CN106591995A - High-quality polyacrylonitrile spinning raw solution preparation method - Google Patents
High-quality polyacrylonitrile spinning raw solution preparation method Download PDFInfo
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Abstract
The invention relates to a high-quality polyacrylonitrile spinning raw solution preparation method. A purpose of the present invention is mainly to solve the problems of low monomer removing efficiency and high CV value of the carbon fiber precursor obtained through spinning in the prior art. The technical scheme of the present invention comprises: a, polymerizing a solvent dimethyl sulfoxide, a first monomer acrylonitrile, a second monomer itaconic acid, an initiator azobisisobutyronitrile and an adjustment agent to obtain a polymerization raw solution; and b, vacuumizing the pressure of a monomer removing kettle to achieve a vacuum degree of 10-1000 mbar, and introducing the mixed gas of dimethyl sulfoxide and an inert gas into the kettle from the bottom portion of the monomer removing kettle when the polymerization solution is beaten into the monomer removing kettle so as to obtain the polyacrylonitrile spinning raw solution with characteristics of residual monomer content of less than 0.3% and uniform and stable solid content, wherein the temperature of the mixed gas is 50-150 DEG C, and the dimethyl sulfoxide content in the mixed gas is 0.1-100% (wt). With the technical scheme, the problems in the prior art are well solved. The preparation method of the present invention can be used for the industrial production of the carbon fiber precursor.
Description
Technical field
The present invention relates to a kind of preparation method of high-quality polyacrylonitrile spinning solution.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the new material that generation nineteen sixty develops rapidly, because it has
Light weight, specific strength height, specific modulus height, high temperature resistant, corrosion-resistant, wear-resisting, resisting fatigue, conduction, heat conduction etc.
Excellent properties, are widely used in the military industries such as satellite, carrier rocket, tactical missile, spacecraft,
Become indispensable material in aerospace industries.Excellent carbon fiber precursor should have thermostability it is high,
The features such as hole is constructed less, few surface defects, compact structure, draftability are good.
Precursor is the premise for producing high-performance carbon fibre.High performance precursor is prepared except needing dividing for spinning solution
Son amount is moderate, and outside preferable hydrophilic, de- single process efficiency of spinning solution is high, and residual list will lack, while
Need relatively stable, uniform solid content.De- single process efficiency of spinning solution is higher, and residual list is less, then spin
The molecular weight distribution of silk stock solution is narrower, beneficial to the stretching of spinning process, it is easy to high-performance precursor is obtained；Spinning is former
Liquid has stable, uniform solid content, then the cv values of precursor are less, precursor stable performance, otherwise, spinning
Journey will occur more lousiness, filament, and spinning process is unstable, wayward, precursor poor-performing；
So ensureing that molecular weight is moderate, and it is preferably hydrophilic to improve de- single-action rate simultaneously, low-residue single drops,
The solid content stable and uniform of control spinning solution.It is many in order to improve the deaeration effect of acrylonitrile spinning solution
Manufacturing enterprise causes stock solution to obtain by the way of specific surface area increase and carries out deaeration using the construction of transformation deaeration kettle, such as specially
Sharp CN101856570 provides for a kind of de- single defoaming device of acrylonitrile stock solution, and the method is to a certain extent
The de- list and deaeration efficiency in continuous production is improve, but because the equipment is suitable for continuous production, is fitted
Stock solution viscosity is also smaller, and high viscous system effect this for the acrylonitrile spinning solution of carbon fiber is not
It is obvious that and for solid content does not stably improve.
