CN108586658A - A kind of preparation method of new multicomponent polyacrylonitrile copolymer and its spinning solution - Google Patents
A kind of preparation method of new multicomponent polyacrylonitrile copolymer and its spinning solution Download PDFInfo
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- CN108586658A CN108586658A CN201810474301.6A CN201810474301A CN108586658A CN 108586658 A CN108586658 A CN 108586658A CN 201810474301 A CN201810474301 A CN 201810474301A CN 108586658 A CN108586658 A CN 108586658A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention is suitable for high-performance fiber manufacturing technology field, provides a kind of new multicomponent polyacrylonitrile copolymer, including：The mass content of main monomer unit acrylonitrile and comonomer unit ethenyl derivatives, the main monomer unit is 90~99.99%, and comonomer unit mass content is 0.001~10%；A kind of preparation method of new multicomponent polyacrylonitrile copolymer spinning solution is additionally provided, including：Main monomer unit acrylonitrile, the one or more of comonomer unit ethenyl derivatives, reaction dissolvent and initiator are added in the reaction vessel with stirring and condensing unit; it is warming up to 35~80 DEG C; logical nitrogen or argon gas; preset time is reacted under nitrogen or argon; then residual monomer and bubble are removed, spinning solution is obtained.A kind of new multicomponent polyacrylonitrile copolymer provided by the invention has compared with high-hydrophilic, compared with low-crystallinity and cyclisation temperature, milder rate of heat release and higher carbon forming rate.
Description
Technical field
The invention belongs to high-performance fiber manufacturing technology field more particularly to a kind of new multicomponent polyacrylonitrile copolymer and
The preparation method of its spinning solution.
Background technology
Carbon fiber is a kind of one-dimensional carbon material of phosphorus content 90% or more, with high-strength, Gao Mo, high temperature resistant, resistance to tired
The characteristics such as labor and thermal conductivity, are widely used in the leading-edge fields such as aerospace, national defense and military and national economy field.For making
There are many kinds for the presoma of standby carbon fiber, wherein plant-scale have polyacrylonitrile, viscose and pitch, wherein polyacrylonitrile-based carbon
The yield of fiber accounts for 90% or more of carbon fiber yield.
But there are the interactions such as strong dipole, hydrogen bond, macromoleculars between the cyano in polyacrylonitrile homopolymer macromolecular
Chain packing is close, and crystallinity is higher, and hydrophily is poor；The pre-oxidation of polyacrylonitrile homopolymer is carried out with free radical Mechanism for ring formation,
It is high to be cyclized temperature, heat release is concentrated, and is easily caused macromolecular chain break, degradation, is reduced and be even unable to get high performance carbon fiber.
Therefore, it is necessary to which certain copolymerization component is added in polymerization, to reduce the reaction activity in preoxidation process, promote cyclisation and
Crosslinking mitigates pre-oxidation exothermic reaction, improves the compactness and uniformity of fiber, improve its intensity.
Invention content
The present invention provides the preparation method of a kind of new multicomponent polyacrylonitrile copolymer and its spinning solution, it is desirable to provide one
Kind has compared with high-hydrophilic, compared with polynary poly- the third of low-crystallinity and cyclisation temperature, milder rate of heat release and higher carbon forming rate
Alkene lonitrile copolymer and preparation method thereof.
The present invention provides a kind of new multicomponent polyacrylonitrile copolymers, including：Main monomer unit acrylonitrile and copolymerization are single
The general structure of body unit ethenyl derivatives, the ethenyl derivatives is shown below, the quality of the main monomer unit
Content is 90~99.99%, and the mass content of the comonomer unit is 0.001~10%；
The present invention also provides a kind of preparation methods of new multicomponent polyacrylonitrile copolymer spinning solution, including walk as follows
Suddenly：
By one or more, the reaction of the main monomer unit acrylonitrile, the comonomer unit ethenyl derivatives
Solvent and initiator are added in the reaction vessel with stirring and condensing unit, are warming up to 35~80 DEG C, lead to nitrogen or argon gas,
Preset time is reacted under nitrogen or argon, is then removed residual monomer and bubble, is obtained spinning solution.
