CN103696035B - A kind of method removing HCl in PPTA-pulp production process - Google Patents
A kind of method removing HCl in PPTA-pulp production process Download PDFInfo
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- CN103696035B CN103696035B CN201310654403.3A CN201310654403A CN103696035B CN 103696035 B CN103696035 B CN 103696035B CN 201310654403 A CN201310654403 A CN 201310654403A CN 103696035 B CN103696035 B CN 103696035B
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Abstract
The invention discloses a kind of method removing HCl in PPTA-pulp production process, belong to Macroscopic single crystal field.Method of the present invention, first dissolves in containing the solvent of calcium chloride completely by p-phenylenediamine (PPD) powder, then the molar weight adding pulverous CaO, CaO is the twice of p-phenylenediamine (PPD) molar weight; Then add paraphthaloyl chloride at twice, the time interval is 2 ~ 5min, high-speed stirred reaction 0.5 ~ 3h; In reaction system, add pulverous CaO again, stirring reaction 3 ~ 5min, obtain faint yellow PPTA slurries; Finally the PPTA slurries of preparation are diluted, and by its by volume 2:1 ~ 4:1 add 1-METHYLPYRROLIDONE and water composition solidification liquid in, high speed shear, can obtain PPTA pulp through washing drying after suction filtration.Method of the present invention effectively removes byproduct of reaction HCl, improves the molecular weight of PPTA-pulp, reduces the corrosion of HCl to consersion unit and the pollution to environment.
Description
Technical field
The present invention relates to a kind of method removing HCl in PPTA-pulp production process, belong to Macroscopic single crystal field.
Background technology
P-aramid fiber (PPTA) pulp and PPTA pulp, in China also known as Fanglun l414 pulp (PPTA-pulp).PPTA-pulp is the nearly 20 years PPTA differentiated products grown up.PPTA pulp filoplume enriches, and has the tail end of tip-like; Rough surface branch trouble structure is many, and specific area is large.Its appearance and rise mainly as asbestos desirable alternative fiber and compete in encapsulant, reinforcing material and friction material 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 strength is large, specific stiffness is high, shock resistance, outstanding corrosion resistance and self-extinguishment, the features such as good high-temperature stability and saturating Electromagnetic performance, are widely used in the fields such as high temperature insulating material, Aero-Space and high-performance electronic equipment.
At present, preparing the most frequently used method of Fanglun slurry cake is cryogenic fluid direct polycondensation method.In PPTA-pulp preparation process, paraphthaloyl chloride and p-phenylenediamine (PPD) generation polycondensation reaction can produce accessory substance HCl.The generation of HCl has the harm of two aspects: on the one hand, and the delay of HCl in solution system causes the positive reaction speed of reacting to decline, and reduces the degree of polymerization and the molecular weight of p-aramid fiber; On the other hand, the spilling of HCl can cause corrosion to equipment, thus causes in commercial process, and maintenance cost and the reinvestment expense of equipment increase.So how to remove the HCl in PPTA-pulp preparation process in time, be related to the molecular weight of end product, be also related to production cost, become the difficult point in current PPTA-pulp preparation process and key technology.
The Yoon of Korea S proposes with in the reaction system of 1-METHYLPYRROLIDONE and metal halide, pyridine (Py) in EP0104410, adds p-phenylenediamine (PPD) and paraphthaloyl chloride carries out polycondensation reaction.Here pyridine is alkalescent, and the HCl that can generate with polycondensation reaction reacts, and plays the object of deacidification agent.But, pyridine foul smelling, and have hypotoxicity, make solvent recovery become more complicated and severe operational environment.
The patent of Di Ren company of Japan: JP60-135515 reports the method similar to Yoon method, they carry out polymerization process in two steps, the amount of paraphthaloyl chloride that first time adds and the mol ratio of added p-phenylenediamine (PPD) are 0.65:1, form the performed polymer of reduced viscosity=2.5, then ammonia is passed into, HCl in neutralization reactant, then add acyl chlorides, high-speed stirred and make the PPTA pulp of reduced viscosity=7.2.The object passing into ammonia is also the HCl that absorption polycondensation reaction generates, and same ammonia has stench, causes very poor impact to experimental implementation environment, and ammonia is undesirable for the adsorption effect of HCl.
