CN106435828A - Preparation method of electrospun high-performance polyphenyl derivative/polyimide composite nanofibers - Google Patents
Preparation method of electrospun high-performance polyphenyl derivative/polyimide composite nanofibers Download PDFInfo
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- CN106435828A CN106435828A CN201610846857.4A CN201610846857A CN106435828A CN 106435828 A CN106435828 A CN 106435828A CN 201610846857 A CN201610846857 A CN 201610846857A CN 106435828 A CN106435828 A CN 106435828A
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- Prior art keywords
- composite nano
- nano fiber
- methyl
- polyimides composite
- pyrrolidone
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 35
- 239000004642 Polyimide Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229920001721 polyimide Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920006389 polyphenyl polymer Polymers 0.000 title abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001523 electrospinning Methods 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 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
- 150000001555 benzenes Chemical class 0.000 claims description 36
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- -1 polyphenylene Polymers 0.000 claims description 23
- 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
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 17
- 229910052756 noble gas Inorganic materials 0.000 claims description 12
- 150000002835 noble gases Chemical class 0.000 claims description 12
- 238000010041 electrostatic spinning Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- 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
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical class CCN1CCCCC1=O VUQMOERHEHTWPE-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
- GVDQKJQFVPXADH-UHFFFAOYSA-N 1-propan-2-ylpiperidin-2-one Chemical class CC(C)N1CCCCC1=O GVDQKJQFVPXADH-UHFFFAOYSA-N 0.000 claims description 3
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 claims description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound 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
- 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 compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 claims description 3
- 229960001930 valpromide Drugs 0.000 claims description 3
- LPRJTTSNPNSAEB-UHFFFAOYSA-N 1-ethyl-3-methylpyrrole Chemical compound CCN1C=CC(C)=C1 LPRJTTSNPNSAEB-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 abstract description 11
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 23
- 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 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- NIQCNGHVCWTJSM-UHFFFAOYSA-N dimethyl benzenedicarboxylate Natural products COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 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
- 238000010992 reflux Methods 0.000 description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 6
- 229960001826 dimethylphthalate Drugs 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
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-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
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 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
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 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
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 2
- IVVVGBHWWAJRAY-UHFFFAOYSA-N 1-ethyl-3-methylpyrrolidin-2-one Chemical compound CCN1CCC(C)C1=O IVVVGBHWWAJRAY-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 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
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 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
- 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
- 239000000126 substance Substances 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
- 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
- 241001274660 Modulus Species 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008331 benzenesulfonamides Chemical class 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
- 238000005138 cryopreservation Methods 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-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
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- IAYUQKZZQKUOFL-UHFFFAOYSA-N pyridine-2,3,5,6-tetramine Chemical compound NC1=CC(N)=C(N)N=C1N IAYUQKZZQKUOFL-UHFFFAOYSA-N 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
- 238000007493 shaping process 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nonwoven Fabrics (AREA)
Abstract
A preparation method of electrospun high-performance polyphenyl derivative/polyimide composite nanofibers comprises steps as follows: (1) o-benzene-dicarboxyl-terminated substituted benzene oligomer monomers and aromatic tetramine monomers are dissolved in a solvent, and a precursor solution is prepared; (2) polyamic acid is added to the precursor solution, a mixed solution is formed, nanofibers are formed with an electrospinning method, and the mole ratio of polyamic acid to the substituted benzene oligomer monomers is (0.1-5):1; (3) the nanofibers are subjected to heat treatment after being dried, and the polyphenyl derivative/polyimide composite nanofibers are obtained.
Description
Technical field
The present invention relates to a kind of preparation method of composite nano fiber, particularly to a kind of electrospinning high-performance poly benzenesulfonamide derivative
The preparation method of thing/polyimides composite nano fiber.
Background technology
Polyphenyl is the rigid chain polymer that a class is connected by phenyl, has excellent heat-resisting quantity, and the heat in nitrogen is divided
Up to 900 DEG C of solution temperature, can at 400 DEG C life-time service；There is the characteristics such as excellent resistance to chemical attack, 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., can be used for chemical industry equipment under mal-condition, aerospace equipment, high-speed cruising military
On device, it may also be used for High temperature ion exchanger resin.
