CN110670350B - Silicone oil-free agent for carbon fiber precursor - Google Patents
Silicone oil-free agent for carbon fiber precursor Download PDFInfo
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- CN110670350B CN110670350B CN201910879745.2A CN201910879745A CN110670350B CN 110670350 B CN110670350 B CN 110670350B CN 201910879745 A CN201910879745 A CN 201910879745A CN 110670350 B CN110670350 B CN 110670350B
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- aromatic
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- carbon atoms
- carbon fiber
- oil
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 57
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 38
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002243 precursor Substances 0.000 title claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 10
- -1 aromatic ester compound Chemical class 0.000 claims abstract description 48
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 18
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims abstract description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 9
- 239000000194 fatty acid Substances 0.000 claims abstract description 9
- 229930195729 fatty acid Natural products 0.000 claims abstract description 9
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims abstract description 7
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical class CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 70
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 14
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- QMKYBPDZANOJGF-UHFFFAOYSA-K benzene-1,3,5-tricarboxylate(3-) Chemical compound [O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-K 0.000 claims description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 45
- 230000008569 process Effects 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- 230000003647 oxidation Effects 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 239000000835 fiber Substances 0.000 description 33
- 229920002239 polyacrylonitrile Polymers 0.000 description 19
- 238000004945 emulsification Methods 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229920002545 silicone oil Polymers 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000007774 longterm Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- 229920013822 aminosilicone Polymers 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- D06M13/10—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 oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
-
- 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
- D06M13/10—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 oxygen
- D06M13/165—Ethers
- D06M13/17—Polyoxyalkyleneglycol ethers
-
- 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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/419—Amides having nitrogen atoms of amide groups substituted by hydroxyalkyl or by etherified or esterified hydroxyalkyl groups
-
- 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
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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
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Landscapes
- 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 discloses a silicone oil-free agent for carbon fiber precursors, which comprises an aromatic ester compound, aromatic polyoxyethylene ether and an amine compound in a mass ratio of 50-80: 10-35: 1-5 aqueous emulsions dispersed in water; the aromatic ester compound comprises one or more of benzene tricarboxylate, phthalate, hydroxybenzoate and ethoxylated bisphenol higher fatty acid ester; the aromatic polyoxyethylene ether comprises one or more of alkylphenol polyoxyethylene and bisphenol A polyoxyethylene; the amine compound comprises one or more of ethoxylated lauramide and aliphatic long-chain quaternary ammonium salt; and the aromatic ester compound has a mass residual rate of 80-98% at 300 ℃ in an air atmosphere, and the mass ratio of the aromatic ester compound to the nonvolatile component of the oil agent is 50-80%. The method can effectively reduce the roller sticking degree in the protofilament production process, prevent PAN monofilaments from being stuck and doubled in the pre-oxidation process, and has certain hydrophilicity and heat resistance.
Description
Technical Field
The invention relates to a silicon-free oil agent, in particular to a silicon-free oil agent for carbon fiber precursors, and belongs to the technical field of textile oil agents.
Background
The carbon fiber has good specific strength and specific elastic modulus, so the carbon fiber is widely used as a reinforcing material in the field of advanced composite materials. The industrial production method of carbon fiber is that Polyacrylonitrile (PAN) fiber bundle is pre-oxidized in oxidizing atmosphere between 200 ℃ and 400 ℃ to obtain non-combustible and non-fusible pre-oxidized fiber, and then carbonized in inert atmosphere such as nitrogen at high temperature of at least 1000 ℃ to obtain carbon fiber.
In the pre-oxidation process, the process temperature exceeds the softening point of the PAN precursor, the PAN precursor can be softened or even melted under the action of heat, adjacent monofilaments can be bonded with each other, and the multi-single-filament fibers are combined together, so that the phenomenon of bonding and doubling is generated. The adhesion and doubling of PAN monofilaments can directly cause the increase of broken filaments, the performance and the grade of fibers are reduced, and severe fibers can even cause the breakage of the filaments, thereby influencing the normal operation of production.
To solve this problem, the industrial solution is to treat the raw filaments with a special oil solution to form a protective film having good heat resistance on the surface layer of the PAN fibers, thereby separating the filaments from each other and preventing them from blocking at high temperature. The oil used is generally a silicone oil, that is, an oil containing a silicone-based substance as a main component.
The silicon oil agent has good film forming property, heat resistance, antistatic property and friction resistance, and can effectively prevent the PAN fiber from being adhered and doubled in the pre-oxidation process in actual use, but the silicon oil agent also has some defects. In the heat treatment process of the fiber, the oil agent attached to the fiber is volatilized and decomposed to cause pollution to equipment, the hydrophobicity is strong, and the uniform dispersibility on the wet fiber obtained after spinning is not good.