Compared with prior art, the present invention advantageous effect is：A kind of new multicomponent polyacrylonitrile provided by the invention is total
The preparation method of polymers and its spinning solution, including main monomer unit acrylonitrile and comonomer unit ethenyl derivatives are led to
Cross provide it is this novel using ethenyl derivatives as the polynary polyacrylonitrile copolymer of comonomer so that its have improve it is poly-
The hydrophily of acrylonitrile reduces the crystallinity of polyacrylonitrile, reduces cyclisation initial temperature, mitigates cyclization rate of heat release and carries
The effect of the carbon yield of high carbon fiber.
Description of the drawings
Fig. 1 is the differential scanning heat of polyacrylonitrile homopolymer provided in an embodiment of the present invention and polynary polyacrylonitrile copolymer
Analysis chart；
Fig. 2 is the hot weightless picture of polyacrylonitrile homopolymer provided in an embodiment of the present invention and polynary polyacrylonitrile copolymer.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The technical issues of, carbon low yield poor for polyacrylonitrile fibril structure existing in the prior art, is theoretically added
Unsaturated acid monomer can improve the hydrophily of polyacrylonitrile, and acid monomer can also cause cyclization, drop with ionic mechanism
The activation energy of low cyclization makes cyclization be controlled, such as common acrylic acid, methacrylic acid and itaconic acid copolymerization
Monomer；And the bulk effect that unsaturated esters monomer can then utilize ester group larger, which is added, reduces the cohesive energy of polyacrylonitrile, changes
The permeability of kind oxygen, so as to improve the spinnability of spinning solution.Therefore, it is total to devise a kind of novel polynary polyacrylonitrile by the present invention
Polymers has many advantages, such as lower cyclization temperature, mild cyclisation rate of heat release and higher carbon yield.
Lower mask body introduces a kind of new multicomponent polyacrylonitrile copolymer provided by the invention, including：Main monomer unit third
Alkene nitrile and comonomer unit ethenyl derivatives, shown in the general structure such as formula (1) of the ethenyl derivatives, the main list
The mass content of body unit is 90~99.99%, and comonomer unit mass content is 0.001~10%；
Wherein, R1, R2, R3 and R4 are one or more combinations in following structures：Singly-bound, alkylidene, oxygen, sulphur ,-
SO- ,-SO2- or-CO-；A1, A2, A3 and A4 are one or more combinations in following structures：Hydrogen, hydroxyl, sulfydryl, amino, cyanogen
Base, isocyano group, thiocyano, nitro, carboxyl, carbamoyl, amide groups, thiocarbamoyl, sulfonic group, chlorosulfonyl,
Halogen is respectively when necessary the alkyl of substituent group, alkoxy, alkylthio group, Alkylsulfinyl, alkyl amino, dialkyl amido,
Alkoxy carbonyl, dialkoxy phosphate, dialkoxy sulfate, alkenyl, alkenyl oxygen, alkenyl amino, alkylidene ammonia
Base, alkenyl oxygen carbonyl, alkynyl, alkynyloxy, alkynylamino, alkynyl oxygen carbonyl, naphthenic base, cycloalkyloxy, cycloalkyl-alkyl, ring
Alkyl alkoxy, ring alkylidene amino, cyclo alkoxy carbonyl, cycloalkyl alkoxy carbonyl, aryl, aryloxy group, aryl alkyl, virtue
Base alkoxy, aryl carbonyl oxygen, aryl-alkoxy carbonyl, heterocycle, hydridization base alkyl, heterocyclylalkoxy, aryl carbonyl oxygen,
Aryl-alkoxy carbonyl, heterocycle, heterocyclylalkyl group, hydridization base alkyl, heterocyclylalkoxy or heterocyclealkoxycarbonyl.
