CN1068831A - The manufacture method of high molecular aromatic polyamide - Google Patents
The manufacture method of high molecular aromatic polyamide Download PDFInfo
- Publication number
- CN1068831A CN1068831A CN 91107457 CN91107457A CN1068831A CN 1068831 A CN1068831 A CN 1068831A CN 91107457 CN91107457 CN 91107457 CN 91107457 A CN91107457 A CN 91107457A CN 1068831 A CN1068831 A CN 1068831A
- Authority
- CN
- China
- Prior art keywords
- add
- halogenide
- aromatic polyamide
- manufacture method
- high molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004760 aramid Substances 0.000 title claims abstract description 10
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000009987 spinning Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- -1 amino aromatic series acyl chlorides Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- HYTCSCBDAFJMIP-UHFFFAOYSA-N 3-ethyl-1,1-dimethylurea Chemical compound CCNC(=O)N(C)C HYTCSCBDAFJMIP-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
The manufacture method of high molecular aromatic polyamide belongs to a kind of spinning that is used for, the macromolecular material manufacture method of papermaking pulp and system film.It uses the halogenide of silicon in manufacturing processed, the halogenide of titanium or the halogenide of boron are as dewatering agent, and this dewatering agent can be protected the aromatic dicarboxylic acyl chlorides, and polycondensation is not had influence.Organic solvent in the polymerization reaction system just needn't be re-refined like this, and reactive system also needn't be dry, and the result can obtain high molecular aromatic polyamide.
Description
The invention belongs to a kind of spinning that is used for, the macromolecular material manufacture method of papermaking pulp and system film.
In prior art, the plant-scale preparation of aromatic polyamide normally with the hydrochloride of aromatic diamine and aromatic dicarboxylic acyl chlorides or amino aromatic series acyl chlorides in organic solvent, adopt solution polycondensation, interfacial polycondensation or emulsion polycondensation carry out.Particularly with spinning, papermaking pulp and system film are purpose, adopt solution polycondensation more, can obtain being directly used in spinning like this, the slurries of papermaking pulp and system film.Because the aromatic dicarboxylic acyl chlorides that uses in the reaction is subjected to moisture content influence in the moisture content and equipment in the solvent, very easily hydrolysis becomes unit acyl chlorides or diprotic acid, make aromatic diamine and aromatic dicarboxylic acyl chlorides in the reaction etc. mole ratio change, so be difficult to obtain the high-molecular weight aromatic polyamide.In order to obtain the high-molecular weight aromatic polyamide, the organic solvent that uses in the polymerization must carry out complicated making with extra care, so that the water content in the solvent is controlled at about 100ppm.The process for purification of organic solvent is generally rectifying, promptly uses azeotropic dehydrations such as benzene or toluene earlier, adds hydrolith underpressure distillation more then in still kettle, and the positive fraction that obtains uses molecular sieve drying standby again.Such as among the Japanese kokai publication hei 2-99611 report, make with extra care the organic solvent N-Methyl pyrrolidone with rectificating method.Such as among the Japanese Patent Publication 47-10863 report, come tetrahydrofuran (THF) is advanced shape dehydration with sodium Metal 99.5.Report among the Japanese kokai publication sho 55-139424 for another example, N-Methyl pyrrolidone is dewatered with molecular sieve.Above-mentioned solvent dehydration method is the big but also complicated operation of rectifier unit investment not only, and energy consumption is big, and solvent also has certain loss.Use molecular sieve drying, not only molecular sieve itself adsorbs a certain amount of solvent, and brings a large amount of ash in solvent into, and is influential to last product property, and molecular sieve also is difficult to reuse simultaneously.Sodium Metal 99.5 has highly explosive inflammableness, therefore also is not suitable for industrial production and uses.Moisture content has influence on the polymerization in above-mentioned solvent, and the water capacity of polymerization reaction kettle inwall also influences the carrying out of polyreaction, therefore must be to the reactor heat drying, and coolant seal is standby under logical nitrogen.
