CN102532529A - Method for preparing terephthaloyl phenylenediamine resin through low-temperature solution out-of-phase polycondensation - Google Patents
Method for preparing terephthaloyl phenylenediamine resin through low-temperature solution out-of-phase polycondensation Download PDFInfo
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- CN102532529A CN102532529A CN201210004071XA CN201210004071A CN102532529A CN 102532529 A CN102532529 A CN 102532529A CN 201210004071X A CN201210004071X A CN 201210004071XA CN 201210004071 A CN201210004071 A CN 201210004071A CN 102532529 A CN102532529 A CN 102532529A
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Abstract
The invention relates to a method for preparing terephthaloyl phenylenediamine resin through low-temperature solution out-of-phase polycondensation, which comprises the following steps of: (1) adding a N-methyl pyrrolidone-cosolvent in a reaction vessel, introducing nitrogen, agitating at a room temperature, adding phenylenediamine and cooling solution to 15 DEG C below zero-30 DEG C after dissolution; (2) adding a low-boiling point micromolecule non-polar solvent in the solution obtained in the step (1), agitating till the dispersion is homogeneous, adding terephthaloyl chloride with a total content of 1/5-3/5, adding an acid absorbent and reacting for 20-40 minutes at a temperature of 15 DEG C below zero-10 DEG C; and (3) controlling the temperature of the solution obtained in the step (2) to 15 DEG C below zero-30 DEG C and adding surplus terephthaloyl chloride to obtain the terephthaloyl phenylenediamine resin after the end of reaction. The preparation method has the advantages of simplicity, low cost, better heat radiation, lower requirement on a reaction instrument, longer condensation occurrence time and stable reaction, and the resin with higher molecular weight is obtained.
Description
Technical field
The invention belongs to the preparation field of poly P phenylene diamine terephthalamide resin, the polycondensation of particularly a kind of cryogenic fluid out-phase prepares the method for poly P phenylene diamine terephthalamide resin.
Background technology
PPTA type aramid fiber is the mesomorphism spinning solution that in the vitriol oil, is formed by PPTA (PPTA) resin dissolves, processes through the spinning processes of overdrying spray silk spinning, and staple has the Kevlar of Du Pont, Supreme Being people's Twaron etc.The most outstanding performance of p-aramid fiber is HS, high-modulus and outstanding characteristics such as thermotolerance, resistance to chemical attack and light specific gravity, is a kind of high-performance fiber.The polymeric performance of PPTA directly determines the performance of fiber, spin HS, high-modulus PPTA fiber, and the reduced viscosity of the polymkeric substance of PPTA must be more than 5.0dl/g, and the performance of the high more then spun PPTA fiber of molecular weight is good more.
Preparing PPTA polymer method commonly used is low-temperature solution polycondensation; Be about to monomer TPC and PPDA in aprotic polar solvent such as N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), hexamethylphosphoramide amide type solvents such as (HMPA), under the condition of gentleness, carry out polycondensation.But it is found that afterwards that HMPA had carcinogenesis, and recovery is upward difficult, uses the acid amides-salt solvent system of comparison safety in the industry instead.Because the NMP solubility property is more less better than HMPA, therefore can increase its solvability, now NMP/CaCl through adding aided metal calcium chloride, lithium chloride
2Solvent system is widely used in industry, but this system gel phenomenon takes place relatively early when carrying out the PPTA polymerization, and gel can hinder the continuation growth of molecular weight prematurely.
And domestic less about report in this respect, patent CN 200610023364.7 discloses with NEP/CaCl
2As polymer solvent, though postponed the time of gelation, its solubility property does not have great change.Patent CN 101781399A discloses a kind of with N, and N-dimethyl-imidazolinone (DMI) is a solvent, though this method contaminative is smaller, solvability is better relatively in the production process, and the price of DMI is high more a lot of than NMP.
