CN105085797B - A kind of polyacrylonitrile-based carbon fiber spinning solution and preparation method thereof - Google Patents
A kind of polyacrylonitrile-based carbon fiber spinning solution and preparation method thereof Download PDFInfo
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- CN105085797B CN105085797B CN201510543669.XA CN201510543669A CN105085797B CN 105085797 B CN105085797 B CN 105085797B CN 201510543669 A CN201510543669 A CN 201510543669A CN 105085797 B CN105085797 B CN 105085797B
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- 238000009987 spinning Methods 0.000 title claims abstract description 70
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 30
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 28
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 162
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 24
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 60
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 13
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 10
- 230000031709 bromination Effects 0.000 claims description 7
- 238000005893 bromination reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 2
- 230000005587 bubbling Effects 0.000 claims 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 16
- 238000009833 condensation Methods 0.000 description 16
- 230000005494 condensation Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 238000010907 mechanical stirring Methods 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 10
- 230000010148 water-pollination Effects 0.000 description 10
- CWNNYYIZGGDCHS-UHFFFAOYSA-N 2-methylideneglutaric acid Chemical group OC(=O)CCC(=C)C(O)=O CWNNYYIZGGDCHS-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- -1 Alkene nitrile Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 description 2
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical class C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 2
- 0 CN(C)CC*(C(O)=O)=C Chemical compound CN(C)CC*(C(O)=O)=C 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- APLSTDSMMPCXFT-UHFFFAOYSA-N C=C(CCN(CCO)CCO)C(O)=O Chemical compound C=C(CCN(CCO)CCO)C(O)=O APLSTDSMMPCXFT-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- OQTRPSFMBXCQIY-UHFFFAOYSA-N azane;2-methylidenebutanedioic acid Chemical compound N.OC(=O)CC(=C)C(O)=O OQTRPSFMBXCQIY-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention provides a kind of polyacrylonitrile-based carbon fiber spinning solutions and preparation method thereof, the spinning solution is prepared by the reaction solution containing monomer, radical initiator and solvent through copolymerization, the mass concentration of monomer described in the reaction solution is 15-35%, the radical initiator is the 0.2-1.0% of the total monomer weight, and surplus is solvent；The monomer includes the comonomer of the acrylonitrile monemer and 0.5-5% that account for monomer gross mass 95-99.5%；The comonomer is the hydrophilic co-monomer of the group of methylene butyric acid containing 2-.The preparation method includes the following steps：1) it adds raw materials into reaction kettle, is stirred according to the ratio, nitrogen is bubbled 10-40min；2) under nitrogen protection, in 50-70 DEG C of isothermal reaction 6-36h；3) residual monomer and bubble are removed, spinning solution is obtained.The comonomer designed in the present invention is not only that the hydrophilic fine and close agent of resin can be improved, and can also be effectively improved Oxygen permeation and spinnability, the spinning solution that the present invention obtains has high-hydrophilic and good exothermicity.
Description
Technical field
The present invention relates to a kind of carbon fiber spinning solutions and preparation method thereof, and in particular to a kind of polyacrylonitrile-based carbon fibre spinning
Silk liquid and preparation method thereof.
Background technology
Carbon fiber possesses high specific strength, high ratio modulus, heat-resisting, resistant to chemical etching, resistance to as a kind of novel structural material
The features such as friction, heat shock resistance, conduction, heat conduction, radioresistance, good damping, damping, noise reduction, is widely used in aviation boat
It, the civil uses such as leading-edge fields and advanced sports goods, medical instrument such as national defense and military.The presoma for preparing carbon fiber has
Very much, but up to the present, only polyacrylonitrile, viscose glue and the pitch, wherein polyacrylonitrile-radical of commercial scale are obtained
Carbon fiber yield accounts for 90% or more.
The carbon fiber highest tensile strength that at present prepared by experiment is 9.03Gpa, only 5% or so of theoretical value 180Gpa.
