CN115044326B - High-solid-content quick setting adhesive and preparation method thereof - Google Patents
High-solid-content quick setting adhesive and preparation method thereof Download PDFInfo
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- CN115044326B CN115044326B CN202210411033.XA CN202210411033A CN115044326B CN 115044326 B CN115044326 B CN 115044326B CN 202210411033 A CN202210411033 A CN 202210411033A CN 115044326 B CN115044326 B CN 115044326B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000000853 adhesive Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title description 7
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 239000004816 latex Substances 0.000 claims abstract description 43
- 229920000126 latex Polymers 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000006184 cosolvent Substances 0.000 claims abstract description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 239000012792 core layer Substances 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical group CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012874 anionic emulsifier Substances 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical group NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- JDXQSTLUHNAVMN-UHFFFAOYSA-M sodium propane-2-sulfonate prop-2-enamide Chemical group [Na+].NC(=O)C=C.CC(C)S([O-])(=O)=O JDXQSTLUHNAVMN-UHFFFAOYSA-M 0.000 claims description 2
- VFSRCMUUHLBQPY-UHFFFAOYSA-N sodium;ethene Chemical compound [Na+].[CH-]=C VFSRCMUUHLBQPY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000004834 spray adhesive Substances 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- 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 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 1
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 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
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
- C09J111/02—Latex
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-solid-content quick setting adhesive, which comprises the following components in parts by mass: 45-75 parts of aqueous neoprene latex, 15-40 parts of mixed polymerized monomers, 5-20 parts of pure water, 0.15-0.6 part of mixed emulsifying agent, 0.04-0.15 part of water-soluble initiator, 0.6-1.2 parts of pH value regulator, 0.08-0.4 part of external crosslinking agent and 0-5 parts of cosolvent; the mixed polymerized monomer comprises 65-88% of main monomer, 0.5-5% of first functional monomer, 10-30% of second functional monomer and 0.1-2% of third functional monomer. The latex particles in the high-solid-content quick setting adhesive prepared by the invention have a core-shell structure, neoprene latex is a core layer, acrylic ester and the like are shell layers, the stability is good, the adhesive has high solid content, high construction efficiency, environmental friendliness and excellent adhesive property.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-solid-content quick setting adhesive and a preparation method thereof.
Background
The water-based quick setting adhesive is applied to a single or two substrate surfaces in a spray coating, roller coating, knife coating and other modes, and can realize quick bonding within 10-20s by applying small force, and the bonded substrate can be directly subjected to next construction or use without drying. The water-based quick setting adhesive is also commonly called water-based spray adhesive, water-based machine-passing adhesive, water-based roller adhesive and the like, and is widely applied to the fields of soft furniture such as textile products, mattress sofa processing, shoe material bags, automobile or motor train interior decoration processing and the like. The spraying/passing glue sold in the market at present mainly comprises a solvent type adhesive containing styrene-butadiene block copolymer (SBS) and a water type adhesive containing chlorine Ding Jiaoru.
The SBS solvent type spray adhesive has the advantages of high adhesive speed and high adhesive strength, but the content of the solvent is generally more than 60%, and the solvent is benzene series, lipid, ketone, hydrocarbon and the like. In the use process, the defects of high storage risk, inflammability, explosiveness, high-volatility organic matter (VOCs) emission and toxicity to human bodies exist, so that the child seat is more and more severely limited by the national and market, the spray sizing material of the child seat disclosed in Chinese patent document with the publication number of CN112724894A uses hydrocarbon solvents, the influence on human health is large, and the child seat needs to be fireproof and explosion-proof in the use process.
