CN119102014A - Silicon-free carbon fiber spinning oil and preparation method thereof - Google Patents
Silicon-free carbon fiber spinning oil and preparation method thereof Download PDFInfo
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- CN119102014A CN119102014A CN202411456113.2A CN202411456113A CN119102014A CN 119102014 A CN119102014 A CN 119102014A CN 202411456113 A CN202411456113 A CN 202411456113A CN 119102014 A CN119102014 A CN 119102014A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 78
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 78
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000009987 spinning Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 81
- 239000003921 oil Substances 0.000 claims abstract description 60
- -1 carbon chain imidazoline quaternary ammonium salt Chemical class 0.000 claims abstract description 54
- 150000002148 esters Chemical class 0.000 claims abstract description 46
- 238000009499 grossing Methods 0.000 claims abstract description 42
- 239000002216 antistatic agent Substances 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- AKDNDOBRFDICST-UHFFFAOYSA-N methylazanium;methyl sulfate Chemical compound [NH3+]C.COS([O-])(=O)=O AKDNDOBRFDICST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 239000003899 bactericide agent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- LPGFSDGXTDNTCB-UHFFFAOYSA-N [3-(16-methylheptadecanoyloxy)-2,2-bis(16-methylheptadecanoyloxymethyl)propyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCC(C)C)(COC(=O)CCCCCCCCCCCCCCC(C)C)COC(=O)CCCCCCCCCCCCCCC(C)C LPGFSDGXTDNTCB-UHFFFAOYSA-N 0.000 claims description 15
- 239000004359 castor oil Substances 0.000 claims description 13
- 235000019438 castor oil Nutrition 0.000 claims description 13
- 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 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229920006197 POE laurate Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 229940049964 oleate Drugs 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 101000695172 Agalychnis dacnicolor Plasticin-DA1 Proteins 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 claims 11
- 239000003240 coconut oil Substances 0.000 claims 5
- 235000019864 coconut oil Nutrition 0.000 claims 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- 239000003755 preservative agent Substances 0.000 claims 3
- 230000002335 preservative effect Effects 0.000 claims 3
- 238000004513 sizing Methods 0.000 claims 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 19
- 230000002421 anti-septic effect Effects 0.000 abstract description 19
- 239000013530 defoamer Substances 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 235000013162 Cocos nucifera Nutrition 0.000 abstract description 2
- 244000060011 Cocos nucifera Species 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 36
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229920002239 polyacrylonitrile Polymers 0.000 description 10
- 239000005639 Lauric acid Substances 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000008041 oiling agent Substances 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the technical field of spinning oil, and particularly relates to a silicon-free carbon fiber spinning oil and a preparation method thereof. The spinning oil comprises the following components of 40-55 parts of ester smoothing agent, 10-15 parts of surfactant, 10-20 parts of composite antistatic agent, 4-8 parts of glycerol, 5-8 parts of bundling agent, 0.2-2 parts of antioxidant, 0.1-1 part of defoamer, 0.5-2 parts of antiseptic bactericide, 0-6 parts of emulsifier and 100-150 parts of water, wherein the composite antistatic agent consists of long carbon chain imidazoline quaternary ammonium salt and coco methyl ammonium methyl sulfate. The ester substance is used as the smoothing agent, so that the problem that silicon-containing oxide, carbide and other impurities are easy to form in the pre-oxidation and carbonization processes when the silicon oil is used as the carbon fiber spinning oil is solved. The cocoanut methyl ammonium methyl sulfate and the glycerol improve the dispersion performance of the long carbon chain imidazoline quaternary ammonium salt, and the prepared silicon-free carbon fiber spinning oil has excellent thermal stability, so that the technical problems that the existing oil product for carbon fibers has a large number of sticking rollers and filaments and is difficult to consider antistatic performance are solved.
Description
Technical Field
The invention belongs to the technical field of spinning oil, and particularly relates to a silicon-free carbon fiber spinning oil and a preparation method thereof.
Background
The carbon fiber is a novel inorganic fiber material, has a plurality of excellent performances such as corrosion resistance, radiation resistance, heat transfer, high temperature resistance, high specific modulus, electric conduction, fatigue resistance, high specific strength, shock absorption, small relative density, noise reduction and the like, and belongs to typical high-performance fibers. Due to the excellent properties, the carbon fiber is widely applied to the advanced fields of aerospace, exploration universe, military national defense, artificial satellites and the like, and meanwhile, the carbon fiber is also applied to civil industries such as advanced sports goods, automobile weight reduction, medical equipment, infrastructure and the like by virtue of the special properties. In 1959, the technology route for producing polyacrylonitrile-based carbon fiber was invented by the osaka industrial test, and the invention of the technology advances the development of the carbon fiber industry, so far, the technology is the main technology for producing carbon fiber.
