CN106435828B - Electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method - Google Patents
Electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method Download PDFInfo
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- CN106435828B CN106435828B CN201610846857.4A CN201610846857A CN106435828B CN 106435828 B CN106435828 B CN 106435828B CN 201610846857 A CN201610846857 A CN 201610846857A CN 106435828 B CN106435828 B CN 106435828B
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- nano fiber
- polyphenylene derivatives
- methyl
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- -1 polyphenylene Polymers 0.000 title claims abstract description 43
- 229920000265 Polyparaphenylene Polymers 0.000 title claims abstract description 34
- 239000002121 nanofiber Substances 0.000 title claims abstract description 34
- 239000004642 Polyimide Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 229920001721 polyimide 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 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000001555 benzenes Chemical class 0.000 claims abstract description 31
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NCNWTBAWLAFYDR-UHFFFAOYSA-N 1,6-dimethylpiperidin-2-one Chemical class CC1CCCC(=O)N1C NCNWTBAWLAFYDR-UHFFFAOYSA-N 0.000 claims description 3
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical class CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 claims description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical class CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical class CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 claims description 3
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 2
- LPRJTTSNPNSAEB-UHFFFAOYSA-N 1-ethyl-3-methylpyrrole Chemical class CCN1C=CC(C)=C1 LPRJTTSNPNSAEB-UHFFFAOYSA-N 0.000 claims 1
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical class CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 22
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000009987 spinning Methods 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 8
- 238000004900 laundering Methods 0.000 description 8
- 210000003739 neck Anatomy 0.000 description 8
- 229920006389 polyphenyl polymer Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 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 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 238000005259 measurement 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
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical class CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- GVDQKJQFVPXADH-UHFFFAOYSA-N 1-propan-2-ylpiperidin-2-one Chemical class CC(C)N1CCCCC1=O GVDQKJQFVPXADH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 210000004700 fetal blood Anatomy 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
Electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method, include the following steps：(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, precursor solution is made；(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, by method of electrostatic spinning formation nanofiber, the molar ratio of the polyamic acid and substituted benzene oligomer monomer is (0.1-5)：1；(3) it after drying above-mentioned nanofiber, is heat-treated to get polyphenylene derivatives/polyimides composite nano fiber.
Description
Technical field
The present invention relates to a kind of preparation method of composite nano fiber, more particularly to a kind of electrospinning high-performance polyphenyl derives
The preparation method of object/polyimides composite nano fiber.
Background technology
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 parts, 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.
Invention content
In order to solve prior art problem, a kind of electrospinning high-performance polyphenylene derivatives of the first aspect of the present invention offer/poly-
Acid imide composite nano fiber preparation method, includes the following steps：
(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, are made
Precursor solution；
(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, is received by method of electrostatic spinning formation
The molar ratio of rice fiber, the polyamic acid and substituted benzene oligomer monomer is (0.1-5)：1；
(3) it after drying above-mentioned nanofiber, is heat-treated fine to get polyphenylene derivatives/polyimides composite Nano
Dimension.
In some embodiments, the general structure of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end is：
Wherein R1Selected from CH3O-、In one kind.
In some embodiments, the general structure of the tetramines aromatic is：
Wherein R2It is selected fromMiddle one kind.
In some embodiments, the polyamic acid is prepared by the raw material comprising diamines and dianhydride.
In some embodiments, the solvent is selected from n,N-Dimethylformamide, N, N- diethylformamides, N, N-
Dimethylacetylamide, N, N- diethyl acetamides, N, N- Valpromides, N, N- dimethyl benzamides, N- methyl -2- pyrroles
Pyrrolidone, N- ethyl-2-pyrrolidones, N- isopropyls -2-Pyrrolidone, N- isobutyl groups -2-Pyrrolidone, N- n-propyls -2-
Pyrrolidones, N- normal-butyls -2-Pyrrolidone, n-cyclohexyl-2-pyrrolidone, N- methyl -3- N-methyl-2-2-pyrrolidone Ns, N-
Ethyl -3- methyl-pyrrolidons, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyls -2-
Piperidones, N- isopropyl -2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidines ketone, dimethyl are sub-
At least one of sulfone, diethyl sulfoxide, sulfolane, diphenyl sulphone (DPS).