In order to ensure the construction safety and control VOCs, the current research is focused on the development of aqueous spraying glue or aqueous cross-machine glue, for example, china patent document with publication number CN110003800A discloses a modified styrene-butadiene latex environment-friendly spraying glue, the invention utilizes modified styrene-butadiene latex, aqueous tackifier, styrene-acrylic emulsion, plasticizer and ammonia water to prepare the aqueous spraying glue for furniture, bags and other industries, but the aqueous spraying glue has larger smell in the spraying use process by adopting the ammonia water, the polarization rate of the styrene-butadiene latex and the styrene-acrylic emulsion is low, and the adhesive effect of the modified styrene-butadiene latex on polar materials such as polyurethane sponge, polyester cloth and the like is general; the Chinese patent document with publication number of CN113105842A discloses a water-based halogen-free spray adhesive, the main component of the water-based halogen-free spray adhesive is natural latex containing ammonia, the odor is heavy in the spraying process, and high-temperature treatment is needed after spraying and bonding, so that the energy consumption is high, and the production efficiency is also influenced; chinese patent publication No. CN109897577a discloses an aqueous spray for BOPP film/paperboard sealing, which is prepared from natural latex modified conventional acrylic emulsion, and is specifically used for BOPP film/paperboard sealing.
The water-based spray glue or the water-based laminator glue which is actually used in the market at present takes water-based neoprene latex as a main material and is compounded with acrylic ester latex with low pH value and an auxiliary agent, or a double-component mode is adopted to realize quick shaping. The aqueous spray adhesive using neoprene latex as a main body has the advantages of low VOCs emission, safe storage and high adhesive strength. However, the existing aqueous neoprene latex type adhesive also has the following problems:
(1) The solid content of the water-based neoprene latex-type water-based quick setting adhesive in the existing market is generally 45-50%, and even more, the solid content is adjusted to 25-30% in order to ensure the storage stability of the adhesive, and the water content in the adhesive is large, so that the time for drying a product after sizing is long, the construction efficiency of the product is influenced, and the adhesive also becomes a pain point in the industry;
(2) In the prior art, in order to realize a rapid bonding effect, the pH value of the neoprene latex needs to be adjusted to 7-9 or even lower, the storage and transportation stability of the neoprene latex can be greatly reduced under the condition of lower pH value, and the neoprene latex can be broken in the storage, transportation or use process and can not be used;
therefore, development of a high-solid-content water-based rapid sizing adhesive, thereby greatly reducing the waiting time after sizing and properly improving the transportation stability of the water-based adhesive are very important.
Disclosure of Invention
In order to solve the problems of low construction efficiency and low transportation stability of the water-based rapid setting adhesive in the prior art, the invention provides the high-solid water-based rapid setting adhesive, wherein latex particles in the adhesive have a core-shell structure, neoprene latex is a core layer, acrylic ester and the like are shell layers, the stability is good, the adhesive has high solid content, high construction efficiency, environmental friendliness and excellent bonding performance.
The technical scheme adopted is as follows:
the high-solid-content quick setting adhesive comprises the following components in parts by mass: 45-75 parts of aqueous neoprene latex, 15-40 parts of mixed polymerized monomers, 5-20 parts of pure water, 0.15-0.6 part of mixed emulsifying agent, 0.04-0.15 part of water-soluble initiator, 0.6-1.2 parts of pH value regulator, 0.08-0.4 part of external crosslinking agent and 0-5 parts of cosolvent;
the mixed polymerization monomer comprises a main monomer, a first type functional monomer, a second type functional monomer and a third type functional monomer;
the main monomer is at least two of butyl acrylate, isooctyl acrylate, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, and accounts for 65-88% of the weight of the mixed polymerization monomer; preferably, the main monomer is a mixture of butyl acrylate and methyl methacrylate, and the weight ratio of the main monomer to the methyl methacrylate is 80-88%.
The first type functional monomer is methacrylic acid or acrylic acid, accounting for 0.5-5% of the weight of the mixed polymerized monomer, and carboxyl in the first type functional monomer can form hydrogen bond acting force, so that the mechanical strength of the polymer is improved, and meanwhile, the adhesive property between the adhesive and a substrate is facilitated. The preferable weight ratio of the first type of functional monomer to the mixed polymerized monomer is 1-3%, and the phenomenon of water phase nucleation and excessive emulsion viscosity easily occurs when the content of the first type of functional monomer is excessive, so that the preparation of high solid content is not facilitated.
