CN105709612B - A kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling - Google Patents
A kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling Download PDFInfo
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- CN105709612B CN105709612B CN201510632605.7A CN201510632605A CN105709612B CN 105709612 B CN105709612 B CN 105709612B CN 201510632605 A CN201510632605 A CN 201510632605A CN 105709612 B CN105709612 B CN 105709612B
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000004760 aramid Substances 0.000 title claims abstract description 66
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 66
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000009987 spinning Methods 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- -1 trifluoromethyl diphenyl tetracarboxylic acids Chemical class 0.000 claims description 14
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000003205 fragrance Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- NLNRQJQXCQVDQJ-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 NLNRQJQXCQVDQJ-UHFFFAOYSA-N 0.000 claims description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- UIMPSNPKHVULAQ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetramine Chemical class NC1=C(N)C=CC2=C(N)C(N)=CC=C21 UIMPSNPKHVULAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- FJVIHKKXPLPDSV-UHFFFAOYSA-N 4-phenoxybenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=CC=C1 FJVIHKKXPLPDSV-UHFFFAOYSA-N 0.000 claims description 2
- 125000006840 diphenylmethane group Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000011701 zinc Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 208000035475 disorder Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003190 poly( p-benzamide) Polymers 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 1
- NHSBKQKXSFSCQL-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)N.NN Chemical compound C(C1=CC=CC=C1)(=O)N.NN NHSBKQKXSFSCQL-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001616 biphenylenes Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Artificial Filaments (AREA)
- Polyamides (AREA)
Abstract
A kind of preparation method of the poly- pyrrole throat aromatic polyamides composite membrane based on molecule assembling.The invention discloses a kind of methods preparing poly- pyrrole throat/aromatic polyamides composite membrane, and it includes following steps：(1) preparation of aromatic polyamides mixed solution, including aromatic polyamides, organic solvent, Zn1.5Ga1.5Y0.5O4.5Nano particle, lithium chloride；(2) preparation of spinning mixture：Aromatic polyamides mixed solution obtained by (1) is added in tetramine monomers and four acid monomers；(3) spinning mixture obtained by (2) is subjected to electrostatic spinning, presoma nano fibrous membrane is made；(4) presoma nano fibrous membrane obtained by (3) is heat-treated, poly- pyrrole throat/aromatic polyamides composite membrane is made.
Description
Technical field
The present invention relates to a kind of methods preparing macromolecule organic hybrid films.More particularly it relates to which one kind is based on
The preparation method of the molecule assembling macromolecule organic hybrid films of electrostatic spinning technique.
Background technology
The UF membrane novel separation technology energy-efficient as one has been completed since half a century from laboratory to extensive
The transformation of commercial Application.Membrane separation technique has efficient, energy saving, ring due to having separation, concentration, purifying and refined function concurrently
Protect, molecular level filtering and filter the features such as simple, easily controllable, therefore, be widely used to food, medicine, biology, environmental protection,
The fields such as chemical industry, metallurgy, the energy, oil, water process, electronics, bionical, produce huge economic benefit and social benefit,
As one of most important means in current separation science.The maximum problem that macromolecule organic film is encountered in application field be by
In fouling membrane and caused by separating property decline, therefore to the organic membrane modifying of macromolecule enhance its separating property and resistance tocrocking at
For the Main way of research.Concentration polarization is reduced, the antifouling property and antioxygenic property of film are improved, film properties is maintained to stablize simultaneously
It is one of main trend of development of membrane separation technique to extend membrane lifetime.
Poly- pyrrole throat has good heat-resisting quantity, inoxidizability as a kind of rigid poly- heteroaromatic macromolecule polyalcohol
And tensile strength, the decomposition temperature of the poly- pyrrole throat in part (BBB or BBL) are even more than 700 DEG C, can form high performance macromolecule
Organic film.But poly- pyrrole throat is difficult to melt, and is also insoluble in usual vehicle, machinability is greatly limited, while right
Its exploitation applied causes greatly to hinder.Equally, the insoluble characteristic that do not melt so that melting electrostatic spinning or solution cannot be used
Electrostatic spinning processes such polymer.It is to be dissolved in tetracarboxylic acid, chlorosulfonic acid etc. that tradition, which prepares poly- pyrrole throat crude fibre or film,
It processes and obtains in super strong proton acid.In addition, the carboxylic acid amine salt solution prepared by acid anhydrides and tetramine monomers polymerization easily coagulates again
Glue phenomenon, and it is not easy to maintain, it is also difficult to it is used for electrostatic spinning.
