CN102747451B - Spinning solution of polyacrylonitrile-based carbon fibers - Google Patents
Spinning solution of polyacrylonitrile-based carbon fibers Download PDFInfo
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- CN102747451B CN102747451B CN201110098939.2A CN201110098939A CN102747451B CN 102747451 B CN102747451 B CN 102747451B CN 201110098939 A CN201110098939 A CN 201110098939A CN 102747451 B CN102747451 B CN 102747451B
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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 developing rapidly in generation nineteen sixty, because of excellent properties such as it has that quality is light, specific strength is high, specific modulus is high, high temperature resistant, corrosion-resistant, wear-resisting, antifatigue, conduction, heat conduction, be widely used in the military industries such as satellite, carrier rocket, tactical missile, spaceship, become indispensable material in space flight and aviation industry.Excellent carbon fiber with precursor should have that heat resistance is high, hole is constructed less, the feature such as few surface defects, compact structure, draftability are good.
Initial copolymer structure and performance have determined structure and the performance of final carbon fiber.Therefore, from polyacrylonitrile is synthetic, set about, determine 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, good spinnability etc.
Applied chemistry study dimethyl sulfoxide (DMSO) used in Changchun is as solvent, by 2,2'-Azobis(2,4-dimethylvaleronitrile), cause acrylonitrile and copolymerization monomer polymerization, the molecular weight of copolymer of gained is between 10～900,000, molecular weight distribution is (patent No. 200710056083.6) below 2.3, the spinning solution viscosity of this system gained is large, and spinnability compares poor.Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences application acrylonitrile, dimethyl formamide, distilled water, azodiisobutyronitrile and chain-transferring agent are at 50～70 ℃ after homopolymerization, make the spinning solution (patent No.: 02130023.3), synthetic like this spinning solution, molecular weight is too small, is difficult to the spinning solution of processability excellence.
Summary of the invention
Technical problem to be solved by this invention is in existing spinning solution, when copolymer content is 25～35% in stoste, exists spinning solution viscosity large, and the problem that gelatin phenomenon is serious provides a kind of spinning solution of new polyacrylonitrile-based carbon fibre.This spinning solution has when high polymer content is 25～35%, has spinning modest viscosity, the advantage that gel content is few.
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 spinning solution of polyacrylonitrile-based carbon fibre, in parts by weight, comprises following component:
A) 65～75 parts of DMFs;
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 by one-step method under initator 2,2'-Azobis(2,4-dimethylvaleronitrile) exists;
Wherein the viscosity of spinning solution is 90～180paS at 50 ℃, can pass through 1 μ m filter membrane.
In technique scheme, in copolymer, 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.In copolymer, the first monomer weight umber preferable range is 96～99 parts, 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 the present invention relates to is prepared by the following method; by 65～75 parts of solvent N; dinethylformamide, 25～35 part of first monomer acrylonitrile and the second monomer itaconic acid, initator 2,2'-Azobis(2,4-dimethylvaleronitrile); add in reactor; at reactive material, be under the gas shield of inertia; at 40～50 ℃, reaction, then deviates from residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution.
The present invention selects N, dinethylformamide is as spin solvent, because N, dinethylformamide is large for the solubility of polyacrylonitrile, so can prepare the spinning solution that solid content is relatively high, the spinning solution viscosity simultaneously preparing remains on 90～180paS at 50 ℃, and spinning property is excellent.In the present invention, owing to selecting 2,2'-Azobis(2,4-dimethylvaleronitrile), be initator, reaction is carried out at low temperatures, can obtain by one-step method that solid content is high, molecular weight is moderate, narrow molecular weight distribution, the polyacrylonitrile spinning solution solution that gel content is few,
Adopt the solution of the present invention, the polyacrylonitrile spinning solution obtaining, molecular weight can reach 120,000, molecular weight distribution≤3, its viscosity can be controlled at 90～180paS at 50 ℃, and gel content is few, can pass through the filtration of 1 μ m filter membrane, obtain good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Former liquid and preparation method thereof: the spinning solution the present invention relates to is prepared by the following method; by solvent, the first monomer acrylonitrile and the second monomer itaconic acid, initator; add in reactor; at reactive material, be under the gas shield of inertia and react; then deviate from residual monomer and bubble, obtain polyacrylonitrile copolymer spinning solution.
