CN114182532B - Polyacrylonitrile-based carbon fiber low-ash precursor oiling agent - Google Patents
Polyacrylonitrile-based carbon fiber low-ash precursor oiling agent Download PDFInfo
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- 239000008041 oiling agent Substances 0.000 title claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 27
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 title claims abstract description 16
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 36
- -1 polysiloxane Polymers 0.000 claims abstract description 35
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 34
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 34
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- AKDNDOBRFDICST-UHFFFAOYSA-N methylazanium;methyl sulfate Chemical compound [NH3+]C.COS([O-])(=O)=O AKDNDOBRFDICST-UHFFFAOYSA-N 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 125000002252 acyl group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 3
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract description 4
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 70
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 25
- 239000000835 fiber Substances 0.000 description 25
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- SOBYTUYXBBGSHH-UHFFFAOYSA-N bis(2-hydroxyethyl)-methylazanium;methyl sulfate Chemical compound COS(O)(=O)=O.OCCN(C)CCO SOBYTUYXBBGSHH-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 231100000461 EC20 Toxicity 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CMPOVQUVPYXEBN-UHFFFAOYSA-N bis(2-hydroxyethyl)-methylazanium;chloride Chemical compound Cl.OCCN(C)CCO CMPOVQUVPYXEBN-UHFFFAOYSA-N 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-O bis(2-hydroxyethyl)-methylazanium Chemical compound OCC[NH+](C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
-
- 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
- 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
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- 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
- D06M15/6436—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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- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a polyacrylonitrile-based carbon fiber low-ash precursor oiling agent, which mainly solves the problem of high ash residue of the prior art precursor oiling agent of the carbon fiber oiling agent in the prior art. The invention adopts polyacrylonitrile-based carbon fiber low-ash precursor oiling agent, which comprises the following effective components in parts by weight: 10-20 parts of high-carbon fatty alcohol polyoxyethylene ether; 10-20 parts of aliphatic polyhydroxy methyl ammonium methyl sulfate; 10-20 parts of polyether polyol; 40-60 parts of side chain amino modified polysiloxane; the aliphatic polyhydroxy methyl amine methyl sulfate is shown in the following structural formula, wherein R 1 、R 2 Independently selected from alkylene groups having 1 to 6 carbon atoms, R 3 Selected from alkyl groups having 1 to 6 carbon atoms, R 4 The technical proposal of the aliphatic radical with 8-23 carbon atoms solves the problem well, has excellent heat resistance, cohesion, smoothness and antistatic property, and can be used for producing polyacrylonitrile-based carbon fiber precursor.
Description
Technical Field
The invention relates to a polyacrylonitrile-based carbon fiber low-ash precursor oiling agent.
Background
The carbon fiber is a special fiber composed of carbon elements, has the characteristics of high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like, and has wide application in aspects of aerospace, automobiles, buildings, daily life and the like. According to different raw materials, the carbon fiber mainly comprises a polyacrylonitrile base, an asphalt base and a viscose base 3, wherein the polyacrylonitrile base carbon fiber is optimal in performance and maximum in productivity, and accounts for more than 90% of the total yield of the carbon fiber worldwide.
The oiling agent is an important auxiliary agent for producing carbon fibers, and is one of key technologies for ensuring the smooth production process of the carbon fibers, reducing the problems of broken filaments, doubling and the like, effectively reducing microscopic defects of carbon fiber precursors and improving the quality of the carbon fibers. At present, carbon fiber oiling agents are mainly divided into two main types, namely organic silicone oil agents with polydimethylsiloxane as a main component, and organic oiling agents with ethylene oxide adducts of polyester or long-chain fatty amide of long-chain fatty acid and polyalcohol as a main component.
Compared with the common civil spinning oil, the carbon fiber manufacturing conditions are very harsh, the precursor is firstly subjected to a pre-oxidation process at 200-300 ℃ under the air atmosphere before being formed into the carbon fiber, and then is subjected to a low-temperature carbonization process at 300-800 ℃ and a high-temperature carbonization process at more than 800 ℃ under the protection of inert gas, so that the carbon fiber precursor is required to have the properties of smoothness, antistatic property and bundling property, and also required to have sufficient oxidation resistance (under the air atmosphere) and high-temperature resistance (under the inert gas atmosphere) so as to avoid the adhesion or doubling of monofilaments due to local heat during pre-oxidation and low-temperature carbonization, and besides, the residue of the oil is required to be as little as possible after high-temperature carbonization, so that ash residue after 800 ℃ is required to be as little as possible, and the carbon fiber surface defects caused by the residual surface of the oil are avoided.
