CN105524212B - A kind of method for homogenization preparation of polyacrylonitrile-base carbon fiber spinning primary fluid - Google Patents
A kind of method for homogenization preparation of polyacrylonitrile-base carbon fiber spinning primary fluid Download PDFInfo
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- 238000009987 spinning Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 20
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012530 fluid Substances 0.000 title claims abstract description 14
- 238000000265 homogenisation Methods 0.000 title claims abstract description 5
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 40
- 229920006350 polyacrylonitrile resin Polymers 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 7
- 238000005360 mashing Methods 0.000 claims abstract description 7
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 2
- 150000002825 nitriles Chemical class 0.000 claims 2
- 229920001155 polypropylene Polymers 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 abstract description 35
- 239000007787 solid Substances 0.000 abstract description 15
- 230000018044 dehydration Effects 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 abstract description 6
- 229910001867 inorganic solvent Inorganic materials 0.000 abstract description 4
- 239000003049 inorganic solvent Substances 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 15
- 239000002243 precursor Substances 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
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- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- 239000004753 textile Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
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Abstract
The invention discloses a kind of method for homogenization preparation of polyacrylonitrile-base carbon fiber spinning primary fluid.This method dissolves the two-step process of polyacrylonitrile resin using aqueous suspension polymerization and inorganic solvent.The NaSCN aqueous solutions of polyacrylonitrile resin and a concentration of 25~32wt% are mixed first, the content for controlling resin is 15~25wt%, and mashing, pulp mixture are disperseed at a temperature of 8~25 DEG C；Then NaSCN aqueous solutions are added thereto, control resin content is 8~12wt%, and on the basis of the total amount of NaSCN and water, NaSCN contents are 38~50wt%, stirs to PAN and is completely dissolved at 70~90 DEG C；Finally preheat thick stoste to 70~95 DEG C, deaeration, dehydration, it is multistage, cycle is multiple, obtain spinning solution.The spinning solution uniformity that the present invention obtains significantly improves, and solid content is high, meets the requirement of carbon fiber spinning primary fluid high densification solidification.
Description
Technical field
The present invention relates to TEXTILE CHEMICALS technical fields, and in particular to a kind of polyacrylonitrile-base carbon fiber spinning primary fluid it is equal
Matter preparation method.
Background technology
Industrially there are two types of preparation methods for most widely used polyacrylonitrile-base carbon fiber spinning primary fluid in carbon fiber at present：
First, acrylonitrile and comonomer, solvent, initiator etc. are mixed in reaction kettle, it is polymerize under certain reaction temperature
Obtain polyacrylonitrile matrix, then by processing such as de- list, deaeration, filterings after, obtain the spinning solution for meeting spinning requirement for spinning
Silk.Another method is that acrylonitrile and comonomer, initiator etc. are mixed in reaction kettle, certain reaction temperature, when
Between under polymerize, obtain polyacrylonitrile powder by the processing such as de- single, washing, dry, then with solvent such as DMF, DMAc,
It is molten to be dissolved as polyacrylonitrile using suitable temperature for the mixing such as DMSO, concentrated nitric acid, ZnCl2 aqueous solutions and NaSCN aqueous solutions
Liquid, then after the processing such as deaeration, filtering, the spinning solution for meeting spinning requirement is obtained for spinning.Above-mentioned first method is usual
The method that referred to as one-step method solution polymerization process prepares polyacrylonitrile-base carbon fiber spinning primary fluid.Above-mentioned second method is usual
The method that referred to as two-step process prepares polyacrylonitrile-base carbon fiber spinning primary fluid.
Cyano in polyacrylonitrile (PAN) has big dipole so that PAN strands are arranged in the form of screw cylindrical, when this
When a little coiled strands are put together, neighbouring cyano will take antiparallel manner arrangement to form strong interaction, thus,
Impart the structure of PAN chain high-sequentials.Also interaction results in answering for their solution behavior exactly between this cyano
Polygamy.PAN is soluble in DMF, DMAc, DMSO, concentrated nitric acid, ZnCl2 aqueous solutions and NaSCN aqueous solutions.It is various
Gel behavior can be all shown in solution, this brings some troubles to the solution-polymerized SBR of PAN fiber, is mainly manifested in spinning solution
Filtration difficulty, the sprinkler operational period is short, and plug-hole easily occurs for nozzle, and production stability is poor, and spinneret state is easily deteriorated, precursor discreteness
Can lousiness, fracture of wire etc. easily occur greatly.Therefore, it to realize the high performance of PAN fiber, control the condensed state structure ten of PAN solution
Divide important.
