CN108504313B - Acrylate powder adhesive with core-shell structure and preparation method thereof - Google Patents
Acrylate powder adhesive with core-shell structure and preparation method thereof Download PDFInfo
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- CN108504313B CN108504313B CN201810236590.6A CN201810236590A CN108504313B CN 108504313 B CN108504313 B CN 108504313B CN 201810236590 A CN201810236590 A CN 201810236590A CN 108504313 B CN108504313 B CN 108504313B
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- emulsion
- acrylate
- monomer
- core
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 239000000853 adhesive Substances 0.000 title claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 239000000839 emulsion Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000001694 spray drying Methods 0.000 claims abstract description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000007853 buffer solution Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- -1 polyoxyethylene sec-octylphenol Polymers 0.000 claims description 5
- 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 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a core-shell structure water-based acrylate powder adhesive and a preparation method thereof. The preparation method comprises the steps of adding the emulsifier into water, adding the soft monomer, the hard monomer and the functional monomer, uniformly mixing, and magnetically stirring to form the pre-emulsion. Heating to 75-80 ℃, adding a buffer solution into the reactor, and adding N2Dripping 20-50% of pre-emulsion and 1/2-3/4% of initiator in mass in an atmosphere, and stirring for reaction to prepare primary emulsion; after heat preservation, dropwise adding the rest initiator and the pre-emulsion, adding a chain transfer agent, after dropwise adding, preserving heat for 1-2 h, cooling and discharging; adding coupling agent, nano calcium carbonate or SiO2Dispersing in water solution of PVA, ultrasonic treating at room temperature, and spray drying. The powder adhesive disclosed by the invention is environment-friendly and non-toxic, ensures the bonding performance, has good water resistance, can be used under complex and precise conditions, and is low in production cost, simple to operate and short in required time.
Description
Technical Field
The invention relates to a pressure-sensitive adhesive, in particular to a core-shell structure water-based acrylate powder adhesive and a preparation method thereof; belongs to the field of pressure sensitive adhesive material production.
Background
The water-based acrylate pressure-sensitive adhesive is developed rapidly in recent years, is widely applied to aspects such as medical adhesive tapes, labels, conductive adhesives, surface protection adhesive tapes and pressure-sensitive labels, and has the advantages of low cost, safety, no public nuisance, easy synthesis operation, short polymerization time, strong rheological controllability and the like compared with solvent-based acrylate pressure-sensitive adhesives; along with the improvement of environmental awareness, the non-toxic and pollution-free aqueous acrylate adhesive is increasingly emphasized, and the demand and application range of the adhesive are expanded and are in a continuously rising trend. However, the aqueous acrylate pressure-sensitive adhesive has strong bonding performance, and is difficult to be applied to complex and precise spaces, such as the fixation of screw parts, which limits the use of the aqueous acrylate pressure-sensitive adhesive.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the preparation method of the water-based acrylate powder adhesive with the core-shell structure is obtained by improving the preparation of the acrylate pressure-sensitive adhesive by using a simple and efficient experimental scheme, so that the preparation method is environment-friendly, low in cost and beneficial to further development and transformation of products.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of acrylate powder adhesive with a core-shell structure comprises the following steps:
1) adding an emulsifier into water, then adding a soft monomer, a hard monomer and a functional monomer, uniformly mixing, and magnetically stirring for 10-30 min to form a pre-emulsion; the soft monomer, the hard monomer and the functional monomer form a monomer; the addition amount of the emulsifier is 1-3% of the total mass of the monomers; the addition amount of the water is 20-40% of the total mass of the monomers;
the soft monomer is one or more of vinyl acetate, ethyl methacrylate, isooctyl acrylate, isodecyl acrylate, hydroxyethyl acrylate, cyclohexyl acrylate and butyl acrylate; the addition amount of the soft monomer is 65-82% of the total mass of the monomers;
the functional monomer is one or more of itaconic acid, acrylic acid, methacrylic acid, acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the addition amount of the functional monomer is 1-1.5% of the total mass of the monomer;
the hard monomer is one or more of methyl methacrylate, acrylonitrile, styrene and methyl acrylate; the addition amount of the hard monomer is 12-17% of the total mass of the monomers;
2) heating to 75-80 ℃, adding a buffer solution into the reactor, and adding N2In an atmosphere, simultaneously dripping 20-50% of pre-emulsion and 1/2-3/4% of initiator by mass, and stirring for reaction for 30-60 min to prepare initial emulsion; after the temperature is kept for 10-40 min, dropwise adding the rest initiator and pre-emulsion, and adding a chain transfer agent for 3-4 h;
3) after the dropwise adding is finished, preserving the heat at the temperature of 80-90 ℃ for 1-2 h, cooling and discharging to form an emulsion;
4) adding coupling agent, nano calcium carbonate or SiO into the step 3)2Dispersing the polyvinyl alcohol aqueous solution at 40-50 ℃ for 3-15 min, and then carrying out ultrasonic treatment at room temperature for 10-30 min; the coupling agent is one or more of gamma-aminopropyltriethoxysilane, 3-glycidyl ether propyl methyldiethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, vinyl trimethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma- (methacryloyloxy) propyl trimethoxysilane;
5) and 4) spray drying the product obtained in the step 4) to obtain the acrylate powder adhesive with the core-shell structure.
