CN105714400B - A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat nanofiber - Google Patents
A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat nanofiber Download PDFInfo
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- CN105714400B CN105714400B CN201510633460.2A CN201510633460A CN105714400B CN 105714400 B CN105714400 B CN 105714400B CN 201510633460 A CN201510633460 A CN 201510633460A CN 105714400 B CN105714400 B CN 105714400B
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- pyrrole throat
- tackified polymeric
- ammonium carboxylate
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000002121 nanofiber Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001523 electrospinning Methods 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 22
- 230000003068 static effect Effects 0.000 claims abstract description 4
- -1 Ammonium carboxylate salts Chemical class 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 30
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 26
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 abstract description 5
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000011259 mixed solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000835 fiber Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- 238000010041 electrostatic spinning Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 7
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000004040 pyrrolidinones Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The present invention provides the preparation methods that a kind of molecule based on electrospinning assembles poly- pyrrole throat nanofiber, include the following steps：Poly- pyrrole throat precursor solution containing Tackified polymeric is provided；Poly- pyrrole throat precursor solution, obtains composite nano fiber described in Static Spinning；Thermally decompose the Tackified polymeric in the composite nano fiber, poly- pyrrole throat monomer is first converted into polyamic acid ammonium salt in temperature-rise period, and then conversion obtains poly- pyrrole throat nanofiber under final high temperature.
Description
Technical field
This disclosure relates to a kind of preparation methods of nanofiber.More specifically, this disclosure relates to one kind to be based on
The molecule of electrospinning assembles the preparation method of poly- pyrrole throat nanofiber.
Background technique
Poly- pyrrole throat is the trapezoidal or half trapezoidal poly- heteroaromatic macromolecule polyalcohol of a kind of rigidity, has good heat-resisting quantity
And inoxidizability, the decomposition temperature of the poly- pyrrole throat in part are more than 700 DEG C.It is fine that this polymer fiber is not only a kind of heat-resistant fireproof
Dimension, or a kind of high-intensitive, the high-performance fiber of high-modulus.So far from the sixties in last century, which has obtained
Extensive research is usually to be polymerized in the high boiling solvents high temperature such as polyphosphoric acids.Since poly- pyrrole throat neither melts,
Ordinary organic solvents are also insoluble in, machinability is greatly limited, while the exploitation being applied to causes greatly
It hinders.Moreover, its insoluble characteristic that do not melt makes that the quasi polymer cannot be prepared with melting electrostatic spinning or solution electrostatic spinning
Nano-scale fiber.In addition, tradition prepares poly- pyrrole throat crude fibre or film is to be dissolved in the superpower matter such as methanesulfonic acid, chlorosulfonic acid
It processes and obtains in sub- acid, these solvent toxicities are strong, easily cause environmental pollution.
Hence it is highly desirable to which by the improvement of formula and production technology, the more environmentally friendly method of use prepares nanoscale
Polypyrron fibre.
Summary of the invention
To solve the above-mentioned problems, one aspect of the present invention, which discloses a kind of molecule based on electrospinning and assembles poly- pyrrole throat, receives
The preparation method of rice fiber, includes the following steps：
Poly- pyrrole throat precursor solution containing Tackified polymeric is provided；
Poly- pyrrole throat precursor solution, obtains composite nano fiber described in Static Spinning；
Decompose the Tackified polymeric in the composite nano fiber at high temperature, meanwhile, poly- pyrrole throat monomer was heating up
Acyl is condensed to form polyamic acid ammonium salt in journey, and poly- pyrrole throat nanofiber is converted under final high temperature.
Preferably, the poly- pyrrole throat precursor solution of the offer containing Tackified polymeric includes：
Ammonium carboxylate salts containing tetracid and tetramine are provided, and
The ammonium carboxylate salts and Tackified polymeric solution are contacted, poly- pyrrole throat precursor solution is formed.
In one embodiment, the tetracid is selected from following at least one：
In one embodiment, the tetramine is selected from following at least one：
In one embodiment, in the ammonium carboxylate salts, the weight of tetracid and tetramine and the ammonium carboxylate salt is accounted for
The 20%~50% of solution weight.