Firstly, in the process of manufacturing and pre-oxidizing the raw silk, silicon oil partially falls off from fibers and is attached to a roller, intermolecular or intramolecular crosslinking is generated under the action of heat to form jelly, the smoothness of the surface of the roller is seriously affected after long-term accumulation, and the phenomenon of winding and sticking to the roller is caused, so that the increase of the raw silk or the winding of the silk is caused. Secondly, in the carbonization process at higher temperature, the silicon oil is thermally graded to generate inorganic silicides such as silicon oxide, silicon carbide, silicon nitride and the like. These substances are deposited in large quantities on the inner walls of the retort and in the exhaust channels, and have to be shut down and cleaned frequently. Finally, silicone oil is a main source of carbon fiber ash, and in some fields with strict requirements on the fiber ash, such as the field of carbon/carbon composite materials, the silicon remaining in the carbon fiber can have serious adverse effects on key properties such as strength and ablation resistance of the material, so that the using amount of the silicone oil needs to be strictly limited.
Many solutions have been proposed to solve the above problems of the silicone oils. The basic idea is to reduce the content of silicon-based substances in the oil agent as much as possible until the oil agent does not contain silicon. For example:
patent CN 102965944 (document 1) proposes a PAN protofilament generation technology, in which a protofilament is oiled twice, the first oiling uses polybasic ester as the main component, and the second oiling uses aromatic ester and amino silicone oil as the main components;
patent CN 101326313 (document 2) proposes an oil agent using an ester compound having 3 or more ester groups in the molecule and a silicone oil as essential components;
patent CN 103582730 (document 3) proposes a carbon fiber precursor oil agent containing at least one of a hydroxybenzoate, cyclohexanedicarboxylate ester, and an isophorone diisocyanate fatty alcohol adduct;
patent CN 105442097 (document 4) proposes a silicone-free oil agent containing two specific types of substances;
patent CN 107740206 (document 5) proposes a method for producing a low-ash PAN-based carbon fiber using a highly heat-resistant silicone-free oil composed of a saturated linear monoester, a hindered phenol-based antioxidant and a surfactant.
In documents 1,2 and 3, a silicon-based substance and a non-silicon substance are used as main active ingredients of the oil agent, and the content of the silicone oil in the nonvolatile component varies, but the above problem cannot be solved completely if the silicone oil is contained, and particularly ash content of the fiber. In addition, the two-stage oiling method adopted in document 1 additionally increases the equipment cost compared with one-step oiling. In document 3, the aliphatic ester compound used has insufficient heat resistance, and there is room for improvement in the effect of preventing the blocking of monofilaments. Both of documents 4 and 5 use a silicone oil-free agent, but the effective components in document 4 require several steps to be synthesized, and the production process is complicated; the aliphatic monohydric ester used in document 5 has the same problem as that of document 3, and both of them cannot obtain carbon fibers having excellent performance.
To sum up, in the technology in the field, silicone oil is used to ensure the performance and quality of the fiber, but the problems of roller sticking, deposition in a furnace and fiber ash exist, or a low-silicon or silicone oil-free agent is used, although the problem of silicon oil can be solved to a certain extent, the prevention effect on monofilament adhesion is poor, the performance of the obtained carbon fiber is unsatisfactory, and perfect balance cannot be realized from two aspects. And the active modified groups in the silicone oil are subjected to a crosslinking reaction under the action of heat, so that the main reason for the roller sticking of the silicone oil is that the more the number of the modified groups is, the higher the activity is, and the more obvious the roller sticking is. Inorganic silicide generated by decomposition of silicone oil at high temperature is a main source of deposition in a high-temperature furnace and final carbon fiber ash. The above-mentioned problems inevitably occur as long as the modified silicone oil is used as the main component of the oil agent.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide the silicon-free oil agent for the carbon fiber precursor, which can realize that the oil agent has good heat resistance, effectively reduce the roller sticking degree in the precursor production process, effectively prevent the PAN monofilament from being adhered and doubled in the pre-oxidation process and simultaneously have certain hydrophilicity.