The polyacrylonitrile-base carbon fiber spinning primary fluid making 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 by 0.6% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 6.3 ten thousand, and molecular weight distribution is 2.71, and spinning solution viscosity is 91Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[embodiment 2]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, wherein acrylonitrile accounts for 99% of total monomer, itaconic acid accounts for 1% of total monomer, and copolymer is by causing by 0.6% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 7.3 ten thousand, and molecular weight distribution is 2.53, and spinning solution viscosity is 132Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[embodiment 3]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 65% N, dinethylformamide is as solvent, 35% acrylonitrile and itaconic acid copolymer, wherein acrylonitrile accounts for 99% of total monomer, itaconic acid accounts for 1% of total monomer, and copolymer is by causing by 0.6% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 7.5 ten thousand, and molecular weight distribution is 2.76, and spinning solution viscosity is 146Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[embodiment 4]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, wherein acrylonitrile accounts for 96% of total monomer, itaconic acid accounts for 4% of total monomer, and copolymer is by causing by 0.6% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 6.5 ten thousand, and molecular weight distribution is 2.74, and spinning solution viscosity is 134Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[embodiment 5]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, wherein acrylonitrile accounts for 97.5% of total monomer, itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing by 0.6% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 6.9 ten thousand, and molecular weight distribution is 2.78, and spinning solution viscosity is 115Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[embodiment 6]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, wherein acrylonitrile accounts for 97.5% of total monomer, itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing by 0.2% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 8.5 ten thousand, and molecular weight distribution is 2.01, and spinning solution viscosity is 174Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[embodiment 7]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, wherein acrylonitrile accounts for 97.5% of total monomer, itaconic acid accounts for 2.5% of total monomer, and copolymer is by causing by 1% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 5.8 ten thousand, and molecular weight distribution is 2.89, and spinning solution viscosity is 165Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
[comparative example 1]
The stoste of preparing according to the preparation method of embodiment 1, it consists of: 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, 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, molecular weight distribution is 5.88, spinning solution viscosity is 48Pas, spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane, but molecular weight is too low, distribute too wide, viscosity is low, and spinning solution poor performance can not be as the spinning solution of carbon fibre precursor.
[comparative example 2]
The stoste of preparing according to the preparation method of embodiment 1, 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 by 0.6% 2,2'-Azobis(2,4-dimethylvaleronitrile).This spinning solution molecular weight is 16.8 ten thousand, and molecular weight distribution is 2.15, and spinning solution viscosity is 350Pas (50), spinning solution gel content is many, can not pass through the filtration of 1 μ m filter membrane, could filter with 10 μ m filter membranes, molecular weight is too high, and viscosity is excessive, and spinning solution spinnability is poor.
Claims (1)
1. the preparation method of the spinning solution of a polyacrylonitrile-based carbon fibre, by solvent, the first monomer acrylonitrile and the second monomer itaconic acid, initator, add in reactor, at reactive material, be under the gas shield of inertia and react, then deviate from residual monomer and bubble, obtain polyacrylonitrile copolymer spinning solution;
The polyacrylonitrile-base carbon fiber spinning primary fluid making consists of: by weight percentage, 70% N, dinethylformamide is as solvent, 30% acrylonitrile and itaconic acid copolymer, wherein, by weight percentage, acrylonitrile accounts for 97.5% of total monomer, itaconic acid accounts for 2.5% of total monomer, and copolymer is to be caused by the 2,2'-Azobis(2,4-dimethylvaleronitrile) that accounts for copolymer weight 0.2%; This spinning solution molecular weight is 8.5 ten thousand, and molecular weight distribution is 2.01, and spinning solution viscosity is 174Pas, and spinning solution gel content is few, can pass through the filtration of 1 μ m filter membrane.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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