In one embodiment, in the ammonium carboxylate salts, the molar ratio of tetracid and tetramine is 1.05:1~0.95:
1。
In one embodiment, the inherent viscosity of the Tackified polymeric solution is 2.0~4.5.
In one embodiment, the Tackified polymeric in polyvinylpyrrolidone and polyethylene oxide one
Kind or two kinds.
In one embodiment, the weight of the Tackified polymeric accounts for the 5% of the poly- pyrrole throat precursor solution weight
~30%.
In one embodiment, make 150 DEG C of program that the Tackified polymeric in the composite nano fiber thermally decomposes
Constant temperature 60min, 280 DEG C of constant temperature 60min, 430 DEG C of constant temperature 20min, finally anneal at 450~550 DEG C 2~30min.
In one embodiment, the ammonium carboxylate salt in the composite nano fiber is made to be converted into polyamic acid at 150 DEG C
Ammonium salt；Poly- pyrrole throat is converted at 430-550 DEG C.
Another aspect of the present invention relates to the poly- pyrrole throat nanofibers being prepared with any method.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Detailed description of the invention
Fig. 1 is in the specific embodiment of the invention, and (figure A's scanning electron microscope (SEM) photograph of the 7 poly- pyrrole throat nanofiber of gained of embodiment exists
It is tested under 50 microns, figure B is tested under 20 microns).
Fig. 2 indicate the poly- pyrrole throat nanofiber of the gained of embodiment 7 mechanical strength at different temperatures, elongation at break and
Modulus.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily to understand
Open content.A large amount of terms can be referred in following description and claims, these terms are defined as following meanings.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise.
" any ", " optional " or " optionally " refer to that the item described thereafter or event may or may not occur,
And the description includes the situation that event occurs and the situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
One aspect of the present invention is related to the preparation method that a kind of molecule based on electrospinning assembles poly- pyrrole throat nanofiber, packet
Include following steps：
Poly- pyrrole throat precursor solution containing Tackified polymeric is provided；
Poly- pyrrole throat precursor solution, obtains composite nano fiber described in electrostatic spinning；
Thermally decompose the Tackified polymeric in the composite nano fiber, poly- pyrrole throat monomer is first converted into temperature-rise period
Then polyamic acid ammonium salt is converted into poly- pyrrole throat nanofiber under final high temperature.
Preferably, the poly- pyrrole throat precursor solution of the offer containing Tackified polymeric includes：
Ammonium carboxylate salts containing tetracid and tetramine are provided, and
Make the ammonium carboxylate salts and Tackified polymeric solution blending, forms poly- pyrrole throat precursor solution.
The term " ammonium carboxylate salts " of the application, which refers to for tetracid and tetramine monomers to be dissolved in organic good solvent, to be obtained
It arrives, by molecule assembling, (weak acid-base function or electrostatic attraction effect between carboxylic acid and amino are that this be assembled into is divided greatly to monomer
The power of son) ammonium carboxylate salts are formed, so that the appearance of gel is prevented, such as：It can will rub under conditions of being lower than 25 DEG C
You are than being 1:1 tetracid and tetramine monomers is dissolved in DMAc, and between 30%-35%, magnetic agitation 2h is obtained controlled concentration
It arrives.
In one embodiment, the tetracid is selected from following at least one：
Preferably, the tetracid is selected from following at least one：
It is highly preferred that the tetracid is selected from following at least one：
In one embodiment, the tetramine is selected from following at least one：
Preferably, the tetramine is selected from following at least one：
It is highly preferred that the tetramine is：
Being used to prepare the organic good solvents of the ammonium carboxylate salts, there is no particular restriction, as long as can make tetracid and tetramine
It dissolves or is partly dissolved, dimethyl sulfoxide, N-Methyl pyrrolidone, n,N-Dimethylformamide and N, N- can be selected from
Any one of dimethyl acetamide is several；But preferably, it is used to prepare the organic good solvent of the ammonium carboxylate salts
For DMAC N,N' dimethyl acetamide.
In one embodiment, in the ammonium carboxylate salts, the weight of tetracid and tetramine and the ammonium carboxylate salt is accounted for
The 20%~50% of solution weight；Preferably, the weight of tetracid and tetramine and account for the ammonium carboxylate salts weight 30%~
40%；It is highly preferred that the weight of tetracid and tetramine and accounting for the 35% of the ammonium carboxylate salts weight.