U.S. Pat 4038259 is reported in the N-methyl sky alkane ketone solution carries out the technology that polycondensation prepares the linear polyphenylene sulfide resin, and has successfully carried out suitability for industrialized production.
The method of above-mentioned synthetic PPTA all is to adopt the method for low temperature solution polymerization, because polymerization reaction heat is big, so the control of polymerization process heat is the key in the PPTA preparation engineering always.Though adopt solution polymerization can reduce reactant viscosity, thereby reduce reaction system viscosity, thereby improve the control of heat.But from the angle of polymerization reaction engineering, suspension polymerization not only can reduce speed of response, and can improve heat control.
Summary of the invention
Technical problem to be solved by this invention provides the method that the polycondensation of a kind of cryogenic fluid out-phase prepares the poly P phenylene diamine terephthalamide resin; This method has characteristics simple to operate, that cost is low; Particularly thermal diffusivity is relatively good in the production process; Requirement to reaction kit is lower, and it is long to occur changing the phenomenon time with fixed attention, stable reaction.
A kind of cryogenic fluid out-phase of the present invention polycondensation prepares the method for poly P phenylene diamine terephthalamide resin, comprises
(1) in reactor drum, add N-Methyl pyrrolidone-solubility promoter, logical nitrogen stirs under the room temperature, adds Ursol D then, makes solution be cooled to-15～30 ℃ after the dissolving, and wherein the concentration of Ursol D is 0.3～0.5mol/L;
(2) in the solution that step (1) obtains, add lower boiling small molecules non-polar solvent; Be stirred to and be uniformly dispersed; The 1/5-3/5 that adds the p-phthaloyl chloride total amount then; Add acid absorber again, at-15～10 ℃ of reaction 20-40min, wherein the concentration of absorption agent is 0～2.5 times of Ursol D monomer molar concentration;
The temperature of the solution that (3) step (2) is obtained is controlled at-15～30 ℃, adds remaining p-phthaloyl chloride then, stirs; Gel, rod climbing phenomenon appear in reaction, stopped reaction after being blended, washing at last; Remove and desolvate, drying promptly gets the pale yellow powder poly P phenylene diamine terephthalamide.
The preparation method of the N-Methyl pyrrolidone-solubility promoter described in the step (1) is: feed nitrogen, in container, add N-Methyl pyrrolidone NMP, and then add solubility promoter, 40-80 ℃ of following stirring and dissolving, be cooled to room temperature, get final product.
The mass ratio of described N-Methyl pyrrolidone and solubility promoter is 5: 1～50: 1, and described solubility promoter is CaCl
2Or LiCl.
Described N-Methyl pyrrolidone is handled through molecular sieve drying, and concrete operations are that molecular sieve was dried by the fire 4～8 hours in high temperature (400-600 ℃), put in the N-Methyl pyrrolidone at 120 ℃ then; Described CaCl
2Be powder, earlier 200～500 ℃ of bakings 0.5-6 hour, then at CaCl
2When being 100～200 ℃, uses powder temperature.
The Ursol D that is added in the step (1) and the mol ratio of the total add-on of p-phthaloyl chloride are 1: 1.
Lower boiling small molecules non-polar solvent described in the step (2) is pentane or normal hexane, and the volume ratio of itself and N-Methyl pyrrolidone is 1: 5～3: 1.
Lower boiling small molecules non-polar solvent described in the step (2) is handled through molecular sieve drying, and concrete operations are that molecular sieve was dried by the fire 4～8 hours in high temperature (400-600 ℃), put in the lower boiling small molecules non-polar solvent at 120 ℃ then.
Absorption agent described in the step (2) is a pyridine.
The content of moisture is 0～500ppm in the resulting solution of step (2).
Reagent used among the present invention is the commercially available prod, and wherein the purity of PPDA and TPC is all greater than 98%.