In some embodiments, described be heat-treated includes：Under the conditions of existing for inert gas, be heated to 300 DEG C-
500℃。
In some embodiments, described be heat-treated includes：Under the conditions of existing for inert gas, be heated to 350 DEG C-
450℃。
In some embodiments, described be heat-treated includes：Under the conditions of existing for inert gas, it is heated to 420 DEG C.
In some embodiments, the inert gas is selected from least one of nitrogen, argon gas.
The second aspect of the present invention provides polyphenylene derivatives/polyimides composite nano fiber, uses side as described above
What method was prepared.
For the substituted benzene oligomer that the present invention is blocked using adjacent dicarboxyl benzene as module units, tetramines aromatic is hinge agent, and is added
Enter polyamic acid, polyphenylene derivatives/polyimides composite nano fiber is obtained by method of electrostatic spinning.Polyamic acid is in hot-cast socket
Be transformed into polyimides, and the low molecular weight polyphenylene derivative chain for adjacent dicarboxyl benzene being blocked as linking point using acid imide in the process
It is connected into the polyphenylene derivatives of macromolecule.
Specific implementation mode
The first aspect of the present invention provides a kind of electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation
Method includes the following steps：
(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, are made
Precursor solution；
(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, is received by method of electrostatic spinning formation
The molar ratio of rice fiber, the polyamic acid and substituted benzene oligomer monomer is (0.1-5)：1；
(3) it after drying above-mentioned nanofiber, is heat-treated fine to get polyphenylene derivatives/polyimides composite Nano
Dimension.
The substituted benzene oligomer of adjacent dicarboxyl benzene sealing end
In some embodiments, the general structure of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end is：
Wherein R1Selected from CH3O-、In one kind.
R1PreferablyGroup.
Work as R1ForWhen group, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene sealing end is：
A. coupling reaction is blocked
0.1mol2,5- dichloro benzophenones are added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Reaction monomers, 0.01mol 4- bromos rutgers are made as end-capping reagent, the rear 0.011mol nickel chloride bipyridyls that are added
Catalyst, 0.33mol zinc powders make reducing agent, and 0.044mol triphenylphosphines make complexing agent, and 250mL removes water dimethylacetylamide
(DMAc) be used as reaction dissolvent, poured into while hot in 500mL absolute methanols after the reaction 20 hours of 80 DEG C of controlling reaction temperature carry out it is molten
Agent exchanges, and after 6 hours, filters, then wash away zinc powder with dilute hydrochloric acid, remaining triphenylphosphine in finally being reacted only with massive laundering,
80 DEG C of dryings of vacuum obtain the poly- to benzene analog derivative of rutgers sealing end for 12 hours.
Blocking coupling reaction synthetic route is：
B. end group hydrolysis
First step reaction is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, product is made, is added
0.4mol sodium hydroxides, 120mL tetrahydrofurans, 80mL distilled water, back flow reaction 8 hours is cooling, is 30% with mass fraction
It is 3 that dilute sulfuric acid, which adjusts pH value, and heating is boiled to there is powder sample precipitation, and with massive laundering to neutrality, 80 DEG C of vacuum are dry after suction filtration
Dry 12 hours, obtain withThe polyphenyl analog derivative blocked for the phthalic acid of substituent group.Its molecular weight ranges
760g/mol-2553g/mol, degree of polymerization 2-12.
End group hydrolysis synthetic route is：
Tetramines aromatic
In some embodiments, the general structure of the tetramines aromatic is：
Wherein R2It is selected fromMiddle one kind.