The content of the invention
The technical problem to be solved in the present invention is that the de- single-action rate of the carbon fiber spinning primary fluid prepared in prior art is low,
A kind of larger problem of carbon fibre precursor performance CV value obtained by spinning, there is provided system of high-quality spinning solution
Preparation Method, the preparation method has high de- single-action rate, high solids content, such that it is able to obtain high compactness, high-strength
The advantage of degree carbon fibre precursor.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of high-quality spinning solution
Preparation method, comprises the following steps：
A, by solvent, the first monomer, second comonomer and initiator polymerization obtain be polymerized stock solution；
B, the pressure of de- one-pot is evacuated to vacuum for 10-1000mbar, polymer fluid is being squeezed into into de- single
During kettle, keep vacuum and the mixed of dimethyl sulfoxide and noble gases is passed through into kettle from de- one-pot bottom
Gas is closed, mixed gas temperature is 50-150 DEG C, and the content of dimethyl sulfoxide is 0.1-100%, and dnockout terminates
Continue afterwards to keep vacuum and be passed through mixed gas until obtaining polymerization stock solution of the residual single amount less than 0.3%；
C, the polymerization stock solution by residual single amount less than 0.3% obtain the polyacrylonitrile copolymer spinning original through deaeration
Liquid.
In above-mentioned technical proposal, the solvent can using all kinds of solvents well-known to those skilled in the art and its
Mixture, for example but does not limit in DMF, dimethyl acetylamide and dimethyl sulfoxide
At least one, more preferably dimethyl sulfoxide.
In above-mentioned technical proposal, first monomer can adopt all kinds of monomers well-known to those skilled in the art
In one kind, be selected generally from acrylonitrile.
In above-mentioned technical proposal, the second comonomer can be different from the using well-known to those skilled in the art
One kind in all kinds of monomers of one monomer, for example but do not limit selected from itaconic acid, itaconic acid methyl ester, itaconic acid ethyl ester,
β-itaconic acid n-butyl, acrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl methacrylate etc.,
More preferably itaconic acid.
In above-mentioned technical proposal, the initiator can be with azo-initiator well-known to those skilled in the art
Any one, those skilled in the art can carry out conventional selection, for example but not limit selected from the isobutyl of azo two
Nitrile.
In above-mentioned technical proposal, raw materials used quality proportioning is in step a, initiator：First monomer
It is 0.0040～0.0080 with second comonomer quality sum：1, the first monomer and second comonomer quality sum：Institute
The gross mass for having raw material is 0.20～0.30：1；First monomer：Second comonomer is 96～99.9：0.1；It is described
In step b, noble gases include at least in nitrogen, helium, neon, argon, Krypton or xenon
Kind；Purity inert gas are 97%～99.999%；In step b, the pressure for being filled with mixed gas
For 0.01-0.3MPa；In step b, the temperature of the polymer fluid is 50-80 DEG C；In step c,
Deaeration temperature is 50-60 DEG C, and vacuum is 10-500mbar, and inclined heated plate is 24-72h.
The present invention in de- one-pot bottom due to being filled with the collective effect of mixed gas and evacuation, and mixed gas are suitable
Profit makes acrylonitrile monemer more easily be separated spinning solution by spinning liquid, so as to improve de- single-action rate,
And effectively reduce the residual quantity of acrylonitrile in spinning solution；And, compared with pure inert gas, mixed gas
In sulfoxide be condensed into liquid, and be uniformly distributed in spinning liquid, so as to offset the sulfoxide volatilization that vacuum belt is come,
Make the uniformity increase of spinning solution and solid content is adjustable.