Factors such as the content of monomeric concentration, monomeric mol ratio, water cut, pyridine add-on, initial temperature, calcium chloride, calcium chloride drying mode are all influential to the polymeric logarithmic viscosity number of PPTA in the polycondensation process.Accurately control the mol ratio of reaction monomers, the water cut that as far as possible reduces in the solvent system will make the logarithmic viscosity number of product that raising is by a relatively large margin arranged.
The present invention is solvent with the N-Methyl pyrrolidone, adds low-boiling non-solvents such as pentane, normal hexane as dispersion agent, transmits heat and heat radiation thereby can improve.Requirement to temperature in the system is not very strict in the case, and temperature can be reacted at-15～30 ℃.It is relatively good that this method has in the characteristics simple to operate, that cost is low, particularly production process thermal diffusivity, lower to the requirement of reaction kit, and it is long to occur changing the phenomenon time with fixed attention, stable reaction.
The present invention is a raw material with p-phthaloyl chloride (TPC) and Ursol D (PPDA), NMP/CaCl
2System is a solvent, on the basis of this solvent, adds the lower boiling solvent of nonpolar small molecules, N-Methyl pyrrolidone/CaCl in this system
2In mass ratio be 50: 1～5: 1, the volume ratio of N-Methyl pyrrolidone/low boiling point solvent system is 5: 1～1: 3.
In N-Methyl pyrrolidone/calcium chloride solvent/small molecules lower boiling non-polar solvent system, carry out the low temperature solution polymerization of PPTA (PPTA), obtained the PPTA of high logarithmic viscosity number, confirmed polymerization process condition.
In N-Methyl pyrrolidone/calcium chloride solvent/small molecules lower boiling non-polar solvent, carried out the PPTA low temperature solution polymerization; Be reflected in this system than the gentleness of carrying out in N-Methyl pyrrolidone/calcium chloride solvent system; The time ratio that needed temperature does not need very low gel phenomenon to take place is later, and the polymeric molecular weight of PPTA increases.
Beneficial effect
Preparing method of the present invention is simple, and cost is low, adds low-boiling non-solvents such as pentane, normal hexane as dispersion agent; Thermal diffusivity is relatively good, and is lower to the requirement of reaction kit, and it is long to occur changing the phenomenon time with fixed attention; Stable reaction, and obtained the higher resin of molecular weight ratio.
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 the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to 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
The molecular sieve of 4A type 400 ℃ of high-temperature bakings 8 hours, is poured into a certain amount of molecular sieve respectively in the solvent that fills NMP, normal hexane, pentane when being cooled to 120 ℃.With the calcium chloride powder 200 ℃ of high-temperature bakings 6 hours; In container, add the NMP that handled, feed nitrogen, add 150 ℃ calcium chloride (CaCl
2) powder, the weight ratio of N-Methyl pyrrolidone and calcium chloride is 50: 1, in 50 ℃ of stirrings, dissolving, is cooled to room temperature, obtains NMP/CaCl
2Solvent.
NMP/CaCl with 100ml
2Solvent joins in the glass reactor that the stainless steel stirring rod is housed, and feeds the protection of exsiccant high pure nitrogen, at room temperature, adds Ursol D powder 4.3243g in the time of stirring; After treating that it dissolves fully, be cooled to-5 ℃, add the normal hexane of 20ml, be stirred to and be uniformly dispersed; Add the 3.2574g p-phthaloyl chloride, add the pyridine of 1ml, continue to stir, react second crowd of p-phthaloyl chloride 4.8861g of adding after 30 minutes; Strengthen stirring velocity, react about 5-10 minute existing gelatin phenomenon, continue to stir and be broken into powder to gel piece in 30 minutes, wash at last; Remove and to desolvate, drying finally obtains logarithmic viscosity number and is 5.2 pale yellow powder.
Embodiment 2
The molecular sieve of 4A type 500 ℃ of high-temperature bakings 5 hours, is poured into a certain amount of molecular sieve respectively in the solvent that fills NMP, normal hexane, pentane when being cooled to 120 ℃.With the calcium chloride powder 220 ℃ of high-temperature bakings 4 hours; In container, add the NMP that handled, feed nitrogen, add 150 ℃ calcium chloride (CaCl
2) powder, the weight ratio of N-Methyl pyrrolidone and calcium chloride is 10: 1, in 50 ℃ of stirrings, dissolving, is cooled to room temperature.