The oil agent used for carbon fiber production in the industry at present mainly adopts organic silicone oil agent, and has better smoothness and heat resistance compared with non-silicon organic oil agent. For example, in the chinese patent documents CN200910234655.4 and CN201410420266.1, amino silicone oil with different viscosities is used as main components, and polyether modified silicone oil and epoxy modified silicone oil are added to improve uniformity and heat resistance of the system, so that spinning is smooth after oiling, and phenomena such as yarn breakage, yarn doubling and the like are avoided. The oil agent has higher ash content and is easy to cause the phenomena of blockage of heat dissipation holes of equipment and the like.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of high ash residue of the prior art precursor oiling agent, and the novel polyacrylonitrile-based carbon fiber low-ash precursor oiling agent is provided, which not only has good oxidation resistance and heat resistance, but also has very low ash residue, and the obtained oiling agent has excellent cohesion, smoothness and antistatic performance, and can well meet the production requirements of the polyacrylonitrile-based carbon fiber precursor.
The second technical problem to be solved by the invention is the application of the oiling agent.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
the polyacrylonitrile-based carbon fiber low-ash precursor oiling agent comprises the following effective components in parts by weight:
10-20 parts of high-carbon fatty alcohol polyoxyethylene ether;
10-20 parts of aliphatic polyhydroxy methyl ammonium methyl sulfate;
10-20 parts of polyether polyol;
40-60 parts of side chain amino modified polysiloxane;
the aliphatic polyhydroxy methyl amine methyl sulfate is shown in the following structural formula 1:
structural formula 1;
R 1 、R 2 independently selected from alkylene groups having 1 to 6 carbon atoms, R 3 Selected from alkyl groups having 1 to 6 carbon atoms, R 4 Selected from aliphatic groups having 8 to 23 carbon atoms.
The technical key of the invention is that the oil agent has less ash content due to the inclusion of the compound shown in the structural formula 1 and the polyether polyol. The prior art adopts the cationic surfactant related to the structure, and the oil agent has more ash.
In the above technical scheme, as non-limiting examples, the weight parts of the high-carbon fatty alcohol polyoxyethylene ether are 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts and the like.
In the above technical scheme, as non-limiting examples, the weight parts of aliphatic polyhydroxy methyl ammonium methyl sulfate are 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and the like.
In the above technical scheme, as non-limiting examples, the weight parts of polyether polyol are 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, etc.
In the above technical scheme, as non-limiting examples, the weight parts of the side chain amino modified polysiloxane are 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts and so on.
In the above technical solution, as a non-limiting example: r is R 1 、R 2 Independently is an alkylene group having 2 atoms, R 1 、R 2 Independently is an alkylene group of 3 atoms, R 1 、R 2 Independently is an alkylene group of 4 atoms, R 1 、R 2 Independently an alkylene group having 5 atoms, and the like.
In the above technical solution, as a non-limiting example: r is R 3 Alkyl of 2, R 3 Alkyl of 3, R 3 Alkyl of 4, R 3 Alkyl of 5, and the like.
In the above technical solution, as a non-limiting example: r is R 4 Is aliphatic group with 9 carbon atoms, R 4 Is aliphatic group with 10 carbon atoms, R 4 Is aliphatic group having 11 carbon atoms, R 4 Is C12 aliphatic radical, R 4 Is aliphatic group having 13 carbon atoms, R 4 Is aliphatic group with 14 carbon atoms, R 4 Is aliphatic group with 15 carbon atoms, R 4 Is aliphatic group with 16 carbon atoms, R 4 Is aliphatic group having 17 carbon atoms, R 4 Is aliphatic group with 18 carbon atoms, R 4 Is aliphatic group with 19 carbon atoms, R 4 Is a C2-C0 fatty group, R 4 Is aliphatic group with 21 carbon atoms, R 4 Is a C22 aliphatic group, etc.