Using the solution of the present invention, the polyacrylonitrile carbon fiber precursor for obtaining, filament strength is 5～8cN/dtex,
Precursor intensity coefficient of dispersion CV is 5-10%, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated：
Specific embodiment
【Embodiment 1】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 98 that Jing is distilled:2nd, solid content 20%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.5wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 60 DEG C, the pressure of de- one-pot is evacuated to into vacuum for 30mbar,
Then obtained polymerization stock solution is slowly squeezed in de- one-pot, and dimethyl is passed through into kettle from de- one-pot bottom
The mixed gas of sulfoxide and nitrogen, mixed gas temperature is 80 DEG C, and the content of dimethyl sulfoxide is 40%, is beaten
Material continues to keep vacuum after terminating and is passed through blender gas until obtaining residual single amount less than 0.3%；
C, through temperature be 55 DEG C, vacuum is 20mbar, and the deaeration of 48h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Spinning solution is entered after measuring pump-metered, again passing by 3 μm of filtrations after spinning head is extruded
1st road coagulating bath, 20 DEG C of coagulation bath temperature, concentration is 50%, and draw ratio is -30%, and the 2nd road coagulating bath is
40 DEG C, concentration is 40%, and draw ratio is 100%, and the 3rd road coagulating bath is 60 DEG C, and concentration is 30%, draw ratio
For 105%, as-spun fibre is obtained；As-spun fibre carries out the road drawing-off of hot water 3,3 roads heat after the solidification of 3 roads
Water drawing temperature is respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.2,1.4 and 2.Through 3
After road hot water drawing-off, strand carries out 9 road washings, and by the way of ladder-elevating temperature, 1-3 roads washing temperature is 50 DEG C,
4-6 roads washing temperature is 60 DEG C, and 7-9 roads washing temperature is 70 DEG C, and water rinses do not carry out drawing-off.Wash
To fiber carry out carrying out compacting by drying after 1 road oils, temperature is 90 DEG C, followed by once oiling,
After oiling, the 2nd road compacting by drying is carried out, the temperature of compacting by drying is 120 DEG C, then carries out steam and leads
Stretch, the pressure of steam drafting is 0.2Mpa, and draw ratio is 2 times, and last fiber carries out being received after steam thermal finalization
Silk, obtains high-performance carbon fibre precursor, and the pressure of steam thermal finalization is 0.2Mpa.Precursor is strong obtained by final
Spend for 6.1CN/dtex, CV values are 8.2%.
【Embodiment 2】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 97 that Jing is distilled:3rd, solid content 20%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.4wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 50 DEG C, then obtained polymerization stock solution is placed in de- one-pot, will
The pressure of de- one-pot is evacuated to vacuum for 50mbar；And it is sub- that dimethyl is passed through into kettle from de- one-pot bottom
The mixed gas of sulfone and noble gases, mixed gas temperature is 100 DEG C, and the content of dimethyl sulfoxide is 80%,
Dnockout continues to keep vacuum after terminating and is passed through blender gas until obtaining residual single amount less than 0.3%；
C, through temperature be 60 DEG C, vacuum is 20mbar, and the deaeration of 48h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.8CN/dtex, CV value is 8.3%.
【Embodiment 3】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 98 that Jing is distilled:2nd, solid content 22%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.5wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 65 DEG C, then obtained polymerization stock solution is placed in de- one-pot, will
The pressure of de- one-pot is evacuated to vacuum for 40mbar；And it is sub- that dimethyl is passed through into kettle from de- one-pot bottom
The mixed gas of sulfone and noble gases, mixed gas temperature is 110 DEG C, and the content of dimethyl sulfoxide is 10%,
Dnockout continues to keep vacuum after terminating and is passed through blender gas until obtaining residual single amount less than 0.3%；
C, through temperature be 50 DEG C, vacuum is 20mbar, and the deaeration of 56h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.7CN/dtex, CV value is 8.7%.
【Embodiment 4】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 98 that Jing is distilled:2nd, solid content 20%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.7wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 60 DEG C, then obtained polymerization stock solution is placed in de- one-pot, will
The pressure of de- one-pot is evacuated to vacuum for 40mbar；And it is sub- that dimethyl is passed through into kettle from de- one-pot bottom
The mixed gas of sulfone and noble gases, mixed gas temperature is 70 DEG C, and the content of dimethyl sulfoxide is 30%,
Dnockout continues to keep vacuum after terminating and is passed through blender gas until obtaining residual single amount less than 0.3%；
E, through temperature be 55 DEG C, vacuum is 100mbar, and the deaeration of 36h when being obtains high-performance poly third
Alkene lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.6CN/dtex, CV value is 8.7%.
【Embodiment 5】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 99 that Jing is distilled:1st, solid content 23%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.7wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 70 DEG C, then obtained polymerization stock solution is placed in de- one-pot, will
The pressure of de- one-pot is evacuated to vacuum for 30mbar；And it is sub- that dimethyl is passed through into kettle from de- one-pot bottom
The mixed gas of sulfone and noble gases, mixed gas temperature is 90 DEG C, and the content of dimethyl sulfoxide is 60%,
Dnockout continues to keep vacuum after terminating and is passed through blender gas until obtaining residual single amount less than 0.3%；
E, through temperature be 60 DEG C, vacuum is 50mbar, and the deaeration of 54h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.9CN/dtex, CV value is 8.3%.
