160 ℃ of temperature, dissolved 1～80 hour, the formation total solid content is 3～40% stable homogeneous spinning solution, and the mass mixing ratio of its cellulose, polyethylene base class high polymer is 99.5: 0.5～60: 40;
(2) after filtration, deaeration is after 3～120 hours, solidify through coagulating bath from the stoste thread of spinneret orifice ejection to be spun to the as-spun fibre element;
(3) drawn, washing, bleaching again, again through oiling, drying process, cellulose blending fibre.
2. the solvent method for preparing of cellulose blending fibre according to claim 1 is characterized in that: described comminuted fibres element is to adopt the degree of polymerization 400～2500, and the native cellulose of alpha-cellulose content 90%～100% is through mechanical crushing.
3. the solvent method for preparing of cellulose blending fibre according to claim 1, it is characterized in that: described polyethylene base class high polymer is homopolymers or multiple copolymer, and molecular weight is 30000～300000.
4. the solvent method for preparing of cellulose blending fibre according to claim 3, it is characterized in that: described homopolymers or multiple copolymer are PMA, polymethyl methacrylate, polyvinyl acetate, polyacrylonitrile, polymaleic anhydride or polyvinyl alcohol.
5. the solvent method for preparing of cellulose blending fibre according to claim 1, it is characterized in that: described ionic liquid is made up of CATION and anion, and its CATION is that substituting group is hydrogen, C
1～C
6Alkyl, vinyl, propenyl, cyclobutenyl, ethoxy, hydroxypropyl, alkoxyl in one or more quaternary ammonium alkyl ion, alkyl quaternary phosphonium ion, alkyl imidazole ion, alkyl pyridine ion;
Its anion is halide ion, BF
4 -, PF
4 -, SCN
-, CN
-, OCN
-, CNO
-, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, (CF
3SO
2)
2Cl
-In one or more.
6. the solvent method for preparing of cellulose blending fibre according to claim 1, it is characterized in that: the spinning in the described step (2) is wet spinning, dry-jet wet spinning or melts and sprays wet spinning and carry out spinning, wherein coagulating bath is the ionic liquid aqueous solution of water or 0～60%, coagulation bath temperature is 0～90 ℃, and spinning speed is 5～150 meters/minute.
7. the solvent method for preparing of cellulose blending fibre according to claim 1, it is characterized in that: described stretching is that the one or more combination in anxiety stretching, jet stretch, plasticization drawing, air bath after-drawing or retraction stretches, and total drawing ratio is 1～200%.
8. the solvent method for preparing of cellulose blending fibre according to claim 1, it is characterized in that: described blended fiber is blend staple fibre or long filament, and fibre strength is 1～5cN/dtex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100346803A CN101240454A (en) | 2008-03-14 | 2008-03-14 | Solvent method for preparing cellulose mixing fibre and application thereof |
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|---|---|---|---|
| CNA2008100346803A CN101240454A (en) | 2008-03-14 | 2008-03-14 | Solvent method for preparing cellulose mixing fibre and application thereof |
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| CN101240454A true CN101240454A (en) | 2008-08-13 |
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| CNA2008100346803A Pending CN101240454A (en) | 2008-03-14 | 2008-03-14 | Solvent method for preparing cellulose mixing fibre and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2199319A1 (en) * | 2008-12-19 | 2010-06-23 | Gambro Lundia AB | Virus filter |
| CN102851774A (en) * | 2012-06-06 | 2013-01-02 | 武汉纺织大学 | Method for improving viscose fiber strength |
| CN102978737A (en) * | 2012-11-28 | 2013-03-20 | 东华大学 | Method for preparing blend fibers of celluloses and high-fluidity elastomers |
| CN103184582A (en) * | 2013-03-18 | 2013-07-03 | 山东海龙股份有限公司 | Preparation method of PVA composite high-strength high-modulus cellulose fiber |
| CN104264278A (en) * | 2014-09-25 | 2015-01-07 | 哈尔滨欧替药业有限公司 | Viscose with moisture-absorbing, crimpness and moisture regaining performances for suppository carrier |
| CN107090607A (en) * | 2017-05-26 | 2017-08-25 | 恒天海龙（潍坊）新材料有限责任公司 | A kind of preparation method of PVA/ cellulose composite fibers |
| CN108048950A (en) * | 2017-12-11 | 2018-05-18 | 苏州欧博时装有限公司 | A kind of garment material with moisture-keeping function |
| CN112981642A (en) * | 2021-02-06 | 2021-06-18 | 福建宏远集团有限公司 | Preparation method of bamboo/cotton blended fiber yarn |
-
2008
- 2008-03-14 CN CNA2008100346803A patent/CN101240454A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2199319A1 (en) * | 2008-12-19 | 2010-06-23 | Gambro Lundia AB | Virus filter |
| CN102851774A (en) * | 2012-06-06 | 2013-01-02 | 武汉纺织大学 | Method for improving viscose fiber strength |
| CN102978737A (en) * | 2012-11-28 | 2013-03-20 | 东华大学 | Method for preparing blend fibers of celluloses and high-fluidity elastomers |
| CN102978737B (en) * | 2012-11-28 | 2014-10-15 | 东华大学 | Method for preparing blend fibers of celluloses and high-fluidity elastomers |
| CN103184582A (en) * | 2013-03-18 | 2013-07-03 | 山东海龙股份有限公司 | Preparation method of PVA composite high-strength high-modulus cellulose fiber |
| CN104264278A (en) * | 2014-09-25 | 2015-01-07 | 哈尔滨欧替药业有限公司 | Viscose with moisture-absorbing, crimpness and moisture regaining performances for suppository carrier |
| CN104264278B (en) * | 2014-09-25 | 2016-04-20 | 哈尔滨欧替药业有限公司 | A kind of have the viscose of the curling moisture regain performance of moisture absorption for suppository carrier |
| CN107090607A (en) * | 2017-05-26 | 2017-08-25 | 恒天海龙（潍坊）新材料有限责任公司 | A kind of preparation method of PVA/ cellulose composite fibers |
| CN107090607B (en) * | 2017-05-26 | 2020-12-01 | 恒天海龙（潍坊）新材料有限责任公司 | Preparation method of PVA/cellulose composite fiber |
| CN108048950A (en) * | 2017-12-11 | 2018-05-18 | 苏州欧博时装有限公司 | A kind of garment material with moisture-keeping function |
| CN112981642A (en) * | 2021-02-06 | 2021-06-18 | 福建宏远集团有限公司 | Preparation method of bamboo/cotton blended fiber yarn |
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Open date: 20080813 |