Name the method that specific embodiment introduction makes this spinning solution：
Embodiment 1：
By initiator azodiisobutyronitrile, main monomer acrylonitrile, ethenyl derivatives comonomer, solvent dimethyl sulfoxide (DMSO)
It is added in the reaction kettle with condensation and mechanical stirring device.Added Material Percentage is：Main monomer acrylonitrile is that monomer is total
The 98% of quality, ethenyl derivatives comonomer are the 2% of monomer gross mass, and initiator azodiisobutyronitrile is the total matter of monomer
The 0.5% of amount, monomer gross mass percent concentration are 20%.It is stirred at room temperature, leads to nitrogen after 30 minutes, in nitrogen protection
Under, then 60 DEG C of isothermal reaction 8h remove residual monomer and bubble, obtain spinning solution.The polynary polyacrylonitrile copolymer of gained
Weight average molecular weight be 5.2 ten thousand, molecular weight distribution 3.25.
Embodiment 2：
By initiator azodiisobutyronitrile, main monomer acrylonitrile, ethenyl derivatives comonomer, solvent dimethyl sulfoxide (DMSO)
It is added in the reaction kettle with condensation and mechanical stirring device.Added Material Percentage is：Main monomer acrylonitrile is that monomer is total
The 96% of quality, ethenyl derivatives comonomer are the 4% of monomer gross mass, and initiator azodiisobutyronitrile is the total matter of monomer
The 0.5% of amount, monomer gross mass percent concentration are 20%.It is stirred at room temperature, leads to nitrogen after 30 minutes, in nitrogen protection
Under, then 60 DEG C of isothermal reaction 8h remove residual monomer and bubble, obtain spinning solution.The polynary polyacrylonitrile copolymer of gained
Weight average molecular weight be 4.2 ten thousand, molecular weight distribution 3.75.
Embodiment 3：
By initiator azodiisobutyronitrile, main monomer acrylonitrile, ethenyl derivatives comonomer, solvent dimethyl sulfoxide (DMSO)
It is added in the reaction kettle with condensation and mechanical stirring device.Added Material Percentage is：Main monomer acrylonitrile is that monomer is total
The 98% of quality, ethenyl derivatives comonomer are the 2% of monomer gross mass, and initiator azodiisobutyronitrile is the total matter of monomer
The 0.5% of amount, monomer gross mass percent concentration are 20%.It is stirred at room temperature, leads to nitrogen after 30 minutes, in nitrogen protection
Under, then 60 DEG C of isothermal reaction 12h remove residual monomer and bubble, obtain spinning solution.The polynary polyacrylonitrile copolymer of gained
Weight average molecular weight be 10.6 ten thousand, molecular weight distribution 2.34.
Embodiment 4：
By initiator azodiisobutyronitrile, main monomer acrylonitrile, ethenyl derivatives comonomer, solvent dimethyl sulfoxide (DMSO)
It is added in the reaction kettle with condensation and mechanical stirring device.Added Material Percentage is：Main monomer acrylonitrile is that monomer is total
The 98% of quality, ethenyl derivatives comonomer are the 2% of monomer gross mass, and initiator azodiisobutyronitrile is the total matter of monomer
The 0.5% of amount, monomer gross mass percent concentration are 20%.It is stirred at room temperature, leads to nitrogen after 30 minutes, in nitrogen protection
Under, 60 DEG C of isothermal reactions for 24 hours, then remove residual monomer and bubble, obtain spinning solution.The polynary polyacrylonitrile copolymer of gained
Weight average molecular weight be 15.1 ten thousand, molecular weight distribution 2.58.
Embodiment 5：
By initiator azodiisobutyronitrile, main monomer acrylonitrile, ethenyl derivatives comonomer, solvent dimethyl sulfoxide (DMSO)
It is added in the reaction kettle with condensation and mechanical stirring device.Added Material Percentage is：Main monomer acrylonitrile is that monomer is total
The 96% of quality, ethenyl derivatives comonomer are the 4% of monomer gross mass, and initiator azodiisobutyronitrile is the total matter of monomer
The 0.5% of amount, monomer gross mass percent concentration are 23%.It is stirred at room temperature, leads to nitrogen after 30 minutes, in nitrogen protection
Under, then 60 DEG C of isothermal reaction 8h remove residual monomer and bubble, obtain spinning solution.The polynary polyacrylonitrile copolymer of gained
Weight average molecular weight be 4.8 ten thousand, molecular weight distribution 4.11.