For polymer chain architecture, high molecular weight and high stereoregularity are to improve the main path of carbon fiber performance,
For precursor structure, high compactness, high orientation are the main paths for improving carbon fiber performance.Because high molecular weight causes
Close structure can improve the intensity of PAN fiber, and relatively narrow molecular weight distribution can make fiber each section uniform intensity distribution,
So that fibrous mechanical property is more excellent.However the requirement of the high molecular weight of carbon fibre precursor, high stereoregularity, high compactness,
Polyacrylonitrile-base carbon fiber spinning primary fluid, which is prepared, to two-step process brings difficulty, it is weaker inorganic molten for solvability
The dissolving of agent is even more difficulty.First, the high stereoregularity and high molecular weight of PAN chains, it is difficult that diffusion is entered to make solvent molecule,
The solution of PAN chains twine be finally reached to be formed molecular level dissolving it is also highly difficult, also easily form microgel, keep filter operation tired
Difficulty, production stability is poor, and end breakage rate is high.Secondly, the requirement of high compactness usually requires that the solid content of spinning solution is higher, from
And make in spinning coagulation forming, empty less, compact structure.But higher spinning solution solid content, and increased to dissolving
Difficulty.Dissolving is that a solvent molecule penetrates into the process that a homogeneous solution system is eventually formed in polymer macromolecule chain,
Polymer solids level is high, and solvent content is few, and the time that dissolution equilibrium is finally reached in solvent infiltration polymer macromolecule chain is just grown,
And dissolving easily occur it is uneven, or even generate gel particle.Furthermore the solvability of inorganic solvent is weaker, restricts two
Footwork technique prepares uniform polyacrylonitrile base carbon fiber precursors spinning solution, and it is poly- also to constrain two-step process preparation high-performance
Acrylonitrile base carbon fiber precursor.Such as 12~15%PAN solution of solvent NaSCN dissolvings and the 28~32% of solvent DMF dissolving
PAN solution compared to much smaller, it means that PAN may be easier to occur in NaSCN aqueous solutions than organic solvents such as DMF
Gel (although the NaSCN aqueous solutions of PAN may it is more more stable than the DMF of PAN or DMSO solution-because of PAN/ organic solvent systems
It is sensitive to the moisture in air, the absorption of water will cause gel to generate, and significantly reduce stoste stability).
For improving precursor compact structure, amine high by introducing hydrophily Chinese patent ZL2010101916445
Spinning solution or coagulating bath are carried out ammoniated treatment by comonomer, and solvent and non-solvent are in fibre when to make spinning coagulation forming
Double diffusion speed slows down in dimension, inhibits the generation of hole, improves the compactness of precursor.But amine comonomer forms work not yet
The synthetic method of industry, there are the introducings of amine comonomer or ammonification process can make production site operation environmental degradation, adds
The problem of acute equipment extent of corrosion.In addition, Chinese patent application 2008102273120 is when polyacrylonitrile dissolves, it is molten in tradition
A kind of low-boiling dilution solubilizer is added in enzymatic hydrolysis system, the polyacrylonitrile solution of uniform low viscosity is made, using subtracting after filter
Pressure-off is waved, and the polyacrylonitrile spinning solution of uniform high solids content (high concentration) is finally obtained；High solids content polyacrylonitrile spinning
Stoste advantageously forms the precursor of compact texture.But due to adding solubilizer in this technical process, the inevitable shape in precursor
At a kind of impurity, it is unfavorable for the carbon fiber of application and preparation requirement harshness.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of two-step processes to prepare the poly- of homogeneous
The method of acrylonitrile base carbon fiber spinning solution.Its method is simple, poly- by using inorganic solvent (such as NaSCN) uniform dissolution
Acrylonitrile resin obtains homogeneous, composition is stablized, the PAN spinning solutions of high solids content.