For polyacrylonitrile-based carbon fibre, good precursor is the key that prepare high-strength carbon fibre, and to obtain good poly- third
Alkene nitrile precursor will then set about from the performance and optimization spinning technique of polyacrylonitrile polymer spinning solution.From the homogeneity of structure and
From the point of view of carbon yield, homo-polypropylene nitrile seems ideal, however homo-polypropylene nitrile causes cyclisation with free radical mechanism at high temperature
Reaction, the easy fracture of wire of heat release concentration in preoxidation process.Therefore, it is necessary to which certain copolymerization component is added in the polymer, with
The reaction activity in preoxidation process is reduced, cyclisation and crosslinking are promoted, pre-oxidation exothermic reaction is mitigated, improves the cause of carbon fiber
Close property and uniformity improve its intensity.
Carbon fiber industry generally uses unsaturated carboxylic acid and esters of unsaturated carboxylic acids as the first and second comonomers to poly-
Acrylonitrile carries out modification by copolymerization.Carboxyl can cause cyclization with ionic mechanism at high temperature, reduce the activation of cyclization
Can and cyclization be made to be controlled；Esters of unsaturated carboxylic acids is then to reduce to gather using the bulk effect of ester group or the larger side group of volume
The cohesive energy of acrylonitrile improves the permeability of oxygen, so as to improve the spinnability of polymer solution.
US4336022 and No. 4603041 disclosed in U.S. Patent, improves the hydrophily of polyacrylonitrile resin, can solve to spin
The method of the whiting devitrification phenomenon of solidification strand in silk process of setting.This is because the hydrophily for improving polyacrylonitrile resin is advantageous
In the diffusion velocity for inhibiting water in process of setting, the hole in solidification strand is eliminated；And after hydrophily increase, precursor is in vapor
It can preferably be combined infiltration, water that can play plasticization to polyacrylonitrile resin, make precursor in heat in drafting process with vapor
It is more easy to be drafted when water drawing-off, precursor internal flaw is also more easy to make up, to prepare the original that high-performance carbon fibre provides high quality
Silk.The hydrophilic raising of polyacrylonitrile fibril, first has to find and is prepared with the comonomer of the good hydrophilic property of acrylonitrile compolymer
Spinning solution, then ammonification is carried out to spinning solution after polymerization.There is document report using itaconic acid ammonium as comonomer
The hydrophily that polyacrylonitrile resin can be improved, when increasing degree of draft, strand porosity, intensity, elongation at break etc. is significantly
It is promoted.Separately there is document report to improve the hydrophily and exothermicity of polypropylene-based resin as comonomer using acrylamide
Energy.But the reactivity ratio difference of above two monomer and acrylonitrile is all very big, it is difficult to obtain the uniform acrylonitrile compolymer of chain structure
Object.
In order to improve the gas double diffusion problem in pre-oxidation carbonisation and improve spinnability, people are in comonomer
Big side group is introduced, such as ester group and heterocycle (five-ring heterocycles or hexa-member heterocycle), is dropped using the bulk effect of these big side groups
The cohesive energy of low PAN, in addition these big side group structures can also destroy the crystallization of PAN, so that crystal grain is become smaller, gas is double to be expanded to get through
Dissipate channel.200710056082.1 a number Chinese patent reports a series of vinyl imidazole salt as polyacrylonitrile carbon fiber spinning
The comonomer of liquid, the results showed that vinyl imidazole salt can significantly improve the hydrophily of polyacrylonitrile copolymer resin, and its
The volumetric of molecule can also improve the spinnability of polyacrylonitrile copolymer resin.No. 201010166991.2 China of an another piece
A kind of high-performance carbon fibre spinning solution of the structural unit of alkanone containing allyl imidazole of patent report, the spinning solution have preferable
Hot property and good hydrophily.The method of this novel copolymerized monomer molecule of design is to improve spinning solution performance, improves carbon fiber
The compactness and uniformity of dimension improve its intensity and provide new thinking.
Invention content：
The object of the present invention is to provide a kind of improved polyacrylonitrile-based carbon fiber spinning solutions and preparation method thereof.By setting
Count a kind of comonomer of novel high-hydrophilic, be prepared high-hydrophilic, excellent exothermicity polyacrylonitrile-based carbon fibre
Spinning solution.
To achieve the goals above, the present invention takes following technical scheme：
A kind of polyacrylonitrile-based carbon fiber spinning solution, the spinning solution is by containing monomer, radical initiator and solvent
Reaction solution be prepared through copolymerization, by mass percentage, the mass concentration of monomer described in the reaction solution is
15-35%, the radical initiator are the 0.2-1.0% of the monomer gross mass, and surplus is solvent；The monomer includes accounting for
The acrylonitrile monemer of monomer gross mass 95-99.5% and the comonomer of 0.5-5%；The comonomer is the fourth of methylene containing 2-
The hydrophilic co-monomer of acid groups, the radical initiator are azodiisobutyronitrile, and the solvent is dimethyl sulfoxide (DMSO).
First preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the quality of monomer described in the reaction solution
A concentration of 18-25%, the radical initiator are the 0.2-0.6% of the total monomer weight, and the monomer includes accounting for monomer
The acrylonitrile monemer of gross mass 99-99.5% and the comonomer of 0.5-1%.
Second preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the quality of monomer described in the reaction solution
A concentration of 20%, the radical initiator is the 0.5% of the total monomer weight, and the monomer includes accounting for monomer gross mass
99.3% acrylonitrile monemer and 0.7% comonomer.
The third preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the parent of the group of methylene butyric acid containing 2-
The general structure of water comonomer is as follows：
Wherein, A is hydrophilic radical.
4th preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the hydrophilic radical A is carboxyl, described
Hydrophilic co-monomer is 2- methyleneglutaric acids, and structural formula is as follows：
5th preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the hydrophilic radical A are dimethylamino
Base, the hydrophilic co-monomer are 4- dimethylamino -2- methylene-succinic acids, and structural formula is as follows：
6th preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the hydrophilic radical A are bis- (2- hydroxyls
Ethyl) amino, the hydrophilic co-monomer is 4- (bis- (2- hydroxyethyls) amine) -2- methylene-succinic acids, and structural formula is as follows：
7th preferred embodiment of the polyacrylonitrile-based carbon fiber spinning solution, the hydrophilic radical A are bromination front three
Base ammonium, the hydrophilic co-monomer are bromination 3- carbonyls-N, N, N- front three butyl- 3- alkene -1- ammonium salts, and structural formula is as follows：
A kind of preparation method of the polyacrylonitrile-based carbon fiber spinning solution, described method includes following steps：
1) under stirring, reaction is added in acrylonitrile monemer, comonomer, azodiisobutyronitrile and dimethyl sulfoxide (DMSO) according to the ratio
In kettle, nitrogen is bubbled 10-40min；
2) under nitrogen atmosphere protection, the constant temperature 6-36h at 50-70 DEG C；
3) residual monomer and bubble are removed, spinning solution is obtained.
First optimal technical scheme of the preparation method of the polyacrylonitrile-based carbon fiber spinning solution, the nitrogen are bubbled
Time is 30min, under nitrogen protection, for 24 hours in 60 DEG C of constant temperature.
The structure of the acrylonitrile being prepared by the technical solution/allyl imidazole alkanone random copolymer is as follows：
Wherein, A is selected from one of following structures：
Compared with the latest prior art, the present invention has following excellent effect：
1) the novel copolymerized monomer that the present invention designs has preferable hydrophily, and volume is larger.Its bulk effect can drop
The cohesive energy of oligomerisation of propene nitrile resin, improves the permeance property of oxygen, improves the spinnability of polymer solution, these four copolymerization are single
Body is not only that the hydrophilic fine and close agent of resin can be improved, and can also be effectively improved Oxygen permeation and spinnability.Using acrylonitrile/new
The method of type comonomer has obtained high-hydrophilic and the good spinning solution of exothermicity；
2) weight average molecular weight of present copolymer is can be controlled between 7-20 ten thousand, and gained resin carries out contact angle test,
The result shows that the contact angle of copolymer and water is reduced to 37.6 ° or so from 65.3 ° compared with homopolymer.To homo-polypropylene nitrile and altogether
Polymers carry out powder X-ray RD test the crystallinity of polymer is reduced to 33.9% from 49.9%, 100 face crystallite dimensions fromIt falls toThis shows that novel copolymerized monomer can not only improve resin hydrophily, and can also be effectively improved can spin
Property；
3) it is found in the DSC research process of four kinds of copolymers of the invention, compared with homo-polypropylene nitrile, methylene butyric acid containing 2-
The novel copolymerized monomer of group can make the Exotherm Onset Temperature of copolymer be reduced to 140-170 DEG C, and exothermic peak is widened, rate of heat release
It reduces.Therefore the novel copolymerized monomer of the group of methylene butyric acid containing 2- can also improve the exothermicity of copolymer；
4) the novel copolymerized monomer of the group of methylene butyric acid containing 2- of the invention improves oxygen as resin hydrophily is improved
Permeance property, the exothermicity multiple functions of the spinnability and improvement copolymer that improve polymer solution, therefore are compared
For acrylonitrile/unsaturated carboxylic acid/esters of unsaturated carboxylic acids used by before, the distribution of macromolecular chain structure sequence can pass through
Change process conditions to be controlled, obtains more uniform chain structure.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 2- methyleneglutaric acids, solvent dimethyl Asia
Sulfone is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage matches：Main monomer propylene
Nitrile is the 98% of monomer gross mass, the 2% of comonomer 2- methyleneglutaric acid monomer gross mass.The quality of azodiisobutyronitrile
It is the 0.5% of monomer gross mass, monomer gross mass percent concentration is 20%.It is stirred at room temperature, nitrogen is bubbled 30 minutes
Afterwards, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, residual monomer and bubble is then removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 15.2 ten thousand；The contact angle of copolymer and water