In order to achieve the above object, the present invention adopts the following technical solutions:
a silicone oil-free agent for carbon fiber precursors comprises an aromatic ester compound A, an aromatic polyoxyethylene ether B and an amine compound C in a mass ratio of (50-80): (10-35): (1-5) an aqueous emulsion formed by dispersing in water;
the aromatic ester compound A comprises one or more of benzene tricarbamate, phthalate, hydroxybenzoate and ethoxylated bisphenol A higher fatty acid ester;
the aromatic polyoxyethylene ether B comprises one or more of alkylphenol polyoxyethylene and bisphenol A polyoxyethylene;
the amine compound C comprises one or more of ethoxylated lauramide and aliphatic long-chain quaternary ammonium salt;
the average particle size of the emulsion is 50-500 nm, the particle size is less than 50nm, the emulsion is difficult to achieve by using a common emulsification method, and the emulsification cost is greatly improved; if the particle size exceeds 500nm, the stability of the emulsion is poor, and the uniform adhesion of the oil agent on the fiber surface is affected. The content of nonvolatile components in the aqueous emulsion is 5-50 wt%; the solid content is lower than 10%, the production and transportation cost of the oil agent is obviously increased, and the production capacity is not improved; if the content exceeds 50%, the stability of the oil emulsion is poor, the long-term storage is not facilitated, demulsification with different degrees is easy to generate in the using process, and the phenomenon of nonuniform oiling is caused.
The benzene tricarboxylate is 1,2, 4-benzene tricarboxylate or 1,2, 3-benzene tricarboxylate or 1,3, 5-benzene tricarboxylate;
wherein the structural formula of the trimellitic ester is as follows:
the benzene tricarbamate in the invention has a structure shown in the formula 1 or similar to the formula 1. Similarly, it means that the relative positions of the three ester groups in the benzene ring may be changed, that is, the benzenetricarboxylate represented by formula 1 is 1,2, 4-benzenetricarboxylate (trimellitate), and in addition, 1,2, 3-benzenetricarboxylate (hemibenzoate) and 1,3, 5-benzenetricarboxylate (trimesate).
In the formula 1, R1、R2、R3Respectively is a hydrocarbon group with 7-13 carbon atoms; r in formula 11、R2、R3May be the same or different. From the aspect of the difficulty of synthesis and production, the three groups are more convenient to be used as the same group. The carbon number is more than 7, so that the thermal stability of the benzoic acid ester can be ensured, and the effect of preventing the melting and doubling of monofilaments in the pre-oxidation process is ensured; if the number of carbon atoms exceeds 20, the viscosity of the benzoic acid ester is too high, which makes emulsification difficult, and gel and emulsion breaking are likely to occur after emulsification, which is disadvantageous for long-term stable use of the oil agent, and in addition, the phenomenon of non-uniform oiling is likely to occur during use.
The benzene tricarboxylate is prepared by esterification reaction of benzene tricarboxylic acid and aliphatic monohydric alcohol with 7-13 carbon atoms. Thus, R in formula 11、R2、R3The group is derived from aliphatic monohydric alcohol with 7-13 carbon atoms. The carbon atoms may be saturated or contain a bis group as long as the number of carbon atoms is between 7 and 13The unsaturated group such as a bond may be a straight chain or may have a branched chain. Preferably, a saturated hydrocarbon group having 9 to 12 carbon atoms is used.
The benzoic acid tribasic ester is obtained by condensation esterification reaction of benzene tricarboxylic acid and aliphatic monobasic acid with 7-13 carbon atoms under the condition of no catalyst or existence of known esterification reaction catalyst such as stannate, titanium compound, etc. In order to reduce side reactions, the esterification reaction is preferably carried out in an inert atmosphere, and the reaction temperature is controlled between 180 ℃ and 230 ℃. The molar ratio of the benzene tricarboxylic acid to the aliphatic monohydric alcohol as the raw material in the esterification reaction is 1mol, and the aliphatic alcohol is 1.0 to 1.2 mol. In the case of using a catalyst, after completion of the reaction, the catalyst should be deactivated and then removed with an adsorbent, or the remaining catalyst may adversely affect the properties of the carbon fiber.
The phthalate is 1, 2-phthalate or 1, 3-phthalate or 1, 4-phthalate;
wherein, the structural formula of the 1, 2-phthalic acid ester is as follows:
the phthalic acid ester in the present invention has a structure represented by the above formula 2 or a structure similar to the formula 2. Here, the term "similar" means that the relative positions of two ester groups in a benzene ring may be changed, that is, the phthalate represented by formula 2 is 1, 2-phthalate (phthalate), and in addition, 1, 3-phthalate (isophthalate) and 1, 4-phthalate (terephthalate).