But, polyphenyl is not melt insoluble polymer, difficult shaping, difficult processing.Using introducing substituent group 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
Dissolubility in organic solvent remains on less, and because solubility property is poor, the molecular weight of typically synthesized polyphenylene derivatives is all
Low, it is difficult to be prepared into electro spinning nano fiber.
Content of the invention
In order to solve prior art problem, a first aspect of the present invention a kind of electrospinning high-performance poly benzene derivative of offer/poly-
Acid imide composite nano fiber preparation method, comprises the following steps：
(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene end-blocking and tetramines aromatic monomer are dissolved in solvent, are obtained
Precursor solution；
(2) in above-mentioned precursor solution, add polyamic acid, form mixed solution, formed by method of electrostatic spinning and receive
Rice fiber, described polyamic acid is (0.1-5) with the mol ratio of substituted benzene oligomer monomer：1；
(3) after above-mentioned nanofiber being dried, carry out heat treatment, obtain final product polyphenylene derivatives/polyimides composite Nano fine
Dimension.
In some embodiments, the general structure of the described substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is：
Wherein R1Selected from CH3O-、One of.
In some embodiments, the general structure of described tetramines aromatic is：
Wherein R2It is selected fromMiddle one kind.
In some embodiments, described polyamic acid is prepared by the raw material comprising diamidogen and dianhydride.
In some embodiments, described solvent is selected from DMF, N, N- diethylformamide, N, N-
Dimethyl acetylamide, N, N- diethyl acetamide, N, N- Valpromide, N, N- dimethyl benzamide, N- methyl -2- pyrrole
Pyrrolidone, N- ethyl-2-pyrrolidone, N- isopropyl -2-Pyrrolidone, N- isobutyl group -2-Pyrrolidone, N- n-pro-pyl -2-
Ketopyrrolidine, N- normal-butyl -2-Pyrrolidone, CHP, N- methyl -3- N-methyl-2-2-pyrrolidone N, N-
Ethyl -3- methyl-pyrrolidon, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyl -2-
Piperidones, N- isopropyl -2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidine ketone, dimethyl are sub-
At least one in sulfone, diethyl sulfoxide, sulfolane, diphenyl sulphone (DPS).
In some embodiments, described heat treatment includes：Noble gases exist under conditions of, be heated to 300 DEG C-
500℃.
In some embodiments, described heat treatment includes：Noble gases exist under conditions of, be heated to 350 DEG C-
450℃.
In some embodiments, described heat treatment includes：Under conditions of noble gases exist, it is heated to 420 DEG C.
In some embodiments, at least one in nitrogen, argon for the described noble gases.
A second aspect of the present invention provides polyphenylene derivatives/polyimides composite nano fiber, using side as above
Method prepares.
As module unitss, tetramines aromatic is hinge agent to the substituted benzene oligomer that the present invention is blocked with adjacent dicarboxyl benzene, and plus
Enter polyamic acid, polyphenylene derivatives/polyimides composite nano fiber is obtained by method of electrostatic spinning.Polyamic acid is in hot-cast socket
During be transformed into polyimides, and the low molecular weight polyphenylene derivant chain for linking point, adjacent dicarboxyl benzene being blocked with acid imide
It is connected into the polyphenylene derivatives of macromolecule.
Specific embodiment
A first aspect of the present invention provides a kind of electrospinning high-performance poly benzene derivative/polyimides composite nano fiber preparation
Method, comprises the following steps：
(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene end-blocking and tetramines aromatic monomer are dissolved in solvent, are obtained
Precursor solution；
(2) in above-mentioned precursor solution, add polyamic acid, form mixed solution, formed by method of electrostatic spinning and receive
Rice fiber, described polyamic acid is (0.1-5) with the mol ratio of substituted benzene oligomer monomer：1；
(3) after above-mentioned nanofiber being dried, carry out heat treatment, obtain final product polyphenylene derivatives/polyimides composite Nano fine
Dimension.
The substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking
In some embodiments, the general structure of the described substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is：
Wherein R1Selected from CH3O-、One of.
R1It is preferablyGroup.
Work as R1ForDuring group, the preparation method of the substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is：
A. block coupling reaction
Add 0.1mol2,5- dichloro benzophenone in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen
Reaction monomers, 0.01mol 4- bromo dimethyl phthalate, as end-capping reagent, adds 0.011mol Nickel dichloride. bipyridyl to make afterwards
Catalyst, reducing agent made by 0.33mol zinc powder, and 0.044mol triphenylphosphine does chelating agent, 250mL eliminating water dimethyl acetylamide
(DMAc) as reaction dissolvent, the reaction of 80 DEG C of controlling reaction temperature pour into while hot after 20 hours carry out in 500mL absolute methanol molten
Agent exchanges, after 6 hours, sucking filtration, then wash away zinc powder with dilute hydrochloric acid, the triphenylphosphine of residual in finally being reacted with massive laundering is net,
80 DEG C of dryings of vacuum obtain within 12 hours dimethyl phthalate end-blocking poly- to benzene analog derivative.
Blocking coupling reaction synthetic route is：
B. end group hydrolysis
Add first step reaction that product is obtained in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen, add
0.4mol sodium hydroxide, 120mL oxolane, 80mL distilled water, back flow reaction 8 hours, cooling, is 30% with mass fraction
It is 3 that dilute sulfuric acid adjusts pH value, and heated and boiled to there being powder sample to separate out, with massive laundering to neutrality, after sucking filtration, do by 80 DEG C of vacuum
Dry 12 hours, obtain withPolyphenyl analog derivative for the phthalic acid end-blocking 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 described tetramines aromatic is：
Wherein R2It is selected fromMiddle one kind.
The instantiation of the tetramines aromatic that the present invention provides can include, for example：3,3', 5,5'- biphenyl tetramine, 3,
3', 4,4'- biphenyl tetramine, 1,2,3,5- equal benzene tetramine, 2,3,5,6- pyridine tetramine, 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', 4,4'- bis trifluoromethyl hexichol urotropine, 2,3,3', 4'- double three
Methyl fluoride hexichol urotropine, 1,4,5,8- naphthalene tetramine, 2,4,5,7- naphthalene tetramine, 2,3,6,7- naphthalene tetramine.
Polyamic acid
In some embodiments, described polyamic acid is prepared by the raw material comprising diamidogen and dianhydride.
Described diamidogen is 4,4 '-diaminodiphenyl ether (ODA), and described dianhydride is pyromellitic acid dianhydride (PMDA).
The synthetic reaction of described polyamic acid is carried out under nitrogen protection, to keep reactant not oxidized and to keep dry
Dry.First by a certain percentage diamidogen and solvent are added in there-necked flask, so that diamidogen is completely dissolved under agitation, be then dividedly in some parts
Dianhydride, at low temperature stirring reaction obtain the polyamic acid solution of pale yellow transparent, cryopreservation is stand-by.
Electrostatic spinning
Electrostatic spinning described in step (2) is a kind of special fiber fabrication process, and polymer solution or melt are strong
Carry out jet spinning in electric field.Under electric field action, the drop at syringe needle can be changed into conical (i.e. " taylor cone ") from spherical, and
Extend from conical tip and obtain fiber filaments.This mode can produce the polymer filaments of nanometer grade diameter.
The condition that described electrostatic spinning is adopted is：Spinning temperature is less than 30 DEG C；Preferably, spinning temperature is 5-30 DEG C；
It is highly preferred that spinning temperature is 10-25 DEG C.
Spinning voltage is 10-40kV；Preferably, spinning voltage is 10-30kV；It is highly preferred that spinning voltage is 20-
30kV；Spinning receiving range solidifies distance for 10-40cm；Preferably, spinning receiving range is 15-35cm；It is highly preferred that spinning
Silk receiving range is 16cm.
