CN1081199C - Preparation of directly spun poly p-phthalamide terephthalate - Google Patents
Preparation of directly spun poly p-phthalamide terephthalate Download PDFInfo
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- CN1081199C CN1081199C CN99109420A CN99109420A CN1081199C CN 1081199 C CN1081199 C CN 1081199C CN 99109420 A CN99109420 A CN 99109420A CN 99109420 A CN99109420 A CN 99109420A CN 1081199 C CN1081199 C CN 1081199C
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Abstract
The present invention relates to a method in which p-phenylene diamine and one or two kinds of diamine modified monomers are respectively added and terephthaloyl chloride is added in two batches. One class of directly-spun type poly p-phthalamide terephthalate is prepared in an amide-alkali metal system or/and an alkaline earth metal system. The inherent viscosity of the product can stably reach more than 4.0. The product has good dissolution performance. The method can realize direct spinning with polymerized primary liquid.
Description
The present invention relates to the preparation method of a class modification PPTA, promptly in the polymerization system of the p-phthaloyl chloride of classics and Ursol D, add two amine modified monomers (the 3rd or/and the 4th monomer), by regulating monomeric kind, proportioning, order of addition(of ingredients), controlling polymers molecular weight and chain structure can be stablized its logarithmic specific concentration viscosity and are reached more than 4.0, have good chemical resistance, thermotolerance, solubility property is good, and available polymerization stoste direct fabrics.
Aromatic polyamide is the important lyotropic liquid crystal polymer of a class, and wherein PPTA receives much attention especially, can make one of organic fibre that present intensity is the highest, modulus is maximum through solvent spinning with it.The part yet the Fanglun 1414 also comes with some shortcomings, good inadequately as solvability, resistance to fatigue and toughness, thereby limited its nearly step application greatly, also brought great difficulty to process for processing.So, PPTA is carried out the focus that modification has become people's concern in recent years.At present, the modification of PPTA normally adds modified monomer and carries out copolymerization, the molecular weight of telomerized polymer and chain structure.The prior art similar to the present invention has: the patent CN1036777A of China Textile University, CN1037554A, adopt P, and P-diaminobenzene piperazine, P, P-diaminobenzene formyl piperazine is as third and fourth monomer.The Japan TEIJIN EP441338A2 of house journal then adopts:
As the comonomer modification PPTA, wherein: n=1-3, R
p, R '
qBe methyl or methoxy.The patent US5039785 and the US5189141 of U.S. DU PONT company then add in Ursol D and p-phthaloyl chloride
Come modification.More than the common feature of these patents be to introduce two amine materials improve PPTA as modified monomer (the 3rd or/and the 4th monomer) character; as improve resistance to fatigue; improve solvability; but because the structure of the diamines monomer of introducing is different; the activity of acidylate and Ursol D are also inequality; above method is added to modified monomer (the 3rd or/and the 4th monomer) in the solvent with Ursol D; react simultaneously with p-phthaloyl chloride the dissolving back, and the distribution that causes the polymer chain structural unit is because of active different change of the acidylate of each diamines monomer.
The object of the present invention is to provide the preparation method of a class modification PPTA, by regulating monomeric kind, proportioning, order of addition(of ingredients), controlling polymers molecular weight and chain structure, in the hope of polymer dissolution and thermal characteristics significant improvement is arranged all, to make the PPTA resin of the enough polymeric solution direct fabrics of energy.
Technical characterictic of the present invention is: Ursol D and modified monomer (the 3rd or/and the 4th monomer) add (pertinent literature is simultaneously and adds) respectively, and p-phthaloyl chloride also adds in batches.At first add modified monomer (the 3rd or/and the 4th monomer), add first p-phthaloyl chloride again, after reaction for some time, add Ursol D again, add remaining p-phthaloyl chloride again.By regulating the consumption of first p-phthaloyl chloride, the molecular-weight average of controlling polymers, the distribution of control modified monomer (the 3rd or/and the 4th monomer) in polymer chain makes that the segmented structure of polymkeric substance is controlled, batch charging and reinforced comparing once, the thermal characteristics of resulting polymers is better.Key problem in technology of the present invention is the selection of the consumption and the modified monomer of monomeric order of addition(of ingredients), first p-phthaloyl chloride.
A class modification PPTA involved in the present invention is made up of fragrant dicarboxyl unit with following repeating structure and aromatic diamines base unit, wherein: n=1-3, R
p, R '
qBe methyl or methoxy.
