CN106480530B - The preparation method of electrospinning high-performance polyphenylene derivatives nanofiber - Google Patents
The preparation method of electrospinning high-performance polyphenylene derivatives nanofiber Download PDFInfo
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- polyphenylene derivatives
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- pyrrolidone
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 58
- -1 polyphenylene Polymers 0.000 title claims abstract description 31
- 229920000265 Polyparaphenylene Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001523 electrospinning Methods 0.000 title claims abstract description 21
- 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001555 benzenes Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 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
- 239000000178 monomer Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 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
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-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
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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 14
- 238000001035 drying Methods 0.000 description 12
- 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
- 238000005259 measurement Methods 0.000 description 10
- 125000001424 substituent group Chemical group 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
- 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
- 229940113088 dimethylacetamide Drugs 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
- 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
- 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
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001816 cooling Methods 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
- 206010013786 Dry skin Diseases 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 238000011056 performance test Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000001556 precipitation Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 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
- 230000000052 comparative effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 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
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- BSJWDQYZFBYNIM-UHFFFAOYSA-N 1,3,4,5-tetramethylpyrrolidin-2-one Chemical compound CC1C(C)N(C)C(=O)C1C BSJWDQYZFBYNIM-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000006978 adaptation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002238 attenuated effect 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
- 238000003486 chemical etching Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 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
- 238000005516 engineering process 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of preparation methods of electrospinning high-performance polyphenylene derivatives nanofiber, comprising the following steps: (1) the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer is dissolved in solvent, precursor solution is made；(2) it in above-mentioned precursor solution, is added into silk agent, forms spinning mixed solution, blended nanofiber presoma is formed by method of electrostatic spinning；(3) it after above-mentioned blended nanofiber presoma being dried, is heat-treated, obtains polyphenylene derivatives nanofiber.It is relatively low that the method overcomes the polyphenylene derivatives molecular weight that general synthetic method obtains, it is difficult to the shortcomings that being prepared into high-performance polyphenylene derivatives nanofiber.Polyphenylene derivatives nanofiber is obtained with good mechanical performances such as high tenacity, high intensity, high-modulus, moderate elongations by this method.
Description
Technical field
The present invention relates to a kind of preparation methods of polyphenylene derivatives nanofiber, more particularly it relates to Electrospinning Method
The method for preparing polyphenylene derivatives nanofiber.
Background technique
Polyphenyl is a kind of rigid chain polymer connected by phenyl, has excellent heat-resisting quantity, the heat in nitrogen point
Solution temperature is up to 900 DEG C, can be used for a long time at 400 DEG C；With characteristics such as excellent resistant to chemical etching, rub resistance, radiation hardness；
There is good electrical property and the self-lubricating property better than graphite simultaneously.Polyphenyl can be used as high temperature resistant, radiation resistant paint or gluing
Agent, high-temperature wearable components, ablation resistant material etc., chemical industry equipment, aerospace equipment, the high-speed cruising that can be used under mal-condition are military
On device, it may also be used for High temperature ion exchanger resin.
But polyphenyl is not molten insoluble polymer, hardly possible forming, hardly possible processing.Substituent group is introduced using on main chain phenyl ring
Method, its dissolubility can be improved.But huge benzoyl is even introduced on main chain phenyl ring, this polyphenylene derivatives exist
Solubility in organic solvent remains on less, and since solubility property is poor, the molecular weight of general synthesized polyphenylene derivatives is all
It is relatively low, it is difficult to be prepared into electro spinning nano fiber.
For the substituted benzene oligomer that the present invention is blocked using adjacent dicarboxyl benzene as assembling unit, tetramines aromatic is hinge agent, is passed through
Method of electrostatic spinning obtains polyphenylene derivatives nanofiber.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation sides of electrospinning high-performance polyphenylene derivatives nanofiber
Method, comprising the following steps:
(1) the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, forerunner is made
Liquid solution；
(2) it in the precursor solution described in step (1), is added into silk agent, forms spinning mixed solution, pass through Static Spinning
Silk method forms blended nanofiber presoma；
(3) it after blended nanofiber presoma described in step (2) being dried, 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 sealing end:
Wherein R1Selected from such as flowering structure:
CH3O-、In any one.