The objective of the invention is, provide a kind of short-cut method to solve in the reactive system moisture content the influence of polycondensation, and to the not influence of performance of product.Organic solvent in the polycondensation reaction system just needn't be re-refined like this, and reactor also needn't be dry, and the result can obtain high molecular aromatic polyamide.
Principal feature of the present invention is to use the halogenide of silicon in polycondensation, as silicon tetrachloride, and trichlorosilane etc.; The halogenide of titanium, as titanium tetrachloride, titanous chloride etc.; The halogenide of boron, as boron trichloride, boron trifluoride, this class material such as boron tribromide is as dewatering agent.These dewatering agents shield to the aromatic dicarboxylic acyl chlorides, and the moisture content in the polycondensation system is played destruction, and polycondensation and polycondensation product are not had bad influence.
The consumption of these dewatering agents decide the sensitivity of moisture content on what and reaction system of the original water content of solvent, and generally the mole ratio of desirable these dewatering agents and water is more than or equal to 1/4, and is suitable when excessive when such dewatering agent, and polycondensation is not had influence yet.
Its general formula of the aromatic diamine that uses among the present invention is H
2N-Ar
1-NH
2As Ursol D, mphenylenediamine, 4,4 '-benzidine, 4,4 '-diphenylmethane diamine, 4,4 '-the phenyl ether diamines, 3,4 '-the phenyl ether diamines, 4,4 '-the sulfobenzide diamines, 3,3 '-the sulfobenzide diamines, 4,4 '-the diphenyl sulfide diamines, tolylene diamine, 1, the 5-naphthylene diamine, the change and the thing that have halogen or methyl substituents on the phenyl ring of piperazine and these aromatic diamines all can use.
Its general formula of aromatic dicarboxylic acyl chlorides that uses among the present invention is ClOC-Ar
2-COCl.As p-phthaloyl chloride, m-phthaloyl chloride, 2,6-naphthalene dimethyl chloride, 4,4 '-the phenyl ether dimethyl chloride, 4,4 '-compound that has halogenic substituent on the phenyl ring of di-formyl chloride and these aromatic series diacid chlorides all can use.
Its general formula of hydrochloride of the amino aromatic series acyl chlorides that uses among the present invention is HClH
2N-Ar
3-CDCl.Ar
3Can be the contraposition phenyl, a position phenyl, xenyl etc., desirable its a kind of or use more than two kinds.
The organic solvent that uses among the present invention has N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, tetramethyl-urea, the dimethyl ethyl urea, hexamethylphosphoramide, tetrahydrofuran (THF) etc. one or two or more kinds.
Aromatic polyamide resin logarithmic specific concentration viscosity (η) assay method is as follows among the present invention: get 0.5 gram dried resin, room temperature is dissolved in 100 milliliters the vitriol oil, uses determination of ubbelohde viscometer down at 30 ℃, is calculated as follows:
〔η〕＝2.303log（η
rel）/C
In the formula, η
Rel: the relative viscosity of resin
C: the concentration of solution
Be embodiments of the invention and reference examples below:
Embodiment one: add 1000 milliliters N-Methyl pyrrolidone (water ratio 800ppm) and 3.8 gram silicon tetrachlorides in reactor, under nitrogen protection, stirred 30 minutes, add 43.256 gram Ursol D, after the dissolving, be cooled to 0 ℃ under the room temperature.Add 81.21 gram powdery p-phthaloyl chlorides under the violent stirring, exothermic heat of reaction, reaction system become sticky thick gradually, became solid materials in about 20 minutes, continued to stir about 4 hours altogether, reaction finishes, material is through fully washing, and polymer logarithmic specific concentration viscosity [η]=5.7 is measured in oven dry.Its vitriol oil that is dissolved in 99.8% is carried out dry-wet spinning, the fibre strength that obtains reach 20 the gram/
Embodiment two: add 45 kilograms of N,N-DIMETHYLACETAMIDEs (water ratio 1000ppm) and 212.5 gram silicon tetrachlorides in 100 liter enamel reaction stills; under nitrogen protection; stir after 30 minutes; add 5.4 kilograms of mphenylenediamines again; dissolve under the room temperature; all after the dissolving; be cooled to-5 ℃ under agitation; add 10.15 kilograms of m-phthaloyl chlorides in 3 minutes and react rapid heat release, reacting kettle jacketing leads to refrigerated water, and control reaction temperature is no more than 65 ℃; react after 3 hours; add 2 kilograms of calcium oxide, continue to stir 4 hours, reaction finishes the logarithmic specific concentration viscosity [η]=1.75 of sampling and measuring resin.