NMP/CaCl with 100ml
2Solvent joins in the glass reactor that the stainless steel stirring rod is housed, and feeds the protection of exsiccant high pure nitrogen, at room temperature; Add Ursol D powder 4.3243g when stirring, treat that it dissolves fully after, be cooled to certain temperature; The normal hexane that adds 50ml is stirred to and is uniformly dispersed adding 3.2574g p-phthaloyl chloride; The pyridine that adds 1ml continues to stir, and reacts to add second crowd of p-phthaloyl chloride 4.8861g after 30 minutes; Strengthen stirring velocity, react about 10-25 minute existing gelatin phenomenon, continue stirring 30 minutes to gel piece and be broken into powder.Final acquisition logarithmic viscosity number is 5.54 pale yellow powder.
Embodiment 3
The molecular sieve of 4A type 600 ℃ of high-temperature bakings 4 hours, is poured into a certain amount of molecular sieve respectively in the solvent that fills NMP, normal hexane, pentane when being cooled to 120 ℃.With the calcium chloride powder 250 ℃ of high-temperature bakings 4 hours; In container, add the NMP that handled, feed nitrogen, add 150 ℃ calcium chloride (CaCl
2) powder, the weight ratio of N-Methyl pyrrolidone and calcium chloride is 5: 1, in 50 ℃ of stirrings, dissolving, is cooled to room temperature.
The NMP/CaCl2 solvent of 100ml is joined in the glass reactor that the stainless steel stirring rod is housed, feed the protection of exsiccant high pure nitrogen, at room temperature; Add Ursol D powder 4.3243g when stirring, treat that it dissolves fully after, be cooled to certain temperature; The normal hexane that adds 100ml is stirred to and is uniformly dispersed adding 3.2574g p-phthaloyl chloride; The pyridine that adds 1ml continues to stir, and reacts to add second crowd of p-phthaloyl chloride 4.8861g after 30 minutes; Strengthen stirring velocity, react about 20-25 minute existing gelatin phenomenon, continue stirring 30 minutes to gel piece and be broken into powder.Final acquisition logarithmic viscosity number is 5.1 pale yellow powder.
Embodiment 4
The molecular sieve of 4A type 400 ℃ of high-temperature bakings 8 hours, is poured into a certain amount of molecular sieve respectively in the solvent that fills NMP, normal hexane, pentane when being cooled to 120 ℃.With the calcium chloride powder 200 ℃ of high-temperature bakings 6 hours; In container, add the NMP that handled, feed nitrogen, add 150 ℃ calcium chloride (CaCl
2) powder, the weight ratio of N-Methyl pyrrolidone and calcium chloride is 50: 1, in 50 ℃ of stirrings, dissolving, is cooled to room temperature.
The NMP/CaCl2 solvent of 100ml is joined in the glass reactor that the stainless steel stirring rod is housed, feed the protection of exsiccant high pure nitrogen, at room temperature; Add Ursol D powder 4.3243g when stirring, treat that it dissolves fully after, be cooled to certain temperature; The pentane that adds 20ml is stirred to and is uniformly dispersed adding 3.2574g; The pyridine that adds 1ml continues to stir, and reacts to add second crowd of p-phthaloyl chloride 4.8861g after 30 minutes; Strengthen stirring velocity, react about 5-10 minute existing gelatin phenomenon, continue stirring 30 minutes to gel piece and be broken into powder.Final acquisition logarithmic viscosity number is 4.8 pale yellow powder.