It is 43.3 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 167 DEG C, thermal discharge 2421Jg- 1。
Embodiment 2
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 2- methyleneglutaric acids, solvent dimethyl Asia
Sulfone is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage proportioning is main monomers acrylonitrile
It is the 97% of monomer gross mass, comonomer 2- methyleneglutaric acids are the 3% of monomer gross mass.The quality of azodiisobutyronitrile
It is the 0.5% of monomer gross mass, monomer mass a concentration of 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, in nitrogen
In 60 DEG C of isothermal reactions 6 hours under protection, residual monomer and bubble are then removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 11.4 ten thousand；The contact angle of copolymer and water
It is 42.1 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 163 DEG C, thermal discharge 2186Jg-1。
Embodiment 3
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 2- methyleneglutaric acids, solvent dimethyl Asia
Sulfone is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage matches：Main monomer propylene
Nitrile is the 96% of monomer gross mass, and comonomer 2- methyleneglutaric acids are the 4% of monomer gross mass.The matter of azodiisobutyronitrile
Amount is the 0.5% of monomer gross mass, monomer mass a concentration of 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, in nitrogen
In 60 DEG C of isothermal reactions 24 hours under gas shielded, residual monomer and bubble are then removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 11.8 ten thousand；The contact angle of copolymer and water
It is 39.7 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 154 DEG C, thermal discharge 1976Jg-1。
Embodiment 4
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 2- methyleneglutaric acids, solvent dimethyl Asia
Sulfone is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage proportioning is main monomers acrylonitrile
It is the 99.3% of monomer gross mass, comonomer 2- methyleneglutaric acids are the 0.7% of monomer gross mass.Azodiisobutyronitrile
Quality is the 0.5% of monomer gross mass, monomer mass a concentration of 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes,
In 60 DEG C of isothermal reactions 30 hours under nitrogen protection, residual monomer and bubble are then removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 13.4 ten thousand；The contact angle of copolymer and water
It is 38.9 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 145 DEG C, thermal discharge 1784Jg-1。
Embodiment 5
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- dimethylamino -2- methylene-succinic acids,
Solvent dimethyl sulfoxide (DMSO) is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage matches
Main monomer acrylonitrile is the 98% of monomer gross mass, and comonomer 4- dimethylamino -2- methylene-succinic acids are monomer gross mass
2%.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, monomer mass a concentration of 20%.Stirring is mixed at room temperature
It closes, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then removes residual monomer and bubble,
Obtain spinning solution.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 14.5 ten thousand；The contact angle of copolymer and water
It is 42.1 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 165 DEG C, thermal discharge 2309Jg-1。
Embodiment 6
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- dimethylamino -2- methylene-succinic acids,
Solvent dimethyl sulfoxide (DMSO) is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage matches
Main monomer acrylonitrile is the 97% of monomer gross mass, and comonomer 4- dimethylamino -2- methylene-succinic acids are monomer gross mass
3%.The quality of azodiisobutyronitrile is the 0.25% of monomer gross mass, monomer mass a concentration of 20%.Stirring is mixed at room temperature
It closes, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then removes residual monomer and bubble,
Obtain spinning solution.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 12.4 ten thousand；The contact angle of copolymer and water
It is 41.3 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 157 DEG C, thermal discharge 2217Jg-1。
Embodiment 7
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- dimethylamino -2- methylene-succinic acids,
Solvent dimethyl sulfoxide (DMSO) is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage matches
Main monomer acrylonitrile is the 96% of monomer gross mass, and comonomer 4- dimethylamino -2- methylene-succinic acids are monomer gross mass
4%.The quality of azodiisobutyronitrile is the 0.75% of monomer gross mass, monomer mass a concentration of 20%.Stirring is mixed at room temperature
It closes, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then removes residual monomer and bubble,
Obtain spinning solution.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 13.8 ten thousand；The contact angle of copolymer and water
It is 40.5 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 144 DEG C, thermal discharge 1953Jg-1。
Embodiment 8
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- dimethylamino -2- methylene-succinic acids,
Solvent dimethyl sulfoxide (DMSO) is added in the reaction kettle with condensation and mechanical stirring device.Added material quality percentage matches
Main monomer acrylonitrile is the 99.3% of monomer gross mass, and comonomer 4- dimethylamino -2- methylene-succinic acids are the total matter of monomer
The 0.7% of amount.The quality of azodiisobutyronitrile is the 1% of monomer gross mass, monomer mass a concentration of 20%.Stirring is mixed at room temperature
It closes, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then removes residual monomer and bubble,
