CN102199249A - High molecular weight acrylonitrile terpolymer and preparation method thereof - Google Patents
High molecular weight acrylonitrile terpolymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to acrylonitrile terpolymer and a preparation method thereof, which mainly solves the problem that acrylonitrile/acrylamide/beta-acrylonitrileitaconic acid ester terpolymer is not related in the prior art. The general formula is shown as the description, wherein m=2,001-4,000; n=5-400; k=5-400; the weight-average molecular weight of the terpolymer is between 150,000 and 400,000; and the molecular weight distribution index is between 1.5 and 2.5. By the technical scheme of the terpolymer and the preparation method thereof, the problem is better solved, and the invention can be applied to industrial production of high performance polyacrylonitrile spinning solution.
Description
Technical field
The present invention relates to a kind of high molecular ternary acrylonitrile compolymer body and preparation method thereof.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the type material that develops rapidly the sixties in 20th century, has both had the intrinsic person's character of carbon material, has the soft workability of textile fibres again, is dual-use novel material of new generation.The fine or not key of carbon fiber performance is the quality of precursor, and carbon fiber manufacturer is all the top-secret technology of polyacrylonitrile fibril production technology as the production carbon fiber in the world.Domesticly also fall behind because of the polyacrylonitrile fibril production technology just, make carbon fiber in output with all differ greatly qualitatively with foreign level.Therefore, the high-performance carbon fibre interpolymer is the prerequisite of producing high-performance carbon fibre.
As high performance carbon fiber interpolymer, should have following performance: 1, the molecular weight distribution of polymkeric substance is narrower in the interpolymer, and is evenly distributed; 2, improve the wetting ability of spinning solution and the compactness of strand; 3, reduce in the oxidation carbonization process cyclisation temperature etc.Therefore, when selecting comonomer, above-mentioned requirements be should satisfy, second monomer and the 3rd monomer in the acrylonitrile polymerization process, added usually.The big more options of comonomer commonly used contain carboxylic acid group's unsaturated ethylene vinyl compound.List the reactivity ratio of vinyl cyanide and other monomer reactions below, vinyl cyanide (AN)/vinylformic acid (AA): r (AN)=0.35, r (AA)=1.15; Acrylonitrile/methyl acrylate: r (AN)=0.25, r (MA)=0.75; Vinyl cyanide/methylene-succinic acid (IA): r (AN)=0.865, r (IA)=0.568; Vinyl cyanide/methyl methacrylate (MMA): r (NA)=0.18, r (MMA)=1.35; Vinyl cyanide/acrylamide (AAM): r (AN)=0.875, r (AAM)=1.375.Because the reactivity ratio of methylene-succinic acid and vinyl cyanide is the most approaching, so be the comonomer of using always in carbon fiber stoste preparation process.Wetting ability is poor, the heat release peak width is narrow and the shortcoming of spinning property difference but methylene-succinic acid and the polymerization of vinyl cyanide binary still exist; Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences discloses three Chinese invention patent (application numbers: 02130021.6,02130023.2,02130024.0), their first synthesis of acrylonitrile homopolymer, in reaction solution, feed ammonia then, reacted 2 hours down at 80～100 ℃, make part functional group be converted into carboxyl and amide group, indirectly the synthesis of ternary interpolymer.This method can be improved the wetting ability of polyacrylonitrile effectively.Yet the reaction of ammonia and polyacrylonitrile viscous fluid is the heterogeneous reaction of a complexity, and the mass transfer difficulty reacts wayward, and circulation ratio is relatively poor.