Embodiment 5
The molecular sieve of 4A type 500 ℃ of high-temperature bakings 5 hours, is poured into a certain amount of molecular sieve respectively in the solvent that fills NMP, normal hexane, pentane when being cooled to 120 ℃.With the calcium chloride powder 220 ℃ of high-temperature bakings 4 hours; In container, add the NMP that handled, feed nitrogen, add 150 ℃ calcium chloride (CaCl
2) powder, the weight ratio of N-Methyl pyrrolidone and calcium chloride is 10: 1, in 50 ℃ of stirrings, dissolving, is cooled to room temperature.
The NMP/CaCl2 solvent of 100ml is joined in the glass reactor that the stainless steel stirring rod is housed, feed the protection of exsiccant high pure nitrogen, at room temperature; Add Ursol D powder 4.3243g when stirring, treat that it dissolves fully after, be cooled to certain temperature; The pentane that adds 50ml is stirred to and is uniformly dispersed adding 3.2574g p-phthaloyl chloride; The pyridine that adds 1ml continues to stir, and reacts to add second crowd of p-phthaloyl chloride 4.8861g after 30 minutes; Strengthen stirring velocity, react about 15-20 minute existing gelatin phenomenon, continue stirring 30 minutes to gel piece and be broken into powder.Final acquisition logarithmic viscosity number is 5.21 pale yellow powder.
Embodiment 6
The molecular sieve of 4A type 600 ℃ of high-temperature bakings 4 hours, is poured into a certain amount of molecular sieve respectively in the solvent that fills NMP, normal hexane, pentane when being cooled to 120 ℃.With the calcium chloride powder 250 ℃ of high-temperature bakings 4 hours; In container, add the NMP that handled, feed nitrogen, add 150 ℃ calcium chloride (CaCl
2) powder, the weight ratio of N-Methyl pyrrolidone and calcium chloride is 5: 1, in 50 ℃ of stirrings, dissolving, is cooled to room temperature.
The NMP/CaCl2 solvent of 100ml is joined in the glass reactor that the stainless steel stirring rod is housed, feed the protection of exsiccant high pure nitrogen, at room temperature; Add Ursol D powder 4.3243g when stirring, treat that it dissolves fully after, be cooled to certain temperature; The pentane that adds 100ml is stirred to and is uniformly dispersed adding 3.2574g p-phthaloyl chloride; The pyridine that adds 1ml continues to stir, and reacts to add second crowd of p-phthaloyl chloride 4.8861g after 30 minutes; Strengthen stirring velocity, react about 15-25 minute existing gelatin phenomenon, continue stirring 30 minutes to gel piece and be broken into powder.Final acquisition logarithmic viscosity number is 5.56 pale yellow powder.
Claims (9)
1. cryogenic fluid out-phase polycondensation prepares the method for poly P phenylene diamine terephthalamide resin, comprises
(1) in reactor drum, add N-Methyl pyrrolidone-solubility promoter, logical nitrogen stirs under the room temperature, adds Ursol D then, makes solution be cooled to-15～30 ℃ after the dissolving, and wherein the concentration of Ursol D is 0.3～0.5mol/L;
(2) in the solution that step (1) obtains, add lower boiling small molecules non-polar solvent; Be stirred to and be uniformly dispersed; The 1/5-3/5 that adds the p-phthaloyl chloride total amount then; Add acid absorber again, at-15～10 ℃ of reaction 20-40min, wherein the concentration of absorption agent is 0～2.5 times of Ursol D monomer molar concentration;
The temperature of the solution that (3) step (2) is obtained is controlled at-15～30 ℃, adds remaining p-phthaloyl chloride then, stirs; Gel, rod climbing phenomenon appear in reaction, stopped reaction after being blended, washing at last; Remove and desolvate, drying promptly gets poly P phenylene diamine terephthalamide.
2. a kind of cryogenic fluid out-phase according to claim 1 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin; It is characterized in that: the compound method of the N-Methyl pyrrolidone-solubility promoter described in the step (1) is: feed nitrogen; In container, add N-Methyl pyrrolidone NMP, and then add solubility promoter, 40-80 ℃ of following stirring and dissolving; Be cooled to room temperature, get final product.