Early researchers performed a great deal of research effort. The raw materials used for producing the carbon fiber are numerous, and early research work proves that PAN, asphalt, polyimide, viscose fiber, polybenzothiazole and the like are known as raw materials which can be used in the production process of the carbon fiber. PAN-based, viscose-based and pitch-based carbon fibers can meet the requirements of production development and the application of a carbon fiber industry chain. Asphalt-based carbon fiber has the advantages of wide material sources, high yield and the like, but has a plurality of problems which are difficult to solve in the actual production process due to more impurities and unstable structure, and is not applied to mass production. Viscose-based carbon fibers, which have low thermal conductivity, low density, easy purification, and good biocompatibility, are used in particular fields, especially in medical and hygienic fields, because of their many advantages. Certain components in the viscose-based carbon fiber cause certain harm to the environment, and the use amount of the viscose-based carbon fiber is limited by the disadvantage. The polyacrylonitrile fiber is a synthetic fiber which is woven by using a high molecular polymer produced by copolymerization of a first monomer acrylonitrile and a second and a third monomer. Because PAN-based fiber is easy to prepare, has low requirements on production conditions, and has little environmental pollution and low cost, the PAN-based fiber becomes the fiber with the most wide application in the fiber industry chain.
The carbon fiber precursor oiling agent has the functions of reducing friction static electricity and friction coefficient, smoothing the surface of the fiber, softening the texture, reducing the defects of the surface of the fiber, improving the strength of the fiber, acting between monofilaments and adding bundling property, drafting property and fiber splitting property to the fiber bundle. Many defects exist on the surface of the carbon fiber precursor, and these defects are the main factors for breaking the carbon fibers. The method can reduce the filament breakage phenomenon in the carbonization process caused by the surface defects of the fiber and improve the application performance of the carbon fiber through various modified oiling agents with different functional groups. Therefore, the special oiling agent for producing the carbon fiber with excellent performance is an important precondition for producing the high-performance carbon fiber precursor.
Disclosure of Invention
In order to overcome the defects in the prior art, the first aim of the invention is to provide a silicon-free carbon fiber spinning oil.
The second aim of the invention is to provide a preparation method of the silicon-free carbon fiber spinning oil.
In order to achieve the first object, the present invention is achieved by the following technical scheme:
The silicon-free carbon fiber spinning oil is particularly suitable for polyacrylonitrile carbon fiber spinning oil, and comprises the following components in parts by weight:
40-55 parts of ester smoothing agent, 10-15 parts of surfactant, 10-20 parts of composite antistatic agent, 4-8 parts of glycerol, 5-8 parts of bundling agent, 0.2-2 parts of antioxidant, 0.1-1 part of defoamer, 0.5-2 parts of antiseptic bactericide, 0-6 parts of emulsifier and 100-150 parts of water, wherein the composite antistatic agent consists of long carbon chain imidazoline quaternary ammonium salt and coco methyl ammonium methyl sulfate, the dosage of coco methyl ammonium methyl sulfate is greater than that of the long carbon chain imidazoline quaternary ammonium salt, and the dosage of the long carbon chain imidazoline quaternary ammonium salt is not 0.
In the prior art, silicone oil is generally used as a main component of the carbon fiber spinning oil, and the carbon fiber spinning oil has the characteristic of good heat resistance, but the type of oil is easy to form impurities such as silicon-containing oxides and carbides in the pre-oxidation and carbonization processes, so that the performance of the carbon fiber is affected. The currently used non-silicone oil agent is not resistant to high temperature, has poor local compatibility and is easy to generate microscopic phase separation. In order to solve the problem, the invention uses the ester substance as the smoothing agent, the ester smoothing agent has good high temperature resistance, can reduce friction coefficient between fibers and between metal and fibers, prevent fibers from wearing, keep uniform and lower tension and protect the surfaces of the fibers.
