CN115322287A - Water-proofing agent using reactive non-ionic emulsifier and preparation method thereof - Google Patents
Water-proofing agent using reactive non-ionic emulsifier and preparation method thereof Download PDFInfo
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- CN115322287A CN115322287A CN202211119544.0A CN202211119544A CN115322287A CN 115322287 A CN115322287 A CN 115322287A CN 202211119544 A CN202211119544 A CN 202211119544A CN 115322287 A CN115322287 A CN 115322287A
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- Prior art keywords
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- monomer
- fluorine
- acrylate
- methacrylate
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 239000012875 nonionic emulsifier Substances 0.000 title claims abstract description 11
- 238000004078 waterproofing Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- 239000011737 fluorine Substances 0.000 claims abstract description 38
- 238000004132 cross linking Methods 0.000 claims abstract description 32
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 15
- -1 alkyl (methyl) acrylate Chemical compound 0.000 claims abstract description 12
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 19
- 239000005871 repellent Substances 0.000 claims description 15
- 230000002940 repellent Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical group O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 8
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- ILCOCZBHMDEIAI-UHFFFAOYSA-N 2-(2-octadecoxyethoxy)ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCO ILCOCZBHMDEIAI-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229940098760 steareth-2 Drugs 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims 1
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 8
- 150000001450 anions Chemical class 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 16
- 239000004677 Nylon Substances 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- 241000272041 Naja Species 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention provides a waterproof agent using a reactive nonionic emulsifier, which comprises the following components in percentage by mass: 7 to 21 percent of fluorine-containing alkyl acrylate, 5 to 15 percent of non-fluorine non-crosslinking monomer, 1 to 5 percent of non-fluorine non-crosslinking hard monomer, 3 to 10 percent of halogen-containing olefin monomer, 1 to 5 percent of crosslinking monomer, 2 to 15 percent of organic solvent, 0.01 to 0.5 percent of molecular weight regulator, 1 to 8 percent of surfactant, 0.01 to 0.5 percent of initiator and the balance of water; the non-fluorine non-crosslinking monomer is univalent straight-chain alkyl (methyl) acrylate with the carbon chain length of more than or equal to 8; the non-fluorine non-crosslinking hard monomer is alkyl (meth) acrylate with a carbon chain less than or equal to 4; the surfactant is a compound of a cationic surfactant and a nonionic surfactant; the cationic surfactant accounts for 20-40 wt% of the compound. The waterproof agent is waterproof under the combined action of the components; the stability is good; the paint has strong yellowing resistance and anion resistance, stable performance and is suitable for more severe application scenes.
Description
Technical Field
The invention belongs to the technical field of waterproof agents, and particularly relates to a waterproof agent using a reactive nonionic emulsifier and a preparation method thereof.
Background
In emulsion polymerization, a proper amount of emulsifier is added to play roles of emulsification, dispersion and solubilization and play a key role in the stability of the emulsion. The fluorine-containing waterproof agent has excellent performance, a large amount of perfluoroalkyl acrylate is required to be used in the synthesis process, the fluorine-containing material has strong hydrophobicity, and in order to maintain the stability of the emulsion of the fluorine-containing waterproof agent, a large amount of hydrophilic emulsifier is required to be used in the actual synthesis process, the emulsifier is adsorbed on the surface of emulsion particles in a physical adsorption mode and is easy to desorb, so that the emulsion is unstable, a fluorocarbon chain is not easy to fix on the surface of a fabric, and the emulsifier is remained on the surface of the fabric after the fabric is finished and shaped by the waterproof agent, so that the waterproof effect is reduced due to the hydrophilicity of the emulsifier. The reactive emulsifier has a good emulsifying effect, can be copolymerized with monomers in a reaction system, can improve the stability of the emulsion, can better fix fluorocarbon chains on the surface of a fabric, can resist anions and improve the stability of the emulsion in the using process.
The use of the water repellent using the cationic surfactant is limited in many ways, for example, the water repellent cannot be co-bathed with an anionic assistant, cloth to be finished needs to be cleaned, and the finished cloth is easy to yellow.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a waterproofing agent using a reactive nonionic emulsifier, which has excellent waterproofing performance, and a method for preparing the same.
