CN106480530A - The preparation method of electrospinning high-performance poly benzene derivative nanofiber - Google Patents
The preparation method of electrospinning high-performance poly benzene derivative nanofiber Download PDFInfo
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- CN106480530A CN106480530A CN201610846595.1A CN201610846595A CN106480530A CN 106480530 A CN106480530 A CN 106480530A CN 201610846595 A CN201610846595 A CN 201610846595A CN 106480530 A CN106480530 A CN 106480530A
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- nanofiber
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- benzene derivative
- performance poly
- methyl
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001523 electrospinning Methods 0.000 title claims abstract description 22
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title description 4
- 239000000243 solution Substances 0.000 claims abstract description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000001555 benzenes Chemical class 0.000 claims abstract description 42
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- -1 polyphenylene Polymers 0.000 claims abstract description 16
- 229920000265 Polyparaphenylene Polymers 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 230000000903 blocking effect Effects 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- NCNWTBAWLAFYDR-UHFFFAOYSA-N 1,6-dimethylpiperidin-2-one Chemical class CC1CCCC(=O)N1C NCNWTBAWLAFYDR-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- IVVVGBHWWAJRAY-UHFFFAOYSA-N 1-ethyl-3-methylpyrrolidin-2-one Chemical compound CCN1CCC(C)C1=O IVVVGBHWWAJRAY-UHFFFAOYSA-N 0.000 claims description 2
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical class CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 claims description 2
- GVDQKJQFVPXADH-UHFFFAOYSA-N 1-propan-2-ylpiperidin-2-one Chemical class CC(C)N1CCCCC1=O GVDQKJQFVPXADH-UHFFFAOYSA-N 0.000 claims description 2
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229960001930 valpromide Drugs 0.000 claims description 2
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical class CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 claims 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- 229920006389 polyphenyl polymer Polymers 0.000 description 11
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 10
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical class C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000004900 laundering Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 210000003739 neck Anatomy 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009941 weaving Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- LJYJFKXQKHSSEB-UHFFFAOYSA-N naphthalene-1,4,5,8-tetramine Chemical compound C1=CC(N)=C2C(N)=CC=C(N)C2=C1N LJYJFKXQKHSSEB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
-
- 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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
Abstract
The invention discloses a kind of preparation method of electrospinning high-performance poly benzene derivative nanofiber, comprises the following steps：(1) the substituted benzene oligomer for blocking adjacent dicarboxyl benzene and tetramines aromatic monomer are dissolved in solvent, and precursor solution is obtained；(2) in above-mentioned precursor solution, an agent is added into, spinning mixed solution is formed, blending nanofiber presoma is formed by method of electrostatic spinning；(3) after being dried above-mentioned blending nanofiber presoma, it is heat-treated, is obtained polyphenylene derivatives nanofiber.It is low that the method overcomes the polyphenylene derivatives molecular weight that general synthetic method obtains, it is difficult to is prepared into the shortcoming of high-performance poly benzene derivative nanofiber.Polyphenylene derivatives nanofiber is obtained by this method there is the good mechanical performances such as high tenacity, high intensity, high-modulus, moderate elongation.
Description
Technical field
The present invention relates to a kind of preparation method of polyphenylene derivatives nanofiber, more particularly it relates to Electrospinning Method
The method for preparing polyphenylene derivatives nanofiber.
Background technology
Polyphenyl is the rigid chain polymer that a class is connected by phenyl, and with excellent heat-resisting quantity, the heat in nitrogen is divided
Up to 900 DEG C of solution temperature, can at 400 DEG C Long-Time Service；With characteristics such as excellent resistance to chemical attack, rub resistance, radiation hardness；
While having good electrical property and the self-lubricating property better than graphite.Polyphenyl can be used as high temperature resistant, radiation resistant paint or gluing
Agent, high-temperature wearable parts, ablation resistant material etc., can be used for chemical industry equipment under mal-condition, aerospace equipment, high-speed cruising military
On device, it may also be used for High temperature ion exchanger resin.
