CN117513011A - High-performance polyacrylonitrile carbon fiber precursor oiling agent and preparation method thereof - Google Patents
High-performance polyacrylonitrile carbon fiber precursor oiling agent and preparation method thereof Download PDFInfo
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- CN117513011A CN117513011A CN202311432037.7A CN202311432037A CN117513011A CN 117513011 A CN117513011 A CN 117513011A CN 202311432037 A CN202311432037 A CN 202311432037A CN 117513011 A CN117513011 A CN 117513011A
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- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 41
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 41
- 239000008041 oiling agent Substances 0.000 title claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims abstract description 46
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000002216 antistatic agent Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 11
- 239000000835 fiber Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000005611 electricity Effects 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000004804 winding Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004671 silicon softener Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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Abstract
A high-performance polyacrylonitrile carbon fiber precursor oiling agent and a preparation method thereof. 20-40 parts of surfactant, 40-60 parts of epoxy modified linear polydimethylsiloxane, 5-15 parts of special modified high-viscosity high-ammonia-value silicone oil, 10-30 parts of amino, polyether and other active group modified silicone oil, 10-30 parts of epoxy modified silicone oil, 3-8 parts of modified organosilicon softener, 1-5 parts of elastic finishing agent, 1-5 parts of antistatic agent, 20-30 parts of ethylene glycol monobutyl ether and 200-300 parts of deionized water. The oiling agent disclosed by the invention has good stability, antistatic property, heat resistance and bundling property for PAN carbon fiber precursor, solves the problem of roller sticking of precursor during a drying process, reduces the generation of broken filaments and broken filaments, improves the quality of carbon fiber precursor, greatly reduces the generation of phenomena of broken filaments, doubling and burning of precursor during pre-oxidation and carbonization, and can be used for preparing high-strength carbon fibers.
Description
Technical Field
The invention relates to the technical field of high-performance carbon fiber preparation, in particular to a polyacrylonitrile carbon fiber precursor oiling agent for high performance and a preparation method thereof.
Background
In the production process of PAN carbon fiber, because of the fine filament bundles, the friction among filament bundles and equipment are serious, a large amount of static electricity is generated, which is not beneficial to the winding of the filament; in addition, friction can cause the surface damage of the precursor to form a large number of defects, which can cause the conditions of filament, filament breakage, adhesion, hot melting, even burning and the like to easily occur in the subsequent pre-oxidation and carbonization processes, and the production of high-performance carbon fibers is not facilitated.
It is generally believed that the strands are protected with a carbon fiber dope. On one hand, the oiling agent is an organic matter, has high resistance and certain lubricity, and can effectively reduce the generation of static electricity and damage to the precursor when the oiling agent is coated on the surface of the precursor; on the other hand, the precursor oiling agent has the function of improving the processability of the fiber, and some functional auxiliary agents added into the oiling agent can endow the precursor with the characteristics of smoothness, softness, cohesion, high temperature resistance and the like, and the oiling agent acts between monofilaments to increase the bundling property, the drafting property and the fiber splitting property of the precursor fiber bundle.
However, research and development of the domestic PAN precursor oiling agent are relatively backward, and a large gap still exists compared with foreign countries, and the oiling agent for producing the domestic high-performance carbon fiber at present mainly depends on import, has high price, is limited by people and seriously hinders development of the domestic carbon fiber industry. Accordingly, there is an urgent need to develop an oiling agent for producing high-performance PAN carbon fiber precursors.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-performance polyacrylonitrile carbon fiber precursor oiling agent for improving the heat resistance and the surface friction coefficient of a precursor. The invention also provides a preparation method for producing the oil agent.
The technical problem to be solved by the invention is realized by the following technical scheme, and the oiling agent for the high-performance polyacrylonitrile carbon fiber precursor is characterized in that: according to the weight portion, the emulsion with the stable particle diameter of 250-350nm is obtained by a phase inversion emulsification method from 20-40 portions of surfactant, 40-60 portions of epoxy-modified linear polydimethylsiloxane, 5-15 portions of modified high-viscosity high-ammonia-value silicone oil, 10-30 portions of amino polyether active group modified silicone oil, 10-30 portions of epoxy modified silicone oil, 3-8 portions of modified organosilicon softener, 1-5 portions of elastic finishing agent, 1-5 portions of antistatic agent, 20-30 portions of organic solvent and 200-300 portions of deionized water.