【Comparative example 1】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 98 that Jing is distilled:2nd, solid content 20%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.5wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 60 DEG C, the pressure of de- one-pot is evacuated to vacuum for 30mbar,
Under stirring, polymerization stock solution is added in de- one-pot, the rotating speed of stirring paddle is 40r/h, carries out de- list,
And finally make the residual quantity of acrylonitrile monemer in spinning liquid be less than 0.3%；
E, through temperature be 55 DEG C, vacuum is 20mbar, and the deaeration of 48h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.3CN/dtex, CV value is 10.6%.
【Comparative example 2】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 97 that Jing is distilled:3rd, solid content 20%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.5wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 70 DEG C, the pressure of de- one-pot is evacuated to vacuum for 20mbar,
Under stirring, polymerization stock solution is added in de- one-pot, the rotating speed of stirring paddle is 100r/h, and finally makes spinning
The residual quantity of acrylonitrile monemer is less than 0.3% in silk liquid；
E, through temperature be 60 DEG C, vacuum is 30mbar, and the deaeration of 48h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.1CN/dtex, CV value is 10.9%.
【Comparative example 3】
It is prepared by a, stock solution：Acrylonitrile (AN), itaconic acid (IA) in proportion 99 that Jing is distilled:1st, solid content 23%,
Azodiisobutyronitrile (AIBN) is accounted for the 0.7wt% of comonomer, is added to as solvent with dimethyl sulfoxide (DMSO)
In reactor, under nitrogen protection, react 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 into 70 DEG C, then obtained polymerization stock solution is placed in de- one-pot, will
The pressure of de- one-pot is evacuated to vacuum for 30mbar；And nitrogen, nitrogen are passed through into kettle from de- one-pot bottom
Temperature degree is 90 DEG C, carries out de- list, obtains stock solution of the residual single amount less than 0.3%；
E, through temperature be 60 DEG C, vacuum is 50mbar, and the deaeration of 54h when being obtains high-performance polypropylene
Lonitrile copolymer spinning solution.
Gained stock solution is carried out into spinning, spinning condition is same as Example 1, the intensity of final gained precursor is
5.5CN/dtex, CV value is 9.0%.
Claims (9)
1. a kind of preparation method of polyacrylonitrile spinning solution, comprises the following steps：
A, by solvent, the first monomer, second comonomer and initiator polymerization obtain be polymerized stock solution；
B, the pressure of de- one-pot is evacuated to vacuum for 10-1000mbar, during polymer fluid to be squeezed into de- one-pot, keep vacuum and the mixed gas of dimethyl sulfoxide and noble gases are 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%, and dnockout continues to keep vacuum after terminating and is passed through mixed gas until obtaining polymerization stock solution of the residual single amount less than 0.3%；
C, the polymerization stock solution by residual single amount less than 0.3% obtain the polyacrylonitrile copolymer spinning solution through deaeration.
2. the preparation method of polyacrylonitrile spinning solution according to claim 1, it is characterised in that raw materials used quality proportioning is, initiator：First monomer is 0.0040～0.0080 with second comonomer quality sum：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.
3. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that first monomer is selected from acrylonitrile.
4. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that in step b, noble gases include at least one in nitrogen, helium, neon, argon, Krypton or xenon；Purity inert gas are 97%～99.999%.
5. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that the second comonomer is selected from itaconic acid.
6. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that the initiator is selected from azodiisobutyronitrile.
7. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that in step b, the pressure for being filled with mixed gas is 0.01-0.3MPa.
8. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that in step b, the temperature of the polymer fluid is 50-80 DEG C.
9. the preparation method of high-quality polyacrylonitrile spinning solution according to claim 1, it is characterised in that in step c, deaeration temperature is 50-60 DEG C, and vacuum is 10-500mbar, and inclined heated plate is 24-72h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107353368A (en) * | 2017-08-28 | 2017-11-17 | 江苏恒神股份有限公司 | The ammonifying device of PAN polymer fluids |
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