CN1546552A - Semi-continuous preparation method of poly p-phenylene terephthalamide resin - Google Patents
Semi-continuous preparation method of poly p-phenylene terephthalamide resin Download PDFInfo
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- CN1546552A CN1546552A CNA2003101094313A CN200310109431A CN1546552A CN 1546552 A CN1546552 A CN 1546552A CN A2003101094313 A CNA2003101094313 A CN A2003101094313A CN 200310109431 A CN200310109431 A CN 200310109431A CN 1546552 A CN1546552 A CN 1546552A
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Abstract
The invention discloses a semi-continuous preparation method of poly p-phenylene terephthalamide resin which comprises the steps of, proceeding pre-polycondensation to p-phenylene diamine and part of the paraphthaloyl chloride into the dissolvent architecture of solvent and assisting solvent, charging in pre-polymerization member and the remaining paraphthaloyl chloride powder into double bolt extrusion machine, letting in dried liquid ammonia to neutralize the hydrogen chloride gas produced in the reaction, and charging macromolecular addictive polyvinylpyrrolidone into the double bolt extrusion machine to obtain the polymer.
Description
Technical field
The present invention relates to the preparation method of PPTA resin, relating in particular to the twin screw extruder is the semicontinuous method for preparing the PPTA resin of main reactor.
Background technology
The PPTA resin, be preparation high strength, high-modulus, resistant to elevated temperatures special fibre p-aramid fiber and raw material with aramid pulp of high wear resistance, high dispersion, can be made into specific tenacity with it is that 5～6 times of steel wire, specific modulus are 2～3 times of steel wire, 350 ℃ of pyritous aramid fibers of ability and as the desirable surrogate of asbestos, make insulation paper high temperature resistant, rub resistance, be widely used in departments such as space flight and aviation, traffic communication, chemical industry.
The method of existing preparation PPTA resin has usually:
(1) intermittence type polymerization
USP 5,726, and 275 disclose a kind of method of batch preparation high quality poly P phenylene diamine terephthalamide resin.Be that Ursol D and p-phthaloyl chloride are in N-N-methyl-2-2-pyrrolidone N--calcium chloride solvent system, batchwise polymerization prepares the PPTA resin, be reflected at have one have simultaneously stir and the cylindrical reactor vessel of the mixing gear of granulation in carry out, when p-phthaloyl chloride adds fashionable, reaction system is subjected to gyrate stirring, the polymkeric substance that generates is pulverized, i.e. the pulverizing of polyreaction and polymerisate is carried out in same reaction vessel.Gyrate alr mode can guarantee the reaction system thorough mixing, is swift in response to carry out, and obtains the polymkeric substance of higher inherent viscosity.
This method prepares the PPTA resin can only carry out in batches, and efficient is lower and be more difficult to get the resin of stable performance.
(2) continous way polymerization
CN 1048710A discloses the continuous condensed method for preparing the high viscosity PPTA.Ursol D is carried out precondensation with the part p-phthaloyl chloride earlier in N-N-methyl-2-2-pyrrolidone N--calcium chloride solvent system, add again enter polycondensation in the exhaust twin screw extruder after remaining fusion p-phthaloyl chloride mixes in self-cleaning type twin shaft mixing tank, add additive such as pyridine compound such as pyridine, α-Jia Jibiding, beta-picoline waits the limiting viscosity that improves the PPTA resin.It is solvent that this method has not only been avoided with the hexamethylphosphoramide with carcinogenesis (HMPA) as USP 3850888 patent reports such as grade, and solved as stopping up easily with the jet mixer batch mixing that USP 3884881 is reported, influence continuous condensed problem such as carry out smoothly.
But the shortcoming of this method is to have used in polymerization process pyridine compound with foul smell such as pyridine as acid absorber, make solvent recuperation become more complexity and severe operational environment, and p-phthaloyl chloride adds mixing tank with molten state through volume pump, reach and the unusual difficulty of mol ratio such as Ursol D.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of semicontinuous method for preparing the PPTA resin, to overcome the heat radiation difficulty that prior art exists, easily cause the defective of local superheating, and in the serialization polycondensation process, apparatus for feeding costliness, Measuring Precision require high unfavorable factor.
