CN106591995B - The preparation method of high-quality polyacrylonitrile spinning solution - Google Patents
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Abstract
The present invention relates to a kind of preparation method of high-quality polyacrylonitrile spinning solution, mainly solve to take off that single-action rate is lower in the prior art, the larger problem of the resulting carbon fibre precursor performance CV value of spinning.The present invention by using: a, solvent dimethyl sulfoxide, the first monomers acrylonitrile, second comonomer itaconic acid and initiator azodiisobutyronitrile, regulator are polymerize to obtain polymerization stoste；B, the pressure of de- one-pot is evacuated to vacuum degree is 10-1000mbar, during polymer fluid is squeezed into de- one-pot, the mixed gas of dimethyl sulfoxide and inert gas is passed through into kettle from de- one-pot bottom, mixed gas temperature is 50-150 DEG C, the content of dimethyl sulfoxide is 0.1-100% (wt) in mixed gas, available residual single amount is less than 0.3%, the technical solution of the polyacrylonitrile spinning solution of solid content stable and uniform preferably resolves the problem, in the industrial production for the carbon fibre precursor that can be used for.
Description
Technical field
The present invention relates to a kind of preparation methods of high-quality polyacrylonitrile spinning solution.
Background technique
Polyacrylonitrile (PAN) base carbon fibre is the new material that develops rapidly of generation nineteen sixty, because its with light weight,
The excellent properties such as specific strength height, specific modulus height, high temperature resistant, corrosion-resistant, wear-resisting, antifatigue, conductive, thermally conductive, are widely used in
The military industries such as satellite, carrier rocket, tactical missile, spaceship, it has also become indispensable material in aerospace industries.
Excellent carbon fiber Wesy precursor should have heat resistance is high, hole constructs less, few surface defects, compact structure, draftability are good etc.
Feature.
Precursor is the premise for producing high-performance carbon fibre.Prepare molecular weight of the high performance precursor in addition to needing spinning solution
Moderate, outside preferable hydrophily, de- single process efficiency of spinning solution wants high, and residual list will lack, while be also required for more stable, equal
Even solid content.De- single process efficiency of spinning solution is higher, and residual list is less, then the molecular weight distribution of spinning solution is relatively narrow, benefit
In the stretching of spinning process, it is easy to that high-performance precursor is made；Spinning solution has stable, uniform solid content, then the cv value of precursor
Smaller, precursor performance is stablized, and otherwise, spinning process will will appear more lousiness, filament, and spinning process is unstable, not easily-controllable
System, precursor performance are poor；
So guaranteeing that molecular weight is moderate, it is preferably hydrophilic to improve de- single-action rate simultaneously, low-residue single, control are dropped
The solid content stable and uniform of spinning solution.In order to improve the deaeration effect of acrylonitrile spinning solution, many manufacturing enterprises are used
The construction of deaeration kettle is transformed so that the mode that stoste obtains specific surface area increase carries out deaeration, as patent CN101856570 is provided with
A kind of de- single defoaming device of acrylonitrile stoste, this method improve de- list and deaeration effect in continuous production to a certain extent
Rate, but since the equipment is suitable for continuous production, the stoste viscosity being applicable in is also smaller, for the propylene of carbon fiber Wesy
This high viscous system effect of nitrile spinning solution is not it is obvious that and not improving for solid content stabilization.
Summary of the invention
The technical problem to be solved by the present invention is to the de- single low efficiency of the carbon fiber spinning primary fluid prepared in the prior art, spinning
The larger problem of resulting carbon fibre precursor performance CV value, provides a kind of preparation method of high-quality spinning solution, the preparation
Method has high de- single-action rate, high solids content, the advantages of so as to obtain high compactness, high-strength carbon fiber precursor.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of preparation of high-quality spinning solution
Method, comprising the following steps:
A, solvent, the first monomer, second comonomer and initiator are polymerize to obtain polymerization stoste；
B, the pressure of de- one-pot is evacuated to vacuum degree is 10-1000mbar, in the mistake that polymer fluid is squeezed into de- one-pot
Cheng Zhong keeps vacuum degree and is passed through the mixed gas of dimethyl sulfoxide and inert gas, gaseous mixture into kettle from de- one-pot bottom
Temperature is 50-150 DEG C, and the content of dimethyl sulfoxide is 0.1-100%, continues to keep vacuum degree after dnockout and be passed through mixed
Gas is closed until obtaining residual single polymerization stoste of the amount less than 0.3%；
C, residual polymerization stoste of single amount less than 0.3% is obtained into the polyacrylonitrile copolymer spinning solution by deaeration.
