CN102418162B - Preparation method of ultraviolet-light-resistant thiophene-structure-containing polybenzoxazole fibre - Google Patents
Preparation method of ultraviolet-light-resistant thiophene-structure-containing polybenzoxazole fibre Download PDFInfo
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- CN102418162B CN102418162B CN 201110217620 CN201110217620A CN102418162B CN 102418162 B CN102418162 B CN 102418162B CN 201110217620 CN201110217620 CN 201110217620 CN 201110217620 A CN201110217620 A CN 201110217620A CN 102418162 B CN102418162 B CN 102418162B
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- thiophene
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- terephthalic acid
- complex salt
- dioctyl phthalate
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- 239000000835 fiber Substances 0.000 title claims abstract description 74
- 229920002577 polybenzoxazole Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 192
- 150000003839 salts Chemical class 0.000 claims abstract description 64
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 44
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 33
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 14
- LBHYQZOIQOEFQP-UHFFFAOYSA-N dioctyl benzene-1,2-dicarboxylate thiophene Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.S1C=CC=C1 LBHYQZOIQOEFQP-UHFFFAOYSA-N 0.000 claims abstract description 12
- KUMOYHHELWKOCB-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;dihydrochloride Chemical compound Cl.Cl.NC1=CC(N)=C(O)C=C1O KUMOYHHELWKOCB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 90
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 64
- 229960001755 resorcinol Drugs 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 229930192474 thiophene Natural products 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 26
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 230000006750 UV protection Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 239000012530 fluid Substances 0.000 abstract 1
- 230000004224 protection Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000032683 aging Effects 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 238000002166 wet spinning Methods 0.000 description 11
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 10
- 238000012423 maintenance Methods 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- SETKSSWXKOMVCZ-UHFFFAOYSA-N [Na].[Na].C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.S1C=CC=C1 Chemical compound [Na].[Na].C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.S1C=CC=C1 SETKSSWXKOMVCZ-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a preparation process of a thiophene-structure-containing polybenzoxazole fibre. The preparation process comprises the following steps of: firstly, respectively mixing 4,6-diamino resorcinol dihydrochloride with terephthalic acid and thiophene dioctyl phthalate to obtain corresponding composite salts; then carrying out condensation reaction on the two composite salts in a phosphorus pentoxide/polyphosphoric acid solvent system under the protection of inert gas; and transferring a reactive fluid into spinning equipment after reaction is finished, so as to prepare the fibre. The method provided by the invention can be used for solving the problem that the solubility difference between terephthalic acid and 2,5-thiophene dioctyl phthalate in the polyphosphoric acid is great in the prior art; cost is low, and the preparation process is environmentally-friendly; and the obtained copolymerization resin has good uniformity, and the ultraviolet resistance of the fibre is improved.
Description
Technical field
The present invention relates to a kind of high-performance poly benzoxazole fiber preparation method, more specifically, relate to a kind of preparation method who contains thiophene structure polybenzoxazole fibers.
Background technology
High-performance poly [(1,4)-phenylene 2, and 6-(1,2-d:5,4-d)-Ben Bing Er oxazole] (being called for short PBO) fiber has excellent intensity, modulus, heat resistance and flame resistance, but its resistance to UV aging can be relatively poor.Japan Japan spins company and once the photostability of pbo fiber carried out test, and the result shows: be exposed under 6 months the condition of daylight, its modulus only is original 35%.People such as woods blue sky report: the sun-resistant poor-performing of pbo fiber, the time that is exposed in the ultraviolet ray is more long, and intensity descends more many.After particularly passing through the Exposure to Sunlight of 40h, the fracture strength of pbo fiber only be original 37% (the woods blue sky, the mechanical property of all quiet .PBO-AS fibers is inquired into. Shanghai textile technology, 2004,32 (1): 5-7.).In recent years, people prepare the polybenzoxazole fibers that contains the thiophene structure by the modification by copolymerization means, compare with pbo fiber, have not only improved its ultraviolet-resistant performance, and kept heat endurance and the mechanical performance suitable with pbo fiber, development and the application of pbo fiber is of great importance.
