CN103724615B - The supersonic induced method preparing PPTA-pulp - Google Patents
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Abstract
The invention discloses a kind of supersonic induced method preparing PPTA-pulp, belong to field of chemical fiber preparation.Method of the present invention, first dissolves in containing the solvent of calcium chloride completely by Ursol D powder; Then add p-phthaloyl chloride at twice, the mass ratio that front and back are twice is 1:9 ~ 9:1, and the timed interval is 2 ~ 5min, Vltrasonic device is opened after second time adds p-phthaloyl chloride, ultrasonic frequency is 28 ~ 120kHz, polycondensation 0.2 ~ 2h, obtains faint yellow PPTA slurries; Again the PPTA slurries N-Methyl pyrrolidone of preparation is diluted, and by its by volume 2:1 ~ 4:1 add N-Methyl pyrrolidone and water composition solidification liquid in, high speed shear forms the pulp fibers of chopped strand shape, can obtain PPTA pulp after suction filtration through washing drying.Ppta-pulp fibre form prepared by the present invention is good, and specific surface area is high, and the filoplume shape constitutional features of pulp is obvious, has excellent resistance to elevated temperatures simultaneously.
Description
Technical field
The present invention relates to a kind of supersonic induced method preparing PPTA-pulp, belong to field of chemical fiber preparation.
Background technology
PPTA-pulp (PPTA-pulp) is the differentiated product of nearly p-aramid fiber (PPTA) grown up for 20 years.It is the fibrillation product of a kind of high dispersing that first du pont company in 1984 develops.The chemical structure of aramid pulp is identical with PPTA, remains the excellent properties of the aramid fiber overwhelming majority, as performances such as heat-resisting, wear-resisting, dimensional stabilizings, but makes it have the long stapled physical property of some difference PPTA.The density of aramid pulp is 1.41-1.42, more smaller than PPTA macrofiber, grows thickly in lint fento in surface, and filoplume enriches, coarse as wood pulp.
The appearance of aramid pulp and rise mainly as asbestos desirable alternative fiber and compete in sealing material, strongthener and friction materials with glass fibre and carbon fiber.In addition, the p-aramid paper that PPTA pulp is prepared from by the wet-formed technique of papermaking, there is specific mass light, specific tenacity is large, specific rigidity is high, shock resistance, outstanding erosion resistance and self-extinguishing, the features such as good high-temperature stability and saturating Electromagnetic performance, are widely used in the fields such as high temperature insulating material, aerospace and high-performance electronic equipment.
But the conventional fabrication techniques-sulfuric acid fiber spinning from crystalline state method of PPTA-pulp, difficulty is large, cost is high.PPTA long filament is prepared as USP3869430 proposes to adopt poly P phenylene diamine terephthalamide vitriol oil liquid crystal solution to carry out spinning, through the short staple fibre being cut into 20mm length of special cutting facility, carry out fibrillation beating again, make the surperficial roughen of fiber, filoplumeization formation aramid pulp.This spinning cutting preparation method is except polymkeric substance spinning solution prepared by needs, and also need to carry out the technique such as spinning moulding, winding cut-out, technical process is long, needs special cutting facility, cost intensive.
The people such as YoonHan-Sik report at N-Methyl pyrrolidone-calcium chloride-pyridine (NMP-CaCl
2-pY) in the solvent system formed, Ursol D (PPDA) and p-phthaloyl chloride (TPC) carry out polycondensation and generate liquid crystalline polymer solution rapidly, continue reaction and form frozen glue body.But it employs a large amount of pyridines in the course of the polymerization process, solution is reclaimed and becomes more complicated and severe operational environment.
So the preparation problem of PPTA-pulp is still the difficult problem in aramid fiber field.Domestic still do not have industrialized production, the production and selling of PPTA-pulp still monopolize by the advanced country such as the U.S., Russia.At present, world's aramid fiber ultimate production about 35000 tons/year, Consumption of China amount has reached more than 1500 ton/year, is mainly used in the fields such as high temperature insulating material, aerospace and high-performance electronic equipment.These essential domains concern national Integrate technologies strength, rank among advanced country's ranks future most important for China.Therefore, a preparation difficult problem for PPTA-pulp needs solution badly.
