CN101759837A - Method for preparing polyacrylonitrile spinning solution for high-performance carbon fiber in ionic liquid - Google Patents
Method for preparing polyacrylonitrile spinning solution for high-performance carbon fiber in ionic liquid Download PDFInfo
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- CN101759837A CN101759837A CN200910234312A CN200910234312A CN101759837A CN 101759837 A CN101759837 A CN 101759837A CN 200910234312 A CN200910234312 A CN 200910234312A CN 200910234312 A CN200910234312 A CN 200910234312A CN 101759837 A CN101759837 A CN 101759837A
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Abstract
The invention relates to a method for a preparing polyacrylonitrile spinning solution for a high-performance carbon fiber in an ionic liquid. The method comprises the following steps: sequentially adding a monomer in an acrylonitrile binary copolymerization system or a monomer in an acrylonitrile ternary polymerization system into the ionic liquid, dissolving at the room temperature, adding an evocating agent, and charging inactive gas for free radical polyreaction, stopping the polyreaction with ice-bath after reaction, solidifying the polymerisate with water and obtaining the polyacrylonitrile material after repeated water rinsing, oven drying and purification, and mixing to dissolve the obtained polyacrylonitrile powder material with dimethyl sulfoxide as the solution, thereby obtaining the polyacrylonitrile spinning solution with high-performance carbon fiber. In the method, the ionic liquid is used as the reaction solvent, with a wide melting point range, thereby facilitating the control of the polymerization temperature, and greatly speeding up the polymerization; and the obtained polyacrylonitrile has high molecular weight and narrow molecular weight distribution, thereby facilitating the preparation of the polyacrylonitrile precursor with stable performance for carbon fiber, improving the productivity and reducing the cost.
Description
Technical field
The invention belongs to a kind of high-performance fiber preparation method of spinning dope, relate in particular to a kind of method that in ionic liquid, prepares polyacrylonitrile spinning solution for high-performance carbon fiber.
Background of invention
Carbon fiber has high ratio modulus, high specific strength, good characteristic such as high temperature resistant, corrosion-resistant, has been widely used in every field.PAN-based carbon fiber is that vinyl cyanide is arranged is that the unitary polymkeric substance of main molecules chain structure is handled through high temperature cabonization through spinning again and formed.
Be used to prepare the superpolymer polyacrylonitrile of polyacrylonitrile-base carbon fiber spinning primary fluid, can be divided into radical polymerization, anionoid polymerization, polycoordination etc. by its reaction mechanism.At present, using maximum is radical polymerization, and its implementation method has solution polymerization, suspension polymerization, aqueous phase precipitation polymerization.Wherein in the method for solution polymerization, the solvent that is adopted comprises strong solution, liquor zinci chloridi and the nitric acid etc. of dimethyl formamide DMF, N,N-DIMETHYLACETAMIDE DMAc, dimethyl sulfoxide (DMSO) DMSo, Sodium Thiocyanate 99 NaSCN.The solution polymerization of vinyl cyanide in these solvents has that polymerization system viscosity is low, mixing and advantages such as heat transfer is easier to, easy temperature control system, but also exist a lot of shortcomings,, rate of polymerization low as monomer concentration slowly causes throughput and plant factor low, and shifted by the molecular chain that solvent causes and to make molecular weight reduce and molecular weight distribution becomes greatly.Particularly separated from solvent reclaims the cost increased, and to HUMAN HEALTH, harm that environmental pollution brought, is unfavorable for the preparation and the development of high-performance polyacrylonitrile-based carbon fiber spinning solution.
Preparation molecular weight height and the polyacrylonitrile-base carbon fiber spinning primary fluid of narrow molecular weight distribution is the research emphasis of carbon fibre precursor preparation process always.This is because high molecular weight can improve the intensity of polyacrylonitrile fibril, and narrower molecular weight distribution can make fiber each several part intensity distribution even, make fibrous mechanical property better and can less continuous production in the fracture of wire phenomenon, enhance productivity.
Chinese patent CN 1536107A discloses a kind of preparation method of polyacrylonitrile spinning solution, vinyl cyanide and a spot of methyl acrylate, methylene-succinic acid is dissolved in carries out polymerization in homogeneous phase in the 49%-54% sodium thiocyanate solution.Contain the sodium Metal 99.5 ion in its polyacrylonitrile fibril that makes, thereby cause its carbon fiber performance to reduce greatly.
