CN101545148A - Method for melt spinning of polyacrylonitrile PAN by taking imidazole ionic fluid as plasticizing agent - Google Patents
Method for melt spinning of polyacrylonitrile PAN by taking imidazole ionic fluid as plasticizing agent Download PDFInfo
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- CN101545148A CN101545148A CN200910048603A CN200910048603A CN101545148A CN 101545148 A CN101545148 A CN 101545148A CN 200910048603 A CN200910048603 A CN 200910048603A CN 200910048603 A CN200910048603 A CN 200910048603A CN 101545148 A CN101545148 A CN 101545148A
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Abstract
The invention relates to a method for melt spinning of polyacrylonitrile PAN by taking imidazole ionic fluid as a plasticizing agent. The method comprises the following steps: (1) evenly mixing polyacrylonitrile powder which is dried to an anhydrous state with ionic fluid; (2) adding the mixture into a hopper of a double-screw spinning machine, regulating the rotating speed of screws of between 40 and 120 revolutions/minute, setting the spinning temperature of between 170 and 220 DEG C, and carrying out melt spinning; directly carrying out dry heat stretching on filament which is spun by a spinneret plate without water bath with stretching temperature of between 80 and 180 DEG C and stretching times of between 1 and 8 times; and (3) washing the stretched fiber with water, and carrying out heat setting and winding on the fiber to obtain the polyacrylonitrile fiber. The method has low cost, reduces environmental pollution, and is applicable to industrial production; and the produced fiber can be subjected to super stretching, has a section without a cavity structure, and improves the strength.
Description
Technical field
The invention belongs to polyacrylonitrile melt spinning field, particularly relating to a kind of imidazole type ion liquid is the polyacrylonitrile (PAN) melt spinning method of plasticizer.
Background technology
A main character of polyacrylonitrile resin is exactly its high-melting-point (317 ℃), when heating also not fusion just decompose, therefore can only produce polyacrylonitrile fibre with solvent spinning.Industrialized wet spinning and dry spinning all will be used a large amount of poisonous or mordant chemical solvents, and must carry out the recovery and the purification of solvent in process of production, fiber washing and dry and " three wastes " processing.If can realize MELT SPINNING OF ACRYLIC FIBER, not only save solvent consumption, and saved solvent recovery process and equipment and water-washing process, can reduce production costs greatly, eliminate because the serious problem of environmental pollution that uses solvent to cause.
Nineteen fifty-two Coxe has at first reported and increased the temperature that a spot of water just can be reduced to its fusing point the melt-spun requirement in the polyacrylonitrile analog copolymer.His invention highly significant because it for MELT SPINNING OF ACRYLIC FIBER provide a kind of may.Hereafter, particularly recent two decades comes, abroad the melt-spun to polyacrylonitrile fibre has carried out a large amount of research, as cyanamide company, E.I.Du Pont Company, the BP Chemical company of the U.S., and the mitsubishi rayon of Japan, Yi Kesi synthetic fibre company, company of Asahi Chemical Industry etc.
The PAN melt spinning is summarized following two kinds of approach: 1. plasticising melt spinning, 2. non-plasticizing melt spinning.Wherein the plasticising melt spinning mainly comprises the following aspects: 1. solvent plasticising: use DMSO, PC (propylenecarbonate) etc.The PAN powder can fusion, extrusion molding continuously under PC plasticising.As: being the PAN of 50:50 and PC mixture to mass ratio shows that in the rheological Properties of 180 ℃ and 240 ℃ its blend fluid is the shear force thinning fluid, and its viscosity is less than the PE of the extrusion molding level of routine; 2. non-with base polymer plasticising: PEG is arranged according to the literature, and Asahi Chemical Co.Ltd prepares polyacrylonitrile fibre with polyacrylonitrile and PEG blend melt spinning, and the intensity of fiber can reach 4.68cN/dtex; 3. the polyacrylonitrile plasticising of low molecular mass: mitsubishi rayon once had report, copolymer with 91 parts acrylonitrile and methyl acrylate (the copolymerization proportioning is 85: 15 mass ratioes), reduced viscosity is 0.68, with 9 parts the another kind of acrylonitrile and the copolymer of methyl acrylate (the copolymerization proportioning is 85: 15 mass ratioes), molecular mass is 4800, mixing the back melt extrudes at 215 ℃, speed with 1200m/min is spun into silk, and in boiling water, be pulled to 4 times, the line density of gained fiber is 1.17dtex, brute force is 5.26cN/dtex, and extension at break is 12.3%.Can also suitably reduce simultaneously the AN unit content of the low molecular mass polyacrylonitrile that plasticising uses, also fusible spinning reaches necessarily required fiber; 4. water plasticising: this method is studied at most.Polyacrylonitrile and quantitative water