Ultrasonic wave is the sound wave of frequency higher than 20000Hz, and it can impel the of short duration liquefaction of the emulsification of liquid, the dispersion of solid and gel as a kind of mechanical vibration effect.Ultrasonic wave is considered to be unfavorable for gel formation within a very long time.But scholar's research shows at present, because the wavelength of sound is much larger than the size of molecule, therefore between ultrasonic wave and chemical substance, do not have the interaction of direct molecular level.When ultrasonic wave is propagated in liquid medium, cavatition produces instantaneous high temperature, High Pressure impels system that a series of phonochemical reaction occurs.
In sum, it is excessive to there is equipment investment cost in prior art, difficult solvent recovery, add the deficiencies such as large and the seriously polluted and product property of acid binding agent toxicity is unstable, the present invention adopts supersonic induced method to prepare PPTA-pulp, avoid the deficiencies in the prior art, significantly can improve the performance of product, there is the difference of essence with prior art.
Summary of the invention
The object of the invention is to prepare PPTA-pulp investment in machinery and equipment cost greatly, complex process for solving tradition; General cryogenic fluid direct polycondensation method technology of preparing adds acid binding agent, expensive, and environmental pollution is serious, the problems such as difficult solvent recovery, and provides a kind of supersonic induced method preparing PPTA-pulp.
The object of the invention is to be achieved through the following technical solutions:
The supersonic induced method preparing PPTA-pulp of the present invention, concrete preparation process is as follows:
1) at N
2provide protection under, preparation N-Methyl pyrrolidone-calcium chloride solvent system; In this solvent system, add Ursol D (PPDA) powder while stirring, make it dissolve completely, form N-Methyl pyrrolidone-calcium chloride solution that volumetric molar concentration is the PPDA of 0.25 ~ 0.45mol/L;
2) reaction system is cooled to 5 ~-20 DEG C, adds p-phthaloyl chloride (TPC) powder at twice, after adding TPC powder for the first time, high-speed stirring, stir speed (S.S.) is 500 ~ 4000r/min; Add interval for twice 2 ~ 5 minutes, after being added by remaining TPC powder, close whipping appts, mole total amount adding TPC for twice is equal with the molar weight of PPDA, and the mass ratio that front and back add TPC for twice is 1:9 ~ 9:1; Open ultrasonic wave when second time adds TPC and carry out polycondensation, the reaction times is 0.2 ~ 2h, and ultrasonic frequency is 28 ~ 120kHz, obtains faint yellow PPTA slurries;
3) the PPTA slurries N-Methyl pyrrolidone of preparation is diluted to PPTA slurry volume accounts for PPTA slurries and N-Methyl pyrrolidone volume sum 50 ~ 80%, obtain the PPTA slurries after diluting;
4), under normal temperature, N-Methyl pyrrolidone and water are mixed to get solidification liquid by the volume ratio of 4:1 ~ 6:1;
5) by the 3rd) PPTA slurries after the dilution that obtains of step add the 4th) in the solidification liquid that obtains of step, PPTA slurries after dilution and the volume ratio of solidification liquid are 2:1 ~ 4:1, high-speed stirring 10 ~ 25min forms the pulp fibers of chopped strand shape, stir speed (S.S.) is 3000 ~ 4000r/min, can obtain PPTA pulp after suction filtration through washing drying.
Beneficial effect
(1) the present invention adopts hyperacoustic " cavatition " to prepare PPTA-pulp, and be different from conventional fabrication techniques, do not need special cutting facility, technique is simple; Compared with general cryogenic fluid direct polycondensation method, do not need to add expensive acid binding agent, can not pollute environment;
(2) technique simple and stable proposed by the invention, the aramid pulp of preparation, fibre shape is good, and the filoplume shape constitutional features of pulp is obvious, has excellent resistance to elevated temperatures simultaneously;
(3) preparation theory of the present invention is different from existing technology of preparing, solves a preparation difficult problem for existing PPTA-pulp, for large-scale industrial production provides possibility;
(4) in preparation process of the present invention, hyperacoustic periodicity effect is conducive to the hair feather fractures of pulp, be equivalent to the pulping process in existing technology of preparing, improve the specific surface area of PPTA-pulp, be conducive to the application of PPTA-pulp in high-grade, precision and advanced field.
Embodiment
Below in conjunction with embodiment, content of the present invention is further described.
