CN102747451A - Spinning solution of polyacrylonitrile-based carbon fibers - Google Patents
Spinning solution of polyacrylonitrile-based carbon fibers Download PDFInfo
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- CN102747451A CN102747451A CN2011100989392A CN201110098939A CN102747451A CN 102747451 A CN102747451 A CN 102747451A CN 2011100989392 A CN2011100989392 A CN 2011100989392A CN 201110098939 A CN201110098939 A CN 201110098939A CN 102747451 A CN102747451 A CN 102747451A
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Abstract
The invention relates to a novel spinning solution of polyacrylonitrile-based carbon fibers to mainly problems of too large viscosity and easy gel generation of spinning solutions in the prior art. The spinning solution of the polyacrylonitrile-based carbon fibers comprises the following components, by weight, 65-75 parts of N,N-dimethyl formamide, and 25-35 parts of a copolymer, wherein the copolymer is obtained through carrying out a one step method on a first monomer acrylonitrile and a second monomer itaconic acid in the presence of an initiator azobisisoheptonitrile. The solution prepared through adopting above technical scheme well solves the problems, and can be applied to the industrial production of carbon fiber precursors.
Description
Technical field
The present invention relates to a kind of spinning solution of polyacrylonitrile-based carbon fibre.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the new material that develops rapidly in generation nineteen sixty; Because of excellent properties such as it has light weight, specific strength is high, specific modulus is high, high temperature resistant, corrosion-resistant, wear-resisting, antifatigue, conduction, heat conduction; Be widely used in military industries such as satellite, carrier rocket, tactical missile, spaceship, become indispensable material in the space flight and aviation industry.Excellent carbon fiber with precursor should have that heat resistance height, hole are constructed less, characteristics such as few surface defects, compact structure, draftability are good.
Initial copolymer structure and performance have determined the structure and the performance of final carbon fiber.Therefore, set about from polyacrylonitrile is synthetic, confirm the effect of different comonomers to polyacrylonitrile structure and performance, the development of carrying out polyacrylonitrile fibril is necessary.In order to obtain excellent polyacrylonitrile fibril, will select excellent properties spinning solution system.And the acrylonitrile spinning solution of function admirable should possess following performance: moderate molecular weight, Narrow Molecular Weight Distribution, better spinnability etc.
Changchun applied chemistry research institute with dimethyl sulfoxide (DMSO) as solvent; Cause acrylonitrile and copolymerization monomer polymerization with ABVN; The molecular weight of copolymer of gained is between 10～900,000; Molecular weight distribution is (patent No. 200710056083.6) below 2.3, and the spinning solution viscosity of this system gained is big, and spinnability compares relatively poor.Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences uses acrylonitrile, dimethyl formamide, distilled water, azodiisobutyronitrile and chain-transferring agent after 50～70 ℃ of following homopolymerizations; Make the spinning solution (patent No.: 02130023.3); Synthetic like this spinning solution; Molecular weight is too small, is difficult to the excellent spinning solution of processability.
Summary of the invention
Technical problem to be solved by this invention is in the existing spinning solution, when copolymer content is 25～35% in the stoste, exists spinning solution viscosity big, and the problem that gelatin phenomenon is serious provides a kind of spinning solution of new polyacrylonitrile-based carbon fibre.It is 25～35% o'clock that this spinning solution has at high polymer content, has the spinning modest viscosity, the advantage that gel content is few.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of spinning solution of polyacrylonitrile-based carbon fibre in parts by weight, comprises following component:
A) 65～75 parts of N, dinethylformamide;
B) 25～35 parts of copolymers, molecular weight of copolymer is 6～120,000, molecular weight distribution≤3, copolymer is selected from that the first monomer acrylonitrile and the second monomer itaconic acid make through one-step method in the presence of the initator ABVN;
Wherein the viscosity of spinning solution is 90～180paS under 50 ℃, can pass through 1 μ m filter membrane.