In the formula 2, R4、R5Respectively is a hydrocarbon group with 8-15 carbon atoms; r in formula 24、R5May be the same or different. From the aspect of difficulty of synthesis and production, the two groups are taken as the same group, which is convenient. The carbon number is more than 8, so that the thermal stability of the phthalic acid ester can be ensured, and the effect of preventing the monofilament from melting and doubling in the pre-oxidation process is ensured; if the number of carbon atoms exceeds 15, phthalic acidThe ester has too high viscosity, is difficult to emulsify, is easy to generate gel and emulsion breaking after emulsification, is not beneficial to long-term stable use of the oil agent, and is easy to generate the phenomenon of non-uniform oiling in the using process.
The phthalic acid ester is prepared from phthalic acid and aliphatic monohydric alcohol with the carbon atom number of 8-15 through esterification reaction. Thus, R in formula 24、R5The group is derived from aliphatic monohydric alcohol with 7-13 carbon atoms. The unsaturated group may be saturated or may contain an unsaturated group such as a double bond as long as the number of carbon atoms is between 8 and 15, and may be linear or branched. Preferably, a saturated hydrocarbon group having 10 to 13 carbon atoms is used.
The synthesis or production of phthalic acid esters is similar to the above-described benzenetricarboxylic acid esters, and therefore, will not be described in detail.
The above hydroxy benzoate is 1-hydroxy-4-benzoate or 1-hydroxy-2-benzoate or 1-hydroxy-3-benzoate;
wherein, the structural formula of the 1-hydroxy-4-benzoate is as follows:
the hydroxybenzoate in the present invention has a structure as shown in formula 3 above or similar to formula 3. Similarly, it means that the relative positions of the hydroxyl group and the ester group in the benzene ring may be changed, that is, the hydroxybenzoic acid ester represented by formula 3 is 1-hydroxy-4-benzoate (p-hydroxybenzoate), except for 1-hydroxy-2-benzoate (o-hydroxybenzoate) and 1-hydroxy-3-benzoate (m-hydroxybenzoate).
In the formula 3, R6Is a hydrocarbon group having 10 to 20 carbon atoms. The carbon number is only more than 10, so that the thermal stability of the hydroxybenzoate can be ensured, and the effect of preventing the melt doubling of monofilaments in the pre-oxidation process is ensured; if the number of carbon atoms exceeds 20, the viscosity of the hydroxybenzoates becomes too high, the emulsification becomes difficult, gels and emulsions tend to occur after the emulsification, the long-term stable use of the oil agent is not facilitated, and the use thereof is not facilitatedThe phenomenon of uneven oiling is easily generated in the process.
The hydroxybenzoate is prepared by esterification reaction of hydroxybenzoic acid and aliphatic monohydric alcohol with 10-20 carbon atoms. Thus, R in formula 36The group is derived from aliphatic monohydric alcohol with 10-20 carbon atoms. The unsaturated group may be saturated or may contain an unsaturated group such as a double bond, and may be linear or branched as long as the number of carbon atoms is 10 to 20. In general, the number of carbon atoms is preferably 12 to 18.
The synthesis of hydroxybenzoates is analogous to the benzene tricarboxylates and phthalic acid esters described above. And will not be described in detail herein.
The structural formula of the ethoxylated bisphenol A fatty acid ester is as follows:
in the formula 4, R7、R8Respectively is a hydrocarbon group with 7-15 carbon atoms; in the formula 4, R7、R8They may be the same or different, and are preferably the same in terms of the difficulty of synthesis and production. As long as the carbon number is more than 7, the good thermal stability of the ethoxylated bisphenol A fatty acid ester can be maintained, and the effect of preventing the adhesion and doubling of monofilaments in the pre-oxidation process is ensured; if the number of carbon atoms is 15 or less, it is ensured that the problems of excessive viscosity, easy gelling, difficult emulsification, and uneven oil application to the filament bundle do not occur. The number of carbon atoms is preferably 11 to 13. The hydrocarbon group is preferably a saturated straight-chain hydrocarbon group.
m and n are required to be between 2 and 4, and the two can be the same or different. If the amount is less than 2, the hydrophilicity of the compound is poor, and emulsification is difficult, and the stability of the resulting emulsion is poor, while if it is more than 4, the heat resistance of the compound cannot be ensured. In addition, in a single molecule, m and n are integers, but even if the proportion of each raw material substance is strictly limited in the production process, the actually obtained ethoxylated bisphenol A fatty acid ester is a mixture of different values of m and n, and in this case, m and n may not be integers (average values of various integer values) as a whole.
The above four substances may be used alone or in combination of two or more. However, the aromatic ester compound A used in the present invention should have a residual mass ratio of 80 to 98% at 300 ℃ in an air atmosphere, whether used alone or in combination.
