CN1037554A - Synthesizing of PPTA quadripolymer - Google Patents
Synthesizing of PPTA quadripolymer Download PDFInfo
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- CN1037554A CN1037554A CN 88105520 CN88105520A CN1037554A CN 1037554 A CN1037554 A CN 1037554A CN 88105520 CN88105520 CN 88105520 CN 88105520 A CN88105520 A CN 88105520A CN 1037554 A CN1037554 A CN 1037554A
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- diaminobenzene
- piperazine
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Abstract
The present invention is synthetic for the quadripolymer of the PPTA of improvement fatigue durability, belongs to the synthetic of macromolecular compound.In acid amides-alkaline-earth metal dicyandiamide solution, add a spot of the 3rd monomer P by p-phenylenediamine (PPD) and paraphthaloyl chloride, P '-diaminobenzene piperazine and the 4th monomer P, P '-diaminobenzene formyl piperazine generates the quadripolymer with high molecular.It is good that its logarithmic specific concentration viscosity can reach 4.5～5.5 solubility properties, has industrial value.
Description
The invention relates to the synthetic of the PPTA quadripolymer (hereinafter to be referred as quadripolymer) that improves fatigue performance, belong to the synthetic of macromolecular compound.
As everyone knows, homopolymer fibre (PPTA fiber) is the resistant to elevated temperatures special fibre of a kind of high-strength, high mould, yet its fatigue performance is relatively poor.In Chinese patent application numbers 87101102, propose to adopt to add the 3rd monomer copolymerization, to improve its fatigue performance for this reason.The synthetic commonly used cryogenic solution copolycondensation method of copolymer, earlier with a kind of alkali metal or alkali salt (as CaCl
2, MgCl
2, LiCl etc.) be dissolved in and form amidic-salt solution in the amide solvent, the diaminourea piperazines monomer gram molecule proportioning in accordance with regulations of p-phenylenediamine (PPD) of one of monomer and interpolation is dissolved in this solution, add another kind of monomer paraphthaloyl chloride while stirring, be lower than 80 ℃, stirring reaction under the normal pressure is till the copolymer that generates suitable molecular weight.Because the adding of diaminourea piperazine has improved fatigue performance, if but only use a kind of the 3rd monomer, want to improve significantly the fatigue performance of fiber, then will add a large amount of the 3rd monomers (15～50%), the performances such as intensity that cause fiber cost to increase fiber also descend to some extent.
The present invention uses two kinds of benzene piperazines the 3rd monomers simultaneously, adopt quarternary copolymerized method, add two kinds of benzene piperazine monomers, total amount is less than 10%, can make the flexing times of fatigue of fiber improve 80～200%, and that the intensity of copolymer fibre, modulus reduce is very few, and has good resistance to elevated temperatures, and solubility property also obviously improves.Therefore, the preparation method of this quadripolymer has industrial value.
Improve the fatigue performance of fiber with copolymerization method, the 3rd monomer commonly used has p, p '-diaminobenzene piperazine (
), 4,4 '-diaminodiphenyl ether (
), 4,4 '-diaminodiphenylmethane (
), 4,4 '-diamino-diphenyl sulfone (
).
Among the JP.76-136917 with p, p '-when the diaminobenzene piperazine is the 3rd monomer,, can improve the fatigue durability of copolymer fibre again preferably though copolymer fibre can keep the high strength and the high-modulus of former PPTA fiber.But only at p, the content of p '-diaminobenzene piperazine accounts for 10 of total diamine contents～50% o'clock, could improve the fatigue durability of fiber more significantly.And to add the 3rd so many monomer, can increase the cost of this modified fibre undoubtedly greatly.JP.75-107210 proposes to use p, p '-diaminobenzene formyl piperazine is the 3rd monomer, and the logarithmic specific concentration viscosity of copolymer is low so, and along with p, the increase of p '-diaminobenzene formyl piperazine consumption and sharply reducing, thus the modified fibre of high-strength and high-modulus be can not get.Therefore, p, p '-diaminobenzene formyl piperazine obviously are unfavorable as the 3rd monomer separately.
