CN100489012C - Polymerizing solution reusing method for polymerization of paraphthaolyl p-phenylenediamine - Google Patents
Polymerizing solution reusing method for polymerization of paraphthaolyl p-phenylenediamine Download PDFInfo
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- CN100489012C CN100489012C CNB2006100377713A CN200610037771A CN100489012C CN 100489012 C CN100489012 C CN 100489012C CN B2006100377713 A CNB2006100377713 A CN B2006100377713A CN 200610037771 A CN200610037771 A CN 200610037771A CN 100489012 C CN100489012 C CN 100489012C
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Abstract
The present invention relates to the polymerizing solution reusing method for synthesis of polyparapthaolyl p-phenylenediamine, and belongs to the field of polymer material synthesizing technology. After p-phenylenediamine and polyparapthaolyl chloride are low temperature condensated in a solvent system comprising N-methyl pyrrolidone and calcium chloride, the reacted system is neutralized with neutralizing agent, polymer is washed, and through further filtering, collecting filtrate and washing liquid, dewatering, desalting, distilling, and rectifying, the solvent is purified and recovered for reuse. The present invention has the advantages of controlled product pH value, no decomposition of solvent, high purity of the recovered solvent, high solvent recovering rate, and environment friendship.
Description
Technical field
The invention belongs to the synthetic field of macromolecular material, relate to the recycle method of polymer solvent in a kind of PPTA building-up reactions.
Background technology
The method that Ursol D and p-phthaloyl chloride low-temperature polycondensation in N-Methyl pyrrolidone (NMP)-calcium chloride solvent system is made PPTA (PPTA) is a known technology.After polycondensation finished, product need be removed solvent and salt through adding water washing after the neutralizing treatment, N-Methyl pyrrolidone solvent and salt, oligopolymer, and do not have the raw material of reaction to enter washing water together.The processing discharge fee of washing water is quite big, and the solvent of costliness can not be recycled in a large number, causes a large amount of wastes, and production cost is increased greatly.Therefore, how to reclaim polymer solvent in PPTA is synthetic, make it recycle, be the research topic that more domestic research institutions are engaged in always.Patent (CN1052247C) discloses a kind of synthetic PPTA polymerization solvent recovery method, and it is that the polycondensate underpressure distillation is steamed solvent, again in and the filtered and recycled solvent utilize again.The underpressure distillation under 30-130 ℃ of temperature of this method, the N-Methyl pyrrolidone solvent is decomposed fast in acid situation to be reduced yield and influences PPTA quality product and yield, and recovered solvent has the sewage discharge of a large amount of washing PPTA as not reaching the reuse requirement without further handling.
The object of the present invention is to provide a kind of not can because of solvent in sour environment, reclaim cause the N-Methyl pyrrolidone solvent to decompose fast reducing yield and ensure the PPTA quality product and yield, solvent recovering rate are high, low recycle method reaction needed, that can reduce polymer solvent in the PPTA building-up reactions that the poison sewage discharging is beneficial to environmental protection that satisfies of using of recovered solvent water content.
The objective of the invention is to reach like this: after Ursol D and p-phthaloyl chloride low temperature poly condensation in N-Methyl pyrrolidone-calcium chloride solvent system finishes, be neutralized to neutrality with neutralizing agent, add deionized water or recycle-water washing PPTA again, filter then, collect filtered liquid, washings, dewater again, desalination, slightly heat up in a steamer, rectifying, purify and reclaim the solvent cycle utilization, described dehydration is for adopting the underpressure distillation dehydration, pounds per square inch absolute (psia) is controlled at 3.0-5.0KPa, the still temperature control is at 70-90 ℃, described desalination is controlled at 0.1-1.0KPa for adopting the mixed solvent after the desalination still will dewater at pounds per square inch absolute (psia), and the still temperature control steams desalination with solvent under 150-200 ℃.
The recycle method of polymer solvent in the PPTA building-up reactions of the present invention is characterized in that the water content of described solvent system N-Methyl pyrrolidone-calcium chloride is＜120ppm.
The recycle method of polymer solvent in the PPTA building-up reactions of the present invention is characterized in that described neutralizing agent is carbonate, oxide compound or the oxyhydroxide of alkaline-earth metal.
The recycle method of polymer solvent in the PPTA building-up reactions of the present invention is characterized in that neutralizing agent preferably CaCO3 or CaO or Ca (OH)
2
The recycle method of polymer solvent in the PPTA building-up reactions of the present invention, it is characterized in that described slightly heating up in a steamer is the solvent after the desalination to be entered crude steam kettle slough the oligopolymer that produces in preceding component and the reaction, pounds per square inch absolute (psia) is controlled at 0.1-3.0KPa, and the still temperature control is at 70-130 ℃.
The recycle method of polymer solvent in the PPTA building-up reactions of the present invention, it is characterized in that described rectifying is the solvent through slightly heating up in a steamer to be entered rectifying tower further purify, the pounds per square inch absolute (psia) of tower still is controlled at 0.1-3.0KPa, and the still temperature control is at 70-130 ℃.