Chinese patent CN 1401675A discloses employing organic solvent and water as polymerisation medium, has solved polymerization system heterogeneity, the slow problem of polymerization velocity, but the molecular weight of polyacrylonitrile size and molecular weight distribution are not seen obvious change.
The clear 63-35819 of Japanese Patent JK. discloses a kind of employing DMF and water as polymerisation medium, obtains weight-average molecular weight and be 800,000 polyacrylonitrile, and molecular weight distribution is 3.4, though molecular weight is bigger, molecular weight distribution is still wider.
Summary of the invention
The technical problem to be solved in the present invention is at the deficiencies in the prior art, a kind of method for preparing polyacrylonitrile spinning solution for high-performance carbon fiber in ionic liquid is provided, present polyacrylonitrile spinning solution for carbon fiber molecular weight distribution is wide, quality stability is poor, speed of reaction is wide-ranging and solvent for use has intensive corrodibility and volatility to tackle, and causes serious environmental to pollute.
The technical problem to be solved in the present invention is achieved through the following technical solutions, and a kind of method for preparing polyacrylonitrile spinning solution for high-performance carbon fiber in ionic liquid is characterized in comprising the following steps:
(1) monomer in the vinyl cyanide binary copolymerization system or the monomer in the vinyl cyanide ternary copolymerization system are added in the ionic liquid successively, the room temperature dissolving adds initiator, and feeds rare gas element, carries out Raolical polymerizable.
Described ionic liquid has following general structure:
Wherein, R1, R2, R3, R4 and R5 distinguish the substituting group on the imidazole ring, are selected from the fatty group of replacement or unsubstituted 1 to 20 carbon atom independently of one another.X-is selected from following negatively charged ion: BF
4 -, PF
6 -, Cl
-, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
2C
-A kind of.
(2) reaction finishes the back and stops polyreaction with ice bath, obtains the polyacrylonitrile powder with the solid polymerisate of water-setting and after washing the oven dry purifying repeatedly.
(3) utilize dimethyl sulfoxide (DMSO) as solvent with the above-mentioned polyacrylonitrile powder stirring and dissolving that obtains, obtain the high-performance carbon fibre polyacrylonitrile spinning solution.
The technical problem to be solved in the present invention can also come further to realize by the following technical programs, described binary copolymerization system is the copolymerization system of vinyl cyanide and methylene-succinic acid, and described terpolymers is the copolymerization system of vinyl cyanide, methylene-succinic acid and methyl acrylate.
The technical problem to be solved in the present invention can also come to realize that further described initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) by the following technical programs; Described rare gas element is nitrogen or argon gas.
The technical problem to be solved in the present invention can also be come further realization by the following technical programs, and described Raolical polymerizable temperature is 40-70 ℃, and the reaction times is 0.5-8 hour, and reaction conversion ratio is 40-95%.
The technical problem to be solved in the present invention can also come further to realize by the following technical programs, it is that reaction solution volume 3-10 times normal-temperature water is carried out polymkeric substance and solidified that described washing oven dry purifying is meant with volume, with temperature is that normal temperature to 90 ℃, quality are the 2-5 water washing doubly 3-5 time of solids, and 65 ℃ of following vacuum-dryings are to constant weight.
The technical problem to be solved in the present invention can also come further to realize by the following technical programs, and step (2) is described solidifies, washs, filters the washings that obtains, and the ionic liquid physical efficiency that obtains after the processed repeatedly is recycled and reused for above-mentioned reaction.
The technical problem to be solved in the present invention can also come further to realize by the following technical programs, the described dimethyl sulfoxide (DMSO) of utilizing is as solvent, solvent temperature is 40-70 ℃, sulfoxide concentration 70-95%, polyacrylonitrile powder concentration 5-35%, dissolving stirring velocity 20-150rpm, dissolution time 5-10 hour, through after the deaeration, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber.