People such as Chen Y have reported the polybenzoxazole polymer that contains the thiophene structure, its preparation method is with 4,6-diamino resorcin dihydrochloride and terephthalic acid (TPA) and 2,5-thiophene dioctyl phthalate joins in a certain amount of polyphosphoric acids and the phosphorus pentoxide system, carry out polycondensation reaction at a certain temperature, obtain containing polybenzoxazole (the Chen Y of thiophene structure, et al.Spectral modulation and exciton mingration in thiophene-based polybenzobisoxazole random copolymers with donor-acceptor architectures.Macromolecules, 2005,38 (23): 9873-9877.).Chinese invention patent CN101643545A has also reported the synthetic of the polybenzoxazole polymer that contains the thiophene structure, its preparation method is as follows: at first with 4,6-diamino resorcin dihydrochloride, part phosphorus pentoxide, polyphosphoric acids, terephthalic acid (TPA), thiophene dioctyl phthalate add in the reactor, agitating heating also progressively heats up, under 40～100 ℃ of conditions, reacted 10～24 hours, reducing pressure during this time removes hydrogen chloride, is removed (not having HCl with pH detection paper system produces) fully until hydrogen chloride; And then add remaining phosphorus pentoxide, and progressively heat up and under 130～220 ℃ of conditions, reacted 60～108 hours, obtain containing the polybenzoxazole of thiophene structure.
This preparation method has the following disadvantages: 4,6-diamino resorcin dihydrochloride need be reduced pressure in polyphosphoric acids in (1) reaction removes HCl, and this is crossed range request HCl and must remove fully, otherwise influences reactivity.Since 4, the very easily oxidation of 6-diamino resorcin, and so for necessary anaerobic in the anti-oxidation requirement system, equipment is had relatively high expectations, and it is longer to remove the HCl time, the HCl of generation is, and equipment corrosion is serious; (2) because terephthalic acid (TPA) solubility in polyphosphoric acids is very low, require the particle diameter of terephthalic acid (TPA) less than 5 microns usually; (3) because terephthalic acid (TPA) and 2,5-thiophene dioctyl phthalate dissolubility difference in polyphosphoric acids are big, cause 4,6-diamino resorcin dihydrochloride and terephthalic acid (TPA), 2,5-thiophene dioctyl phthalate reaction speed is different, and the copolymer resins that obtains is inhomogeneous.
Summary of the invention
The improved preparation method who contains thiophene structure polybenzoxazole fibers who the object of the present invention is to provide a kind of cost reduction, environmental friendliness, UV resistant performance to strengthen.
The preparation that ultraviolet resistance of the present invention contains thiophene structure polybenzoxazole fibers comprises the steps:
(1) with monomer 4,6-diamino resorcin dihydrochloride makes corresponding complex salt with monomers terephthalic acid and thiophene dioctyl phthalate respectively;
(2) under inert gas shielding, two kinds of complex salt of step (1) are carried out condensation reaction in phosphorus pentoxide/polyphosphoric acids dicyandiamide solution;
(3) the end reaction liquid after step (2) reaction is finished is transferred to and is made fiber in the spinning equipment;
(4) remove the residual phosphoric acid of the described fiber of step (3) respectively with dilute sodium hydroxide aqueous solution and water, namely obtain the polybenzoxazole fibers that contains the thiophene structure of the present invention after drying.