Aromatic polyamides refer at least 85% amido bond and the connected long chain synthetic polyamide of two aromatic rings.The macromolecule
Material has good heat resistance and greasy property, and since there are phenyl ring for its macromolecular main chain, being made into film can have preferably
Pressure tightness, and stable chemical performance has good repellence for weak acid, weak base and most of organic solvent.But it is fragrant
The light fastness of fragrant polyamide is poor, if being exposed to the sun in the sunlight, intensity is decreased obviously, so it is generally necessary to photostabilizer, which is added, to be prevented
This situation.Therefore it is highly desirable to a kind of method that can prepare poly- pyrrole throat/aromatic polyamides composite membrane, poly- pyrrole throat can either be solved
The problem of being difficult to electrostatic spinning, and the problem of aromatic polyamides light resistance difference can be improved, while the resistance tocrocking of composite membrane is improved,
Maintain separating property.
Invention content
In order to solve the above technical problems, the present invention provides a kind of poly- pyrrole throat/aromatic polyamides composite membrane of molecule assembling
Preparation method can prepare the poly- pyrrole throat/aromatic polyamides composite membrane haveing excellent performance using this method, and for preparing answers
Higher separating property can be maintained in water process separation field by closing film.
One aspect of the present invention provides a kind of preparation side of the poly- pyrrole throat/aromatic polyamides composite membrane assembled based on molecule
Method includes the following steps：
(1) aromatic polyamides are dissolved in organic solvent, Zn is added in stirring1.5Ga1.5Y0.5O4.5Powder of nanometric particles, so
Ultrasonic vibration is carried out after lithium chloride is added immediately afterwards, makes Zn1.5Ga1.5Y0.5O4.5Nano particle is scattered in solution, and fragrance is made
Polyamide mixed solution；
(2) tetracid and tetramine monomers are added in the aromatic polyamides mixed solution, spinning mixed solution is made；
(3) (2) described spinning mixed solution is subjected to electrostatic spinning, presoma nano fibrous membrane is made；
(4) it will be heat-treated after the vacuum drying of gained presoma nano fibrous membrane in (3), it is poly- that poly- pyrrole throat/fragrance be made
Amide composite membrane.
In one embodiment, the weight percent of each component is as follows in the aromatic polyamides mixed solution：Fragrance
5%~30wt.% of polyamide, organic solvent 60%~85wt.%, Zn1.5Ga1.5Y0.5O4.50.1%~5wt.% of nano particle,
3%~7wt.% of lithium chloride.
In one embodiment, the molecular weight of the aromatic polyamides is 20000~80000 dalton.
In one embodiment, the organic solvent is n,N-dimethylacetamide, dimethylformamide, O-phthalic
Any one in dimethyl phthalate, N-Methyl pyrrolidone, dimethyl sulfoxide, diphenyl sulphone (DPS).
In one embodiment, the Zn1.5Ga1.5Y0.5O4.5The grain size of nano particle is 30~60nm.
In one embodiment, the Zn1.5Ga1.5Y0.5O4.5Crystal belong to hexagonal crystal system, bottom surface is regular hexagon,
The length of side isHighly it isZn, Ga, Y, O form hexagonal prisms structure, and Zn is located at 12 vertex and top and bottom of hexagonal prisms
The heart, O be located at hexagonal prisms body-centered and endways six seamed edge midpoints, Ga and Y disorder distributions in the tetrahedron gap that O is formed,
The ratio of Ga and Y is 3: 1.
In one embodiment, in the spinning mixed solution total concentration of tetracid and tetramine be 30~35wt.%, four
The molar ratio of acid and tetramine is 0.5~2.
In one embodiment, four acid monomers are 3,3 ', 4,4 '-bibenzene tetracarboxylics, 3,3 ', 4,4 '-benzophenone
Tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl ether tetraformics, 3,3 ', 4,4 '-diphenyl methane tetracarboxylic acids, 3,3 ', 4,4 '-bis trifluoromethyls
Diphenyl tetracarboxylic acid, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics, 1,2,4,5- benzene tetracarboxylic acids, 3,3 ', 4,4 '-diphenyl thio-ether tetrformates, 3,3 ',
Any one or a few combination in 4,4 '-triphen diether tetracids.