First polyacrylonitrile resin raw material is made with aqueous suspension polymerization technique in the present invention；Again by the polyacrylonitrile resin of powdery
It is dispersed in dilute NaSCN aqueous solutions, the dissolving of resin, the spinning being had good uniformity then is completed with the shorter time
Thick stoste；Finally using the multistage method continuously vacuumized, the moisture in polyacrylonitrile solution is removed, the solid content of solution is improved
(concentration), obtains spinning solution.It can be used for the PAN precursor of spun structure densification, can effectively improve the intensity of carbon fiber.
It is the specific technical solution of the present invention below.
A kind of method for homogenization preparation of polyacrylonitrile-base carbon fiber spinning primary fluid uses aqueous suspension polymerization and inorganic
Solvent dissolves the two-step process of polyacrylonitrile resin；It is as follows：
(1) it is 5~30 DEG C by the polyacrylonitrile resin and temperature that are prepared by aqueous suspension polymerization technique, a concentration of
The NaSCN aqueous solutions of 25~32wt% mix, and the content control of polyacrylonitrile resin is 15~25wt% in mixture, remains mixed
It closes object temperature of charge and carries out dispersion mashing for 8~25 DEG C, so that polyacrylonitrile resin is dispersed in NaSCN aqueous solutions and form slurry
Shape mixture；
(2) 100~140 DEG C of NaSCN aqueous solutions are further added in the paste mixture that step (1) obtains, maintain
Mixture temperature of charge be 70~95 DEG C be stirred it is homogeneous, until polyacrylonitrile resin is completely dissolved to get the thick stoste of spinning；
The content control of polyacrylonitrile resin is 8~12wt% in thick stoste at this time, on the basis of the total amount of NaSCN and water, NaSCN
Content control be 38~50wt%；
(3) the thick stoste of spinning that process steps (2) obtain is heated to 70~80 DEG C, then stitches drop by the grid vacuumized
The efficient deaeration tower of membranous type removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 15~45 DEG C；
(4) stoste that step (3) obtains is heated to 75~85 DEG C, it is high then to stitch film-lowering type by the two level grid vacuumized
Deaeration tower is imitated, bubble and moisture are removed；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 35~55 DEG C；
(5) stoste that step (4) obtains is heated to 80~95 DEG C, it is high then to stitch film-lowering type by the three-level grid vacuumized
Deaeration tower is imitated, bubble and moisture are removed；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 40~58 DEG C；
(6) stoste that step (5) obtains is filtered, temperature adjustment, pressure regulation, obtain and meet the spinning solution of spinning requirement.
The polyacrylonitrile resin that aqueous suspension polymerization technique is prepared described in above-mentioned steps (1) is copolymer, is glued equal
Molecular weight is 60000~200000, and comonomer includes acrylonitrile, itaconic acid and methyl acrylate, acrylonitrile, itaconic acid and third
The weight ratio of e pioic acid methyl ester is 100：(0.7~8)：(0~10), preferred weight ratio are 100：(2.5~5)：(0~5).
In above-mentioned steps (1), polyacrylonitrile resin is preferably mixed with temperature for 10~20 DEG C of NaSCN aqueous solutions.Mixing
In object, it is 17~20wt% that the content of polyacrylonitrile resin, which preferably controls,.It is 10~20 DEG C preferably to maintain mixture temperature of charge
Carry out dispersion mashing；Dispersion mashing is carried out preferably with high shear dispersion device or high shear homogenous unit.
It is 9.5~11.5wt% that the content of polyacrylonitrile resin, which preferably controls, in above-mentioned steps (2), in mixture；With
On the basis of the total amount of NaSCN and water, it is 40~48wt% that the content of NaSCN, which preferably controls,.The paste mixture is best
It maintains temperature to be 75~85 DEG C and is stirred homogeneous dissolving, stir homogeneous dissolving and carried out preferably with high shear homogenous unit.
In above-mentioned steps (3), it is preferred that thick stoste is heated to 72~76 DEG C, and the temperature difference of deaeration tower is 19~30 DEG C.
In above-mentioned steps (4), it is preferred that stoste is heated to 76~80 DEG C, and the temperature difference of deaeration tower is 38~50 DEG C.