The mass residual rate means a thermal weight loss curve of a sample obtained by using a thermogravimetric analyzer, and the mass residual rate at 300 ℃ is obtained from the curve. If the mass residual rate is less than 80 percent, the heat resistance is insufficient, a large amount of the PAN precursor is decomposed in the pre-oxidation process, and the PAN precursor cannot be effectively protected to prevent the PAN precursor from adhesion and doubling; the mass residual ratio is more than 98%, and it is practically difficult for the ester compound to appear.
The residual mass ratio of the aromatic ester-based compound a can be varied to some extent by adjusting the number of atoms and the structure of the R group, that is, the hydrocarbon group in each of the above-mentioned compounds. Generally, the larger the number of carbon atoms, the smaller the unsaturated group, and the better the heat resistance of the molecule. However, the number of carbon atoms of each hydrocarbon group should be noted not to exceed the aforementioned range because if the number of carbon atoms is too large, the emulsifying property thereof is affected.
The mass proportion of the aromatic ester compound A in the non-volatile components of the finish (i.e., all the components except water in the finish emulsion) should be between 50 and 80%. If the proportion is less than 50 percent, the heat resistance of the oil agent is insufficient, and the phenomenon of adhesion and doubling among monofilaments cannot be effectively prevented; if the proportion exceeds 80%, it is difficult to obtain a stable emulsion.
The ethoxylated bisphenol A fatty acid ester is prepared by using ethoxylated bisphenol A and aliphatic monobasic acid as raw materials.
The structural formula of the alkylphenol polyoxyethylene is as follows:
in the formula 5, R9Is the number of carbon atomsAn alkyl group of 6 to 12, and r is an integer of 2 to 20.
The structural formula of the bisphenol A polyoxyethylene ether is as follows:
in the formula 6, p and q are integers of 2-20 respectively.
The aromatic polyoxyethylene ethers in formulas 5 and 6 are mainly used as an emulsifier in the present invention to realize emulsification of the aromatic ester compound a in water. Besides the function of an emulsifier, the oil also has certain lubricating and softening functions. According to the numerical difference of r, p and q, the thermal property, the emulsifying property and the like of the emulsion are obviously different. Generally, the larger the values of r, p and q, the more hydrophilic groups in the molecule, the more hydrophilic the molecule, the better the emulsifying ability, but the heat resistance is also lowered; the smaller the values of r, p and q, the less hydrophilic the resulting emulsion, but the higher the heat resistance.
The aromatic polyoxyethylene ether may be used in a variety of different forms depending on the numerical values of r, p and q, and one of them may be selected, or a variety of forms may be mixed, and it is preferable to use at least two or more forms of the aromatic polyoxyethylene ether, which are different in r, p and q, in view of the overall effect. In the mixing process, the optimal proportioning can be realized by combining the HLB (hydrophilic-lipophilic balance) value of a reference system with the actual test effect.
The mass proportion of the aromatic polyoxyethylene ether B in the nonvolatile components of the oil solution is 10-35%. If the proportion is less than 10 percent, the oil agent is difficult to emulsify, and stable emulsion with small enough grain diameter can not be obtained; if the proportion exceeds 35%, the heat resistance of the entire oil agent is lowered, which is disadvantageous in obtaining a high-performance carbon fiber product.
The amine compound C, such as ethoxylated lauramide, aliphatic long-chain quaternary ammonium salt and the like, plays the roles of an emulsifier, an antistatic agent and an antibacterial agent in the invention. The proportion thereof by mass in all nonvolatile components should be between 1 and 5%. If the ratio is less than 1%, the bundling property of the fibers is deteriorated due to the action of static electricity, which may affect the stability of production and the quality of the product; if it is higher than 5%, the ratio of the other components is required to be adjusted downward, and it is considered to be disadvantageous in view of the whole to achieve the object of the present invention.
In addition to the three substances, on the premise of not influencing the effect of the invention, a small amount of at least one auxiliary additive selected from an antioxidant, a pH regulator, an antifoaming agent, a preservative and a stabilizer can be added into the oil agent according to the requirement, and the mass percentage of the auxiliary additive in the nonvolatile components of the oil emulsion is between 0.1 and 5 percent.
The silicon-free oil agent (aqueous emulsion) of the invention uses water which is preferably deionized water; the emulsification method is not particularly limited, and includes the equipment used and the specific process, and generally known emulsification methods such as a high shear emulsification method, an ultrasonic emulsification method, and a method of emulsification using equipment such as a homogenizer and a high pressure homogenizer may be used. Different emulsification methods are used, the particle size of the obtained emulsion can be different, and the emulsion is properly selected according to the comprehensive consideration of actual conditions, such as production cost, production efficiency, product performance requirements and the like.