become molten mass under certain pressure and temperature, be pressed into filament spinning component with extruder, spray into path and stretching.Be full of water vapour in the path, to prevent in the melt sharply evaporation and make the strand foaming of moisture.The distinguishing feature of this method is only to use cheap and nontoxic water, can save solvent recovery process and equipment, to the pollution of environment seldom.That water plasticising molten spinning polyacrylonitrile fibre can be used for is knitting, fur, woollen blanket, knitting wool etc.Bibliographical information is arranged, the polyacrylonitrile fibre of water plasticising melt spinning spinning can be made carbon fibre precursor, molecular mass is 100,000 to 250,000, intensity reaches 3.6cN/dtex, Young's modulus is 97cN/dtex, the average brute force that carbonization gets carbon fiber is 15cN/dtex, and Young's modulus is 1080～1310cN/dtex, and velocity of sound modulus is greater than 1000cN/dtex.It is the space flight grade carbon fiber that precursor constitutes that nearest U.S. Celion carbon fiber company has also developed by water plasticising molten spinning polyacrylonitrile fibre.Water plasticising melt-spun polyacrylonitrile fibre also can be made heat resistance fiber.The hydration melt is mobile bad but also there is some problems: a. in this method, and the screw rod extrusion pressure is bigger; B. the water evaporation is too fast to make the coarse or generation micropore of fiber surface in order to avoid in solidification process, and makes fibrous mechanical property degenerate, so will keep the saturated vapor of certain pressure in spinning shaft, this has just proposed certain requirement to equipment; C. but the temperature range of the melt-spun of hydration melt is narrower, the difficult control of technology.Therefore, the industrialization of still being unrealized so far.
Summary of the invention
Technical problem to be solved by this invention provides the polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid is a plasticizer, and this method cost is low, reduces environmental pollution, is suitable for suitability for industrialized production; The fiber that makes can super drawing, and the cross section do not have empty structure, and intensity is improved.
The polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid of the present invention is a plasticizer comprises:
(1) the polyacrylonitrile powder and the ionic liquid that will be dried to anhydrous state mixes, and wherein polyacrylonitrile and ion liquid mass ratio are between 1:1～1:0.25;
(2) mixture that step (1) is obtained joins in the hopper of twin-screw spinning machine, adjusts screw speed at 40-120r/min, and spinning temperature is set at 170-220 ℃, carries out melt spinning; The spun filament of spinnerets is without water-bath, but directly by xeothermic stretching, wherein draft temperature is 80-180 ℃, and draw ratio is 1-8 times;
(3) fiber after will stretching is washed, and removes ionic liquid wherein, then HEAT SETTING, reeling obtains polyacrylonitrile fibre.
Described step (1) plasticizer is a disubstituted imidazole type ionic liquid, and its version is as follows:
R wherein
1Be methyl or butyl; R
2Be methyl, ethyl, n-pro-pyl, isopropyl, butyl, normal-butyl, sec-butyl or isobutyl group; X is chlorion (Cl
-), bromide ion (Br
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6 -).
The preferred basic imidazole salts of chlorination 1-methyl-3-([EMIM] Cl), chloridization 1-methyl-3-butyl imidazole salt ([BMIM] Cl), the basic imidazole salts of bromination 1-methyl-3-([EMIM] Br), the basic tetrafluoroborate of 1-methyl-3-([EMIM] BF in the described disubstituted imidazole type ionic liquid
4), 1-methyl-3-butyl imidazole tetrafluoroborate ([BMIM] BF
4), the basic imidazoles hexafluoro of 1-methyl-3-borate ([EMIM] PF
6), 1-methyl-3-butyl imidazole hexafluoro borate ([BMIM] PF
6).
Described step (2) is through the spun PAN filament of melt spinning, and the hot-stretch temperature is controlled between 80-180 ℃, and draw ratio is between original 1-8 times.
Fiber washing temperature after described step (3) stretches is controlled between 70-90 ℃.
Beneficial effect
(1) MELT SPINNING OF ACRYLIC FIBER of the present invention, avoided the use of a large amount of poisonous or mordant chemical solvent, and do not need to carry out the recovery of solvent in process of production and purify to reach " three wastes " processing, not only save solvent consumption, and solvent recovery process and equipment and water-washing process have been saved, can reduce production costs greatly, eliminate because the serious problem of environmental pollution that uses solvent to cause;
(2), make the PAN fiber of high-strength high orientation by ion liquid plasticization;
(3) the PAN fiber that obtains by this melt spinning method is behind the eccysis ionic liquid, seldom contain empty structure, very fine and close, unlike the precursor that solvent spinning obtains, form a large amount of holes owing to double diffusion, so this also helps the raising of precursor intensity.