In above-mentioned steps (5), it is preferred that stoste is heated to 85~90 DEG C, and the temperature difference of deaeration tower is 45~55 DEG C.
In the present invention, the vacuum dehydration step cycle of above-mentioned steps (3), step (4) and step (5) can also be carried out repeatedly,
The stoste composition expected from the acquisition.
In the present invention, the NaSCN aqueous solutions ZnCl described in above-mentioned steps (1) and step (2)2Aqueous solution or HNO3Water
Solution substitutes.
In the present invention, above-mentioned steps (3), step (4) and step (5), which also are adapted for spinning solution group, becomes PAN+ solvents+water
(or other low volatility components) system.
The key problem in technology of the present invention is improved in spinning solution preparation process：First, by polyacrylonitrile resin elder generation
It is dissolved, is uniformly dissolved again after being dispersed in NaSCN aqueous solutions；Secondly, thick stoste is controlled in dissolving to be low admittedly to contain
Amount makes PAN dissolve uniform, thorough；Then, then by Multi-stage heating, vacuum defoamation and the process of dehydration, high solids content is obtained
Spinning solution, meet when spinning solution goes out spinneret orifice uniformly, the requirement of fine and close solidification.
Inventor find, low temperature, low concentration NaSCN aqueous solutions make polyacrylonitrile resin become easier to disperse.Simultaneously
Dispersion mashing is carried out using high shear dispersion device or high shear homogenous unit, it is very good that a kind of mobile performance can be obtained
Paste mixture.Polyacrylonitrile resin content is lower in paste mixture, and the dispersity of paste mixture is more uniform, this non-
After often the NaSCN aqueous solutions of higher concentration are added in uniform paste mixture so that the dissolving then carried out becomes very easy.
And the purpose that NaSCN aqueous solutions are added in step (2) is exactly to adjust the concentration resin content of NaSCN.
Inventor also found, in course of dissolution, the thick stoste solid content of acquisition is lower, and dissolving is more uniform.It is this low solid
Through subsequent multiple deaeration and dehydration, the high solids content of 14wt%~15wt% finally can be obtained again in the thick stoste of content, meets
Manufacture the spinning solution that compactness precursor requires.The present invention is further known through a large number of experiments simultaneously, by consolidating for thick stoste
Content maintains 9.5~11.5wt%, on the basis of the total amount of NaSCN and water, the content of NaSCN preferably controls as 40~
Constantly, dissolving is best by 48wt%.Course of dissolution can by traditional dissolution kettle long agitation complete；Height can also be used
Shearing dispersal device or high shear homogenous unit impose material that fierce stirring is homogeneous to be completed, this can greatly improve dissolving
Efficiency reduces dissolution time.
In addition, the present invention stitches the efficient deaeration tower of film-lowering type in step (3), step (4) and step (5), by using grid,
And suitable heating temperature and the deaeration temperature difference are controlled, so that finally obtained spinning solution composition is reached the height of 14wt%~15%wt
Solid content.Grid in the present invention stitch the efficient deaeration tower of film-lowering type so that stoste uniform falling liquid film in deaeration tower, film surface repeat more
Newly, moisture removal evenly, avoids the generation of " micelle " secondary in deaeration, dehydration.
Compared to the prior art, preparation method of the invention is simple, using this method can be made homogeneous, composition stablize,
The PAN spinning solutions of high solids content, and then for the PAN precursor of textile structural densification.
Specific implementation mode
Below by specific embodiment, the invention will be further described.Poly- the third of technical solution of the present invention record
Alkene nitrile resin comonomer matches and molecular weight ranges are that polyacrylonitrile base carbon fiber precursors prepare institute commonly.This field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims institute
The range of restriction.Since the itaconic acid content and molecular weight of resin are higher, the dispersibility in NaSCN aqueous solutions is poorer, tree
The methyl acrylate content of fat is higher, and dissolving is also easier to.In order to preferably show that the effect of the present invention, embodiment use clothing health
Acid content and molecular weight is relatively high, polyacrylonitrile resin without methyl acrylate.Those skilled in the art be easy, it is envisioned that
After itaconic acid content and polymer molecular weight reduce, methyl acrylate content increases, above-mentioned technical proposal will be easier to implement
And obtain better effect.