The silicon-free oil agent can be diluted to a certain extent as required in actual use. Deionized water is preferably used during dilution, a certain amount of deionized water is slowly added to dilute the oil agent to the required concentration while the oil agent is kept stirred, and then the stirring is continued for half an hour. The diluted oil emulsion can be used for oiling the PAN precursor fiber bundle by an immersion method, a spray method, or the like, and the immersion method is industrially used in many cases in view of equipment cost, uniformity of oiling, and the like.
The amount of finish oil adhering to the PAN fiber, that is, the amount of finish oil, is generally controlled to be 0.5 to 2%. If the oiling amount is too small, the proper effect cannot be achieved, and the stable production and the final performance of the carbon fiber are not good; the oiling amount is more than 2%, so that not only can the waste of the oil agent be caused, the production cost is improved, but also a large amount of oil agent can be decomposed and volatilized in the subsequent heat treatment process, and the deposition amount in the furnace and the treatment amount of waste gas are increased. The amount of oil added to the yarn was measured according to the following method:
a certain amount of protofilament samples are taken and dried for 2 hours at 105 ℃, the mass of the protofilament samples is measured and recorded as W1, the protofilament samples are placed in a Soxhlet extractor, acetone (or organic solvent with proper gas) is added, the temperature is raised to 50 ℃, and the protofilament samples are extracted for 4 hours. The sample was removed, dried at 105 ℃ for 2 hours and the mass was determined and reported as W2. The amount of oil applied was calculated according to the following formula:
the oil amount (wt%) is (W1-W2)/W1.
The number of the filaments of the carbon fiber precursor fiber bundle applicable to the invention is between 1000-; the number of the single filaments is less than 1000, the production efficiency is very low, the fiber cost is high, and after the number of the single filaments exceeds 96000, the oiling uniformity and the uniformity of the subsequent carbon fiber performance are obviously influenced.
The invention has the advantages that:
according to the silicon-free oil agent for the carbon fiber precursor, substances which contain aromatic ring structures with high heat resistance stability and hydrophilic groups such as esters in molecules are selected as main effective components of the oil agent, and the emulsifier selects the surfactant which has better heat resistance and contains aromatic rings in molecules, so that the oil agent has good heat resistance, the PAN monofilaments are effectively prevented from being softened, adhered and doubled in the pre-oxidation process, and meanwhile, the silicone-free oil agent has certain hydrophilicity and can conveniently realize emulsification; has better surface affinity with PAN monofilament, can be uniformly attached to the surface of the fiber, and ensures the quality uniformity of the fiber.
Compared with the traditional silicon oil agent, the silicon-free oil agent can effectively reduce the roller sticking phenomenon in the protofilament generation process, can effectively prevent the adhesion and doubling of filaments in the pre-oxidation process, has small deposition amount in the carbonization process, and can obtain carbon fibers with low ash content and excellent mechanical property; the raw materials are easy to obtain, the synthesis steps are simple and easy to operate, the modification requirement on the existing equipment is low, the preparation method can be properly adjusted according to actual use, and the preparation method comprises the steps of preparing the components and the proportion of the oil agent, the specific type of the aromatic ester compound, the heat resistance of the aromatic ester compound, the specific type of the aromatic polyoxyethylene ether, the solid content of the emulsion, the particle size of the emulsion and the like, and has strong practicability and wide applicability.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Various evaluation and measurement methods in the present invention are as follows:
heat-resistant residual ratio: the temperature was raised to 400 ℃ at a temperature rise rate of 10 ℃/min in an air atmosphere using a thermogravimetric analyzer (NETZSCH TG 209F3, germany scale), and the heat-resistant residual rate at 300 ℃ was obtained from the obtained thermogravimetric curve.
Emulsion particle size: measured using a laser particle sizer (malvern, Mastersizer 2000, uk).
Carbon fiber ash: the method is carried out according to the national standard GB/T1429-2009 method for measuring the ash content of the carbon material.
Roller sticking degree in the protofilament production process: one month of continuous production, the number of times the roll surface was cleaned during the period was counted and evaluated according to the following criteria: a is 2 times or less, B is 2-4 times, and C is 5 times or more.
Adhesion and doubling in the pre-oxidation process: the pre-oxidized fiber bundle was cut to a length of 3mm, dispersed in acetone, stirred for 10min, dispersed on filter paper, and the number of doubling between monofilaments was counted under a magnifying glass. The following criteria were used: the number of A is less than 5, the number of B is 5-10, and the number of C is more than 10.