In one embodiment, the general structure of tetramines aromatic are as follows:
Wherein R2Selected from such as flowering structure:
In any one or the combination of several of them.
In one embodiment, it is selected from silk agent: one or both of PVP or PMMA.
In one embodiment, solvent is selected from: n,N-Dimethylformamide, N, N- diethylformamide, 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, n-cyclohexyl-2-pyrrolidone, N- methyl -3- N-methyl-2-2-pyrrolidone N, N- ethyl -
3- methyl-pyrrolidon, N- methyl -3,4,5- trimethyl -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, two
Ethyl-sulfoxide, sulfolane, any one or a few combination in diphenyl sulphone (DPS).
In one embodiment, under the conditions of heat treatment includes: existing for the inert gas, 300 DEG C~500 are heated to
℃。
In one embodiment, under the conditions of heat treatment includes: existing for the inert gas, 350 DEG C~450 are heated to
℃。
In one embodiment, existing for the inert gas under the conditions of, 420 DEG C are heated to.
In one embodiment, inert gas is arbitrary a kind of in nitrogen or argon gas.
It is another object of the present invention to provide the polyphenylene derivatives nanofibers that the method is prepared.
Compared with prior art, the invention has the benefit that
The present invention is used with the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end as main assembling unit, 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 relatively low, it is difficult to the shortcomings that being prepared into high-performance polyphenylene derivatives 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, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific term have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
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 should be understood as specifically disclosing 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 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range be intended to include 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. frequency of occurrence) 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 quantity obviously refers to singular.
The present invention provides a kind of preparation methods of electrospinning high-performance polyphenylene derivatives nanofiber, comprising the following steps:
(1) the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, forerunner is made
Liquid solution；
(2) it in the precursor solution described in step (1), is added into silk agent, forms spinning mixed solution, pass through Static Spinning
Silk method forms blended nanofiber presoma；
(3) it after blended nanofiber presoma described in step (2) being dried, is heat-treated, obtains polyphenyl and spread out
Biological nano fiber.
The substituted benzene oligomer of adjacent dicarboxyl benzene sealing end:
The substituted benzene oligomer structure general formula of heretofore described adjacent dicarboxyl benzene sealing end:
Wherein R1Any one in such as flowering structure:
CH3O-；R1It is preferred that
Group.
Work as R1ForWhen group, the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end the preparation method comprises the following steps:
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
As end-capping reagent, 3.317g is added in benzophenone reaction monomers, 2.7308g (0.01mol) 4- bromo rutgers afterwards
(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 reaction dissolvent is made in 250ml water removal dimethyl acetamide (DMAc), and it is small to control 80 DEG C of reaction temperature reactions 20
When after pour into carry out exchange of solvent in 500ml anhydrous methanol while hot, after 6 hours, filter, then wash away zinc powder with dilute hydrochloric acid, finally
Remaining triphenylphosphine in being reacted only with massive laundering, 80 DEG C of dryings of vacuum obtain 22.6g rutgers envelope for 12 hours
Gather to benzene analog derivative, yield 90% at end.
Block coupling reaction synthetic route are as follows:
B. end group hydrolysis
The first step is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device and reacts obtained product
16g (0.4mol) sodium hydroxide is added in 22.6g, and 120ml tetrahydrofuran, 80ml distilled water is back flow reaction 8 hours, cooling, uses
It is 3 that the dilute sulfuric acid of concentration 30%, which adjusts pH value, and heating is boiled to there is powder sample precipitation, with massive laundering to neutrality, after suction filtration
80 DEG C be dried in vacuo 12 hours, obtain 20.34g withThe polyphenyl class blocked for the phthalic acid of substituent group is spread out
Biology, yield 90%.Its molecular weight ranges 760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route are as follows:
Tetramines aromatic:
In step (1) in the preparation of precursor solution, there are four " the tetramines aromatic monomer " refers to that aromatic contains
The compound of amino.