But, polyphenyl is not molten insoluble polymer, difficult shaping, difficult processing.Using introducing substituent on main chain phenyl ring
Method, its dissolubility can be improved.But on main chain phenyl ring, huge benzoyl is even introduced, this polyphenylene derivatives exist
Solubility in organic solvent is remained on less, and as solubility property is poor, the molecular weight of general synthesized polyphenylene derivatives is all
Low, it is difficult to be prepared into electro spinning nano fiber.
As module units, tetramines aromatic is hinge agent to the substituted benzene oligomer that the present invention is blocked with adjacent dicarboxyl benzene, passes through
Method of electrostatic spinning obtains polyphenylene derivatives nanofiber.
Content of the invention
In order to solve the above problems, the invention provides a kind of preparation side of electrospinning high-performance poly benzene derivative nanofiber
Method, comprises the following steps：
(1) the substituted benzene oligomer for blocking adjacent dicarboxyl benzene and tetramines aromatic monomer are dissolved in solvent, and forerunner is obtained
Liquid solution；
(2) in the precursor solution described in step (1), an agent is added into, spinning mixed solution is formed, by Static Spinning
Silk method forms blending nanofiber presoma；
(3), after being dried the blending nanofiber presoma described in step (2), it is heat-treated, obtains polyphenyl and spread out
Biological nano fiber.
In one embodiment, the general structure of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking：
Wherein R1Selected from following structure：
CH3O-、In any one.
In one embodiment, the general structure of tetramines aromatic is：
Wherein R2Selected from following structure：
In any one or a few combination.
In one embodiment, an agent is become to be selected from：One or two in PVP or PMMA.
In one embodiment, solvent is selected from：DMF, N, N- DEF, N, N- diformazan
Yl acetamide, N, N- diethyl acetamide, N, N- Valpromide, N, N- dimethyl benzamide, N- methyl -2- pyrrolidines
Ketone, N- ethyl-2-pyrrolidone, N- isopropyl -2-Pyrrolidone, N- isobutyl group -2-Pyrrolidone, N- n-propyl -2- pyrroles
Alkanone, N- normal-butyl -2-Pyrrolidone, CHP, N- methyl -3- N-methyl-2-2-pyrrolidone N, N- ethyl -
3- methyl-pyrrolidon, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyl -2- piperidines
Ketone, N- isopropyl -2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidine ketone, dimethyl sulfoxide (DMSO), two
Any one or a few combination in ethyl-sulfoxide, sulfolane, diphenyl sulphone (DPS).
In one embodiment, heat treatment includes：Under conditions of inert gas is present, 300 DEG C～500 are heated to
℃.
In one embodiment, heat treatment includes：Under conditions of inert gas is present, 350 DEG C～450 are heated to
℃.
In one embodiment, under conditions of inert gas presence, 420 DEG C are heated to.
In one embodiment, inert gas is arbitrary a kind of in nitrogen or argon gas.
Further object is that providing the polyphenylene derivatives nanofiber that methods described is prepared.
Compared with prior art, beneficial effects of the present invention are:
The present invention is adopted with the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking as main module units, and tetramines aromatic is hinge
Agent, obtains polyphenylene derivatives nanofiber by method of electrostatic spinning.The method overcomes the polyphenyl that general synthetic method obtains and spreads out
Biotinylated molecular weight is low, it is difficult to be prepared into the shortcoming of high-performance poly benzene derivative nanofiber.Polyphenyl is obtained by this method to spread out
Biological nano fiber has the good mechanical performances such as high tenacity, high intensity, high-modulus, moderate elongation.
The above-mentioned of the application and other features, aspect and advantage are more readily understood with reference to described further below.
Specific embodiment
Unless otherwise defined, all technology used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " synonymous with "comprising".Term "comprising" used herein, " including ",
" with ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily solely those key elements, but can include other not expressly listed key element or
The intrinsic key element of this kind of composition, step, method, product or device.
Conjunction " Consists of " excludes any key element that does not point out, step or component.If be used in claim, this
It is closed that phrase will make claim so as to not comprising the material in addition to the material that those describe, but relative normal
Except rule impurity.When phrase " Consists of " is occurred in and is rather than immediately following after theme in the clause of claim main body,
Which is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When number range is herein described, unless otherwise indicated, otherwise the scope be intended to include its end value and
All integers within the range and fraction.
