CN102400239B - Method for manufacturing polyacrylonitrile base carbon fiber precursor - Google Patents
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- CN102400239B CN102400239B CN 201010284576 CN201010284576A CN102400239B CN 102400239 B CN102400239 B CN 102400239B CN 201010284576 CN201010284576 CN 201010284576 CN 201010284576 A CN201010284576 A CN 201010284576A CN 102400239 B CN102400239 B CN 102400239B
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Abstract
A method for manufacturing a polyacrylonitrile base carbon fiber precursor. The method comprises steps of: 1) mixing polyacrylonitrile resin and NaSCN aqueous solution with a temperature of 2-10 DEG C and a concentration of 25-32wt%, maintaining at 8-16 DEG C and carrying out disperse beating to disperse resin uniformly and form a slurry mixture; 2) further adding NaSCN aqueous solution in the slurry, controlling a resin content at 8-14wt.% and a NaSCN content at 45.0-58.5% calculated by a total amount of the NaSCN and water, maintaining at 100-140 DEG C and stirring till complete dissolving of the resin, so as to obtain a spinning stock solution; 3) removing bubbles from the spinning stock solution, filtering and spraying on the filament, and solidifying into a nascent fibre by a coagulating bath; 4) washing the nascent fibre with water and carrying out a post treatment to obtain a polyacrylonitrile base carbon fiber precursor product. The spinning stock solution has obviously enhanced uniformity and contains no undissolved ''micelle''; spinning and the post treatment are stationary and smooth; and the precursor has better and more stable quality.
Description
Technical field
The present invention relates to a kind of method of making polyacrylonitrile base carbon fiber precursors, is solvent with the NaSCN aqueous solution particularly, makes the method for polyacrylonitrile base carbon fiber precursors by two-step process.
Background technology
Polyacrylonitrile is higher than decomposition temperature because of fusing point, and polyacrylonitrile fibre must adopt the manufacturing of solution spinning technique, and is traditional as two-step method NaSCN aqueous solution wet spinning, so far widely by industrial applications.For the spinning of two-step method solution, the uniformity of spinning solution is very important, polymer dissolution not exclusively and " micelle " that form will cause filter or filament spinning component to stop up, so that produce the phenomenons such as slurry, spillage, fracture of wire and doubling that stagnate, can be by filter and filament spinning component than " micelle " of small particle diameter, but can cause the bar of fiber to do the decline of uniformity and even physical property.Equally by the preparation of solution spinning technique, it is comparable that carbon fiber product is far from general fibre to the pursuit of mechanical performance, can infer for the manufacture of the precursor of polyacrylonitrile-based carbon fibre, and the uniformity to spinning solution when its precursor prepares has more harsh requirement.
As spin solvent, the concentration that the NaSCN aqueous solution is suitable is 45.0～58.5wt.%, in order to guarantee that simultaneously spinning solution has good fiber mobile and that make that compactness is preferably arranged, the content that polyacrylonitrile resin is suitable in the spinning solution is 8～14wt.%.In the prior art, the preparation of spinning solution comprises two steps in traditional two-step method NaSCN aqueous solution wet spinning process, before this polyacrylonitrile resin was flooded with the minor N aSCN aqueous solution, make the abundant swelling of polyacrylonitrile resin, be used for the NaSCN concentration of aqueous solution of dipping generally a little less than the concentration of spin solvent, the content of polyacrylonitrile resin is about 25wt.% in the dipping material; Material after the swelling adds the high slightly NaSCN aqueous solution of concentration then again and at high temperature imposes to stir to dissolve and obtain spinning solution.Finish from the dissolving that swells to of resin, required time was generally more than 20 hours, and whole process is quite slow.Be that the polyacrylonitrile fibre manufacturer of representative has released a kind of former liquid and preparation method thereof of once finishing dissolving with Japanese Exlan company, it is not directly added dry polyacrylonitrile resin filter cake with polymerization process and is scattered in and forms slurry in the water, be that the NaSCN aqueous solution of 50～60wt.% mixes by required proportioning with concentration again, under the condition of heating, make material by high shear dispersion or homogenous unit, mixed material is subjected to strong mechanical shearing in device, fluid power is sheared, centrifugal extruding, comprehensive active forces such as liquid layer friction and turbulent flow impact, resin obtains dissolving fast.Its advantage be dissolving fast and thoroughly since do not add the dried resin filter cake in fact resin also be in solvent swelling state, therefore with preceding method like the difference of not having essence.