In one embodiment, in the ammonium carboxylate salts, the molar ratio of tetracid and tetramine is 1.05:1~0.95:
1；Preferably, the molar ratio of tetracid and tetramine is 1.01:1~0.99:1；It is highly preferred that the molar ratio of tetracid and tetramine is 1:1.
The term " Tackified polymeric solution " of the application is that Tackified polymeric is dissolved in organic good solvent to obtain.For
The inherent viscosity of the Tackified polymeric solution of the application is 2.0~4.5；Preferably, the characteristic of the Tackified polymeric solution is viscous
Degree is 3.3~4.0；It is highly preferred that the inherent viscosity of the Tackified polymeric solution is 3.7.
In one embodiment, the Tackified polymeric in polyvinylpyrrolidone and polyethylene oxide one
Kind or two kinds.
Being used to prepare the organic good solvent of the Tackified polymeric solution, there is no particular restriction, as long as can make Tackified polymeric
Dissolution, it is adducible to have dimethyl sulfoxide, N-Methyl pyrrolidone, n,N-Dimethylformamide and N, N- dimethyl
Acetamide etc.；But the organic good solvent for preferably, being used to prepare the Tackified polymeric solution is n,N-dimethylacetamide.
In one embodiment, the weight of the Tackified polymeric accounts for the 5% of the poly- pyrrole throat precursor solution weight
~30%；Preferably, the weight of the Tackified polymeric accounts for the 10%~20% of the poly- pyrrole throat precursor solution weight；It is more excellent
Selection of land, the weight of the Tackified polymeric account for the 15% of the poly- pyrrole throat precursor solution weight.
The term " electrostatic spinning " of the application is a kind of special fiber fabrication process, and polymer solution or melt are in forceful electric power
Jet spinning is carried out in.Under electric field action, the drop at needle point can be become conical (i.e. " taylor cone ") from spherical shape, and from
Conical tip extends to obtain fiber filaments.It is anode 15KV, cathode-that electrostatic spinning process, which is preferably spinning voltage, in the application
2KV, the distance of needle point to reception device are 25cm, and are collected to obtain the composite Nano fibre of fiber orientation with high-speed rotating flywheel
Tie up band.
The program for thermally decomposing the Tackified polymeric in the composite nano fiber in the application is preferably 150 DEG C of constant temperature
60min, 280 DEG C of constant temperature 60min, 430 DEG C of constant temperature 20min, finally anneal at 450~550 DEG C 2~30min.
The another aspect of the application is related to the poly- pyrrole throat nanofiber that the either method is prepared.
The application includes following implementation：
The preparation method of poly- pyrrole throat nanofiber is prepared described in 1. the content of present invention of embodiment, including is walked as follows
Suddenly：
Poly- pyrrole throat precursor solution containing Tackified polymeric is provided；
Poly- pyrrole throat precursor solution, obtains composite nano fiber described in Static Spinning；
Thermally decompose the Tackified polymeric in the composite nano fiber, poly- pyrrole throat monomer is first converted into temperature-rise period
Then polyamic acid ammonium salt is converted into poly- pyrrole throat nanofiber under final high temperature.
The method of 2. embodiment 1 of embodiment, wherein the poly- pyrrole throat presoma of the offer containing Tackified polymeric is molten
Liquid includes：
Ammonium carboxylate salts containing tetracid and tetramine are provided, and
Make the ammonium carboxylate salts and Tackified polymeric solution blending, forms poly- pyrrole throat precursor solution.
The method of 3. embodiment 2 of embodiment, wherein the tetracid is selected from following at least one：
The method of 4. embodiment 3 of embodiment, the tetracid are
The method of 5. embodiment 2 of embodiment, wherein the tetramine is selected from following at least one：
The method of 6. embodiment 5 of embodiment, the tetramine are
The method of any one of 7 embodiment 1-6 of embodiment, wherein the organic good solvent of ammonium carboxylate salts is selected from two
Any one of methyl sulfoxide, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide are several
Kind.
The method of 8. embodiment 7 of embodiment, wherein the organic good solvent of ammonium carboxylate salts is N, N- dimethyl second
Amide.
