CN103243412B - Preparation method of high-performance organic fibers on basis of 3,3'4,4'-tetra-aminobiphenyl hydrochloride - Google Patents
Preparation method of high-performance organic fibers on basis of 3,3'4,4'-tetra-aminobiphenyl hydrochloride Download PDFInfo
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Abstract
The invention relates to a preparation method of high-performance organic fibers, particularly a preparation method of high-performance organic fibers on the basis of 3,3'4,4'-tetra-aminobiphenyl hydrochloride. The invention aims to solve the common problems of poor interfacial binding property and low interfacial shear strength between fibers and resin substrate due to smooth surface, low activity and low soakage tendency with resin in the traditional PBO (poly(p-phenylene-2,6-benzobisoxazole)) fibers. The method comprises the following steps: adding 4,6-diamino-resorcinol hydrochloride, 3,3'4,4'-tetra-aminobiphenyl hydrochloride, 2,5-dihydroxyterephthalic acid, polyphosphoric acid and phosphorus pentoxide into a polymerization kettle, dissolving by heating, adding phosphorus pentoxide, heating, adding polymethylphenylsiloxane, heating, filtering, degassing, extruding, preparing protofibrils, washing with water, washing with alcohol, washing with alkali, drying, and heating in a nitrogen protective atmosphere to obtain the high-performance organic fibers. The tensile strength of the high-performance organic fibers reaches 2.3-4.8 GPa.
Description
Technical field
The invention belongs to high-performance organic fibre preparing technical field, be specifically related to a kind of new preparation process of novel high-performance organic fiber.
Background technology
Traditional PBO preparation method mainly contains following two kinds: 1, with 4,6-diamino resorcin hydrochlorate and paraphthaloyl chloride or terephthalic acid (TPA) first remove HCl under the condition of polyphosphoric acids, and then heat up polymerization reaction take place, and the polymer of gained after filtration, spinning solution is obtained after degassed process, spinning solution is extruded by spinnerets through screw extruder, through air bath, and pickling, alkali cleaning, volume is rich, obtains the pbo fiber that diameter is about 15 microns, obtains the pbo fiber of high-modulus after Overheating Treatment.2, complex salt is made with 4,6-diaminoresorcinol hydrochloride and equimolar terephthalic acid (TPA).Complex salt and polyphosphoric acids are stirred well rear intensification to be polymerized, the polymer of gained after filtration, spinning solution is obtained after degassed process, spinning solution is extruded by spinnerets through screw extruder, through air bath, and pickling, alkali cleaning, volume is rich, obtains the pbo fiber that diameter is about 15 microns, obtains the pbo fiber of high-modulus after Overheating Treatment.The obtained fiber of above-mentioned conventional method has following deficiency: 1, surface very smooth, the polymer of gained in chemical constitution without any active group, therefore with the binding ability difference very of resin.Although 2, traditional pbo fiber heat resistance in organic fiber is relatively high, still far away from inorfil, therefore limited in the development of some fields.
Summary of the invention
The object of the invention is to solve traditional pbo fiber ubiquity fiber surface smooth and active low, not easily infiltrate with resin, cause the interfacial adhesion between fiber and resin matrix poor, the problem that interface shear strength is low, and provide a kind of based on 3, the preparation method of 3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre.
One of the present invention is based on 3, 3', 4, the preparation method of 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, carry out according to following steps: one, by 4, 6-diamino resorcin hydrochlorate, 3, 3', 4, 4'-tetra-amino-biphenyl hydrochloride, 2, 5-dihydric para-phthalic acid, polyphosphoric acids and first part of phosphorus pentoxide, be under the condition being less than 20mmHg at system pressure, be warming up to 20 DEG C of reaction 6h successively, be warming up to 40 DEG C of reaction 120h, be warming up to 20 DEG C of reaction 18h, be warming up to 60 DEG C of reaction 24h, add second part of phosphorus pentoxide again, after temperature is 100 DEG C of reaction 24h, after adding PSI, be react 24h under the condition of 140 DEG C successively in temperature, be after reacting 48h under the condition of 195 DEG C in temperature, obtain crude product polymer, two, crude product polymer step one obtained after filtration, after degassed, is extruded with double screw extruder, is obtained spinning solution, three, spinning solution step 2 obtained, adopts dry-jet wet spinning process to prepare as-spun fibre, four, as-spun fibre step 3 obtained through washing, alcohol wash, alkali cleaning, after drying, under nitrogen protection 150 ~ 600 DEG C process 0.5h, must based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre,
Wherein, the molal quantity of the 2,5-Dihydroxyterephthalic acid described in step one is 4,6-diaminoresorcinol hydrochloride and 3,3', the molal quantity sum of 4,4'-tetra-amino-biphenyl hydrochloride;
The addition of the polyphosphoric acids described in step one is 3 times of the gross mass of 4,6-diaminoresorcinol hydrochloride, 3,3', 4,4'-tetra-amino-biphenyl hydrochlorides and 2,5-Dihydroxyterephthalic acid;
The mass ratio of part phosphorus pentoxide of first described in step one and polyphosphoric acids is 1:3;
The mass ratio of part phosphorus pentoxide of second described in step one and polyphosphoric acids is 1:15;
The mass ratio of the PSI described in step one and polyphosphoric acids is 0.01 ~ 0.17:1.