Obtain spinning solution.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 13.4 ten thousand；The contact angle of copolymer and water
It is 38.7 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 139 DEG C, thermal discharge 1795Jg-1。
Embodiment 9
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 98% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid is the 2% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, monomer mass concentration
It is 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then
Residual monomer and bubble are removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 12.6 ten thousand；The contact angle of copolymer and water
It is 41.9 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 165 DEG C, thermal discharge 2492Jg-1。
Embodiment 10
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 97% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid is the 3% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, monomer mass concentration
It is 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then
Residual monomer and bubble are removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 14.5 ten thousand；The contact angle of copolymer and water
It is 40.2 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 153 DEG C, thermal discharge 2141Jg-1。
Embodiment 11
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 96% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid is the 4% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, monomer mass concentration
It is 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then
Residual monomer and bubble are removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 13.9 ten thousand；The contact angle of copolymer and water
It is 39.7 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 150 DEG C, thermal discharge 1877Jg-1。
Embodiment 12
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer 4- (bis- (2- hydroxyethyls) amine) -2- methylenes
Base succinic acid, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 99.3% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, and comonomer 4- (bis- (2- hydroxyethyls) amine) -2- is sub-
Dimethyl succinic acid is the 0.7% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, monomer mass
A concentration of 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours,
Then residual monomer and bubble are removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 11.7 ten thousand；The contact angle of copolymer and water
It is 38.4 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 165 DEG C, thermal discharge 2368Jg-1。
Embodiment 13
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer bromination 3- carbonyls-N, N, N- front three butyl- 3-
Alkene -1- ammonium salts, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 98% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 3- carbonyls-N, N, N- front three butyl- 3- alkene -1-
Ammonium salt is the 2% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, and monomer mass is a concentration of
20%.It is stirred, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then takes off at room temperature
Except residual monomer and bubble, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 12.3 ten thousand；The contact angle of copolymer and water
It is 40.2 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 166 DEG C, thermal discharge 2329Jg-1。
Embodiment 14
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer bromination 3- carbonyls-N, N, N- front three butyl- 3-
Alkene -1- ammonium salts, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 97% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 3- carbonyls-N, N, N- front three butyl- 3- alkene -1-
Ammonium salt is the 3% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, and monomer mass is a concentration of
20%.It is stirred, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then takes off at room temperature
Except residual monomer and bubble, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 11.9 ten thousand；The contact angle of copolymer and water
It is 39.0 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 155 DEG C, thermal discharge 2270Jg-1。
Embodiment 15
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer bromination 3- carbonyls-N, N, N- front three butyl- 3-
Alkene -1- ammonium salts, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 96% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 3- carbonyls-N, N, N- front three butyl- 3- alkene -1-
Ammonium salt is the 4% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, and monomer mass is a concentration of
20%.It is stirred, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then takes off at room temperature
Except residual monomer and bubble, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 13.6 ten thousand；The contact angle of copolymer and water
It is 38.1 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 149 DEG C, thermal discharge 1985Jg-1。
Embodiment 16
By initiator azodiisobutyronitrile, main monomer acrylonitrile, comonomer bromination 3- carbonyls-N, N, N- front three butyl- 3-
Alkene -1- ammonium salts, solvent dimethyl sulfoxide (DMSO) are added in the reaction kettle with condensation and mechanical stirring device.Added material quality hundred
It is the 99.3% of monomer gross mass for main monomers acrylonitrile to divide than proportioning, comonomer 3- carbonyls-N, N, N- front three butyl- 3- alkene-
1- ammonium salts are the 0.7% of monomer gross mass.The quality of azodiisobutyronitrile is the 0.5% of monomer gross mass, monomer mass concentration
It is 20%.It is stirred at room temperature, after nitrogen is bubbled 30 minutes, under nitrogen protection in 60 DEG C of isothermal reactions 24 hours, then
Residual monomer and bubble are removed, spinning solution is obtained.