In some embodiments, described solvent is selected from DMF, N, N- diethylformamide, N, N-
Dimethyl acetylamide, N, N- diethyl acetamide, N, N- Valpromide, N, N- dimethyl benzamide, N- methyl -2- pyrrole
Pyrrolidone, N- ethyl-2-pyrrolidone, N- isopropyl -2-Pyrrolidone, N- isobutyl group -2-Pyrrolidone, N- n-pro-pyl -2-
Ketopyrrolidine, N- normal-butyl -2-Pyrrolidone, CHP, N- methyl -3- N-methyl-2-2-pyrrolidone N, N-
Ethyl -3- methyl-pyrrolidon, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyl -2-
Piperidones, N- isopropyl -2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidine ketone, dimethyl are sub-
At least one in sulfone, diethyl sulfoxide, sulfolane, diphenyl sulphone (DPS).
In some embodiments, described heat treatment includes：Noble gases exist under conditions of, be heated to 300 DEG C-
500℃.
In some embodiments, described heat treatment includes：Noble gases exist under conditions of, be heated to 350 DEG C-
450℃.
In some embodiments, described heat treatment includes：Under conditions of noble gases exist, it is heated to 420 DEG C.
In some embodiments, at least one in nitrogen, argon for the described noble gases.
A second aspect of the present invention provides polyphenylene derivatives/polyimides composite nano fiber, using side as above
Method prepares.
As module unitss, tetramines aromatic is hinge agent to the substituted benzene oligomer that the present invention is blocked with adjacent dicarboxyl benzene, and plus
Enter polyamic acid, polyphenylene derivatives/polyimides composite nano fiber is obtained by method of electrostatic spinning.Polyamic acid is in hot-cast socket
During be transformed into polyimides, and the low molecular weight polyphenylene derivant chain for linking point, adjacent dicarboxyl benzene being blocked with acid imide
It is connected into the polyphenylene derivatives of macromolecule.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following examples are only used
In the invention will be further described it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential improvement made according to the content of foregoing invention and adjustment, still fall within protection scope of the present invention.
In addition, if not having other explanations, raw materials used is all commercially available.
Embodiment 1
Electrospinning high-performance poly benzene derivative/polyimides composite nano fiber preparation method,
(1) by the substituted benzene oligomer monomer of adjacent dicarboxyl benzene end-blocking and tetramines aromatic monomer with mol ratio 1：1 is dissolved in
In solvent, prepared precursor solution；
(2) in above-mentioned precursor solution, add polyamic acid, form mixed solution, formed by method of electrostatic spinning and receive
Rice fiber, described polyamic acid is 0.1 with the mol ratio of substituted benzene oligomer monomer：1；
(3) after above-mentioned nanofiber being dried, carry out heat treatment, obtain final product polyphenylene derivatives/polyimides composite Nano fine
Dimension.
The structural formula of the substituted benzene oligomer of described adjacent dicarboxyl benzene end-blocking is：
Wherein R1For
The preparation method of substituted benzene oligomer of described neighbour's dicarboxyl benzene end-blocking is：
A. block coupling reaction
Add 0.1mol2,5- dichloro benzophenone in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen
Reaction monomers, 0.01mol 4- bromo dimethyl phthalate, as end-capping reagent, adds 0.011mol Nickel dichloride. bipyridyl to make afterwards
Catalyst, reducing agent made by 0.33mol zinc powder, and 0.044mol triphenylphosphine makees chelating agent, and 250mL eliminating water dimethyl acetylamide is made anti-
Answer solvent, 80 DEG C of reactions of controlling reaction temperature are poured into while hot after 20 hours and carried out solvent exchange in 500mL absolute methanol, 6 hours
Afterwards, sucking filtration, then wash away zinc powder with dilute hydrochloric acid, the triphenylphosphine of residual, 80 DEG C of dryings of vacuum in finally being reacted with massive laundering is net
Obtain within 12 hours gathering to benzene analog derivative of dimethyl phthalate end-blocking.
