CN117005198A - Short carbon chain fluorine-containing finishing agent and preparation and application thereof - Google Patents
Short carbon chain fluorine-containing finishing agent and preparation and application thereof Download PDFInfo
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- CN117005198A CN117005198A CN202310958322.6A CN202310958322A CN117005198A CN 117005198 A CN117005198 A CN 117005198A CN 202310958322 A CN202310958322 A CN 202310958322A CN 117005198 A CN117005198 A CN 117005198A
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- Prior art keywords
- fluorine
- monomer
- finishing agent
- acrylate
- carbon chain
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 91
- 239000004744 fabric Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005871 repellent Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- 239000004753 textile Substances 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- -1 acrylic ester Chemical class 0.000 claims description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 230000004224 protection Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 125000000373 fatty alcohol group Chemical group 0.000 claims description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 2
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- 239000012224 working solution Substances 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000005728 strengthening Methods 0.000 abstract description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000003995 emulsifying agent Substances 0.000 description 31
- 229910052799 carbon Inorganic materials 0.000 description 22
- 238000004132 cross linking Methods 0.000 description 15
- 229920000742 Cotton Polymers 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000011258 core-shell material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004078 waterproofing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001409 amidines Chemical class 0.000 description 3
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QBECDXJGYFRACA-UHFFFAOYSA-N (4-phenylphenyl)methyl prop-2-enoate Chemical compound C1=CC(COC(=O)C=C)=CC=C1C1=CC=CC=C1 QBECDXJGYFRACA-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 210000002268 wool Anatomy 0.000 description 1
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Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the technical field of fabric water-repellent and oil-repellent finishing agents, and particularly relates to a short carbon chain fluorine-containing finishing agent and preparation and application thereof, wherein the finishing agent comprises, by weight, 2-5% of cationic surfactant, 2-5% of nonionic surfactant, 5-15% of acrylate monomer, 15-25% of short chain fluorine-containing acrylate monomer, 0.1-0.5% of initiator and 50-60% of water; compared with the prior art, the long-acting high-performance short-carbon-chain perfluorinated acrylate waterproof and oilproof agent is prepared based on the side chain strengthening orientation technology based on the key problem of how to improve the lasting low surface energy performance, and can be applied to the waterproof and oilproof finishing fields of industrial textiles and high-end fabrics.
Description
Technical Field
The invention relates to the technical field of fabric water-repellent and oil-repellent finishing agents, in particular to a short carbon chain fluorine-containing finishing agent and preparation and application thereof.
Background
Currently, functional and environmental textiles are being developed vigorously and will become the mainstay of new century textile products. With the increasing enhancement of environmental awareness and self-protection awareness, the requirements on textiles are gradually expanded from the aspects of softness, comfort, moisture absorption, ventilation and the like to the aspects of antibacterial sanitation, water resistance, oil resistance, pollution resistance, non-ironing crease resistance, radiation resistance, ultraviolet resistance, flame retardance, medical protection and the like, and the development and application of various novel fibers and the development of novel processes and novel technologies are gradually realized, and the requirements on functional after-finishing are pushed by the increasingly developed demands of high technology, high added value and the like.
The three-proofing finishing is water-repellent, oil-repellent, antifouling and other multifunctional finishing. The three-proofing finishing agent is a textile finishing agent which is applied to fabric such as cotton, wool, silk, chemical fiber and blend fiber and can change the surface property of the fabric, so that the fabric is not easy to be wetted or stained by water, common oil and dirt, and the three-proofing finishing agent is various, such as: the waterproof and waterproof agent comprises a waterproof and waterproof agent, a waterproof and waterproof agent and a waterproof and waterproof agent. The octafluorocarbons-based finishing agent has good effect but contains harmful substances such as ammonium perfluorooctanoate (hereinafter, PFOA) and perfluorooctane sulfonate (hereinafter, PFOS). Such finishes have therefore been limited in use worldwide.