The carbon current fiber industry generally adopts is that the method for vinyl cyanide/unsaturated carboxylic acid/esters of unsaturated carboxylic acids terpolymer prepares spinning solution, wherein the main effect of unsaturated carboxylic acid is to reduce the cyclisation temperature, widen exothermic peak, relax the rate of heat release of precursor in the preoxidation cyclization process, be not easy when preoxidation, to occur fracture of wire.And the main effect of esters of unsaturated carboxylic acids is a spinning property of improving interpolymer, makes carefully dawnization of precursor.But ternary is free-radical polymerized is a very complicated process, and especially controllability is poorer under reactivity ratio between monomer differs than the situation of big and high conversion.Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences discloses three patents (application number: 200410011039.X, 200510016572.X, 200710056329.X) and discloses a kind of novel comonomer vinyl cyanide/β-itaconic ester, vinyl cyanide/methylene-succinic acid/β-itaconic ester, vinyl cyanide/methylene-succinic acid/β-methylene-succinic acid acid amides respectively.This reactivity ratio of monomer and vinyl cyanide near and have the bi-functional monomer of unsaturated carboxylic acid and two kinds of comonomer functions of esters of unsaturated carboxylic acids concurrently, its objective is and reduce the cyclisation temperature, widen exothermic peak, improve spinning property, though but can improve spinning property through our above-mentioned characteristic that experimental results show that, but the heat release peak width is still narrow, and molecular weight wider distribution during binary polymerization.Patent (application number: 200710056083.6) disclose the employing 2,2'-Azobis(2,4-dimethylvaleronitrile) and replaced Diisopropyl azodicarboxylate, add chain-transfer agent, adopt vinyl cyanide/acrylate/methylene-succinic acid (or vinylformic acid, methacrylic acid), can make the interpolymer of high molecular, narrow molecular weight distributions, but still can not solve the narrow shortcoming of exothermic peak.
Summary of the invention
One of technical problem to be solved by this invention is the vinyl cyanide/acrylamide/β-itaconic ester interpolymer problem that does not relate in the prior art, and a kind of new high molecular ternary acrylonitrile compolymer body and preparation method thereof is provided.This interpolymer has the heat release peak width, molecular weight height, the advantage of narrow molecular weight distribution.Two of technical problem to be solved by this invention provides preparation method a kind of and one of technical solution problem corresponding interpolymer.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ternary acrylonitrile compolymer body comprises following general formula:
m＝2001～4000；n＝5～400；k＝5～400
Wherein the interpolymer weight-average molecular weight is between 150000 to 400000; Molecular weight distributing index is between 1.5 to 2.5.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of acrylonitrile compolymer body may further comprise the steps:
A) with the 2,2'-Azobis(2,4-dimethylvaleronitrile) being initiator, is comonomer with vinyl cyanide, acrylamide, β-itaconic ester, is solvent to be selected from least a in dimethyl sulfoxide (DMSO), dimethyl formamide or the N,N-DIMETHYLACETAMIDE.
B) in the desired amount solvent, monomer, initiator are mixed, join in the reactor, use with reaction to be the inert gasses displacement for several times, under 30～50 ℃ of temperature, reacted 6～48 hours, remove residual monomer and bubble, obtain ternary acrylonitrile compolymer body.
It is characterized in that in the technique scheme by weight percentage: vinyl cyanide accounts for 90～99% of total monomer weight, acrylamide accounts for 0.1～5% of total monomer weight, β-itaconic ester accounts for total monomer weight 0.1～5%, and it is 15～30% that comonomer accounts for total system weight percent concentration; β-itaconic ester is selected from least a in β-methylene-succinic acid methyl esters, β-methylene-succinic acid ethyl ester, β-methylene-succinic acid propyl ester or the β-itaconic acid n-butyl; It is 70～85% that solvent accounts for total system weight percent concentration; Initiator amount is 0.2～1% of a comonomer weight.