Additionally, key element of the present invention or the indefinite article " one kind " before component and " one " are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also includes plural form, unless the quantity substantially refers to singulative.
The invention provides a kind of preparation method of electrospinning high-performance poly benzene derivative nanofiber, comprises the following steps：
(1) the substituted benzene oligomer for blocking adjacent dicarboxyl benzene and tetramines aromatic monomer are dissolved in solvent, and forerunner is obtained
Liquid solution；
(2) in the precursor solution described in step (1), an agent is added into, spinning mixed solution is formed, by Static Spinning
Silk method forms blending nanofiber presoma；
(3), after being dried the blending nanofiber presoma described in step (2), it is heat-treated, obtains polyphenyl and spread out
Biological nano fiber.
The substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking：
The substituted benzene oligomer structure formula of heretofore described adjacent dicarboxyl benzene end-blocking：
Wherein R1Any one in following structure：
CH3O-；R1It is preferred that
Group.
Work as R1ForDuring group, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is：
A. coupling reaction is blocked
25.11g (0.1mol) 2,5- dichloro is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Benzophenone reaction monomers, 2.7308g (0.01mol) 4- bromo rutgers add 3.317g afterwards as end-capping reagent
(0.011mol) nickel chloride bipyridyl makees catalyst, and 21.45g (0.33mol) zinc powder makees reducing agent, 11.54g (0.044mol) three
Phenylphosphine makees complexing agent, and 250ml eliminating water dimethylacetylamide (DMAc) makees reaction dissolvent, and 80 DEG C of reactions 20 of controlling reaction temperature are little
When after poured in 500ml absolute methanol while hot and carry out exchange of solvent, after 6 hours, suction filtration, then wash away zinc powder with watery hydrochloric acid, finally
Only the triphenylphosphine remained in being reacted with massive laundering, the drying 12 hours of 80 DEG C of vacuum obtain 22.6g rutgers envelope
That held is poly- to benzene analog derivative, yield 90%.
Blocking coupling reaction synthetic route is：
B. end group hydrolysis
In the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, add first step reaction that product is obtained
22.6g, adds 16g (0.4mol) NaOH, 120ml tetrahydrofuran, 80ml distilled water, back flow reaction 8 hours, cooling, use
It is 3 that the dilute sulfuric acid of concentration 30% adjusts pH value, and heating is boiled to there is powder sample to separate out, with massive laundering to neutrality, after suction filtration
80 DEG C be vacuum dried 12 hours, obtain 20.34g withThe polyphenyl class blocked for the phthalic acid of substituent is spread out
Biology, yield 90%.Its molecular weight ranges 760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route is：
Tetramines aromatic：
In step (1) in the preparation of precursor solution, " the tetramines aromatic monomer " refers to that four are contained in the fragrant same clan
The compound of amino.
Exemplary tetramines aromatic monomer includes, but are not limited to：
3,3', 5,5'- biphenyl tetramine, 3,3', the equal benzene tetramine of 4,4'- biphenyl tetramine, 1,2,3,5-, 2,3,5,6- pyridine four
Amine, 4- methyl -2,3,5,6- pyridine tetramine, 3,3', 5,5'- benzophenone tetramine, 3,3', 4,4'- benzophenone tetramine, 2,3,3',
4'- diphenyl ether tetramine, 3,3', 5,5'- diphenyl ether tetramine, 3,3', 4,4'- diphenyl ether tetramine, 3,3', 4,4'- diphenyl sulphone (DPS) tetramine,
3,3', 5,5'- diphenyl sulphone (DPS) tetramine, 3,3', 5,5'- diphenyl methane tetramine, 3,3', 4,4'- diphenyl methane tetramine, 2,2',
3,3'- diphenyl methane tetramine, 2,2', 3,4- diphenyl methane tetramine, 3,3', 4,4'- bis trifluoromethyl hexichol urotropine, 3,
3', 5,5'- bis trifluoromethyl hexichol urotropine, 2,2', 3,3'- bis trifluoromethyl hexichol urotropine, 2,2', the double trifluoros of 4,4'-
Methyldiphenyl urotropine, 2,3,3', 4'- bis trifluoromethyl hexichol urotropine, 1,4,5,8- naphthalene tetramine, 2,4,5,7- naphthalene tetramine,
The combination of any one or more in 2,3,6,7- naphthalene tetramine.