In above-mentioned technical proposal, the solvent can use all kinds of solvents well-known to those skilled in the art and its mixing
Object, such as but do not limit selected from least one of n,N-Dimethylformamide, dimethyl acetamide and dimethyl sulfoxide, into one
Step is preferably dimethyl sulfoxide.
In above-mentioned technical proposal, first monomer can be using in all kinds of monomers well-known to those skilled in the art
One kind being selected generally from acrylonitrile.
In above-mentioned technical proposal, the second comonomer can be different from the first list using well-known to those skilled in the art
One of all kinds of monomers of body, such as but do not limit selected from itaconic acid, itaconic acid methyl esters, itaconic acid ethyl ester, β-itaconic acid n-butyl,
Acrylic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate etc., further preferably itaconic acid.
In above-mentioned technical proposal, the initiator can be with appointing in azo-initiator well-known to those skilled in the art
It anticipates one kind, those skilled in the art can carry out conventional selection, such as but not limit selected from azodiisobutyronitrile.
In above-mentioned technical proposal, raw materials used quality proportioning is initiator in the step a: the first monomer and the second list
The sum of weight is 0.0040~0.0080:1, the first monomer and second comonomer quality sum: the gross mass of all raw materials is
0.20~0.30:1；First monomer: second comonomer is 96~99.9:0.1；In the step b, inert gas includes being selected from nitrogen
At least one of gas, helium, neon, argon gas, Krypton or xenon；Purity inert gas is 97%~99.999%；The step
In rapid b, the pressure for being filled with mixed gas is 0.01-0.3MPa；In the step b, the temperature of the polymer fluid is 50-80
℃；In the step c, deaeration temperature is 50-60 DEG C, vacuum degree 10-500mbar, inclined heated plate 24-72h.
The present invention is since under the collective effect that de- one-pot bottom is filled with mixed gas and vacuumizes, mixed gas is smoothly led to
Spinning solution is crossed, acrylonitrile monemer is made more easily to be separated spinning solution, to improve de- single-action rate, and is effectively reduced
The residual quantity of acrylonitrile in spinning solution；Moreover, the sulfoxide in mixed gas is condensed into liquid compared with pure inert gas, and
It is uniformly distributed in spinning solution, to offset the volatilization of vacuum bring sulfoxide, the uniformity of spinning solution is made to increase and contain admittedly
It measures adjustable.
Using the solution of the present invention, obtained polyacrylonitrile carbon fiber precursor, filament strength is 5~8cN/dtex, precursor
Intensity coefficient of dispersion CV is 5-10%, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated:
Specific embodiment
[embodiment 1]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 20% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.5wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 60 DEG C, it is 30mbar that the pressure of de- one-pot, which is evacuated to vacuum degree, then will
Obtained polymerization stoste is slowly squeezed into de- one-pot, and the mixed of dimethyl sulfoxide and nitrogen is passed through into kettle from de- one-pot bottom
Gas is closed, mixed gas temperature is 80 DEG C, and the content of dimethyl sulfoxide is 40%, continues to keep vacuum degree after dnockout and lead to
Enter mixer gas until obtaining residual single amount less than 0.3%；
It c, is 55 DEG C, vacuum degree 20mbar through excess temperature, the deaeration of 48h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
It is solidifying to enter the 1st after measuring pump-metered, again passing by 3 μm of filterings for spinning solution after squeezing out by spinning head
Gu bath, 20 DEG C of coagulation bath temperature, concentration 50%, draw ratio is -30%, and the 2nd coagulating bath is 40 DEG C, and concentration 40% is led
It stretches than being 100%, the 3rd coagulating bath is 60 DEG C, and concentration 30%, draw ratio 105% obtains as-spun fibre；As-spun fibre
After 3 solidifications, 3 drawing-off of hot water is carried out, 3 hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple point
It Wei 1.2,1.4 and 2.After 3 hot water drawing-offs, strand carries out 9 washings, by the way of ladder-elevating temperature, the washing of the road 1-3
Temperature is 50 DEG C, and the road 4-6 washing temperature is 60 DEG C, and the road 7-9 washing temperature is 70 DEG C, and water rinses are without drawing-off.It washes
To fiber carry out 1 oil after carry out compacting by drying, temperature is 90 DEG C, followed by once oiling, after oiling, progress
2nd compacting by drying, the temperature of compacting by drying are 120 DEG C, then carry out steam drafting, the pressure of steam drafting is
0.2Mpa, draw ratio are 2 times, and last fiber receives silk after carrying out steam thermal finalization, obtains high-performance carbon fibre precursor, steam heat is fixed
The pressure of type is 0.2Mpa.The intensity of final gained precursor is 6.1CN/dtex, and CV value is 8.2%.