Because bifunctional monomer's β-itaconic ester has carboxyl and ester group simultaneously concurrently among the present invention, the characteristic of acrylamide possess hydrophilic property and reduction cyclisation temperature, two kinds of comonomers and main monomer vinyl cyanide reactivity ratio are approaching, and cause with 2,2'-Azobis(2,4-dimethylvaleronitrile) low temperature, the interpolymer molecule amount height that makes, narrow molecular weight distribution confirms it is vinyl cyanide/acrylamide/β-itaconic acid n-butyl terpolymer body structure through infrared spectra and ultimate analysis.Adopt technical solution of the present invention, can obtain the heat release peak width and reach 97 ℃, weight-average molecular weight can reach 300,000, the interpolymer of molecular weight distributing index in 1.5～2.0 scopes.Obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
By 800: 196: 1.5: 2.5: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), use nitrogen replacement at normal temperatures three times, 35 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-itaconic acid n-butyl terpolymers, confirm it is this ternary structural, m=2778 through infrared spectra and ultimate analysis, n=30, k=50; The interpolymer weight-average molecular weight is 25.8 ten thousand, and molecular weight distributing index is 1.72.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=215 ℃, heat release end temp T
2=308 ℃, Δ T=T
2-T
1=93 ℃, the exothermic peak broad.
[embodiment 2]
By 800: 196: 3: 1: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), use nitrogen replacement at normal temperatures four times, 40 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-itaconic acid n-butyl terpolymers, confirm it is this ternary structural through infrared spectra and ultimate analysis, the interpolymer weight-average molecular weight is 18.2 ten thousand, m=1995, n=75, k=25 molecular weight distributing index are 1.69.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=214 ℃, heat release end temp T
2=304 ℃, Δ T=T
2-T
1=90 ℃.
[embodiment 3]
By 800: 196: 2: 2: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-methylene-succinic acid ethyl ester, 2,2'-Azobis(2,4-dimethylvaleronitrile), use nitrogen replacement at normal temperatures five times, 50 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-methylene-succinic acid ethyl ester terpolymers, confirm it is this ternary structural through infrared spectra and ultimate analysis, m=1556, n=25, k=25 interpolymer weight-average molecular weight is 15.6 ten thousand, and molecular weight distributing index is 1.87.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=212 ℃, heat release end temp T
2=306 ℃, Δ T=T
2-T
1=94 ℃.
[embodiment 4]
By 800: 198: 1: 1: 1 weight ratio took by weighing dimethyl formamide, vinyl cyanide, acrylamide, β-itaconic acid n-butyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), use argon replaces at normal temperatures three times, 35 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-itaconic acid n-butyl terpolymers, confirm it is this ternary structural through infrared spectra and ultimate analysis, m=2578, n=35, k=35 interpolymer weight-average molecular weight is 25.9 ten thousand, and molecular weight distributing index is 1.97.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=219 ℃, heat release end temp T
2=311 ℃, Δ T=T
2-T
1=92 ℃.
[embodiment 5]
By 800: 198: 1.5: 0.5: 1 weight ratio took by weighing N,N-DIMETHYLACETAMIDE, vinyl cyanide, acrylamide, β-methylene-succinic acid methyl esters, 2,2'-Azobis(2,4-dimethylvaleronitrile), use the argon replaces secondary at normal temperatures, 40 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-methylene-succinic acid methyl esters terpolymers, confirm it is this ternary structural through infrared spectra and ultimate analysis, m=1898, n=35, k=9 interpolymer weight-average molecular weight is 18.6 ten thousand, and molecular weight distributing index is 1.86.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=217 ℃, heat release end temp T
2=311 ℃, Δ T=T
2-T
1=94 ℃.
[embodiment 6]
By 700: 196: 2: 2: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), use helium replacement at normal temperatures three times, 35 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-itaconic acid n-butyl terpolymers, confirm it is this ternary structural through infrared spectra and ultimate analysis, the interpolymer weight-average molecular weight is 27.9 ten thousand, m=2878, n=45, k=45 molecular weight distributing index are 1.77.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=219 ℃, heat release end temp T
2=311 ℃, Δ T=T
2-T
1=92 ℃.
[embodiment 7]
By 1000: 194: 3: 3: 1.2 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), use helium replacement at normal temperatures four times, 35 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-itaconic acid n-butyl terpolymers, confirm it is this ternary structural through infrared spectra and ultimate analysis, m=2358, n=75, k=75 interpolymer weight-average molecular weight is 23.7 ten thousand, and molecular weight distributing index is 1.77.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=220 ℃, heat release end temp T
2=319 ℃, Δ T=T
2-T
1=97 ℃.