The technical problem to be solved by the invention can be further solved by the following technical scheme, and the surfactant is a mixture of fatty acid polyoxyethylene ester A-103 and castor oil polyoxyethylene ether EL-80.
The technical problem to be solved by the invention can be further solved by the following technical scheme, wherein the epoxy value of the epoxy-terminated modified linear polydimethylsiloxane is 0.07-0.09mmol/g.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the ammonia value of the modified high-viscosity high-ammonia-value silicone oil is 0.6+/-10%mmol/g; the viscosity at 25 ℃ is 10000-20000mpa.s.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the viscosity of the amino polyether active group modified silicone oil at 25 ℃ is 1000-2000mPa.s.
The technical problem to be solved by the invention can be further solved by the following technical scheme, wherein the epoxy value of the epoxy modified silicone oil is 0.30+/-0.05 mmol/g.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the modified organosilicon softener is a weak cation auxiliary agent.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the elastic finishing agent is silicone oil containing self-crosslinking groups.
The technical problem to be solved by the invention can be further solved by the following technical scheme, wherein the antistatic agent is a high-temperature resistant compound containing reactive groups and hydrophilic groups.
The technical problem to be solved by the invention can be further solved by the following technical scheme, wherein the organic solvent is ethylene glycol monobutyl ether.
The preparation process of high performance PAN carbon fiber precursor oil includes mixing required silicone oil in a homogenizing mixer, emulsifying with water to phase change, and regulating pH to 5-7 with glacial acetic acid to obtain stable emulsion with particle size of 250-350 nm.
Further, firstly stirring at a high speed for 30min, then slowly adding 30-40 parts of water for continuous stirring, after the whole is changed to O/W, rapidly adding the rest of water and ethylene glycol monobutyl ether, adding glacial acetic acid for regulating the pH, reducing the stirring speed after the whole is changed to W/O, and homogenizing for 15min to obtain the particle size of the emulsion of 250-350 nm.
Compared with the prior art, the invention improves the heat resistance of the precursor by introducing the epoxy modified silicone oil, on one hand, obviously reduces the generation of oil dirt in the drying process and eliminates the phenomenon of sticking rollers, and effectively prevents the precursor from generating the conditions of yarn breakage, yarn doubling, adhesion and the like in the pre-oxidation process; the modified silicone oil with various active groups such as amino, polyether and the like can not only increase the wettability of the oil, but also be directionally adsorbed on the surface of the fiber to reduce the friction coefficient between the fibers; some functional auxiliary agents are added to eliminate static electricity generated in the production process of the precursor, and endow the fiber with the characteristics of softness, elasticity, bundling and the like. The high-performance oiling agent for PAN carbon fiber precursor is prepared after actual application and multiple adjustment, and meets the production requirement.
Detailed Description
The following further describes the specific technical solutions of the present invention, so that the purpose, technical solutions and advantages of the embodiments of the present invention will be more apparent to those skilled in the art to further understand the present invention, and the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments, but not limitations on the claims thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The high-performance polyacrylonitrile carbon fiber precursor oiling agent is prepared from 20-40 parts by weight of surfactant, 40-60 parts by weight of epoxy-terminated modified linear polydimethylsiloxane, 5-15 parts by weight of modified high-viscosity high-ammonia-value silicone oil, 10-30 parts by weight of amino polyether active group modified silicone oil, 10-30 parts by weight of epoxy modified silicone oil, 3-8 parts by weight of modified organic silicon softener, 1-5 parts by weight of elastic finishing agent, 1-5 parts by weight of antistatic agent, 20-30 parts by weight of organic solvent and 200-300 parts by weight of deionized water through a phase inversion emulsification method to obtain emulsion with stable particle size of 250-350 nm.
The surfactant is a mixture of fatty acid polyoxyethylene ester A-103 and castor oil polyoxyethylene ether EL-80.
The epoxy value of the end epoxy modified linear polydimethylsiloxane is 0.07-0.09mmol/g.