The specific example of tetramines aromatic provided by the invention can enumerate, such as：3,3', 5,5'- biphenyl tetramine, 3,
The equal benzene tetramine of 3', 4,4'- biphenyl tetramine, 1,2,3,5-, 2,3,5,6- pyridines tetramine, 4- methyl -2,3,5,6- pyridines 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)s tetramine, 3,3', 5,5'- diphenyl sulphone (DPS)s tetramine, 3,3', 5,
5'- diphenyl methanes tetramine, 3,3', 4,4'- diphenyl methanes tetramine, 2,2', 3,3'- diphenyl methanes 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', 4,4'- bis trifluoromethyl hexichol urotropine, 2,3,3', 4'- bis- three
Methyl fluoride hexichol urotropine, 1,4,5,8- naphthalenes tetramine, 2,4,5,7- naphthalenes tetramine, 2,3,6,7- naphthalene tetramines.
Polyamic acid
In some embodiments, the polyamic acid is prepared by the raw material comprising diamines and dianhydride.
The diamines is 4,4 '-diaminodiphenyl ethers (ODA), and the dianhydride is pyromellitic acid dianhydride (PMDA).
The synthetic reaction of the polyamic acid carries out under nitrogen protection, to keep reactant not oxidized and keep dry
It is dry.First diamines and solvent are added in three-necked flask by a certain percentage, so that diamines is completely dissolved under stiring, is then added portionwise
Dianhydride is stirred to react to obtain the polyamic acid solution of pale yellow transparent at low temperature, and Cord blood is for use.
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 is used by the electrostatic spinning：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 10-30kV；It is highly preferred that spinning voltage is 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 spinning
It is 16cm that silk, which receives distance,.
In some embodiments, the solvent is selected from n,N-Dimethylformamide, N, N- diethylformamides, N, N-
Dimethylacetylamide, N, N- diethyl acetamides, N, N- Valpromides, N, N- dimethyl benzamides, N- methyl -2- pyrroles
Pyrrolidone, N- ethyl-2-pyrrolidones, N- isopropyls -2-Pyrrolidone, N- isobutyl groups -2-Pyrrolidone, N- n-propyls -2-
Pyrrolidones, N- normal-butyls -2-Pyrrolidone, n-cyclohexyl-2-pyrrolidone, N- methyl -3- N-methyl-2-2-pyrrolidone Ns, N-
Ethyl -3- methyl-pyrrolidons, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyls -2-
Piperidones, N- isopropyl -2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidines ketone, dimethyl are sub-
At least one of sulfone, diethyl sulfoxide, sulfolane, diphenyl sulphone (DPS).
In some embodiments, described be heat-treated includes：Under the conditions of existing for inert gas, be heated to 300 DEG C-
500℃。
In some embodiments, described be heat-treated includes：Under the conditions of existing for inert gas, be heated to 350 DEG C-
450℃。
In some embodiments, described be heat-treated includes：Under the conditions of existing for inert gas, it is heated to 420 DEG C.
In some embodiments, the inert gas is selected from least one of nitrogen, argon gas.
The second aspect of the present invention provides polyphenylene derivatives/polyimides composite nano fiber, uses side as described above
What method was prepared.
For the substituted benzene oligomer that the present invention is blocked using adjacent dicarboxyl benzene as module units, tetramines aromatic is hinge agent, and is added
Enter polyamic acid, polyphenylene derivatives/polyimides composite nano fiber is obtained by method of electrostatic spinning.Polyamic acid is in hot-cast socket
Be transformed into polyimides, and the low molecular weight polyphenylene derivative chain for adjacent dicarboxyl benzene being blocked as linking point using acid imide in the process
It is connected into the polyphenylene derivatives of macromolecule.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of 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
Electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method,
(1) by the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer with molar ratio 1：1 is dissolved in
In solvent, precursor solution is made；
(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, is received by method of electrostatic spinning formation
The molar ratio of rice fiber, the polyamic acid and substituted benzene oligomer monomer is 0.1：1；
(3) it after drying above-mentioned nanofiber, is heat-treated fine to get polyphenylene derivatives/polyimides composite Nano
Dimension.