The objective of the invention is to overcome a kind of fatigue durability that can improve copolymer fibre preferably of above-mentioned defect finding, use third and fourth monomer of copolymerization again as few as possible.The present invention is fully by means of adding an amount of p, the advantage that copolymer viscosity rises during p '-diaminobenzene piperazine, remedy and add p, the deficiency that copolymer viscosity descends during p '-diaminobenzene formyl piperazine, select appropriate processing condition, p, p '-diaminobenzene formyl piperazine is as the way of the 4th monomer, quaternary copolycondensation is carried out in the effect (seeing accompanying drawing 1 and accompanying drawing 2) that produces cooperative effect, thereby only reach and synthesize suitable molecular weight copolymer with a spot of the 3rd monomer and the 4th monomer, by the dry-wet spinning of routine, just obtained good fatigue performance and kept high-strength, the modified fibre of high-modulus.
Main points of the present invention are the quarternary copolymerized of aromatic amides, in the amidic-salt solvent, add p-phenylenediamine (PPD) (PPD), an amount of p, basic piperazine of p '-diamino and p, p '-diaminobenzene formyl piperazine, and paraphthaloyl chloride (TCL), stirring makes reaction temperature remain on-5 ℃～50 ℃ under normal pressure, shown in the formula composed as follows of copolymer:
The the 3rd, the 4th monomer gram molecule content that adds can reach 5%≤(c+d)/(a+c+d)≤30%.The gram molecule content of p-phenylenediamine (PPD) is 95%～70%.
Amide solvent used in the present invention can be N-Methyl pyrrolidone (NMP).N, N '-dimethylacetylamide (DMA), employed alkaline-earth metal are calcium chloride (CaCl
2), lithium chloride (LiCl), wherein the alkaline-earth metal consumption is 4～7%(wt%) of an acid amides consumption.
Best implementation step of the present invention is: add N-Methyl pyrrolidone in aggregation container, at N
2Add CaCl under the protection
2To dissolving, add p-phenylenediamine (PPD) (PPD) and an amount of p, p '-diaminobenzene piperazine and p earlier, p '-diaminobenzene formyl piperazine adds paraphthaloyl chloride (TPC) powder then, quickens to stir, reacted 15 minutes down at-5～50 ℃, obtain pale yellow powder shape quadripolymer.Leave standstill then, elutriation, washing, filtration, drying, mensuration logarithmic specific concentration viscosity η
Inh(measuring temperature is 30 ℃):
In the formula: the t-flow of solution is through the capillary time
t
0-solvent streams is through the capillary time
The concentration of C-solution
Said method η
InhCan reach 4.5～5.5.The gained condensate is dissolved in 100%H
2SO
4In, through dry-wet spinning, extrusion molding, promptly get copolymer fibre behind the washing and drying, this fiber not only has characteristic (the fiber number 2.5d of Kevlar high-strength and high-modulus, elongation 4.5～6.0%, modulus 400～500g/d, intensity 18～22g/d) has good fatigue performance (improving 1～2 times than Kevlar) again.
Be embodiments of the invention below.
Example 1: in reactor, add 30mlNMP, add 1.5 gram CaCl again
2, at N
2Protection dissolving down; add 1.1664 gram (0.0108mol) p-phenylenediamine (PPD) and 0.1608 gram (0.0006mol) p then; p '-diaminobenzene piperazine and 0.1944 gram (0.0006mol) p; p '-diaminobenzene formyl piperazine; add 2.436 gram (0.012mol) paraphthaloyl chlorides while stirring, accelerate mixing speed, reaction remains on 20～50 ℃; carried out 10～30 minutes, and obtained η at last
InhIt is 4.75 copolymer.Through the fiber of spinning technique, its anti-times of fatigue in the wrong is 12000 times.
Example 2: in 30mlNMP, add 1.8 gram CaCl
2, at N
2Protection adds 1.20528 gram (0.01116mol) p-phenylenediamine (PPD) and 0.19296 gram (0.00072mol) p down; p '-diaminobenzene piperazine and p; p '-diaminobenzene formyl piperazine 0.03888 gram (0.00012mol); add 2.436 gram (0.012mol) paraphthaloyl chlorides while stirring; reaction remains on 20～50 ℃; carried out 10～30 minutes, and got η
InhBe 5.01 copolymer, its anti-times of fatigue in the wrong is 15200 times.