In one embodiment, the tetramine monomers be 3,3 ', 4,4 '-biphenyl tetramines, 1,2,4,5- benzene tetramines, 2,3,
5,6, bis- (3 ', the 4 '-diamino phenoxy) benzene of-tetramine yl pyridines, 3,3 ', 4,4 '-tetramino diphenyl sulfides, Isosorbide-5-Nitrae-, 1,3- are bis-
Bis- (3 ', the 4 '-diamino phenoxy) benzene of (3 ', 4 '-diamino phenoxy) benzene, 1,2-, 4,4 '-bis- (2- diamino phenoxies) two
Benzene sulfone, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,5,6- tetramino naphthalenes, 3,3 ', 4,
Any one or a few combination in 4 '-tetramino diphenyl-methanes.
In one embodiment, described be heat-treated includes：Presoma nano fibrous membrane after the drying is placed in
50-80min is handled under 130-150 DEG C of any temperature condition；It then heats under 280-320 DEG C of any temperature condition and handles 50-
70min；Finally anneal under 470-550 DEG C of any temperature condition 10-20min；The heating rate of entire processing procedure is 2~4
℃/min。
Another aspect of the present invention is related to a kind of poly- pyrrole throat/aromatic polyamides composite film material, the composite film material by
The above method of the present invention is prepared.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily understood
Open content.A large amount of terms can be referred in following description and claims, these terms are defined as following meanings.
" optionally " or refer to " optionally " that the item described thereafter or event may or may not occur, and this is retouched
State the situation that the situation occurred including event and event do not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
" polymer " indicates the polymerizable compound prepared by monomer or the different types of monomer polymerization of same type.
General term " polymer " includes term " homopolymer ", " copolymer " etc..
" copolymer " indicates the polymer by preparing at least two distinct types of monomer polymerization, including term
" bipolymer ", " terpolymer " also includes the polymer for preparing four kinds or more monomer polymerizations；" binary copolymerization
Object " usually indicates the polymer prepared by two kinds of different monomers.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
One aspect of the present invention provides a kind of preparation side of the poly- pyrrole throat/aromatic polyamides composite membrane assembled based on molecule
Method includes the following steps：
(1) aromatic polyamides are dissolved in organic solvent, Zn is added in stirring1.5Ga1.5Y0.5O4.5Powder of nanometric particles, so
Ultrasonic vibration is carried out after lithium chloride is added immediately afterwards, makes Zn1.5Ga1.5Y0.5O4.5Nano particle is scattered in solution, and fragrance is made
Polyamide mixed solution；
(2) tetracid and tetramine monomers are added in the aromatic polyamides mixed solution, spinning mixed solution is made；
(3) (2) described spinning mixed solution is subjected to electrostatic spinning, presoma nano fibrous membrane is made；
(4) it will be heat-treated after the vacuum drying of gained presoma nano fibrous membrane in (3), it is poly- that poly- pyrrole throat/fragrance be made
Amide composite membrane.
Terminology used in the present invention " poly- pyrrole throat " is polymerized polymer by tetramine and tetracid, is by aromatic ring or naphthalene nucleus etc.
Trapezoidal (BBL) or half ladder polymer (BBB) made of being connected with imidazoles and pyrrole ring.
Terminology used in the present invention " aromatic polyamides " refers at least 85% amido bond and the connected long-chain of two aromatic rings
Synthesizing polyamides polymer.