Embodiment 1:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 3.78g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to 5 DEG C, adds the TPC powder of 7.10g at twice, after adding the TPC powder of 3.55g for the first time, high-speed stirring, stir speed (S.S.) is 500r/min; After 3min, add the TPC powder of residue 3.55g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 78kHz, and the reaction times is 1h, obtains faint yellow PPTA slurries; The PPTA slurries 50mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (40ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 3000r/min, shearing the pulp fibers that 10min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 3mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 18m
2/ g.
Embodiment 2:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 3.78g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to 0 DEG C, adds the TPC powder of 7.10g at twice, after adding the TPC powder of 0.71g for the first time, high-speed stirring, stir speed (S.S.) is 1000r/min; After 3min, add the TPC powder of residue 6.39g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 78kHz, and the reaction times is 1h, obtains faint yellow PPTA slurries; The PPTA slurries 50mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (50ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 2500r/min, shearing the pulp fibers that 15min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 2.7mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 16m
2/ g.
Embodiment 3:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 2.70g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to-10 DEG C, adds the TPC powder of 5.08g at twice, after adding the TPC powder of 2.54g for the first time, high-speed stirring, stir speed (S.S.) is 1500r/min; After 4min, add the TPC powder of residue 2.54g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 68kHz, and the reaction times is 0.5h, obtains faint yellow PPTA slurries; The PPTA slurries 40mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (60ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 2000r/min, shearing the pulp fibers that 10min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 2.5mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 15m
2/ g.
Embodiment 4:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 3.24g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to-15 DEG C, adds the TPC powder of 6.08g at twice, after adding the TPC powder of 3.04g for the first time, high-speed stirring, stir speed (S.S.) is 2000r/min; After 5min, add the TPC powder of residue 3.04g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 68kHz, and the reaction times is 1h, obtains faint yellow PPTA slurries; The PPTA slurries 60mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (40ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 3000r/min, shearing the pulp fibers that 10min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 2.7mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 16m
2/ g.
Embodiment 5:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 3.78g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to 5 DEG C, adds the TPC powder of 7.10g at twice, after adding the TPC powder of 2.13g for the first time, high-speed stirring, stir speed (S.S.) is 2500r/min; After 4min, add the TPC powder of residue 4.97g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 48kHz, and the reaction times is 0.5h, obtains faint yellow PPTA slurries; The PPTA slurries 50mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (50ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 2000r/min, shearing the pulp fibers that 20min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 1.9mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 14m
2/ g.
Embodiment 6:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 3.78g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to-20 DEG C, adds the TPC powder of 7.10g at twice, after adding the TPC powder of 4.97g for the first time, high-speed stirring, stir speed (S.S.) is 3000r/min; After 5min, add the TPC powder of residue 2.13g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 48kHz, and the reaction times is 1h, obtains faint yellow PPTA slurries; The PPTA slurries 50mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (60ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 3500r/min, shearing the pulp fibers that 10min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 2.3mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 16m
2/ g.
Embodiment 7:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 4.33g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to 5 DEG C, adds the TPC powder of 8.12g at twice, after adding the TPC powder of 4.06g for the first time, high-speed stirring, stir speed (S.S.) is 3500r/min; After 2min, add the TPC powder of residue 4.06g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 120kHz, and the reaction times is 0.5h, obtains faint yellow PPTA slurries; The PPTA slurries 40mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (50ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 2000r/min, shearing the pulp fibers that 20min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 2.7mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 14m
2/ g.
Embodiment 8:
At N
2provide protection under, preparation 100mlN-methyl-2-pyrrolidone-calcium chloride (NMP-CaCl
2) solvent system, wherein the quality of calcium chloride is 8.95g; Add the PPDA powder of 4.87g while stirring; After it dissolves completely, with ice-salt bath, reaction system is cooled to-15 DEG C, adds the TPC powder of 9.14g at twice, after adding the TPC powder of 4.57g for the first time, high-speed stirring, stir speed (S.S.) is 4000r/min; After 3min, add the TPC powder of residue 4.57g, close whipping appts, open ultrasonic wave simultaneously and carry out polycondensation, ultrasonic frequency is 120kHz, and the reaction times is 1h, obtains faint yellow PPTA slurries; The PPTA slurries 50mlNMP of preparation is diluted, and these slurries are sprayed in the solidification liquid that the NMP (40ml) of high speed shear and water (10ml) forms, stir speed (S.S.) is 2500r/min, shearing the pulp fibers that 15min forms chopped strand shape, after suction filtration, PPTA pulp can be obtained through washing drying.