Electrostatic spinning：
Electrostatic spinning described in step (2) is a kind of special fiber fabrication process, and polymer solution or melt are strong
Jet spinning is carried out in electric field.Under electric field action, the drop at syringe needle can be changed into conical (i.e. " taylor cone ") from spherical, and
Extend from conical tip and obtain fiber filaments.This mode can produce the polymer filaments of nanometer grade diameter.
The condition adopted by the electrostatic spinning is：Spinning temperature is less than 30 DEG C；Preferably, spinning temperature is 5～30 DEG C；
It is highly preferred that spinning temperature is 10～25 DEG C.
Spinning voltage is 10～40KV；Preferably, spinning voltage is 10～30KV；It is highly preferred that spinning voltage be 20～
30KV；It is 10～40cm that spinning receives distance i.e. solidification distance；Preferably, it is 15～35cm that spinning receives distance；It is highly preferred that
It is 16cm that spinning receives distance.
The scope of the nanofiber diameter of electrostatic spinning：50～500nm；Preferably, the scope of nanofiber diameter：100
～400nm；It is highly preferred that nanofiber diameter is 200～300nm.
Drying means described in step (3) refers to 30-50 degree drying of reducing pressure.
Refer to be heated to 300 DEG C～500 DEG C under conditions of indifferent gas is present during heat treatment described in step (3).
As one kind preferred embodiment, heating-up temperature is 350 DEG C～450 DEG C.
As one kind preferred embodiment, heating-up temperature is 420 DEG C.
As one kind preferred embodiment, inert gas is any one in nitrogen or argon gas.
As one kind preferred embodiment, the molecular weight of PVP is between 10000-1300000.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some nonessential modifications and adaptations that content according to foregoing invention is made, still fall within protection scope of the present invention.
In addition, if not having other explanations, raw materials used is all commercially available.
Embodiment 1：
At ambient temperature, by mol ratio be 1:1 withBlock for the adjacent dicarboxyl benzene of substituted radical
Substituted benzene oligomer and 3,3', 4,4'- biphenyl tetramine are added in DMF solution, magnetic agitation 2h, shape
Become mixed solution, and be labeled as solution A.
In solution A, appropriate PVP (Mr=30000) is weighed, is made into the solution that concentration is 30%.Under room temperature, magnetic force is stirred
1h is mixed, 1h is stood, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 14cm and voltage is 21kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 40 degree and is dried, 420 DEG C are heated under condition of nitrogen gas and obtain benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking：
A. coupling reaction is blocked
25.11g (0.1mol) 2,5- dichloro is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Benzophenone reaction monomers, 2.7308g (0.01mol) 4- bromo rutgers add 3.317g afterwards as end-capping reagent
(0.011mol) nickel chloride bipyridyl makees catalyst, and 21.45g (0.33mol) zinc powder makees reducing agent, 11.54g (0.044mol) three
Phenylphosphine makees complexing agent, and 250ml eliminating water dimethylacetylamide (DMAc) makees reaction dissolvent, and 80 DEG C of reactions 20 of controlling reaction temperature are little
When after poured in 500ml absolute methanol while hot and carry out exchange of solvent, after 6 hours, suction filtration, then wash away zinc powder with watery hydrochloric acid, finally
Only the triphenylphosphine remained in being reacted with massive laundering, the drying 12 hours of 80 DEG C of vacuum obtain 22.6g rutgers envelope
That held is poly- to benzene analog derivative, yield 90%.
Blocking coupling reaction synthetic route is：
B. end group hydrolysis
In the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, add first step reaction that product is obtained
22.6g, adds 16g (0.4mol) NaOH, 120ml tetrahydrofuran, 80ml distilled water, back flow reaction 8 hours, cooling, use
It is 3 that the dilute sulfuric acid of concentration 30% adjusts pH value, and heating is boiled to there is powder sample to separate out, with massive laundering to neutrality, after suction filtration
80 DEG C be vacuum dried 12 hours, obtain 20.34g withThe polyphenyl class blocked for the phthalic acid of substituent is spread out
Biology, yield 90%.Its molecular weight ranges 760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route is：
Embodiment 2：
At ambient temperature, by mol ratio be 1:1 withBlock for the adjacent dicarboxyl benzene of substituted radical
Substituted benzene oligomer and 3,3', 5,5'- benzophenone tetramines are added in DMF solution, magnetic agitation 2h,
Mixed solution is formed, and is labeled as solution A.