The present invention comprises following beneficial effect:
1, method therefor of the present invention is owing to adding 3,3', and 4,4'-tetra-amino-biphenyl hydrochloride, introduces-NH in the polymer molecule of gained, and such molecular structure more easily and resin-bonded.Compared with the pbo fiber prepared under equal conditions, after impregnation wound and solidified, the shear strength of the NOL ring sample of gained is as index, investigate the impact of two kinds of fibrous composite performances, two groups of parallel laboratory tests are averaged, and result shows that the fiber cutting intensity prepared by the present invention is the highest can promote 30%.
2, method therefor of the present invention is owing to adopting 2,5-dihydric para-phthalic acid is another monomer, two-OH are introduced in the polymer molecule of gained, it can with the methoxyl group generation grafting polycondensation of PSI, form the organic-silicon-modified fiber with appropriately crosslinked density, it is compared with traditional pbo fiber, and the existence of a large amount of phenyl makes it better with the compatibility of resin, also reduces internal stress of resin simultaneously.
3, method therefor of the present invention adopts organosilicon preparation a kind of based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, after heat treatment, heat resistance and the oxidation resistance of fiber are all improved, and experimental result to show that compared with the pbo fiber prepared under equal conditions heat resistance is the highest can promote 25%.
4, the one prepared of method therefor of the present invention is based on 3,3', and 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, TENSILE STRENGTH can reach 2.3 ~ 4.8GPa.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: the one of present embodiment is based on 3, 3', 4, the preparation method of 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, carry out according to following steps: one, by 4, 6-diamino resorcin hydrochlorate, 3, 3', 4, 4'-tetra-amino-biphenyl hydrochloride, 2, 5-dihydric para-phthalic acid, polyphosphoric acids and first part of phosphorus pentoxide, be under the condition being less than 20mmHg at system pressure, be warming up to 20 DEG C of reaction 6h successively, be warming up to 40 DEG C of reaction 120h, be warming up to 20 DEG C of reaction 18h, be warming up to 60 DEG C of reaction 24h, add second part of phosphorus pentoxide again, after temperature is 100 DEG C of reaction 24h, after adding PSI, be react 24h under the condition of 140 DEG C successively in temperature, be after reacting 48h under the condition of 195 DEG C in temperature, obtain crude product polymer, two, crude product polymer step one obtained after filtration, after degassed, is extruded with double screw extruder, is obtained spinning solution, three, spinning solution step 2 obtained, adopts dry-jet wet spinning process to prepare as-spun fibre, four, as-spun fibre step 3 obtained through washing, alcohol wash, alkali cleaning, after drying, under nitrogen protection 150 ~ 600 DEG C process 0.5h, must based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre,
Wherein, the molal quantity of the 2,5-Dihydroxyterephthalic acid described in step one is 4,6-diaminoresorcinol hydrochloride and 3,3', the molal quantity sum of 4,4'-tetra-amino-biphenyl hydrochloride;
The addition of the polyphosphoric acids described in step one is 3 times of the gross mass of 4,6-diaminoresorcinol hydrochloride, 3,3', 4,4'-tetra-amino-biphenyl hydrochlorides and 2,5-Dihydroxyterephthalic acid;
The mass ratio of part phosphorus pentoxide of first described in step one and polyphosphoric acids is 1:3;
The mass ratio of part phosphorus pentoxide of second described in step one and polyphosphoric acids is 1:15;
The mass ratio of the PSI described in step one and polyphosphoric acids is 0.01 ~ 0.17:1.