In above-mentioned preparation method, tetramine and tetracid form ammonium carboxylate salts and are difficult to be received to prepare with the method for electrostatic spinning
Rice fiber, the addition of aromatic polyamides copolymer can play the effect of tackifier, mixed solution enabled to be easy to Static Spinning
Silk.Zn1.5Ga1.5Y0.5O4.5The addition of nano particle not only remains the original excellent characteristic of composite membrane, also improves well
The surface energy of composite membrane enhances the hydrophily of film, improves the resistance tocrocking of film.Zn simultaneously1.5Ga1.5Y0.5O4.5Nano particle belongs to
N-type semiconductor, the electronics in valence band can receive the energy in ultraviolet light and transition occur, and shielding absorbs ultraviolet light, solves fragrance
The problem of polyamide light resistance difference.Pore former is played the role of in the addition of lithium chloride.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the weight percent of each component is as follows in the aromatic polyamides mixed solution：Aromatic polyamides 5%~
30wt.%, organic solvent 60%~85wt.%, Zn1.5Ga1.5Y0.5O4.50.1%~5wt.% of nano particle, lithium chloride 3%~
7wt.%.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the aromatic polyamides are poly(p-benzamide), poly(p-phenylene terephthalamide), poly- heteroaromatic are poly-
Amide SVM, poly, poly- (2- chlorine is to phenylene-terephthalamide), poly- (4,4 '-amide biphenylenes
Terephthalamide), poly- (3,4 '-diaminodiphenyl ethers support poly P phenylene diamine terephthalamide), poly- (4,4 '-diaminodiphenyl ethers
Support terephthalamide), it is poly- to one kind in benzamide hydrazine.Preferably poly- heteroaromatic polyamide SVM, structure are as follows：
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the molecular weight of the aromatic polyamides is 20000~80000 dalton.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the organic solvent be n,N-dimethylacetamide, dimethylformamide, repefral,
Any one in N-Methyl pyrrolidone, dimethyl sulfoxide, diphenyl sulphone (DPS).
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the Zn1.5Ga1.5Y0.5O4.5The synthesis step of nano particle is as follows：
(1) it feeds intake by certain Zn/Ga/Y molar ratios, by ZnSO4·7H2O：Ga2(SO4)3·16H2O：Y2(SO4)3·8H2O
Molar ratio be 5~7: 2~4: 0.5~2 mixed solution and pH value be 8 NaOH and Na2CO3Mixed solution, at normal temperatures
It is rapidly added in full back-mixing liquid film reactor and is sufficiently mixed simultaneously, reaction nucleation, then flow back slurries crystallization 30 at 100 DEG C
~180min is filtered, and washing obtains filter cake.
(2) by filter cake, the deionized water of 80 parts by weight, 0.02 parts by weight zircoaluminate obtained by above-mentioned (1) of 20 parts by weight
Coupling agent is added in reaction kettle, and it is 80~90 DEG C to be heated to temperature, is stirred to react 20~40min, by reaction mixture filtering, 60
~70 DEG C of dryings 20~for 24 hours, obtain modified product.
(3) (2) described modified product is placed in Muffle furnace, 400~600 is risen to the heating rate of 4~5 DEG C/min
DEG C, 3~4h is calcined, Zn is obtained1.5Ga1.5Y0.5O4.5Nano particle.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the Zn1.5Ga1.5Y0.5O4.5The grain size of nano particle is 30~60nm.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the Zn1.5Ga1.5Y0.5O4.5Crystal belong to hexagonal crystal system, bottom surface is regular hexagon, and the length of side isHighly it isZn, Ga, Y, O form hexagonal prisms structure, and Zn is located at 12 vertex of hexagonal prisms and the upper and lower center of area, O are located at
The body-centered of hexagonal prisms and endways six seamed edge midpoints, Ga and Y disorder distributions are in the tetrahedron gap that O is formed, the ratio of Ga and Y
Example is 3: 1.
Wherein, above-mentioned Zn1.5Ga1.5Y0.5O4.5Sample structure with RigakuD/max-3B type x-ray powder diffraction instruments survey
Fixed, X-ray wavelength X isCan also be that other instruments well known by persons skilled in the art measure.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the ultrasonic vibration time is 20~30min.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, four acid monomers be 3,3 ', 4,4 '-bibenzene tetracarboxylics, 3,3 ', 4,4 '-benzophenone tetracarboxylics, 3,
3 ', 4,4 '-diphenyl ether tetraformics, 3,3 ', 4,4 '-diphenyl methane tetracarboxylic acids, 3,3 ', 4,4 '-bis trifluoromethyl diphenyl four
Formic acid, Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics, 1,2,4,5- benzene tetracarboxylic acids, 3,3 ', 4,4 '-diphenyl thio-ether tetrformates, 3,3 ', 4,4 '-three
Any one or a few combination in benzene diether tetracid, preferably 3,3 ', 4,4 '-bis trifluoromethyl diphenyl tetracarboxylic acids, knot
Structure formula is as follows：
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the tetramine monomers are 3,3 ', 4,4 '-biphenyl tetramines, 1,2,4,5- benzene tetramines, 2,3,5,6 ,-tetramine
Yl pyridines, 3, bis- (3 ', the 4 '-diamino phenoxy) benzene of 3 ', 4,4 '-tetramino diphenyl sulfides, Isosorbide-5-Nitrae-, 1,3- bis- (3 ', 4 '-two