Description of drawings
Fig. 1-the 1st, PAN/[BMIM] Cl PAN fibre section, washing back SEM photo during for 1:1;
Fig. 1-2 is that PAN//[BMIM] Cl is PAN fibre section, a 1:1 washing back SEM photo;
Fig. 2 is PAN/[BMIM] the DMA curve of PAN fiber when Cl is 1:1;
Fig. 3-the 1st, PAN/[BMIM] Cl is PAN fibre section, 1.2:1 washing back SEM photo;
Fig. 3-the 2nd, PAN/[BMIM] Cl is PAN fibre section, 1.2:1 washing back SEM photo;
Fig. 4 is PAN/[BMIM] fiber that makes of Cl system do not wash before the graph of relation of Tg and PAN content.
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
At first with polyacrylonitrile powder and [BMIM] BF
4Ratio with mass ratio 1:1 mixes in high-speed mixer, transfers to then and carries out melt spinning on the twin-screw spinning machine; Twin-screw spinning machine screw speed is 50r/min, the feed zone temperature is made as 185 ℃, the fluxing zone temperature is 190 ℃, the melt zone temperature is 185 ℃, the spinnerets draw ratio is 1:3, the aperture is 0.5mm, with spun silk through elementary xeothermic stretching, the xeothermic stretching of secondary, wash, oil, HEAT SETTING makes the PAN fiber.The PAN fibre strength is 2.8cN/dtex, and elongation at break is 19.0%.
Embodiment 2
At first with polyacrylonitrile powder and [EMIM] BF
4Ratio with mass ratio 1.2:1 mixes in high-speed mixer, transfers to then and carries out melt spinning on the twin-screw spinning machine.Adjusting twin-screw spinning machine screw speed is 75r/min, the feed zone temperature is made as 180 ℃, the fluxing zone temperature is 185 ℃, the melt zone temperature is 180 ℃, the spinnerets draw ratio is 1:3, the aperture is 0.5mm, with spun silk through elementary xeothermic stretching, the xeothermic stretching of secondary, wash, oil, HEAT SETTING makes the PAN fiber.The PAN fibre strength is 3.6cN/dtex, and elongation at break is 10.9%.
Embodiment 3
At first the polyacrylonitrile powder is mixed in high-speed mixer with the ratio of mass ratio 1:1 with [BMIM] Cl, transfer to then and carry out melt spinning on the twin-screw spinning machine.Adjusting twin-screw spinning machine screw speed is 70r/min, the feed zone temperature is made as 185 ℃, the fluxing zone temperature is 190 ℃, the melt zone temperature is 190 ℃, and the spinnerets draw ratio is 1:3, and the aperture is 0.5mm, with spun silk through elementary xeothermic stretching, the xeothermic stretching of secondary, wash, oil, HEAT SETTING makes the PAN fiber, the PAN fibre strength is 4.0cN/dtex,, elongation at break is 16.9%.Fig. 1 is PAN fibre section, a washing back SEM photo.Fig. 2 is PAN/[BMIM] the DMA curve of PAN fiber when Cl is 1:1.
Embodiment 4
At first the polyacrylonitrile powder is mixed in high-speed mixer with the ratio of mass ratio 1.2:1 with [BMIM] Cl, transfer to then and carry out melt spinning on the twin-screw spinning machine.Adjusting twin-screw spinning machine screw speed is 60r/min, the feed zone temperature is made as 180 ℃, the fluxing zone temperature is 185 ℃, the melt zone temperature is 185 ℃, the spinnerets draw ratio is 1:3, and the aperture is 0.5mm, with spun silk through elementary xeothermic stretching, the xeothermic stretching of secondary, wash, oil, HEAT SETTING makes the PAN fiber, the PAN fibre strength is 4.0cN/dtex, and elongation at break is 14.3%.Fig. 3 is PAN fibre section, a washing back SEM photo.
Claims (6)
1. polyacrylonitrile (PAN) melt spinning method that imidazole type ion liquid is a plasticizer comprises:
(1) the polyacrylonitrile powder and the ionic liquid that will be dried to anhydrous state mixes, and wherein polyacrylonitrile and ion liquid mass ratio are 1:1～1:0.25;
(2) mixture that step (1) is obtained joins in the hopper of twin-screw spinning machine, and the adjustment screw speed is 40-120r/min, and spinning temperature is set at 170-220 ℃, carries out melt spinning; The spun filament of spinnerets is without water-bath, but directly by xeothermic stretching, wherein draft temperature is 80-180 ℃, and draw ratio is 1-8 times;
(3) fiber after will stretching is washed, then HEAT SETTING, reeling obtains the polyacrylonitrile (PAN) fiber.