The ammonia value of the modified high-viscosity high-ammonia-value silicone oil is 0.6+/-10% mmol/g; the viscosity at 25 ℃ is 10000-20000mpa.s.
The viscosity of the amino polyether active group modified silicone oil at 25 ℃ is 1000-2000mPa.s.
The epoxy value of the epoxy modified silicone oil is 0.30+/-0.05 mmol/g.
The modified organosilicon softener is a weak cation auxiliary agent.
The elastic finishing agent is silicone oil containing self-crosslinking groups.
The antistatic agent is a high-temperature resistant compound containing reactive groups and hydrophilic groups.
The organic solvent is ethylene glycol monobutyl ether.
According to the preparation method for the high-performance PAN carbon fiber precursor oiling agent, required silicone oil is added into a homogenizing mixer according to the proportion, the mixture is stirred uniformly, water is added for emulsification and phase inversion, glacial acetic acid is added for regulating the pH to 5-7, and the stable emulsion with the particle size of 250-350nm is obtained.
Firstly stirring at a high speed for 30min, slowly adding 30-40 parts of water, continuously stirring, quickly adding the rest water and ethylene glycol monobutyl ether and adding glacial acetic acid to adjust the pH after the whole is changed to O/W, reducing the stirring speed after the whole is changed to W/O, and homogenizing for 15min to obtain the particle size of the emulsion of 250-350 nm.
The embodiment 1 is a high-performance polyacrylonitrile carbon fiber precursor oiling agent, which comprises the following components in parts by weight:
30 parts of surfactant, including 20 parts of fatty acid polyoxyethylene ester A-103 and 10 parts of castor oil polyoxyethylene ether EL-80;
50 parts of epoxy-terminated modified linear polydimethylsiloxane with an epoxy value of 0.07-0.09mmol/g;
5 parts of special modified high-viscosity high-ammonia-value silicone oil, wherein the ammonia value is 0.6 (+ -10%) mmol/g;
20 parts of modified silicone oil with various active groups such as amino, polyether and the like, and the viscosity of the modified silicone oil is 1000-2000mPa.s (25 ℃);
20 parts of epoxy modified silicone oil, wherein the epoxy value is 0.30+/-0.05 mmol/g;
4 parts of modified organosilicon softener which is a weak cation auxiliary agent;
1 part of elastic finishing agent is silicone oil containing self-crosslinking groups;
1 part of antistatic agent which is a compound containing reactive groups and hydrophilic groups and resists high temperature;
30 parts of ethylene glycol monobutyl ether serving as an organic solvent.
Adding the components into a homogenizing mixer, stirring uniformly, adding water, emulsifying, inverting, adding acetic acid, regulating pH to 6, and obtaining stable emulsion with the particle size of 283 nm. The prepared oiling agent has the heat resistance of 415 ℃, the residual weight of about 72%, the oiling rate of precursor wires of about 0.72%, less oil dirt of a drying roller, no sticking of the roller, reduced generation of broken wires and broken wires, improved quality of carbon fiber precursor wires, greatly reduced generation of phenomena of broken wires, wire doubling, adhesion, combustion and the like in the pre-oxidation and carbonization processes, and 0.02% of ash content of the carbon fiber, and can be used for producing T700-strength carbon fibers.
Example 2, a high performance polyacrylonitrile carbon fiber precursor oiling agent, which consists of the following components in parts by weight:
30 parts of surfactant, including 20 parts of fatty acid polyoxyethylene ester A-103 and 10 parts of castor oil polyoxyethylene ether EL-80;
60 parts of epoxy-terminated modified linear polydimethylsiloxane with an epoxy value of 0.07-0.09mmol/g;
15 parts of special modified high-viscosity high-ammonia-value silicone oil, wherein the ammonia value is 0.6 (+ -10%) mmol/g;
30 parts of ethylene glycol monobutyl ether serving as an organic solvent.
Adding the components into a homogenizing mixer, uniformly stirring, adding water, emulsifying and inverting to obtain stable emulsion with the particle size of 236 nm. The prepared oiling agent has the heat resistance of 354 ℃ and the residual weight of about 69%, the oiling rate of the precursor is about 0.6%, the drying roller is free from oil dirt and is not stuck, however, the precursor is hard, has easy deformation in winding, has broken filaments and serious broken filaments in the pre-oxidation and carbonization processes, and is not beneficial to production.