In the above technical solution, the higher fatty alcohol-polyoxyethylene ether preferably has a structure of R 5 (OCH 2 CH 2 )n 1 OH, wherein R is 5 Selected from C12-C22 alkyl groups, n 1 ＝10-40。R 5 Such as, but not limited to, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl. n is n 1 Such as, but not limited to, 12, 15, 17, 20, 22, 25, 27, 30, 32, 35, 37, etc.
In the above technical scheme, preferably, the polyether polyol is selected from glycerol polyoxyethylene ether or trihydroxymethane polyoxyethylene ether.
In the above technical scheme, the total epoxy addition amount of the polyether polyol is preferably 20-40. Such as, but not limited to, polyether polyols, are 22, 25, 27, 30, 32, 35, 37, etc.
In the above technical scheme, the side chain amino modified polysiloxane is preferably selected from side chain part monoamino modified polysiloxanes shown in the following structural formula 2:
structural formula 2;
wherein R is 6 Selected from alkylene groups having 2 to 10 carbon atoms, b/(a+b+c) =0.1 to 1.R is R 6 Such as, but not limited to: an alkylene group having 3 carbon atoms, an alkylene group having 4 carbon atoms, an alkylene group having 5 carbon atoms, an alkylene group having 6 carbon atoms, an alkylene group having 7 carbon atoms, an alkylene group having 8 carbon atoms, an alkylene group having 9 carbon atoms, and the like. b/(a+b+c) is for example but not limited to: 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, etc.
In the above technical scheme, the side chain amino modified polysiloxane of the structural formula 2 preferably has a kinematic viscosity of 300-2000cP at 25 ℃. For example, but not limited to, the side chain amino modified polysiloxane of formula 2 has a kinematic viscosity of 400cP, 500cP, 600cP, 700cP, 800cP, 900cP, 1000cP, 1100cP, 1200cP, 1300cP, 1400cP, 1500cP, 1600cP, 1700cP, 1800cP, 1900cP, etc
In the above technical scheme, the side chain amino modified polysiloxane is preferably at least one selected from side chain part diamino modified polysiloxanes shown in the following structural formula 3:
structural formula 3;
wherein R is 7 And R is 8 Independently selected from alkylene groups having 2 to 10 carbon atoms, e/(d+e+f) =0.1 to 1. Such as but not limited to R 7 And R is 8 The independent method is as follows: an alkylene group having 3 carbon atoms, an alkylene group having 4 carbon atoms, an alkylene group having 5 carbon atoms, an alkylene group having 6 carbon atoms, an alkylene group having 7 carbon atoms, an alkylene group having 8 carbon atoms, an alkylene group having 9 carbon atoms, and the like. For example, but not limited to, e/(d+e+f) is: 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, etc.
In the above technical scheme, the kinematic viscosity of the side chain amino modified polysiloxane shown in the structural formula 3 is preferably 1000-5000cP at 25 ℃. Such as, but not limited to, the side chain amino modified polysiloxanes of formula 3 have kinematic viscosities of 1500cP, 2000cP, 2500cP, 3000cP, 3500cP, 4000cP, 4500cP, etc., at 25 ℃.
In the above technical scheme, preferably, the filament oil agent is an emulsion comprising water and the active ingredients, and the weight concentration of the active ingredients in the emulsion is 1-5%. Such as but not limited to 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% by weight of active ingredient in the emulsion, etc.
For comparison, compounds commonly used in the compounds of formula 1 in the specific embodiments may be further represented by the following structural formula:
wherein R is 9 Alkyl or acyl of C8-C20, e.g. but not limited to R 9 Is C9 alkyl or acyl, R 9 Is C10 alkyl or acyl, R 9 Is C11 alkyl or acyl, R 9 Is C12 alkyl or acyl, R 9 Is C13 alkyl or acyl, R 9 Is C14 alkyl or acyl, R 9 Is C15 alkyl or acyl, R 9 Is C16 alkyl or acyl, R 9 Is C17 alkyl or acyl, R 9 Alkyl or acyl of C18, and the like. For comparison, more commonly [3- (dodecaoxo) -2-hydroxypropyl ] is used]Bis (2-hydroxyethyl) methyl ammonium methyl sulfate.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the application of the precursor oiling agent in the production of polyacrylonitrile-based carbon fibers in the technical scheme of one of the technical problems.