To further achieve the object of the present invention, preferably, the emulsifier is one or more of polyoxyethylene sec-octylphenol ether-10 (OP-10), Sodium Dodecyl Sulfate (SDS), nonylphenol polyoxyethylene ether (TX-10), disodium ethoxylated nonylphenol sulfosuccinate half ester, sodium dodecylbenzenesulfonate (LAS), and Tween 20 (Tween-20).
Preferably, the buffer solution is 0.5 wt% to 0.7 wt% of NaHCO3An aqueous solution.
Preferably, the initiator is one or more of ammonium sulfate, potassium persulfate, sodium bisulfite and azobisisobutyronitrile.
Preferably, the addition amount of the initiator is 0.1-0.8% of the total mass of the monomers.
Preferably, the chain transfer agent is dodecyl mercaptan, and the using amount of the chain transfer agent is 0.1-0.5% of the total mass of the monomers.
Preferably, the spray drying process parameters are that the inlet temperature is 150-180 ℃, the outlet temperature is 75-90 ℃, and the drying time is 3-10 min.
Preferably, the coupling agent accounts for 0.01-0.15% of the mass of the emulsion; the nano calcium carbonate or SiO2Accounting for 2-5% of the mass of the emulsion; the polyvinyl alcohol aqueous solution accounts for 10-30 wt% of the emulsion.
Preferably, the total adding amount of the buffer solution is 0.1-0.5% of the total amount of the monomers; the total addition amount of the initiator is 0.4-2.0% of the total amount of the monomers; the addition amount of the chain transfer agent is 0.1-0.8% of the total amount of the monomers.
The acrylate powder adhesive with the core-shell structure prepared by the preparation method; the pressure-sensitive adhesive is white powder, the initial adhesion reaches 12-19#, the peeling force is 9.0-13.0N/25mm, and the permanent adhesion is 200-350 h; the water absorption rate is 1.2-15.0%, and the solid content is 70-85%.
The whole reaction process in the step 1) and the step 2) is carried out under the condition of stirring, and the stirring speed is 150-350 r/min.
Compared with the prior art, the invention has the following advantages:
1) the invention discloses a coupling agent and hydrophobic nano material modified acrylate polymer emulsion, and utilizes the coupling agent to make hydrophobic nano SiO2Or calcium carbonate and acrylate polymer are uniformly and firmly combined together and nano SiO is utilized2Or the strong bonding energy between the calcium carbonate and the coupling agent and the base material greatly enhances the adhesive property of the pressure-sensitive adhesive.
2) The powder pressure-sensitive adhesive prepared by spray drying is different from the existing liquid adhesive, the product is solid, can be packaged by paper bags like cement, does not need to be packaged by an iron bucket or a plastic bucket, can greatly reduce the cost, can reduce Volatile Organic Compounds (VOC), and is convenient to transport and store for a long time.