[embodiment 2]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 97:3, solid content 20% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.4wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 50 DEG C, then obtained polymerization stoste is placed in de- one-pot, by de- one-pot
Pressure be evacuated to vacuum degree be 50mbar；And the mixed of dimethyl sulfoxide and inert gas is passed through into kettle from de- one-pot bottom
Gas is closed, mixed gas temperature is 100 DEG C, and the content of dimethyl sulfoxide is 80%, continues to keep vacuum degree simultaneously after dnockout
Mixer gas is passed through until obtaining residual single amount less than 0.3%；
It c, is 60 DEG C, vacuum degree 20mbar through excess temperature, the deaeration of 48h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.8CN/
Dtex, CV value are 8.3%.
[embodiment 3]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 22% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.5wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 65 DEG C, then obtained polymerization stoste is placed in de- one-pot, by de- one-pot
Pressure be evacuated to vacuum degree be 40mbar；And the mixed of dimethyl sulfoxide and inert gas is passed through into kettle from de- one-pot bottom
Gas is closed, mixed gas temperature is 110 DEG C, and the content of dimethyl sulfoxide is 10%, continues to keep vacuum degree simultaneously after dnockout
Mixer gas is passed through until obtaining residual single amount less than 0.3%；
It c, is 50 DEG C, vacuum degree 20mbar through excess temperature, the deaeration of 56h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.7CN/
Dtex, CV value are 8.7%.
[embodiment 4]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 20% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.7wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 60 DEG C, then obtained polymerization stoste is placed in de- one-pot, by de- one-pot
Pressure be evacuated to vacuum degree be 40mbar；And the mixed of dimethyl sulfoxide and inert gas is passed through into kettle from de- one-pot bottom
Gas is closed, mixed gas temperature is 70 DEG C, and the content of dimethyl sulfoxide is 30%, continues to keep vacuum degree after dnockout and lead to
Enter mixer gas until obtaining residual single amount less than 0.3%；
It e, is 55 DEG C, vacuum degree 100mbar through excess temperature, the deaeration of 36h obtains high-performance polyacrylonitrile copolymerization when being
Object spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.6CN/
Dtex, CV value are 8.7%.
[embodiment 5]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 99:1, solid content 23% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.7wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 70 DEG C, then obtained polymerization stoste is placed in de- one-pot, by de- one-pot
Pressure be evacuated to vacuum degree be 30mbar；And the mixed of dimethyl sulfoxide and inert gas is passed through into kettle from de- one-pot bottom
Gas is closed, mixed gas temperature is 90 DEG C, and the content of dimethyl sulfoxide is 60%, continues to keep vacuum degree after dnockout and lead to
Enter mixer gas until obtaining residual single amount less than 0.3%；
It e, is 60 DEG C, vacuum degree 50mbar through excess temperature, the deaeration of 54h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.9CN/
Dtex, CV value are 8.3%.
[comparative example 1]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 20% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.5wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 60 DEG C, it is 30mbar that the pressure of de- one-pot, which is evacuated to vacuum degree, in stirring shape
Under state, polymerization stoste is added in de- one-pot, the revolving speed of agitating paddle is 40r/h, carries out de- list, and finally make third in spinning solution
The residual quantity of alkene nitrile monomer is less than 0.3%；
It e, is 55 DEG C, vacuum degree 20mbar through excess temperature, the deaeration of 48h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.3CN/
Dtex, CV value are 10.6%.
[comparative example 2]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 97:3, solid content 20% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.5wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 70 DEG C, it is 20mbar that the pressure of de- one-pot, which is evacuated to vacuum degree, in stirring shape
Under state, polymerization stoste is added in de- one-pot, the revolving speed of agitating paddle is 100r/h, and finally makes acrylonitrile monemer in spinning solution
Residual quantity less than 0.3%；
It e, is 60 DEG C, vacuum degree 30mbar through excess temperature, the deaeration of 48h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.1CN/
Dtex, CV value are 10.9%.