Resin for the manufacture of polyacrylonitrile fibre is not homopolymers, generally should contain second comonomer of 2～10wt.%, and is commonly used as methyl acrylate, and the effect of second monomer is to increase polyacrylonitrile molecule chain flexibility and elasticity.Polyacrylonitrile resin second monomer for the manufacture of carbon fibre precursor generally partly replaces or replaces fully methyl acrylate commonly used with furoate clothing, this is because furoate clothing is except having the effect identical with methyl acrylate, the more important thing is the anionic cyclization reaction that can cause acrylonitrile unit, reduce the initial temperature of cyclization, make the pre-oxidation of precursor more steady and efficient.Different with methyl acrylate is, the furoate clothing molecule contains two carboxyls that hydrophily is stronger, and this makes the water imbibition of resin and the ability that is dissolved in the NaSCN aqueous solution obviously strengthen.Polyacrylonitrile resin is generally powdery in addition, very easily reunites, and after resin was met the NaSCN aqueous solution, the rapid water absorption and swelling of aggregate outermost resin also was partly dissolved, and formed comparatively fine and close gelatinous layer, and the resin that is wrapped up by gelatinous layer will be difficult to be soaked into by solvent.Very unfortunate, this skin for the intensity of the resin groups aggressiveness of gelatinous layer with the reducing and improve of particle diameter, " micelle " of tiny particle diameter is in case form, being broken and dissolving to become very difficult.Be understood that easily no matter take which kind of mode to dissolve, toner is scattered in the NaSCN aqueous solution equably.Just the difficulty of disperseing in the NaSCN aqueous solution owing to the polyacrylonitrile resin that contains the furoate clothing comonomer greatly increases, therefore, the preparation means of spinning solution is difficult to the polyacrylonitrile base carbon fiber precursors spinning solution that obtains to have good uniformity in the existing two-step method NaSCN aqueous solution wet spinning process, often leave more " micelle " in the stoste, thereby influence stability and the precursor product quality of spinning.
Summary of the invention
The invention provides a kind of method of making polyacrylonitrile base carbon fiber precursors, technical problem to be solved is that spinning solution is when preparing, the polyacrylonitrile resin of powdery is dispersed in before dissolving in the NaSCN aqueous solution, and can finish dissolving resin with the short time subsequently, obtain the very good spinning solution of uniformity.
Below be the concrete technical scheme of the present invention:
A kind of method of making polyacrylonitrile base carbon fiber precursors, the manufacturing raw material polyacrylonitrile resin of precursor is copolymer, viscosity average molecular weigh is 50000～180000, comonomer comprises acrylonitrile, furoate clothing and methyl acrylate, the weight ratio of each comonomer is: when acrylonitrile=100, furoate clothing=0.7～8.0, methyl acrylate=0～10.0.
Manufacture process comprises:
1) polyacrylonitrile resin and temperature are that 2～10 ℃ and concentration are the NaSCN aqueous solution of 25～32wt.%, the content of polyacrylonitrile resin is controlled to be 15～25wt.% in the mixture, keep the mixture temperature of charge and be 8～16 ℃ and disperse making beating, polyacrylonitrile resin is dispersed in the NaSCN aqueous solution forms paste mixture;
2) process 1) further add the NaSCN aqueous solution in the paste mixture that obtains, the content of polyacrylonitrile resin is controlled to be 8～14wt.% in the mixture at this moment, total amount with NaSCN and water is benchmark, the content of NaSCN is controlled to be 45.0～58.5wt.%, keep the mixture temperature of charge and be 100～140 ℃ and stir even matter, dissolve fully until polyacrylonitrile resin, satisfy spinning solution;
3) process 2) spinning solution that obtains is through removing bubble and filtering back spray silk, and passing through the coagulating bath solidification forming is as-spun fibre, and coagulating bath is the NaSCN aqueous solution of 8～16wt.%, and coagulation bath temperature is-5～16 ℃;
4) process 3) as-spun fibre that obtains makes the polyacrylonitrile base carbon fiber precursors product through washing and last handling process, and last handling process comprises drawing-off, oils and compacting by drying.