[embodiment 8]
By 750: 194: 4: 2: 0.8 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-methylene-succinic acid propyl ester, 2,2'-Azobis(2,4-dimethylvaleronitrile), use nitrogen replacement at normal temperatures five times, 30 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, obtain vinyl cyanide/acrylamide/β-methylene-succinic acid propyl ester terpolymers, confirm it is this ternary structural, m=2878 through infrared spectra and ultimate analysis, n=75, k=50; The interpolymer weight-average molecular weight is 30.7 ten thousand, and molecular weight distributing index is 1.97.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=209 ℃, heat release end temp T
2=306 ℃, Δ T=T
2-T
1=97 ℃.
[comparative example 1]
By 800: 196: 2: 2: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, methylene-succinic acid, β-itaconic acid n-butyl, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 10.8 ten thousand, and molecular weight distributing index is 3.57.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=241 ℃, heat release end temp T
2=287 ℃, Δ T=T
2-T
1=46 ℃.
[comparative example 2]
By 800: 196: 2: 2: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, β-methylene-succinic acid acid amides, β-itaconic acid n-butyl, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 10.1 ten thousand, and molecular weight distributing index is 3.69.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=240 ℃, heat release end temp T
2=286 ℃, Δ T=T
2-T
1=46 ℃.
[comparative example 3]
By 800: 196: 4: 1 weight ratio took by weighing dimethyl formamide, vinyl cyanide, methylene-succinic acid, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 11.8 ten thousand, and molecular weight distributing index is 2.76.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=241 ℃, heat release end temp T
2=285 ℃, Δ T=T
2-T
1=44 ℃.
[comparative example 4]
By 800: 196: 4: 1 weight ratio took by weighing N,N-DIMETHYLACETAMIDE, vinyl cyanide, β-methylene-succinic acid methyl esters, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 10.8 ten thousand, and molecular weight distributing index is 2.96.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=235 ℃, heat release end temp T
2=281 ℃, Δ T=T
2-T
1=46 ℃, exothermic peak is narrower.
[comparative example 5]
By 800: 196: 2: 2: 1 weight ratio took by weighing N,N-DIMETHYLACETAMIDE, vinyl cyanide, methylene-succinic acid, methyl acrylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), use nitrogen replacement at normal temperatures three times, 40 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 17.8 ten thousand, and molecular weight distributing index is 2.12.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=240 ℃, heat release end temp T
2=291 ℃, Δ T=T
2-T
1=51 ℃.
[comparative example 6]
By 800: 198: 1: 1: 1 weight ratio took by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, methylene-succinic acid, methyl acrylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), use nitrogen replacement at normal temperatures three times, 45 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 15.8 ten thousand, and molecular weight distributing index is 2.02.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=243 ℃, heat release end temp T
2=291 ℃, Δ T=T
2-T
1=48 ℃.
[comparative example 7]
Weight ratio by 800/196/2/2/1 takes by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 11.6 ten thousand, and molecular weight distributing index is 2.57.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=211 ℃, heat release end temp T
2=293 ℃, Δ T=T
2-T
1=84 ℃.
[comparative example 8]
Weight ratio by 800/198/1/1/1 takes by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 11.9 ten thousand, and molecular weight distributing index is 2.37.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=209 ℃, heat release end temp T
2=291 ℃, Δ T=T
2-T
1=82 ℃.
[comparative example 9]
Weight ratio by 700/198/1.5/0.5/1 takes by weighing dimethyl sulfoxide (DMSO), vinyl cyanide, acrylamide, β-itaconic acid n-butyl, Diisopropyl azodicarboxylate, use nitrogen replacement at normal temperatures three times, 60 ℃ of polyreactions 24 hours, vacuum removal residual monomer and bubble, the interpolymer weight-average molecular weight is 11.6 ten thousand, and molecular weight distributing index is 2.66.Heat is analyzed DSC and is shown Exotherm Onset Temperature T
1=207 ℃, heat release end temp T
2=292 ℃, Δ T=T
2-T
1=85 ℃.