The technical key of the invention is the selection of the components of the oiling agent, and under the condition that the components of the oiling agent are disclosed by the invention, a person skilled in the art can reasonably select the method and the technological parameters for using the oiling agent.
The using method of the oil agent comprises the following steps: accurately weighing a certain amount of water, slowly adding into 20wt% of oil solution under stirring, preparing into the oil solution concentration required by the production process, and placing into an oil solution tank for use.
The stability of the oil emulsion is measured by adopting static stability, and the measuring temperature is 25℃: the 20wt% oil emulsion was stirred for 1 hour to allow for uniform mixing, then allowed to stand for timing and the time required for emulsion delamination was observed. The longer the time required for delamination, the more stable the emulsion.
The method for testing oxidation resistance, heat resistance and residual quantity of oil agent comprises heating oil agent in oven at 105deg.C for 5 hr, then adopting thermal weight loss analyzer of PE company in America, taking about 30mg of dried sample, heating at 10deg.C/min under air atmosphere until it reaches 240 deg.C, standing for 1 hr, and recording residual quantity r 1 The more numerical valueThe better the oxidation resistance is greatly demonstrated. Switching the atmosphere to nitrogen, continuously maintaining the heating rate at 10 ℃/min until the temperature reaches 450 ℃, staying for 30s, and recording the residual quantity r 2 The larger the value is, the better the heat resistance is, the heating is continued until the temperature reaches 900 ℃, and the final residual quantity r of the oil agent is recorded 3 The smaller the number, the less the finish eventually remains.
The method for measuring the ash content of the oil agent comprises the following steps: accurately weighing about 5g of oiling agent, heating at 150 ℃ on an electric plate for 1h to evaporate water, putting into a muffle furnace for burning at 750 ℃ for 4h, cooling, weighing, and calculating residual ash.
The method for measuring the average particle size of the oil agent comprises the following steps: the measurement was carried out using a Mastersizer 2000 type laser particle size analyzer. According to the method, a file in a menu bar of an initial interface is opened, deionized water in a beaker at the left lower side of an accessory is replaced, after about 800mL is filled, a green button at the front side of the accessory is pressed, a pump starts to operate, at the moment, manual operation (M) measured in the menu bar can be selected, the background of automatic test of an instrument can be observed, if the background display is smaller than 80 (preferably smaller than 40), a sample pool of the instrument is considered to be clean, (otherwise, water in the beaker is replaced and the sample pool is repeatedly cleaned), sample information is selected in the menu bar of a measurement display interface, a file name is set, a dispersant option, water is selected according to the beginning in the menu bar, the instrument automatically detects the background, according to a prompt of the left lower foot of an operation interface, a pretreated sample is added, the solubility of the instrument is kept between 10-20%, the sample is tested by clicking, and the instrument automatically gives a result.
The kinematic viscosity was measured using a viscometer model SYD-2010, and the sample was first placed in a viscometer and placed in a constant temperature bath at 25℃for 10 minutes. And after the constant temperature is finished, the liquid in the viscometer is washed back and forth for three times up and down by the ear washing ball, then the liquid is sucked above the upper scale mark, the corresponding timing key is pressed when the liquid falls back to the upper scale mark, and the corresponding timing key is pressed again when the liquid flows to the lower scale mark. The instrument was repeated three times and the automatically calculated viscosity was remembered.
The invention is further illustrated by the following description and examples in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a thermal weight loss spectrum of the oil of example 1.
Detailed Description
Example 1
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate (structural formula is shown as below), 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents an addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is as shown in the structural formula 2) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 92 days, and the average particle size of the oil is 187nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝89.21％,r 2 = 51.58%) and little final residue, r 3 For ease of statistics, = 3.202%, ash=0.24%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
[3- (dodecaoxo) -2-hydroxypropyl ] bis (2-hydroxyethyl) methyl ammonium methyl sulfate, CAS:18602-17-0.
Example 2
15 parts of cetyl alcohol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (tetradecyloxy) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate (structural formula is shown as below), 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents an addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is as shown in the structural formula 2) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 88 days, and the average particle size of the oil is 189nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝88.67％,r 2 = 51.32%) and little final residue, r 3 For ease of statistics, = 3.512%, ash=0.45%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
[3- (tetradecyloxy) -2-hydroxypropyl ] bis (2-hydroxyethyl) methyl ammonium methyl sulfate, CAS:99260-28-3.