With the microscope with cross millimeter graduated scale, measure pulp sample and be about 1mg, average, obtaining mean length is 2.9mm;
Take the vacuum-drying 4 hours at 45 DEG C of 1.0g sample, the specific surface area adopting BET nitrogen adsorption methods to measure PPTA-pulp is 16m
2/ g.
Claims (1)
1. the supersonic induced method preparing PPTA-pulp, is characterized in that: concrete preparation process is as follows:
1) at N
2provide protection under, preparation N-Methyl pyrrolidone-calcium chloride solvent system; In this solvent system, add Ursol D (PPDA) powder while stirring, make it dissolve completely, form N-Methyl pyrrolidone-calcium chloride solution that volumetric molar concentration is the PPDA of 0.25 ~ 0.45mol/L;
2) reaction system is cooled to 5 ~-20 DEG C, adds p-phthaloyl chloride (TPC) powder at twice, after adding TPC powder for the first time, high-speed stirring, stir speed (S.S.) is 500 ~ 4000r/min; Add interval for twice 2 ~ 5 minutes, after being added by remaining TPC powder, close whipping appts, mole total amount adding TPC for twice is equal with the molar weight of PPDA, and the mass ratio that front and back add TPC for twice is 1:9 ~ 9:1; Open ultrasonic wave when second time adds TPC and carry out polycondensation, the reaction times is 0.2 ~ 2h, and ultrasonic frequency is 28 ~ 120kHz, obtains faint yellow PPTA slurries;
3) the PPTA slurries N-Methyl pyrrolidone of preparation is diluted to PPTA slurry volume accounts for PPTA slurries and N-Methyl pyrrolidone volume sum 50 ~ 80%, obtain the PPTA slurries after diluting;
4), under normal temperature, N-Methyl pyrrolidone and water are mixed to get solidification liquid by the volume ratio of 4:1 ~ 6:1;
5) by the 3rd) PPTA slurries after the dilution that obtains of step add the 4th) in the solidification liquid that obtains of step, PPTA slurries after dilution and the volume ratio of solidification liquid are 2:1 ~ 4:1, high-speed stirring 10 ~ 25min forms the pulp fibers of chopped strand shape, stir speed (S.S.) is 3000 ~ 4000r/min, can obtain PPTA pulp after suction filtration through washing drying.
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CN115044995B (en) * | 2022-06-17 | 2024-01-19 | 中化学科学技术研究有限公司 | Para-aramid pulp fiber and preparation method thereof |
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US5021123A (en) * | 1989-04-03 | 1991-06-04 | E. I. Du Pont De Nemours And Company | Process for producing paper from a poly(paraphenylene terephthalamide) fibrous gel |
EP0303247B1 (en) * | 1987-08-10 | 1994-03-23 | E.I. Du Pont De Nemours And Company | Aramid staple prepared by spinning |
CN102560737A (en) * | 2010-12-09 | 2012-07-11 | 烟台泰和新材料股份有限公司 | One-step preparation method of para aramid fibrids |
CN102649842A (en) * | 2012-05-11 | 2012-08-29 | 河南城建学院 | Method for synthesizing PPTA (poly-p-phenylene terephthamide) with high inherent viscosity |
-
2013
- 2013-12-05 CN CN201310653419.2A patent/CN103724615B/en not_active Expired - Fee Related
Patent Citations (4)
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---|---|---|---|---|
EP0303247B1 (en) * | 1987-08-10 | 1994-03-23 | E.I. Du Pont De Nemours And Company | Aramid staple prepared by spinning |
US5021123A (en) * | 1989-04-03 | 1991-06-04 | E. I. Du Pont De Nemours And Company | Process for producing paper from a poly(paraphenylene terephthalamide) fibrous gel |
CN102560737A (en) * | 2010-12-09 | 2012-07-11 | 烟台泰和新材料股份有限公司 | One-step preparation method of para aramid fibrids |
CN102649842A (en) * | 2012-05-11 | 2012-08-29 | 河南城建学院 | Method for synthesizing PPTA (poly-p-phenylene terephthamide) with high inherent viscosity |
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"聚对苯酰胺浆粕的制备";赵玮等;《合成纤维》;20060525(第5期);第1-3页 * |
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