In addition, Japanese Di Ren company proposes the method removing HCl between preparation in the fiber process of position in CN1341169: after completion of the polymerization reaction, and the HCl that a part generates is with Ca (OH)
2solvent dispersion neutralization, the neutralization ratio of the HCl of generation is 10%, then, adds the aqueous solution of NaOH in a solvent, and the NaCl of generation precipitates press filtration removing, and gained solid content is the CaCl containing polymer benchmark 15% in the solution of 14%
2, this method filter pressure is bigger than normal, 3.92 × 10
5about Pa.
In sum, it is expensive mainly to there is acid binding agent in prior art, and environmental pollution is serious, and removes the inefficient problem of HCl.The present invention adopts cheap calcium oxide, removes the successful of HCl, the stable performance of product.The difference of essence is there is with prior art.Along with the increase of the demand of PPTA-pulp, remove byproduct of reaction HCl, all particularly important for the quality and improvement operation processing environment improving PPTA-pulp.
Summary of the invention
The object of the invention is to prepare that to there is acid binding agent in PPTA-pulp process expensive for solving existing cryogenic fluid direct polycondensation method, environmental pollution is serious, and remove the problems such as HCl efficiency is low, and a kind of method removing HCl in PPTA-pulp production process is provided.
The object of the invention is to be achieved through the following technical solutions:
A kind of method removing HCl in PPTA-pulp production process of the present invention, concrete steps are as follows:
1) 1-METHYLPYRROLIDONE (NMP) is heated to 50 ~ 80 DEG C; Add the calcium chloride (CaCl that high-temperature activation is crossed
2), be stirred to and dissolve completely, CaCl
2at NMP-CaCl
2mass fraction in system is 4% ~ 8%;
2) by above-mentioned reaction system cool to room temperature, add p-phenylenediamine (PPD) (PPDA) powder while stirring, form the NMP-CaCl that molar concentration is the PPDA of 0.25 ~ 0.45mol/L
2solution; Add pulverous calcium oxide (CaO) again, the molar weight of CaO is the twice of the molar weight of PPDA, then reaction system is cooled to 0 ~-15 DEG C, add paraphthaloyl chloride (TPC) powder at twice, first time adds high-speed stirred after TPC powder, after the 2 ~ 5min of interval, second time adds TPC, and continue high-speed stirred reaction 0.5 ~ 3h, stir speed (S.S.) is 1000 ~ 5000r/min; Front and back add the identical in quality of TPC for twice, and mole total amount adding TPC for twice is equal with the molar weight of PPDA;
3) in reaction system, add pulverous CaO again, be stir 3 ~ 5min under the condition of 1000 ~ 5000r/min in stir speed (S.S.), obtain faint yellow PPTA slurries, the quality of this step CaO is the 2nd) step adds 0.5 ~ 2% of CaO quality;
4) the PPTA slurries NMP of preparation is diluted to PPTA slurry volume accounts for PPTA slurries and 1-METHYLPYRROLIDONE volume sum 50 ~ 80%, obtain the PPTA slurries after diluting;
5), under normal temperature, NMP and water are mixed to get solidification liquid by the volume ratio of 4:1 ~ 6:1;
6) by the 4th) PPTA slurries after the dilution that obtains of step add the 5th) 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 stirred 10 ~ 25min forms the pulp fibers of staple fiber shape, stir speed (S.S.) is 3000 ~ 4000r/min, can obtain PPTA pulp after suction filtration through washing drying.
Beneficial effect
(1) present invention process is simple, and the depickling material cost of use is cheap; Do not use pyridine, triethylamine etc. expensive and the virose acid binding agent of tool, saved cost, substantially improved the operating environment in process of manufacture.
(2) the present invention removes HCl in time in the stage of reaction, greatly reduces the corrosion of HCl to production equipment, extends the service life of equipment, in commercial process, can reduce maintenance cost and the reinvestment expense of equipment.
(3) the present invention just started to remove HCl in the polycondensation reaction stage, the CaCl that calcium oxide and HCl reaction generate
2again can as cosolvent, further raising p-aramid fiber solubility in a solvent, and PPTA-pulp solubility in a solvent increases, the positive reaction speed of polycondensation reaction greatly can be impelled again to increase, thus the molecular weight of end product and the degree of polymerization are significantly improved.Solve the problem that cryogenic fluid direct polycondensation method preparation process middle-molecular-weihydroxyethyl is too low.