The recycle method of polymer solvent in the PPTA building-up reactions of the present invention is characterized in that described purification is the solvent through rectifying to be entered purification column carry out further dehydration and purification.
The advantage of the inventive method is: earlier polymkeric substance is carried out neutralizing treatment so that the pH value of control product, reclaim solvent after the washing water that will contain solvent separate with product P PTA in advance again and operate, thereby can avoid the decomposition of solvent; The purity that reclaims solvent is more than 99.5%, and moisture content can satisfy recycling requirement fully less than 100PPm; Solvent recovering yield can reach more than 91%, has obvious economic benefit; Owing to reclaimed the NMP that is suitable for reuse effectively, therefore helped environmental protection.
Embodiment
Embodiment one:
In the 500ml stainless steel cauldron of quick whipping appts is housed, feed exsiccant nitrogen, after heat temperature raising carries out drying, add the people and be dissolved with 6%CaCl
2Nmp solvent 150 gram, the solvent system water content is less than 100ppm.At N
2Protection adds Powdered Ursol D 6.0000 grams of people down in about 10 ℃.After treating that Ursol D fully dissolves, be cooled to below 5 ℃, add people's p-phthaloyl chloride 11.2800 grams rapidly, quicken simultaneously to stir to be the crumb shape, add neutralizing agent CaCO until polymkeric substance with ice-water bath
3To neutrality, add deionized water wash PPTA, filtration, drying again and obtain the yellow powder shaped polymer, its logarithmic ratio viscosity is 5.5.Collect filtered liquid, washings, the control pounds per square inch absolute (psia) is at 3.0-5.0KPa, and the still temperature is carried out underpressure distillation and sloughed a large amount of water in the time of 70-90 ℃, steams the water reuse.Mixed solvent after the dehydration and salt enter the desalination still, and pounds per square inch absolute (psia) is at 0.1-1.0KPa in the control still, and the still temperature steams solvent at 150-200 ℃, slough the salt of reaction adding and the salt that neutralization produces.Solvent after the desalination enters crude steam kettle, and pounds per square inch absolute (psia) is at 0.1-3.0KPa in the control still, and the still temperature is sloughed the oligopolymer that produces in preceding component and the reaction at 70-130 ℃.The solvent of sloughing preceding component and oligopolymer enters rectifying tower and further purifies, and the pounds per square inch absolute (psia) of control tower still is at 0.1-3.0KPa, and the still temperature obtains purity and reaches more than 99.5% at 70-130 ℃, and moisture content is less than the solvent of 200ppm.This solvent is entered purification column carry out purifying, obtain purity and reach more than 99.9%, moisture content is nmp solvent 130.4391 grams of 45ppm, solvent recovering rate 92.51%, and sealing is preserved and is used to return the polymerization recycle.
Embodiment two:
Feed exsiccant nitrogen in the 500ml stainless steel cauldron of quick whipping appts is housed, after heat temperature raising carried out drying, adding was dissolved with 6%CaCl
2Nmp solvent 150 gram, the solvent system water content is less than 100ppm.At N
2Protection adds Powdered Ursol D 6.0000 grams of people down in about 10 ℃.After treating that Ursol D fully dissolves, be cooled to below 5 ℃ with ice-water bath, add people's p-phthaloyl chloride 11.2800 grams rapidly, quicken simultaneously to stir to be the crumb shape until polymkeric substance, add neutralizing agent CaO to neutrality, add the washing of deionized water or recycle-water PPTA, filtration again, drying obtains the yellow powder shaped polymer, its logarithmic ratio viscosity is 6.2.Collect filtered liquid, washings, the control pounds per square inch absolute (psia) is at 3.0-5.0KPa, and the still temperature is carried out underpressure distillation and sloughed a large amount of water in the time of 70-90 ℃, steams the water reuse.Mixed solvent after the dehydration and salt enter the desalination still, and pounds per square inch absolute (psia) is at 0.1-1.0KPa in the control still, and the still temperature steams solvent at 150-200 ℃, slough the salt of reaction adding and the salt that neutralization produces.Solvent after the desalination enters crude steam kettle, and pounds per square inch absolute (psia) is at 0.1-3.0KPa in the control still, and the still temperature is sloughed the oligopolymer that produces in preceding component and the reaction at 70-130 ℃.The solvent of sloughing preceding component and oligopolymer enters rectifying tower and further purifies, and the pounds per square inch absolute (psia) of control tower still is at 0.1-3.0KPa, and the still temperature obtains purity and reaches more than 99.5% at 70-130 ℃, and moisture content is less than the solvent of 200ppm.This solvent is entered purification column carry out purifying, obtain purity and reach more than 99.9%, moisture content is nmp solvent 130.5519 grams of 33.7ppm, solvent recovering rate 92.59%, and sealing is preserved and is used to return the polymerization recycle.