Beneficial effect of the present invention:
(1) polyacrylonitrile spinning solution for high-performance carbon fiber viscosity-average molecular weight of the present invention is 6.0 * 10
4-1.4 * 10
5Molecular weight distribution is 1.3-1.8, the weight content of polyacrylonitrile base polymer is 5-35% in the polyacrylonitrile spinning solution, molecular weight is higher and molecular weight distribution is narrower, the solid content of spinning solution is higher, can make the polyacrylonitrile fibril for carbon fiber of stable performance, and can enhance productivity, reduce cost.
(2) adopting ionic liquid is reaction solvent, and its melting range is wide, in the polymeric reaction temperature scope, helps the control of temperature of reaction, and can accelerate the speed of polyreaction greatly.
Embodiment
A kind of method for preparing polyacrylonitrile spinning solution for high-performance carbon fiber in ionic liquid comprises the following steps:
(1) monomer in the vinyl cyanide binary copolymerization system or the monomer in the vinyl cyanide ternary copolymerization system are added in the ionic liquid successively, the room temperature dissolving adds initiator, and feeds rare gas element, carries out Raolical polymerizable.
(2) reaction finishes the back and stops polyreaction with ice bath, obtains the polyacrylonitrile powder with the solid polymerisate of water-setting and after washing the oven dry purifying repeatedly.
(3) utilize dimethyl sulfoxide (DMSO) as solvent with the above-mentioned polyacrylonitrile powder stirring and dissolving that obtains, obtain the high-performance carbon fibre polyacrylonitrile spinning solution.
Binary copolymerization system described in the present invention is the copolymerization system of vinyl cyanide and methylene-succinic acid, and described terpolymers is the copolymerization system of vinyl cyanide, methylene-succinic acid and methyl acrylate.
Ionic liquid described in the present invention has following general structure:
Wherein, R1, R2, R3, R4 and R5 distinguish the substituting group on the imidazole ring, are selected from the fatty group of replacement or unsubstituted 1 to 20 carbon atom independently of one another.X-is selected from following negatively charged ion: BF
4 -, PF
6 -, Cl
-, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
2C
-A kind of.
Initiator described in the present invention is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described rare gas element is nitrogen or argon gas.
Raolical polymerizable temperature described in the present invention is 40-70 ℃, and the reaction times is 0.5-8 hour, and reaction conversion ratio is 40-95%.
It is that reaction solution volume 3-10 normal-temperature water is doubly carried out polymkeric substance and solidified that washing described in the present invention oven dry purifying is meant with volume, is that normal temperature to 90 ℃, quality are 2-5 times water washing 3-5 time of solids with temperature, and 65 ℃ of following vacuum-dryings are to constant weight.
Step among the present invention (2) is described solidifies, washs, filters the washings that obtains, and the ionic liquid physical efficiency that obtains after the processed repeatedly is recycled and reused for above-mentioned reaction.
Utilize dimethyl sulfoxide (DMSO) as solvent described in the present invention, solvent temperature is 40-70 ℃, sulfoxide concentration 70-95%, polyacrylonitrile powder concentration 5-35%, dissolving stirring velocity 20-150rpm, dissolution time 5-10 hour,, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber through after the deaeration.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment one
Under the room temperature with acrylonitrile monemer, methylene-succinic acid monomer and ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate respectively in 20%, 1% and 79% massfraction ratio; stirring makes it the thorough mixing dissolving; add a small amount of initiator A IBN again, and will feed nitrogen protection in the polymeric kettle.Temperature is risen to 58 ℃ of reactions 4 hours, and the reaction conversion ratio that records polymkeric substance is 65%.
With volume is that the normal-temperature water of 5 times of reaction solution volumes is carried out polymkeric substance and solidified, and is that 70 ℃, quality are 3 times the water washing 4 times of solids with temperature, and 65 ℃ of following vacuum-dryings are to constant weight.The viscosity-average molecular weight that records prepared polyacrylonitrile is 8.0 * 10
4, molecular weight distribution is 1.4.
Use dimethyl sulfoxide (DMSO) as solvent again, solvent temperature is 65 ℃, sulfoxide concentration 75%, and polyacrylonitrile powder concentration 25%, dissolving stirring velocity 50rpm, dissolution time 5 hours through after the deaeration, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber.