B. end group hydrolysis
Add first step reaction that product is obtained in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen, add
0.4mol sodium hydroxide, 120mL oxolane, 80mL distilled water, back flow reaction 8 hours, cooling, dilute with mass fraction 30%
Sulfur acid for adjusting pH value is 3, and to there being powder sample to separate out, with massive laundering to neutrality, after sucking filtration, 80 DEG C are vacuum dried heated and boiled
12 hours, obtain withPolyphenyl analog derivative for the phthalic acid end-blocking of substituent group.
Described tetramines aromatic is 3,3', 4,4'- biphenyl tetramine.
Described solvent is DMF.
Described polyamic acid is prepared by 4,4 '-diaminodiphenyl ether and pyromellitic acid dianhydride, and preparation method is：By 4,
4 '-diaminodiphenyl ether is dissolved in DMF, adds equimolar pyromellitic acid dianhydride under nitrogen protection,
Ice bath stirs 5h, obtains final product.
Described heat treatment includes：Under conditions of nitrogen exists, it is heated to 420 DEG C.
Embodiment 2
Electrospinning high-performance poly benzene derivative/polyimides composite nano fiber preparation method,
(1) by the substituted benzene oligomer monomer of adjacent dicarboxyl benzene end-blocking and tetramines aromatic monomer with mol ratio 1：1 is dissolved in
In solvent, prepared precursor solution；
(2) in above-mentioned precursor solution, add polyamic acid, form mixed solution, formed by method of electrostatic spinning and receive
Rice fiber, described polyamic acid is 5 with the mol ratio of substituted benzene oligomer monomer：1；
(3) after above-mentioned nanofiber being dried, carry out heat treatment, obtain final product polyphenylene derivatives/polyimides composite Nano fine
Dimension.
The structural formula of the substituted benzene oligomer of described adjacent dicarboxyl benzene end-blocking is：
Wherein R1For
The preparation method of substituted benzene oligomer of described neighbour's dicarboxyl benzene end-blocking is：
A. block coupling reaction
Add 0.1mol2,5- dichloro benzophenone in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen
Reaction monomers, 0.01mol 4- bromo dimethyl phthalate, as end-capping reagent, adds 0.011mol Nickel dichloride. bipyridyl to make afterwards
Catalyst, reducing agent made by 0.33mol zinc powder, and 0.044mol triphenylphosphine makees chelating agent, and 250mL eliminating water dimethyl acetylamide is made anti-
Answer solvent, 80 DEG C of reactions of controlling reaction temperature are poured into while hot after 20 hours and carried out solvent exchange in 500mL absolute methanol, 6 hours
Afterwards, sucking filtration, then wash away zinc powder with dilute hydrochloric acid, the triphenylphosphine of residual, 80 DEG C of dryings of vacuum in finally being reacted with massive laundering is net
Obtain within 12 hours gathering to benzene analog derivative of dimethyl phthalate end-blocking.
B. end group hydrolysis
Add first step reaction that product is obtained in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen, add
0.4mol sodium hydroxide, 120mL oxolane, 80mL distilled water, back flow reaction 8 hours, cooling, dilute with mass fraction 30%
Sulfur acid for adjusting pH value is 3, and to there being powder sample to separate out, with massive laundering to neutrality, after sucking filtration, 80 DEG C are vacuum dried heated and boiled
12 hours, obtain withPolyphenyl analog derivative for the phthalic acid end-blocking of substituent group.
Described tetramines aromatic is 3,3', 4,4'- biphenyl tetramine.
Described solvent is DMF.
Described polyamic acid is prepared by 4,4 '-diaminodiphenyl ether and pyromellitic acid dianhydride, and preparation method is：By 4,
4 '-diaminodiphenyl ether is dissolved in DMF, adds equimolar pyromellitic acid dianhydride under nitrogen protection,
Ice bath stirs 5h, obtains final product.
Described heat treatment includes：Under conditions of nitrogen exists, it is heated to 420 DEG C.