In the technique scheme, in parts by weight, the first monomer weight umber is 90～99.9 parts in the copolymer, and the second monomer weight umber is 0.1～10 part.The first monomer weight umber preferable range is 96～99 parts in the copolymer, and the second monomer preferable range is 1～4 part; The initiator amount preferable range of using is 0.2～1.0% of copolymer weight.
The spinning solution that the present invention relates to prepares through following method; With 65～75 parts of solvent N, dinethylformamide, 25～35 part of first monomer acrylonitrile and the second monomer itaconic acid, initator ABVN add in the agitated reactor; Be under the inert gasses protection at reactive material; 40～50 ℃ of reactions down, deviate from residual monomer and bubble then, obtain polyacrylonitrile copolymer spinning solution.
The present invention selects N for use; Dinethylformamide is as spin solvent; Be that dinethylformamide is big for the solubility of polyacrylonitrile, so can prepare the high relatively spinning solution of solid content because of N; The spinning solution viscosity for preparing simultaneously remains on 90～180paS under 50 ℃, spinning property is excellent.Because to select ABVN for use be initator, make reaction carry out at low temperatures among the present invention, can obtain solid content height, moderate, the narrow molecular weight distribution of molecular weight through one-step method, the polyacrylonitrile spinning solution solution that gel content is few,
Adopt scheme of the present invention, the polyacrylonitrile spinning solution that obtains, molecular weight can reach 120,000; Molecular weight distribution≤3, its viscosity can be controlled at 90～180paS under 50 ℃, and gel content is few; Can obtain better technical effect through the filtration of 1 μ m filter membrane.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Former liquid and preparation method thereof: the spinning solution that the present invention relates to prepares through following method; With solvent, the first monomer acrylonitrile and the second monomer itaconic acid, initator; Add in the agitated reactor; Be reaction under the inert gasses protection at reactive material, deviate from residual monomer and bubble then, obtain polyacrylonitrile copolymer spinning solution.
The polyacrylonitrile-base carbon fiber spinning primary fluid that makes consists of: 75% N; Dinethylformamide is as solvent, 25% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 99% of total monomer; Itaconic acid accounts for 1% of total monomer, and copolymer is by causing with 0.6% ABVN.This spinning solution molecular weight is 6.3 ten thousand, and molecular weight distribution is 2.71, and spinning solution viscosity is 91Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 2]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% N; Dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 99% of total monomer; Itaconic acid accounts for 1% of total monomer, and copolymer is by causing with 0.6% ABVN.This spinning solution molecular weight is 7.3 ten thousand, and molecular weight distribution is 2.53, and spinning solution viscosity is 132Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 3]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 65% N; Dinethylformamide is as solvent, 35% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 99% of total monomer; Itaconic acid accounts for 1% of total monomer, and copolymer is by causing with 0.6% ABVN.This spinning solution molecular weight is 7.5 ten thousand, and molecular weight distribution is 2.76, and spinning solution viscosity is 146Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 4]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% N; Dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 96% of total monomer; Itaconic acid accounts for 4% of total monomer, and copolymer is by causing with 0.6% ABVN.This spinning solution molecular weight is 6.5 ten thousand, and molecular weight distribution is 2.74, and spinning solution viscosity is 134Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 5]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% N; Dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 97.5% of total monomer; Itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing with 0.6% ABVN.This spinning solution molecular weight is 6.9 ten thousand, and molecular weight distribution is 2.78, and spinning solution viscosity is 115Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 6]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% N; Dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 97.5% of total monomer; Itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing with 0.2% ABVN.This spinning solution molecular weight is 8.5 ten thousand, and molecular weight distribution is 2.01, and spinning solution viscosity is 174Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 7]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% N; Dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 97.5% of total monomer; Itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing with 1% ABVN.This spinning solution molecular weight is 5.8 ten thousand, and molecular weight distribution is 2.89, and spinning solution viscosity is 165Pas, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[comparative example 1]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% N; Dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 97.5% of total monomer; Itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing with 0.6% azodiisobutyronitrile.This spinning solution molecular weight is 2.3 ten thousand, and molecular weight distribution is 5.88, and spinning solution viscosity is 48Pas; The spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane, but molecular weight is low excessively; It is too wide to distribute; Viscosity is low, and the spinning solution poor performance can not be as the spinning solution of carbon fibre precursor.