Carbon fiber tensile strength: according to the national standard GB/T26749-2011 determination of tensile property of carbon fiber impregnated yarn.
The production process of the protofilament specifically comprises the following steps: according to the components and mass ratio of the oil agent shown in the table 1, the aromatic ester compound A, the aromatic polyoxyethylene ether B and the amine compound C are mixed and stirred uniformly, deionized water is slowly added while stirring is kept, and emulsification is carried out by using a homogenizer to obtain an emulsion with the solid content of 30 wt%. The particle size of the emulsion was measured. Diluting the emulsion to 2% with water, and adding into an upper oil tank with circulation function for use.
Dissolving PAN copolymer obtained by copolymerizing acrylonitrile and methacrylic acid in dimethyl sulfoxide to prepare spinning solution with the concentration of 21%, and spraying the spinning solution into a coagulation bath consisting of dimethyl sulfoxide water solution with the temperature of 60 ℃ and the concentration of 65% through a spinneret plate with the pore diameter of 60 mu m and the pore number of 12000 to coagulate into filaments. The fiber bundle was drawn while washing off the solvent in a rinsing bath at a draw ratio of 3 to obtain a water-swollen fiber bundle.
And guiding the fiber bundle in the water swelling state into an oil feeding tank for oiling treatment. Then, the resultant was dried and densified by a hot roll having a surface temperature of 150 ℃ and then drawn 5 times in water vapor having a pressure of 0.5MPa to obtain a carbon fiber precursor fiber bundle having a single yarn number of 12000 and a single yarn fineness of 1.1 dtex.
The oil solutions of examples 1 to 7 and comparative examples 1 to 3 in table 1 were used to evaluate the degree of sticking in the course of production of a raw yarn.
The pre-oxidation process specifically comprises the following steps: the obtained precursor fiber bundle is pre-oxidized for 45 minutes in a pre-oxidation furnace with temperature gradient zones at 220-280 ℃ to obtain pre-oxidized fiber. The pre-oxidation process was used to evaluate the degree of blocking and doubling of the strand.
And (3) carbonizing the pre-oxidized fiber for 3 minutes in a carbonization furnace with temperature gradient subareas at 400-1400 ℃ in a nitrogen atmosphere to obtain the carbonized fiber. The above procedure was used to determine the ash content of the carbon fiber tow and the tensile strength of the carbon fibers.
The results of the measurement of the composition ratio and the performance of the oils of examples 1 to 7 and comparative examples 1 to 3 are shown in the following table 1:
TABLE 1
The materials in table 1 are specifically as follows:
a1: a compound of formula 1, R1、R2、R3Is isodecyl group, and has heat-resisting residual rate of 90%;
a2: a compound of formula 2, R4、R5Dodecyl, the heat-resistant residual rate is 83 percent;
a3: a compound represented by the formula 3, R69-octadecenyl, the heat-resistant residual rate is 85 percent;
a4: a compound represented by the formula 4, R7、R8Dodecyl, m and n are both 4, and the heat-resistant residual rate is 87%;
b1: polyoxyethylene nonyl phenyl ether, OP-4;
b2: polyoxyethylene nonyl phenyl ether, OP-10;
b3: bisphenol A polyoxyethylene ether, BPE-6;
c1: diethoxy lauramide;
c2, dodecyl dimethyl ammonium chloride;
d1: amino silicone oil with viscosity of 2300mm2(ii)/s, ammonia equivalent 6000 g/mol;
d2: amino silicone oil with a viscosity of 500mm2(ii) ammonia equivalent 2800 g/mol;
d3: polyether silicone oil with viscosity of 300mm2/s。
As can be seen from table 1 above, compared with the conventional silicon-based oil agent comparative examples 1 to 3, the silicon-free oil agents of examples 1 to 7 of the present invention have the roll sticking degree evaluated as a in the raw yarn production process, and the roll sticking phenomenon is greatly improved compared with the conventional silicon-based oil agent; in the aspect of adhesion doubling, the adhesion doubling of the PAN monofilament in the pre-oxidation process can be effectively prevented; in terms of carbon fiber ash content, the carbon fiber ash content of examples 1-7 is 18-35 ppm, which is much lower than that of comparative examples 1-3, is 1987-2869 ppm, and all examples are reduced by about two orders of magnitude compared with silicon oil agent, so that the effect is very obvious; the silicone oil-free agent disclosed by the invention avoids the problems that the traditional silicone oil agent is easy to stick to a roller and the ash content of a fiber product is high, and can effectively prevent adhesion and doubling in a pre-oxidation process to obtain a high-performance carbon fiber product.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (5)