The structural formula of the substituted benzene oligomer of the described adjacent dicarboxyl benzene sealing end is：
Wherein R1For
The preparation method of the substituted benzene oligomer of neighbour's dicarboxyl benzene sealing end is：
A. coupling reaction is blocked
0.1mol2,5- dichloro benzophenones are added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Reaction monomers, 0.01mol 4- bromos rutgers are made as end-capping reagent, the rear 0.011mol nickel chloride bipyridyls that are added
Catalyst, 0.33mol zinc powders make reducing agent, and 0.044mol triphenylphosphines make complexing agent, and 250mL removes water dimethylacetylamide and makees instead
Solvent is answered, is poured into while hot after the reaction 20 hours of 80 DEG C of controlling reaction temperature and carries out exchange of solvent in 500mL absolute methanols, 6 hours
Afterwards, it filters, then zinc powder is washed away with dilute hydrochloric acid, remaining triphenylphosphine in finally being reacted only with massive laundering, 80 DEG C of dryings of vacuum
Obtain within 12 hours the poly- to benzene analog derivative of rutgers sealing end.
B. end group hydrolysis
First step reaction is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, product is made, is added
0.4mol sodium hydroxides, 120mL tetrahydrofurans, 80mL distilled water, back flow reaction 8 hours is cooling, dilute with mass fraction 30%
Sulphur acid for adjusting pH value is 3, and heating is boiled to there is powder sample precipitation, with massive laundering to neutrality, 80 DEG C of vacuum drying after suction filtration
12 hours, obtain withThe polyphenyl analog derivative blocked for the phthalic acid of substituent group.
The tetramines aromatic is 3,3', 4,4'- biphenyl tetramines.
The solvent is n,N-Dimethylformamide.
The polyamic acid is prepared by 4,4 '-diaminodiphenyl ethers and pyromellitic acid dianhydride, and preparation method is：By 4,
4 '-diaminodiphenyl ethers are dissolved in n,N-Dimethylformamide, and equimolar pyromellitic acid dianhydride is added under nitrogen protection,
Ice bath stirring 5h to get.
The heat treatment includes：Under the conditions of existing for nitrogen, it is heated to 420 DEG C.
Embodiment 2
Electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method,
(1) by the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer with molar ratio 1：1 is dissolved in
In solvent, precursor solution is made；
(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, is received by method of electrostatic spinning formation
The molar ratio of rice fiber, the polyamic acid and substituted benzene oligomer monomer is 5：1；
(3) it after drying above-mentioned nanofiber, is heat-treated fine to get polyphenylene derivatives/polyimides composite Nano
Dimension.
The structural formula of the substituted benzene oligomer of the described adjacent dicarboxyl benzene sealing end is：
Wherein R1For
The preparation method of the substituted benzene oligomer of neighbour's dicarboxyl benzene sealing end is：
A. coupling reaction is blocked
0.1mol2,5- dichloro benzophenones are added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Reaction monomers, 0.01mol 4- bromos rutgers are made as end-capping reagent, the rear 0.011mol nickel chloride bipyridyls that are added
Catalyst, 0.33mol zinc powders make reducing agent, and 0.044mol triphenylphosphines make complexing agent, and 250mL removes water dimethylacetylamide and makees instead
Solvent is answered, is poured into while hot after the reaction 20 hours of 80 DEG C of controlling reaction temperature and carries out exchange of solvent in 500mL absolute methanols, 6 hours
Afterwards, it filters, then zinc powder is washed away with dilute hydrochloric acid, remaining triphenylphosphine in finally being reacted only with massive laundering, 80 DEG C of dryings of vacuum
Obtain within 12 hours the poly- to benzene analog derivative of rutgers sealing end.