[comparative example 2]
Stoste according to the preparation method of embodiment 1 preparation; It consists of: 70% dimethyl sulfoxide (DMSO) is as solvent, 30% acrylonitrile and itaconic acid copolymer, and wherein acrylonitrile accounts for 97.5% of total monomer; Itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing with 0.6% ABVN.This spinning solution molecular weight is 16.8 ten thousand, and molecular weight distribution is 2.15, and spinning solution viscosity is 350Pas (50); The spinning solution gel content is many, can not will use 10 μ m filter membranes to filter through the filtration of 1 μ m filter membrane; Molecular weight is too high, and viscosity is excessive, and the spinning solution spinnability is poor.
Claims (4)
1. the spinning solution of a polyacrylonitrile-based carbon fibre in parts by weight, comprises following component:
A) 65～75 parts of N, dinethylformamide;
B) 25～35 parts of copolymers, molecular weight of copolymer is 6～120,000, molecular weight distribution≤3, copolymer is selected from that the first monomer acrylonitrile and the second monomer itaconic acid make through one-step method in the presence of the initator ABVN;
Wherein the viscosity of spinning solution is 90～180paS under 50 ℃, can pass through 1 μ m filter membrane.
2. the spinning solution of polyacrylonitrile-based carbon fibre according to claim 1 is characterized in that in the copolymer that in parts by weight, the first monomer weight umber is 90～99.9 parts, and the second monomer weight umber is 0.1～10 part.
3. the spinning solution of polyacrylonitrile-based carbon fibre according to claim 1 is characterized in that in the copolymer that in parts by weight, the first monomer weight umber is 96～99 parts, and the second monomer weight umber is 1～4 part.
4. the spinning solution of polyacrylonitrile-based carbon fibre according to claim 1 is characterized in that the initiator amount that uses is 0.2～1.0% of copolymer weight.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105603543A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Fibre spinning method for polyacrylonitrile solution |
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| JP2002145939A (en) * | 2000-11-16 | 2002-05-22 | Mitsubishi Rayon Co Ltd | Acrylonitrile-based polymer and carbon material using the same |
| CN101144203A (en) * | 2007-09-18 | 2008-03-19 | 中国科学院长春应用化学研究所 | Method for preparing high molecular weight acrylonitrile copolymer with narrow molecular weight distribution |
| 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 |
| CN101215357A (en) * | 2008-01-07 | 2008-07-09 | 山西恒天纺织新纤维科技有限公司 | Continuous polymerization preparation method for polyacrylonitrile base carbon fiber protofilament spinning fluid |
| CN101781809A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with uniform chain structure and narrow molecular-weight distribution and preparation method thereof |
| CN101805936A (en) * | 2010-03-09 | 2010-08-18 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with high molecular weight and narrow distribution and preparation method thereof |
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Patent Citations (6)
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| JP2002145939A (en) * | 2000-11-16 | 2002-05-22 | Mitsubishi Rayon Co Ltd | Acrylonitrile-based polymer and carbon material using the same |
| CN101144203A (en) * | 2007-09-18 | 2008-03-19 | 中国科学院长春应用化学研究所 | Method for preparing high molecular weight acrylonitrile copolymer with narrow molecular weight distribution |
| 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 |
| CN101215357A (en) * | 2008-01-07 | 2008-07-09 | 山西恒天纺织新纤维科技有限公司 | Continuous polymerization preparation method for polyacrylonitrile base carbon fiber protofilament spinning fluid |
| CN101781809A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with uniform chain structure and narrow molecular-weight distribution and preparation method thereof |
| CN101805936A (en) * | 2010-03-09 | 2010-08-18 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with high molecular weight and narrow distribution and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603543A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Fibre spinning method for polyacrylonitrile solution |
| CN105603543B (en) * | 2014-11-20 | 2018-06-08 | 中国石油化工股份有限公司 | The silk spraying method of polyacrylonitrile solution |
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