In solution A, appropriate PMMA is weighed, be made into the solution that concentration is 40%.Magnetic agitation 1h under room temperature, standing
1h, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 16cm and voltage is 25kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 50 degree and is dried, 450 DEG C are heated under condition of nitrogen gas and obtain benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is with embodiment 1.
Embodiment 3：
At ambient temperature, by mol ratio be 1:1 withSeal for the adjacent dicarboxyl benzene of substituted radical
The substituted benzene oligomer at end and 3,3', 4,4'- biphenyl tetramine are added in METHYLPYRROLIDONE solution, magnetic agitation 2h,
Mixed solution is formed, and is labeled as solution A.
In solution A, appropriate PVP (Mr=30000) is weighed, is made into the solution that concentration is 40%.Under room temperature, magnetic force is stirred
1h is mixed, 1h is stood, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 20cm and voltage is 20kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 60 degree and is dried, 350 DEG C are heated under condition of nitrogen gas and obtain benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking：
A. coupling reaction is blocked
25.11g (0.1mol) 2,5- dichloro is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Methyl benzoate, 2.7308g (0.01mol) 4- bromo rutgers add 3.317g afterwards as end-capping reagent
(0.011mol) nickel chloride bipyridyl makees catalyst, and 21.45g (0.33mol) zinc powder makees reducing agent, 11.54g (0.044mol) three
Phenylphosphine makees complexing agent, and 250ml eliminating water dimethylacetylamide (DMAc) makees reaction dissolvent, and 80 DEG C of reactions 20 of controlling reaction temperature are little
When after poured in 500ml absolute methanol while hot and carry out exchange of solvent, after 6 hours, suction filtration, then wash away zinc powder with watery hydrochloric acid, finally
Only the triphenylphosphine remained in being reacted with massive laundering, the drying 12 hours of 80 DEG C of vacuum obtain 22.6g rutgers envelope
That held is poly- to benzene analog derivative, yield 86%.
B. end group hydrolysis
In the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, add first step reaction that product is obtained
22.6g, adds 16g (0.4mol) NaOH, 120ml tetrahydrofuran, 80ml distilled water, back flow reaction 8 hours, cooling, use
It is 3 that the dilute sulfuric acid of concentration 30% adjusts pH value, and heating is boiled to there is powder sample to separate out, with massive laundering to neutrality, after suction filtration
80 DEG C be vacuum dried 12 hours, obtain 20.34g with
For the polyphenyl analog derivative that the phthalic acid of substituent is blocked, yield 88%.Its molecular weight
Scope 760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route is：
Embodiment 4：
At ambient temperature, by mol ratio be 1:1 withSeal for the adjacent dicarboxyl benzene of substituted radical
The substituted benzene oligomer at end and 3,3', 5,5'- benzophenone tetramines are added in DMF solution, magnetic agitation
2h, forms mixed solution, and is labeled as solution A.
In solution A, appropriate PVP (Mr=30000) is weighed, is made into the solution that concentration is 40%.Under room temperature, magnetic force is stirred
1h is mixed, 1h is stood, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 20cm and voltage is 20kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 60 degree and is dried, 300 DEG C are heated under condition of nitrogen gas and obtain benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is with embodiment 3.
Embodiment 5：
At ambient temperature, by mol ratio be 1:1 withSeal for the adjacent dicarboxyl benzene of substituted radical
The substituted benzene oligomer at end and 3,3', 5,5'- diphenyl ether tetramines are added in DMF solution, magnetic agitation
2h, forms mixed solution, and is labeled as solution A.
In solution A, appropriate PVP (Mr=30000) is weighed, is made into the solution that concentration is 40%.Under room temperature, magnetic force is stirred
1h is mixed, 1h is stood, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 13cm and voltage is 23kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 40 degree and is dried, 420 DEG C are heated under condition of nitrogen gas and obtain benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is with embodiment 3.