B. end group hydrolysis
First step reaction is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, product is made, is added
0.4mol sodium hydroxides, 120mL tetrahydrofurans, 80mL distilled water, back flow reaction 8 hours is cooling, dilute with mass fraction 30%
Sulphur acid for adjusting pH value is 3, and heating is boiled to there is powder sample precipitation, with massive laundering to neutrality, 80 DEG C of vacuum drying after suction filtration
12 hours, obtain withThe polyphenyl analog derivative blocked for the phthalic acid of substituent group.
The tetramines aromatic is 3,3', 4,4'- biphenyl tetramines.
The solvent is n,N-Dimethylformamide.
The polyamic acid is prepared by 4,4 '-diaminodiphenyl ethers and pyromellitic acid dianhydride, and preparation method is：By 4,
4 '-diaminodiphenyl ethers are dissolved in n,N-Dimethylformamide, and equimolar pyromellitic acid dianhydride is added under nitrogen protection,
Ice bath stirring 5h to get.
The heat treatment includes：Under the conditions of existing for nitrogen, it is heated to 420 DEG C.
Embodiment 3
Electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method,
(1) by the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer with molar ratio 1：1 is dissolved in
In solvent, precursor solution is made；
(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, is received by method of electrostatic spinning formation
The molar ratio of rice fiber, the polyamic acid and substituted benzene oligomer monomer is 1：1；
(3) it after drying above-mentioned nanofiber, is heat-treated fine to get polyphenylene derivatives/polyimides composite Nano
Dimension.
The structural formula of the substituted benzene oligomer of the described adjacent dicarboxyl benzene sealing end is：
Wherein R1For
The preparation method of the substituted benzene oligomer of neighbour's dicarboxyl benzene sealing end is：
A. coupling reaction is blocked
0.1mol2,5- dichloro benzophenones are added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device
Reaction monomers, 0.01mol4- bromos rutgers are urged as end-capping reagent, the rear 0.011mol nickel chloride bipyridyls that are added
Agent, 0.33mol zinc powders make reducing agent, and 0.044mol triphenylphosphines make complexing agent, and 250mL water removal dimethylacetylamides react
Solvent pours into after the reaction 20 hours of 80 DEG C of controlling reaction temperature and carries out exchange of solvent in 500mL absolute methanols while hot, after 6 hours,
It filters, then washes away zinc powder with dilute hydrochloric acid, remaining triphenylphosphine in finally being reacted only with massive laundering, 80 DEG C of dryings 12 of vacuum are small
When obtain the poly- to benzene analog derivative of rutgers sealing end.
B. end group hydrolysis
First step reaction is added in the flask with four necks,round bottom equipped with nitrogen protection reflux condensate device, product is made, is added
0.4mol sodium hydroxides, 120mL tetrahydrofurans, 80mL distilled water, back flow reaction 8 hours is cooling, dilute with mass fraction 30%
Sulphur acid for adjusting pH value is 3, and heating is boiled to there is powder sample precipitation, with massive laundering to neutrality, 80 DEG C of vacuum drying after suction filtration
12 hours, obtain withFor the polyphenyl analog derivative of the O-phthalic acid blocked of substituent group.
The tetramines aromatic is 3,3', 4,4'- biphenyl tetramines.
The solvent is n,N-Dimethylformamide.
The polyamic acid is prepared by 4,4 '-diaminodiphenyl ethers and pyromellitic acid dianhydride, and preparation method is：By 4,
4 '-diaminodiphenyl ethers are dissolved in n,N-Dimethylformamide, and equimolar pyromellitic acid dianhydride is added under nitrogen protection,
Ice bath stirring 5h to get.
The heat treatment includes：Under the conditions of existing for nitrogen, it is heated to 420 DEG C.
Performance test
1. fibre diameter measures
Pattern and fibre diameter carry out observation survey using scanning electron microscope (VEGA3LMU, Tescan companies of Czech)
Fixed, diameter range is ± 20nm.