The method of 9. embodiment 1 of embodiment, wherein the inherent viscosity of Tackified polymeric solution is 2.0~4.5.
The method of 10. embodiment 9 of embodiment, wherein the inherent viscosity of Tackified polymeric solution is 3.7.
The method of any one of 11. embodiment 1-10 of embodiment, wherein the weight of the Tackified polymeric account for it is described
The 5%~30% of the total weight of the mixed solution of ammonium carboxylate salts and the Tackified polymeric solution.
The method of 12. embodiment 11 of embodiment, wherein to account for the ammonium carboxylate salt molten for the weight of the Tackified polymeric
The 15% of the total weight of the mixed solution of liquid and the Tackified polymeric solution.
The method of any one of 13. embodiment 1-12 of embodiment, wherein making the thickening in the composite nano fiber
The program of polymer thermal decomposition is 150 DEG C of constant temperature 60min, 280 DEG C of constant temperature 60min, 430 DEG C of constant temperature 20min, finally 450~
Anneal 2~30min at 550 DEG C.
Above embodiment is further defined below by embodiment and the present invention is specifically described.Having must
Wanting indicated herein is, following embodiment is served only for that the invention will be further described, should not be understood as protecting model to the present invention
The limitation enclosed, some nonessential improvement and tune that professional and technical personnel in the field makes according to the content of aforementioned present invention
It is whole, still fall within protection scope of the present invention.
Raw material：
All tetracids and tetramine are purchased from CTI, Sigma Aldrich, Alfa Aesar or SCRC, and directly use,
Without being further purified.Dimethyl sulfoxide, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
Purchased from Sinopharm Chemical Reagent Co., Ltd., polyvinylpyrrolidone is purchased from BASF (PVP-K series), polyethylene oxide purchase
From DOW Chemical (POLYOX WSR N series).
The inherent viscosity of polyvinylpyrrolidone and polyethylene oxide tests to obtain by capillary viscometer.
Four acid monomers used correspond to following chemical structural formulas：
Tetramine monomers used correspond to following chemical structural formulas：
Embodiment 1
It is 1.01 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 20g G-1 and A-1 be dissolved in the two of 80g
In methyl sulfoxide, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyvinylpyrrolidone (inherent viscosity 3.0) of 10g is taken to be added in the dimethyl sulfoxide of 90g, stirring 4h makes it
After mixing, the ammonium carboxylate salts of above-mentioned preparation are added, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 460 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 2
It is 0.99 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 50g G-6 and A-2 be dissolved in the N- of 50g
In methyl pyrrolidone, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyethylene oxide (inherent viscosity 4.5) of 60g is taken to be added in the N-Methyl pyrrolidone of 40g, stirring 4h makes it
After mixing, the ammonium carboxylate salts of above-mentioned preparation are added, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 3
It is 1 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 30g G-5 and A-4 be dissolved in the N- first of 70g
In base pyrrolidones, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyethylene oxide (inherent viscosity 4.0) of 20g is taken to be added in the N-Methyl pyrrolidone of 80g, stirring 4h makes it
After mixing, the ammonium carboxylate salts of above-mentioned preparation are added, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 4
It is 1 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 35g G-5 and A-6 be dissolved in the N- first of 65g
In base pyrrolidones, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyethylene oxide (inherent viscosity 3.3) of 20g is taken to be added in the N-Methyl pyrrolidone of 80g, stirring 4h makes it
After mixing, the ammonium carboxylate salts of above-mentioned preparation are added, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 5
It is 1 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 35g G-5 and A-6 be dissolved in the N- first of 65g
In base pyrrolidones, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyethylene oxide (inherent viscosity 3.3) of 20g is taken to be added in the n,N-Dimethylformamide of 80g, stirring 4h makes
The ammonium carboxylate salts of above-mentioned preparation are added after mixing in it, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 6
It is 1 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 35g G-5 and A-6 be dissolved in the N, N- of 65g
In dimethyl acetamide, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyethylene oxide (inherent viscosity 3.3) of 30g is taken to be added in the n,N-dimethylacetamide of 70g, stirring 4h makes
The ammonium carboxylate salts of above-mentioned preparation are added after mixing in it, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 7
It is 1 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 35g G-5 and A-1 be dissolved in the N, N- of 65g
In dimethyl acetamide, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyethylene oxide (inherent viscosity 3.7) of 30g is taken to be added in the n,N-dimethylacetamide of 70g, stirring 4h makes
The ammonium carboxylate salts of above-mentioned preparation are added after mixing in it, stir the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Embodiment 8
It is 1 by molar ratio under conditions of being lower than 25 DEG C:1 and gross weight be 35g G-5 and A-2 be dissolved in the N, N- of 65g
In dimethyl acetamide, after magnetic agitation 2h, ammonium carboxylate salts are obtained.