Under the direction of the U.S. Environmental Protection Agency (EPA), 3M companies began to phase out the production of PFOS, PFOA and its precursors and related compounds in 2000. The European Union release G/TBT/N/EU/731, release of REACH regulatory amendment draft, restrictions on the production and release of longer fluorocarbon chains (perfluorocarboxylic acids containing 9 to 14 carbon atoms), salts and related substances within the European Union. The draft requires that C9-C14 perfluorocarboxylic acids and salts thereof must not be used or put into the european union market when the total concentration of C9-C14 perfluorocarboxylic acids related substances is greater than or equal to 25ppb, or greater than or equal to 260ppb, as a component of another substance, in a mixture or in an article. The perfluorooctanoic acid (PFOA) and its salt content is limited to 0.025ug/m2 in the 2020 edition recently issued by Oeko-tex Standard 100.
Compared with the traditional eight-carbon waterproof agent, the six-carbon waterproof agent does not contain PFOS, PFOA, APEO, formaldehyde and other forbidden substances, is easy to degrade and is environment-friendly.
The production enterprises of the short-chain fluorine-containing acrylic ester three-proofing finishing agent are very few in China. Most of the domestic researches are still in laboratory and theoretical research stage and have a distance from commercialization.
Li Xiaowei from Donghua university is prepared from self-made N-propyl-N-hydroxyethyl perfluorohexyl sulfonic acid amine by alcoholysis reaction to obtain N-propyl perfluorohexyl sulfonic acid amino ethyl acrylic acid vinegar (C6F 13SO2N (C3H 7) CH2CH2 OCOCH=CH 2) containing perfluoro short carbon chain acrylate monomer, and emulsion polymerizing the obtained fluoro monomer with octadecyl acrylate and 2 hydroxyethyl acrylate to obtain the fabric finishing agent. And then the finishing agent is applied to pure cotton fabrics, the concentration of the finishing agent is 60g/L, the baking temperature is 160 ℃, the baking time is 120S, the contact angle of the treated pure cotton fabrics to water is 138.5 degrees, the oil repellency grade 4 is excellent, and the water resistance is excellent.
Qian Haihong of Jiangnan university uses four-carbon short chain fluorine-containing monomer, octadecyl acrylate (SA) and Butyl Acrylate (BA) as basic monomer, glycidyl Methacrylate (GMA) as crosslinking monomer, and under the action of auxiliary emulsifier dodecyl mercaptan (SH), compound emulsifier Cetyl Trimethyl Ammonium Bromide (CTAB) and polyoxyethylene lauryl ether system, quaternary fluorine-containing acrylate copolymer miniemulsion is prepared. The finishing agent is used for finishing cotton fabrics, the contact angle of the cotton fabrics is 153.6 degrees, the contact angle of the cotton fabrics is 123.7 degrees, the water repellency grade is 5 grades, and the oil repellency grade is 3 grades.
Li Lixin the NT-X carbon hexafluoro water-repellent and oil-repellent finishing agent of foreign Nano-Tex company is adopted, and the treated fabric can keep good hand feeling on pure cotton, polyester woven and nylon woven fabrics, and has advantages in water-repellent and oil-repellent, washing resistance, friction resistance, corrosion resistance and the like.
The Zhejiang macro group began in 2004 to study the replacement of C8-based fluorine-containing finishes with C6 and C9 fluorine-containing finishes. However, it is difficult, but not impossible, to control the reaction conditions to ensure termination of the reaction within the desired carbon chain range, in that the end product of the telomerization process to prepare perfluoroalkyl compounds is a mixture of different carbon chains with a broad distribution of carbon chains.
The mechanism of the action of the water-proof and oil-proof agent is that a layer of film is formed on the outer surface of the substrate, and the surface tension of the film is lower than that of common liquid, so that the film has the functions of water repellency, oil repellency and dirt resistance. The low surface energy of the fluoropolymer itself is responsible for the low surface tension of the film. Meanwhile, according to the surface physical chemistry principle, the surface layer of the film is in contact with the outside, the interaction between the surface layer of the film and the outside determines the surface tension, and other parts of the film except the surface layer have little influence on the surface tension. Therefore, the water-proof and oil-proof agent film can obtain low surface energy and satisfactory treatment effect only by adopting the fluoropolymer to form the surface layer. Under such conditions, if the other portion of the film is free of fluorine, the use of fluorine-containing (meth) acrylate monomers can be reduced. In addition, because of the high price of the fluorine-containing (methyl) acrylate monomer, pollution and energy consumption exist in the production process, and the dosage of the fluorine-containing (methyl) acrylate monomer needs to be reduced as much as possible.
The core-shell emulsion technology can lead the composition of the emulsion particle shell polymer to be different from that of the core polymer through particle design, the shell layer is in contact with the outside of the film after film formation, the core is in the combination of the inner layer and the textile, and the concentration of the fluorine-containing (methyl) acrylate monomer of the core is obviously lower than that of the shell layer, even the fluorine-containing (methyl) acrylate monomer is not added, thus the dosage of the fluorine-containing (methyl) acrylate monomer can be reduced. There are many publications and patents published in this regard, but there are more or less the following disadvantages:
1. in some existing finishing agent emulsions, although a synthesis process of enrichment of fluorine-containing methacrylate monomers in a shell layer is adopted, the hydrophilicity of the shell layer is far smaller than that of a core part, and phase inversion exists in the synthesis and storage processes, so that the use effect of the finishing agent emulsion is affected; during the preparation process, the emulsion can stabilize the morphology of the core-shell through crosslinking, but can also influence the enrichment of the fluoropolymer on the surface layer during the film forming of the finishing agent;
2. the existing finishing agent has poor durability of water and oil resistance, namely, the water and oil resistance agent has poor bonding fastness with fibers, especially textiles with cotton components; secondly, most of the prior art is to obtain durability on fabrics by adding a bridging agent after preparing emulsion, and such design cannot meet the requirement from the practical point of view.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a short carbon chain fluorine-containing finishing agent for solving the technical problems, and preparation and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a short carbon chain fluorine-containing finishing agent is characterized by comprising the following components in percentage by weight
2-5% of a cationic surfactant,
2-5% of nonionic surfactant,
5 to 15 percent of acrylic ester monomer,
15-25% of short-chain fluorine-containing acrylate monomer,
0.1 to 0.5% of an initiator, and
50-60% water.
Further, the cationic surfactant is one or more of octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and dodecyl trimethyl ammonium chloride.
Further, the nonionic surfactant is fatty alcohol polyoxyethylene ether.
Further, the acrylate monomer is one or more of stearyl methacrylate, 4-biphenylmethanol acrylate and hydroxyethyl methacrylate.
Further, the acrylate monomer may be one or more of 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, behenyl acrylate, and behenyl methacrylate.
Further, the short-chain fluorine-containing acrylate monomer has a general formula of C n F 2n+1 C 2 H 4 OCOCR=CH 2 Wherein, the method comprises the steps of, wherein,
r is selected from C 1 ~C 2 An alkyl group; n is 4, 5 or 6.
Further, the initiator is one of azo diiso Ding Mi hydrochloride, azo diisobutyl amidine hydrochloride, potassium persulfate, sodium persulfate and ammonium persulfate.
A preparation method of a short carbon chain fluorine-containing finishing agent comprises the following steps:
s1, mixing a cationic surfactant, a nonionic surfactant, an acrylic ester monomer, a short-chain fluorine-containing acrylic ester monomer and water, and emulsifying by using a homogenizer to obtain a pre-emulsion;
s2, introducing nitrogen into the pre-emulsion for 30 minutes, heating to 50-80 ℃, dropwise adding an aqueous solution of an initiator under the protection of nitrogen, and reacting for 2-6 hours under the heat preservation;
s3, cooling to 20-25 ℃ to obtain the finishing agent.
Further, the fluorine-containing finishing agent is applied as a fabric waterproof finishing agent.
The using method of the fluorine-containing finishing agent comprises the following steps:
i, preparing working solution: 30g/L to 50g/L,
II, finishing on the fabric: the padding method is adopted, one padding is adopted, the liquid carrying rate is 30-40%,
III, baking: baking at 160-180deg.C for one minute.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the invention takes perfluorohexane acrylate monomer, non-fluorine monomer and non-fluorine crosslinking monomer as raw materials, adopts a core-shell emulsion polymerization method, takes cation-nonionic compound surfactant as an emulsifier, and prepares the fluorine-containing waterproof finishing agent in a semi-continuous feeding mode;
2. compared with the common six-carbon waterproof agent, the product has wider adaptability to fabrics, can meet the common waterproof processing requirement, is suitable for three-proofing finishing with high oil resistance, and has alcohol resistance;
3. compared with the traditional carbon eight waterproof agent, the carbon six three-proofing finishing agent does not contain PFOS, PFOA, APEO and other non-environment-friendly substances, and can meet the processing requirements of carbon six environment-friendly waterproof orders at home and abroad.
Drawings
FIG. 1 is a plot of emulsion conversion and emulsion gel rate for emulsions at different concentrations of emulsifier according to an embodiment of the present invention.
FIG. 2 is a plot of emulsion conversion and emulsion gel rate for emulsions at different concentrations of fluoromonomer according to an embodiment of the present invention.
FIG. 3 is a plot of emulsion conversion and emulsion gel rate for emulsions at different concentrations of functional monomer according to an embodiment of the present invention.
FIG. 4 is a plot of emulsion conversion and emulsion gel rate for emulsions at different concentrations of crosslinking monomer according to an embodiment of the present invention.
FIG. 5 is a flow chart of a preparation process of an embodiment of the present invention.
FIG. 6 is a schematic diagram of the reaction equation of the six-carbon waterproofing agent of the present invention.
FIG. 7 is a schematic representation of the particle size distribution of the finish of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
The invention relates to a short carbon chain fluorine-containing finishing agent, which is prepared by taking perfluorohexyl ethyl acrylate monomer (C6F), non-fluorine monomer (octadecyl methacrylate (SMA), 4-diphenyl methanol acrylate (BPMA)) and non-fluorine crosslinking monomer (hydroxyethyl methacrylate (HEMA)) as raw materials, adopting a core-shell emulsion polymerization method and taking a cation-nonionic compound surfactant as an emulsifier in a semi-continuous feeding mode, and comprises the following specific implementation processes:
the amount of the emulsifier and the monomer used in the core-shell emulsion polymerization process can have great influence on the stability of the emulsion and the water and oil repellent effect, so that the conditions of the emulsifier and the monomer used in the emulsion polymerization reaction need to be determined.
1. Selection of emulsifiers
Emulsifiers are generally classified into nonionic and ionic types. When one type of emulsifier is used alone, the emulsion system is very unstable, and demulsification and delamination are easy to occur, and even precipitation occurs. Therefore, the nonionic emulsifier or the ionic emulsifier is used together, so that the emulsification effect can be improved, the stability of the emulsion can be maintained, and the synergistic effect can be achieved; in addition, the nonionic emulsifier is added into the emulsifying system, so that the charge density of the surface of the monomer liquid drop can be obviously reduced, free radicals are promoted to enter the liquid drop more easily, and the polymerization reaction rate is improved.
2. Selection of the amount of emulsifier
The mass ratio of the raw materials is fixed: C6F: SMA: BPMA: hema=12: 10:3:1, an initiator azo diisobutyl amidine hydrochloride is 0.8% of the mass of a monomer, the reaction temperature is 70 ℃, the reaction time is 4 hours, and the polymerization reaction is carried out under different emulsifier concentrations; the prepared emulsion takes the emulsion conversion rate and the gel rate as evaluation indexes to determine the influence of the using amount of the emulsifying agent on emulsion polymerization reaction, and the experimental result is shown in figure 1.
As can be seen from FIG. 1, when the amount of the emulsifier is small, the monomer conversion rate is low, the gel rate is high, the conversion rate increases with the increase of the amount of the emulsifier, and the gel rate decreases; the method is characterized in that the more the emulsifier is used, the larger the emulsifier is covered on the surface of the monomer liquid drop, the larger the droplet is prevented from being collided to form, the gel rate is reduced, meanwhile, the emulsifier can reduce the particle size of the monomer liquid drop dispersed in the system, the specific surface area is increased, the reactive places are increased, the monomer can be fully polymerized, and the monomer conversion rate is improved.
When the concentration of the emulsifier reaches more than 6%, the monomer conversion rate is reduced along with the increase of the using amount of the emulsifier; the dosage of the emulsifier is increased, the place of polymerization reaction is increased, the free radical service life is prolonged, the conversion rate is gradually increased, but the emulsion becomes very viscous due to the excessive dosage of the emulsifier, molecular chains are entangled together, gel is increased, the stability is reduced, the diffusion of the monomer is influenced, and the conversion rate of the monomer is reduced; therefore, the amount of the mixed emulsifier was 6%.
3. Selection of the amount of fluoromonomer
The fluorine-containing monomer is the most important component in the emulsion polymerization reaction, the water and oil repellency of the finishing agent can be directly influenced by the amount of the fluorine-containing monomer, the price of the fluorine-containing monomer is quite high, and the price of a final product can be increased by using the fluorine-containing monomer excessively; and the fluorine-containing monomer is polymerized on the shell through a core-shell emulsion polymerization technology, so that the fluorine-containing monomer is mainly concentrated on the surface of the film in the film forming process, thereby effectively changing the surface property of the polymer and simultaneously not greatly improving the cost.
The mass ratio of the raw materials is fixed: SMA: BPMA: hema=10: 3:1, initiator azo diisobutylamidine hydrochloride (AIBA) is 0.8% of monomer mass, the concentration of the composite emulsifier is 6%, the reaction temperature is 70 ℃, the reaction time is 4 hours, and the polymerization reaction is carried out under different fluorine-containing monomer concentrations. The prepared emulsion takes emulsion conversion rate and gel rate as evaluation indexes to determine the influence of the dosage of fluorine-containing monomers on emulsion polymerization reaction, and the experimental result is shown in figure 2.
As can be seen from fig. 2, the conversion and the gel rate are not greatly changed with the increase of the amount of the fluorine-containing monomer, but when the amount of the fluorine-containing monomer exceeds 14%, both the conversion and the polymerization stability are lowered; the side chain in the polymer is a longer fluorine-containing monomer, the hydrophobicity is stronger, when the dosage of the fluorine-containing monomer is lower, the dispersion of monomer droplets in the water phase can be smoothly carried out, but when the concentration of the monomer is increased to a certain value, the strong hydrophobicity of the fluorine-containing monomer causes unstable polymerization reaction, so that the conversion rate is reduced, and the gel rate is increased; so that the amount of the fluorine-containing monomer is selected to be 14%.
4. The amount of functional monomer is preferably
According to the side chain strengthening orientation technology, the fluorine-containing monomer is copolymerized with 4-biphenylmethanol acrylic ester, the rigid biphenyl group strengthens the orientation arrangement of fluorine-containing carbon chain segments, the retraction of the polymer body in the process of contacting with water is inhibited, the dynamic water repellency is greatly improved, and the water and oil resistance of the finishing agent can be improved.
The mass ratio of the raw materials is fixed: C6F: SMA: hema=14: 10:1, initiator azo diisobutylamidine hydrochloride (AIBA) is 0.8% of monomer mass, the concentration of the composite emulsifier is 6%, the reaction temperature is 70 ℃, the reaction time is 4 hours, and the polymerization reaction is carried out under different 4-biphenylmethanol acrylic acid ester (BPMA) monomer concentrations. The prepared emulsion takes emulsion conversion rate and gel rate as evaluation indexes to determine the influence of the dosage of fluorine-containing monomers on emulsion polymerization reaction, and the experimental result is shown in figure 3.
As can be seen from FIG. 3, the addition amount of the functional monomer is small, the influence on the overall conversion rate of the polymer reaction is small, and when the use amount of the functional monomer is 4%, the gel starts to rise and increases, which is probably due to the fact that the functional monomer has strong hydrophobicity, the solubility in water is small, the system is easy to be unstable, and gel is easy to be generated in the polymerization process, so that the application performance of the functional monomer is influenced, and the optimal use amount of the functional monomer is 4%.
5. The amount of crosslinking monomers is preferably
Hydroxyethyl methacrylate (HEMA) is used as a cross-linking agent monomer, and the monomer contains two active groups, can participate in polymerization, and can also perform cross-linking reaction with a matrix, so that a polymer chain segment and fibers form covalent bonding, the fastness is improved, and the washing fastness is improved.
The mass ratio of the raw materials is fixed: C6F: SMA: BPMA = 14:10: and 4, an initiator azo diisobutylamidine hydrochloride (AIBA) is 0.8% of the mass of the monomer, the concentration of the composite emulsifier is 6%, the reaction temperature is 70 ℃, the reaction time is 4 hours, and the polymerization reaction is carried out under different crosslinking monomer concentrations. The prepared emulsion takes emulsion conversion rate and gel rate as evaluation indexes to determine the influence of the amount of crosslinking monomers on emulsion polymerization reaction, and the experimental result is shown in figure 4.
As can be seen from FIG. 4, the addition of the crosslinking monomer is smaller, and the overall conversion and gel rate of the polymer reaction are less affected.
Hydroxyethyl methacrylate is taken as a crosslinking monomer and is covalently bonded with the fiber mainly through "-OH", so that a reticular crosslinking structure is formed, fluorine-containing chain segments are tightly and orderly fixed on the surface of the fabric, the rearrangement of the fluorine-containing chain segments is inhibited, and the water and oil repellent effect of the fabric is improved; however, when the amount of the crosslinking monomer is too large, the amount of hydrophilic groups in the polymer macromolecule is too large, and although the degree of crosslinking with the fabric is increased, the hydrophilicity is increased due to the adhesion of the polar groups on the surface of the fiber, and the water-repellent and oil-repellent effects are reduced. Therefore, in consideration of the above, hydroxyethyl methacrylate was selected to be 1.0%.
6. Preparation process of finishing agent
Based on the results of the above steps, the preparation was performed according to the preparation process route diagram shown in fig. 5.
Pre-emulsifying seed emulsion: firstly, respectively adding a core monomer (octadecyl methacrylate (SMA), 4-diphenyl methanol acrylic ester (BPMA) and hydroxyethyl methacrylate (HEMA)), a shell monomer (perfluorohexyl ethyl acrylate (C6F), octadecyl methacrylate (SMA), 4-diphenyl methanol acrylic ester (BPMA) and hydroxyethyl methacrylate (HEMA)) into an emulsifier solution with the design mass of 1/3, and pre-emulsifying for 1h to obtain a pre-emulsion.
Synthesis of core-shell structure copolymerization emulsion: adding nitrogen into a 500mL four-port round bottom flask equipped with a thermometer, an electric stirrer, a nitrogen introduction device and a reflux condenser, introducing nitrogen to remove oxygen, sequentially adding the rest 1/3 of aqueous solution of the emulsifier, 1/2 of pre-emulsion of the nuclear monomer and 1/3 of azo diisobutyl amidine hydrochloride serving as an initiator, stirring and mixing uniformly, heating to 70 ℃ for polymerization, reacting for 20-30min, and respectively and slowly dripping the rest nuclear monomer and the 1/3 of initiator solution by using a dropping funnel to obtain the seed nuclear emulsion.
And (3) in the seed nuclear emulsion, preserving heat for 30min, respectively dripping the shell monomer pre-emulsion and the rest 1/3 initiator solution through a dropping funnel, and finally preserving heat and starting timing at the same time, and ending the reaction until the designed reaction time is reached. Naturally cooling to room temperature after the reaction is finished, stopping stirring, and filtering and discharging to obtain the six-carbon waterproof agent emulsion; the specific reaction equation is shown in FIG. 6.