Fragrance dicarboxyl unit:
Aromatic diamines base unit:
Solvent of the present invention is selected from acid amides-an alkali metal salt (or/and alkaline earth salt) system that contains tertiary amine compounds, generally be selected from N-Methyl pyrrolidone-lithium chloride, N-Methyl pyrrolidone-calcium chloride, N, N-methylacetamide-calcium chloride is preferably from N-Methyl pyrrolidone-lithium chloride, N-Methyl pyrrolidone-calcium chloride.Tertiary amine compounds can be triethylamine, pyridine compounds and their, generally is selected from pyridine, picoline, ethylpyridine, and addition is generally 0.1～2.5 moles per litre of solvent, and the best is 0.3～1.5 moles per litre of solvent.The addition of an alkali metal salt (or/and alkaline earth salt) be an alkali metal salt (or/and alkaline earth salt) with the ratio of diamines total amount generally in 0.10-0.60 (mol ratio), preferably between 0.15-0.30 (mol ratio).
Two amine materials of position, para-orientation between modified monomer of the present invention (the 3rd or/and the 4th monomer) is selected from:
Wherein: n=1-3, R
p, R '
qBe methyl or methoxy.Generally be selected from mphenylenediamine, 4,4 '-diaminodiphenyl oxide and 3,3 '-dimethoxy-biphenyl diamines.
The preparation method of a class modification PPTA involved in the present invention is as follows:
At first modified monomer (the 3rd or/and the 4th monomer) is joined in the solvent, after treating its dissolving, be cooled to 0～10 ℃, add first p-phthaloyl chloride then, accelerate stirring velocity, reaction begins to carry out, react after 1-15 minute, add Ursol D again, elevated temperature dissolves it fully, system is cooled to 0～10 ℃ again, adds remaining p-phthaloyl chloride while stir.Stirring reaction 1-15 minute, product is warming up to 50-90 ℃ then, keep 0.5-3h, quiet to spending the night.The polymer of gained is added a small amount of distilled water, pulverize and filter, again with cold water and hot wash repeatedly to remove solvent, LiCl, hydrochloric acid and the pyridine that remains in the polymkeric substance, be neutral until washing, again that polymkeric substance is dry more than 5 hours under 100 ℃, promptly get the polymkeric substance of suitable molecular weight and structure.The consumption of modified monomer is that the ratio of modified monomer and diamines is generally 0.05～0.9 (mol ratio), is preferably 0.3～0.6 (mol ratio).The ratio that first amount that adds p-phthaloyl chloride is p-phthaloyl chloride and diamines is generally 0.1～0.8 (mol ratio), is preferably 0.2～0.5 (mol ratio).
Further specify the present invention below in conjunction with embodiment, Comparative Examples, but and the scope of unrestricted claim protection of the present invention.
Embodiment 1:
The stainless steel agitator being housed and being connected with in the 250ml glass polymerization reactor of drying nitrogen, be heated to 150 ℃ and remove the moisture that is attached on the wall.After the cooling; under nitrogen protection, add the N-Methyl pyrrolidone solution 50ml that contains anhydrous LiCl of 1.000g and 2.85ml pyridine; it is Powdered 4 to add 0.801g, 4 '-diaminodiphenyl oxide, 0.432g mphenylenediamine; after treating its dissolving; with ice-water bath solution is dropped to 0～5 ℃, add the Powdered p-phthaloyl chloride of 0.975g then, suitably accelerate stirring velocity; reaction solution viscosity increases; after 5 minutes, add the Powdered Ursol D of 1.298g, be warmed up to 30～40 ℃ of dissolvings fully after; with ice-water bath solution is dropped to 0～5 ℃; add the 3.106g p-phthaloyl chloride while stirring, accelerate simultaneously to stir the rapid increase of reaction solution viscosity; the liquid level projection; rod climbing phenomenon taking place after several minutes and occur gelation very soon, continue to stir after 5 minutes, product is warming up to 70～80 ℃ then; keep 1～2hr, standing over night.The polymer of gained is added a small amount of distilled water, pulverize and filter, again with cold water and hot wash repeatedly to remove solvent, LiCl, hydrochloric acid and the pyridine that remains in the polymer, show neutral until washing, again with polymkeric substance dry 5H under 100 ℃, promptly get yellow dry polymer, record logarithmic specific concentration viscosity η
Inh=4.32dl/g.Its thermal weight loss 10% temperature is 826K.Logarithmic specific concentration viscosity η
InhAdopt one point method to measure with Ubbelohde viscometer down at 25 ℃, solvent is 98% the vitriol oil; Thermal weight loss adopts Du Pont TGA-2050 instrument test, and heat-up rate is 20 ℃/min (following identical).