The second type of functional monomer is a cyclic acrylate functional monomer, accounting for 10-30% of the weight of the mixed polymerization monomer, and is at least one of isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, adamantyl acrylate, adamantyl methacrylate and 3, 5-trimethylcyclohexyl acrylate; the introduction of the cyclic acrylate monomer is beneficial to reducing the viscosity of the emulsion in the preparation of the high-solid-content emulsion, and the cyclic monomer is beneficial to rapidly establishing the strength of the adhesive after demulsification and film formation. Preferably, the second type functional monomer is isobornyl acrylate, benzyl methacrylate or cyclohexyl methacrylate, and the weight ratio is 10-15%.
The third type of functional monomer is a normal temperature self-crosslinking monomer, and accounts for 0.1-2% of the weight of the mixed polymerization monomer, and comprises diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate (AAEM), N-methylol acrylamide (NMA), glycidyl Methacrylate (GMA), hydroxyethyl methacrylate (HEMA) or hydroxyethyl modified acrylamide (HEAA).
With the addition of the self-crosslinking monomer, the emulsion breaking and film forming of the emulsion are facilitated, and the crosslinking among emulsion particles is formed under the water loss condition, so that the final mechanical strength after film forming is improved. Preferably, the third type of functional monomer is diacetone acrylamide, and the weight ratio is 0.5-2%.
The glass transition temperature of the mixed polymerization monomer is-30-20 ℃ according to FOX equation; preferably, the glass transition temperature of the mixed polymerization monomer is-25-5 ℃. The design of the glass transition temperature can ensure that the adhesive is initially adhered in a wet state, and the wet state adhesive film formed after emulsion breaking of emulsion particles and the final dried adhesive film have good mechanical properties under the action of external force after the adhesive is sized, so that the temperature of the adhesive in the use process can be higher than 5 ℃, and the storage temperature of the water-based adhesive is generally higher than 5 ℃ and is convenient to store.
Preferably, the aqueous neoprene latex is medium-high crystallinity neoprene latex, and the solid content is 48-55%, and more preferably 53-55%. In the use process of the water-based quick setting adhesive, the adhesive strength needs to be established after 10-20 seconds under smaller external force after spraying and roller coating, mainly utilizes the crystallization property of neoprene latex, and the quick crystallization is beneficial to the adhesive to achieve the adhesive effect as soon as possible under the external force.
The external cross-linking agent is adipic Acid Dihydrazide (ADH), polyfunctional aziridine, carbodiimide or blocked isocyanate. The addition amount of the external crosslinking monomer is 1.0-1.2 times of the mole number of the reaction group of the self-crosslinking monomer, so that the latex particles can be ensured to be completely externally crosslinked finally, and better bonding strength is achieved.
The mixed emulsifier consists of a reactive emulsifier and an anionic emulsifier, wherein the reactive emulsifier comprises but is not limited to acrylamide sodium isopropyl sulfonate, allyloxy hydroxyl sodium sulfonate, allyl alcohol ether sulfate containing double bonds, alcohol ether sulfosuccinate sodium salt containing double bonds or vinyl sodium sulfonate; the anionic emulsifier is a common emulsifier for acrylate emulsion polymerization, such as sodium dodecyl sulfate, and the mass ratio of the reactive emulsifier to the anionic emulsifier in the mixed emulsifier is 1:0.5 to 1.75.
The water-soluble initiator includes, but is not limited to, ammonium persulfate, potassium persulfate, hydrogen peroxide and derivatives thereof, VA-061, VA-044, V501 or V50, etc.
The pH regulator is weak acid including but not limited to boric acid and citric acid.
Preferably, the high-solid-content quick setting adhesive comprises 1-5 parts of cosolvent, wherein the cosolvent is dimethyl carbonate, methyl formate, acetone, butanone or cyclohexane, and the cosolvent can swell and enter latex particles along with the addition of the cosolvent to play a role of a plasticizer, so that the initial adhesion, film forming and bonding properties of the latex are better, the boiling point of the cosolvent is low, the cosolvent can volatilize quickly, and the construction efficiency of a product is further accelerated.