Example 3
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20) [3- (octadecyl oxo) -2-hydroxypropyl ]]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate (structural formula is shown as below), 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents an addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is as shown in the structural formula 2) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 87 days, and the average particle size of the oil is 190nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝87.98％,r 2 = 52.04%) and little final residue, r 3 For ease of statistics, = 3.634%, ash=0.51%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
[3- (octadecyl-oxo) -2-hydroxypropyl ] bis (2-hydroxyethyl) methyl ammonium methyl sulfate, CAS:125464-20-2.
Example 4
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (heptadecacarbonyloxy) -2 hydroxyPropyl group]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate (structural formula is shown as below), 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents an addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is as shown in the structural formula 2) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 85 days, and the average particle size of the oil is 192nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝87.52％,r 2 = 53.16%) and little final residue, r 3 For ease of statistics, = 3.078%, ash=0.36%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
[3- (heptadecacarbonyloxy) -2-hydroxypropyl ] bis (2-hydroxyethyl) methyl ammonium methyl sulfate, CAS:18750-14-6.
Example 5
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate, 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents the addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is shown as the specification) 6 ＝C 2 H 4 45 parts of b/(a+b+c) =0.4, with a viscosity of 1080cP at 25 ℃, and a side chain diamino modified polysiloxane 1 (shown as structural formula 3, wherein R 7 ＝C 6 H 12 ，R 8 ＝C 8 H 16 E/(d+e+f) =0.55, viscosity at 25 ℃ 2500 cP) 15 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 89 days, and the average particle size of the oil is 186nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝89.15％,r 2 =52.68%) and little final residue, r 3 For ease of statistics, the relevant data are listed in tables 1, 2, =2.986%, ash=0.32%. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
Example 6
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate, 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents the addition number of ethylene oxide is 30), and side chain diamino modified polysiloxane 1 (shown as a structural formula 3, wherein R is shown as a structural formula 3) 7 ＝C 6 H 12 ，R 8 ＝C 8 H 16 E/(d+e+f) =0.55, viscosity at 25 ℃ 2500 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 78 days, and the average particle size of the oil is 193nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝89.78％,r 2 =53.45%) and little final residue, r 3 For ease of statistics, = 3.520%, ash=0.56%, the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
Example 7
15 parts of eicosyl polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide) and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate, 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents the addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is shown as the specification) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 82 days, and the average particle size of the oil is 188nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝88.34％,r 2 = 52.37%) and little final residue, r 3 For ease of statistics, = 3.169%, ash=0.38%, and the relevant data are listed in tables 1, 2. The formulated oilThe preparation is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzzing and adhesion.
Example 8
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate, 10 parts of glycerol polyoxyethylene ether alcohol 40 (30 represents the addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is shown as the specification) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 89 days, and the average particle size of the oil is 189nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝89.53％,r 2 =53.29%), little final residue, r 3 For ease of statistics, = 3.318%, ash=0.40%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
Example 9
20 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20) and [3- (dodecaoxo) -2-hydroxypropyl]20 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate, 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents the addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is shown as the specification) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 50 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 95 days, and the average particle size of the oil is 185nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝87.14％,r 2 =51.25%) and little final residue, r 3 For ease of statistics, the relevant data are listed in tables 1, 2, =3.110%, ash=0.28%. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
Comparative example 1