Example 3, a high performance polyacrylonitrile carbon fiber precursor oiling agent, which consists of the following components in parts by weight:
30 parts of surfactant, including 20 parts of fatty acid polyoxyethylene ester A-103 and 10 parts of castor oil polyoxyethylene ether EL-80;
60 parts of epoxy-terminated modified linear polydimethylsiloxane with an epoxy value of 0.07-0.09mmol/g;
15 parts of special modified high-viscosity high-ammonia-value silicone oil, wherein the ammonia value is 0.6 (+ -10%) mmol/g;
10 parts of modified silicone oil with various active groups such as amino, polyether and the like, and the viscosity of the modified silicone oil is 1000-2000mPa.s (25 ℃);
4 parts of modified organosilicon softener which is a weak cation auxiliary agent;
5 parts of elastic finishing agent which is silicone oil containing self-crosslinking groups;
1 part of antistatic agent which is a compound containing reactive groups and hydrophilic groups and resists high temperature;
30 parts of ethylene glycol monobutyl ether serving as an organic solvent.
Adding the components into a homogenizing mixer, stirring uniformly, adding water, emulsifying, inverting, adding acetic acid, regulating pH to 6, and obtaining stable emulsion with particle diameter of 368 nm. The prepared oiling agent has the heat resistance of 402 ℃, the residual weight of about 70 percent, the oiling rate of the precursor of about 0.65 percent, more oil dirt of a drying roller, difficult cleaning and serious roller sticking, and is not beneficial to production.
Example 4, a high performance polyacrylonitrile carbon fiber precursor oiling agent, which consists of the following components in parts by weight:
30 parts of surfactant, including 20 parts of fatty acid polyoxyethylene ester A-103 and 10 parts of castor oil polyoxyethylene ether EL-80;
50 parts of epoxy-terminated modified linear polydimethylsiloxane with an epoxy value of 0.07-0.09mmol/g;
5 parts of special modified high-viscosity high-ammonia-value silicone oil, wherein the ammonia value is 0.6 (+ -10%) mmol/g;
20 parts of modified silicone oil with various active groups such as amino, polyether and the like, and the viscosity of the modified silicone oil is 1000-2000mPa.s (25 ℃);
20 parts of epoxy modified silicone oil, wherein the epoxy value is 0.30+/-0.05 mmol/g;
4 parts of modified organosilicon softener which is a weak cation auxiliary agent;
1 part of elastic finishing agent is silicone oil containing self-crosslinking groups;
1 part of antistatic agent which is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and is not resistant to high temperature;
30 parts of ethylene glycol monobutyl ether serving as an organic solvent.
Adding the components into a homogenizing mixer, stirring uniformly, adding water, emulsifying, inverting, adding acetic acid, regulating pH to 6, and obtaining stable emulsion with particle diameter of 386 nm. The prepared oiling agent has the heat resistance of 436 ℃, the residual weight of about 75%, the oiling rate of the precursor of about 0.67%, less oil dirt of a drying roller and no sticking to the roller, but has the problems of large static electricity, poor bundling property, vapor drawing yarn breakage, yarn winding in the winding process and the like, and is unfavorable for production.
TABLE 1 Performance data for carbon fibers produced using the finishes of the examples
In conclusion, the heat resistance of the precursor is improved by introducing a proper amount of epoxy modified silicone oil, oil scale generated in a drying process after the precursor is oiled is obviously reduced, the phenomenon of sticking to rollers is eliminated, and the problems of yarn breakage, yarn doubling, adhesion and the like of the precursor in the pre-oxidation process are effectively prevented. In addition, by adding various active group modified silicone oil such as amino, polyether and the like, not only is the wettability of the oil agent improved, but also the friction coefficient between fibers is reduced by directionally adsorbing the oil agent on the surfaces of the fibers. Some functional auxiliary agents are introduced, so that static electricity in the production process of the precursor is eliminated, the fiber is endowed with the characteristics of softness, elasticity, bundling and the like, and the production requirement of the T700-level high-performance carbon fiber is met.