Present embodiment comprises following beneficial effect:
1, present embodiment method therefor is owing to adding 3,3', and 4,4'-tetra-amino-biphenyl hydrochloride, introduces-NH in the polymer molecule of gained, and such molecular structure more easily and resin-bonded.Compared with the pbo fiber prepared under equal conditions, after impregnation wound and solidified, the shear strength of the NOL ring sample of gained is as index, investigate the impact of two kinds of fibrous composite performances, two groups of parallel laboratory tests are averaged, and result shows that the fiber cutting intensity prepared by present embodiment is the highest can promote 30%.
2, present embodiment method therefor is owing to adopting 2,5-dihydric para-phthalic acid is another monomer, two-OH are introduced in the polymer molecule of gained, it can with the methoxyl group generation grafting polycondensation of PSI, form the organic-silicon-modified fiber with appropriately crosslinked density, it is compared with traditional pbo fiber, and the existence of a large amount of phenyl makes it better with the compatibility of resin, also reduces internal stress of resin simultaneously.
3, present embodiment method therefor adopts organosilicon preparation a kind of based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, after heat treatment, heat resistance and the oxidation resistance of fiber are all improved, and experimental result to show that compared with the pbo fiber prepared under equal conditions heat resistance is the highest can promote 25%.
4, the one prepared of present embodiment method therefor is based on 3,3', and 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, TENSILE STRENGTH can reach 2.3 ~ 4.8GPa.
Detailed description of the invention two: present embodiment and detailed description of the invention one are unlike the 4,6-diaminoresorcinol hydrochloride, 3,3' described in step one, 4, the purity of 4'-tetra-amino-biphenyl hydrochloride and 2,5-Dihydroxyterephthalic acid is all greater than 99.5%, and monomelic impurities is all less than 0.2%.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike: the mass ratio of the PSI described in step one and polyphosphoric acids is 0.05 ~ 0.10:1.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: the mass percentage of the polyphosphoric acids described in step one is 79%.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 300:1.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 250:1.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six unlike: draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 230:1.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven unlike: draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 210:1.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight unlike: draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 205:1.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine unlike: draw ratio time prepared by the as-spun fibre described in step 3 is 201:1.Other is identical with one of detailed description of the invention one to nine.
Beneficial effect of the present invention is verified by following examples:
Embodiment 1
The one of the present embodiment based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, carry out according to following steps:
One, first by 4 of 1.065Kg, 6-diamino resorcin hydrochlorate, 1.801Kg 3, 3', 4, 4'-tetra-amino-biphenyl hydrochloride, 1.981Kg 2, 5-dihydric para-phthalic acid, the phosphorus pentoxide of 14.541Kg polyphosphoric acids and 4.847Kg adds in polymeric kettle, be under the condition of 20mmHg at system pressure, be heated to 20 DEG C of reaction 6h successively, be heated to 40 DEG C of reaction 120h, be heated to 20 DEG C of reaction 18h, be heated to 60 DEG C of reaction 24h, after adding the phosphorus pentoxide of 0.969Kg again, be heated to 100 DEG C of reaction 24h, add the PSI of 1Kg again, be heated to 140 DEG C of reaction 24h successively, be heated to 195 DEG C of reaction 48h, obtain crude product polymer, two, crude product polymer step one obtained, adopt 10 microns of filter discs to filter, collect filtrate, degassed (time degassed, pressure is 10mmHg), extrudes with double screw extruder, obtains spinning solution, three, spinning solution step 2 obtained adopts dry-jet wet spinning process to prepare protofilament (draw ratio in preparation is 210:1), through washing (deionized water washes 1 time), alcohol wash (absolute ethyl alcohol is washed, and washes 1 time), (mass percentage is the NaOH solution of 10% in alkali cleaning, wash 1 time), after dry (dry at 140 DEG C), under nitrogen protection, be 300 DEG C in temperature and process 0.5h, must based on 3, 3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre.
The present embodiment obtained based on 3,3', the heat resistance of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre is 550 DEG C, and modulus is 190GPa.TENSILE STRENGTH is 4.1GPa.