Embodiment 6：
By initiator azodiisobutyronitrile, main monomer acrylonitrile, ethenyl derivatives comonomer, solvent dimethyl sulfoxide (DMSO)
It is added in the reaction kettle with condensation and mechanical stirring device.Added Material Percentage is：Main monomer acrylonitrile is that monomer is total
The 98% of quality, ethenyl derivatives comonomer are the 2% of monomer gross mass, and initiator azodiisobutyronitrile is the total matter of monomer
The 1.0% of amount, monomer gross mass percent concentration are 23%.It is stirred at room temperature, leads to nitrogen after 30 minutes, in nitrogen protection
Under, 60 DEG C of isothermal reactions for 24 hours, then remove residual monomer and bubble, obtain spinning solution.The polynary polyacrylonitrile copolymer of gained
Weight average molecular weight be 6.7 ten thousand, molecular weight distribution 1.76.
Polynary polyacrylonitrile copolymer provided by the invention has the hydrophily for improving polyacrylonitrile, reduces polyacrylonitrile
Crystallinity, reduce cyclisation initial temperature, mitigate cyclization rate of heat release, improve the effect of the carbon yield of carbon fiber.Such as Fig. 1
Shown, the starting cyclisation temperature of prepared polynary polyacrylonitrile copolymer is relatively low, and heat release section is broadening, cyclization heat release speed
Rate is slow.As shown in Fig. 2, the thermal stability of prepared polynary polyacrylonitrile copolymer is improved, while carbon yield
It is improved.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. a kind of new multicomponent polyacrylonitrile copolymer, which is characterized in that including：Main monomer unit acrylonitrile and comonomer list
The general structure of first ethenyl derivatives, the ethenyl derivatives is shown below, the mass content of the main monomer unit
It is 90~99.99%, the mass content of the comonomer unit is 0.001~10%；
2. new multicomponent polyacrylonitrile copolymer as described in claim 1, which is characterized in that the ethenyl derivatives structure
In R1, R2, R3 and R4 be following structures in one or more combinations：Singly-bound, alkylidene, oxygen, sulphur ,-SO- ,-SO2- or-
CO-；A1, A2, A3 and A4 are one or more combinations in following structures：Hydrogen, hydroxyl, sulfydryl, amino, cyano, isocyano group, cyanogen
Sulfenyl, nitro, carboxyl, carbamoyl, amide groups, thiocarbamoyl, sulfonic group, chlorosulfonyl, halogen or when necessary
It is respectively the alkyl of substituent group, alkoxy, alkylthio group, Alkylsulfinyl, alkyl amino, dialkyl amido, alkoxy carbonyl, two
Alkoxy phosphate, dialkoxy sulfate, alkenyl, alkenyl oxygen, alkenyl amino, alkylidene amino, alkenyl oxygen carbonyl
Base, alkynyl, alkynyloxy, alkynylamino, alkynyl oxygen carbonyl, naphthenic base, cycloalkyloxy, cycloalkyl-alkyl, cycloalkyl alkoxy, ring
Alkylidene amino, cyclo alkoxy carbonyl, cycloalkyl alkoxy carbonyl, aryl, aryloxy group, aryl alkyl, alkoxy aryl, aryl
Oxygen carbonyl, aryl-alkoxy carbonyl, heterocycle, hydridization base alkyl, heterocyclylalkoxy, aryl carbonyl oxygen, alkoxy aryl carbonyl
Base, heterocycle, heterocyclylalkyl group, hydridization base alkyl, heterocyclylalkoxy or heterocyclealkoxycarbonyl.