1. The silicone-free agent for the carbon fiber precursor is characterized by comprising an aromatic ester compound A, an aromatic polyoxyethylene ether B and an amine compound C in a mass ratio of (50-80): (10-35): (1-5) an aqueous emulsion formed by dispersing in water;
the aromatic ester compound A comprises one or more of benzene tricarbamate, phthalate, hydroxybenzoate and ethoxylated bisphenol A higher fatty acid ester;
the aromatic polyoxyethylene ether B comprises one or more of alkylphenol polyoxyethylene and bisphenol A polyoxyethylene;
the amine compound C comprises one or more of ethoxylated lauramide and aliphatic long-chain quaternary ammonium salt;
the aromatic ester compound A has a mass residual rate of 80-98% at 300 ℃ in an air atmosphere, and the mass percentage of the aromatic ester compound A in the nonvolatile components of the oil agent is 50-80%;
the benzene tricarboxylate is 1,2, 4-benzene tricarboxylate or 1,2, 3-benzene tricarboxylate or 1,3, 5-benzene tricarboxylate;
wherein the structural formula of the trimellitic ester is as follows:
in the formula 1, R1、R2、R3Respectively is a hydrocarbon group with 7-13 carbon atoms;
the benzene tricarboxylate is prepared by esterification reaction of benzene tricarboxylic acid and aliphatic monohydric alcohol with 7-13 carbon atoms;
the phthalate is 1, 2-phthalate or 1, 3-phthalate or 1, 4-phthalate;
wherein, the structural formula of the 1, 2-phthalic acid ester is as follows:
in the formula 2, R4、R5Respectively is a hydrocarbon group with 8-15 carbon atoms;
the phthalic acid ester is prepared by esterification reaction of phthalic acid and aliphatic monohydric alcohol with 8-15 carbon atoms;
the hydroxybenzoic acid ester is 1-hydroxy-4-benzoate or 1-hydroxy-2-benzoate or 1-hydroxy-3-benzoate;
wherein, the structural formula of the 1-hydroxy-4-benzoate is as follows:
in the formula 3, R6Is a hydrocarbon group with 10-20 carbon atoms;
the hydroxyl benzoate is prepared by esterification reaction of hydroxyl benzoic acid and aliphatic monohydric alcohol with 10-20 carbon atoms;
the structural formula of the ethoxylated bisphenol A higher fatty acid ester is as follows:
in the formula 4, R7、R8Respectively is a hydrocarbon group with 7-15 carbon atoms; m and n are respectively an integer of 2-4;
the ethoxylated bisphenol A fatty acid ester is prepared by taking ethoxylated bisphenol A and aliphatic monobasic acid as raw materials;
the mass proportion of the aromatic polyoxyethylene ether B in the nonvolatile components of the oil solution is 10-35%; the mass ratio of the amine compound C in the nonvolatile components of the oil solution is 1-5%.
2. The silicone-free agent for carbon fiber precursors according to claim 1, wherein the average particle diameter of the aqueous emulsion is 50 to 500nm, and the content of nonvolatile components in the aqueous emulsion is 5 to 50 wt%.
3. The silicone oil-free agent for carbon fiber precursors according to claim 1, wherein the alkylphenol ethoxylates have the following structural formula:
in the formula 5, R9Is an alkyl group having 6 to 12 carbon atoms, and r is an integer of 2 to 20.
4. The silicone oil-free agent for carbon fiber precursor according to claim 1, wherein the bisphenol A polyoxyethylene ether has the following structural formula:
in the formula 6, p and q are integers of 2-20 respectively.
5. The silicone-free agent for carbon fiber precursors according to claim 1, further comprising an auxiliary additive in a mass ratio of 0.1 to 5%, wherein the auxiliary additive is at least one of an antioxidant, a pH adjuster, a defoaming agent, a preservative, and a stabilizer.
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| CN112746354A (en) * | 2020-12-29 | 2021-05-04 | 镇江市高等专科学校 | Preparation method of oil emulsion for carbon fiber precursors |
| CN112726207A (en) * | 2020-12-29 | 2021-04-30 | 镇江市高等专科学校 | Oil agent for carbon fiber precursor production, carbon fiber production method and carbon fiber |
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| JP2004169198A (en) * | 2002-11-18 | 2004-06-17 | Toray Ind Inc | Precursor fiber strand for carbon fiber and method for producing the same |
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