Illustrative 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 bis- 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 become conical (i.e. " taylor cone ") from spherical shape, and
Extend to obtain fiber filaments from conical tip.This mode can produce the polymer filaments of nanometer grade diameter.
Condition used by the electrostatic spinning are as follows: spinning temperature is lower 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, which receives distance i.e. solidification distance,；Preferably, it is 15~35cm that spinning, which receives distance,；It is highly preferred that
It is 16cm that spinning, which receives distance,.
The range of the nanofiber diameter of electrostatic spinning: 50~500nm；Preferably, the range of nanofiber diameter: 100
~400nm；It is highly preferred that nanofiber diameter is 200~300nm.
Drying means described in step (3) refers to decompression 30-50 degree drying.
300 DEG C~500 DEG C are heated under the conditions of finger existing for the indifferent gas when heat treatment described in step (3).
As a preferred embodiment, heating temperature is 350 DEG C~450 DEG C.
As a preferred embodiment, heating temperature is 420 DEG C.
As a preferred embodiment, inert gas is any one in nitrogen or argon gas.
As a preferred embodiment, the molecular weight of PVP is between 10000-1300000.
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
The some nonessential modifications and adaptations made according to the content of foregoing invention, still fall within protection scope of the present invention.
In addition, if illustrated without other, it is raw materials used to be all commercially available.
Embodiment 1:
At room temperature, by molar ratio be 1:1 withIt is blocked for the adjacent dicarboxyl benzene of substituent group
Substituted benzene oligomer and 3,3', 4,4'- biphenyl tetramines are added in n,N-Dimethylformamide solution, magnetic agitation 2h, shape
At mixed solution, and it is labeled as solution A.
In solution A, suitable PVP (Mr=30000) is weighed, is made into the solution that concentration is 30%.Magnetic force stirs at room temperature
1h is mixed, 1h is stood, resulting solution is labeled as B solution.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 14cm and voltage is 21kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 40 degree of drying, 420 DEG C is heated under condition of nitrogen gas and obtains benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end:
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
As end-capping reagent, 3.317g is added in benzophenone reaction monomers, 2.7308g (0.01mol) 4- bromo rutgers afterwards
(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 reaction dissolvent is made in 250ml water removal dimethyl acetamide (DMAc), and it is small to control 80 DEG C of reaction temperature reactions 20
When after pour into carry out exchange of solvent in 500ml anhydrous methanol while hot, after 6 hours, filter, then wash away zinc powder with dilute hydrochloric acid, finally
Remaining triphenylphosphine in being reacted only with massive laundering, 80 DEG C of dryings of vacuum obtain 22.6g rutgers envelope for 12 hours
Gather to benzene analog derivative, yield 90% at end.
Block coupling reaction synthetic route are as follows:
B. end group hydrolysis
The first step is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device and reacts obtained product
16g (0.4mol) sodium hydroxide is added in 22.6g, and 120ml tetrahydrofuran, 80ml distilled water is back flow reaction 8 hours, cooling, uses
It is 3 that the dilute sulfuric acid of concentration 30%, which adjusts pH value, and heating is boiled to there is powder sample precipitation, with massive laundering to neutrality, after suction filtration
80 DEG C be dried in vacuo 12 hours, obtain 20.34g withThe polyphenyl class blocked for the phthalic acid of substituent group is spread out
Biology, yield 90%.Its molecular weight ranges 760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route are as follows:
Embodiment 2:
At room temperature, by molar ratio be 1:1 withIt is blocked for the adjacent dicarboxyl benzene of substituent group
Substituted benzene oligomer and 3,3', 5,5'- benzophenone tetramines are added in n,N-Dimethylformamide solution, magnetic agitation 2h,
Mixed solution is formed, and is labeled as solution A.
In solution A, suitable PMMA is weighed, is made into the solution that concentration is 40%.Magnetic agitation 1h at room temperature is stood
Resulting solution is labeled as B solution by 1h.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 16cm and voltage is 25kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 50 degree of drying, 450 DEG C is heated under condition of nitrogen gas and obtains benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method is the same as that of Example 1 for the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end.
