CN102260919B - Method for homogenizing, solidifying and forming polyacrylonitrile precursor - Google Patents
Method for homogenizing, solidifying and forming polyacrylonitrile precursor Download PDFInfo
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- CN102260919B CN102260919B CN201110180907.7A CN201110180907A CN102260919B CN 102260919 B CN102260919 B CN 102260919B CN 201110180907 A CN201110180907 A CN 201110180907A CN 102260919 B CN102260919 B CN 102260919B
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- coagulating bath
- polyacryl
- homogenizing
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- spinning fluid
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Abstract
The invention discloses a method for homogenizing, solidifying and forming polyacrylonitrile precursor. By adopting a wet spinning technology, a polyacrylonitrile spinning solution trickles in a coagulating bath to be subjected to double diffusions through solvent and precipitator and then solidified and separated so that the polyacrylonitrile precursor is formed. According to the method disclosed by the invention, an ammonia-containing compound is added in the a coagulating bath; the ammonia-containing compound is served as a third component and can be used for retarding the double-diffusion speed in the solidification process of the polyacrylonitrile spinning solution; therefore, the solidifying and forming homogenization is realized; and the high-performance polyacrylonitrile precursor and carbon fibre can be obtained.
Description
Technical field
The present invention relates to polyacrylonitrile fibril preparing technical field, be specifically related to a kind of method for homogenizing, solidifying of polyacrylonitrile fibril.
Background technology
Carbon fiber has low-density, high specific strength, high ratio modulus, numerous excellent properties such as high temperature resistant and corrosion-resistant, in the every field of Aero-Space, defence and military and civilian industry, is used widely.Press raw material route, carbon fiber can be divided into polyacrylonitrile (PAN) base, asphaltic base and viscose glue base three major types type.Wherein, PAN base carbon fibre is because its production technology is simple, production cost is lower and the feature of good mechanical performance, has become a kind of carbon fiber with fastest developing speed, output is the highest, kind is maximum and most widely used.
As everyone knows, high-performance PAN precursor is the prerequisite of preparation high-performance PAN base carbon fibre.Only have and adopt the high-performance PAN precursor of even structure densification just can make high performance PAN base carbon fibre.In PAN precursor production process, solidifying is the committed step of fiberizing, and its impact of homogenieity on precursor structure greatly.In process of setting, the general wet spinning technology that adopts, polyacryl-nitrile spinning fluid is formed to polyacryl-nitrile spinning fluid thread through spinneret orifice eye and enter the coagulating bath that comprises solvent and precipitating agent, solvent in polyacryl-nitrile spinning fluid thread spreads to coagulating bath, precipitating agent in coagulating bath permeates to polyacryl-nitrile spinning fluid thread, form the double diffusion of solvent-precipitating agent, thereby make polyacryl-nitrile spinning fluid thread reach critical concentration, solidify and separate out and form polyacrylonitrile fibril.But solvent-precipitating agent double diffusion effect meeting forms structural defect, this structural defect will be along with follow-up spinning technique heredity be to precursor, and becomes one of principal element determining final carbon fiber performance.As a kind of typical fault of construction, by solidifying, double diffusion causes skin-core structure just, and double diffusion speed is faster, and the cortex construction of formation is thicker.Thick cortex construction is unfavorable for that strand internal solvent is to the water in external diffusion and coagulating bath to strand internal penetration, thereby has hindered the coagulation forming of inner spinning solution, causes forming loose cored structure, produces so-called core-skin dual structure.Therefore, only slow down double diffusion speed, could realize homogenizing of coagulation forming, and then obtain high performance PAN precursor and carbon fiber.
Solidify double diffusion speed and depend primarily on concentration and the temperature of coagulating bath.Coagulating bath concentration is higher, and double diffusion speed is slower; Coagulation bath temperature is lower, and double diffusion speed is slower.Therefore, slow down the double diffusion speed of solidifying, generally all take the method that improves coagulating bath concentration or reduce coagulation bath temperature to realize.But in actual spinning process, coagulating bath concentration can not be set too high, otherwise can be due to the whole coagulation forming of the too little obstruction spinning solution of concentration difference thread, and the surface of nascent strand is produced to swelling action, even cause adhesion.Coagulation bath temperature can not be set too low, need to take into account temperature and the spray silk mode of spinning solution.In wet spinning, generally make the temperature of coagulating bath with the temperature of spinning solution is consistent or approaching as far as possible.
As can be seen here, existing coagulation forming method has significant limitation slowing down aspect double diffusion speed, is difficult to realize homogenizing of coagulation forming, thereby is difficult to obtain high performance PAN precursor and carbon fiber.