Adopt synthetic resin dissolves performance of the present invention to be greatly improved, can realize polymerization stoste direct fabrics, as shown in table 1 through the performance of the preliminary back fiber that stretches:
Table 1 polymerization stoste direct fabrics fibre property
Annotate: the spinning property experiment condition: The hole diameter of spinneret is Φ 0.5mm, and spinning speed is 2m/min: the fibrous mechanical property test condition: test speed is 50mm/min, and testing length is 20mm, and rupture time is 20s, and the thermal stretch temperature is 250-300 ℃.
Embodiment 2:
Polymerization process, proportioning raw materials and processing condition are with embodiment 1, just two amine modified monomers only use a kind of 4,4 '-diaminodiphenyl oxide, without mphenylenediamine, concrete grammar is as follows: the stainless steel agitator being housed and being connected with in the 250ml glass polymerization reactor of drying nitrogen, be heated to 150 ℃ and remove the moisture that is attached on the wall.After the cooling; under nitrogen protection, add the nmp solution 50ml that contains anhydrous LiCl of 1.000g and 2.85ml pyridine; add 1.603g Powdered 4; 4 '-diaminodiphenyl oxide, treat its dissolving after, with ice-water bath solution is dropped to 0～5 ℃; add the Powdered p-phthaloyl chloride of 0.975g then; suitably accelerate stirring velocity, reaction solution viscosity increases, after 5 minutes; add the Powdered Ursol D of 1.298g; after being warmed up to 30～40 ℃ of dissolvings fully, solution is dropped to 0～5 ℃, add the 3.106g p-phthaloyl chloride while stirring with ice-water bath; accelerate simultaneously to stir; the rapid increase of reaction solution viscosity, rod climbing phenomenon takes place and occurs gelation very soon in the liquid level projection after several minutes; continue to stir after 5 minutes; product is warming up to 70～80 ℃ then, keeps 1～2hr, standing over night.The polymer of gained is added a small amount of distilled water, pulverize and filter, again with cold water and hot wash repeatedly to remove solvent, LiCl, hydrochloric acid and the pyridine that remains in the polymer, show neutral until washing, again with polymkeric substance dry 5h under 100 ℃, promptly get yellow dry polymer, record logarithmic specific concentration viscosity η
Inh=4.31dl/g.Its thermal weight loss 10% temperature is 784K.Comparative Examples 1:
Polymerization process, proportioning raw materials and processing condition are with embodiment 1, just two amine modified monomers and Ursol D once add, concrete grammar is as follows: the stainless steel agitator being housed and being connected with in the 250ml glass polymerization reactor of drying nitrogen, be heated to 150 ℃ and remove the moisture that is attached on the wall.After the cooling; under nitrogen protection, add the nmp solution 50ml that contains anhydrous LiCl of 1.000g and 2.85ml pyridine; it is Powdered 4 to add 0.801g, 4 '-diaminodiphenyl oxide, 0.432g mphenylenediamine; 1.298g Ursol D; after treating its dissolving, solution is dropped to 0～5 ℃, add the Powdered p-phthaloyl chloride of 2.040g then with ice-water bath; with ice-water bath solution is dropped to 0～5 ℃; add the 2.041g p-phthaloyl chloride while stirring, accelerate simultaneously to stir the rapid increase of reaction solution viscosity; the liquid level projection; rod climbing phenomenon taking place after several minutes and occur gelation very soon, continue to stir after 5 minutes, product is warming up to 70～80 ℃ then; keep 1～2hr, standing over night.The polymer of gained is added a small amount of distilled water, pulverize and filter, again with cold water and hot wash repeatedly to remove solvent, LiCl, hydrochloric acid and the pyridine that remains in the polymer, show neutral until washing, again with polymkeric substance dry 5h under 100 ℃, promptly get yellow dry polymer, record logarithmic specific concentration viscosity η
Inh=4.48dl/g.Its thermal weight loss 10% temperature is 811K.Comparative Examples 2:
Polymerization process, proportioning raw materials and processing condition are with embodiment 2, just two amine modified monomers and Ursol D once add, concrete grammar is as follows: the stainless steel agitator being housed and being connected with in the 250ml glass polymerization reactor of drying nitrogen, be heated to 150 ℃ and remove the moisture that is attached on the wall.After the cooling; under nitrogen protection, add the nmp solution 50ml that contains anhydrous LiCl of 1.000g and 2.85ml pyridine; add 1.603g Powdered 4; 4 '-diaminodiphenyl oxide, the 1.298g Ursol D, treat its dissolving after; with ice-water bath solution is dropped to 0～5 ℃; add the Powdered p-phthaloyl chloride of 2.040g then, solution is dropped to 0～5 ℃, add the 2.041g p-phthaloyl chloride while stirring with ice-water bath; accelerate simultaneously to stir; the rapid increase of reaction solution viscosity, rod climbing phenomenon takes place and occurs gelation very soon in the liquid level projection after several minutes; continue to stir after 5 minutes; product is warming up to 70～80 ℃ then, keeps 1～2hr, standing over night.The polymer of gained is added a small amount of distilled water, pulverize and filter, again with cold water and hot wash repeatedly to remove solvent, LiCl, hydrochloric acid and the pyridine that remains in the polymer, show neutral until washing, again with polymkeric substance dry 5h under 100 ℃, promptly get yellow dry polymer, record logarithmic specific concentration viscosity η
Inh=4.48.Its thermal weight loss 10% temperature is 773K.
As seen, adopt the temperature of feed way gained modifying aramid fiber resin of the present invention under identical thermal weight loss to want high, prove that its thermostability is better.
Claims (15)
- The preparation method of 1 one class directly spun poly poly P phenylene diamine terephthalamides, it is characterized in that: Ursol D and one or both two amines modified monomers add respectively, the mixture of one or both between two amine modified monomers are selected from the two amine materials of position, para-orientation:N=1-3 wherein, R p, R ' qBe methyl or methoxy, p-phthaloyl chloride also adds in two batches, at first one or both two amines modified monomers are joined in the solvent, and then add first p-phthaloyl chloride, after reaction for some time, add Ursol D again, add remaining p-phthaloyl chloride again, the preparation method is as follows: at first one or both two amines modified monomers are joined in the solvent, treat its dissolving after, be cooled to 0～10 ℃, under agitation one or many or continuous the dropping add first p-phthaloyl chloride then, and reaction begins to carry out, and reacts after 1-15 minute, add Ursol D again, elevated temperature dissolves it fully, system is cooled to 0～10 ℃ again, under agitation one or many or the remaining p-phthaloyl chloride of dropping adding continuously, stirring reaction 1-15 minute, product is warming up to 50-90 ℃ then, kept 0.5-3 hour, after question response is finished, adopt classic methods to carry out aftertreatment, obtain the directly spun poly poly P phenylene diamine terephthalamide.
- 2 preparation methods according to claim 1 is characterized in that modified monomer is selected from mphenylenediamine, 4,4 '-diaminodiphenyl oxide, 3, the mixture of one or both in 3 '-dimethoxy-biphenyl diamines.
- 3 preparation methods according to claim 1, the consumption that it is characterized in that modified monomer is that the ratio of modified monomer and diamines is 0.05～0.9 (mol ratio).
- 4 preparation methods according to claim 3, the consumption that it is characterized in that modified monomer is that the ratio of modified monomer and diamines is 0.3～0.6 (mol ratio).
- 5 preparation methods according to claim 1, it is characterized in that solvent be selected from contain tertiary amine compounds acid amides-an alkali metal salt or/and the alkaline-earth metal salt system.
- 6 preparation methods according to claim 5 is characterized in that solvent is selected from N-Methyl pyrrolidone-lithium chloride or N-Methyl pyrrolidone-calcium chloride or the N that contains tertiary amine compounds, N-methylacetamide-calcium chloride system.
- 7 preparation methods according to claim 6 is characterized in that solvent is selected from N-Methyl pyrrolidone-lithium chloride or the N-Methyl pyrrolidone-calcium chloride system that contains tertiary amine compounds.
- 8 according to each described preparation method of claim 5-7, it is characterized in that tertiary amine compounds is selected from triethylamine, pyridine compounds and their.