Embodiment two
Under the room temperature with acrylonitrile monemer, methylene-succinic acid monomer and ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate respectively in 20%, 1% and 79% massfraction ratio; stirring makes it the thorough mixing dissolving; add a small amount of initiator A IBN again, and will feed nitrogen protection in the polymeric kettle.Temperature is risen to 55 ℃ of reactions 4 hours, and the reaction conversion ratio that records polymkeric substance is 58%.
With volume is that the normal-temperature water of 5 times of reaction solution volumes is carried out polymkeric substance and solidified, and is that 70 ℃, quality are 3 times the water washing 4 times of solids with temperature, and 65 ℃ of following vacuum-dryings are to constant weight.The viscosity-average molecular weight that records prepared polyacrylonitrile is 9.6 * 10
4, molecular weight distribution is 1.6.
Use dimethyl sulfoxide (DMSO) as solvent again, solvent temperature is 65 ℃, sulfoxide concentration 75%, and polyacrylonitrile powder concentration 25%, dissolving stirring velocity 50rpm, dissolution time 5 hours through after the deaeration, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber.
Embodiment three
Under the room temperature with acrylonitrile monemer, methylene-succinic acid monomer and ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate respectively in 20.5%, 0.5% and 79% massfraction ratio; stirring makes it the thorough mixing dissolving; add a small amount of initiator A IBN again, and will feed nitrogen protection in the polymeric kettle.Temperature is risen to 58 ℃ of reactions 4 hours, and the reaction conversion ratio that records polymkeric substance is 69%.
With volume is that the normal-temperature water of 5 times of reaction solution volumes is carried out polymkeric substance and solidified, and is that 70 ℃, quality are 3 times the water washing 4 times of solids with temperature, and 65 ℃ of following vacuum-dryings are to constant weight.The viscosity-average molecular weight that records prepared polyacrylonitrile is 12.5 * 10
5, molecular weight distribution is 1.5.
Use dimethyl sulfoxide (DMSO) as solvent again, solvent temperature is 65 ℃, sulfoxide concentration 75%, and polyacrylonitrile powder concentration 25%, dissolving stirring velocity 50rpm, dissolution time 5 hours through after the deaeration, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber.
Embodiment four
Under the room temperature with acrylonitrile monemer, methylene-succinic acid monomer and ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate respectively in 20%, 1% and 79% massfraction ratio; stirring makes it the thorough mixing dissolving; add a small amount of initiator A IBN again, and will feed nitrogen protection in the polymeric kettle.Temperature is risen to 53 ℃ of reactions 4 hours, and the reaction conversion ratio that records polymkeric substance is 52%.
With volume is that the normal-temperature water of 5 times of reaction solution volumes is carried out polymkeric substance and solidified, and is that 70 ℃, quality are 3 times the water washing 4 times of solids with temperature, and 65 ℃ of following vacuum-dryings are to constant weight.The viscosity-average molecular weight that records prepared polyacrylonitrile is 12.8 * 10
5, molecular weight distribution is 1.3.
Use dimethyl sulfoxide (DMSO) as solvent again, solvent temperature is 65 ℃, sulfoxide concentration 75%, and polyacrylonitrile powder concentration 25%, dissolving stirring velocity 50rpm, dissolution time 5 hours through after the deaeration, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber.
Claims (7)
1. a method for preparing the high-performance carbon fibre polyacrylonitrile spinning solution in ionic liquid comprises the following steps:
(1) monomer in the vinyl cyanide binary copolymerization system or the monomer in the vinyl cyanide ternary copolymerization system are added in the ionic liquid successively, the room temperature dissolving adds initiator, and feeds rare gas element, carries out Raolical polymerizable;
Used ionic liquid has following general structure:
Wherein, R
1, R
2, R
3, R
4And R
5Distinguish the substituting group on the imidazole ring, be selected from the fatty group of replacement or unsubstituted 1 to 20 carbon atom independently of one another, X
-Be to be selected from following negatively charged ion: BF
4 -, PF
6 -, Cl
-, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
2C
-A kind of;
(2) reaction finishes the back and stops polyreaction with ice bath, obtains the polyacrylonitrile powder with the solid polymerisate of water-setting and after washing the oven dry purifying repeatedly;
(3) utilize dimethyl sulfoxide (DMSO) as solvent with the above-mentioned polyacrylonitrile powder stirring and dissolving that obtains, obtain the high-performance carbon fibre polyacrylonitrile spinning solution.