The polyvinylpyrrolidone (inherent viscosity 3.5) of 30g is taken to be added in the n,N-dimethylacetamide of 70g, stirring
4h makes it after mixing, and the ammonium carboxylate salts of above-mentioned preparation are added, and stirs the mixed solution that suitable spinning is made.
Mixed solution obtained above is subjected to electrostatic spinning, spinning voltage control is anode 15KV, cathode -2KV, needle point
Distance to reception device is 25cm.It collects to obtain the composite nano fiber band of fiber orientation using high-speed rotating flywheel.It will
Obtained composite nano fiber band dry 6h in 60 DEG C of vacuum.
Composite nano fiber band obtained above is heat-treated, the program of processing is 150 DEG C of constant temperature 60min, 280 DEG C
Constant temperature 60min, finally anneal under the conditions of 550 DEG C 10min.The heating rate of entire treatment process is controlled in 3 DEG C/min, and
It is carried out under the protection of high pure nitrogen.
Test method
Inherent viscosity：It tests to obtain using capillary viscometer.
Nanofiber diameter：It is measured using scanning electron microscope VEGA 3SBU (Czech Republic).
Mechanical strength：It uses the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)
Measurement, test temperature are 460~580 DEG C.
Test result see the table below 1 and attached drawing 1,2.
Table 1 (test temperature is 500 DEG C)
As can be seen that the present invention is successfully prepared the poly- pyrrole of nanoscale by the improvement of technique from upper table 1 and attached drawing 1,2
Throat fiber, and gained polypyrron fibre also has good mechanical strength, higher disconnected at very high temperatures (460 DEG C or more)
Elongation and very high modulus are split, advantageous effects of the invention are thus provided.
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
Combined 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 it is inaccurate due to and not
The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended
Claim covering.
Claims (2)
1. the preparation method that a kind of molecule based on electrospinning assembles poly- pyrrole throat nanofiber, which is characterized in that include the following steps：
Poly- pyrrole throat precursor solution containing Tackified polymeric is provided；
Poly- pyrrole throat precursor solution, obtains composite nano fiber described in Static Spinning；
The Tackified polymeric in the composite nano fiber is set to thermally decompose to yield poly- pyrrole throat nanofiber；
Wherein, the poly- pyrrole throat precursor solution of the offer containing Tackified polymeric includes：
Ammonium carboxylate salts containing tetracid and tetramine are provided, and
The ammonium carboxylate salts and Tackified polymeric solution are contacted, poly- pyrrole throat precursor solution is formed；
The tetracid is selected from following at least one：
The tetramine is selected from following at least one：
In the ammonium carboxylate salts, the weight of tetracid and tetramine and the 20%~50% of the ammonium carboxylate salts weight is accounted for；
In the ammonium carboxylate salts, the molar ratio of tetracid and tetramine is (1.05: 1)~(0.95: 1)；
The inherent viscosity of the Tackified polymeric solution is 3.0~4.5；
The Tackified polymeric is selected from one or both of polyvinylpyrrolidone and polyethylene oxide；
The weight of the Tackified polymeric accounts for the 5%~30% of the poly- pyrrole throat precursor solution weight；
150 DEG C of constant temperature 60min of the program for thermally decomposing the Tackified polymeric in the composite nano fiber, 280 DEG C of constant temperature
60min, 430 DEG C of constant temperature 20min, finally anneal at 450~550 DEG C 2~30min.
2. the poly- pyrrole throat nanofiber that method of claim 1 is prepared.
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| CN103087337A (en) * | 2011-11-01 | 2013-05-08 | 清华大学 | Polypyrrolone/sulfonated polymer composite proton exchange membrane material, and preparation method and application thereof |
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