CN102260919A - Method for homogenizing, solidifying and forming polyacrylonitrile precursor - Google Patents
Method for homogenizing, solidifying and forming polyacrylonitrile precursor Download PDFInfo
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- CN102260919A CN102260919A CN2011101809077A CN201110180907A CN102260919A CN 102260919 A CN102260919 A CN 102260919A CN 2011101809077 A CN2011101809077 A CN 2011101809077A CN 201110180907 A CN201110180907 A CN 201110180907A CN 102260919 A CN102260919 A CN 102260919A
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- coagulating bath
- homogenizes
- forming method
- coagulation forming
- polyacryl
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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 the polyacrylonitrile fibril preparing technical field, be specifically related to a kind of coagulation forming method that homogenizes 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, is used widely in the every field of Aero-Space, defence and military and civilian industry.Press raw material route, carbon fiber can be divided into polyacrylonitrile (PAN) base, asphaltic base and viscose glue base three major types type.Wherein, the PAN base carbon fibre is because of its production technology is simple, production cost is lower and the characteristics of good mechanical performance, has become a kind of carbon fiber with fastest developing speed, that 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.Have only 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 homogenieity influence to the precursor structure is very big.In process of setting, the general wet spinning technology that adopts, polyacryl-nitrile spinning fluid is formed the polyacryl-nitrile spinning fluid thread through the spinneret orifice eye enter the coagulating bath that comprises solvent and precipitating agent, solvent in the polyacryl-nitrile spinning fluid thread spreads to coagulating bath, precipitating agent in the coagulating bath permeates to the polyacryl-nitrile spinning fluid thread, promptly form solvent-precipitating agent double diffusion, thereby make the 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 along with follow-up spinning technique heredity to precursor, and become one of principal element of the final carbon fiber performance of decision.Double diffusion causes skin-core structure by solidifying just as a kind of typical fault of construction, and double diffusion speed is fast more, and the cortex construction of formation is thick more.Thick cortex construction is unfavorable for the water of strand internal solvent in external diffusion and coagulating bath to the strand internal penetration, thereby has hindered the coagulation forming of inner spinning solution, causes forming loose cored structure, promptly 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 the concentration and the temperature of coagulating bath.Coagulating bath concentration is high more, and double diffusion speed is then slow more; Coagulation bath temperature is low more, and double diffusion speed is then slow more.Therefore, slow down the double diffusion speed of solidifying, the method for generally all taking to improve coagulating bath concentration or reduce coagulation bath temperature realizes.But in actual spinning process, coagulating bath concentration can not be set too high, otherwise can be because the whole coagulation forming of the too little obstruction spinning solution of concentration difference thread, and the surface of nascent strand is produced swelling action, even causes adhesion.Coagulation bath temperature can not be set low, need take into account the temperature and the spray silk mode of spinning solution.In wet spinning, the temperature of the temperature of coagulating bath and spinning solution is consistent or approaching.
This shows that existing coagulation forming method has significant limitation aspect the double diffusion speed slowing down, and 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 of slowing down aspect the double diffusion speed at 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 that the technical scheme that above-mentioned technical purpose adopts is: a kind of coagulation forming method that homogenizes of polyacrylonitrile fibril, adopt the wet spinning technology, polyacryl-nitrile spinning fluid is formed the polyacryl-nitrile spinning fluid thread through the spinneret orifice eye enter coagulating bath, described coagulating bath comprises solvent and precipitating agent, solvent in the described polyacryl-nitrile spinning fluid thread spreads to coagulating bath, precipitating agent in the coagulating bath permeates to the polyacryl-nitrile spinning fluid thread, thereby make the polyacryl-nitrile spinning fluid thread reach critical concentration, solidify and separate out and form polyacrylonitrile fibril, it is characterized in that: also include ammoniation in the described coagulating bath.
Comprise solvent and precipitating agent in the coagulating bath, the present invention adds ammoniation in coagulating bath, regulates and control double diffusion speed in the polyacryl-nitrile spinning fluid process of setting as the 3rd component.After ammoniation is incorporated in the coagulating bath, combine generation-COO with carboxyl on the polyacrylonitrile polymer of polyacryl-nitrile spinning fluid thread periphery
-NH
4 +, utilize the hydrogen bond action that produces between solvent in ammonium radical ion and the coagulating bath and precipitating agent, slow down double diffused diffusion velocity in the process of setting, realized homogenizing of coagulation forming.
Solvent in the 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 volatilize easily and is poisonous, aspect security, be not so good 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., all can realize effect of the present invention as long as can produce the inorganic ammonium salt of ammonium radical ion, wherein, because the good stability of ammonium dihydrogen phosphate (ADP) and ammonium borate, so preferred these two kinds of inorganic ammonium salts.