3) Finally, the invention adopts a spray drying mode to quickly and efficiently prepare the acrylate powder adhesive with the core-shell structure, uniformly and firmly bonds the coupling agent, the nano particles and the adhesive together, and greatly shortens the required preparation time.
4) Core-shell structure of the inventionThe acrylate powder adhesive not only ensures the bonding performance, but also ensures the hydrophobic nano SiO2Or the existence of calcium carbonate, so that the powder adhesive also has high pressure sensitivity and high water resistance, can be used in the sealing of complex precision equipment, and has the advantages of low production cost, simple operation, environmental protection and wide application prospect.
Detailed Description
The invention will be further illustrated by the following examples for a better understanding of the invention, but the scope of the invention as claimed is not limited to the examples shown.
Example 1
1) Adding 2.0g of OP-10 into a conical flask, adding 50g of deionized water, magnetically stirring until an emulsifier is dissolved, sequentially adding 70g of butyl acrylate, 70g of isooctyl acrylate, 8g of hydroxyethyl acrylate, 15g of vinyl acetate, 20g of methyl methacrylate and 4g of hydroxyethyl methacrylate, and stirring (stirring speed of 300r/min) for 30min to form a pre-emulsion.
2) To a 500ml four-necked flask equipped with a thermometer, a condenser and a stirring device, 0.2g NaHCO was added3Then adding 40ml of deionized water, reacting at 80 ℃, and stirring until the deionized water is dissolved; dividing the pre-emulsion into two parts, simultaneously dripping 30% of pre-emulsion and 15g of ammonium persulfate aqueous solution, and preserving heat for 30min after dripping for 30 min; and simultaneously dropwise adding the rest of pre-emulsion containing 4 drops of dodecyl mercaptan and 6g of ammonium persulfate aqueous solution, and finishing dropwise adding for 3.5 hours.
3) The reaction temperature is increased to 90 ℃, and the temperature is kept for 1h under the stirring condition, so that the water-based acrylate pressure-sensitive adhesive emulsion is obtained.
4) Adding a coupling agent gamma-aminopropyltriethoxysilane accounting for 0.1 percent of the mass of the emulsion, nano calcium carbonate accounting for 3 percent of the mass of the emulsion and a polyvinyl alcohol aqueous solution accounting for 15 percent of the mass of the emulsion in sequence in the step 3), dispersing for 10min at the temperature of 40 ℃ at 5000r/min, and then carrying out ultrasonic treatment for 20min at room temperature.
5) And (3) spray drying the product obtained in the step 4) to obtain the white acrylate powder adhesive with the core-shell structure, wherein the spray drying process parameters are that the inlet temperature is 150 ℃, the outlet temperature is 80 ℃, and the drying time is 8 min.
Example 2
1) Adding 2.0g of sodium dodecyl sulfate into a conical flask, adding 45g of deionized water, magnetically stirring until an emulsifier is dissolved, sequentially adding 60g of butyl acrylate, 80g of isooctyl acrylate, 8g of hydroxyethyl acrylate, 10g of vinyl acetate, 25g of methyl methacrylate and 4g of hydroxyethyl methacrylate, and stirring (stirring speed of 300r/min) for 20min to form a pre-emulsion.
2) To a 500ml four-necked flask equipped with a thermometer, a condenser and a stirring device, 0.3g of NaHCO was added3Then adding 40ml of deionized water, reacting at 80 ℃, and stirring until the deionized water is dissolved; dripping 30% of pre-emulsion and 15g of ammonium persulfate aqueous solution simultaneously, and preserving heat for 30min after dripping for 30 min; and simultaneously dropwise adding the rest of the pre-emulsion and 6g of ammonium persulfate aqueous solution for 3 h.
3) The reaction temperature is increased to 90 ℃, and the temperature is kept for 1.5 hours under the stirring condition, so as to obtain the water-based acrylate pressure-sensitive adhesive emulsion.
4) Adding gamma-aminopropyltriethoxysilane accounting for 0.05 percent of the mass of the emulsion, 3-glycidyl ether propyl methyl diethoxy silane coupling agent accounting for 0.05 percent of the mass of the emulsion, 5 percent of nano calcium carbonate and 15 percent of polyvinyl alcohol aqueous solution in sequence in the step 3), dispersing for 15min at 6000r/min at 40 ℃, and then carrying out ultrasonic treatment for 20min at room temperature.