Although the smoothing agent has certain bundling effect during the pre-oxidation treatment of the fiber, the smoothing agent is easy to melt and adhere together in the pre-oxidation treatment process, the bundling is disordered after the oiling agent is dispersed, the dispersed fiber bundles are broken to generate fuzzing, and the fuzzing agent is easy to be wound on a guide roller, so that the operation is difficult to normally carry out. Although the addition of the water-soluble surfactant can improve the bundling effect, the surfactant may decompose or tarry during the pre-oxidation, and the handling thereof may be difficult. And the fibers such as polyacrylonitrile fibers are hydrophobic and not hygroscopic, and when the fibers or the fibers are contacted with other materials (rollers), the fibers or the fibers can be electrostatically charged, and the fibers are easily wound on a guide roller to cause yarn breakage. In order to improve the high temperature resistance of the oiling agent and solve the problem of hairiness, a certain amount of long carbon chain imidazoline quaternary ammonium salt is added. The long carbon chain imidazoline quaternary ammonium salt adopted by the invention is VARISOFT-3696. VARISOFT 3696-3696 is a long carbon chain imidazoline quaternary ammonium salt fabric treatment agent which is introduced by winning companies. Has good hydrophilicity and good hydrophilic effect on various fibers. The long carbon chain imidazoline quaternary ammonium salt not only has excellent emulsifying property, but also can be used as an antistatic agent. Compared with other antistatic agents, the carbon fiber spinning oil has good thermal stability and greatly improves the high temperature resistance of the carbon fiber spinning oil.
However, the long carbon chain imidazoline quaternary ammonium salt has a long carbon chain structure, so that the viscosity is high, and the imidazoline quaternary ammonium salt is easy to disperse unevenly in emulsion. The invention adds a certain amount of cocoyl methyl ammonium methyl sulfate and glycerol to improve the dispersion performance of the long carbon chain imidazoline quaternary ammonium salt. The cocoyl methyl ammonium methyl sulfate also has certain emulsifying and antistatic properties, contains a quaternary ammonium salt structure, has good compatibility with VARISOFT-3696 long-carbon-chain imidazoline quaternary ammonium salt, and is beneficial to improving the dispersibility of VARISOFT-3696 long-carbon-chain imidazoline quaternary ammonium salt. The glycerol is taken as a polyhydroxy small molecular compound, has excellent moisture absorption performance, has good wettability to fibers such as polyacrylonitrile and the like, and can improve the dispersion performance of the long carbon chain imidazoline quaternary ammonium salt in emulsion.
Further, the composite antistatic agent consists of 1-7 parts of long carbon chain imidazoline quaternary ammonium salt and 9-13 parts of coco methyl ammonium methyl sulfate. Furthermore, the coco methyl ammonium methyl sulfate adopted by the invention is PEG-5 coco methyl ammonium methyl sulfate.
Further, the ester smoothing agent is one or more of pentaerythritol stearate, pentaerythritol tetraisostearate and pentaerythritol oleate.
Further, the surfactant is one or more of PEG400MO, PEG400DO and PEG600 MO.
Further, the bundling agent is one or more of castor oil polyoxyethylene ether, polyoxyethylene laurate and triethanolamine oleic acid soap.
Further, the antioxidant is antioxidant 1010 or antioxidant 1790. Among them, the antioxidant 1790 is excellent in heat resistance and can effectively prevent the oxidative deterioration of the oil agent.
Further, the defoamer is tributyl phosphate, the antiseptic bactericide is Dow chemical KATHON LXE, and the emulsifier is winning TAGAT PD36.TAGAT PD36 has better oxidation resistance and higher thermal stability than esters, and has excellent emulsion stability properties for stabilizing droplet size and improving lubricating properties based on ester oil emulsions.
Further, the long carbon chain imidazoline quaternary ammonium salt is 2-4 parts, and the emulsifier is 2-6 parts.
In order to achieve the second purpose, the invention provides a preparation method of the silicon-free carbon fiber spinning oil, which comprises the following steps of adding an ester smoothing agent, a surfactant, a composite antistatic agent, glycerol, a bundling agent, an antioxidant, a defoaming agent, an antiseptic bactericide and an emulsifier into a reaction kettle according to a proportion, uniformly stirring, and then dripping water for phase inversion emulsification to obtain the silicon-free carbon fiber spinning oil.
Further, the stirring speed is 1000-2000r/min.
The invention has the beneficial effects that:
(1) The invention relates to a silicon-free carbon fiber spinning oil mainly composed of a smoothing agent, a surfactant, a composite antistatic agent, glycerol, a bundling agent and the like. In the process of preparing the oil solution, a plurality of quaternary ammonium salts with different types and models and glycerol are compounded together to complement each other to exert the synergistic effect.