Summary of the invention
Technical purpose of the present invention is in the deficiency slowing down aspect double diffusion speed for the coagulation forming method of existing polyacrylonitrile fibril, a kind of new method of polyacrylonitrile fibril coagulation forming is provided, can effectively slow down the double diffusion speed of solidifying, realize homogenizing of coagulation forming, thereby obtain high-performance PAN precursor and carbon fiber.
The present invention realizes the technical scheme that above-mentioned technical purpose adopts: a kind of method for homogenizing, solidifying of polyacrylonitrile fibril, adopt wet spinning technology, polyacryl-nitrile spinning fluid is formed to polyacryl-nitrile spinning fluid thread through spinneret orifice eye and enter coagulating bath, described coagulating bath comprises solvent and precipitating agent, solvent in described polyacryl-nitrile spinning fluid thread spreads to coagulating bath, precipitating agent in coagulating bath permeates to polyacryl-nitrile spinning fluid thread, thereby make polyacryl-nitrile spinning fluid thread reach critical concentration, solidify and separate out and form polyacrylonitrile fibril, it is characterized in that: in described coagulating bath, also include ammoniation.
In coagulating bath, comprise solvent and precipitating agent, the present invention adds ammoniation in coagulating bath, as the 3rd component, regulates and controls the double diffusion speed in polyacryl-nitrile spinning fluid process of setting.After ammoniation is incorporated in coagulating bath, be combined generation-COO with the carboxyl on the polyacrylonitrile polymer of polyacryl-nitrile spinning fluid thread periphery
-nH
4 +, utilize the hydrogen bond action producing between solvent in ammonium radical ion and coagulating bath and precipitating agent, slow down double diffused diffusion velocity in process of setting, realized homogenizing of coagulation forming.
Solvent in described coagulating bath includes but not limited to dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF) or dimethylacetylamide (DMAc), is preferably dimethyl sulfoxide (DMSO) (DMSO); Precipitating agent includes but not limited to water, ethanol or acetone, is preferably water.
Described ammoniation refers to produce the compound of ammonium radical ion, includes but not limited to organic amine, ammoniacal liquor or inorganic ammonium salt.Because organic amine and ammoniacal liquor easily volatilize and poisonous, aspect security not as inorganic ammonium salt, so ammoniation is preferably inorganic ammonium salt.
Inorganic ammonium salt includes but not limited to carbonic hydroammonium, ammonium dihydrogen phosphate (ADP) or ammonium borate etc., as long as can produce the inorganic ammonium salt of ammonium radical ion, all can realize effect of the present invention, wherein, due to the good stability of ammonium dihydrogen phosphate (ADP) and ammonium borate, so preferred these two kinds of inorganic ammonium salts.
In order to improve homogenizing, solidifying effect, make on the other hand the polyacrylonitrile fibril inside of coagulation forming be difficult for residual ammoniation impurity, in described precipitating agent, the concentration of ammoniation is preferably 1 * 10
-6～1 * 10
-3mol/L.
Described polyacryl-nitrile spinning fluid can adopt conventional solution polymerization process synthetic,, in polymeric kettle, acrylonitrile, comonomer and initator is dissolved in solvent, under solution state, copolyreaction occurs, and obtains polyacryl-nitrile spinning fluid.Wherein, solvent includes but not limited to dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), dimethylacetylamide (DMAc), preferably dimethyl sulfoxide (DMSO) (DMSO); Initator includes but not limited to azo diisobutyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), preferably azo diisobutyl; The percentage that comonomer quality accounts for total monomer (being acrylonitrile and copolymerization monomer mass sum) quality is preferably controlled at 0.3%～3%; Comonomer is generally the carboxylic acids monomers such as itaconic acid, acrylic acid, methacrylic acid, is preferably itaconic acid, and the mass percent that itaconic acid quality accounts for total monomer is preferably controlled at 0.3%～3%, and more preferably 0.5%～1.5%; In the PAN polymer fluid making, adopt weight method to measure solid masses degree, wherein the mass percentage content of solid is preferably controlled at 17%～21%, and more preferably 18%～20%.
Compared with prior art, the present invention adds ammoniation in coagulating bath, ammoniation regulates and controls the double diffusion speed in polyacryl-nitrile spinning fluid process of setting as the 3rd component, slowed down diffusion velocity, realized homogenizing of coagulation forming, thereby obtained high-performance polyacrylonitrile precursor, for high performance carbon fiber, produced and lay a good foundation.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
Take DMSO as solvent, azodiisobutyronitrile are as initator, acrylonitrile and itaconic acid are comonomer, react 20h in polymeric kettle, wherein, the mass percentage content that itaconic acid accounts for total monomer is 1%; Again after, standing and defoaming de-single through vacuum, the PAN spinning solution that the mass percentage content that makes solid is 20%;
Adopt the mode dripping continuously, in the coagulating bath circulatory system, add ammonium dihydrogen phosphate aqueous solution, make the concentration stabilize of ammonium dihydrogen phosphate (ADP) in coagulating bath be controlled at 8 * 10
-4mol/L; Adopting hole count is that the spinnerets that 6000 (being 6k), apertures are 55 μ m is that 60wt%, temperature are the DMSO/H of 50 ℃ in concentration
2in O coagulating bath, carry out wet spinning; Again through drawing-off, wash, oil, be dried, after steam drafting, HEAT SETTING, making fiber number is the PAN precursor of 0.75dtex.