【Examples 1 to 10】
The comonomer of polyacrylonitrile resin for experiment is acrylonitrile, itaconic acid.The weight of acrylonitrile and itaconic acid
Than being 95：5, the viscosity average molecular weigh of polymer is 175000.
By above-mentioned polyacrylonitrile resin powder and NaSCN aqueous solutions by the proportioning input dissolution kettle of setting, material is tieed up
The temperature for being held in setting carries out dispersion mashing using high shear dispersion machine, and residence time of material control is 15~20 when dispersion is beaten
Minute, so that polyacrylonitrile resin is dispersed in NaSCN aqueous solutions and forms paste mixture.Each embodiment feeds intake NaSCN water
The temperature of material is shown in Table 1 when the temperature and concentration of solution, dispersion are beaten.
The higher NaSCN aqueous solutions of concentration are added in paste mixture derived above, polyacrylonitrile tree is carried out to material
The adjusting of fat content and solvent strength, then using high shear homogenizer be stirred it is homogeneous so that resin is dissolved, resin is completely molten
Material is in as clear as crystal shape after solution, obtains the thick stoste of spinning then.When stirring homogeneous when stop of the material in high shear homogenizer
Between control at 1~2 second, each embodiment material proportion adjust after data, the temperature of course of dissolution material be shown in Table 2.
The grid of thick stoste derived above by preheating subsequently into vacuum state stitch the efficient deaeration tower of film-lowering type, thick stoste
By the distributor of top of tower, enter next layer in film flaky along grid seam.It is in staggered arrangement that every layer of grid, which are sewn in tower, makes original
Liquid repeats to update, and increases dehydration area.After multistage deaeration and dehydration, stoste solid content improves, and obtained stoste is transparent, warp
Then spinning solution is obtained after filtering.The deaeration of each embodiment, dehydration conditions are shown in Table 3.
Table 1.
Table 2.
*：NaSCN contents are on the basis of the total amount of NaSCN in material and water.
Table 3
【Comparative example 1~3】
Experiment uses polyacrylonitrile resin identical with Examples 1 to 10, by toner with a concentration of 40wt%'s
NaSCN aqueous solutions are put into required ratio in dissolution kettle, and the content control of resin is 25wt% in material, and material is applied under room temperature
With stirring NaSCN aqueous solution impregnating resins, dip time control is 24 hours, and polyacrylonitrile resin is made fully to be swollen.
Material after swelling adds the higher NaSCN aqueous solutions of concentration, to material carry out polyacrylonitrile resin content and
The adjusting of solvent strength, then using high shear homogenizer be stirred it is homogeneous so that resin is dissolved, resin is completely dissolved rear material
In as clear as crystal shape, spinning solution is obtained then.When stirring homogeneous residence time control of the material in high shear homogenizer 3~
5 minutes, data, the temperature of course of dissolution material after each comparative example material proportion adjusting were shown in Table 3.
Table 3.
In order to investigate embodiment and the uniformity of spinning solution that comparative example obtains, the spinnability index that stoste can be used are come
Compare.Spinnability refers to that fluid is bearing deformability possessed by stable stretched operation, i.e. fluid shape under stretching action
At the ability of continuous strand.Specifically method is：The spinning solution that temperature is 25 DEG C is fitted into hydrostatic column (makes original as possible
The pressure itself of liquid is controlled in bottom line), it stands, deaeration, and cooling perseverance warms to room temperature.Stablize the pressure applied to exist
0.05Mpa measures broken end number per minute and extrusion capacity per minute when fluid strand is broken.It will be appreciated that resin dissolves
More thoroughly, the uniformity of material better, " micelle " content it is fewer, then the material filtered out is the more.Test result is shown in Table 4.