The weight ratio of above-mentioned each comonomer is: when acrylonitrile=100, and furoate clothing=2.5～5.0, methyl acrylate=0～5.0.
Said process 1) temperature of the described NaSCN aqueous solution that mixes with polyacrylonitrile resin is preferably 5～8 ℃; The content of polyacrylonitrile resin preferably is controlled to be 16～20wt.% in the mixture; Preferably keep the mixture temperature of charge and be 10～15 ℃ and disperse making beating; Disperse making beating preferably to adopt high shear dispersal device or high shear homogenous unit to carry out.
Said process 2) content of polyacrylonitrile resin preferably is controlled to be 11～14wt.% in the described mixture; Total amount with NaSCN and water is benchmark, and the content of NaSCN preferably is controlled to be 51.5～58.5wt.%; Preferably keep the mixture temperature of charge and be 110～130 ℃ and stir even matter; Stirring even matter preferably adopts high shear dispersal device or high shear homogenous unit to carry out.
Key problem in technology of the present invention is to improve in the spinning solution preparation process, and polyacrylonitrile resin is dispersed in the NaSCN aqueous solution, and then carries out the dissolving of polymer.The inventor finds that along with the reduction of temperature and NaSCN concentration of aqueous solution, the solubility property of polyacrylonitrile resin presents tangible downward trend, is easier to disperse but become simultaneously.The inventor also further knows by a large amount of experiments, and in 8～16 ℃ scope, resin does not dissolve in concentration is the NaSCN aqueous solution of 25～32wt.% substantially with temperature maintenance, and swelling is also carried out very slowly.Adopt high shear dispersal device or high shear homogenous unit to disperse making beating with this understanding after resin and the NaSCN aqueous solution, can obtain the very good paste mixture of a kind of mobile performance, in paste mixture, the polyacrylonitrile resin powder presents dispersity very uniformly, and content is then the highest can to reach 25wt.%.After this paste mixture adds the NaSCN aqueous solution of higher concentration, the dissolving of carrying out subsequently becomes very easy, in process 2) purpose that adds the NaSCN aqueous solution is to carry out the concentration adjustment of NaSCN and the adjusting of resin content, makes the spinning solution that finally obtains form proportioning in suitable scope.Course of dissolution can impose stirring in traditional dissolution kettle, the time that experience is long slightly finishes; Also can adopt high shear dispersal device or high shear homogenous unit that material is imposed the even matter of fierce stirring and finish, this can significantly improve the efficient of dissolving, reduces dissolution time.But no matter take which kind of dissolution mechanism, can obtain dissolving thorough, the uniform spinning solution of quality.Spinning and last handling process and prior art are identical, can adopt existing conventional technology.
Compared with prior art good effect of the present invention is fairly obvious, through improved spinning solution preparation process and uncomplicated, required time is shorter, the spinning solution uniformity that what is more important obtains obviously improves, substantially do not exist in the stoste in undissolved " micelle ", spinning and back process are steadily smooth, and the precursor quality that obtains is higher more stable.
The invention will be further described below by specific embodiment.The polyacrylonitrile resin comonomer proportioning of technical solution of the present invention record and molecular weight ranges are that the polyacrylonitrile base carbon fiber precursors preparation is used always, because the furoate clothing content of resin and molecular weight are higher, dispersiveness in the NaSCN aqueous solution is poorer, in order to show effect of the present invention better, embodiment adopts the relative higher polyacrylonitrile resin with molecular weight of furoate clothing content.Those skilled in the art predicts easily, and after furoate clothing content and polymer molecular weight reduction, technique scheme will be easier to implement and obtain better effect.
The specific embodiment
One, the preparation of spinning solution
[embodiment 1～10]
The comonomer that is used for the polyacrylonitrile resin of test is acrylonitrile, furoate clothing and methyl acrylate.The weight ratio of each comonomer is: acrylonitrile=100, and furoate clothing=8.0, methyl acrylate=1, the polymer viscosity average molecular weigh is 175000.