Embodiment three: add 160 milliliters of hexamethylphosphoramides (HMPA) (water ratio 800ppm) and 80 milliliters of N,N-DIMETHYLACETAMIDEs (water ratio 1000ppm) and 1.19 gram silicon tetrachlorides in 500 milliliters of reaction flasks, stirring at room 20 minutes, add 10.38 gram Ursol D again, after making its dissolving, be cooled to 3 ℃, add the Powdered p-phthaloyl chloride of 19.5 grams under the high degree of agitation, react rapid heat release, system viscosity increases gradually, until curing, and static spending the night, analyse with depositing in water, clean, oven dry obtains logarithmic specific concentration viscosity and reaches 5.9 polymer.
Embodiment four: add 45 kilograms of N,N-DIMETHYLACETAMIDEs (water ratio 1000ppm) and 212.5 gram silicon tetrachlorides in 100 liter enamel reaction stills; under nitrogen protection; stir after 30 minutes; stop logical nitrogen; change and feed 81.6 gram anhydrous ammonia gas; fully stirred 30 minutes; and then change logical nitrogen (or vacuumizing) into; carried out exhaust 30 minutes; by a strainer N,N-DIMETHYLACETAMIDE is pressed in second exsiccant, the 100 liter enamel reaction stills; under nitrogen protection; add 5.4 kilograms of mphenylenediamines while stirring, dissolve under the room temperature, all dissolve postcooling to-5 ℃; stir fast and add 5.075 kilograms of powdery m-phthaloyl chlorides down; react after 5 minutes, add 5.075 kilograms of powdery m-phthaloyl chlorides again, coreaction is after 3 hours; add 2 kilograms of powdery calcium oxide and continue to stir 4 hours, obtain logarithmic specific concentration viscosity and be 1.85 polymer.Through wet-spinning, fibre strength reach 5 the gram/
Embodiment five: add 180 milliliters of N,N-DIMETHYLACETAMIDEs (water ratio 1000ppm) and 0.93 gram titanium tetrachloride in 500 milliliters of there-necked flasks; logical nitrogen protection; stirred 1 hour; add 21.6 gram mphenylenediamines, stirring and dissolving under the room temperature is all dissolved postcooling to-8 ℃; add 40.7 gram powdery m-phthaloyl chlorides under the high degree of agitation; react after 3 hours and to add 8 gram calcium oxide, continue reaction 2 hours, obtain logarithmic specific concentration viscosity and be 1.9 resin.
Embodiment six: add 21 kilograms of N,N-DIMETHYLACETAMIDEs and 108 gram titanium tetrachlorides in enamel reaction still, logical nitrogen protection was stirred 1 hour; add 6.75 mol 4,4s, 2.25 mol 3; 3 '-diaminodiphenylsulfone(DDS); dissolve under the room temperature, all dissolve postcooling, add 90 mol powdery terephthaldehydes base acyl chlorides to-9 ℃; reacted 3 hours; add 10 kilograms of calcium oxide again, continue reaction 3 hours, obtain logarithmic specific concentration viscosity and be 1.95 resin.