5) And (3) spray drying the product obtained in the step (4) to obtain the white core-shell structure acrylate powder adhesive, wherein the spray drying process parameters are that the inlet temperature is 180 ℃, the outlet temperature is 80 ℃, and the drying time is 10 min.
Example 3
1) Adding 2.0g of nonylphenol polyoxyethylene ether ammonium sulfate into a conical flask, adding 50g of deionized water, magnetically stirring until an emulsifier is dissolved, sequentially adding 70g of butyl acrylate, 70g of isooctyl acrylate, 8g of hydroxyethyl acrylate, 10g of vinyl acetate, 25g of methyl methacrylate and 4g of hydroxyethyl methacrylate, and stirring (stirring speed of 300r/min) for 30min to form a pre-emulsion.
2) To a 500ml four-necked flask equipped with a thermometer, a condenser and a stirring device, 0.2g NaHCO was added3Then adding 50ml of deionized water, reacting at 75 ℃, and stirring until the deionized water is dissolved; dropping 30% of pre-emulsion and 15g of ammonium persulfate aqueous solution simultaneously, and preserving heat for 30min after dropping for 40minmin; and simultaneously dropwise adding the rest of the pre-emulsion and 6g of ammonium persulfate aqueous solution for 3.5 h.
3) The reaction temperature is raised to 85 ℃, and the temperature is kept for 1h under the stirring condition, so that the water-based acrylate pressure-sensitive adhesive emulsion is obtained.
4) Adding gamma-aminopropyltriethoxysilane as coupling agent in 0.1 wt% and SiO in 3 wt% into the emulsion in step 3)2Dispersing polyvinyl alcohol aqueous solution accounting for 20 wt% of the emulsion at 40 ℃ at 4500r/min for 15min, and then performing ultrasonic treatment at room temperature for 20 min.
5) And (3) spray drying the product obtained in the step (4) to obtain the white core-shell structure acrylate powder adhesive, wherein the spray drying process parameters are that the inlet temperature is 160 ℃, the outlet temperature is 80 ℃, and the drying time is 5 min.
Example 4
1) Adding 2.0g of OP-10 into a conical flask, adding 45g of deionized water, magnetically stirring until an emulsifier is dissolved, sequentially adding 70g of butyl acrylate, 78g of isooctyl acrylate, 10g of vinyl acetate, 25g of methyl methacrylate, 2g of hydroxyethyl methacrylate and 2g of acrylic acid, and stirring (stirring speed of 300r/min) for 25min to form a pre-emulsion.
2) To a 500ml four-necked flask equipped with a thermometer, a condenser and a stirring device, 0.3g of NaHCO was added3Then adding 40ml of deionized water, reacting at 80 ℃, and stirring until the deionized water is dissolved; dripping 30% of pre-emulsion and 15g of ammonium persulfate aqueous solution simultaneously, and preserving heat for 30min after dripping for 30 min; and simultaneously dropwise adding the rest of the pre-emulsion and 6g of ammonium persulfate aqueous solution for 3.5 h.
3) The reaction temperature is increased to 90 ℃, and the temperature is kept for 1h under the stirring condition, so that the water-based acrylate pressure-sensitive adhesive emulsion is obtained.
4) Adding gamma-aminopropyl triethoxysilane as coupling agent 0.1 wt% and SiO 5 wt% into the emulsion in sequence in step 3)2Dispersing polyvinyl alcohol aqueous solution accounting for 25 wt% of the emulsion at the temperature of 45 ℃ at 6000r/min for 10min, and then carrying out ultrasonic treatment at room temperature for 15 min.
5) And (3) spray drying the product obtained in the step 4) to obtain the white core-shell structure acrylate powder adhesive, wherein the spray drying process parameters are that the inlet temperature is 170 ℃, the outlet temperature is 85 ℃, and the drying time is 7 min.
The core-shell acrylate powder adhesives obtained in examples 1 to 4 were observed to be white powders.