The invention also provides a preparation method of the high-solid-content quick setting adhesive, which comprises the following steps:
(1) 0.04 to 0.15 part of water-soluble initiator is mixed with the following components in percentage by weight: 70% -90% of the mixture is divided into a first initiator and a second initiator for standby;
(2) Uniformly mixing 5-20 parts of pure water, 0.15-0.6 part of mixed emulsifier and a second initiator, and slowly adding 15-40 parts of mixed polymerization monomer to obtain a pre-emulsion;
(3) Adding 45-75 parts of aqueous neoprene latex, 0.6-1.2 parts of pH value regulator and first initiator into a reactor, and uniformly mixing to obtain kettle bottom liquid;
(4) Heating the kettle bottom liquid in the step (3) to 80-90 ℃, dropwise adding the pre-emulsion in the step (2) into the kettle bottom liquid in a stirring state, controlling the dropwise adding time to be 150-210 min, and keeping the temperature for continuous reaction for 60-90 min after the dropwise adding is finished;
(5) Cooling to room temperature, adding 0.08-0.4 part of external cross-linking agent and 0-5 parts of cosolvent, and stirring uniformly to obtain the high-solid-content quick setting adhesive.
The high-solid-content quick setting adhesive prepared by the method has high solid content, and the solid content of the high-solid-content quick setting adhesive is more than or equal to 60%.
The high-solid water-content rapid setting adhesive prepared by the method has the advantages that latex particles are of a core-shell structure, neoprene latex is of a core layer, acrylic ester and the like are of a shell layer, and the problem of poor stability of the neoprene latex under the condition of low pH value is solved. The pH value of the high-solid-content quick setting adhesive is controlled between 5 and 8, preferably between 6 and 8. Too low a pH can improve quick bonding properties but has poor storage and transport stability; too high pH value can influence the time of quick bonding, influences the efficiency of construction.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the method that neoprene latex and acrylic ester emulsion are adopted for physical mixing, the method can greatly improve the solid content of the water-based adhesive of the product, the solid content is increased to 60% or more, and the adhesive property is excellent; when the adhesive is applied to the downstream, the waiting time of a processed product can be greatly reduced, the construction efficiency is improved, and the adhesive is particularly suitable for processing sponge mattresses.
(2) Through proper monomer selection and polymerization mode, the acrylic ester monomer and the neoprene latex form a core-shell structure, the neoprene latex becomes a core, and the acrylic ester becomes a shell, so that the stability of the neoprene latex in the low pH adhesive can be improved, and the aqueous adhesive with excellent storage and transportation stability can be further obtained.
Detailed Description
The invention is further illustrated by the following examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
In examples 1 to 6, the aqueous neoprene latex was selected as a fast crystallizing type of Showa SD77S neoprene latex having a solids content of 55.0%; mixing an emulsifying agent: the reactive emulsifier is allyloxy decane alcohol polyoxyethylene ether ammonium sulfate (SR-10) of Adiaceae, the anionic emulsifier is sodium dodecyl sulfate (SLS) of Basoff, and the mass ratio of the reactive emulsifier to the anionic emulsifier is 1:1; the water-soluble initiator is ammonium persulfate; the pH regulator is boric acid; the external cross-linking agent is adipic dihydrazide; the cosolvent is dimethyl carbonate.