The invention provides a waterproof agent using a reactive nonionic emulsifier, which comprises the following components in parts by mass:
7 to 21 percent of fluorine-containing alkyl acrylate, 5 to 15 percent of non-fluorine non-crosslinking monomer, 1 to 5 percent of non-fluorine non-crosslinking hard monomer, 3 to 10 percent of halogen-containing olefin monomer, 1 to 5 percent of crosslinking monomer, 2 to 15 percent of organic solvent, 0.01 to 0.5 percent of molecular weight regulator, 1 to 8 percent of surfactant, 0.01 to 0.5 percent of initiator and the balance of water;
the non-fluorine non-crosslinking monomer is a univalent straight-chain alkyl acrylate monomer with the carbon chain length of more than or equal to 8 and/or a univalent straight-chain alkyl methacrylate monomer with the carbon chain length of more than or equal to 8;
the non-fluorine non-crosslinking hard monomer is an alkyl acrylate monomer with a carbon chain length less than or equal to 4 and/or an alkyl methacrylate monomer with a carbon chain length less than or equal to 4;
the surfactant is a compound of a cationic surfactant and a nonionic surfactant; the cationic surfactant accounts for 20-40 wt% of the compound.
In the present invention, the fluoroalkyl acrylate has the general formula CH 2 ＝C(-X)-C(＝O)-Y-Z-R f ；
X is selected from H, a monovalent organic group or halogen;
y is selected from-O-or-NH-;
z is a direct bond or a divalent organic group;
the R is f Is C4-C18 linear chain or branched chain fluoroalkyl.
In the present invention, the non-fluorine non-crosslinking monomer is one or more of lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate and behenyl methacrylate;
the non-fluorine non-crosslinking hard monomer is one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.
In the present invention, the halogen-containing olefin monomer is vinylidene chloride or vinyl chloride.
The crosslinking monomer is one or more of N-hydroxymethyl acrylamide, diacetone acrylamide, 3-chloro-2-hydroxypropyl methacrylate, acetoacetoxy ethyl methacrylate, glycidyl methacrylate and hydroxyethyl methacrylate.
The organic solvent is selected from one or more of dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, acetone and butanone;
the molecular weight regulator is selected from one or more of n-dodecyl mercaptan, mercaptoethanol and n-decyl mercaptan;
the non-ionic surfactant is a compound of a non-reactive non-ionic surfactant and a reactive non-ionic surfactant in a mass ratio of 5-20; the HLB value of the non-reactive nonionic surfactant is less than or equal to 11.
In the present invention, the cationic surfactant is selected from one or more of Solvay TEP-88, TEP-90, craine TQSV-IPA and Nomoon DE-T esterquat;
the non-reactive nonionic surfactant is selected from one or more of AEO-5 (HLB is 10), 1305 (HLB is 10.5), S2 steareth-2 (HLB is 4.9), peregal O-5 (HLB is 8.5-9.5) and span-60 (HLB is 4.7);
the reactive nonionic surfactant is selected from one or more of Japanese adico ER-20, ER-30 and ER-40.
In the present invention, the initiator is selected from one or more of V50, VA044, VA-061 and ammonium persulfate.
The invention provides a preparation method of a waterproof agent using a reactive nonionic emulsifier, which comprises the following steps:
mixing a cationic surfactant, a nonionic surfactant, fluoroalkyl acrylate, a non-fluorine non-crosslinking monomer, a non-fluorine non-crosslinking hard monomer, a crosslinking monomer, an organic solvent and water, heating to 48-53 ℃, melting, stirring and homogenizing to obtain a pre-emulsion;
and (2) cooling the pre-emulsion to 23-28 ℃, then dripping a halogen-containing olefin monomer, uniformly stirring, heating to 58-63 ℃, dripping an aqueous solution of an initiator, heating to 68-73 ℃, reacting for 230-250 min, cooling, and filtering to obtain the waterproof agent.
In the present invention, the homogenization pressure is 38 to 43MPa, and in a specific example, the homogenization pressure is 40MPa.
The invention provides a waterproof agent using a reactive nonionic emulsifier, which comprises the following components in parts by mass: 7 to 21 percent of fluorine-containing alkyl acrylate, 5 to 15 percent of non-fluorine non-crosslinking monomer, 1 to 5 percent of non-fluorine non-crosslinking hard monomer, 3 to 10 percent of halogen-containing olefin monomer, 1 to 5 percent of crosslinking monomer, 2 to 15 percent of organic solvent, 0.01 to 0.5 percent of molecular weight regulator, 1 to 8 percent of surfactant, 0.01 to 0.5 percent of initiator and the balance of water; the non-fluorine non-crosslinking monomer is a univalent linear alkyl acrylate monomer with the carbon chain length of more than or equal to 8 and/or a univalent linear alkyl methacrylate monomer with the carbon chain length of more than or equal to 8; the non-fluorine non-crosslinking hard monomer is an alkyl acrylate monomer with a carbon chain length of less than or equal to 4 and/or a univalent linear alkyl methacrylate monomer with a carbon chain length of more than or equal to 8; the surfactant is a compound of a cationic surfactant and a nonionic surfactant; the cationic surfactant accounts for 20-40 wt% of the compound. The waterproof agent provided by the invention is waterproof under the combined action of the components; the stability is good; the paint has strong yellowing resistance and anion resistance, stable performance and is suitable for more severe application scenes.
Detailed Description
To further illustrate the present invention, a water repellent using a reactive nonionic emulsifier and a method for preparing the same according to the present invention will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
3.2g of esterquat TEP-88,1.1g of AEO-5 (HLB 10), 4.6g of ER-20, and 40g of C were weighed 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 30g of octadecyl acrylate, 5.5g of methyl methacrylate, 32g of dipropylene glycol monomethyl ether, 3.6g of acetoacetoxy ethyl methacrylate, 0.1g of n-dodecyl mercaptan and 172g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min, and homogenized twice under high pressure at 40MPa to form a pre-emulsion;
and (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, heating to 70 ℃ after dripping, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Example 2
2.1g esterquat TEP-88,1.1g AEO-5 (HLB 10), 5.7g ER-20, 45g C were weighed 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 24g of octadecyl acrylate, 5.5g of methyl methacrylate, 32g of dipropylene glycol monomethyl ether, 3.6g of acetoacetoxy ethyl methacrylate, 0.1g of n-dodecyl mercaptan and 181g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min, and homogenized twice under the high pressure of 40MPa to form a pre-emulsion.
And (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, heating to 70 ℃ after dripping, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Example 3
4.5g esterquat TEP-88,1.9g 1305 (HLB 10.5), 4.7g ER-30, 40g C were weighed 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 28g of stearyl acrylate, 5.5g of methyl methacrylate, 35g of tripropylene glycol, 3.6g of acetoacetoxyethyl methacrylate, 0.1g of n-dodecyl mercaptan, and 17 g of water6g of the mixture is put in a beaker, heated to 50 ℃, melted and stirred for 5min at a high speed, and homogenized twice under 40MPa to form pre-emulsion.
And (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, dripping, heating to 70 ℃, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Example 4
3.4g esterquat Kelain TQSV-IPA,1.1g AEO-5 (HLB 10), 5.7g ER-20, 45g C 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 24g of octadecyl acrylate, 5.5g of methyl methacrylate, 32g of dipropylene glycol monomethyl ether, 3.6g of acetoacetoxy ethyl methacrylate, 0.1g of n-dodecyl mercaptan and 181g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min, and homogenized twice under the high pressure of 40MPa to form a pre-emulsion.
And (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, heating to 70 ℃ after dripping, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Example 5
3.4g esterquat TEP-88,1.1g AEO-5 (HLB 10), 5.7g ER-20, 48g C were weighed 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 35g of octadecyl acrylate, 3.1g of butyl acrylate, 32g of dipropylene glycol monomethyl ether, 3.6g of acetoacetoxyethyl methacrylate, 0.1g of n-dodecyl mercaptan and 176g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min and homogenized twice under high pressure at 40MPa to form a pre-emulsion.
And (3) uniformly stirring the pre-emulsion, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, dropwise adding, heating to 70 ℃, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Example 6
Weighing 2.1g of ester quaternary ammonium salt TEP-88,1.2g of peregal O-5 (HLB is 8.5-9.5), 7.0g of ER-30 and 43g of C 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 30g of octadecyl acrylate, 5.5g of methyl methacrylate, 32g of dipropylene glycol monomethyl ether, 3.6g of acetoacetoxy ethyl methacrylate, 0.1g of n-dodecyl mercaptan and 181g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min, and homogenized twice under the high pressure of 40MPa to form a pre-emulsion.
And (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, heating to 70 ℃ after dripping, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Comparative example 1
5.5g esterquat TEP-88,1.1g AEO-5 (HLB 10), 4.2g ER-20, 43g C were weighed 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 30g of octadecyl acrylate, 5.5g of methyl methacrylate, 35g of tripropylene glycol, 3.6g of acetoacetoxyethyl methacrylate, 0.1g of n-dodecyl mercaptan and 176g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min, and homogenized twice under high pressure at 40MPa to form a pre-emulsion.
And (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, dripping, heating to 70 ℃, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
Comparative example 2
The cationic surfactant is octadecyl trimethyl ammonium chloride
Weighing 4.7g of octadecyl trimethyl ammonium chloride 1831,1.1g of AEO-5 (HLB 10), 5.6g of ER-20, 40g of C 6 F 13 C 2 H 4 OCOC(CH 3 )＝CH 2 30g of octadecyl acrylate, 5.5g of methyl methacrylate, 32g of dipropylene glycol monomethyl ether, 3.6g of acetoacetoxy ethyl methacrylate, 0.1g of n-dodecyl mercaptan and 172g of water are put in a beaker, heated to 50 ℃, melted and stirred, stirred at high speed for 5min, and homogenized twice under the high pressure of 40MPa to form a pre-emulsion.
And (3) cooling the pre-emulsion to 25 ℃, dripping 11g of vinylidene chloride, uniformly stirring, heating to 60 ℃, dissolving 0.56g of initiator V50 in water, dripping, heating to 70 ℃, reacting for 4 hours, cooling to normal temperature, and filtering with nylon filter cloth to obtain the waterproof agent.
The fluorine-containing waterproofing agents of the nonionic reactive surfactants prepared in the examples and the comparative examples were subjected to a water-repellent effect test, a storage stability test, a mechanical stability test, a yellowing resistance test, and an anion resistance test, respectively.
A. And (3) testing the waterproof effect:
in order to verify the waterproof effect of the reactive carbon six-waterproofing agent, the waterproof effect can be inspected by a standard method so as to facilitate comparative analysis. In this application, the standard method for testing fabric for water repellency is AATCC-22.
TABLE 1 Water resistance test grades and states
| Water resistance rating | Status of state |
| 100 | The surface is not wet or no water drops are attached |
| 90 | The state of slight water drop adhesion on the surface |
| 80 | Wetting state of individual parts of surface |
| 70 | State of surface half-micro-wetting |
| 50 | State of wetting of the entire surface |
| 0 | State of complete wetting |
B. Storage stability experiment:
and standing the fluorine-containing waterproof agent with the solid content of 30% at 40 ℃ for 30 days, and observing the precipitation condition of the emulsion. And (4) judging the standard: good component: no precipitation at all; Δ: a small amount of precipitate is generated; o: there are many deposits
C. Mechanical stability test:
the fluorine-containing water repellent was diluted to 10g/L with water, stirred with a high-speed disperser at 3000r/min for 30min, and then the solid impurities were filtered with black filter paper. And (4) judging the standard: good: completely free of solid impurities; Δ: a small amount of solid impurities exist; o: there are many solid impurities.
D. Yellowing resistance test:
diluting the fluorine-containing waterproof agent to 50g/L with water, carrying out white Chunzhan one-dip one-roll processing, shaping at 170 ℃, drying, and comparing with a standard colorimetric card. And (4) judging the standard: good component: no yellowing at all; Δ: a little yellowing; o: the yellowing is obvious.
E. Anion resistance test:
diluting the fluorine-containing waterproof agent to 10g/L by using water, taking 100g of diluent, respectively adding 2g of stiffening agent and antistatic agent, mixing and stirring, and standing to observe whether floccules or precipitates are generated. And (4) judging the standard: good: no precipitation at all; Δ: a little precipitate; o: the precipitation was evident.
The fluorine-containing waterproof agent prepared in examples 1 to 6 and comparative examples 1 to 2 is diluted to 10g/L with water according to the test method, cloth samples such as Naja, polyester taffeta, nylon yarn and the like are taken, soaked and rolled, dried at 100 ℃, subjected to setting heat treatment at 170 ℃ for 40 seconds, cooled at room temperature and remoistened, and then the waterproof effect is measured, and the results are shown in Table 2:
TABLE 2 results of performance test of the water repellent prepared in examples and comparative examples
From the above examples, it can be seen that by introducing esterquat (cationic surfactant), a nonionic surfactant with HLB less than 11, and a reactive nonionic surfactant, the carbon six-component water repellent with excellent water repellent effect is prepared, and has improved performance and stability, yellowing resistance, and excellent anion resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A water repellent using a reactive nonionic emulsifier, comprising the following components in mass fraction:
7 to 21 percent of fluorine-containing alkyl acrylate, 5 to 15 percent of non-fluorine non-crosslinking monomer, 1 to 5 percent of non-fluorine non-crosslinking hard monomer, 3 to 10 percent of halogen-containing olefin monomer, 1 to 5 percent of crosslinking monomer, 2 to 15 percent of organic solvent, 0.01 to 0.5 percent of molecular weight regulator, 1 to 8 percent of surfactant, 0.01 to 0.5 percent of initiator and the balance of water;
the non-fluorine non-crosslinking monomer is a univalent straight-chain alkyl acrylate monomer with the carbon chain length of more than or equal to 8 and/or a univalent straight-chain alkyl methacrylate monomer with the carbon chain length of more than or equal to 8;
the non-fluorine non-crosslinking hard monomer is an alkyl acrylate monomer with a carbon chain length of less than or equal to 4 and/or an alkyl methacrylate monomer with a carbon chain length of less than or equal to 4;
the surfactant is a compound of a cationic surfactant and a nonionic surfactant; the cationic surfactant accounts for 20-40 wt% of the compound.
2. The water repellent according to claim 1, wherein the fluorine-containing alkyl acrylate has the formula CH 2 ＝C(-X)-C(＝O)-Y-Z-R f ；
X is selected from H, a monovalent organic group or halogen;
y is selected from-O-or-NH-;
z is a direct bond or a divalent organic group;
said R is f Is C4-C18 linear chain or branched chain fluoroalkyl.
3. A water repellent agent according to claim 1, wherein the non-fluorine non-crosslinking monomer is one or more of dodecyl acrylate, dodecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, behenyl acrylate and behenyl methacrylate;
the non-fluorine non-crosslinking hard monomer is one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.
4. A waterproofing agent according to claim 1 wherein the halogen-containing olefin monomer is vinylidene chloride or vinyl chloride.
5. The water repellent according to claim 1, wherein the crosslinking monomer is one or more of N-methylolacrylamide, diacetone acrylamide, 3-chloro-2-hydroxypropyl methacrylate, acetoacetoxyethyl methacrylate, glycidyl methacrylate and hydroxyethyl methacrylate.
6. A water repellent according to claim 1, wherein said organic solvent is selected from one or more of dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, acetone and methyl ethyl ketone;
the molecular weight regulator is selected from one or more of n-dodecyl mercaptan, mercaptoethanol and n-decyl mercaptan;
the non-ionic surfactant is a compound of a non-reactive non-ionic surfactant and a reactive non-ionic surfactant in a mass ratio of 5-20.
7. A water repellent according to claim 6 wherein the cationic surfactant is selected from one or more of Solvay TEP-88, TEP-90, clariane TQSV-IPA and Nomoon DE-T esterquat;
the non-reactive nonionic surfactant is selected from one or more of AEO-5, 1305, S2 steareth-2, peregal O-5 and span-60;
the reactive nonionic surfactant is selected from one or more of Japanese adico ER-20, ER-30 and ER-40.
8. A method for producing a water repellent using a reactive nonionic emulsifier according to any one of claims 1 to 7, comprising the steps of:
mixing a cationic surfactant, a nonionic surfactant, fluoroalkyl acrylate, a non-fluorine non-crosslinking monomer, a non-fluorine non-crosslinking hard monomer, a crosslinking monomer, an organic solvent and water, heating to 48-53 ℃, and carrying out melt stirring and homogenization to obtain a pre-emulsion;
and (2) cooling the pre-emulsion to 23-28 ℃, then dripping a halogen-containing olefin monomer, uniformly stirring, heating to 58-63 ℃, dripping an aqueous solution of an initiator, heating to 68-73 ℃, reacting for 230-250 min, cooling, and filtering to obtain the waterproof agent.
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| CN113089325A (en) * | 2021-06-08 | 2021-07-09 | 广东德美精细化工集团股份有限公司 | Durable short-chain fluorine-containing water and oil repellent agent and preparation method thereof |
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| CN1620492A (en) * | 2002-01-21 | 2005-05-25 | 大金工业株式会社 | Aqueous water-and oil-repellent dispersion |
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