(4) the present invention does not use Ca (OH)
2solvent dispersion neutralization, this is because react with the HCl of identical mole, calcium oxide generation moisture fewer, have very important impact in the performance of stage of reaction water content on end product.The performance of the more end products of water content is more unstable, and when the present invention removes HCl, the moisture of generation is less, is conducive to the stable performance of end product.
Detailed description of the invention
Below in conjunction with embodiment, content of the present invention is further described.
Embodiment 1:
The NMP of 100ml is heated to 80 DEG C; Add the CaCl of the 4.28g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 2.70g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 2.80g, with ice-salt bath, reaction system is cooled to 0 DEG C, add TPC powder at twice, after adding 2.54gTPC powder for the first time, high-speed stirred, stir speed (S.S.) is 1000r/min; Remaining 2.54g TPC powder is added after 3min; After reaction 1h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 14mg CaO, stir 3min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 40ml NMP, 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 staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 4.0 × 10
4.
Embodiment 2:
The NMP of 100ml is heated to 80 DEG C; Add the CaCl of the 4.28g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 3.24g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 3.36g, with ice-salt bath, reaction system is cooled to-5 DEG C, add TPC powder at twice, after adding 3.04gTPC powder for the first time, high-speed stirred, stir speed (S.S.) is 1500r/min; Remaining 3.04g TPC powder is added after 2min; After reaction 1h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 16.8mg CaO, stir 3min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 60ml NMP, 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 staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 4.2 × 10
4.
Embodiment 3:
The NMP of 100ml is heated to 70 DEG C; Add the CaCl of the 5.40g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 4.33g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 4.48g, with ice-salt bath, reaction system is cooled to-10 DEG C, add TPC powder at twice, after adding 4.06g TPC powder for the first time, high-speed stirred, stir speed (S.S.) is 2000r/min; Remaining 4.06g TPC powder is added after 4min; After reaction 0.5h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 44.8mg CaO, stir 5min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 50ml NMP, 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 3000r/min, shearing the pulp fibers that 20min forms staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 3.6 × 10
4.
Embodiment 4:
The NMP of 100ml is heated to 60 DEG C; Add the CaCl of the 5.40g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 4.87g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 4.48g, with ice-salt bath, reaction system is cooled to-10 DEG C, add TPC powder at twice, after adding 5.04g TPC powder for the first time, high-speed stirred, stir speed (S.S.) is 3000r/min; Remaining 4.57g TPC powder is added after 3min; After reaction 1.5h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 25.2mg CaO, stir 4min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 40ml NMP, 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 staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 4.6 × 10
4.
Embodiment 5:
The NMP of 100ml is heated to 50 DEG C; Add the CaCl of the 4.28g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 2.70g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 2.80g, with ice-salt bath, reaction system is cooled to-20 DEG C, add TPC powder at twice, after adding 2.54gTPC powder for the first time, high-speed stirred, stir speed (S.S.) is 3500r/min; Remaining 2.54g TPC powder is added after 2min; After reaction 1.5h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 28mg CaO, stir 5min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 40ml NMP, 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 staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 3.2 × 10
4.
Embodiment 6:
The NMP of 100ml is heated to 50 DEG C; Add the CaCl of the 6.55g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 3.24g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 3.36g, with ice-salt bath, reaction system is cooled to-15 DEG C, add TPC powder at twice, after adding 3.04gTPC powder for the first time, high-speed stirred, stir speed (S.S.) is 2000r/min; Remaining 3.04g TPC powder is added after 4min; After reaction 0.5h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 16.8mg CaO, stir 3min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 60ml NMP, 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 1500r/min, shearing the pulp fibers that 10min forms staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 4.7 × 10
4.
Embodiment 7:
The NMP of 100ml is heated to 40 DEG C; Add the CaCl of the 5.40g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 4.33g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 4.48g, with ice-salt bath, reaction system is cooled to-5 DEG C, add TPC powder at twice, after adding 4.06g TPC powder for the first time, high-speed stirred, stir speed (S.S.) is 1500r/min; Remaining 4.06g TPC powder is added after 2min; After reaction 1h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 22.4mg CaO, stir 3min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 40ml NMP, 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 10min forms staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 3.7 × 10
4.