Amino-benzene oxygen) benzene, bis- (3 ', the 4 '-diamino phenoxy) benzene of 1,2-, 4,4 '-bis- (2- diamino phenoxies) diphenyl sulphone (DPS)s, 3,
3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,5,6- tetramino naphthalenes, 3,3 ', 4,4 '-four ammonia
Any one or a few combination in base diphenyl-methane.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, temperature is preferably less than 25 DEG C when mixing tetramine and four acid monomers.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the total concentration of tetracid and tetramine is 30~35wt.%, mole of tetracid and tetramine in the spinning solution
Than being 0.5~2, preferably 1.And tetramine monomers are first dissolved in the organic solvent, then gradually add into reaction mixture
Enter four acid monomers.Needing to be vigorously stirred in reaction process keeps reaction mixture uniform.Preferred agitating mode include magnetic agitation,
Mechanical agitation, and then preferred magnetic agitation.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the viscosity of the spinning solution is between 3000~100000mPas.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, during the spinning mixture forms nanofiber presoma by electrostatic spinning, the electrostatic
Spin processes belong to one kind of solution-polymerized SBR.Positive high voltage is typically given to polymer solution, to ground wire or electronegative
During surface is sprayed, make polymer solution that the gimmick of fibrosis occur.Configuration, which sprays, in electrostatic spinning apparatus becomes fibre
The spinning-nozzle of the polymer of the raw material of dimension and the opposite electrode opposed with spinning-nozzle.The opposite electrode is grounded, and is applied high
Voltage makes the polymer solution of electrification fly out from spinning-nozzle to opposite electrode.It in the present invention, can be to being formed between electrode
The spinning mixture is sprayed in electrostatic field to collect using the roller of slow rotation for solution to opposite electrode wire drawing
To nano fibrous membrane.
As spinning-nozzle, preferably internal diameter is 0.1~3mm or so, more preferably 0.1-1mm or so.As nozzle material,
It can be made of metal, or nonmetallic system.Nozzle can then use nozzle as side's electrode if it is made of metal,
Nozzle be it is non-it is metal in the case of, can by the inside of nozzle be arranged electrode, make electric field to the lysate of extrusion act on.
If it is considered that production efficiency, can also use several nozzles.In addition, as nozzle form, usually using the shape of circular cross-section
Shape, but it is different according to type of polymer or usage, the nozzle form of profiled-cross-section can also be used.Preferably, nozzle
Select stainless steel.
Substrate is collected as opposite electrode, the electrode or tabular, band-like made of metal of roll can be used according to purposes
The variously-shaped electrode such as electrode.
To the voltage of application, there is no particular limitation, and adjustable extent is usually 5~40kV, preferably 10~30kV.In addition,
Apply alive polarity can be it is positive or negative in any one.
The distance of spinning-nozzle to opposite electrode depends on carried charge, jet size, spinning solution flow, concentration of dope
Deng, and when spinning voltage is 10~30kV, appropriately distance is 10~40cm.
As the atmosphere with Electrospun is carried out, usually carry out in air, and by the initial discharges such as carbon dioxide electricity
Pressure carries out spinning higher than band Electrospun is carried out in the gas of air, with low-voltage and is possibly realized, and is also prevented from corona discharge etc.
Paradoxical discharge.In addition, in the case where water is the poor solvent of polymer, polymer is precipitated near spinning-nozzle sometimes.Cause
This is carried out to reduce the moisture in air preferably in the air for having passed through drying unit.In order to avoid in spinning mixture
Tetramine monomers are preferably carried out in dry oxygen free air by dioxygen oxidation in air.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, contain tetramine monomers in blend spinning liquid, to avoid tetramine monomers by dioxygen oxidation in air, preferably spins
0~30 DEG C of temperature setting range during silk.
In one embodiment, a kind of poly- pyrrole throat/aromatic polyamides based on molecule assembling of the present invention are compound
In the preparation method of film, the heat treatment includes：By the presoma nano fibrous membrane after the drying be placed in 130-150 DEG C it is any
50-80min is handled under temperature condition；It then heats under 280-320 DEG C of any temperature condition and handles 50-70min；Finally exist
Anneal 10-20min under 470-550 DEG C of any temperature condition；The heating rate of entire processing procedure is 2~4 DEG C/min.As excellent
Choosing, atmospheric condition are the condition of nitrogen gas of high-purity.The Fractional Heat-treatment can be selected in convection furnace, tube type high-temperature furnace, infrared
It is heated in heating furnace.