2. the measurement of the tensile strength of fibre single thread (bioassay standard uses GB/T 9997-88)
It is measured, the result of each sample using JQ03new type Miniature tensions instrument (upper marine morning Digital Equipment Co., Ltd)
It is obtained by the average value of 10 this group of samples
3. the measurement of fibre single thread elongation at break (bioassay standard uses GB/T 9997-88)
It is measured with the miniature control electronic universal testers 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).
Test result is listed in Table 1 below.
Table 1
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express inaccuracy due to and not
The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended
Claim covers.
Claims (9)
1. electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber preparation method, which is characterized in that including following step
Suddenly：
(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene sealing end and tetramines aromatic monomer are dissolved in solvent, forerunner is made
Liquid solution；
(2) in above-mentioned precursor solution, polyamic acid is added, forms mixed solution, Nanowire is formed by method of electrostatic spinning
The molar ratio of dimension, the polyamic acid and substituted benzene oligomer monomer is (0.1-5)：1；
(3) it after drying above-mentioned nanofiber, is heat-treated to get polyphenylene derivatives/polyimides composite nano fiber；Institute
The general structure of substituted benzene oligomer for the adjacent dicarboxyl benzene sealing end stated is：
Wherein R1Selected from CH3O-、In one kind.
2. electrospinning high-performance polyphenylene derivatives as described in claim 1/polyimides composite nano fiber preparation method, special
Sign is that the general structure of the tetramines aromatic is：
Wherein R2It is selected fromMiddle one kind.
3. electrospinning high-performance polyphenylene derivatives as described in claim 1/polyimides composite nano fiber preparation method, special
Sign is that the polyamic acid is prepared by the raw material comprising diamines and dianhydride.
4. electrospinning high-performance polyphenylene derivatives as described in claim 1/polyimides composite nano fiber preparation method, special
Sign is that the solvent is selected from n,N-Dimethylformamide, N, N- diethylformamides, n,N-dimethylacetamide, N, N-
Diethyl acetamide, N, N- Valpromides, N, N- dimethyl benzamides, n-methyl-2-pyrrolidone, N- ethyls -2-
Pyrrolidones, N- isopropyls -2-Pyrrolidone, N- isobutyl groups -2-Pyrrolidone, N- n-propyls -2-Pyrrolidone, the positive fourths of N-
Base -2-Pyrrolidone, n-cyclohexyl-2-pyrrolidone, N- methyl -3- N-methyl-2-2-pyrrolidone Ns, N- ethyl -3- methyl-pyrrols
Alkanone, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyl -2- piperidones, N- isopropyls -
2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidines ketone, dimethyl sulfoxide (DMSO), diethyl sulfoxide, ring
At least one of fourth sulfone, diphenyl sulphone (DPS).
5. electrospinning high-performance polyphenylene derivatives as described in claim 1/polyimides composite nano fiber preparation method, special
Sign is that the heat treatment includes：Under the conditions of existing for inert gas, it is heated to 300 DEG C -500 DEG C.
6. electrospinning high-performance polyphenylene derivatives as described in claim 1/polyimides composite nano fiber preparation method, special
Sign is that the heat treatment includes：Under the conditions of existing for inert gas, it is heated to 350 DEG C -450 DEG C.
7. electrospinning high-performance polyphenylene derivatives as described in claim 1/polyimides composite nano fiber preparation method, special
Sign is that the heat treatment includes：Under the conditions of existing for inert gas, it is heated to 420 DEG C.
8. as prepared by claim 5-7 any one of them electrospinning high-performance polyphenylene derivatives/polyimides composite nano fiber
Method, which is characterized in that the inert gas is selected from least one of nitrogen, argon gas.
9. polyphenylene derivatives/polyimides composite nano fiber, which is characterized in that use claim 1-8 any one of them
What method was prepared.
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