Embodiment 3
Electrospinning high-performance poly benzene derivative/polyimides composite nano fiber preparation method,
(1) by the substituted benzene oligomer monomer of adjacent dicarboxyl benzene end-blocking and tetramines aromatic monomer with mol ratio 1：1 is dissolved in
In solvent, prepared precursor solution；
(2) in above-mentioned precursor solution, add polyamic acid, form mixed solution, formed by method of electrostatic spinning and receive
Rice fiber, described polyamic acid is 1 with the mol ratio of substituted benzene oligomer monomer：1；
(3) after above-mentioned nanofiber being dried, carry out heat treatment, obtain final product polyphenylene derivatives/polyimides composite Nano fine
Dimension.
The structural formula of the substituted benzene oligomer of described adjacent dicarboxyl benzene end-blocking is：
Wherein R1For
The preparation method of substituted benzene oligomer of described neighbour's dicarboxyl benzene end-blocking is：
A. block coupling reaction
Add 0.1mol2,5- dichloro benzophenone in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen
Reaction monomers, 0.01mol4- bromo dimethyl phthalate, as end-capping reagent, adds 0.011mol Nickel dichloride. bipyridyl to urge afterwards
Agent, reducing agent made by 0.33mol zinc powder, and 0.044mol triphenylphosphine makees chelating agent, and 250mL eliminating water dimethyl acetylamide reacts
Solvent, 80 DEG C of reactions of controlling reaction temperature are poured into while hot after 20 hours and are carried out solvent exchange in 500mL absolute methanol, after 6 hours,
Sucking filtration, then wash away zinc powder with dilute hydrochloric acid, the triphenylphosphine of residual in finally being reacted with massive laundering is net, 80 DEG C of dryings 12 of vacuum are little
When obtain dimethyl phthalate end-blocking poly- to benzene analog derivative.
B. end group hydrolysis
Add first step reaction that product is obtained in the flask with four necks,round bottom protecting reflux condensate device equipped with nitrogen, add
0.4mol sodium hydroxide, 120mL oxolane, 80mL distilled water, back flow reaction 8 hours, cooling, dilute with mass fraction 30%
Sulfur acid for adjusting pH value is 3, and to there being powder sample to separate out, with massive laundering to neutrality, after sucking filtration, 80 DEG C are vacuum dried heated and boiled
12 hours, obtain withPolyphenyl analog derivative for the O-phthalic acid blocked of substituent group.
Described tetramines aromatic is 3,3', 4,4'- biphenyl tetramine.
Described solvent is DMF.
Described polyamic acid is prepared by 4,4 '-diaminodiphenyl ether and pyromellitic acid dianhydride, and preparation method is：By 4,
4 '-diaminodiphenyl ether is dissolved in DMF, adds equimolar pyromellitic acid dianhydride under nitrogen protection,
Ice bath stirs 5h, obtains final product.
Described heat treatment includes：Under conditions of nitrogen exists, it is heated to 420 DEG C.
Performance test
1. fibre diameter measures
Pattern and fibre diameter carry out observing survey using scanning electron microscope (VEGA3LMU, Tescan company of Czech)
Fixed, diameter range is ± 20nm.
2. the mensure (bioassay standard adopts GB/T 9997-88) of the tensile strength of fibre single thread
Recorded, the result of every kind of sample using JQ03new type Miniature tension instrument (upper marine morning DEC)
Drawn by the meansigma methodss of 10 this group samples
3. the mensure (bioassay standard adopts GB/T 9997-88) of fibre single thread elongation at break
Measured with CMT8102 miniature control electronic universal tester (Shenzhen SANS material tests company limited)；
4. the mensure of Young's moduluss
Measured using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education company limited).
Test result is listed in Table 1 below.
Table 1
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim
It is intended to the scope as wide as possible requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
The embodiment of the selection of combination explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
The example of feature selectional restriction.And the progress in science and technology will be formed due to language performance inaccurate reason and not
The possible equivalent being presently considered or son are replaced, and these changes also should be interpreted by appended in the conceived case
Claim covers.