Comparative example: under nitrogen protection, in 250 milliliters of exsiccant there-necked flasks, add 90 milliliters of N,N-DIMETHYLACETAMIDEs (water ratio 600ppm) and 10.8 gram mphenylenediamines; after the stirring and dissolving; be cooled to-8 ℃; add 20.35 gram powdery m-phthaloyl chlorides under the high degree of agitation; react and add 3 gram calcium oxide after 3 hours; continue reaction 2 hours, obtain logarithmic specific concentration viscosity and be 0.5 polymer.
Claims (1)
1, a kind of manufacture method of high molecular aromatic polyamide, feature of the present invention are to use the halogenide of silicon in polycondensation, as silicon tetrachloride, and trichlorosilane etc.; The halogenide of titanium, as titanium tetrachloride, titanous chloride etc.; The halogenide of boron, as boron trichloride, boron trifluoride, this class material such as boron tribromide is as dewatering agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107457 CN1068831A (en) | 1991-07-25 | 1991-07-25 | The manufacture method of high molecular aromatic polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107457 CN1068831A (en) | 1991-07-25 | 1991-07-25 | The manufacture method of high molecular aromatic polyamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1068831A true CN1068831A (en) | 1993-02-10 |
Family
ID=4908795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91107457 Pending CN1068831A (en) | 1991-07-25 | 1991-07-25 | The manufacture method of high molecular aromatic polyamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1068831A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065930C (en) * | 1994-09-29 | 2001-05-16 | 纳幕尔杜邦公司 | Poly(p-phenylene terephthalamide) pulp |
-
1991
- 1991-07-25 CN CN 91107457 patent/CN1068831A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065930C (en) * | 1994-09-29 | 2001-05-16 | 纳幕尔杜邦公司 | Poly(p-phenylene terephthalamide) pulp |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI81814C (en) | Process for preparing powdered linear linear polymer | |
| US4172938A (en) | Process for producing polyamides with lactam or urea solvent and CaCl2 | |
| US4868270A (en) | Heterocycle sulfone oligomers and blends | |
| US4698415A (en) | Method for the preparation of polyarylene sulfide with aqueous polyethylene glycol mixture | |
| CN1144227A (en) | Process for preparation of aromatic sulfur-containing polymers | |
| JPS60500961A (en) | Aromatic polymer manufacturing method | |
| US5410037A (en) | Process for silylizing carbohydrates, and use of the silylized carbohydrates | |
| US5066541A (en) | Heterocycle oligomer blends | |
| CN1068831A (en) | The manufacture method of high molecular aromatic polyamide | |
| CN115996969A (en) | Method for producing poly (anthranilamide), poly (anthranilamide) and use thereof | |
| EP0964883A1 (en) | Production of polysuccinimide | |
| JPH0116819B2 (en) | ||
| KR970011638B1 (en) | Method for manufacturing polyamide anion solutions | |
| JPS598728A (en) | Preparation of aromatic polyamide | |
| US5422397A (en) | Binary alloys based on polyether-amides and cycloolefin polymers | |
| CN1075529C (en) | Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether | |
| EP0441338A2 (en) | Wholly aromatic polyamide | |
| CA2000639C (en) | Melt-processible aromatic polyamides | |
| US3932365A (en) | Preparation of high molecular weight polymer from oxalic acid and para-phenylene diisocyanate | |
| JPH03145455A (en) | Production of 2-acrylamide-2-methylpropanesulfonic acid | |
| EP0541510A2 (en) | Wholly aromatic polyamide copolymer | |
| JPH0757800B2 (en) | Aromatic polyamide for pulp | |
| US5006636A (en) | Process for the production of SiO2 containing polybenzamides | |
| JP3384895B2 (en) | Method for producing polyamide resin | |
| US4945153A (en) | Method of producing prepolymer of aromatic polythiazole in the presence of a phosphoric acid compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |