CN116770594A - 一种织物防水用组合物分散液 - Google Patents
一种织物防水用组合物分散液 Download PDFInfo
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- CN116770594A CN116770594A CN202310830623.0A CN202310830623A CN116770594A CN 116770594 A CN116770594 A CN 116770594A CN 202310830623 A CN202310830623 A CN 202310830623A CN 116770594 A CN116770594 A CN 116770594A
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- acrylate
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- 239000006185 dispersion Substances 0.000 title claims abstract description 78
- 239000004744 fabric Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 238000004078 waterproofing Methods 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
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- -1 alkyl acrylic ester Chemical class 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 9
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical group OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 7
- 229920006222 acrylic ester polymer Polymers 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001558 organosilicon polymer Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
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- 239000000839 emulsion Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
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- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 4
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- 238000009736 wetting Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 3
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- 238000006116 polymerization reaction Methods 0.000 description 3
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- XNBCISCTWPSPTF-UHFFFAOYSA-N 4-(3-carboxyprop-1-enylperoxy)but-3-enoic acid Chemical compound C(=O)(O)CC=COOC=CCC(=O)O XNBCISCTWPSPTF-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical class FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
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- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229920000297 Rayon Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- 239000004902 Softening Agent Substances 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
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- 239000010425 asbestos Substances 0.000 description 1
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 239000001632 sodium acetate Substances 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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Abstract
本发明公布一种织物防水用组合物分散液,由端羟基有机硅和丙烯酸酯聚合物形成的杂化分散体、表面活性剂、增溶剂及水组成,丙烯酸酯聚合物至少包含长链烷基丙烯酸酯单体单元、有机硅基丙烯酸酯单体单元和含羟基单体单元;以质量分数计,100质量分数的杂化分散体至多含有端羟基有机硅20质量份,至少含有有机硅基丙烯酸酯单体单元5质量份,至多含有含羟基单体单元8质量份。本发明的织物防水用组合物分散液稳定性好,在对织物进行防水加工处理时连续加工性能优良,经其处理过的织物可以获得良好的手感,且防水性能优异、耐洗性好。
Description
技术领域
本发明涉及织物防水处理技术,尤其涉及一种织物防水用组合物分散液,属于织物防水整理剂生产技术领域。
背景技术
虽然含氟烷基聚合物防水性能优异,但由于含氟烷基聚合物存在累积毒性问题,将逐步被限制使用,因而开发无氟防水剂成为发展趋势。
但现有的无氟防水剂往往存在防水性能不足、容易产生黄变、容易粘辊等问题,而且处理过的织物手感较涩。故亟待开发一种新型的无氟防水剂,已解决以上问题。
发明内容
本发明的目的是提供一种织物防水用组合物分散液,该分散液乳液稳定性好,且其处理过的织物手感柔韧性好、防水性能优异、且耐洗性好。
为了实现本发明的目的,特采用了如下技术方案:
一种织物防水用组合物分散液,由端羟基有机硅和丙烯酸酯聚合物形成的杂化分散体、表面活性剂、增溶剂及水组成。所述的端羟基有机硅用式R1-[Si(CH3)2O]x-Si(CH3)2R2表示,其中R1表示一价含羟基基团,R2表示C1~4的一价烷基或与R1相同,x表示重复单元个数,优选大于等于10;所述的丙烯酸酯聚合物至少包含长链烷基丙烯酸酯单体单元、有机硅基丙烯酸酯单体单元和含羟基单体单元;以质量分数计,100质量分数的杂化分散体至多含有端羟基有机硅20质量份,至少含有有机硅基丙烯酸酯单体单元5质量份,至多含有含羟基单体单元8质量份。
进一步,以质量分数计,100质量分数的杂化分散体中含有5~20质量份的含有端羟基有机硅、含有5~25质量份的有机硅基丙烯酸酯单体单元、含有2~8质量份的含羟基单体单元。
进一步,所述的长链烷基丙烯酸酯单体为(甲基)丙烯酸十二酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十八酯和(甲基)丙烯酸二十二酯中的一种或至少两种的混合物。
更进一步,所述的长链烷基丙烯酸酯单体为丙烯酸十八酯和甲基丙烯酸十八酯中的一种。
进一步,所述的有机硅基丙烯酸酯单体用式CH2=CRCOO-Q-[Si(CH3)2O]y-CH3表示,其中R为H或烷基,Q为二价有机基团,y表示重复单元个数,优选大于等于4。
更进一步,所述的有机硅基丙烯酸酯单体为CH2=C(CH3)COOCH2CH2CH2-[Si(CH3)2O]12.5-CH3。
进一步,所述的含羟基单体为N-羟甲基丙烯酰胺或式CH2=CR′COO-Q′-OH所表示的单体中的一种或至少一种的混合物,其中R′为H或烷基,Q′为二价有机基团。
更进一步,所述的含羟基单体为N-羟甲基丙烯酰胺或CH2=CHCOOCH2CH2OH中的一种。
进一步,所述的端羟基有机硅的数均分子量为2000~3000。
本发明由于采用了上述技术方案,具有以下有益效果:
本发明的织物防水用组合物分散液离心稳定性好,在对织物进行防水加工处理时连续加工性能优良,经其处理过的织物可以获得良好的手感,且防水性能优异、耐洗性好。
具体实施方式
为了便于理解本发明,为使本发明的上述目的、特征和优点能够更加明显易懂,下面对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明,且给出了本发明的较佳实施方式。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施方式。相反地,提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。本发明能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似改进,因此本发明不受下面公开的具体实施例的限制。除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本发明的织物防水用组合物分散液,由端羟基有机硅和丙烯酸酯聚合物形成的杂化分散体、表面活性剂、增溶剂及水组成。其中,端羟基有机硅和丙烯酸酯聚合物形成的杂化分散体及表面活性剂为分散液的有效成分,在对织物进行防水处理后杂化分散体可以为织物提供防水效果,分散体在分散液中稳定存在需要借助表面活性剂的分散作用。增溶剂主要在分散体的形成过程中提供辅助作用,可以促使粒径更小、分散稳定性更好的分散体的形成。水为分散介质,还可以在反应中起到传质传热的作用。为了防止爆聚反应发生,有效成分含量通常不宜超过60wt%,更优选不超过50wt%。为了提高生产效率,有效成分的含量通常也不宜过低,故通常将有效成分的浓度控制在20wt%~45wt%之间。
本发明的织物防水用组合物分散液,其中所述的端羟基有机硅用式R1-[Si(CH3)2O]x-Si(CH3)2R2表示,其中R1表示一价含羟基基团,R2表示C1~4的一价烷基或与R1相同,x表示重复单元个数,优选大于等于10;所述的丙烯酸酯聚合物至少包含长链烷基丙烯酸酯单体单元、有机硅基丙烯酸酯单体单元和含羟基单体单元。本发明的分散液的稳定性和防水效果需要借助以上成分的协同配合才能达到,其中端羟基有机硅的用量不宜过高,否则乳液的稳定性将会受到影响。以质量分数计,100质量份数的杂化分散体中端羟基有机硅的用量不宜超过23质量份,优选为不超过20质量份。有机硅基丙烯酸酯单体单元对本发明分散体的稳定性具有关键性的影响,当无该成分存在时,经反应后形成的分散体乳液在静置后发生分层;当该成分存在但用量较低时,进反应后形成的分散体乳液的稳定性也较差,离心后同样发生分层现象。故以质量分数计,100质量分数的杂化分散体中有机硅基丙烯酸酯单体单元的含量应该在4质量份以上,优选至少为5质量份。本发明的织物防水用组合物分散液需要同水性异氰酸酯固化剂复配使用才能使防水效果及耐洗性能得到有效展现,含羟基单体单元是与异氰酸酯产生作用的成分,当无该成分存在时,防水效果和耐洗性能必然下降;单用量也不宜过高,否则影响手感和初始防水效果。以质量分数计,100质量分数的杂化分散体中含羟基单体单元不宜超过9质量份,优选至多为8质量份。
更优选的以质量分数计,100质量分数的杂化分散体中含有5~20质量份的含有端羟基有机硅、含有5~25质量份的有机硅基丙烯酸酯单体单元、含有2~8质量份的含羟基单体单元。
本发明中所述的长链烷基丙烯酸酯单体可以用式CH2=C(R″)COO-RH表示,其中R″为H或CH3,RH为碳原子数8及以上的长链烷基。RH优选为碳原子数8~22的长链烷基,如:(甲基)丙烯酸十二酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十八酯和(甲基)丙烯酸二十二酯等,长链烷基丙烯酸酯单体可以为以上单体中的一种或至少两种的混合物。更优选的,所述的长链烷基丙烯酸酯单体为丙烯酸十八酯和甲基丙烯酸十八酯中的一种。
本发明中所述的有机硅基丙烯酸酯单体可以用式CH2=CRCOO-Q-[Si(CH3)2O]y-CH3表示,其中R为H或烷基,Q为二价有机基团,y表示重复单元个数,优选大于等于4。更优选为,所述的有机硅基丙烯酸酯单体为CH2=C(CH3)COOCH2CH2CH2-[Si(CH3)2O]12.5-CH3。
本发明中所述的含羟基单体为N-羟甲基丙烯酰胺或式CH2=CR′COO-Q′-OH所表示的单体中的一种或至少一种的混合物,其中R′为H或烷基,Q′为二价有机基团。更优选的,所述的含羟基单体为N-羟甲基丙烯酰胺或CH2=CHCOOCH2CH2OH中的一种。
本发明中所述的端羟基有机硅的数均分子量优选大于1000,更优选为2000~3000。尤其为数均分子量为2500的HO-R1′-[Si(CH3)2O]n-Si(CH3)2-R1′-OH或数均分子量为2800的CH3-[Si(CH3)2O]n-Si(CH3)2-R1′-OH中的一种,其中R1′为二价有机基团,n≥10表示重复单元数。
本发明的织物防水用组合物分散液,其中的表面活性剂为非离子表面活性剂或非离子表面活性剂与阳离子表面活性剂的混合物。非离子表面活性剂通常含有非氟聚醚和/或多羟基基团的亲水段和非氟烃基的疏水段,亲水段和疏水段通过酯健、醚键、氮原子等连接,聚醚基团和多羟基基团通过醚键连接。非离子表面活性剂可列举如下:斯盘系列(S-80、S-40等)、吐温系列(T-60、T-20等)、脂肪醇聚氧乙烯醚/聚氧丙烯醚(AEO-5、AEO-9、AEO-15、异构醇醚E-1306等)、脂肪酸聚氧乙烯/聚氧丙烯酯(LAE-9、聚氧乙烯油酸酯A-105、SG-100等)、脂肪胺聚氧乙烯醚(AC-1810、AC-1820等)。阳离子表面活性剂通常含有季铵盐阳离子基团的亲水段和非氟烃基的疏水段,如十六烷基三甲基氯化铵、十八烷基三甲基氯化铵等。表面活性剂的用量通产为分散体质量用量的3%~15%,以能形成稳定的分散体为准。表面活性剂优选为非离子表面活性剂和阳离子表面活性剂的混合物,尤其为S-80、AEO-9、E-1306、十八烷基三甲基氯化铵的混合物。表面活性剂的用量更优选为分散体质量用量的8.2%。表面活性剂的组成优选为由1.7质量份S-80、1.0质量份AEO-9、0.5质量份E-1306和5质量份十八烷基三甲基氯化铵组成。
本发明的织物防水用组合物分散液可以通过乳液聚合法直接制备;也可以通过溶液共聚法获得丙烯酸酯聚合物溶液,再将端羟基有机硅和乳化剂溶解入溶液中,后加水乳化除去溶剂而获得,优选直接通过乳液聚合法获得。
乳液聚合是在乳化剂存在下,使单体在水中乳化,然后升温至50~95℃的反应温度搅拌聚合3~15h。聚合可以采用油溶性引发剂或水溶性引发剂。油溶性引发剂如偶氮类的偶氮二异丁腈,过氧类的过氧化苯甲酰、二叔丁基过氧化物等。水溶性引发剂如过硫酸钾、过硫酸铵、过硫酸钠、偶氮二异丁基醚盐酸盐、双氧水、3-羧基丙烯基过氧化物等。相对于100质量份的单体,引发剂用量为0.05~5wt%。当选用油溶性引发剂时,优选将引发剂加入单体中再进行乳化;但选用水溶性引发剂时,优选在单体乳化后,再加入引发剂。引发剂优选为偶氮二异丁基醚盐酸盐,用量优选为分散体质量用量的0.6wt%。
为了得到分散均匀、存储稳定性好的分散液,优选在一定温度下(如35~80℃,优选为40~50℃。)先对单体等进行预乳化,之后需进一步进行高压均质、超声破碎或高压过膜等处理中的至少一项。上述处理设备可以产生强度的破碎能量,单体微滴进一步微细化,且稳定性增强。优选进行高压均质处理。
另外,本发明的织物防水用组合物分散液的优选应加入增溶剂。所述的增溶剂为水溶性的酮、醇或醚类溶剂,这类水溶性的溶剂如:丙酮、异丙醇、甘油、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、3-甲氧基-3-甲基-1-丁醇、乙二醇单甲醚、二乙二醇单甲醚、丙二醇单甲醚、二丙二醇单甲醚、乙二醇二甲醚、二乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚等。其中优选为或二丙二醇二甲醚中的一种。其用量优选为单体质量用量的5~45%。其中,增溶剂更优选为二丙二醇,其质量用量更优选为分散体质量用量的25%。
聚合体系中还可以加入链转移剂,以调节聚合物分子量的大小。链转移剂可选自烷基硫醇化合物如丁基硫醇、辛基硫醇、2-巯基乙醇、十二烷基硫醇等,或次磷酸钠、亚硫酸氢钠等无机盐,其中优选为十二烷基硫醇。其用量哟选为单体质量用量的0.1~3%。
根据需要还可以在聚合前或聚合后向体系中添加PH调节剂,如醋酸、醋酸钠、醋酸铵、盐酸、磷酸、磷酸二氢钾、磷酸氢二钠等。
本发明的织物防水处理用组合物分散液可以单独使用,也可以同其它的防水处理液配合使用。其它的防水处理液可以是无氟防水处理液也可以是含氟防水处理液,但应保证与本发明的分散液复配的处理液在离子性上保持一直,否则可能复配液可能发生沉淀。
本发明的织物防水处理用组合物分散液可以采用常用的方法作用于被处理织物上。通常如下:将分散液用水稀释,再通过浸渍涂布、喷雾涂布等方法是处理液黏着于织物上,织物经过压扎、高温干燥得到处理后的织物。另外,处理液中也可以复配入水性异氰酸酯交联剂乳液,在压扎和高温处理后产生交联,使耐洗性进一步提高。也可以根据需要加入柔软剂、防腐剂等其它助剂。通常可将组合物稀释至0.03~3%的质量浓度。
可用本发明的织物防水处理用组合物分散液处理的织物,可列举如下:天然纤维织物(棉纤、麻、动物毛皮等),合成纤维织物(聚酯纤维、聚酰胺纤维、涤纶纤维、聚乙烯醇、聚丙烯腈、聚氯乙烯、聚丙烯等),半合成纤维织物(人造丝、醋酸纤维等),无机纤维织物(玻璃纤维、碳纤维、石棉纤维等),也可以为它们的混合纤维织物。
本发明所用原料均可市售购得,具体如下:
SA:丙烯酸十八酯(购自广州三旺化工材料有限公司)
SMA:甲基丙烯酸十八酯(购自广州三旺化工材料有限公司)
Si单体:CH2=C(CH3)COOCH2CH2CH2-[Si(CH3)2O]125-CH3(购自安徽艾约塔硅油有限公司)
OH单体:CH2=CHCOOCH2CH2OH(购自东莞市鑫阳化工有限公司)
N-OH单体:N-羟甲基丙烯酰胺(购自山东创赢化工有限公司)
IOTA-2110:HO-R1′-[Si(CH3)2O]n-Si(CH3)2-R1′-OH(其中R1′为二价有机基团,n≥10表示重复单元数,数均分子量为2500,购自安徽艾约塔硅油有限公司)
IOTA-2170:CH3-[Si(CH3)2O]n-Si(CH3)2-R1′-OH(其中R1′为二价有机基团,n≥10表示重复单元数,数均分子量为2800,购自安徽艾约塔硅油有限公司)
实施例1
将76质量份SA、10质量份Si单体、5质量份OH单体、25质量份二丙二醇、1.7质量份S-80、1.0质量份AEO-9、0.5质量份E-1306、5质量份十八烷基三甲基氯化铵、196.5质量份水加入反应釜,搅拌升温至40~50℃进行预乳化。然后在30MPa的压力下高压均质30分钟,将均质液转移至反应釜,开启搅拌。将0.6质量份引发剂AIBA溶解入3质量份的水中形成均一溶液,加入反应釜。然后升温至60℃反应3h,再升温至70℃反应3h,继续升温至80℃反应2h,得到本发明的织物防水用组合物分散液。该分散液离心稳定性优良,即分散液在3000rpm/min的离心转速下30分钟未发生分层或沉淀现象。
实施例2~12及对比例1~5
除杂化分散体配方不同外,其余的配方和工艺与实施例1相同。杂化分散体的具体配方详见表1。
表1杂化分散体配方表(表中均为质量份数)
实施例 | SA | SMA | Si单体 | OH单体 | N-OH单体 | 2110 | 2170 |
实施例1 | 76 | --- | 9 | 5 | --- | 10 | --- |
实施例2 | 80 | --- | 5 | 5 | --- | 10 | --- |
实施例3 | 73 | --- | 9 | 8 | --- | 10 | --- |
实施例4 | 66 | --- | 9 | 5 | --- | 20 | --- |
实施例5 | 70 | --- | 15 | 5 | --- | 10 | --- |
实施例6 | 60 | --- | 25 | 5 | --- | 10 | --- |
实施例7 | 81 | --- | 9 | 5 | --- | 5 | --- |
实施例8 | 79 | --- | 9 | 2 | --- | 10 | --- |
实施例9 | --- | 73 | 9 | --- | 6 | --- | 12 |
实施例10 | --- | 76 | 12 | --- | 4 | 8 | --- |
实施例11 | 70 | --- | 10 | --- | 5 | --- | 15 |
实施例12 | 75 | --- | 12 | 5 | --- | --- | 8 |
对比例1 | 85 | --- | --- | 5 | --- | 10 | --- |
对比例2 | 82 | --- | 3 | 5 | --- | 10 | --- |
对比例3 | 71 | --- | 9 | 5 | --- | 25 | --- |
对比例4 | 71 | --- | 9 | 10 | --- | 10 | --- |
对比例5 | 86 | --- | 9 | 5 | --- | --- | --- |
对比例6 | 70 | --- | 25 | 5 | --- | --- | --- |
对比例7 | 95 | --- | --- | 5 | --- | --- | --- |
注:实施例1~12和对比例4~6获得的分散液离心稳定性优良,即分散液在3000rpm/min的离心转速下30分钟未发生分层或沉淀现象。对比例1获得的分散液在反应结束停止搅拌后即发生分层,对比例2和3获得的分散液在3000rpm/min的离心转速下30分钟后出现油漂或分层现象,故对比例1~3无法获得稳定的分散液,将不进行进一步的性能测试。
测试样品制备
将分散液稀释至0.5%的浓度,并加入占有效成分25wt%的水性异氰酸酯固化剂JX-615H(购自东莞江兴实业有限公司),然后对测试织物布料进行处理,再用压机进行压扎,之后150℃的温度热处理布料1分钟,即得到测试样品。性能测试方法
(1)防水性测试
防水性评价标准按GB/T 4745-1997纺织织物表面抗湿性测定沾水试验执行,详见表2;
表2防水性评价标准:GB/T 4745-1997纺织织物表面抗湿性测定沾水试验
防水等级 | 状态 |
5 | 表面无湿润 |
4 | 表面少量湿润 |
3 | 表面部分湿润 |
2 | 表面湿润 |
1 | 表面全部湿润 |
(2)手感测试
将要测试的面料在室温25℃±2℃,湿度65%±2%的恒温恒湿室内静置24h后,通过手感官进行评价。其中:○:柔软;Δ:一般;×:硬。
(3)连续加工性能测试
配制1Kg浓度为0.5%的分散液,将待处理布料裁剪成20cm×20cm大小,按照样品的制备方法对第一片布料进行处理,之后在按照同样的方法依次对第2~10片布料进行处理。并测试每片布料防水性能,通过防水性能评价分散液的连续加工性。如果第1~n-1块布料的防水等级均为4+以上,第n块布料的防水等级为4+,第n+1块布料的防水等级为4,则该分散液的连续加工性达到n块布料。
(4)耐洗涤性测试
按GB 12799-91抗油抗水防护服安全卫生性能要求中的洗涤试验方法进行洗涤,然后再进行防水性测试。
表3性能测试
以上仅为本发明的具体实施例,但本发明的技术特征并不局限于此。任何以本发明为基础,为实现基本相同的技术效果,所作出地简单变化、等同替换或者修饰等,皆涵盖于本发明的保护范围之中。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (9)
1.一种织物防水用组合物分散液,由端羟基有机硅和丙烯酸酯聚合物形成的杂化分散体、表面活性剂、增溶剂及水组成,其特征在于:所述的端羟基有机硅用式R1-[Si(CH3)2O]x-Si(CH3)2R2表示,其中R1表示一价含羟基基团,R2表示C1~4的一价烷基或与R1相同,x表示重复单元个数,优选大于等于10;所述的丙烯酸酯聚合物至少包含长链烷基丙烯酸酯单体单元、有机硅基丙烯酸酯单体单元和含羟基单体单元;以质量分数计,100质量分数的杂化分散体至多含有端羟基有机硅20质量份,至少含有有机硅基丙烯酸酯单体单元5质量份,至多含有含羟基单体单元8质量份。
2.根据权利要求1所述的织物防水用组合物分散液,其特征在于:以质量分数计,100质量分数的杂化分散体中含有5~20质量份的含有端羟基有机硅、含有5~25质量份的有机硅基丙烯酸酯单体单元、含有2~8质量份的含羟基单体单元。
3.根据权利要求1或2所述的织物防水用组合物分散液,其特征在于:所述的长链烷基丙烯酸酯单体为(甲基)丙烯酸十二酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十八酯和(甲基)丙烯酸二十二酯中的一种或至少两种的混合物。
4.根据权利要求3所述的织物防水用组合物分散液,其特征在于:所述的长链烷基丙烯酸酯单体为丙烯酸十八酯和甲基丙烯酸十八酯中的一种。
5.根据权利要求1或2所述的织物防水用组合物分散液,其特征在于:所述的有机硅基丙烯酸酯单体用式CH2=CRCOO-Q-[Si(CH3)2O]y-CH3表示,其中R为H或烷基,Q为二价有机基团,y表示重复单元个数,优选大于等于4。
6.根据权利要求5所述的织物防水用组合物分散液,其特征在于:所述的有机硅基丙烯酸酯单体为CH2=C(CH3)COOCH2CH2CH2-[Si(CH3)2O]12.5-CH3。
7.根据权利要求1或2所述的织物防水用组合物分散液,其特征在于:所述的含羟基单体为N-羟甲基丙烯酰胺或式CH2=CR′COO-Q′-OH所表示的单体中的一种或至少一种的混合物,其中R′为H或烷基,Q′为二价有机基团。
8.根据权利要求7所述的织物防水用组合物分散液,其特征在于:所述的含羟基单体为N-羟甲基丙烯酰胺或CH2=CHCOOCH2CH2OH中的一种。
9.根据权利要求1或2所述的织物防水用组合物分散液,其特征在于:所述的端羟基有机硅的数均分子量为2000~3000。
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