In the above-mentioned steps (1) 4, following method is preferably adopted in the preparation of 6-diamino resorcin/terephthalic acid (TPA) complex salt:
Use NaOH, KOH, Na
2CO
3Or K
2CO
3Deng the aqueous solution terephthalic acid (TPA) is mixed with the sodium salt of terephthalic acid (TPA) or the aqueous solution of sylvite, with 4,6-diamino resorcin dihydrochloride is mixed with the aqueous solution, make terephthalic acid (TPA) and 4,6-diamino resorcin hydrochlorate mol ratio is two kinds of aqueous solution generation acid-base neutralization reactions of 1: 1, filter, wash after reaction finishes and drying prepares 4,6-diamino resorcin/terephthalic acid (TPA) complex salt.
Described 4, the reaction equation of 6-diamino resorcin/terephthalic acid (TPA) complex salt preparation is as follows:
In the above-mentioned steps (1) 4, following method is preferably adopted in the preparation of 6-diamino resorcin/thiophene dioctyl phthalate complex salt:
Use NaOH, KOH, Na
2CO
3Or K
2CO
3Deng the aqueous solution thiophene dioctyl phthalate is mixed with the sodium salt of thiophene dioctyl phthalate or the aqueous solution of sylvite, with 4, the 6-diamino resorcin hydrochlorate is mixed with the aqueous solution, make thiophene dioctyl phthalate and 4,6-diamino resorcin hydrochlorate mol ratio is two kinds of aqueous solution generation acid-base neutralization reactions of 1: 1, filter, wash after reaction finishes and drying prepares 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt.
Described 4, the reaction equation of 6-diamino resorcin/thiophene dioctyl phthalate complex salt preparation is as follows:
In the above-mentioned steps (2); under inert gas shielding; the reaction equation that 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt are taken place in phosphorus pentoxide/polyphosphoric acids dicyandiamide solution in condensation reaction is as follows:
In the formula, to be x be (100～1) with the ratio of y to the mol ratio of 1,4-phenylene benzo-dioxazole fragment and 2,5-thiophene benzo bisoxazoline fragment: (1～100), and x, y, n are positive integer; Preferably, x is (50～1) with the ratio of y: 1.
In the above-mentioned steps (2), described 4, the mol ratio of 6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt can be (100～1): (1～100), preferred molar ratio are (50～1): 1.
In the above-mentioned steps (2), phosphorus pentoxide in the end reaction liquid/polyphosphoric acids dicyandiamide solution is in phosphorus pentoxide, and its mass concentration is preferred 80%～86%, and more preferably 82%～84%.When resin quality concentration in the reactant liquor is that the molecular resin quality that obtains under 5%～25% the condition is bigger, and be conducive to spinning process.Therefore, resin quality concentration is preferred 5%～25% in the end reaction liquid of this technology, and more preferably 8%～20%.
In the above-mentioned steps (2), preferred 100～220 ℃ of described setting-up point, more preferably 120～200 ℃; Preferred 10～48h of reaction time, more preferably 12～36h.Preferably, react according to temperature-programmed mode.
In the above-mentioned steps (3), preferably, adopt dry-jet wet spinning process that the above-mentioned resin that makes is made fiber.
In the above-mentioned steps (4), preferably, the gained fiber is further removed phosphoric acid residual on the fiber with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain containing the polybenzoxazole fibers of thiophene structure again after the drying.
Technology of the present invention by earlier respectively the beneficial effect of the method for synthetic complex salt and then condensation mainly show: in (1) prior art because of terephthalic acid (TPA) and 2,5-thiophene dioctyl phthalate dissolubility difference in polyphosphoric acids causes greatly obtaining non-homogeneous copolymer resins, causes the fiber UV resistant performance deficiency that makes; The present invention has overcome the big critical technological point of dissolubility difference, thereby obtains the copolymer resins of excellent in uniform, and making ultra-violet resistance thus can excellent fiber.(2) very low owing to terephthalic acid (TPA) solubility in polyphosphoric acids in the prior art, require the particle diameter of terephthalic acid (TPA) less than 5 microns usually; The particle diameter of terephthalic acid (TPA) does not have special requirement among the present invention, thereby can reduce cost.(3) to remove the HCl process long the condensation reaction stage in the prior art, and equipment corrosion is serious; Exist invariably among the present invention and take off HCl step, environmental friendliness.