Example 1
(1) 0.08 part of ammonium persulfate is prepared by mixing 25% by weight: the 75% ratio is divided into 0.02 part of a first initiator and 0.06 part of a second initiator for standby;
(2) Adding 10.8 parts of pure water into an emulsifying kettle, slowly dripping 0.27 part of mixed emulsifying agent (0.135 part of SR-10,0.135 parts of SLS) and 0.06 part of second initiator into the emulsifying kettle, and fully stirring, so as to fully emulsify the mixed polymerized monomers consisting of 15.85 parts of Butyl Acrylate (BA), 6.73 parts of Methyl Methacrylate (MMA), 3.04 parts of isobornyl acrylate, 0.52 part of methacrylic acid (MAA) and 0.26 part of diacetone acrylamide (DAAM) to obtain a pre-emulsion;
(3) Adding 72 parts of aqueous neoprene latex into a reactor with stirring, slowly adding 1.08 parts of boric acid and 0.02 part of first initiator under the stirring condition, and uniformly mixing to obtain kettle bottom liquid for later use;
(4) Heating the kettle bottom liquid in the step (3) to 80-85 ℃, dropwise adding the pre-emulsified liquid in the step (2) into the kettle bottom liquid under the stirring state, controlling the dropwise adding time to be 150-210 min, and keeping the temperature for continuous reaction for 90min after the dropwise adding is finished.
(5) Cooling to room temperature, adding 0.15 part of Adipic Dihydrazide (ADH), uniformly stirring, filtering, and packaging to obtain the high-solid-content quick setting adhesive.
The glass transition temperature of the mixed polymerized monomer in example 1 was-11.3 ℃.
Examples 2 to 4
The procedure of examples 2 to 4 was the same as in example 1, and all the materials were fed in Table 1. The glass transition temperatures of the mixed polymerized monomers in examples 2 to 4 were respectively: -6.3 ℃, -4.5 ℃, -7.3 ℃.
Table 1 raw material ratios in examples 2 to 4
| Example 2 | Example 3 | Example 4 | |
| Neoprene latex | 68 | 65 | 65 |
| Ammonium persulfate | 0.08 | 0.088 | 0.088 |
| First initiator | 0.02 | 0.022 | 0.022 |
| Second initiator | 0.06 | 0.066 | 0.066 |
| Boric acid | 1.02 | 0.98 | 0.98 |
| Pure water | 11.95 | 11.52 | 11.52 |
| Mixed emulsifier | 0.25 | 0.29 | 0.29 |
| Butyl Acrylate (BA) | 13.71 | 16.09 | 16.09 |
| Methyl Methacrylate (MMA) | 7.48 | 8.77 | 8.77 |
| Methacrylic acid (MAA) | 0.50 | 0.59 | 0.59 |
| Diacetone acrylamide (DAAM) | 0.25 | 0.30 | 0.30 |
| Cyclohexyl methacrylate | 3.00 | ||
| Isobornyl acrylate | 3.51 | ||
| Benzyl methacrylate | 3.51 | ||
| Adipic acid dihydrazide | 0.15 | 0.17 | 0.17 |
Examples 5 to 6
The operation steps of examples 5 to 6 are the same as those of example 1, and the material feeding is the same as that of examples 1 and 3, respectively, except that 3 parts of dimethyl carbonate is additionally added in the step (5), and the high-solid-content quick setting adhesive is obtained after stirring for 120 min, standing for 48h, stabilizing, filtering and packaging. Example 5 the solid content after addition of 3 parts by weight of dimethyl carbonate was 59.4%, and the addition amount was reduced by 60% in the actual preparation, and the present invention was further improved by merely adding a cosolvent.
Sample analysis
The performance test method of the aqueous quick setting adhesive comprises the following steps:
the density is 45kg/m 3 A sponge with the thickness of 4cm is cut into 40cm by 4cm; coating the aqueous quick-setting adhesive on the surface of the sponge by a roller coater at the room temperature of more than 5 ℃ and controlling the sizing amount to be 60-200 g/m 2 After the roller coating is finished, another sponge block with the same specification is stacked on the sponge surface coated with the glue within 10s-20min, 2 sponge blocks are placed on a plate pressing machine, the air pressure is controlled to be between 0.2 and 0.6MPa, the sponge blocks are pressed for 10-20s, the sponge blocks are placed at room temperature for 12h after being loosened, and the bonding condition and the moisture drying time of the bonding surfaces of 1h and 12h are respectively observed:
1) And (3) observing and tearing the bonding surfaces of the two sponges for 1h to achieve partial chip breaking (namely 5-20% of area chip breaking), and observing and tearing the bonding surfaces of the two sponges to generate large-area chip breaking (namely more than 50% of area chip breaking) after 12h, so that the adhesive has qualified performance.