Claims (6)
1. ternary acrylonitrile compolymer body comprises following general formula:
m＝2001～4000；n＝5～400；k＝5～400
Wherein the interpolymer weight-average molecular weight is between 150000 to 400000; Molecular weight distributing index is between 1.5 to 2.5.
2. the preparation method of the described acrylonitrile compolymer body of claim 1 may further comprise the steps:
A) with the 2,2'-Azobis(2,4-dimethylvaleronitrile) being initiator, is comonomer with vinyl cyanide, acrylamide, β-itaconic ester, is solvent to be selected from least a in dimethyl sulfoxide (DMSO), dimethyl formamide or the N,N-DIMETHYLACETAMIDE.
B) in the desired amount solvent, monomer, initiator are mixed, join in the reactor, use with reaction to be the inert gasses displacement for several times, under 30～50 ℃ of temperature, reacted 6～48 hours, remove residual monomer and bubble, obtain ternary acrylonitrile compolymer body.
3. according to the preparation method of the described acrylonitrile compolymer body of claim 2, it is characterized in that by weight percentage: vinyl cyanide accounts for 90～99% of total monomer weight, acrylamide accounts for 0.1～5% of total monomer weight, β-itaconic ester accounts for total monomer weight 0.1～5%, and it is 15～30% that comonomer accounts for total system weight percent concentration.
4. the preparation method of acrylonitrile compolymer body according to claim 2 is characterized in that β-itaconic ester is selected from least a in β-methylene-succinic acid methyl esters, β-methylene-succinic acid ethyl ester, β-methylene-succinic acid propyl ester or the β-itaconic acid n-butyl.
5. the preparation method of acrylonitrile compolymer body according to claim 2 is characterized in that it is 70～85% that solvent accounts for total system weight percent concentration.
6. the preparation method of acrylonitrile compolymer body according to claim 2 is characterized in that initiator amount is 0.2～1% of a comonomer weight.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103668524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of low-viscosity high-performance binary acrylonitrile polymer spinning liquor |
| CN104628935A (en) * | 2013-11-06 | 2015-05-20 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
| CN104695037A (en) * | 2015-01-08 | 2015-06-10 | 江南大学 | Preparation method of high-performance polyacrylonitrile-based carbon fiber precursor |
| CN104693348A (en) * | 2015-03-17 | 2015-06-10 | 东华大学 | Method for preparing ternary polyacrylonitrile copolymer applicable to carbon fiber precursor |
| CN104710565A (en) * | 2015-03-17 | 2015-06-17 | 东华大学 | Preparation method of ternary polyacrylonitrile copolymer |
| CN111085088A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Polyacrylonitrile fiber for gas filtration and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103668524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of low-viscosity high-performance binary acrylonitrile polymer spinning liquor |
| CN103668524B (en) * | 2012-09-05 | 2016-07-13 | 中国石油化工股份有限公司 | Low viscosity, high-performance binary acrylonitrile copolymer spinning solution preparation method |
| CN104628935A (en) * | 2013-11-06 | 2015-05-20 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
| CN104628935B (en) * | 2013-11-06 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
| CN104695037A (en) * | 2015-01-08 | 2015-06-10 | 江南大学 | Preparation method of high-performance polyacrylonitrile-based carbon fiber precursor |
| CN104693348A (en) * | 2015-03-17 | 2015-06-10 | 东华大学 | Method for preparing ternary polyacrylonitrile copolymer applicable to carbon fiber precursor |
| CN104710565A (en) * | 2015-03-17 | 2015-06-17 | 东华大学 | Preparation method of ternary polyacrylonitrile copolymer |
| CN111085088A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Polyacrylonitrile fiber for gas filtration and preparation method and application thereof |
| CN111085088B (en) * | 2018-10-23 | 2022-04-05 | 中国石油化工股份有限公司 | Polyacrylonitrile fiber for gas filtration and preparation method and application thereof |
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