Gained spinning solution is tested for the property：Copolymer weight average molecular weight is 13.3 ten thousand；The contact angle of copolymer and water
It is 37.6 °；Under air atmosphere, 5 DEG C/min heatings, DSC Exotherm Onset Temperatures are 141 DEG C, thermal discharge 1893Jg-1。
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, the ordinary skill people of fields
Member, which should be appreciated that, can be modified or replaced equivalently the specific implementation mode of the present invention with reference to above-described embodiment, these
Without departing from any modification of spirit and scope of the invention or equivalent replacement apply pending claims it
It is interior.
Claims (5)
1. a kind of polyacrylonitrile-based carbon fiber spinning solution, the spinning solution is by containing monomer, radical initiator and solvent
Reaction solution is prepared through copolymerization, which is characterized in that by mass percentage, the matter of monomer described in the reaction solution
A concentration of 15-35% is measured, the radical initiator is the 0.2-1.0% of the monomer gross mass, and surplus is solvent；The list
Body includes the comonomer of the acrylonitrile monemer and 0.5-5% that account for monomer gross mass 95-99.5%；The comonomer is containing 2-
The hydrophilic co-monomer of methylene butyric acid group, the radical initiator are azodiisobutyronitrile, and the solvent is two
Methyl sulfoxide；
The general structure of the hydrophilic co-monomer of the group of methylene butyric acid containing 2- is as follows：
Wherein, A is hydrophilic radical；
The hydrophilic radical A is carboxyl, and the structural formula of the hydrophilic co-monomer is as follows：
The hydrophilic radical A is dimethylamino, and the structural formula of the hydrophilic co-monomer is as follows：
The hydrophilic radical A is bis- (2- hydroxyethyls) amino, and the structural formula of the hydrophilic co-monomer is as follows：
The hydrophilic radical A is bromination trimethyl ammonium, and the structural formula of the hydrophilic co-monomer is as follows：
2. polyacrylonitrile-based carbon fiber spinning solution according to claim 1, which is characterized in that single described in the reaction solution
The mass concentration of body is 18-25%, and the radical initiator is the 0.2-0.6% of the total monomer weight, the monomer packet
Include the comonomer of the acrylonitrile monemer and 0.5-1% that account for monomer gross mass 99-99.5%.
3. polyacrylonitrile-based carbon fiber spinning solution according to claim 1, which is characterized in that single described in the reaction solution
The mass concentration of body is 20%, and the radical initiator is the 0.5% of the total monomer weight, and the monomer includes accounting for monomer
The acrylonitrile monemer of gross mass 99.3% and 0.7% comonomer.
4. a kind of preparation method of any polyacrylonitrile-based carbon fiber spinning solutions of claim 1-3, which is characterized in that institute
The method of stating includes the following steps：
1) under stirring, reaction kettle is added in acrylonitrile monemer, comonomer, azodiisobutyronitrile and dimethyl sulfoxide (DMSO) according to the ratio
In, nitrogen is bubbled 10-40min；
2) under nitrogen atmosphere protection, the constant temperature 6-36h at 50-70 DEG C；
3) residual monomer and bubble are removed, spinning solution is obtained.
5. the preparation method of polyacrylonitrile-based carbon fiber spinning solution according to claim 4, which is characterized in that the nitrogen
The bubbling time is 30min, under nitrogen protection, for 24 hours in 60 DEG C of constant temperature.
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