The said PPTA resin of the present invention is the polymkeric substance with following chemical structure:
The present invention be a kind of be the semicontinuous method for preparing the poly P phenylene diamine terephthalamide resin of main reactor with the twin screw extruder, may further comprise the steps:
(1) mol ratio of Ursol D and p-phthaloyl chloride is 1: 1～1: 1.01, Ursol D earlier carries out precondensation with 20～50% p-phthaloyl chloride (TPC) of gross weight in the solvent system of solvent and solubility promoter, generate mobile well preshrunk aggressiveness;
Said solvent is the amides polar solvent, comprises in N-Methyl pyrrolidone, N,N-dimethylacetamide or the hexamethylphosphoric acid triamide one or more;
Said solubility promoter is the muriate of basic metal or alkaline-earth metal, comprises in calcium chloride, lithium chloride, magnesium chloride or the tin chloride one or more;
The weight ratio of solvent and solubility promoter is 1: 0.02～0.15;
The concentration of Ursol D is 0.30～0.50mol/L in the solvent,
The precondensation temperature is-15～35 ℃, and the precondensation time is 5～60 minutes;
(2) preshrunk aggressiveness and remaining p-phthaloyl chloride powder join in the twin screw extruder, and logical exsiccant liquefied ammonia is with the hydrogen chloride gas of neutralization reaction generation;
(3) after p-phthaloyl chloride joins twin screw extruder fully,, extrude the polymer of flaxen crumb shape at the 3rd section adding polymeric additive polyvinylpyrrolidone of twin screw.The residence time of reaction system in double-screw reactor is 2～25 minutes, is preferably 5～20 minutes, and condensation temperature is 30～90 ℃, preferably is controlled at 60～75 ℃; The residence time of material in twin screw can be regulated by parameters such as change machine length, screw rod geometric angle and screw speeds, be generally 2～25 minutes, be preferably 5～20 minutes, the suffered shearing rate of material is higher in the twin screw extruder, reaches 150s
-1More than, help the collision of reactant functional group and the orientation of molecular chain, and gas barrier in position is housed, can constantly get rid of the lower-molecular substance that should generate by vacuumizing, as hydrogenchloride, thereby help improving the molecular weight of polycondensation speed and polymerisate.
The scope of the molecular weight of polyvinylpyrrolidone is below 50 000, and the scope of preferred molecular weight is 1 000～50 000, and consumption is 0.5～10g/100ml solvent.
The adding of polyvinylpyrrolidone can improve the solubility property of polymerisate-PPTA in polymerization system, further improves the molecular weight of polycondensation product.
(4) polymer of extruding was left standstill 1～8 hour, adopt conventional method to collect the PPTA resin, generally comprise and remove solvent, pulverizing, washing, drying and other steps, obtain faint yellow PPTA toner.
Preparing in the method for PPTA resin in the present invention, is 1: 35～60 as the length-to-diameter ratio of the twin screw extruder of main reactor.
Prepare in the method for PPTA resin in the present invention, exsiccant liquefied ammonia adds in the double-screw reactor continuously.
The limiting viscosity of the PPTA resin that the employing aforesaid method makes is 4～7.0dl/g.The limiting viscosity of PPTA (I.V.) is to be solvent with 95～98% the vitriol oil, is made into the solution of 0.5g/100ml, adopts Ubbelohde viscometer, measures under 30 ℃ of constant temperature, calculates by following formula:
η
inh＝ln(t/t
0)/c
T in the formula
0Be the solvent elution time; T is the solution elution time; C is a polymer solution concentration, and unit is g/100ml.
The resin that makes by the present invention, solubility property in the vitriol oil is good, and good spinnability, limiting viscosity are the formed lytropic liquid crystals of the resin of 4～7dl/g, after doing spray one wet spinning, precursor intensity is 20～24g/d, and extension at break is 1～6%, and modulus is 300～500g/d, after thermal stretch, fibre strength is 20～28g/d, and extension at break is 1～4%, and modulus is 600～1000g/d.Fiber colour is good, stable performance, and the good spinnability of resin, institute's fiber colour that spins is good, intensity height, stable performance.
Embodiment
Embodiment 1
In the anhydrous N-Methyl pyrrolidone of 4 500ml (NMP) solution, the Calcium Chloride Powder Anhydrous that adds 0.30kg is mixed with NMP-CaCl
2Solution adds 0.216kg Ursol D (PPDA) about 15 ℃, allow it fully dissolve, and is cooled to 5 ℃, and add 0.100kg p-phthaloyl chloride (TPC) and carry out precondensation, the prepolycondensate that reaction generates, 5 ℃ of following constant temperature are standby being lower than.It is Φ 25 that prepolycondensate is added diameter with remaining 0.306kg p-phthaloyl chloride (TPC) powder, and length-to-diameter ratio is 40, and rotating speed is in the double screw rod extruder of 200rpm, and feeds exsiccant liquefied ammonia.The temperature of control double-screw reactor is at 70 ℃, about 15 minutes, can extrude faint yellow corn powdered polycondensation product, left standstill 2 hours, behind the removal solvent, pulverizing, washing, drying obtain faint yellow PPTA toner, its limiting viscosity is at 5.03dl/g, precursor intensity after doing spray-wet spinning is 21～23g/d, and modulus is 360～370g/d, and elongation at break is 5～6%.