(2) The invention uses the ester substance as the smoothing agent, solves the problem that silicon oil is used as the carbon fiber spinning oil agent to easily form impurities such as silicon-containing oxide and carbide in the pre-oxidation and carbonization processes.
(3) The silicon-free carbon fiber spinning oil prepared by the invention has good antistatic property and excellent thermal stability, reduces friction coefficient and greatly improves the high temperature resistance of the carbon fiber spinning oil.
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
Wherein the long carbon chain imidazoline quaternary ammonium salt used in the examples and the comparative examples is VARISOFT-3696, the antioxidant is 1790, the defoamer is tributyl phosphate, the antiseptic bactericide is Dow chemical KATHON LXE, and the emulsifier is winning TAGAT PD36.
Example 1
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
40 parts of ester smoothing agent, 10 parts of surfactant, 10 parts of composite antistatic agent, 4 parts of glycerol, 5 parts of bundling agent, 0.2 part of antioxidant, 0.1 part of defoamer, 0.5 part of antiseptic bactericide, 2 parts of emulsifier and 100 parts of water, wherein the composite antistatic agent consists of 1 part of long carbon chain imidazoline quaternary ammonium salt and 9 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is 20 parts of pentaerythritol tetraisostearate and 20 parts of pentaerythritol oleate, the surfactant is PEG400MO, and the bundling agent is 3 parts of castor oil polyoxyethylene ether and 2 parts of polyoxyethylene laurate.
Example 2
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
55 parts of ester smoothing agent, 15 parts of surfactant, 17 parts of composite antistatic agent, 8 parts of glycerol, 8 parts of bundling agent, 2 parts of antioxidant, 1 part of defoamer, 2 parts of antiseptic bactericide, 6 parts of emulsifier and 150 parts of water, wherein the composite antistatic agent consists of 4 parts of long carbon chain imidazoline quaternary ammonium salt and 13 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400DO, and the bundling agent is 3 parts of castor oil polyoxyethylene ether, 3 parts of polyoxyethylene laurate and 2 parts of triethanolamine oleic soap.
Example 3
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
40 parts of ester smoothing agent, 15 parts of surfactant, 17 parts of composite antistatic agent, 4 parts of glycerol, 8 parts of bundling agent, 0.2 part of antioxidant, 1 part of defoamer, 1.5 parts of antiseptic bactericide, 5 parts of emulsifier and 150 parts of water, wherein the composite antistatic agent consists of 4 parts of long carbon chain imidazoline quaternary ammonium salt and 13 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is 20 parts of pentaerythritol tetraisostearate and 20 parts of pentaerythritol oleate, the surfactant is PEG600MO, and the bundling agent is castor oil polyoxyethylene ether.
Example 4
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
55 parts of ester smoothing agent, 10 parts of surfactant, 11 parts of composite antistatic agent, 8 parts of glycerol, 5 parts of bundling agent, 0.2 part of antioxidant, 0.1 part of defoamer, 0.5 part of antiseptic bactericide, 1 part of emulsifier and 100 parts of water, wherein the composite antistatic agent consists of 2 parts of long carbon chain imidazoline quaternary ammonium salt and 9 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 5 parts and PEG400DO 5 parts, and the bundling agent is polyoxyethylene laurate.
Example 5
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
45 parts of ester smoothing agent, 11 parts of surfactant, 13 parts of composite antistatic agent, 5 parts of glycerol, 7 parts of bundling agent, 0.8 part of antioxidant, 0.8 part of defoamer, 0.9 part of antiseptic bactericide, 5 parts of emulsifier and 120 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 10 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is 20 parts of pentaerythritol tetraisostearate and 25 parts of pentaerythritol oleate, the surfactant is PEG400MO, and the bundling agent is 3 parts of castor oil polyoxyethylene ether and 4 parts of polyoxyethylene laurate.
Example 6
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
52 parts of ester smoothing agent, 14 parts of surfactant, 17 parts of composite antistatic agent, 7 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 0.5 part of defoamer, 1.8 parts of antiseptic bactericide, 3 parts of emulsifier and 140 parts of water, wherein the composite antistatic agent consists of 4 parts of long carbon chain imidazoline quaternary ammonium salt and 13 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400DO 6 parts and PEG600MO 8 parts, and the bundling agent is triethanolamine oleic soap.