3. a kind of preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 1 or 2, feature
It is, includes the following steps：
By the main monomer unit acrylonitrile, one or more, the reaction dissolvent of the comonomer unit ethenyl derivatives
It is added in the reaction vessel with stirring and condensing unit with initiator, is warming up to 35~80 DEG C, lead to nitrogen or argon gas, in nitrogen
Gas or the lower reaction preset time of argon gas protection, then remove residual monomer and bubble, obtain spinning solution.
4. the preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 3, which is characterized in that institute
The mass concentration for stating ethenyl derivatives is 0.001~10%.
5. the preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 3, which is characterized in that institute
State main monomer unit and the comonomer unit to account for solution gross mass percent concentration be preferably 5~35%.
6. the preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 3, which is characterized in that institute
It is azodiisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile or azo-bis-iso-dimethyl to state initiator, and content is
0.01~5%.
7. the preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 3, which is characterized in that institute
It is dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide or n-vinyl pyrrolidone to state reaction dissolvent.
8. the preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 3, which is characterized in that institute
The addition of comonomer unit is stated in such a way that primary addition, branch are added or are continuously added to.
9. the preparation method of new multicomponent polyacrylonitrile copolymer spinning solution as claimed in claim 3, which is characterized in that institute
State preset time be 0.2~for 24 hours.
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| CN201810474301.6A CN108586658A (en) | 2018-05-17 | 2018-05-17 | A kind of preparation method of new multicomponent polyacrylonitrile copolymer and its spinning solution |
| PCT/CN2019/086772 WO2019218991A1 (en) | 2018-05-17 | 2019-05-14 | Novel polyacrylonitrile copolymer and method for preparing spinning dope thereof |
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| WO2019218991A1 (en) * | 2018-05-17 | 2019-11-21 | 深圳大学 | Novel polyacrylonitrile copolymer and method for preparing spinning dope thereof |
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|---|---|---|---|---|
| CN101158060A (en) * | 2007-11-20 | 2008-04-09 | 中国科学院长春应用化学研究所 | Binary acrylonitrile copolymer spinning fluid and preparation method thereof |
| CN101864028A (en) * | 2010-05-28 | 2010-10-20 | 金发科技股份有限公司 | Preparation method of polyacrylonitrile spinning solution |
| CN105085797A (en) * | 2015-08-28 | 2015-11-25 | 国网智能电网研究院 | Polyacrylonitrile-based carbon fiber spinning solution and preparing method of polyacrylonitrile-based carbon fiber spinning solution |
| CN105524213A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile spinning stock solution |
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| CN103014894B (en) * | 2012-12-12 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of acrylonitrile copolymer spinning solution with low molecular weight distribution |
| CN103030736B (en) * | 2012-12-12 | 2014-12-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method of acrylonitrile copolymer spinning solution with low molecular weight distribution |
| CN103103631B (en) * | 2013-02-27 | 2015-07-01 | 威海拓展纤维有限公司 | Method for preparing polyacrylonitrile carbon fiber precursor |
| CN108586658A (en) * | 2018-05-17 | 2018-09-28 | 深圳大学 | A kind of preparation method of new multicomponent polyacrylonitrile copolymer and its spinning solution |
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- 2018-05-17 CN CN201810474301.6A patent/CN108586658A/en active Pending
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- 2019-05-14 WO PCT/CN2019/086772 patent/WO2019218991A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158060A (en) * | 2007-11-20 | 2008-04-09 | 中国科学院长春应用化学研究所 | Binary acrylonitrile copolymer spinning fluid and preparation method thereof |
| CN101864028A (en) * | 2010-05-28 | 2010-10-20 | 金发科技股份有限公司 | Preparation method of polyacrylonitrile spinning solution |
| CN105524213A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile spinning stock solution |
| CN105085797A (en) * | 2015-08-28 | 2015-11-25 | 国网智能电网研究院 | Polyacrylonitrile-based carbon fiber spinning solution and preparing method of polyacrylonitrile-based carbon fiber spinning solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019218991A1 (en) * | 2018-05-17 | 2019-11-21 | 深圳大学 | Novel polyacrylonitrile copolymer and method for preparing spinning dope thereof |
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Application publication date: 20180928 |