The specific embodiment
The following examples are set forth in more detail to the present invention, rather than limitation of the invention further.Comparative Examples 1 contains polybenzoxazole fibers and the photostability test of thiophene structure for adopting the preparation of Chinese invention patent CN101643545A disclosed method.Except as otherwise noted, " % " wherein is " quality % ".
Comparative Examples 1
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed, under the nitrogen inert gas shielding, add 10.7g (0.05mol) 4,6-diamino resorcin dihydrochloride, 10.5g phosphorus pentoxide, (content is with P for the 119.1g polyphosphoric acids
2O
5Count 84%), 4.2g (0.025mol) terephthalic acid (TPA) and 4.3g (0.025mol) thiophene dioctyl phthalate, be heated with stirring to 40～50 ℃ of reaction 12h, during reduce pressure and remove HCl, and progressively be warming up to 90～100 ℃ of reaction 12h and guarantee to remove fully hydrogen chloride; And then adding 3.508g phosphorus pentoxide, be warming up to 130 ℃ and keep 12h, 150 ℃ of maintenance 12h, 170 ℃ of maintenance 12h, 180 ℃ of maintenance 2h, 200 ℃ of maintenance 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 84.6%.
Embodiment 1
The preparation of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt
Stirring is being housed; in the 125mL four-hole bottle of condenser pipe and thermometer; under the nitrogen inert gas shielding, add 10.66g (0.05mol) 4; 6-diamino resorcin dihydrochloride and 100mL deionized water; in addition 9.30g (0.05mol) terephthalic acid (TPA) is dissolved in preparation disodium terephthalate saline solution in the 200g sodium hydrate aqueous solution (naoh concentration is 2%); and this solution is added dropwise to above-mentioned 4 under 80 ℃ of conditions; in the 6-diamino resorcin dihydrochloride aqueous solution; under 80 ℃ of conditions, react 10min; filter; washing; refiltering also, vacuumize obtains 4,6-diamino resorcin/terephthalic acid (TPA) complex salt.
The preparation of 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt
Stirring is being housed; in the 125mL four-hole bottle of condenser pipe and thermometer; under the nitrogen inert gas shielding, add 10.66g (0.05mol) 4; 6-diamino resorcin dihydrochloride and 100mL deionized water; in addition with 8.60g (0.05mol) 2; 5-thiophene dioctyl phthalate is dissolved in the preparation thiophene dioctyl phthalate disodium salt aqueous solution in the 200g sodium hydrate aqueous solution (naoh concentration is 2%); and this solution is added dropwise to above-mentioned 4 under 80 ℃ of conditions; in the 6-diamino resorcin dihydrochloride aqueous solution; under 80 ℃ of conditions, react 10min; filter; washing; refiltering also, vacuumize obtains 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt.
Contain the preparation of the polybenzoxazole fibers of thiophene structure
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 7.65g (0.025mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 7.80g (0.025mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 10.5g phosphorus pentoxide, (content is with P for the 119.1g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 6h, 150 ℃ to keep 8h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 99.6%.
Embodiment 2
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 12.4g (0.04mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 3.12g (0.01mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, (content is with P for the 10.5g phosphorus pentoxide
2O
5Count 84%), the 119.1g polyphosphoric acids, be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 30 ℃ respectively and keep 6h, 150 ℃ to keep 12h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 94.2%.
Embodiment 3
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 14.99g (0.049mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 0.31g (0.001mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 12.60g phosphorus pentoxide, (content is with P for the 91.36g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 12h, 150 ℃ to keep 12h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 90.1%.
Embodiment 4
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 14.69g (0.048mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 0.62g (0.002mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 16.56g phosphorus pentoxide, (content is with P for the 77.50g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 6h, 150 ℃ to keep 12h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 91.3%.