3. a kind of cryogenic fluid out-phase according to claim 2 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin, it is characterized in that: the mass ratio of described N-Methyl pyrrolidone and solubility promoter is 5: 1～50: 1, and described solubility promoter is CaCl
2Or LiCl.
4. a kind of cryogenic fluid out-phase according to claim 3 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin; It is characterized in that: described N-Methyl pyrrolidone is handled through molecular sieve drying; Concrete operations be with molecular sieve in 400-600 ℃ the baking 4～8 hours, put in the N-Methyl pyrrolidone at 120 ℃ then; Described CaCl
2Be powder, earlier 200～500 ℃ of bakings 0.5-6 hour, then at CaCl
2When being 100～200 ℃, uses powder temperature.
5. a kind of cryogenic fluid out-phase according to claim 1 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin, it is characterized in that: the Ursol D that is added in the step (1) and the mol ratio of the total add-on of p-phthaloyl chloride are 1: 1.
6. a kind of cryogenic fluid out-phase according to claim 1 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin; It is characterized in that: the lower boiling small molecules non-polar solvent described in the step (2) is pentane or normal hexane, and the volume ratio of itself and N-Methyl pyrrolidone is 1: 5～3: 1.
7. a kind of cryogenic fluid out-phase according to claim 1 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin; It is characterized in that: the lower boiling small molecules non-polar solvent described in the step (2) is crossed the molecular sieve drying treatment; Concrete operations be with molecular sieve in 400-600 ℃ the baking 4～8 hours, put in the lower boiling small molecules non-polar solvent at 120 ℃ then.
8. a kind of cryogenic fluid out-phase according to claim 1 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin, it is characterized in that: the absorption agent described in the step (2) is a pyridine.
9. a kind of cryogenic fluid out-phase according to claim 1 polycondensation prepares the method for poly P phenylene diamine terephthalamide resin, it is characterized in that: the content of moisture is 0～500ppm in the resulting solution of step (2).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030804A (en) * | 2012-12-31 | 2013-04-10 | 东华大学 | Preparation method of p-phenylene terephthamide resin through low-temperature solution out-phase polycondensation |
| CN114316256A (en) * | 2021-12-08 | 2022-04-12 | 山东聚芳新材料股份有限公司 | Synthesis method of superfine para-aramid resin |
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| CN101328266A (en) * | 2008-07-08 | 2008-12-24 | 中国石化仪征化纤股份有限公司 | Preparation of high viscosity Poly(p-phenyleneterephthalamide) resin |
| CN101798385A (en) * | 2010-03-15 | 2010-08-11 | 苏州兆达特纤科技有限公司 | Production technology of poly (p-phenytene terephthalamide) resin |
| CN102040733A (en) * | 2010-11-12 | 2011-05-04 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
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| CN101328266A (en) * | 2008-07-08 | 2008-12-24 | 中国石化仪征化纤股份有限公司 | Preparation of high viscosity Poly(p-phenyleneterephthalamide) resin |
| CN101798385A (en) * | 2010-03-15 | 2010-08-11 | 苏州兆达特纤科技有限公司 | Production technology of poly (p-phenytene terephthalamide) resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030804A (en) * | 2012-12-31 | 2013-04-10 | 东华大学 | Preparation method of p-phenylene terephthamide resin through low-temperature solution out-phase polycondensation |
| CN103030804B (en) * | 2012-12-31 | 2015-05-13 | 东华大学 | Preparation method of p-phenylene terephthamide resin through low-temperature solution polycondensation |
| CN114316256A (en) * | 2021-12-08 | 2022-04-12 | 山东聚芳新材料股份有限公司 | Synthesis method of superfine para-aramid resin |
| CN114316256B (en) * | 2021-12-08 | 2023-09-05 | 山东聚芳新材料股份有限公司 | Synthesis method of superfine para-aramid resin |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140129 Termination date: 20170106 |