In order to improve the coagulation forming effect that homogenizes, make the polyacrylonitrile fibril inside of coagulation forming be difficult for residual ammoniation impurity on the other hand, in the described precipitating agent, the concentration of ammoniation is preferably 1 * 10
-6～1 * 10
-3Mol/L.
Described polyacryl-nitrile spinning fluid can adopt solution polymerization process commonly used synthetic, promptly in polymeric kettle, acrylonitrile, comonomer and initator is dissolved in the solvent, under solution state copolyreaction takes place, and obtains polyacryl-nitrile spinning fluid.Wherein, solvent includes but not limited to dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), dimethylacetylamide (DMAc), preferred dimethyl sulfoxide (DMSO) (DMSO); Initator includes but not limited to azo diisobutyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), preferred azo diisobutyl; The percentage that the comonomer quality accounts for total monomer (being acrylonitrile and copolymerization monomer mass sum) quality preferably is controlled at 0.3%～3%; Comonomer is generally carboxylic acids monomers such as itaconic acid, acrylic acid, methacrylic acid, is preferably itaconic acid, and the mass percent that the itaconic acid quality accounts for total monomer preferably is controlled at 0.3%～3%, and more preferably 0.5%～1.5%; In the PAN polymer fluid that makes, adopt weight method to measure the solid masses degree, wherein the mass percentage content of solid preferably is controlled at 17%～21%, and more preferably 18%～20%.
Compared with prior art, the present invention adds ammoniation in coagulating bath, ammoniation is regulated and control double diffusion speed in the polyacryl-nitrile spinning fluid process of setting as the 3rd component, slowed down diffusion velocity, realized homogenizing of coagulation forming, thereby obtained the high-performance polyacrylonitrile precursor, for high performance carbon fiber production is laid a good foundation.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
With DMSO is that solvent, azodiisobutyronitrile are that initator, acrylonitrile and itaconic acid are comonomer, and at polymeric kettle internal reaction 20h, wherein, the mass percentage content that itaconic acid accounts for total monomer is 1%; After vacuum was taken off list, standing and defoaming, the mass percentage content that makes solid was 20% PAN spinning solution again;
Adopt the mode that drips continuously, in the coagulating bath circulatory system, add ammonium dihydrogen phosphate aqueous solution, make that the concentration stabilize of ammonium dihydrogen phosphate (ADP) is controlled at 8 * 10 in the coagulating bath
-4Mol/L; Adopting hole count is that the spinnerets that 6000 (being 6k), apertures are 55 μ m is that 60wt%, temperature are 50 ℃ DMSO/H in concentration
2Carry out wet spinning in the O coagulating bath; Again through drawing-off, wash, oil, after the drying, steam drafting, HEAT SETTING, making fiber number is the PAN precursor of 0.75dtex.
With above-mentioned PAN precursor place successively that 200～260 ℃ air atmosphere carries out that pre-oxidation treatment, 300～800 ℃ nitrogen atmosphere carry out that low-temperature carbonization is handled, 1500～1600 ℃ nitrogen atmosphere carries out that high temperature carbonization is handled, ammonium bicarbonate aqueous solution carries out anodized surface and handles, through washing, drying, starching, drying, coiling again, making TENSILE STRENGTH is that 5.45GPa, stretch modulus are the high-performance PAN base carbon fibre of 284GPa again.
The comparative example 1:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be in coagulating bath, not add ammoniation, making fiber number equally is the PAN precursor of 0.75dtex.
Above-mentioned PAN precursor is passed through pre-oxidation, charing, the process of surface treatment identical with embodiment 1 again, and the TENSILE STRENGTH that makes the 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 the coagulating bath is 1 * 10
-5Mol/L, making fiber number equally is the PAN precursor of 0.75dtex.
Above-mentioned PAN precursor is passed through pre-oxidation, charing, the process of surface treatment identical with embodiment 1 again, and making TENSILE STRENGTH is that 5.29GPa, stretch modulus are the high-performance PAN base carbon fibre of 286GPa.
Embodiment 3:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be that the ammoniation that adds in the coagulating bath circulatory system is an ammonium borate aqueous solution, make the concentration stabilize of coagulating bath mesoboric acid ammonium be controlled at 3 * 10
-5Mol/L, making fiber number equally is the PAN precursor of 0.75dtex.
Again through pre-oxidation, charing, the process of surface treatment identical with embodiment 1, making TENSILE STRENGTH is that 5.51GPa, stretch modulus are the high-performance PAN base carbon fibre of 295GPa with above-mentioned PAN precursor.