Embodiment 3:
At room temperature, by molar ratio be 1:1 withIt is sealed for the adjacent dicarboxyl benzene of substituent group
The substituted benzene oligomer at end and 3,3', 4,4'- biphenyl tetramines are added in n-methyl-2-pyrrolidone solution, magnetic agitation 2h,
Mixed solution is formed, and is labeled as solution A.
In solution A, suitable PVP (Mr=30000) is weighed, is made into the solution that concentration is 40%.Magnetic force stirs at room temperature
1h is mixed, 1h is stood, resulting solution is labeled as B solution.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 20cm and voltage is 20kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 60 degree of drying, 350 DEG C is heated under condition of nitrogen gas and obtains benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end:
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
As end-capping reagent, 3.317g is added in methyl benzoate, 2.7308g (0.01mol) 4- bromo rutgers afterwards
(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 reaction dissolvent is made in 250ml water removal dimethyl acetamide (DMAc), and it is small to control 80 DEG C of reaction temperature reactions 20
When after pour into carry out exchange of solvent in 500ml anhydrous methanol while hot, after 6 hours, filter, then wash away zinc powder with dilute hydrochloric acid, finally
Remaining triphenylphosphine in being reacted only with massive laundering, 80 DEG C of dryings of vacuum obtain 22.6g rutgers envelope for 12 hours
Gather to benzene analog derivative, yield 86% at end.
B. end group hydrolysis
The first step is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device and reacts obtained product
16g (0.4mol) sodium hydroxide is added in 22.6g, and 120ml tetrahydrofuran, 80ml distilled water is back flow reaction 8 hours, cooling, uses
It is 3 that the dilute sulfuric acid of concentration 30%, which adjusts pH value, and heating is boiled to there is powder sample precipitation, with massive laundering to neutrality, after suction filtration
80 DEG C be dried in vacuo 12 hours, obtain 20.34g with
For the polyphenyl analog derivative that the phthalic acid of substituent group blocks, yield 88%.Its molecular weight
Range 760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route are as follows:
Embodiment 4:
At room temperature, by molar ratio be 1:1 withIt is sealed for the adjacent dicarboxyl benzene of substituent group
The substituted benzene oligomer at end and 3,3', 5,5'- benzophenone tetramines are added in n,N-Dimethylformamide solution, magnetic agitation
2h forms mixed solution, and is labeled as solution A.
In solution A, suitable PVP (Mr=30000) is weighed, is made into the solution that concentration is 40%.Magnetic force stirs at room temperature
1h is mixed, 1h is stood, resulting solution is labeled as B solution.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 20cm and voltage is 20kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 60 degree of drying, 300 DEG C is heated under condition of nitrogen gas and obtains benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end is the same as embodiment 3.
Embodiment 5:
At room temperature, by molar ratio be 1:1 withIt is sealed for the adjacent dicarboxyl benzene of substituent group
The substituted benzene oligomer at end and 3,3', 5,5'- diphenyl ether tetramines are added in n,N-Dimethylformamide solution, magnetic agitation
2h forms mixed solution, and is labeled as solution A.
In solution A, suitable PVP (Mr=30000) is weighed, is made into the solution that concentration is 40%.Magnetic force stirs at room temperature
1h is mixed, 1h is stood, resulting solution is labeled as B solution.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 13cm and voltage is 23kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 40 degree of drying, 420 DEG C is heated under condition of nitrogen gas and obtains benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end is the same as embodiment 3.
Embodiment 6:
At room temperature, by molar ratio be 1:1 withIt is blocked for the adjacent dicarboxyl benzene of substituent group
Substituted benzene oligomer and 3,3', 5,5'- diphenyl ether tetramines are added in n,N-Dimethylformamide solution, magnetic agitation 2h,
Mixed solution is formed, and is labeled as solution A.