Embodiment 6：
At ambient temperature, by mol ratio be 1:1 withBlock for the adjacent dicarboxyl benzene of substituted radical
Substituted benzene oligomer and 3,3', 5,5'- diphenyl ether tetramines are added in DMF solution, magnetic agitation 2h,
Mixed solution is formed, and is labeled as solution A.
In solution A, appropriate PMMA is weighed, be made into the solution that concentration is 40%.Magnetic agitation 1h under room temperature, standing
1h, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 8cm and voltage is 17kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 40 degree and is dried, 500 DEG C are heated under condition of nitrogen gas and obtain benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is with embodiment 1.
The polyaniline-nano fiber prepared with embodiment 1-6 is obtained non-weaving cloth as raw material using fusion method.Concrete bag
Containing following steps：
Polymer chips is carried out melting using screw extruder and force feed melt；Polymer melt enter spinneret die it
Front through multilayer detailed catalogue metallic sieve filter；Gear wheel metering pump carries out melt-stoichiometry, and high polymer molten is delivered to molten after accurately measuring
Jet mould head；After melt is transported to die head, it is evenly dispersed to each spinneret orifice through runner, and sprays through spinneret orifice；From mould
While the melt stream of head spinneret orifice extrusion occurs expanded swelling, by the drawing-off of both sides high velocity, hot air stream, in viscosity flow
The melt stream of state is drawn and attenuated rapidly, meanwhile, the air at room temperature of both sides mixes drawing-off stream of hot air, cools and solidifies melt stream
Shaping, forms superfine fibre；Superfine fibre through drawing-off and cooling and solidifying blows to solidifying lace curtaining or rolling in the presence of attenuating blast
Cylinder, fiber are collected on solidifying lace curtaining or cylinder, form nano-fiber for production of non-woven.
Comparative example 1：
At ambient temperature, polystyrene is added in DMF solution, forms magnetic agitation 2h, shape
Become 45% mixed solution, and be labeled as solution A.
In solution A, appropriate PVP (Mr=30000) is weighed, is made into the solution that concentration is 30%.Under room temperature, magnetic force is stirred
1h is mixed, 1h is stood, the solution of gained is labeled as B solution.
B solution will be prepared be placed in device for spinning, regulation solidification distance is 14cm and voltage is 21kV, access on wire netting
Negative pole, will collect polyaniline-nano Precursors of Fibers on the wire netting as negative pole.
The polyaniline-nano Precursors of Fibers for obtaining is reduced pressure 40 degree and is dried, 420 DEG C are heated under condition of nitrogen gas and are prepared
Nanofiber.
Performance test：
1. fibre diameter is determined
Pattern and fibre diameter carry out observation survey using SEM (VEGA3LMU, Tescan company of Czech)
Fixed；
2. the measure (bioassay standard adopt GB 9997-88) of the tensile strength of fibre single thread
Measured, the result of every kind of sample using JQ03new type Miniature tension instrument (upper marine morning DEC)
Drawn by the mean value of 10 group samples
3. the measure (bioassay standard adopt GB 9997-88) of fibre single thread fracture percentage of elongation
Determined with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
4. the measure of Young's modulus
Determined using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education Co., Ltd).
5. electro spinning nano fiber non-weaving cloth rupture percentage of elongation measure
Determined with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
6. the measure of electro spinning nano fiber non-weaving cloth tensile strength
Determined with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
7. the measure of electro spinning nano fiber non-weaving cloth Young's modulus
Determined using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education Co., Ltd).
8. the measure of electro spinning nano fiber non-weaving cloth heat decomposition temperature
Determined with WRT-3P thermal gravimetric analyzer (TGA) (Shanghai Precision Scientific Apparatus Co., Ltd)；
9. the measure of the hot glass transition temperature of electro spinning nano fiber non-weaving cloth
It is to be determined using Diamond Dynamic Mechanical Analyzer (DMA) (Perkin-Elmer, U.S.)；
Above-mentioned test result is shown in Table 1 embodiment the performance test results.