Claims (10)
1. electrospinning high-performance poly benzene derivative/polyimides composite nano fiber preparation method is it is characterised in that include following walking
Suddenly：
(1) the substituted benzene oligomer monomer of adjacent dicarboxyl benzene end-blocking and tetramines aromatic monomer are dissolved in solvent, prepared forerunner
Liquid solution；
(2) in above-mentioned precursor solution, add polyamic acid, form mixed solution, Nanowire is formed by method of electrostatic spinning
Dimension, described polyamic acid is (0.1-5) with the mol ratio of substituted benzene oligomer monomer：1；
(3), after above-mentioned nanofiber being dried, carry out heat treatment, obtain final product polyphenylene derivatives/polyimides composite nano fiber.
2. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, the general structure of the described substituted benzene oligomer of adjacent dicarboxyl benzene end-blocking is：
Wherein R1Selected from CH3O-、One of.
3. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, the general structure of described tetramines aromatic is：
Wherein R2It is selected fromMiddle one kind.
4. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, described polyamic acid is prepared by the raw material comprising diamidogen and dianhydride.
5. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, described solvent is selected from DMF, N, N- diethylformamide, N,N-dimethylacetamide, N, N-
Diethyl acetamide, N, N- Valpromide, N, N- dimethyl benzamide, METHYLPYRROLIDONE, N- ethyl -2-
Ketopyrrolidine, N- isopropyl -2-Pyrrolidone, N- isobutyl group -2-Pyrrolidone, N- n-pro-pyl -2-Pyrrolidone, the positive fourth of N-
Base -2-Pyrrolidone, CHP, N- methyl -3- N-methyl-2-2-pyrrolidone N, N- ethyl -3- methyl-pyrrol
Alkanone, N- methyl -3,4,5- trimethyls -2-Pyrrolidone, N- methyl -2- piperidones, N- ethyl -2- piperidones, N- isopropyl -
2- piperidones, N- methyl -6- methyl -2- piperidones, N- methyl -3- ethyl piperidine ketone, dimethyl sulfoxide, diethyl sulfoxide, ring
At least one in fourth sulfone, diphenyl sulphone (DPS).
6. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, described heat treatment includes：Under conditions of noble gases exist, it is heated to 300 DEG C -500 DEG C.
7. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, described heat treatment includes：Under conditions of noble gases exist, it is heated to 350 DEG C -450 DEG C.
8. electrospinning high-performance poly benzene derivative as claimed in claim 1/polyimides composite nano fiber preparation method, it is special
Levy and be, described heat treatment includes：Under conditions of noble gases exist, it is heated to 420 DEG C.
9. the electrospinning high-performance poly benzene derivative as described in any one of claim 6-8/polyimides composite nano fiber preparation
Method is it is characterised in that described noble gases are selected from nitrogen, at least one in argon.
10. polyphenylene derivatives/polyimides composite nano fiber is it is characterised in that usage right requires described in any one of 1-9
Method prepares.
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| CN101016381A (en) * | 2007-02-07 | 2007-08-15 | 哈尔滨工业大学 | Method of preparing polybenzoxazole-imide and its fiber |
| CN101473080A (en) * | 2006-06-22 | 2009-07-01 | 东洋纺织株式会社 | Polyimide nonwoven fabric and process for production thereof |
| JP2014214401A (en) * | 2013-04-26 | 2014-11-17 | 新日鉄住金化学株式会社 | Polyimide fiber, production method thereof and polyimide for fiber |
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| CN101473080A (en) * | 2006-06-22 | 2009-07-01 | 东洋纺织株式会社 | Polyimide nonwoven fabric and process for production thereof |
| CN101016381A (en) * | 2007-02-07 | 2007-08-15 | 哈尔滨工业大学 | Method of preparing polybenzoxazole-imide and its fiber |
| JP2014214401A (en) * | 2013-04-26 | 2014-11-17 | 新日鉄住金化学株式会社 | Polyimide fiber, production method thereof and polyimide for fiber |
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