Above-mentioned polyacrylonitrile resin powder and the NaSCN aqueous solution are dropped in the dissolution kettle by the proportioning of setting, the temperature that material is maintained at setting adopts the high shear dispersion machine to disperse making beating, residence time of material control was dispersed in the NaSCN aqueous solution polyacrylonitrile resin and forms paste mixture at 15～20 minute when disperseing making beating.Material temperature saw Table 1 when each embodiment fed intake the temperature of the NaSCN aqueous solution and concentration, dispersion making beating.
Add the higher NaSCN aqueous solution of concentration in the paste mixture that more than obtains, material is carried out the adjusting of polyacrylonitrile resin content and solvent strength, adopt the high shear homogenizer to stir even matter then and make resin dissolves, resin dissolves the back material fully and is as clear as crystal shape, obtains spinning solution then.The time of staying control of material in the high shear homogenizer was at 1～5 second when matter was spared in stirring, and data, course of dissolution material temperature after each embodiment material proportion is regulated see Table 2.
Table 1.
Table 2.
*: NaSCN content is benchmark with the total amount of NaSCN in the material and water.
[comparative example 1～3]
The polyacrylonitrile resin identical with embodiment 1～10 adopted in experiment, the NaSCN aqueous solution that with toner and concentration is 40wt.% drops in the dissolution kettle in required ratio, the content of resin is controlled to be 25wt.% in the material, material imposes under normal temperature and stirs with NaSCN aqueous solution impregnating resin, dip time is controlled to be 24 hours, makes the abundant swelling of polyacrylonitrile resin.
Material after the swelling adds the higher NaSCN aqueous solution of concentration again, material is carried out the adjusting of polyacrylonitrile resin content and solvent strength, adopt the high shear homogenizer to stir even matter then and make resin dissolves, resin dissolves the back material fully and is as clear as crystal shape, obtains spinning solution then.The time of staying control of material in the high shear homogenizer was at 3～5 minutes when matter was spared in stirring, and data, course of dissolution material temperature after each comparative example material proportion is regulated see Table 3.
Table 3.
In order to investigate the uniformity of the spinning solution that embodiment and comparative example obtain, measure the filterability of spinning solution earlier with reference to the blockage factor method of testing of filtering flow, concrete method of testing is:
With temperature be 25 ℃ spinning solution under the situation that imposes 150KPa pressure, by the filter of 400 orders or 800 order filter materials is housed, filter jet expansion diameter is 3mm respectively.Discharging 500mL spinning solution under the situation that nozzle is not installed is installed nozzle then earlier, accesses the spinning solution material that leaches in 20 minutes again, weighs the congestion situations when investigating material by filter.Can infer, resin dissolves more thoroughly, the uniformity of material better, " micelle " content is fewer, the material that then leaches is the more.
Test result sees Table 4.
Table 4.
Two, the manufacturing of precursor
[embodiment 11～18, comparative example 4～7]
The spinning solution of selecting for use above-described embodiment and comparative example to obtain adopts conventional method to carry out the manufacturing of polyacrylonitrile base carbon fiber precursors, spinning solution is the spray silk after removing bubble and filtration, process coagulating bath solidification forming is as-spun fibre, coagulating bath is the NaSCN aqueous solution of 8～16wt.%, and coagulation bath temperature is-5～16 ℃.As-spun fibre through washing and drawing-off, oil and last handling process such as compacting by drying is made the polyacrylonitrile base carbon fiber precursors product.
The polyacrylonitrile base carbon fiber precursors main performance index of each embodiment and comparative example sees Table 5.
Table 5.