Embodiment 2
In 4 500mlN-methyl-2-pyrrolidone (NMP) solution, the Calcium Chloride Powder Anhydrous that adds 0.30kg is mixed with NMP-CaCl2 solution, about 20 ℃, add 0.203kg Ursol D (PPDA), allow it fully dissolve, be cooled to 5 ℃, adding 0.22kg p-phthaloyl chloride (TPC) carries out precondensation and carries out precondensation, the prepolycondensate that reaction generates, and 5 ℃ of following constant temperature are standby being lower than.It is Φ 25 that prepolycondensate is added diameter with remaining 0.203kg p-phthaloyl chloride (TPC) powder, length-to-diameter ratio is 40, rotating speed is in the double screw rod extruder of 200rpm, the temperature of control double-screw reactor is at 50 ℃, the 3rd section at twin screw adds 0.27kg PVP K30, about 15 minutes, can extrude faint yellow corn powdered polycondensation product, left standstill 2 hours, and behind the removal solvent, pulverized, washing, drying obtains faint yellow PPTA toner, its limiting viscosity is 5.54dl/g, precursor intensity after doing spray-wet spinning is 22～24g/d, and modulus is 370～380g/d, and elongation at break is 5～6%.
Comparative Examples 1
In 4 500mlN-methyl-2-pyrrolidone (NMP) solution, the Calcium Chloride Powder Anhydrous that adds 0.30kg is mixed with NMP-CaCl
2Solution adds 0.216kg Ursol D (PPDA) about 20 ℃, allow it fully dissolve, and is cooled to 5 ℃, and add 0.203kg p-phthaloyl chloride (TPC) and carry out precondensation, the prepolycondensate that reaction generates, 5 ℃ of following constant temperature are standby being lower than.It is Φ 25 that prepolycondensate is added diameter with remaining 0.203kg p-phthaloyl chloride (TPC) powder, length-to-diameter ratio is 40, rotating speed is in the double screw rod extruder of 200rpm, the temperature of control double-screw reactor is at 50 ℃, at the speed feeding exsiccant liquefied ammonia of opening for feed with 2g/min, and add 0.27kg PVP K30 at the 3rd section of twin screw, about 15 minutes, can extrude faint yellow corn powdered polycondensation product, left standstill 2 hours, after removing solvent, pulverize, washing, drying obtains faint yellow PPTA toner, and its limiting viscosity is at 6.13dl/g, and the precursor intensity after doing spray-wet spinning is 25～27g/d, modulus is 370～390g/d, and elongation at break is 5～6%.
Claims (10)
1. a semicontinuous method for preparing the PPTA resin is characterized in that, may further comprise the steps:
(1) mol ratio of Ursol D and p-phthaloyl chloride is 1: 1～1: 1.01, and Ursol D earlier carries out precondensation with 20～50% p-phthaloyl chloride of gross weight in the solvent system of solvent and solubility promoter;
Said solvent is the amides polar solvent;
Said solubility promoter is the muriate of basic metal or alkaline-earth metal;
The prepolymerization temperature is-15～35 ℃;
(2) preshrunk aggressiveness and remaining p-phthaloyl chloride powder join in the twin screw extruder, and logical liquefied ammonia is with the hydrogen chloride gas of neutralization reaction generation;
(3) after p-phthaloyl chloride joins twin screw extruder fully, in twin screw extruder, add polyvinylpyrrolidone, extrude the polymer of flaxen crumb shape;
(4) polymer of extruding is left standstill, adopt conventional method to collect the PPTA resin.
2. method according to claim 1 is characterized in that, said amides polar solvent comprises one or more in N-Methyl pyrrolidone, N,N-dimethylacetamide or the hexamethylphosphoric acid triamide.
3. method according to claim 1 is characterized in that the muriate of said basic metal or alkaline-earth metal comprises one or more in calcium chloride, lithium chloride, magnesium chloride or the tin chloride.
4. method according to claim 1 is characterized in that the weight ratio of solvent and solubility promoter is 1: 0.02～0.15, and the concentration of Ursol D is 0.30～0.50mol/L in the solvent.
5. method according to claim 1 is characterized in that, the residence time of reaction system in double-screw reactor is 2～25 minutes, and condensation temperature is 30～90 ℃.
6. method according to claim 5 is characterized in that, the residence time is 5～20 minutes, and condensation temperature is 60～75 ℃.