1 embodiment the performance test results of table
By the comparison of embodiment and comparative example, polyphenylene derivatives nanofiber obtained in the method provided using the present invention
With more preferable tensile strength, toughness and modulus, while with moderate elongation.Using polyaniline-nano obtained in the present invention
Fiber non-woven equally has more preferable tensile strength and elongation at break, while with higher heat decomposition temperature, having
Certain resistance to elevated temperatures, thus the Advantageous Effects there is provided the present invention.Electrospinning high-performance polyphenyl of the present invention spreads out
The preparation method of biological nano fiber is simple to operation, and prepared polyphenylene derivatives nanofiber can be widely used in evil
On chemical industry equipment under the conditions of bad, aerospace equipment, high-speed cruising weapon, gathered obtained in the method that this is provided using the present invention
Benzene derivative nanofiber has certain resistance to elevated temperatures, therefore the polyphenylene derivatives nanofiber obtained using this method may be used also
For High temperature ion exchanger resin.
Claims (10)
1. a kind of preparation method of electrospinning high-performance poly benzene derivative nanofiber, it is characterised in that comprise the following steps：
(1) the substituted benzene oligomer for blocking adjacent dicarboxyl benzene and tetramines aromatic monomer are dissolved in solvent, presoma are obtained molten
Liquid；
(2) in the precursor solution described in step (1), an agent is added into, spinning mixed solution is formed, by method of electrostatic spinning
Form blending nanofiber presoma；
(3), after being dried the blending nanofiber presoma described in step (2), it is heat-treated, is obtained polyphenylene derivatives
Nanofiber.
2. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 1, it is characterised in that described
The general structure of substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking be：
Wherein R1Selected from following structure：
CH3O-、In any one.
3. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 1, it is characterised in that described
The general structure of tetramines aromatic be：
Wherein R2Selected from following structure：
In any one
Kind.
4. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 1, it is characterised in that described
An agent that becomes be selected from：One or two combination in PVP and PMMA.
5. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 1, it is characterised in that described
Solvent be selected from：DMF, N, N- DEF, DMA, N, N- diethyl acetyl
Amine, N, N- Valpromide, N, N- dimethyl benzamide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidone, N-
Isopropyl -2-Pyrrolidone, N- isobutyl group -2-Pyrrolidone, N- n-propyl -2-Pyrrolidone, N- normal-butyl -2- pyrrolidines
Ketone, CHP, N- methyl -3- N-methyl-2-2-pyrrolidone N, N- ethyl -3- methyl-pyrrolidon, N- first
Base -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyl -2- piperidones, N- isopropyl -2- piperidones,
N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidine ketone, dimethyl sulfoxide (DMSO), diethyl sulfoxide, sulfolane, hexichol
Any one or a few combination in sulfone.
6. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 1, it is characterised in that described
Heat treatment includes：Under conditions of inert gas is present, 300 DEG C～500 DEG C are heated to.
7. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 6, it is characterised in that described
Heat treatment includes：Under conditions of inert gas is present, 350 DEG C～450 DEG C are heated to.
8. the preparation method of electrospinning high-performance poly benzene derivative nanofiber as claimed in claim 7, it is characterised in that described
Heat treatment includes：Under conditions of inert gas is present, 420 DEG C are heated to.
9. the preparation method of the electrospinning high-performance poly benzene derivative nanofiber as described in claim 6-8 any one, its are special
Levy and be, the inert gas any one in nitrogen and argon gas.
10. a kind of polyphenylene derivatives nanofiber, it is characterised in that usage right requires the method system described in 1-9 any one
For obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898298A (en) * | 2003-12-26 | 2007-01-17 | 新日铁化学株式会社 | Aromatic polyamic acid and polyimide |
| CN105714406A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Molecule assembling-based preparation method of polypyrrolone/nylon composite fiber composite material |
| CN105714472A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/sulfonated polyphenylene oxide composite film and preparation method |
| CN105709611A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/polyimide composite porous catalytic film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898298A (en) * | 2003-12-26 | 2007-01-17 | 新日铁化学株式会社 | Aromatic polyamic acid and polyimide |
| CN105714406A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Molecule assembling-based preparation method of polypyrrolone/nylon composite fiber composite material |
| CN105714472A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/sulfonated polyphenylene oxide composite film and preparation method |
| CN105709611A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/polyimide composite porous catalytic film and preparation method thereof |
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