Example 7
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 13 parts of composite antistatic agent, 6 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 3 parts of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 10 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
Example 8
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 13 parts of composite antistatic agent, 6 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 0 part of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 10 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
Example 9
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 17 parts of composite antistatic agent, 6 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 3 parts of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 7 parts of long carbon chain imidazoline quaternary ammonium salt and 10 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
Comparative example 1
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 19 parts of composite antistatic agent, 0 part of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 3 parts of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 16 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
Comparative example 2
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 3 parts of composite antistatic agent, 16 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 3 parts of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 0 part of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
Comparative example 3
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 13 parts of composite antistatic agent, 2 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 3 parts of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 10 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
Comparative example 4
The silicon-free carbon fiber spinning oil comprises the following components in parts by weight:
48 parts of ester smoothing agent, 13 parts of surfactant, 13 parts of composite antistatic agent, 12 parts of glycerol, 6 parts of bundling agent, 1 part of antioxidant, 1 part of defoamer, 1 part of antiseptic bactericide, 3 parts of emulsifier and 130 parts of water, wherein the composite antistatic agent consists of 3 parts of long carbon chain imidazoline quaternary ammonium salt and 10 parts of PEG-5 coco methyl ammonium methyl sulfate.
The ester smoothing agent is pentaerythritol tetraisostearate, the surfactant is PEG400MO 10 parts and PEG400DO 3 parts, and the bundling agent is castor oil polyoxyethylene ether 2 parts and lauric acid polyoxyethylene ester 4 parts.
The preparation method of the silicon-free carbon fiber spinning oil in the embodiment is the same as that of the comparative example, and specifically comprises the following steps of adding an ester smoothing agent, a surfactant, a composite antistatic agent, glycerol, a bundling agent, an antioxidant, a defoaming agent, an antiseptic bactericide and an emulsifier into a reaction kettle according to a proportion, uniformly stirring at a stirring rate of 1500r/min, and then dripping water for phase inversion emulsification to obtain the silicon-free carbon fiber spinning oil.
Performance test:
1. the silicon-free carbon fiber spinning oil prepared in the above examples and comparative examples was left for 10 days at 60 ℃ to observe whether delamination and turbidity occurred.
2. The polyacrylonitrile precursor is prepared by the silicon-free carbon fiber spinning oil prepared in the above examples and comparative examples, and carbon fiber is prepared by a pre-oxidation and carbonization process. The degree of sticking (A-D, gradually severe from A to D) was observed, the carbon fiber yarn grade (1-5, higher grade, more severe yarn condition) was evaluated, and the yarn strength, modulus, elongation, diameter unevenness, and carbon fiber strength (MPa) were measured.
TABLE 1 Properties of the silicon-free carbon fiber spin finish prepared in example 1-example 9
TABLE 2 Properties of the silicon-free carbon fiber spin finish prepared in comparative examples 1 to 4
As can be seen from the table 1, the long carbon chain imidazoline quaternary ammonium salt added in the invention has excellent emulsifying property, can be used as an antistatic agent, and greatly improves the high temperature resistance of the carbon fiber spinning oil. A certain amount of PEG-5 coco methyl ammonium methyl sulfate and glycerol improve the dispersion performance of the long carbon chain imidazoline quaternary ammonium salt VARISOFT-3696. It can be seen from examples 1-7 and examples 8-9 that the appropriate amount of the long carbon chain imidazoline quaternary ammonium salt and the emulsifier can uniformly adhere the oiling agent to the surface of the fiber, protect the surface of the fiber, collect multiple tows and prevent broken filaments, thereby improving the processability of the fiber and enabling the strength of the carbon fiber to be higher. Comparative examples 1-2 show that coco methyl ammonium methyl sulfate and glycerol improve the dispersion performance of long carbon chain imidazoline quaternary ammonium salt together, and prevent the agglomeration phenomenon of long carbon chain imidazoline quaternary ammonium salt with long chain structure. The cocoanut methyl ammonium methyl sulfate and the glycerol improve the stability of emulsion, and can quickly leak out generated charges, so that certain cohesion exists between fiber monofilaments, and the bundling effect is achieved. Comparative examples 3-4 show that glycerol has excellent hydrophilicity, can improve the wettability of the oil, reduce the contact angle between the oil and the fibers, is beneficial to spreading and film forming of the oil on the surfaces of the fibers, protects the surfaces of the fibers from being damaged in movement, and enables the production process to be carried out smoothly. However, the glycerol is not excessively used, otherwise, the flow of air flow among the individual fibers is affected, so that the fiber surfaces in the carbonization process cannot be fully contacted with an oxidizing medium, and the mechanical properties of the carbon fibers are affected.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
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