Embodiment 5
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 13.77g (0.045mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 1.56g (0.005mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 16.35g phosphorus pentoxide, (content is with P for the 50.07g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 12h, 150 ℃ to keep 12h, 180 ℃ to keep 2h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 92.5%.
Embodiment 6
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 13.77g (0.045mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 1.56g (0.005mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 13.26g phosphorus pentoxide, (content is with P for the 32.97g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 2h, and slowly be warming up to 130 ℃ respectively and keep 4h, 150 ℃ to keep 6h, 180 ℃ to keep 2h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 92.5%.
Embodiment 7
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 1.54g (0.005mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 14.13g (0.045mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 10.5g phosphorus pentoxide, (content is with P for the 119.1g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 6h, 150 ℃ to keep 8h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 99.8%.
Embodiment 8
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 0.15g (0.0005mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 15.54g (0.0495mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 10.5g phosphorus pentoxide, (content is with P for the 119.1g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 6h, 150 ℃ to keep 8h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 99.8%.
Embodiment 9
The preparation process of 4,6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is with embodiment 1.
In the 125mL four-hole bottle of stirring, condenser pipe, drying tube and thermometer is housed; under the nitrogen inert gas shielding, add 15.25g (0.0495mol) 4; 6-diamino resorcin/terephthalic acid (TPA) complex salt, 0.16g (0.0005mol) 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt, 10.5g phosphorus pentoxide, (content is with P for the 119.1g polyphosphoric acids
2O
5Count 84%), be heated with stirring to 120 ℃ of reaction 6h, and slowly be warming up to 130 ℃ respectively and keep 6h, 150 ℃ to keep 8h, 180 ℃ to keep 2h, 200 ℃ to keep 1h, reaction finishes, reactant liquor is transferred in the spinning equipment, adopt dry-jet wet spinning process to make fiber, the gained fiber is further removed residual phosphoric acid with 5% sodium hydrate aqueous solution and water respectively, in vacuum drying chamber, obtain the polybenzoxazole fibers that golden yellow contains the thiophene structure again after the drying.
The polybenzoxazole fibers that will contain the thiophene structure carries out light aging 240h in ZN-P type ultraviolet light and aging case after, strength retention is 90.7%.
Table 1 differential responses condition prepares strength retention after the light aging of polybenzoxazole fibers
Annotate: complex salt 1 is 4,6-diamino resorcin/terephthalic acid (TPA) complex salt; Complex salt 2 is 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt.
Claims (9)
1. a UV resistant contains the preparation method of thiophene structure polybenzoxazole fibers, comprises the steps:
(1) with monomer 4,6-diamino resorcin dihydrochloride makes corresponding complex salt with monomers terephthalic acid and thiophene dioctyl phthalate respectively;
(2) under inert gas shielding, two kinds of complex salt of step (1) are carried out condensation reaction in phosphorus pentoxide/polyphosphoric acids dicyandiamide solution;
(3) the end reaction liquid after step (2) reaction is finished is transferred to and is made fiber in the spinning equipment;
(4) remove the residual phosphoric acid of the described fiber of step (3) respectively with dilute sodium hydroxide aqueous solution and water, namely obtain containing the polybenzoxazole fibers of thiophene structure after drying;
Use NaOH, KOH, Na in the described step (1)
2CO
3Or K
2CO
3The aqueous solution terephthalic acid (TPA) or thiophene dioctyl phthalate are mixed with the sodium salt of terephthalic acid (TPA) or thiophene dioctyl phthalate or the aqueous solution of sylvite, with 4,6-diamino resorcin dihydrochloride is mixed with the aqueous solution, make terephthalic acid (TPA) or thiophene dioctyl phthalate and 4,6-diamino resorcin hydrochlorate mol ratio is two kinds of aqueous solution generation acid-base neutralization reactions of 1: 1, filter, wash after reaction finishes and drying prepares 4,6-diamino resorcin/terephthalic acid (TPA) or thiophene dioctyl phthalate complex salt.