Embodiment 2
The one of the present embodiment based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, carry out according to following steps:
One, first by 4 of 0.533Kg, 6-diamino resorcin hydrochlorate, 2.700Kg 3, 3', 4, 4'-tetra-amino-biphenyl hydrochloride, 1.981Kg 2, 5-dihydric para-phthalic acid, the phosphorus pentoxide of 15.642Kg polyphosphoric acids and 5.214Kg adds in polymeric kettle, be under the condition of 20mmHg at system pressure, be heated to 20 DEG C of reaction 6h successively, be heated to 40 DEG C of reaction 120h, be heated to 20 DEG C of reaction 18h, be heated to 60 DEG C of reaction 24h, after adding the phosphorus pentoxide of 1.043Kg again, be heated to 100 DEG C of reaction 24h, add the PSI of 2Kg again, be heated to 140 DEG C of reaction 24h successively, be heated to 195 DEG C of reaction 48h, obtain crude product polymer, two, crude product polymer step one obtained, adopt 10 microns of filter discs to filter, collect filtrate, degassed (time degassed, pressure is 10mmHg), extrudes with double screw extruder, obtains spinning solution, three, spinning solution step 2 obtained adopts dry-jet wet spinning process to prepare protofilament (draw ratio in preparation is 230:1), through washing (deionized water washes 1 time), alcohol wash (absolute ethyl alcohol is washed, and washes 1 time), (mass percentage is the NaOH solution of 10% in alkali cleaning, wash 1 time), after dry (dry at 150 DEG C), under nitrogen protection, be 350 DEG C in temperature and process 0.5h, must based on 3, 3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre.
The heat resistance of 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibres that the present embodiment is obtained is 520 DEG C, and modulus is 200GPa, and TENSILE STRENGTH is 4.2GPa.
Embodiment 3
The one of the present embodiment based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, carry out according to following steps:
One, first by 4 of 1.600Kg, 6-diamino resorcin hydrochlorate, 3 of 0.900Kg, 3', 4, 4'-tetra-amino-biphenyl hydrochloride, 1.981Kg 2, 5-dihydric para-phthalic acid, the phosphorus pentoxide of 13.444Kg polyphosphoric acids and 4.481Kg adds in polymeric kettle, be under the condition of 20mmHg at system pressure, be heated to 20 DEG C of reaction 6h successively, be heated to 40 DEG C of reaction 120h, be heated to 20 DEG C of reaction 18h, be heated to 60 DEG C of reaction 24h, after adding the phosphorus pentoxide of 0.896Kg again, be heated to 100 DEG C of reaction 24h, add the PSI of 1.5Kg again, be heated to 140 DEG C of reaction 24h successively, be heated to 195 DEG C of reaction 48h, obtain crude product polymer, two, crude product polymer step one obtained, adopt 10 microns of filter discs to filter, collect filtrate, degassed (time degassed, pressure is 10mmHg), extrudes with double screw extruder, obtains spinning solution, three, spinning solution step 2 obtained adopts dry-jet wet spinning process to prepare protofilament (draw ratio in preparation is 205:1), through washing (deionized water washes 1 time), alcohol wash (absolute ethyl alcohol is washed, and washes 1 time), (mass percentage is the NaOH solution of 10% in alkali cleaning, wash 1 time), after dry (dry at 160 DEG C), under nitrogen protection, be 200 DEG C in temperature and process 0.5h, must based on 3, 3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre.
The present embodiment 3,3', the heat resistance of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre is 580 DEG C, and modulus is 210GPa, and TENSILE STRENGTH is 4.5GPa.
To embodiment 1 to embodiment 3 obtained based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre carries out contrast experiment:
Contrast experiment 1:
By in experimental example 13,3', 4,4'-tetra-amino-biphenyl hydrochloride changes equimolar 4,6-diaminoresorcinol hydrochloride into, by 2,5-dihydric para-phthalic acid changes terephthalic acid (TPA) into, does not add PSI, and other parameter is identical with embodiment 1 with condition, prepare pbo fiber, obtained by embodiment 1 based on 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre pbo fiber heat resistance obtained compared with same process improves 25%, and modulus improves 19%.TENSILE STRENGTH improves 5%.After impregnation wound and solidified, the shear strength of the NOL ring sample of gained is as index, investigate the impact of two kinds of fibrous composite performances, two groups of parallel laboratory tests are averaged, result show obtained by embodiment 1 based on 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre pbo fiber shear strength obtained compared with same process improves 30%.
Contrast experiment 2:
Change 3,3', 4,4'-tetra-amino-biphenyl hydrochlorides in experimental example 2 into equimolar 4,6-diamino resorcin hydrochlorate, changes 2,5-Dihydroxyterephthalic acid into terephthalic acid (TPA), do not add PSI, other parameter is identical with embodiment 2 with condition, prepares pbo fiber.Obtained by embodiment 2 based on 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre PBO heat resistance obtained compared with conventional method improves 8%, and modulus improves 15%.TENSILE STRENGTH reduces 8%.After impregnation wound and solidified, the shear strength of the NOL ring sample of gained is as index, investigate the impact of two kinds of fibrous composite performances, two groups of parallel laboratory tests are averaged, result show obtained by embodiment 2 based on 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre pbo fiber shear strength obtained compared with same process improves 11%.