Embodiment 8:
The NMP of 100ml is heated to 80 DEG C; Add the CaCl of the 7.72g that high-temperature activation is crossed
2, be stirred to and dissolve completely; Cool to room temperature, adds 3.78g PPDA powder while stirring; After it dissolves completely, add the pulverous CaO of 3.92g, with ice-salt bath, reaction system is cooled to-5 DEG C, add TPC powder at twice, after adding 3.55g TPC powder for the first time, high-speed stirred, stir speed (S.S.) is 3000r/min; Remaining 3.55g TPC powder is added after 2min; After reaction 1h; Under the condition that stir speed (S.S.) remains unchanged, in reaction system, add 19.6mg CaO, stir 3min, obtain faint yellow PPTA slurries; The PPTA slurries of preparation are diluted with 50ml NMP, 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 staple fiber shape, after suction filtration, PPTA pulp can be obtained through washing drying.
By the 0.125g PPTA-pulp sample dissolution of bone dry in the 25ml concentrated sulfuric acid, measure the reduced viscosity η of the para-aramid fiber under variable concentrations by the method that Ubbelohde viscometer presses GB/T 1632-93 in the water bath with thermostatic control of (30 ± 0.2) DEG C
inh, with η
inhfor ordinate, concentration C is abscissa mapping, is extrapolated to C=0, obtains the inherent viscosity [η] of PPTA-pulp, by formula [η]=7.9 × 10
-5m
η 1.06, calculating sticky equal relative molecular weight is 5.0 × 10
4.
Claims (1)
1. remove a method of HCl in PPTA-pulp production process, it is characterized in that: concrete steps are as follows:
1) 1-METHYLPYRROLIDONE (NMP) is heated to 50 ~ 80 DEG C; Add the calcium chloride (CaCl that high-temperature activation is crossed
2), be stirred to and dissolve completely, CaCl
2at NMP-CaCl
2mass fraction in system is 4% ~ 8%;
2) by above-mentioned reaction system cool to room temperature, add p-phenylenediamine (PPD) (PPDA) powder while stirring, form the NMP-CaCl that molar concentration is the PPDA of 0.25 ~ 0.45mol/L
2solution; Add pulverous calcium oxide (CaO) again, the molar weight of CaO is the twice of the molar weight of PPDA, then reaction system is cooled to 0 ~-15 DEG C, add paraphthaloyl chloride (TPC) powder at twice, first time adds high-speed stirred after TPC powder, after the 2 ~ 5min of interval, second time adds TPC, and continue high-speed stirred reaction 0.5 ~ 3h, stir speed (S.S.) is 1000 ~ 5000r/min; Front and back add the identical in quality of TPC for twice, and mole total amount adding TPC for twice is equal with the molar weight of PPDA;
3) in reaction system, add pulverous CaO again, be stir 3 ~ 5min under the condition of 1000 ~ 5000r/min in stir speed (S.S.), obtain faint yellow PPTA slurries, the quality of this step CaO is the 2nd) step adds 0.5 ~ 2% of CaO quality;
4) the PPTA slurries NMP of preparation is diluted to PPTA slurry volume accounts for PPTA slurries and 1-METHYLPYRROLIDONE volume sum 50 ~ 80%, obtain the PPTA slurries after diluting;
5), under normal temperature, NMP and water are mixed to get solidification liquid by the volume ratio of 4:1 ~ 6:1;
6) by the 4th) PPTA slurries after the dilution that obtains of step add the 5th) 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 stirred 10 ~ 25min forms the pulp fibers of staple fiber shape, stir speed (S.S.) is 3000 ~ 4000r/min, can obtain PPTA pulp after suction filtration through washing drying.
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| CN108550771A (en) * | 2018-06-04 | 2018-09-18 | 珠海恩捷新材料科技有限公司 | Lithium battery diaphragm slurry, lithium battery diaphragm, lithium ion battery and preparation method |
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| CN101456950B (en) * | 2008-10-28 | 2010-12-01 | 烟台氨纶股份有限公司 | Method for preparing high molecular weight poly(p-phenyleneterephthalamide) and products |
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