Claims (12)
1. The utility model provides a polyacrylonitrile carbon fiber precursor oiling agent for high performance which characterized in that: according to the weight portion, the emulsion with the stable particle diameter of 250-350nm is obtained by a phase inversion emulsification method from 20-40 portions of surfactant, 40-60 portions of epoxy-modified linear polydimethylsiloxane, 5-15 portions of modified high-viscosity high-ammonia-value silicone oil, 10-30 portions of amino polyether active group modified silicone oil, 10-30 portions of epoxy modified silicone oil, 3-8 portions of modified organosilicon softener, 1-5 portions of elastic finishing agent, 1-5 portions of antistatic agent, 20-30 portions of organic solvent and 200-300 portions of deionized water.
2. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the surfactant is a mixture of fatty acid polyoxyethylene ester A-103 and castor oil polyoxyethylene ether EL-80.
3. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the epoxy value of the end epoxy modified linear polydimethylsiloxane is 0.07-0.09mmol/g.
4. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the ammonia value of the modified high-viscosity high-ammonia-value silicone oil is 0.6+/-10% mmol/g; the viscosity at 25 ℃ is 10000-20000mpa.s.
5. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the viscosity of the amino polyether active group modified silicone oil at 25 ℃ is 1000-2000mPa.s.
6. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the epoxy value of the epoxy modified silicone oil is 0.30+/-0.05 mmol/g.
7. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the modified organosilicon softener is a weak cation auxiliary agent.
8. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the elastic finishing agent is silicone oil containing self-crosslinking groups.
9. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the antistatic agent is a high-temperature resistant compound containing reactive groups and hydrophilic groups.
10. The oiling agent for high-performance polyacrylonitrile carbon fiber precursor according to claim 1, wherein: the organic solvent is ethylene glycol monobutyl ether.
11. A method for preparing the high-performance PAN carbon fiber precursor oiling agent according to claims 1 to 10, characterized in that: adding the required silicone oil into a homogenizing mixer according to the proportion, uniformly stirring, adding water for emulsification and phase inversion, and adding glacial acetic acid for regulating the pH value to 5-7 to obtain the stable emulsion with the particle size of 250-350 nm.
12. The method for preparing the high-performance PAN carbon fiber precursor oiling agent according to claim 11, wherein: firstly stirring at a high speed for 30min, slowly adding 30-40 parts of water, continuously stirring, quickly adding the rest water and ethylene glycol monobutyl ether and adding glacial acetic acid to adjust the pH after the whole is changed to O/W, reducing the stirring speed after the whole is changed to W/O, and homogenizing for 15min to obtain the particle size of the emulsion of 250-350 nm.
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| CN113897708A (en) * | 2021-11-18 | 2022-01-07 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor and preparation method thereof |
| CN114622417A (en) * | 2022-03-21 | 2022-06-14 | 中复神鹰碳纤维股份有限公司 | Carbon fiber oil capable of quickly crosslinking to form film |
| CN115679481A (en) * | 2022-09-08 | 2023-02-03 | 中复神鹰碳纤维股份有限公司 | Oil agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof |
| CN116536799A (en) * | 2023-04-06 | 2023-08-04 | 东华大学 | Large-tow PAN-based carbon fiber precursor oiling agent and preparation method thereof |
| CN116657286A (en) * | 2023-06-30 | 2023-08-29 | 中复神鹰碳纤维股份有限公司 | Oil solution for ultrahigh-strength carbon fiber precursor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113897708A (en) * | 2021-11-18 | 2022-01-07 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor and preparation method thereof |
| CN114622417A (en) * | 2022-03-21 | 2022-06-14 | 中复神鹰碳纤维股份有限公司 | Carbon fiber oil capable of quickly crosslinking to form film |
| CN115679481A (en) * | 2022-09-08 | 2023-02-03 | 中复神鹰碳纤维股份有限公司 | Oil agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof |
| CN116536799A (en) * | 2023-04-06 | 2023-08-04 | 东华大学 | Large-tow PAN-based carbon fiber precursor oiling agent and preparation method thereof |
| CN116657286A (en) * | 2023-06-30 | 2023-08-29 | 中复神鹰碳纤维股份有限公司 | Oil solution for ultrahigh-strength carbon fiber precursor and preparation method thereof |
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