The products obtained in the above examples were subjected to performance tests, and the results are shown in table 1.
TABLE 1 products for Performance testing
The solids content in table 1 was calculated as follows:
X＝m1/m×100％
in the formula: x is solid content (wt%); m is1Is the total mass (g) of the monomers; m is total mass (g) of the emulsion
The water absorption was calculated as follows:
A＝(a2‐a1)/a1×100％
in the formula: a is water absorption (wt%); a is1Is the mass (g) of the powder adhesive before water absorption; a is2The mass (g) of the powder adhesive after water absorption;
and (3) testing initial adhesion: according to the GB/T4852-2002 standard, measuring the initial adhesion of the adhesive;
and (3) testing the peeling force: measuring the stripping force of the adhesive according to the GB/T2792-1998 standard;
and (3) permanent adhesion testing: the adhesive holding power was measured according to GB/T485-.
As shown in Table 1, the acrylate powder adhesive with the core-shell structure obtained by the invention has good comprehensive properties, including initial adhesion up to 12-16#, stripping force: 9.6-12.4N/25mm, permanent adhesion: 212-347 h; it also has a low water absorption: 7.7% -15.8%, and high solids content: 63% -70%. The defects that the pressure-sensitive adhesive in the prior art is low in 180-degree peel strength, small in permanent adhesion, low in adhesive bonding strength, poor in water resistance and high in viscosity and gel implosion is caused when the solid content exceeds 55% are overcome.
The invention discloses a coupling agent and a hydrophobic nano material modified acrylate polymer emulsion, and the coupling agent is utilized to make the hydrophobic nano materialSiO rice2Or calcium carbonate and acrylate polymer are uniformly and firmly combined together by using nano SiO2Or the strong bonding energy between the calcium carbonate and the coupling agent and the base material greatly enhances the adhesive property of the pressure-sensitive adhesive. Meanwhile, the powder pressure-sensitive adhesive prepared by spray drying is different from the existing liquid adhesive, is solid, can be packaged by paper bags like cement, does not need an iron bucket or a plastic bucket, can greatly reduce the cost, can reduce Volatile Organic Compounds (VOC), and is convenient to transport and store for a long time.
Finally, the invention adopts a spray drying mode to quickly and efficiently prepare the acrylate powder adhesive with the core-shell structure, uniformly and firmly bonds the coupling agent, the nano particles and the adhesive together, and greatly shortens the required preparation time.
The acrylate powder adhesive with the core-shell structure not only ensures the bonding performance, but also ensures the bonding performance due to the coupling agent and the hydrophobic nano SiO2Or the existence of calcium carbonate, so that the powder adhesive also has high pressure sensitivity and high water resistance, can be used in the sealing of complex precision equipment, and has the advantages of low production cost, simple operation, environmental protection and wide application prospect.
It should be noted that the above-mentioned embodiments do not limit the concept and the protection scope of the present invention. Without departing from the concept of the invention, various modifications and improvements of the technical solution of the present invention should fall into the protection scope of the present invention.
Claims (8)
1. A preparation method of acrylate powder adhesive with a core-shell structure is characterized by comprising the following steps:
1) adding an emulsifier into water, then adding a soft monomer, a hard monomer and a functional monomer, uniformly mixing, and magnetically stirring for 10-30 min to form a pre-emulsion; the soft monomer, the hard monomer and the functional monomer form a monomer; the addition amount of the emulsifier is 1-3% of the total mass of the monomers; the addition amount of the water is 20-40% of the total mass of the monomers;
the soft monomer is one or more of isooctyl acrylate, cyclohexyl acrylate and butyl acrylate; the addition amount of the soft monomer is 65-82% of the total mass of the monomers;
the functional monomer is one or more of itaconic acid, acrylic acid, methacrylic acid, acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the addition amount of the functional monomer is 1-1.5% of the total mass of the monomer;
the hard monomer is one or more of methyl methacrylate, acrylonitrile, styrene and methyl acrylate; the addition amount of the hard monomer is 12-17% of the total mass of the monomers;
the sum of the addition amounts of the soft monomer, the hard monomer and the functional monomer is 100 percent;
the emulsifier is one or more of polyoxyethylene sec-octylphenol ether-10, sodium dodecyl sulfate, polyoxyethylene nonyl phenyl ether, disodium ethoxylated nonylphenol sulfosuccinate, sodium dodecyl benzene sulfonate and tween-20;
2) heating to 75-80 ℃, adding a buffer solution into the reactor, and adding N2In an atmosphere, simultaneously dripping 20-50% of pre-emulsion and 1/2-3/4% of initiator by mass, and stirring for reaction for 30-60 min to prepare initial emulsion; after the temperature is kept for 10-40 min, dropwise adding the rest initiator and pre-emulsion, and adding a chain transfer agent for 3-4 h;
3) after the dropwise adding is finished, preserving the heat at the temperature of 80-90 ℃ for 1-2 h, cooling and discharging to form an emulsion;
4) adding coupling agent, nano calcium carbonate or SiO into the step 3)2Dispersing the polyvinyl alcohol aqueous solution at 40-50 ℃ for 3-15 min, and then carrying out ultrasonic treatment at room temperature for 10-30 min; the coupling agent is one or more of gamma-aminopropyltriethoxysilane, 3-glycidyl ether propyl methyldiethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, vinyl trimethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma- (methacryloyloxy) propyl trimethoxysilane;
5) and 4) spray drying the product obtained in the step 4) to obtain the acrylate powder adhesive with the core-shell structure.
2. Core shell according to claim 1The preparation method of the structural acrylate powder adhesive is characterized by comprising the following steps: the buffer solution is 0.5 to 0.7 weight percent of NaHCO3An aqueous solution.
3. The preparation method of the acrylate powder adhesive with the core-shell structure according to claim 1, which is characterized in that: the initiator is one or more of potassium persulfate, sodium bisulfite and azobisisobutyronitrile.
4. The preparation method of the acrylate powder adhesive with the core-shell structure according to claim 1, which is characterized in that: the addition amount of the initiator is 0.1-0.8% of the total mass of the monomers.
5. The preparation method of the acrylate powder adhesive with the core-shell structure according to claim 1, which is characterized in that: the chain transfer agent is dodecyl mercaptan, and the using amount of the chain transfer agent is 0.1-0.5% of the total mass of the monomers.
6. The preparation method of the acrylate powder adhesive with the core-shell structure according to claim 1, which is characterized in that: the spray drying process parameters are that the inlet temperature is 150-180 ℃, the outlet temperature is 75-90 ℃, and the drying time is 3-10 min.
7. The preparation method of the acrylate powder adhesive with the core-shell structure according to claim 1, which is characterized in that: the coupling agent accounts for 0.01-0.15% of the mass of the emulsion; the nano calcium carbonate or SiO2Accounting for 2-5% of the mass of the emulsion; the polyvinyl alcohol aqueous solution accounts for 10-30 wt% of the emulsion.
8. The acrylate powder adhesive with the core-shell structure prepared by the preparation method of any one of claims 1 to 7; the pressure-sensitive adhesive is white powder, the initial adhesion reaches 12-19#, the peeling force is 9.0-13.0N/25mm, and the permanent adhesion is 200-350 h; the water absorption rate is 1.2-15.0%, and the solid content is 70-85%.
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| CN102766241A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Core-shell structured nano-silica/polyacrylate emulsion and its preparation method |
| CN107629736A (en) * | 2017-09-07 | 2018-01-26 | 滁州市光威化工有限公司 | A kind of nano-silicon dioxide modified fire-retardant the High-speed Cigarette Adhesives for Filter Tipping of hud typed acrylate and vinyl acetate emulsion and preparation method |
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| CN102766241A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Core-shell structured nano-silica/polyacrylate emulsion and its preparation method |
| CN107629736A (en) * | 2017-09-07 | 2018-01-26 | 滁州市光威化工有限公司 | A kind of nano-silicon dioxide modified fire-retardant the High-speed Cigarette Adhesives for Filter Tipping of hud typed acrylate and vinyl acetate emulsion and preparation method |
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