During above-mentioned Fractional Heat-treatment, the drying steps can be removed slowly the presoma nano fibrous membrane
It is present in residual solvent in spinning mixture, and prevents because steaming or higher than removing solvent under later stage thermal cyclization high temperature suddenly
Gas and the solvent vapour of high concentration and the possibility for causing deflagration.The heating rate of the Fractional Heat-treatment is preferably 2-4 DEG C/min.
It should be noted that the heating rate of the different temperatures stage preferred above range in Fractional Heat-treatment, but be not limited to select
Identical heating rate.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, and number used in following material is weight
Part.
Raw material：
A1：Poly(p-benzamide)
A2：Poly(p-phenylene terephthalamide)
A3：Poly- heteroaromatic polyamide SVM
B1：N,N-dimethylacetamide
C1：Zn1.5Ga1.5Y0.5O4.5Nano particle (grain size 30nm)
C2：Zn1.5Ga1.5Y0.5O4.5Nano particle (grain size 50nm)
C3：Zn1.5Ga1.5Y0.5O4.5Nano particle (grain size 60nm)
D1：Lithium chloride
E1：Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics
E2：3,3 ', 4,4 '-benzophenone tetracarboxylics
E3：3,3 ', 4,4 '-bis trifluoromethyl diphenyl tetracarboxylic acids
F1：3,3 ', 4,4 '-biphenyl tetramines
F2：1,2,4,5- benzene tetramine
Embodiment 1
1) A1 is dissolved in B1, C1 is added under stirring condition, then ultrasonic vibration is carried out after D1 is added immediately, it is poly- that fragrance is made
The weight percent of amide mixed solution, A1 is 30wt.%, and the weight percent of B1 is 65wt.%, and the weight percent of C1 is
The weight percent of 2wt.%, D1 are 3%.
2) under conditions of less than 25 DEG C, two kinds of monomers of E1 and F1 that molar ratio is 1 are dissolved in above-mentioned solution 1) in, E1
The 30wt.% of spinning mixture quality is accounted for the gross mass of F1, stirring 4h makes it be uniformly mixed.
3) solution obtained above is subjected to electrostatic spinning, spinning voltage control is 10-30KV, and needle point arrives reception device
Distance is 25cm.It collects to obtain nano combined film precursor using the roller of slow rotation.Obtained compound film precursor is existed
Dry 6h in 60 DEG C of vacuum.
4) the nano combined film precursor after drying is placed in 150 DEG C of processing 60min；Then heat to 280 DEG C of constant temperature
60min；Finally anneal under the conditions of 500 DEG C 10min；The heating rate of entire processing procedure is 3 DEG C/min, and in high pure nitrogen
Protection under carry out.
Embodiment 2
As different from Example 1, the aromatic polyamides are A2 to the present embodiment.
Embodiment 3
As different from Example 1, the aromatic polyamides are A3 to the present embodiment.
Embodiment 4
1) A3 is dissolved in B1, C2 is added under stirring condition, then ultrasonic vibration is carried out after D1 is added immediately, it is poly- that fragrance is made
The weight percent of amide mixed solution, A3 is 25wt.%, and the weight percent of B1 is 65wt.%, and the weight percent of C1 is
The weight percent of 5wt.%, D1 are 5%.
2) under conditions of less than 25 DEG C, two kinds of monomers of E1 and F1 that molar ratio is 1 are dissolved in above-mentioned solution 1) in, E1
The 32wt.% of spinning mixture quality is accounted for the gross mass of F1, stirring 4h makes it be uniformly mixed.
3) solution obtained above is subjected to electrostatic spinning, spinning condition is the same as embodiment 1
4) the nano combined film precursor after drying is placed in 140 DEG C of processing 70min；Then heat to 300 DEG C of constant temperature
50min；Finally anneal under the conditions of 520 DEG C 10min；The heating rate of entire processing procedure is 3 DEG C/min, and in high pure nitrogen
Protection under carry out.
Embodiment 5
The present embodiment as different from Example 4, the Zn1.5Ga1.5Y0.5O4.5Nano particle is C3.