7. method according to claim 1 is characterized in that, the scope of the molecular weight of polyvinylpyrrolidone is below 50 000.
8. method according to claim 7 is characterized in that, the scope of the molecular weight of polyvinylpyrrolidone is for being 1 000～50 000, and consumption is 0.5～10g/100ml solvent.
9. method according to claim 1 is characterized in that, the length-to-diameter ratio of twin screw extruder is 1: 35～1: 60.
10. method according to claim 1 is characterized in that exsiccant liquefied ammonia adds in the twin screw extruder continuously.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265326B (en) * | 2008-04-21 | 2010-12-15 | 中国石化仪征化纤股份有限公司 | Method and device for preparing polypara-phthaloyl para-phenylene diamine resin |
| CN101928395A (en) * | 2010-08-16 | 2010-12-29 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyphenylene terephthalamide resin |
| 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 |
| CN101985497A (en) * | 2010-09-28 | 2011-03-16 | 东华大学 | Semi-continuous preparation method for solution of heterocycle-containing aromatic polyamide copolymer |
| CN101691673B (en) * | 2009-10-15 | 2011-09-14 | 浙江金昊特种纤维有限公司 | Preparation technique of ultra-high molecular weight polyethylene fibers |
| CN101617074B (en) * | 2007-02-23 | 2012-02-01 | 3M创新有限公司 | Polymeric fibers and methods of making |
| CN101220148B (en) * | 2007-01-08 | 2012-03-14 | 江苏昊诚皮革新材料有限公司 | Novel preparation technique for poly (p-phenylene terephthalamide) |
| CN102558548A (en) * | 2011-12-15 | 2012-07-11 | 东华大学 | Method for preparing poly(p-phenylene terephthalamide) (PPTA) resin |
| CN106496547A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of poly- paraphenylene terephthalamide to diphenylamines |
| CN110229327A (en) * | 2019-06-05 | 2019-09-13 | 赣州龙邦材料科技有限公司 | A kind of less salt aramid fiber polymeric compound and preparation method thereof |
| CN112375216A (en) * | 2020-11-10 | 2021-02-19 | 蓝星（成都）新材料有限公司 | High molecular weight para-aramid pulp and preparation method thereof |
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2003
- 2003-12-15 CN CN 200310109431 patent/CN1217977C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220148B (en) * | 2007-01-08 | 2012-03-14 | 江苏昊诚皮革新材料有限公司 | Novel preparation technique for poly (p-phenylene terephthalamide) |
| CN101617074B (en) * | 2007-02-23 | 2012-02-01 | 3M创新有限公司 | Polymeric fibers and methods of making |
| 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 |
| CN101265326B (en) * | 2008-04-21 | 2010-12-15 | 中国石化仪征化纤股份有限公司 | Method and device for preparing polypara-phthaloyl para-phenylene diamine resin |
| CN101691673B (en) * | 2009-10-15 | 2011-09-14 | 浙江金昊特种纤维有限公司 | Preparation technique of ultra-high molecular weight polyethylene fibers |
| CN101928395A (en) * | 2010-08-16 | 2010-12-29 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyphenylene terephthalamide resin |
| CN101985497A (en) * | 2010-09-28 | 2011-03-16 | 东华大学 | Semi-continuous preparation method for solution of heterocycle-containing aromatic polyamide copolymer |
| CN102558548A (en) * | 2011-12-15 | 2012-07-11 | 东华大学 | Method for preparing poly(p-phenylene terephthalamide) (PPTA) resin |
| CN102558548B (en) * | 2011-12-15 | 2014-01-29 | 东华大学 | Method for preparing poly(p-phenylene terephthalamide) (PPTA) resin |
| CN106496547A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of poly- paraphenylene terephthalamide to diphenylamines |
| WO2017214743A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Process for preparing poly(terephthaloyl-p-phenylene diamine) |
| CN110229327A (en) * | 2019-06-05 | 2019-09-13 | 赣州龙邦材料科技有限公司 | A kind of less salt aramid fiber polymeric compound and preparation method thereof |
| CN110229327B (en) * | 2019-06-05 | 2022-03-22 | 赣州龙邦材料科技有限公司 | Low-salt aramid polymer and preparation method thereof |
| CN112375216A (en) * | 2020-11-10 | 2021-02-19 | 蓝星（成都）新材料有限公司 | High molecular weight para-aramid pulp and preparation method thereof |
| CN112375216B (en) * | 2020-11-10 | 2023-04-25 | 蓝星（成都）新材料有限公司 | High molecular weight para-aramid pulp and preparation method thereof |
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