Example 3: in 30mlNMP, add 1.8 gram CaCl
2, at N
2Protection adds 1.21824 gram (0.01128mol) p-phenylenediamine (PPD) and 0.12864 gram (0.00048mol) p down; p '-diaminobenzene piperazine and 0.07776 gram (0.00024mol) p; p '-diaminobenzene formyl piperazine; add 2.436 gram (0.012mol) paraphthaloyl chlorides while stirring; reaction keeps 20～40 ℃; carried out 10～15 minutes, and got η
InhBe 4.8 copolymer powder, the anti-times of fatigue in the wrong of its fiber is 14800 times.
Example 4: in 30ml NMP, add 1.8 gram CaCl
2, at N
2Protection adds 1.17936 gram (0.01092mol) p-phenylenediamine (PPD) and 0.25728 gram (0.00096mol) p down; p '-diaminobenzene piperazine and 0.03888 gram (0.00012mol) p; p '-diaminobenzene formyl piperazine; add 2.436 gram (0.012mol) paraphthaloyl chlorides while stirring; reaction keeps 20～40 ℃; carried out 10～15 minutes, and got η
InhBe 5.23 copolymer powder, the anti-times of fatigue in the wrong of its fiber is 17600 times.
Control reference example 1, the polycondensation method identical with example 4 do not add the 3rd monomer p, p '-diaminobenzene piperazine and the 4th monomer p, p '-diaminobenzene formyl piperazine makes pure PPTA condensate, its η
InhBe 5.3, make fiber, its anti-times of fatigue in the wrong 8000 times with same spinning technique.
Control reference example 2, the method identical with example 4 do not add the 4th monomer p, and p '-diaminobenzene formyl piperazine only adds 1.0368 gram p-phenylenediamine (PPD) and 0.6432 gram p, p '-diaminobenzene piperazine and 2.436 gram paraphthaloyl chlorides, copolymer η
InhBe 5.47, the anti-times of fatigue in the wrong of its fiber is 15680 times.
Claims (6)
1, a kind of comprising with p-phenylenediamine (PPD), paraphthaloyl chloride and P
1P ' diaminobenzene piperazine is a monomer, carries out copolycondensation in acid amides alkali salt solvent system, prepares the method for fatigue proof PPTA copolymerization, it is characterized in that adding a kind of the 4th monomer P
1P ' diaminobenzene formyl piperazine, generate quadripolymer, the total amount of the 3rd monomer and the 4th monomer is less than 10% (is benchmark with the diamines total amount), in the amidic-salt solvent, the alkali salt consumption is 2～7%, the total concentration of diamines monomer is 0.2mol/L～0.5mol/L, stirring reaction under the normal pressure, and temperature maintenance is at 5～50 ℃.
2, described synthetic according to claim 1, it is characterized in that the 3rd monomer p, p ' diaminobenzene piperazine, the 4th monomer p, p ' diaminobenzene formyl piperazine adds jointly, and the former consumption is 4～8%, and latter's consumption is 0.5～3%.
3, described synthetic according to claim 1,2, it is characterized in that the 3rd monomer, the total consumption of the 4th monomer are 1～2% less than 10%, the four monomer optimum amount scope.
4, described synthetic according to claim 1,2, it is characterized in that said amidic-salt dicyandiamide solution is N-Methyl pyrrolidone-CaCl
2Solution system.
5, described synthetic according to claim 1,4, the calcium chloride consumption is 4～6% of a N-Methyl pyrrolidone.
6, described synthetic according to claim 1, it is characterized in that the total concentration of diamines monomer in the reaction system or the concentration of acyl chlorides are 0.25～0.45mol/L, the two gram molecule proportioning is-NH
2/-CoCl=1.001～1.010.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105520 CN1037554A (en) | 1988-05-14 | 1988-05-14 | Synthesizing of PPTA quadripolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105520 CN1037554A (en) | 1988-05-14 | 1988-05-14 | Synthesizing of PPTA quadripolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1037554A true CN1037554A (en) | 1989-11-29 |
Family
ID=4833703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105520 Pending CN1037554A (en) | 1988-05-14 | 1988-05-14 | Synthesizing of PPTA quadripolymer |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081199C (en) * | 1999-06-30 | 2002-03-20 | 北京燕山石油化工公司研究院 | Preparation of directly spun poly p-phthalamide terephthalate |
-
1988
- 1988-05-14 CN CN 88105520 patent/CN1037554A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081199C (en) * | 1999-06-30 | 2002-03-20 | 北京燕山石油化工公司研究院 | Preparation of directly spun poly p-phthalamide terephthalate |
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