2. the polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid according to claim 1 is a plasticizer is characterized in that: described step (1) plasticizer is a disubstituted imidazole type ionic liquid.
3. the polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid according to claim 2 is a plasticizer is characterized in that: described disubstituted imidazole type ionic liquid is chlorination 1-methyl-3-hexyl imidazole salts [EMIM] Cl, chloridization 1-methyl-3-butyl imidazole salt [BMIM] Cl, bromination 1-methyl-3-hexyl imidazole salts [EMIM] Br, 1-methyl-3-hexyl tetrafluoroborate [EMIM] BF
4, 1-methyl-3-butyl imidazole tetrafluoroborate [BMIM] BF
4, 1-methyl-3-hexyl imidazoles hexafluoro borate [EMIM] PF
6, 1-methyl-3-butyl imidazole hexafluoro borate [BMIM] PF
6
4. the polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid according to claim 1 is a plasticizer, it is characterized in that: described step (2) is through the spun PAN filament of melt spinning, the hot-stretch temperature is controlled between 80-180 ℃, and draw ratio is between original 1-8 times.
5. the polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid according to claim 1 is a plasticizer is characterized in that: the fiber washing temperature after described step (3) stretches is controlled at 70-90 ℃.
6. the polyacrylonitrile (PAN) melt spinning method that a kind of imidazole type ion liquid according to claim 1 is a plasticizer, it is characterized in that: described step (3) PAN fibre strength is 2.8cN/dtex-8.0cN/dtex, and elongation at break is 10.9%-19.0%.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910048603A CN101545148A (en) | 2009-03-31 | 2009-03-31 | Method for melt spinning of polyacrylonitrile PAN by taking imidazole ionic fluid as plasticizing agent |
| EP10757985.6A EP2415913B1 (en) | 2009-03-31 | 2010-01-11 | Processes for producing carbon fiber precursor |
| JP2012502426A JP5407080B2 (en) | 2009-03-31 | 2010-01-11 | Carbon fiber, its yarn, and preoxidized fiber manufacturing method |
| PCT/CN2010/000036 WO2010111882A1 (en) | 2009-03-31 | 2010-01-11 | Processes for producing carbon fiber, the filament thereof, and pre-oxidized fiber |
| JP2013157802A JP5742065B2 (en) | 2009-03-31 | 2013-07-30 | Method for producing polyacrylonitrile (PAN) fiber |
| JP2013157845A JP5742067B2 (en) | 2009-03-31 | 2013-07-30 | Carbon fiber manufacturing method |
| JP2013157843A JP5733642B2 (en) | 2009-03-31 | 2013-07-30 | Carbon fiber manufacturing method |
| JP2013157840A JP5742066B2 (en) | 2009-03-31 | 2013-07-30 | Method for producing preoxidized fiber |
| US14/518,944 US9476147B2 (en) | 2009-03-31 | 2014-10-20 | Gel spinning process for producing a pan-based precursor fiber |
| US14/519,076 US9428850B2 (en) | 2009-03-31 | 2014-10-20 | Process of making pan-based carbon fiber |
| US14/519,002 US9334586B2 (en) | 2009-03-31 | 2014-10-20 | Process of melt-spinning polyacrylonitrile fiber |
| US14/519,057 US9644290B2 (en) | 2009-03-31 | 2014-10-20 | Process of melt-spinning polyacrylonitrile fiber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910048603A CN101545148A (en) | 2009-03-31 | 2009-03-31 | Method for melt spinning of polyacrylonitrile PAN by taking imidazole ionic fluid as plasticizing agent |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111882A1 (en) * | 2009-03-31 | 2010-10-07 | 东华大学 | Processes for producing carbon fiber, the filament thereof, and pre-oxidized fiber |
| CN102251320A (en) * | 2011-06-30 | 2011-11-23 | 东华大学 | Method for preparing fast-oxidized polyacrylonitrile fiber |
| CN102304786A (en) * | 2011-07-18 | 2012-01-04 | 东华大学 | Method for preparing CNT (carbon nano tube)-polyacrylonitrile fibre by melting spinning |
| CN102485980A (en) * | 2010-12-06 | 2012-06-06 | 财团法人工业技术研究院 | Polyacrylonitrile fiber precursor plasticizer, composition and preparation method of carbon fiber thereof |