Embodiment 6
1) A3 is dissolved in B1, C1 is added under stirring condition, then ultrasonic vibration is carried out after D1 is added immediately, it is poly- that fragrance is made
The weight percent of amide mixed solution, A3 is 20wt.%, and the weight percent of B1 is 71wt.%, and the weight percent of C1 is
The weight percent of 3wt.%, D1 are 6%.
2) under conditions of less than 25 DEG C, two kinds of monomers of E2 and F1 that molar ratio is 1 are dissolved in above-mentioned solution 1) in, E2
The 35wt.% of spinning mixture quality is accounted for the gross mass of F1, stirring 4h makes it be uniformly mixed.
3) solution obtained above is subjected to electrostatic spinning, spinning condition is the same as embodiment 1
4) the nano combined film precursor after drying is placed in 130 DEG C of processing 80min；Then heat to 320 DEG C of constant temperature
50min；Finally anneal under the conditions of 480 DEG C 20min；The heating rate of entire processing procedure is 3 DEG C/min, and in high pure nitrogen
Protection under carry out.
Embodiment 7
As different from Example 6, the tetramine monomers are F2 to the present embodiment.
Embodiment 8
As different from Example 6, four acid monomers are E3 to the present embodiment.
Comparative example 1
1) under conditions of less than 25 DEG C, E1 the and F1 monomers that molar ratio is 1: 1 is dissolved in B1 and obtain ammonium carboxylate salt
The gross mass of solution, E1 and F1 account for the 30wt% of spinning mixture quality, magnetic agitation 4h.
2) above-mentioned ammonium carboxylate salts are subjected to electrostatic spinning, spinning condition and heat treatment condition such as embodiment 1.
Comparative example 2
1) A1 is dissolved in B1, the weight percent of A1 is 30wt.%, and the weight percent of B1 is 70wt.%.
2) under conditions of less than 25 DEG C, two kinds of monomers of E1 and F1 that molar ratio is 1 are dissolved in above-mentioned solution 1) in, E1
The 30wt.% of spinning mixture quality is accounted for the gross mass of F1, stirring 4h makes it be uniformly mixed.
3) solution obtained above is subjected to electrostatic spinning, spinning condition is the same as embodiment 1.
4) the nano combined film precursor after drying is heat-treated, heat treatment condition is the same as embodiment 1.
Test method：
The material that the poly- pyrrole throat/aromatic polyamides composite membrane and comparative example 1,2 obtained to above-described embodiment 1~8 obtains into
Row test, test method are as follows：
(1) heat decomposition temperature measures：
Using WRT-3P types thermal gravimetric analyzer (the permanent Science and Technology Ltd. in Beijing), heating rate is 15 DEG C/min, is surveyed
Gas testing atmosphere is air.
(2) stretch modulus measures：
Stretch modulus is measured according to JISK6251.
(3) strength detection：
It is measured with Q03new type Miniature tensions instrument (upper marine morning Digital Equipment Co., Ltd).
(4) elongation at break：
Mechanical performance uses ShimadzuAG-I type universal testing machines, and elongation at break is by the attached computer software of instrument
It is calculated.
(5) hydrophilicity is evaluated：
Using JC2000C, intravenous infusion contact angle measurement measures.
(6) light fastness can be evaluated：
Using the U.S. Atlas150S+ xenon orphan lamp (1500W+) simulated solar irradiation, air-cooled (Air) fluorescent tube energy, temperature 40
DEG C, humidity 40%.The solarization time is set as 4,6,10,40,100,160h.
Test result is shown in Table 1, table 2
Table 1
2 light fastness testing result of table (the fracture strength loss late of material under different light application times)
Data above can be seen that the ammonium carboxylate salts for being only mixed with tetracid and tetramine monomers nothing during electrostatic spinning
Method forms the poly- pyrrole throat material of regular appearance.A kind of method preparing poly- pyrrole throat/aromatic polyamides composite membrane provided by the invention,
The problem of poly- pyrrole throat is difficult to electrostatic spinning is not only solved, and the problem of aromatic polyamides light resistance difference can be improved, is improved simultaneously
The hydrophily of composite membrane maintains separating property.Poly- pyrrole throat/aromatic polyamides composite membrane prepared by the present invention is with preferable point
Simultaneously from performance, high intensity, stretch modulus, thermal stability and light resistance are also had both, the Advantageous of the present invention is thus provided
Effect.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express inaccuracy due to and not
The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended
Claim covers.