2. a kind of method that in ionic liquid, prepares polyacrylonitrile spinning solution for high-performance carbon fiber according to claim 1, it is characterized in that: described binary copolymerization system is the copolymerization system of vinyl cyanide and methylene-succinic acid, and described terpolymers is the copolymerization system of vinyl cyanide, methylene-succinic acid and methyl acrylate.
3. a kind of method for preparing polyacrylonitrile spinning solution for high-performance carbon fiber in ionic liquid according to claim 1 is characterized in that: used initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described rare gas element is nitrogen or argon gas.
4. a kind of method that in ionic liquid, prepares polyacrylonitrile spinning solution for high-performance carbon fiber according to claim 1, it is characterized in that: described Raolical polymerizable temperature is 40-70 ℃, reaction times is 0.5-8 hour, and reaction conversion ratio is 40-95%.
5. a kind of method that in ionic liquid, prepares polyacrylonitrile spinning solution for high-performance carbon fiber according to claim 1, it is characterized in that: it is that reaction solution volume 3-10 times normal-temperature water is carried out polymkeric substance and solidified that described washing oven dry purifying is meant with volume, with temperature is that normal temperature to 90 ℃, quality are the 2-5 water washing doubly 3-5 time of solids, and 65 ℃ of following vacuum-dryings are to constant weight.
6. a kind of method that in ionic liquid, prepares polyacrylonitrile spinning solution for high-performance carbon fiber according to claim 1, it is characterized in that: step (2) is described solidifies, washs, filters the washings that obtains, and the ionic liquid physical efficiency that obtains after the processed repeatedly is recycled and reused for above-mentioned reaction.
7. a kind of method that in ionic liquid, prepares polyacrylonitrile spinning solution for high-performance carbon fiber according to claim 1, it is characterized in that: utilize dimethyl sulfoxide (DMSO) as solvent, solvent temperature is 40-70 ℃, sulfoxide concentration 70-95%, polyacrylonitrile powder concentration 5-35%, dissolving stirring velocity 20-150rpm, dissolution time 5-10 hour, through after the deaeration, can obtain polyacrylonitrile spinning solution for high-performance carbon fiber.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130572A (en) * | 2014-08-20 | 2014-11-05 | 苏州德宝凯迪新材料有限公司 | Carbon fiber reinforced polyamide composite material and preparation method thereof |
| CN104130572B (en) * | 2014-08-20 | 2017-01-04 | 苏州德宝凯迪新材料有限公司 | A kind of carbon fiber reinforced polyamide composite material and preparation method thereof |
| CN109137122A (en) * | 2018-07-25 | 2019-01-04 | 司彩霞 | A kind of preparation method of ion liquid modified heat-resistance polypropylene nitrile fiber |
-
2009
- 2009-11-24 CN CN2009102343128A patent/CN101759837B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130572A (en) * | 2014-08-20 | 2014-11-05 | 苏州德宝凯迪新材料有限公司 | Carbon fiber reinforced polyamide composite material and preparation method thereof |
| CN104130572B (en) * | 2014-08-20 | 2017-01-04 | 苏州德宝凯迪新材料有限公司 | A kind of carbon fiber reinforced polyamide composite material and preparation method thereof |
| CN109137122A (en) * | 2018-07-25 | 2019-01-04 | 司彩霞 | A kind of preparation method of ion liquid modified heat-resistance polypropylene nitrile fiber |
| CN109137122B (en) * | 2018-07-25 | 2020-09-29 | 欧士曼(台州)高分子科技有限公司 | Preparation method of ionic liquid modified heat-resistant polyacrylonitrile fiber |
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Address after: 222000 No.6 Yunqiao Road, Dapu Industrial Zone, Lianyungang Economic and Technological Development Zone, Jiangsu Province Patentee after: Zhongfu Shenying Carbon Fiber Co.,Ltd. Address before: 222000 No.6 Yunqiao Road, Dapu Industrial Zone, Lianyungang Economic and Technological Development Zone, Jiangsu Province Patentee before: ZHONGFU SHENYING CARBON FIBER Co.,Ltd. |
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