| CN102964524A (en) * | 2012-11-28 | 2013-03-13 | 东华大学 | Method for extruding in-situ grafting modified cellulose through twin screws with ionic liquid serving as solvent |
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| CN103993382A (en) * | 2014-05-30 | 2014-08-20 | 东华大学 | Method for improving pre-oxidation speed of polyacrylonitrile fiber through physical blending |
| US8906278B2 (en) | 2009-03-31 | 2014-12-09 | Donghua University | Process of melt-spinning polyacrylonitrile fiber |
| CN104775174A (en) * | 2014-01-10 | 2015-07-15 | 蒙特美艾意技术有限责任公司 | Process for the production of acrylic fibers |
| CN111101225A (en) * | 2020-01-03 | 2020-05-05 | 镇江市高等专科学校 | Preparation method of polyacrylonitrile nano-fiber |
| CN112695401A (en) * | 2020-12-28 | 2021-04-23 | 镇江市高等专科学校 | Preparation method and application of plasticized melt-spun commercial-grade active PAN precursor |
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2009
- 2009-03-31 CN CN200910048603A patent/CN101545148A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8906278B2 (en) | 2009-03-31 | 2014-12-09 | Donghua University | Process of melt-spinning polyacrylonitrile fiber |
| US9644290B2 (en) | 2009-03-31 | 2017-05-09 | Donghua University | Process of melt-spinning polyacrylonitrile fiber |
| US9476147B2 (en) | 2009-03-31 | 2016-10-25 | Donghua University | Gel spinning process for producing a pan-based precursor fiber |
| US9428850B2 (en) | 2009-03-31 | 2016-08-30 | Donghua University | Process of making pan-based carbon fiber |
| WO2010111882A1 (en) * | 2009-03-31 | 2010-10-07 | 东华大学 | Processes for producing carbon fiber, the filament thereof, and pre-oxidized fiber |
| US9334586B2 (en) | 2009-03-31 | 2016-05-10 | Donghua University | Process of melt-spinning polyacrylonitrile fiber |
| CN102485980A (en) * | 2010-12-06 | 2012-06-06 | 财团法人工业技术研究院 | Polyacrylonitrile fiber precursor plasticizer, composition and preparation method of carbon fiber thereof |
| TWI410436B (en) * | 2010-12-06 | 2013-10-01 | Ind Tech Res Inst | Plasticizing agent, composition for polyacrylonitrile-based precursor and fabrication method of carbon fiber |
| CN102251320B (en) * | 2011-06-30 | 2013-05-08 | 东华大学 | Method for preparing fast-oxidized polyacrylonitrile fiber |
| CN102251320A (en) * | 2011-06-30 | 2011-11-23 | 东华大学 | Method for preparing fast-oxidized polyacrylonitrile fiber |
| CN102304786A (en) * | 2011-07-18 | 2012-01-04 | 东华大学 | Method for preparing CNT (carbon nano tube)-polyacrylonitrile fibre by melting spinning |
| CN102964524B (en) * | 2012-11-28 | 2015-05-13 | 东华大学 | Method for extruding in-situ grafting modified cellulose through twin screws with ionic liquid serving as solvent |
| CN102964524A (en) * | 2012-11-28 | 2013-03-13 | 东华大学 | Method for extruding in-situ grafting modified cellulose through twin screws with ionic liquid serving as solvent |
| CN104775174A (en) * | 2014-01-10 | 2015-07-15 | 蒙特美艾意技术有限责任公司 | Process for the production of acrylic fibers |
| CN104775174B (en) * | 2014-01-10 | 2018-07-27 | 蒙特美艾意技术有限责任公司 | The method for producing acrylic fibre |
| CN103774276B (en) * | 2014-01-13 | 2016-05-04 | 东华大学 | Adopt physical blending to prepare the method for lignin/polyacrylonitrile blended melt spun fibre |
| CN103774276A (en) * | 2014-01-13 | 2014-05-07 | 东华大学 | Method for preparing lignin/polyacrylonitrile blended melt-spun fiber by adopting physical blending |
| CN103993382A (en) * | 2014-05-30 | 2014-08-20 | 东华大学 | Method for improving pre-oxidation speed of polyacrylonitrile fiber through physical blending |
| CN103993382B (en) * | 2014-05-30 | 2016-06-08 | 东华大学 | A kind of method improving polyacrylonitrile fibre pre-oxidation speed by physical blending |
| CN111101225A (en) * | 2020-01-03 | 2020-05-05 | 镇江市高等专科学校 | Preparation method of polyacrylonitrile nano-fiber |
| CN112695401A (en) * | 2020-12-28 | 2021-04-23 | 镇江市高等专科学校 | Preparation method and application of plasticized melt-spun commercial-grade active PAN precursor |
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