[comparative example 3]
A, prepared by stoste: by acrylonitrile (AN), itaconic acid (IA) 99:1, solid content 23% in proportion through distilling, azo
Bis-isobutyronitrile (AIBN) accounts for the 0.7wt% of comonomer, is that solvent is added in reactor with dimethyl sulfoxide (DMSO), in nitrogen
Under gas shielded, is reacted 20 hours under 60 DEG C of steady temperature, obtain binary acrylonitrile copolymer spinning fluid；
B, the temperature of de- one-pot is risen to 70 DEG C, then obtained polymerization stoste is placed in de- one-pot, by de- one-pot
Pressure be evacuated to vacuum degree be 30mbar；And nitrogen is passed through into kettle from de- one-pot bottom, nitrogen temperature is 90 DEG C, is carried out
It is de- single, obtain residual single stoste of the amount less than 0.3%；
It e, is 60 DEG C, vacuum degree 50mbar through excess temperature, the deaeration of 54h obtains high-performance polyacrylonitrile copolymer when being
Spinning solution.
Gained stoste is subjected to spinning, spinning condition is same as Example 1, and the intensity of final gained precursor is 5.5CN/
Dtex, CV value are 9.0%.
Claims (8)
1. a kind of preparation method of polyacrylonitrile spinning solution, comprising the following steps:
A, solvent, the first monomer, second comonomer and initiator are polymerize to obtain polymerization stoste；
B, the pressure of de- one-pot is evacuated to vacuum degree is 10-1000mbar, during polymer fluid is squeezed into de- one-pot,
It keeps vacuum degree and is passed through the mixed gas of dimethyl sulfoxide and inert gas, mixed gas temperature into kettle from de- one-pot bottom
It is 50-150 DEG C, the pressure of mixed gas is 0.01-0.3MPa；The content of dimethyl sulfoxide is 10%-80%, after dnockout
Continue to keep vacuum degree and is passed through mixed gas until obtaining residual single polymerization stoste of the amount less than 0.3%；
C, residual polymerization stoste of single amount less than 0.3% is obtained into the polyacrylonitrile copolymer spinning solution by deaeration.
2. the preparation method of polyacrylonitrile spinning solution according to claim 1, it is characterised in that raw materials used quality is matched
Than for initiator: the first monomer is 0.0040~0.0080:1, the first monomer and second comonomer matter with second comonomer quality sum
The sum of amount: the gross mass of all raw materials is 0.20~0.30:1；First monomer: second comonomer is 96~99.9:0.1.
3. the preparation method of polyacrylonitrile spinning solution according to claim 1, it is characterised in that the first monomer choosing
From acrylonitrile.
4. the preparation method of polyacrylonitrile spinning solution according to claim 1, which is characterized in that in the step b,
Inert gas includes selected from least one of nitrogen, helium, neon, argon gas, Krypton or xenon；Purity inert gas is 97%
~99.999%.
5. the preparation method of polyacrylonitrile spinning solution according to claim 1, it is characterised in that the second comonomer choosing
From itaconic acid.
6. the preparation method of polyacrylonitrile spinning solution according to claim 1, it is characterised in that the initiator is selected from
Azodiisobutyronitrile.
7. the preparation method of polyacrylonitrile spinning solution according to claim 1, which is characterized in that in the step b,
The temperature of the polymer fluid is 50-80 DEG C.
8. the preparation method of polyacrylonitrile spinning solution according to claim 1, which is characterized in that in the step c,
Deaeration temperature is 50-60 DEG C, vacuum degree 10-500mbar, inclined heated plate 24-72h.
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| 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 |
| CN102171255A (en) * | 2008-10-03 | 2011-08-31 | 英尼奥斯欧洲有限公司 | Method for the production of polymers |
| CN102199794A (en) * | 2010-03-26 | 2011-09-28 | 中国石油化工股份有限公司 | Method for removing acrylonitrile monomer in spinning solution |
| CN102747452A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of acrylonitrile copolymer spinning solution |
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| KR101617891B1 (en) * | 2010-06-30 | 2016-05-04 | 코오롱인더스트리 주식회사 | Manufacturing method of carbon fiber |
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| CN1067900A (en) * | 1991-05-17 | 1993-01-13 | 联合碳化化学品及塑料技术公司 | From olefin polymer, remove the degas method of unconverted monomer |
| CN102171255A (en) * | 2008-10-03 | 2011-08-31 | 英尼奥斯欧洲有限公司 | Method for the production of polymers |
| 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 |
| CN102199794A (en) * | 2010-03-26 | 2011-09-28 | 中国石油化工股份有限公司 | Method for removing acrylonitrile monomer in spinning solution |
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