Contrast experiment 3:
Change 3,3', 4,4'-tetra-amino-biphenyl hydrochlorides in experimental example 3 into equimolar 4,6-diamino resorcin hydrochlorate, changes 2,5-Dihydroxyterephthalic acid into terephthalic acid (TPA), do not add PSI, other parameter is identical with embodiment 3 with condition, prepares pbo fiber.Obtained by embodiment 3 based on 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre PBO heat resistance obtained compared with conventional method improves 15%, and modulus improves 9%.TENSILE STRENGTH improves 18%.After impregnation wound and solidified, the shear strength of the NOL ring sample of gained is as index, investigate the impact of two kinds of fibrous composite performances, two groups of parallel laboratory tests are averaged, result show obtained by embodiment 3 based on 3,3', 4, the 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre pbo fiber shear strength obtained compared with same process improves 22%.
In sum, the present invention, by adding the composites such as organosilicon in the course of the polymerization process, successfully prepares a kind of based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre.
Claims (9)
1. one kind based on 3, 3', 4, the preparation method of 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that described based on 3, 3', 4, the preparation method of 4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre carries out according to following steps: one, by 4, 6-diamino resorcin hydrochlorate, 3, 3', 4, 4'-tetra-amino-biphenyl hydrochloride, 2, 5-dihydric para-phthalic acid, polyphosphoric acids and first part of phosphorus pentoxide, be under the condition being less than 20mmHg at system pressure, be warming up to 20 DEG C of reaction 6h successively, be warming up to 40 DEG C of reaction 120h, be warming up to 20 DEG C of reaction 18h, be warming up to 60 DEG C of reaction 24h, add second part of phosphorus pentoxide again, after temperature is 100 DEG C of reaction 24h, after adding PSI, be react 24h under the condition of 140 DEG C successively in temperature, be after reacting 48h under the condition of 195 DEG C in temperature, obtain crude product polymer, two, crude product polymer step one obtained after filtration, after degassed, is extruded with double screw extruder, is obtained spinning solution, three, spinning solution step 2 obtained, adopts dry-jet wet spinning process to prepare as-spun fibre, four, as-spun fibre step 3 obtained through washing, alcohol wash, alkali cleaning, after drying, under nitrogen protection 150 ~ 600 DEG C process 0.5h, must based on 3,3', 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre,
Wherein, the molal quantity of the 2,5-Dihydroxyterephthalic acid described in step one is 4,6-diaminoresorcinol hydrochloride and 3,3', the molal quantity sum of 4,4'-tetra-amino-biphenyl hydrochloride;
The addition of the polyphosphoric acids described in step one is 3 times of the gross mass of 4,6-diaminoresorcinol hydrochloride, 3,3', 4,4'-tetra-amino-biphenyl hydrochlorides and 2,5-Dihydroxyterephthalic acid;
The mass ratio of part phosphorus pentoxide of first described in step one and polyphosphoric acids is 1:3;
The mass ratio of part phosphorus pentoxide of second described in step one and polyphosphoric acids is 1:15;
The mass ratio of the PSI described in step one and polyphosphoric acids is 0.068:1,0.127:1 or 0.11:1.
2. one according to claim 1 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, is characterized in that 4 described in step one, 6-diamino resorcin hydrochlorate, 3,3', 4,4'-tetra-amino-biphenyl hydrochloride and 2, the purity of 5-dihydric para-phthalic acid is all greater than 99.5%, and monomelic impurities is all less than 0.2%.
3. one according to claim 1 is based on 3,3', and the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, is characterized in that the mass percentage of the polyphosphoric acids described in step one is 79%.
4. one according to claim 1 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 300:1.
5. one according to claim 4 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 250:1.
6. one according to claim 5 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 230:1.
7. one according to claim 6 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 210:1.
8. one according to claim 7 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that draw ratio time prepared by the as-spun fibre described in step 3 is 201 ~ 205:1.
9. one according to claim 8 is based on 3,3', the preparation method of 4,4'-tetra-amino-biphenyl hydrochloride high-performance organic fibre, it is characterized in that draw ratio time prepared by the as-spun fibre described in step 3 is 201:1.
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