Claims (10)
1. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling, includes the following steps：
(1) aromatic polyamides are dissolved in organic solvent, Zn is added in stirring1.5Ga1.5Y0.5O4.5Then powder of nanometric particles is stood
Ultrasonic vibration is carried out after lithium chloride is added, makes Zn1.5Ga1.5Y0.5O4.5Nano particle is scattered in solution, and fragrance polyamides is made
Amine mixed solution；
(2) tetracid and tetramine monomers are added in the aromatic polyamides mixed solution, spinning mixed solution is made；
(3) (2) described spinning mixed solution is subjected to electrostatic spinning, presoma nano fibrous membrane is made；
(4) it will be heat-treated after the vacuum drying of gained presoma nano fibrous membrane in (3), poly- pyrrole throat/aromatic polyamides be made
Composite membrane.
2. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The weight percent of each component is as follows in the wherein described aromatic polyamides mixed solution：5%~30wt.% of aromatic polyamides, has
Solvent 60%~85wt.%, Zn1.5Ga1.5Y0.5O4.50.1%~5wt.% of nano particle, 3%~7wt.% of lithium chloride.
3. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The molecular weight of the wherein described aromatic polyamides is 20000~80000 dalton.
4. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The wherein described organic solvent is n,N-dimethylacetamide, dimethylformamide, repefral, N- crassitudes
Any one in ketone, dimethyl sulfoxide, diphenyl sulphone (DPS).
5. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The wherein described Zn1.5Ga1.5Y0.5O4.5The grain size of nano particle is 30~60nm.
6. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The wherein described Zn1.5Ga1.5Y0.5O4.5Crystal belong to hexagonal crystal system, bottom surface is regular hexagon, and the length of side isHighly it isZn, Ga, Y, O form hexagonal prisms structure, and Zn is located at 12 vertex of hexagonal prisms and the upper and lower center of area, and O is located at hexagonal prisms
Body-centered and endways six seamed edge midpoints, for Ga and Y disorder distributions in the tetrahedron gap that O is formed, the ratio of Ga and Y are 3: 1.
7. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The total concentration of tetracid and tetramine is 30~35wt.% in the wherein described spinning mixed solution, and the molar ratio of tetracid and tetramine is 0.5
~2.
8. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
The wherein described tetracid monomer is 3,3 ', 4,4 '-bibenzene tetracarboxylics, 3,3 ', 4,4 '-benzophenone tetracarboxylics, 3,3 ', 4,4 '-hexichol
Ether tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl methane tetracarboxylic acids, 3,3 ', 4,4 '-bis trifluoromethyl diphenyl tetracarboxylic acids, Isosorbide-5-Nitrae, 5,8-
Naphthalenetetracarbacidic acidic, 1,2,4,5- benzene tetracarboxylic acids, 3, in 3 ', 4,4 '-diphenyl thio-ether tetrformates, 3,3 ', 4,4 '-triphen diether tetracids
Any one or a few combination；The wherein described tetramine monomers be 3,3 ', 4,4 '-biphenyl tetramines, 1,2,4,5- benzene tetramines, 2,3,5,
6, bis- (3 ', the 4 '-diamino phenoxy) benzene of-tetramine yl pyridines, 3,3 ', 4,4 '-tetramino diphenyl sulfides, Isosorbide-5-Nitrae-, 1,3- are bis-
Bis- (3 ', the 4 '-diamino phenoxy) benzene of (3 ', 4 '-diamino phenoxy) benzene, 1,2-, 4,4 '-bis- (2- diamino phenoxies) two
Benzene sulfone, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,5,6- tetramino naphthalenes, 3,3 ', 4,
Any one or a few combination in 4 '-tetramino diphenyl-methanes.
9. a kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling according to claim 1,
Wherein described be heat-treated includes：Presoma nano fibrous membrane after the drying is placed under 130-150 DEG C of any temperature condition
Handle 50-80min；It then heats under 280-320 DEG C of any temperature condition and handles 50-70min；Finally appoint at 470-550 DEG C
Anneal 10-20min under one temperature condition；The heating rate of entire processing procedure is 2~4 DEG C/min.
10. a kind of poly- pyrrole throat/aromatic polyamides composite film material, according to the preparation of claim 1~9 any one of them method
At.
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