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 fiber number equally is the PAN precursor of 0.75dtex.
Again through pre-oxidation, charing, the process of surface treatment identical with embodiment 3, making TENSILE STRENGTH is that 5.59GPa, stretch modulus are the high-performance PAN base carbon fibre of 298GPa with above-mentioned PAN precursor.
Embodiment 5:
Adopt polymerization and the spinning technique identical with embodiment 1, unique different be that the ammoniation that adds in the coagulating bath circulatory system is an ammonium borate aqueous solution, make the concentration stabilize of coagulating bath mesoboric acid ammonium be controlled at 1 * 10
-6Mol/L, making fiber number equally is the PAN precursor of 0.75dtex.
Again through pre-oxidation, charing, the process of surface treatment identical with embodiment 1, making TENSILE STRENGTH is that 5.28GPa, stretch modulus are the high-performance PAN base carbon fibre of 285GPa with above-mentioned PAN precursor.
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 fiber number equally is the PAN precursor of 0.75dtex.
Again through pre-oxidation, charing, the process of surface treatment identical with embodiment 3, making TENSILE STRENGTH is that 5.35GPa, stretch modulus are the high-performance PAN base carbon fibre of 304GPa with above-mentioned PAN precursor.
Above-mentioned specific embodiment specifically describes the present invention, but it must be noted that, the content that the present invention comprised is not limited thereto, under the prerequisite that does not break away from 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 claims of the present invention equally.
Claims (10)
1. the coagulation forming method that homogenizes of a polyacrylonitrile fibril, adopt the wet spinning technology, polyacryl-nitrile spinning fluid is formed the polyacryl-nitrile spinning fluid thread through the spinneret orifice eye enter coagulating bath, described coagulating bath comprises solvent and precipitating agent, solvent in the described polyacryl-nitrile spinning fluid thread spreads to coagulating bath, precipitating agent in the coagulating bath permeates to the polyacryl-nitrile spinning fluid thread, thereby make the polyacryl-nitrile spinning fluid thread reach critical concentration, solidify and separate out and form polyacrylonitrile fibril, it is characterized in that: also include ammoniation in the described coagulating bath.
2. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 1, it is characterized in that: described ammoniation is organic amine, ammoniacal liquor or inorganic ammonium salt.
3. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 2, it is characterized in that: described inorganic ammonium salt comprises carbonic hydroammonium, ammonium dihydrogen phosphate (ADP) or ammonium borate.
4. according to the coagulation forming method that homogenizes of claim 1,2 or 3 described polyacrylonitrile fibrils, it is characterized in that: in the described coagulating bath, the concentration of ammoniation is 1 * 10
-6～1 * 10
-3Mol/L.
5. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 1, it is characterized in that: the solvent in the described coagulating bath is dimethyl sulfoxide (DMSO), dimethyl formamide or dimethylacetylamide.
6. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 1, it is characterized in that: the precipitating agent in the described coagulating bath is water, ethanol or acetone.
7. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 1, it is characterized in that: described polyacryl-nitrile spinning fluid is the solution copolymerization thing of acrylonitrile and carboxylic acids monomer.
8. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 7, it is characterized in that: described carboxylic acids monomer is itaconic acid, acrylic acid or methacrylic acid.
9. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 7, it 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%.
10. the coagulation forming method that homogenizes of polyacrylonitrile fibril according to claim 1, it is characterized in that: in the described polyacryl-nitrile spinning fluid, the mass percentage content of solid is 17%～21%.
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Cited By (8)
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| 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 |
| 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 |
| CN104420008A (en) * | 2013-08-30 | 2015-03-18 | 中国石油天然气股份有限公司 | Coagulating bath compound ammoniation method for improving surface morphology of PAN-based carbon fiber |
| CN106283224A (en) * | 2015-06-11 | 2017-01-04 | 吉林奇峰化纤股份有限公司 | A kind of wet method has greatly the preparation method of light acrylon |
| CN106939439A (en) * | 2017-05-05 | 2017-07-11 | 中复神鹰碳纤维有限责任公司 | A kind of coagulation forming method of continuous shallow trench polyacrylonitrile carbon fiber precursor |
| CN112941657A (en) * | 2021-01-27 | 2021-06-11 | 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106939439A (en) * | 2017-05-05 | 2017-07-11 | 中复神鹰碳纤维有限责任公司 | A kind of coagulation forming method of continuous shallow trench polyacrylonitrile carbon fiber precursor |
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| CN112941657A (en) * | 2021-01-27 | 2021-06-11 | 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 |
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