Above-mentioned PAN precursor is placed in to the air atmosphere of 200～260 ℃ successively to carry out pre-oxidation treatment, the nitrogen atmosphere of 300～800 ℃ and carries out that high temperature carbonization processing is carried out in low-temperature carbonization processing, the nitrogen atmosphere of 1500～1600 ℃, ammonium bicarbonate aqueous solution carries out anodized surface processing, again through washing, dry, starching, drier, reel, making TENSILE STRENGTH is the high-performance PAN base carbon fibre that 5.45GPa, stretch modulus are 284GPa.
Comparative example 1:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be in coagulating bath, not add ammoniation, making equally fiber number is the PAN precursor of 0.75dtex.
Above-mentioned PAN precursor is passed through to pre-oxidation, charing, the process of surface treatment identical with embodiment 1 again, and the TENSILE STRENGTH that makes PAN base carbon fibre is that 5.13GPa, stretch modulus are 276GPa.
Embodiment 2:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be that the concentration of controlling ammonium dihydrogen phosphate (ADP) in coagulating bath is 1 * 10
-5mol/L, making equally fiber number is the PAN precursor of 0.75dtex.
Above-mentioned PAN precursor is passed through to pre-oxidation, charing, the process of surface treatment identical with embodiment 1 again, and making TENSILE STRENGTH is the high-performance PAN base carbon fibre that 5.29GPa, stretch modulus are 286GPa.
Embodiment 3:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be that the ammoniation adding in the coagulating bath circulatory system is ammonium borate aqueous solution, make the concentration stabilize of coagulating bath mesoboric acid ammonium be controlled at 3 * 10
-5mol/L, making equally fiber number is the PAN precursor of 0.75dtex.
By above-mentioned PAN precursor, again through pre-oxidation, charing, the process of surface treatment identical with embodiment 1, making TENSILE STRENGTH is the high-performance PAN base carbon fibre that 5.51GPa, stretch modulus are 295GPa.
Embodiment 4:
Adopt polymerization and the spinning technique identical with embodiment 3, unique different be that the concentration of controlling coagulating bath mesoboric acid ammonium is 5 * 10
-4mol/L, making equally fiber number is the PAN precursor of 0.75dtex.
By above-mentioned PAN precursor, again through pre-oxidation, charing, the process of surface treatment identical with embodiment 3, making TENSILE STRENGTH is the high-performance PAN base carbon fibre that 5.59GPa, stretch modulus are 298GPa.
Embodiment 5:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be that the ammoniation adding in the coagulating bath circulatory system is ammonium borate aqueous solution, make the concentration stabilize of coagulating bath mesoboric acid ammonium be controlled at 1 * 10
-6mol/L, making equally fiber number is the PAN precursor of 0.75dtex.
By above-mentioned PAN precursor, again through pre-oxidation, charing, the process of surface treatment identical with embodiment 1, making TENSILE STRENGTH is the high-performance PAN base carbon fibre that 5.28GPa, stretch modulus are 285GPa.
Embodiment 6:
Adopt polymerization and the spinning technique identical with embodiment 3, unique different be that the concentration of controlling coagulating bath mesoboric acid ammonium is 1 * 10
-3mol/L, making equally fiber number is the PAN precursor of 0.75dtex.
By above-mentioned PAN precursor, again through pre-oxidation, charing, the process of surface treatment identical with embodiment 3, making TENSILE STRENGTH is the high-performance PAN base carbon fibre that 5.35GPa, stretch modulus are 304GPa.
Above-mentioned specific embodiment specifically describes the present invention, but it must be noted that, the content that the present invention comprises is not limited to this, do not departing under the prerequisite of essential scope of the present invention, can do various modifications, replacement and variation to the present invention, these equivalents belong to the limited range of the claims in the present invention book equally.