Through the preparation process, the production capacity is increased, and the detection data of the six-carbon waterproof agent emulsion are shown in the following table;
| project | Test conditions | Index (I) | Lot 1 | Batch 2 | Lot 3 |
| Appearance of | Test tube method | Milky white emulsion | Qualified product | Qualified product | Qualified product |
| Water-solubility | Thinning method | No sediment and no floating matter | Qualified product | Qualified product | Qualified product |
| Density of | Specific gravity cup, 23+ -2 DEG C | 1.04-1.14g/cm 3 | 1.06 | 1.07 | 1.06 |
| pH value of | PH meter | 2.5±1.0 | 2.68 | 2.90 | 2.75 |
| Solid content | 105℃×3h | 34±1% | 33.52% | 34.39% | 34.14% |
| Gel fraction | Filtering and weighing | Less than 1.5% | 0.45% | 0.37% | 0.39% |
| Yield rate | Weight calculation | 95% or more | 96.51% | 97.84% | 98.29% |
Product stability
| Carbon six waterproofing agent | Test conditions | Lot 1 | Batch 2 | Lot 3 |
| Storage stability | Sealing and storing for 6 months | Non-layered precipitation | Non-layered precipitation | Non-layered precipitation |
| Mechanical stability | Rotational speed 2000r/min, centrifugation 10 min | Non-demulsification | Non-demulsification | Non-demulsification |
| Dilution stability | 5 times, 10 times and 100 times of the diluted solution, and storing for 7 days | Non-layered precipitation | Non-layered precipitation | Non-layered precipitation |
| Weather resistance stability | Low temperature resistant at-5 deg.c for 7d and high temperature resistant at 60 deg.c for 48 hr | Non-layered precipitation | Non-layered precipitation | Non-layered precipitation |
As shown in the table, the emulsion of the six carbon waterproofing agents has good storage stability, mechanical stability, dilution stability and weather resistance stability, and the synthetic emulsion sample has good stability and is convenient to store and use.
7. Particle size analysis of the emulsion
The size and distribution of the emulsion particle size are an important technical index of the polymer emulsion, and can directly influence the application performance of the carbon six waterproof agent finishing agent emulsion on fabrics. The particle size distribution was measured by a nanoparticle size and potential analyzer, and the results are shown in FIG. 7.
As can be seen from FIG. 7, the particles of the emulsion of the hexa-carbon waterproof agent are mainly distributed between 70 nm and 130nm, and the average particle diameter is 110nm, which indicates that the emulsion of the hexa-carbon waterproof agent is monodisperse and has very narrow distribution area without large particle aggregation, and the emulsion has good stability.
8. Finishing agent application
The carbon six waterproof and oilproof finishing agent is not only suitable for the water and oil repellent finishing of synthetic fiber fabrics, but also can be applied to natural fiber fabrics and blended fabrics thereof. The finishing agent contains an internal crosslinking agent, can endow fabrics with better waterproof and oil-proof durability, and can improve the wash-wear performance. Meanwhile, the modified polyester fiber can be processed by matching with other finishing agents, so that the process and flow are shortened for manufacturers, the production cost is saved, and the cost performance of the product is improved.
The carbon six waterproof and oilproof finishing agent emulsion prepared under the optimal synthesis process condition is applied to the water and oil repellent after-finishing of chemical fiber fabrics (polyester taffeta and nylon yarn spinning) and natural fiber fabrics (pure cotton yarn card), and the performances of waterproof and oilproof agents, stiffening agents, softening agents, antistatic agents and the like are tested by comparing the same type of carbon six waterproof agents in the market.
The results of the initial water and oil repellency test are shown in the following table:
1. water repellency properties: measured according to AATCC 22-2017;
2. oil repellency: measured according to AATCC 118-2007 standard;
water and oil repellency wash resistance test (10 times, 20 times of home wash):
and (3) testing the performance of other functional auxiliary agents for waterproofing agent assembly:
by comparison, the performance of the finishing agent is superior to that of the commercially available carbon six waterproof agent, and the finishing agent has higher waterproof and oil-proof performance.
The invention is detected by a quality supervision and detection center, and the table is shown as follows:
| application process | Is suitable for padding and shaping |
| Solid content | 34±1% |
| Main component | Fluorocarbon copolymer |
| pH value of | 2.5±1.0 |
| Ion type | Weak cations |
| Solubility of | Diluting with water at arbitrary ratio |
| Waterproof property on cotton (30 g/L) | 90 minutes |
| Oil resistance on cotton (30 g/L) | Grade 6 |
| Polyester cotton waterproof property (30 g/L) | 90-100 min |
| Polyester cotton oil resistance (30 g/L) | Grade 6 |
From the above table, it can be seen that the performance of the product reaches a more advanced technical level.