Embodiment three:
In the 500ml stainless steel cauldron of quick whipping appts is housed, feed exsiccant nitrogen, after heat temperature raising carries out drying, add the people and be dissolved with 6%CaCl
2Nmp solvent 150 gram, the solvent system water content is less than 100ppm.At N
2Protection adds Powdered Ursol D 6.0000 grams of people down in about 10 ℃.After treating that Ursol D fully dissolves, be cooled to below 5 ℃, add people's p-phthaloyl chloride 11.2800 grams rapidly, quicken simultaneously to stir to be the crumb shape, add neutralizing agent Ca (OH) until polymkeric substance with ice-water bath
2To neutrality, add the washing of deionized water or recycle-water PPTA, filtration again, drying obtains the yellow powder shaped polymer, its logarithmic ratio viscosity is 6.1.Collect filtered liquid, washings, the control pounds per square inch absolute (psia) is at 3.0-5.0KPa, and the still temperature is carried out underpressure distillation and sloughed a large amount of water in the time of 70-90 ℃, steams the water reuse.Mixed solvent after the dehydration and salt enter the desalination still, and pounds per square inch absolute (psia) is at 0.1-1.0KPa in the control still, and the still temperature steams solvent at 150-200 ℃, slough the salt of reaction adding and the salt that neutralization produces.Solvent after the desalination enters crude steam kettle, and pounds per square inch absolute (psia) is at 0.1-3.0KPa in the control still, and the still temperature is sloughed the oligopolymer that produces in preceding component and the reaction at 70-130 ℃.The solvent of sloughing preceding component and oligopolymer enters rectifying tower and further purifies, and the pounds per square inch absolute (psia) of control tower still is at 0.1-3.0KPa, and the still temperature obtains purity and reaches more than 99.5% at 70-130 ℃, and moisture content is less than the solvent of 200ppm.This solvent is entered purification column carry out purifying, obtain purity and reach more than 99.9%, moisture content is nmp solvent 129.0996 grams of 10.2ppm, solvent recovering rate 91.56%, and sealing is preserved and is used to return the polymerization recycle.
Claims (6)
1. the recycle method of polymer solvent in the PPTA building-up reactions, after it is characterized in that Ursol D and p-phthaloyl chloride low temperature poly condensation in N-Methyl pyrrolidone-calcium chloride solvent system finishes, be neutralized to neutrality with neutralizing agent, add deionized water or recycle-water washing PPTA again, filter then, collect filtered liquid, washings, dewater again, desalination, slightly heat up in a steamer, rectifying, purify and reclaim the solvent cycle utilization, described dehydration is for adopting the underpressure distillation dehydration, pounds per square inch absolute (psia) is controlled at 3.0-5.0KPa, the still temperature control is at 70-90 ℃, described desalination is controlled at 0.1-1.0KPa for adopting the mixed solvent after the desalination still will dewater at pounds per square inch absolute (psia), and the still temperature control steams desalination with solvent under 150-200 ℃.
2. the recycle method of polymer solvent in the PPTA building-up reactions according to claim 1 is characterized in that the water content of described solvent system N-Methyl pyrrolidone-calcium chloride is＜120ppm.
3. the recycle method of polymer solvent in the PPTA building-up reactions according to claim 1 is characterized in that described neutralizing agent is carbonate, oxide compound or the oxyhydroxide of alkaline-earth metal.
4. method according to claim 3 is characterized in that neutralizing agent is CaCO3 or CaO or Ca (OH)
2
5. the recycle method of polymer solvent in the PPTA building-up reactions according to claim 1, it is characterized in that described slightly heating up in a steamer is the solvent after the desalination to be entered crude steam kettle slough the oligopolymer that produces in preceding component and the reaction, pounds per square inch absolute (psia) is controlled at 0.1-3.0KPa, and the still temperature control is at 70-130 ℃.
6. the recycle method of polymer solvent in the PPTA building-up reactions according to claim 1, it is characterized in that described rectifying is the solvent through slightly heating up in a steamer to be entered rectifying tower further purify, the pounds per square inch absolute (psia) of tower still is controlled at 0.1-3.0KPa, and the still temperature control is at 70-130 ℃.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101289548B (en) * | 2007-04-16 | 2011-11-30 | 常熟市贝斯特皮革有限公司 | Novel method for recovering solvent for polymerization of poly(p-phenytene terephthalamide) |
| CN101550233B (en) * | 2008-04-03 | 2011-04-20 | 中国神马集团有限责任公司 | Method for continuously recycling solvent-flux for industrially compounding PPTA |
| CN101550232B (en) * | 2008-04-03 | 2011-01-05 | 中国神马集团有限责任公司 | Method for continuously preparing anhydrous solvent for synthesizing PPTA |
| CN103570940B (en) * | 2012-08-06 | 2016-05-25 | 中国石化仪征化纤有限责任公司 | The processing method of the Polymerization Waste that a kind of p-aramid fiber produces in polymerization production process |
| CN103172902B (en) * | 2013-04-19 | 2015-12-09 | 江苏中核华纬工程设计研究有限公司 | The circulation utilization method of solvent in a kind of PPTA reaction |
| CN106565985A (en) * | 2015-10-12 | 2017-04-19 | 中国石化仪征化纤有限责任公司 | Continuous recycling method for solvent in para-aramid polymerization waste |
| CN112940246B (en) * | 2021-04-15 | 2022-09-06 | 中芳特纤股份有限公司 | Efficient energy-saving washing method of poly (p-phenylene terephthalamide) resin |
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