2. preparation method according to claim 1 is characterized in that, in the step (2) 4, the mol ratio of 6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is (100～1): (1～100).
3. preparation method according to claim 2 is characterized in that, and is described 4, and the mol ratio of 6-diamino resorcin/terephthalic acid (TPA) complex salt and 4,6-diamino resorcin/thiophene dioctyl phthalate complex salt is (50～1): 1.
4. preparation method according to claim 1 is characterized in that, phosphorus pentoxide/polyphosphoric acids dicyandiamide solution is in phosphorus pentoxide in the end reaction liquid in the step (2), and its mass concentration is 80%～86%.
5. preparation method according to claim 4 is characterized in that, phosphorus pentoxide in the described end reaction liquid/polyphosphoric acids dicyandiamide solution is in phosphorus pentoxide, and its mass concentration is 82%～84%.
6. preparation method according to claim 1 is characterized in that, resin quality concentration is 5%～25% in described step (2) the end reaction liquid.
7. preparation method according to claim 6 is characterized in that, resin quality concentration is 8%～20% in the described end reaction liquid.
8. preparation method according to claim 1 is characterized in that, reaction temperature is 100～220 ℃ in the described step (2), and the reaction time is 10～48h.
9. preparation method according to claim 8 is characterized in that, described reaction temperature is 120～200 ℃, and the reaction time is 12～36h.
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| CN 201110217620 CN102418162B (en) | 2011-08-01 | 2011-08-01 | Preparation method of ultraviolet-light-resistant thiophene-structure-containing polybenzoxazole fibre |
| PCT/CN2011/081436 WO2013016901A1 (en) | 2011-08-01 | 2011-10-27 | Method for manufacturing uv-resistant polybenzoxazole fiber containing thiophene structure |
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| CN113322535B (en) * | 2020-02-28 | 2022-12-06 | 吉林师范大学 | Method for preparing poly (terephthalic acid-2- (hexyl-5-alkenyl) -succinic acid-1, 4-benzodioxazole) fiber |
| CN111778581B (en) * | 2020-06-17 | 2022-10-11 | 安徽三宝棉纺针织投资有限公司 | Far infrared heating and weather-resistant graphene nylon yarn and preparation process thereof |
| CN115787126B (en) * | 2022-12-02 | 2024-07-09 | 安徽威驰化工有限责任公司 | Method for preparing high-performance organic fibers based on pyridine hydrochloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US526667A (en) * | 1894-09-25 | Frederick b | ||
| CN101643545A (en) * | 2009-08-17 | 2010-02-10 | 大连化工研究设计院 | Polybenzobisoxazole polymer containing thiophenic sulfur and preparation method thereof |
| CN101724138A (en) * | 2009-11-20 | 2010-06-09 | 大连化工研究设计院 | Preparation method of poly-2,5-thiophene benzo bisoxazoline |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US526667A (en) * | 1894-09-25 | Frederick b | ||
| CN101643545A (en) * | 2009-08-17 | 2010-02-10 | 大连化工研究设计院 | Polybenzobisoxazole polymer containing thiophenic sulfur and preparation method thereof |
| CN101724138A (en) * | 2009-11-20 | 2010-06-09 | 大连化工研究设计院 | Preparation method of poly-2,5-thiophene benzo bisoxazoline |
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| Spectral Modulation and Exciton Migration in Thiophene-Based Polybenzobisoxazole Random Copolymers with Donor-Acceptor Architectures;Yan Chen et al;《Macromolecules》;20051020;第38卷;9873 * |
| Yan Chen et al.Spectral Modulation and Exciton Migration in Thiophene-Based Polybenzobisoxazole Random Copolymers with Donor-Acceptor Architectures.《Macromolecules》.2005,第38卷9873. |
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