In solution A, suitable PMMA is weighed, is made into the solution that concentration is 40%.Magnetic agitation 1h at room temperature is stood
Resulting solution is labeled as B solution by 1h.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 8cm and voltage is 17kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 40 degree of drying, 500 DEG C is heated under condition of nitrogen gas and obtains benzo
Imidazoles is the polyaniline-nano fiber of hinge point.
Wherein, the preparation method is the same as that of Example 1 for the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end.
Non-woven cloth is made using fusion method as raw material in the polyaniline-nano fiber being prepared using embodiment 1-6.Specific packet
Containing following steps:
Melt simultaneously force feed melt to polymer chips using screw extruder；Polymer melt enter spinneret die it
It is preceding to be filtered through multilayer detailed catalogue metallic sieve；Gear wheel metering pump carries out melt-stoichiometry, and high polymer molten is sent after accurately measuring to molten
Jet mould head；After melt is transported to die head, it is evenly dispersed by runner to each spinneret orifice, and sprayed through spinneret orifice；From mould
While the melt stream generation extruding that head spinneret orifice squeezes out swells, by the drawing-off of two sides high velocity heated air streams, it is in viscosity flow
The melt stream of state is drawn and attenuated rapidly, meanwhile, the air at room temperature of two sides mixes drawing-off stream of hot air, cools and solidifies melt stream
Forming forms superfine fibre；Superfine fibre through drawing-off and cooling and solidifying blows to solidifying lace curtaining or rolling under the action of attenuating blast
Cylinder, fiber are collected on solidifying lace curtaining or roller, and nano-fiber for production of non-woven is formed.
Comparative example 1:
At room temperature, polystyrene is added in n,N-Dimethylformamide solution, forms magnetic agitation 2h, shape
At 45% mixed solution, and it is labeled as solution A.
In solution A, suitable PVP (Mr=30000) is weighed, is made into the solution that concentration is 30%.Magnetic force stirs at room temperature
1h is mixed, 1h is stood, resulting solution is labeled as B solution.
B solution will be prepared to be placed in device for spinning, adjusting solidification distance is 14cm and voltage is 21kV, is accessed on wire netting
Cathode will be collected into polyaniline-nano Precursors of Fibers on the wire netting as cathode.
Obtained polyaniline-nano Precursors of Fibers is depressurized into 40 degree of drying, 420 DEG C is heated under condition of nitrogen gas and is prepared
Nanofiber.
Performance test:
1. fibre diameter measures
Pattern and fibre diameter use scanning electron microscope (VEGA3LMU, Tescan company of Czech) to carry out observation survey
It is fixed；
2. the measurement of the tensile strength of fibre single thread (measurement standard uses GB 9997-88)
It is measured, the result of every kind of sample using JQ03new type Miniature tension instrument (upper marine morning Digital Equipment Co., Ltd)
It is obtained by the average value of 10 this group of samples
3. the measurement that fibre single thread is broken percentage of elongation (measurement standard uses GB 9997-88)
It is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
4. the measurement of Young's modulus
It is measured using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education Co., Ltd).
5. the measurement of electro spinning nano fiber non-woven cloth fracture percentage of elongation
It is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
6. the measurement of electro spinning nano fiber non-woven cloth tensile strength
It is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
7. the measurement of electro spinning nano fiber non-woven cloth Young's modulus
It is measured using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education Co., Ltd).
8. the measurement of electro spinning nano fiber non-woven cloth thermal decomposition temperature
It is measured with WRT-3P thermal gravimetric analyzer (TGA) (Shanghai Precision Scientific Apparatus Co., Ltd)；
9. the measurement of the hot glass transition temperature of electro spinning nano fiber non-woven cloth
It is to be measured using Diamond Dynamic Mechanical Analyzer (DMA) (Perkin-Elmer, the U.S.)；
Above-mentioned test result is shown in Table 1 embodiment the performance test results.