The six-carbon waterproof and oilproof finishing agent copolymerization emulsion with a core-shell structure is prepared by a semi-continuous feeding mode, and the nonionic emulsifier and the cationic emulsifier are compounded according to a proportion by adopting different types of emulsifiers, so that the emulsion polymerization process is stable, the shearing resistance, the thinning stability and the storage stability of the emulsion are good, and the factory large-scale production is facilitated;
the water-proof and oil-proof performance of the finishing agent is improved by introducing the reinforced fluorine-containing carbon chain segment orientation arrangement through a side chain reinforced orientation technology; introducing a crosslinking monomer to enable the waterproof agent polymer chain segment and the fiber to form covalent bonding, so that the fastness is improved, and the washability is improved; through the improvement of the series of monomers, the original characteristics of the six-carbon waterproof agent are maintained, and the integral waterproof and washable performance is improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention, but one skilled in the art can make common changes and substitutions within the scope of the technical solution of the present invention.
Claims (10)
1. A short carbon chain fluorine-containing finishing agent is characterized by comprising the following components in percentage by weight
2-5% of a cationic surfactant,
2-5% of nonionic surfactant,
5 to 15 percent of acrylic ester monomer,
15-25% of short-chain fluorine-containing acrylate monomer,
0.1 to 0.5% of an initiator, and
50-60% water.
2. The short carbon chain fluorine-containing finishing agent according to claim 1, wherein the cationic surfactant is one or more of octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and dodecyl trimethyl ammonium chloride.
3. The fluorine-containing finishing agent according to claim 1, wherein the nonionic surfactant is a fatty alcohol polyoxyethylene ether.
4. The short carbon chain fluorine-containing finishing agent according to claim 1, wherein the acrylic acid ester monomer is one or more of stearyl methacrylate, 4-biphenylmethanol acrylic acid ester and hydroxyethyl methacrylate.
5. The short carbon chain fluorochemical finish according to claim 4 wherein said acrylate monomer is further one or more of 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, behenyl acrylate, and behenyl methacrylate.
6. The short carbon chain fluorochemical finish of claim 1 wherein the short chain fluoroacrylate monomer has the formula C n F 2n+1 C 2 H 4 OCOCR=CH 2 Wherein, the method comprises the steps of, wherein,
r is selected from C 1 ~C 2 An alkyl group; n is 4, 5 or 6.
7. The short carbon chain fluorine-containing finishing agent according to claim 1, wherein the initiator is one of azobisiso Ding Mi hydrochloride, azobisisobutylamidine hydrochloride, potassium persulfate, sodium persulfate and ammonium persulfate.
8. The method for preparing a short carbon chain fluorine-containing finishing agent according to any one of claims 1 to 7, comprising the steps of:
s1, mixing a cationic surfactant, a nonionic surfactant, an acrylic ester monomer, a short-chain fluorine-containing acrylic ester monomer and water, and emulsifying by using a homogenizer to obtain a pre-emulsion;
s2, introducing nitrogen into the pre-emulsion for 30 minutes, heating to 50-80 ℃, dropwise adding an aqueous solution of an initiator under the protection of nitrogen, and reacting for 2-6 hours under the heat preservation;
s3, cooling to 20-25 ℃ to obtain the finishing agent.
9. Use of a short carbon chain fluorine-containing finish according to claims 1-7 as a water-repellent finish for textiles.
10. A method of using a short carbon chain fluorochemical finish according to claims 1 to 7 comprising the steps of:
i, preparing working solution: 30g/L to 50g/L,
II, finishing on the fabric: the padding method is adopted, one padding is adopted, the liquid carrying rate is 30-40%,
III, baking: baking at 160-180deg.C for one minute.
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| CN107602754A (en) * | 2017-09-19 | 2018-01-19 | 绍兴文理学院 | A kind of preparation method and applications of the polymer containing short fluorocarbon chain |
| CN108250350A (en) * | 2018-02-08 | 2018-07-06 | 江南大学 | A kind of preparation and its application of short-chain fluorine-containing copolymer water-refusing oil-refusing finishing agent |
| CN112458755A (en) * | 2020-11-18 | 2021-03-09 | 湖南隆森化工有限公司 | Fluorine-containing fabric finishing agent and preparation method thereof |
| CN116289215A (en) * | 2023-02-24 | 2023-06-23 | 浙江理工大学桐乡研究院有限公司 | Short-chain fluorine-containing polyacrylate three-proofing finishing agent for cotton, preparation method and application thereof |
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