- 9 preparation methods according to claim 8 is characterized in that tertiary amine compounds is selected from pyridine, picoline, ethylpyridine.
- 10 preparation methods according to claim 5, the addition that it is characterized in that tertiary amine compounds is 0.1～2.5 moles per litre of solvent.
- 11 preparation methods according to claim 10, the addition that it is characterized in that tertiary amine compounds is 0.3～1.5 moles per litre of solvent.
- 12 preparation methods according to claim 5 is characterized in that an alkali metal salt or/and the addition of alkaline earth salt is that an alkali metal salt is or/and the ratio of alkaline earth salt and diamines total amount is 0.10-0.60 (mol ratio).
- 13 preparation methods according to claim 12 is characterized in that an alkali metal salt or/and the addition of alkaline earth salt is that an alkali metal salt is or/and the ratio of alkaline earth salt and diamines total amount is 0.15-0.30 (mol ratio).
- 14 preparation methods according to claim 1 is characterized in that the ratio that first amount that adds p-phthaloyl chloride is p-phthaloyl chloride and diamines is 0.1～0.8 (mol ratio).
- 15 preparation methods according to claim 14 is characterized in that the ratio that first amount that adds p-phthaloyl chloride is p-phthaloyl chloride and diamines is 0.2～0.5 (mol ratio).
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| CN99109420A CN1081199C (en) | 1999-06-30 | 1999-06-30 | Preparation of directly spun poly p-phthalamide terephthalate |
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| CN1081199C true CN1081199C (en) | 2002-03-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345885C (en) * | 2004-04-14 | 2007-10-31 | 邢哲 | Synthetic method for poly terephthalyl terephaldiamine polymer |
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| CN101781399B (en) * | 2010-03-04 | 2012-11-07 | 江苏工业学院 | Method for preparing poly-phenylenediformyl p-phenylenediamine resin by low temperature polycondensation |
| CN102174771B (en) * | 2011-01-28 | 2013-02-13 | 钟洲 | Method for making additive meta-aramid paper |
| CN103467736A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Polymerization method capable of effectively controlling phase transformation in PPTA (poly-p-phenylene terephthamide) synthesis process |
| CN113045751B (en) * | 2021-04-30 | 2023-05-09 | 中化高性能纤维材料有限公司 | Preparation method and application of coating solution based on aromatic polyamide |
| CN113201277B (en) * | 2021-05-17 | 2022-09-27 | 江苏方圆芳纶研究院有限公司 | Aramid insulating paint |
| CN113402970B (en) * | 2021-05-24 | 2022-09-27 | 江苏方圆芳纶研究院有限公司 | Aramid wire enamel |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031845A (en) * | 1987-09-07 | 1989-03-22 | 中国纺织大学 | Synthesizing of the PPTA multipolymer of resistance to fatigue |
| CN1036777A (en) * | 1988-04-19 | 1989-11-01 | 中国纺织大学 | Photostabilization Fanglun 1414 and synthetic |
| CN1037554A (en) * | 1988-05-14 | 1989-11-29 | 中国纺织大学 | Synthesizing of PPTA quadripolymer |
| US5039785A (en) * | 1989-12-05 | 1991-08-13 | E. I. Du Pont De Nemours And Company | Preparation of aromatic polyamide having pendant carboxyl groups |
| EP0441338A2 (en) * | 1990-02-09 | 1991-08-14 | Teijin Limited | Wholly aromatic polyamide |
-
1999
- 1999-06-30 CN CN99109420A patent/CN1081199C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031845A (en) * | 1987-09-07 | 1989-03-22 | 中国纺织大学 | Synthesizing of the PPTA multipolymer of resistance to fatigue |
| CN1036777A (en) * | 1988-04-19 | 1989-11-01 | 中国纺织大学 | Photostabilization Fanglun 1414 and synthetic |
| CN1037554A (en) * | 1988-05-14 | 1989-11-29 | 中国纺织大学 | Synthesizing of PPTA quadripolymer |
| US5039785A (en) * | 1989-12-05 | 1991-08-13 | E. I. Du Pont De Nemours And Company | Preparation of aromatic polyamide having pendant carboxyl groups |
| EP0441338A2 (en) * | 1990-02-09 | 1991-08-14 | Teijin Limited | Wholly aromatic polyamide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345885C (en) * | 2004-04-14 | 2007-10-31 | 邢哲 | Synthetic method for poly terephthalyl terephaldiamine polymer |
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