Table 4
Claims (9)
1. a kind of method for homogenization preparation of polyacrylonitrile-base carbon fiber spinning primary fluid, aqueous suspension polymerization and inorganic molten is used
The two-step process of polyacrylonitrile resin is dissolved in agent, which is characterized in that is as follows：
(1) be 5~30 DEG C by the polyacrylonitrile resin and temperature that are prepared by aqueous suspension polymerization technique, it is a concentration of 25~
The NaSCN aqueous solutions of 32wt% mix, and the content control of polyacrylonitrile resin is 15~25wt% in mixture, maintains mixture
Temperature of charge is 8~25 DEG C and carries out dispersion mashing, so that polyacrylonitrile resin is dispersed in formation pulpous state in NaSCN aqueous solutions mixed
Close object；
(2) 100~140 DEG C of NaSCN aqueous solutions are further added in the paste mixture that step (1) obtains, maintain mixing
Object temperature of charge be 70~95 DEG C be stirred it is homogeneous, until polyacrylonitrile resin is completely dissolved to get the thick stoste of spinning；At this time
The content control of polyacrylonitrile resin is 8~12wt% in thick stoste, meanwhile, on the basis of the total amount of NaSCN and water,
The content control of NaSCN is 38~50wt%；
(3) the thick stoste of spinning that step (2) obtains is heated to 70~80 DEG C, it is efficient then to stitch film-lowering type by the grid vacuumized
Deaeration tower removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 15~35 DEG C；
(4) stoste that step (3) obtains is heated to 75~85 DEG C, then stitching film-lowering type by the two level grid vacuumized efficiently takes off
Bubble column removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 35~55 DEG C；
(5) stoste that step (4) obtains is heated to 80~95 DEG C, then stitching film-lowering type by the three-level grid vacuumized efficiently takes off
Bubble column removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 45~58 DEG C；
(6) stoste that step (5) obtains is filtered, temperature adjustment, pressure regulation, obtain and meet the spinning solution of spinning requirement.
2. preparation method according to claim 1, which is characterized in that in step (1), polyacrylonitrile resin and temperature are 10
~20 DEG C of NaSCN aqueous solutions mixing.
3. preparation method according to claim 1, which is characterized in that in step (1), in the mixture, polypropylene
The content control of nitrile resin is 17~20wt%.
4. preparation method according to claim 1, which is characterized in that in step (2), in the thick stoste, polypropylene
The content control of nitrile resin is 9.5~11.5wt%.
5. preparation method according to claim 1, which is characterized in that in step (2), in the thick stoste, with NaSCN
On the basis of the total amount of water, the content control of NaSCN is 40~48wt%.
6. preparation method according to claim 1, which is characterized in that in step (3), thick stoste is heated to 72~76 DEG C,
The temperature difference of deaeration tower is 19~30 DEG C；
7. preparation method according to claim 1, which is characterized in that in step (4), stoste is heated to 76~80 DEG C, takes off
The temperature difference of bubble column is 38~50 DEG C；
8. preparation method according to claim 1, which is characterized in that in step (5), stoste is heated to 85~90 DEG C, takes off
The temperature difference of bubble column is 45~55 DEG C.
9. preparation method according to claim 1, which is characterized in that the vacuum of step (3), step (4) and step (5) is de-
Water step cycle repeatedly carries out, the stoste composition expected from the acquisition.
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| CN108977938A (en) * | 2018-06-05 | 2018-12-11 | 中国石油化工股份有限公司 | The method that sodium sulfocyanate method prepares polyacrylonitrile powder lot dispersing slurry |
| CN111321479B (en) * | 2018-12-13 | 2023-07-25 | 中国石油化工股份有限公司 | Preparation method of graphene/polyacrylonitrile spinning solution |
| CN114045569A (en) * | 2021-12-02 | 2022-02-15 | 山东越神新材料科技有限公司 | A method for preparing high-quality polyacrylonitrile spinning stock solution by a mixed solvent system two-step method |
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| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Preparation method of ultra-high molecular weight polyacrylonitrile-based carbon fiber spinning dope |
| CN101717470A (en) * | 2009-11-26 | 2010-06-02 | 中复神鹰碳纤维有限责任公司 | Preparation method of high-viscosity spinning solution suitable for dry-jet wet spinning |
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| CN1536107A (en) * | 2003-04-04 | 2004-10-13 | 中国石油天然气集团公司 | Preparation method of polyacrylonitrile carbon raw yarn |
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Preparation method of ultra-high molecular weight polyacrylonitrile-based carbon fiber spinning dope |
| CN101717470A (en) * | 2009-11-26 | 2010-06-02 | 中复神鹰碳纤维有限责任公司 | Preparation method of high-viscosity spinning solution suitable for dry-jet wet spinning |
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