15 parts of cetyl alcohol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide is 20), 15 parts of octadecyl trimethyl ammonium bromide, 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents the addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown as structural formula 2, wherein R is represented by the following formula 2) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the oil has good stability, the layering time is 7 days, and the average particle size of the oil is 1015nm. Oil oxidation resistance and heat resistance are general (r) 1 ＝78.56％,r 2 = 43.28%) and finally has a lot of residues, r 3 For ease of statistics, = 7.895%, ash=2.56%, the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
Comparative example 2
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium chloride (the structural formula is shown in the specification), 10 parts of glycerol polyoxyethylene ether alcohol 30 (30 represents the addition number of ethylene oxide is 30), and side chain monoamino modified polysiloxane 1 (shown in the structural formula 2, wherein R is as shown in the specification) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the stability of the oil is generally that the layering time is 58 days, and the average particle size of the oil is 196nm. The oil solution has good oxidation resistance and heat resistance (r) 1 ＝89.95％,r 2 =55.43%) and finally has a lot of residues, r 3 For ease of statistics, = 9.361%, ash=4.18%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
[3- (dodecaoxo) -2-hydroxypropyl ] bis (2-hydroxyethyl) methyl ammonium chloride. CAS number: 6200-40-4
Comparative example 3
15 parts of hexadecanol polyoxyethylene ether 20 (20 represents the addition number of ethylene oxide to 20), and [3- (dodecaoxo) -2-hydroxypropyl]15 parts of bis (2-hydroxyethyl) methyl ammonium methyl sulfate, 10 parts of octyl phenol polyoxyethylene ether 6 (6 represents the addition number of ethylene oxide is 6), and side chain monoamino modified polysiloxane 1 (shown as a structural formula 2, wherein R is shown as a specification) 6 ＝C 2 H 4 B/(a+b+c) =0.4, and the viscosity at 25 ℃ is 1080 cP) 60 parts. Evenly stirring at room temperature, slowly adding deionized water, and preparing into oil with 20% effective concentration, wherein the stability of the oil is generally that the layering time is 57 days, and the average particle size of the oil is 191nm. Oil oxidation resistance and heat resistance are general (r) 1 ＝80.15％,r 2 =45.86%) and finally has a lot of residues, r 3 For ease of statistics, = 7.854%, ash=3.75%, and the relevant data are listed in tables 1, 2. The formulated oiling agent is prepared into 2% emulsion concentration for fiber oiling evaluation, and the obtained fiber is smooth, soft, free of fuzziness and adhesion.
TABLE 1
TABLE 2
Claims (8)
1. The polyacrylonitrile-based carbon fiber low-ash precursor oiling agent comprises the following effective components in parts by weight:
10-20 parts of high-carbon fatty alcohol polyoxyethylene ether;
10-20 parts of aliphatic polyhydroxy methyl ammonium methyl sulfate;
10-20 parts of polyether polyol;
40-60 parts of side chain amino modified polysiloxane;
the aliphatic polyhydroxy methyl ammonium methyl sulfate is shown in the following structural formula 1:
structural formula 1;
wherein R is 9 Is C8-C20 alkyl or acyl; the structure of the high-carbon fatty alcohol polyoxyethylene ether is R 5 (OCH 2 CH 2 )n 1 OH, wherein R is 5 Selected from C12-C22 alkyl groups, n 1 =10-40; the polyether polyol is selected from glycerol polyoxyethylene ether or trihydroxy methane polyoxyethylene ether; the polyether polyol has a total epoxy addition of 20 to 40.
2. The protofilament oil according to claim 1, characterized in that said side chain amino-modified polysiloxane is selected from side chain moiety monoamino-modified polysiloxanes represented by the following structural formula 2:
structural formula 2;
wherein R is 6 Selected from alkylene groups having 2 to 10 carbon atoms, b/(a+b+c) =0.1 to 1.
3. The protofilament oiling agent according to claim 2, wherein the side chain amino-modified polysiloxane of the structural formula 2 has a kinematic viscosity of 300 to 2000cP at 25 ℃.
4. The protofilament oil according to claim 1, characterized in that the side chain amino-modified polysiloxane is selected from at least one of side chain partially diamino-modified polysiloxanes represented by the following structural formula 3:
structural formula 3;
r in (B) 7 Selected from alkylene groups having 2 to 10 carbon atoms, R 8 Selected from alkyl groups having 2 to 10 carbon atoms, e/(d+e+f) =0.1 to 1。
5. The protofilament oiling agent according to claim 4, wherein the side chain amino-modified polysiloxane of the formula 3 has a kinematic viscosity of 1000 to 5000cP at 25 ℃.
6. The dope of claim 1, wherein said dope comprises an emulsion of water and said active ingredient.
7. The filament oil according to claim 6, wherein the concentration by weight of the active ingredient in the emulsion is 1 to 5%.
8. The use of the protofilament oiling agent according to any of claims 1 to 7 in the production of polyacrylonitrile-based carbon fibers.
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