Claims (10)
1. method of making polyacrylonitrile base carbon fiber precursors, the manufacturing raw material polyacrylonitrile resin of precursor is copolymer, viscosity average molecular weigh is 50000～180000, comonomer comprises acrylonitrile, furoate clothing and methyl acrylate, the weight ratio of each comonomer is: when acrylonitrile=100, furoate clothing=0.7～8.0, methyl acrylate=0～10.0, manufacture process comprises:
1) polyacrylonitrile resin and temperature are that 2～10 ℃ and concentration are the NaSCN aqueous solution of 25～32wt.%, the content of polyacrylonitrile resin is controlled to be 15～25wt.% in the mixture, keep the mixture temperature of charge and be 8～16 ℃ and disperse making beating, polyacrylonitrile resin is dispersed in the NaSCN aqueous solution forms paste mixture;
2) process 1) further add the NaSCN aqueous solution in the paste mixture that obtains, the content of polyacrylonitrile resin is controlled to be 8～14wt.% in the mixture at this moment, total amount with NaSCN and water is benchmark, the content of NaSCN is controlled to be 45.0～58.5wt.%, keep the mixture temperature of charge and be 100～140 ℃ and stir even matter, dissolve fully until polyacrylonitrile resin, satisfy spinning solution;
3) process 2) spinning solution that obtains is through removing bubble and filtering back spray silk, and passing through the coagulating bath solidification forming is as-spun fibre, and coagulating bath is the NaSCN aqueous solution of 8～16wt.%, and coagulation bath temperature is 5～16 ℃;
4) process 3) as-spun fibre that obtains makes the polyacrylonitrile base carbon fiber precursors product through washing and last handling process, and last handling process comprises drawing-off, oils and compacting by drying.
2. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that the weight ratio of described each comonomer is: when acrylonitrile=100, and furoate clothing=2.5～5.0, methyl acrylate=0～5.0.
3. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that process 1) temperature of the described NaSCN aqueous solution that mixes with polyacrylonitrile resin is 5～8 ℃.
4. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that process 1) content of polyacrylonitrile resin is controlled to be 16～20wt.% in the described mixture.
5. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that described process 1) in keep the mixture temperature of charge be 10～15 ℃ disperse the making beating.
6. make the method for polyacrylonitrile base carbon fiber precursors according to claim 1 or 5, it is characterized in that process 1) described dispersion making beating adopts high shear dispersal device or high shear homogenous unit to carry out.
7. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that process 2) content of polyacrylonitrile resin is controlled to be 11～14wt.% in the described mixture.
8. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that process 2) total amount with NaSCN and water in the described mixture is benchmark, the content of NaSCN is controlled to be 51.5～58.5wt.%.
9. the method for manufacturing polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that described process 2) in keep the mixture temperature of charge and be 110～130 ℃ and stir even matter.
10. according to the method for claim 1 or 9 described manufacturing polyacrylonitrile base carbon fiber precursors, it is characterized in that process 2) matter employing high shear dispersal device is spared in described stirring or the high shear homogenous unit carries out.
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| CN103710776A (en) * | 2012-10-08 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber raw liquid |
| CN105586655B (en) * | 2014-10-21 | 2019-01-04 | 中国石油化工股份有限公司 | A method of it homogenizes and prepares polyacrylonitrile base carbon fiber precursors |
| CN105525362B (en) * | 2014-10-21 | 2019-03-19 | 中国石油化工股份有限公司 | The method for homogenization preparation of high molecular weight, high concentration polyacrylonitrile-base carbon fiber spinning primary fluid |
| CN105586654B (en) * | 2014-10-21 | 2018-11-20 | 中国石油化工股份有限公司 | The method that inorganic solvent method prepares polyacrylonitrile base carbon fiber precursors |
| 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 |
| CN111088538B (en) * | 2018-10-23 | 2021-06-18 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile fiber for asphalt mixture |
| CN116065250A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Polyacrylonitrile spinning solution and preparation method and application thereof |
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| CN101597820A (en) * | 2009-06-09 | 2009-12-09 | 东华大学 | A kind of preparation method of polyacrylonitrile-based carbon fibre |
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| JP4924469B2 (en) * | 2008-02-25 | 2012-04-25 | 東レ株式会社 | Carbon fiber precursor fiber and method for producing carbon fiber |
| JP2010100970A (en) * | 2008-10-24 | 2010-05-06 | Toray Ind Inc | Method for producing carbon fiber |
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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 |
| CN101165237A (en) * | 2006-10-18 | 2008-04-23 | 中国石化上海石油化工股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber protofilament |
| CN101597820A (en) * | 2009-06-09 | 2009-12-09 | 东华大学 | A kind of preparation method of polyacrylonitrile-based carbon fibre |
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