1 embodiment the performance test results of table
Through embodiment compared with comparative example, polyphenylene derivatives nanofiber made from method provided by the invention is used
With better tensile strength, toughness and modulus, while there is moderate elongation.Using polyaniline-nano produced by the present invention
Fiber non-woven equally has better tensile strength and elongation at break, while having higher thermal decomposition temperature, has
Certain high temperature resistance, thus provide advantageous effects of the invention.Electrospinning high-performance polyphenyl of the present invention spreads out
The preparation method of biological nano fiber is simple to operate, and prepared polyphenylene derivatives nanofiber can be widely used in evil
On chemical industry equipment, aerospace equipment, high-speed cruising weapon under the conditions of bad, gather made from method provided by the invention since this is used
Benzene derivative nanofiber has certain high temperature resistance, therefore may be used also using the polyphenylene derivatives nanofiber that this method obtains
For High temperature ion exchanger resin.
Claims (9)
1. a kind of preparation method of electrospinning high-performance polyphenylene derivatives nanofiber, which comprises the following steps:
(1) the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, it is molten that presoma is made
Liquid；
(2) it in the precursor solution described in step (1), is added into silk agent, forms spinning mixed solution, pass through method of electrostatic spinning
Form blended nanofiber presoma；
(3) it after blended nanofiber presoma described in step (2) being dried, is heat-treated, obtains polyphenylene derivatives
Nanofiber；
The general structure of the substituted benzene oligomer of the adjacent dicarboxyl benzene sealing end are as follows:
Wherein R1Selected from such as flowering structure:
CH3O-、
In any one.
2. the preparation method of electrospinning high-performance polyphenylene derivatives nanofiber as described in claim 1, which is characterized in that described
Tetramines aromatic general structure are as follows:
Wherein R2Selected from such as flowering structure:
In any one.
3. the preparation method of electrospinning high-performance polyphenylene derivatives nanofiber as described in claim 1, which is characterized in that described
Be selected from silk agent: the combination of one or both of PVP and PMMA.
4. the preparation method of electrospinning high-performance polyphenylene derivatives nanofiber as described in claim 1, which is characterized in that described
Solvent be selected from: n,N-Dimethylformamide, N, N- diethylformamide, n,N-dimethylacetamide, N, N- diethyl acetyl
Amine, N, N- Valpromide, N, N- dimethyl benzamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N-
Isopropyl -2-Pyrrolidone, N- isobutyl group -2-Pyrrolidone, N- n-propyl -2-Pyrrolidone, N- normal-butyl -2- pyrrolidines
Ketone, n-cyclohexyl-2-pyrrolidone, N- methyl -3- N-methyl-2-2-pyrrolidone N, N- ethyl -3- methyl-pyrrolidon, N- first
Base -3,4,5- trimethyl -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, diethyl sulfoxide, sulfolane, hexichol
Any one or a few combination in sulfone.
5. the preparation method of electrospinning high-performance polyphenylene derivatives nanofiber as described in claim 1, which is characterized in that described
Under the conditions of heat treatment includes: existing for the inert gas, it is heated to 300 DEG C~500 DEG C.
6. the preparation method of electrospinning high-performance polyphenylene derivatives nanofiber as claimed in claim 5, which is characterized in that described
Under the conditions of heat treatment includes: existing for the inert gas, it is heated to 350 DEG C~450 DEG C.
7. the preparation method of electrospinning high-performance polyphenylene derivatives nanofiber as claimed in claim 6, which is characterized in that described
Under the conditions of heat treatment includes: existing for the inert gas, it is heated to 420 DEG C.
8. the preparation method of the electrospinning high-performance polyphenylene derivatives nanofiber as described in claim 6-7 any one, special
Sign is, any one of the inert gas in nitrogen and argon gas.
9. a kind of polyphenylene derivatives nanofiber, which is characterized in that prepared using method described in claim 1-8 any one
It obtains.
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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 |
| CN105709611A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/polyimide composite porous catalytic film and preparation method thereof |
| CN105714472A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/sulfonated polyphenylene oxide composite film and preparation method |
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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 |
| CN105709611A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/polyimide composite porous catalytic film and preparation method thereof |
| CN105714472A (en) * | 2015-09-29 | 2016-06-29 | 江西师范大学 | Polypyrrolone/sulfonated polyphenylene oxide composite film and preparation method |
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