Claims (5)
1. the method for homogenizing, solidifying of a polyacrylonitrile fibril, adopt wet spinning technology, polyacryl-nitrile spinning fluid is formed to polyacryl-nitrile spinning fluid thread through spinneret orifice eye and enter coagulating bath, described coagulating bath comprises solvent and precipitating agent, solvent in described polyacryl-nitrile spinning fluid thread spreads to coagulating bath, precipitating agent in coagulating bath permeates to polyacryl-nitrile spinning fluid thread, thereby make polyacryl-nitrile spinning fluid thread reach critical concentration, solidify and separate out and form polyacrylonitrile fibril, it is characterized in that: in described coagulating bath, also include ammoniation, described ammoniation is ammonium borate, the concentration of described ammonium borate is 1 * 10
-6～1 * 10
-3mol/L,
Described polyacryl-nitrile spinning fluid is the copolymer solution of acrylonitrile and carboxylic acids monomer; Solvent in described coagulating bath is dimethyl sulfoxide (DMSO), dimethyl formamide or dimethylacetylamide;
After being incorporated in coagulating bath, described ammonium borate is combined generation-COO with the carboxyl on the polyacrylonitrile polymer of polyacryl-nitrile spinning fluid thread periphery
-nH
4 +, utilize the hydrogen bond action producing between solvent in this ammonium radical ion and coagulating bath and precipitating agent to slow down double diffusion speed in process of setting, thereby realize homogenizing of coagulation forming.
2. the method for homogenizing, solidifying of polyacrylonitrile fibril according to claim 1, is characterized in that: the precipitating agent in described coagulating bath is water, ethanol or acetone.
3. the method for homogenizing, solidifying of polyacrylonitrile fibril according to claim 1, is characterized in that: described carboxylic acids monomer is itaconic acid, acrylic acid or methacrylic acid.
4. the method for homogenizing, solidifying of polyacrylonitrile fibril according to claim 1, is characterized in that: the percentage that the quality of described carboxylic acids monomer accounts for acrylonitrile and carboxylic acids monomer mass sum is 0.3%～3%.
5. the method for homogenizing, solidifying of polyacrylonitrile fibril according to claim 1, is characterized in that: in described polyacryl-nitrile spinning fluid, the mass percentage content of solid is 17%～21%.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677209A (en) * | 2012-05-22 | 2012-09-19 | 中国科学院山西煤炭化学研究所 | Coagulating bath solution of polyacrylonitrile-based protofilament, preparation method and application |
| CN104420008B (en) * | 2013-08-30 | 2017-07-14 | 中国石油天然气股份有限公司 | A kind of coagulating bath, which is combined ammonification, improves the method for PAN base carbon fibre configurations of surface |
| CN103614801A (en) * | 2013-12-03 | 2014-03-05 | 国家电网公司 | Method for preparing high-crystallinity polyacrylonitrile nascent fiber |
| CN103952797A (en) * | 2014-04-23 | 2014-07-30 | 北京化工大学 | Preparation method of wet-process high-strength polyacrylonitrile-based carbon fiber |
| CN106283224B (en) * | 2015-06-11 | 2019-08-20 | 吉林奇峰化纤股份有限公司 | A kind of wet process has greatly the preparation method of light acrylic fibers |
| CN106939439B (en) * | 2017-05-05 | 2020-06-26 | 中复神鹰碳纤维有限责任公司 | Solidification forming method of continuous shallow trench polyacrylonitrile carbon fiber precursor |
| CN112941657B (en) * | 2021-01-27 | 2022-04-19 | 山东非金属材料研究所 | Spinning forming method of poly (p-phenylene-benzobisoxazole) fibers |
| CN115976674A (en) * | 2022-12-29 | 2023-04-18 | 江苏恒神股份有限公司 | Polyacrylonitrile precursor, preparation method thereof and carbon fiber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2833887B2 (en) * | 1991-09-17 | 1998-12-09 | 株式会社クラレ | Method for producing polyvinyl alcohol fiber with excellent strength |
| CN1752302A (en) * | 2004-09-23 | 2006-03-29 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN101724922A (en) * | 2009-11-26 | 2010-06-09 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN101768791A (en) * | 2010-02-10 | 2010-07-07 | 北京化工大学 | Polyacrylonitrile-based hollow carbon fiber precursor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280041A (en) * | 2008-05-28 | 2008-10-08 | 北京化工大学 | Acrylic nitrile-containing polymerization composition for carbon fibre and preparation thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2833887B2 (en) * | 1991-09-17 | 1998-12-09 | 株式会社クラレ | Method for producing polyvinyl alcohol fiber with excellent strength |
| CN1752302A (en) * | 2004-09-23 | 2006-03-29 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN101724922A (en) * | 2009-11-26 | 2010-06-09 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN101768791A (en) * | 2010-02-10 | 2010-07-07 | 北京化工大学 | Polyacrylonitrile-based hollow carbon fiber precursor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP第2833887号B2 1998.10.02 |
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