2) After pressing and fixing, the sponge block is placed on an electronic scale, the time length from the sponge to the constant weight is observed, and the drying time length is compared with the drying time length of the existing water-based adhesive on the market under the conditions of equal rubberizing amount, equal room temperature and humidity under the condition of the same rubberizing amount.
The comparative sample 1 is prepared by the inventor by adopting a physical blending mode of neoprene latex, acrylic ester latex and boric acid, and has the solid content of 50 percent and the market mark of C750.
Comparative sample 2 was prepared by the inventors using a physical blend of neoprene latex, acrylate emulsion and boric acid, with a solids content of 38% and a water-based spray with a market designation of C738.
TABLE 2 results of Performance comparison analysis of the adhesives prepared in examples 1 to 6 with the comparative samples
From the data analysis in Table 2, under the condition of high sizing amount and the same room temperature and humidity, the bonding performance of the product is consistent, but the solid content of the adhesive prepared by the embodiment is higher than that of the adhesive prepared by the market, which is obviously beneficial to the rapid drying of the moisture in the sponge after construction; but at low sizing (45 g/m 2 ) The adhesion performance of the comparative sample 2 is not achieved under the condition of (1), and the initial adhesion performance of the comparative sample is poor; the sizing amount is further reduced to 30g/m 2 When the adhesive with the auxiliary solvent is added, the excellent adhesive performance can still be kept at 1h, and other samples are unqualified, so that the adhesive is favorable for quick drying and further improving the adhesive performance of the product along with the addition of the auxiliary solvent.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. The high-solid-content quick setting adhesive is characterized by comprising the following components in parts by weight: 45-75 parts of aqueous neoprene latex, 15-40 parts of mixed polymerized monomers, 5-20 parts of pure water, 0.15-0.6 part of mixed emulsifying agent, 0.04-0.15 part of water-soluble initiator, 0.6-1.2 parts of pH value regulator, 0.08-0.4 part of external cross-linking agent and 1-5 parts of cosolvent;
the mixed polymerization monomer comprises a main monomer, a first type functional monomer, a second type functional monomer and a third type functional monomer; the glass transition temperature of the mixed polymerization monomer is-30-20 ℃;
in the mixed polymerization monomer, the main monomer is a mixture of butyl acrylate and methyl methacrylate, and the weight ratio of the main monomer to the mixture is 80-88%; the first functional monomer is methacrylic acid, and the weight ratio of the first functional monomer to the methacrylic acid is 1-3%; the second functional monomer is isobornyl acrylate, benzyl methacrylate or cyclohexyl methacrylate, and the weight ratio is 10-15%; the third type of functional monomer is diacetone acrylamide, and the weight ratio of the third type of functional monomer is 0.5-2%;
the cosolvent is dimethyl carbonate;
the latex particles in the high-solid-content quick setting adhesive are of a core-shell structure, the neoprene latex is a core layer, and the acrylic ester is a shell layer.
2. The high-solid-content quick setting adhesive according to claim 1, wherein the solid content of the aqueous neoprene latex is 48-55%.
3. The high solids aqueous quick setting adhesive according to claim 1, wherein the external crosslinking agent is adipic acid dihydrazide, polyfunctional aziridine, carbodiimide or blocked isocyanate.
4. The high-solid water-containing quick setting adhesive according to claim 1, wherein the mixed emulsifier consists of a reactive emulsifier and an anionic emulsifier, and the reactive emulsifier is acrylamide sodium isopropyl sulfonate, allyloxy hydroxyl sulfonate, allyl alcohol ether sulfate, double-bond alcohol ether sulfosuccinate sodium salt or vinyl sodium sulfonate; the mass ratio of the reactive emulsifier to the anionic emulsifier in the mixed emulsifier is 1:0.5 to 1.75.
5. The method for preparing the high-solid-content quick setting adhesive according to claim 1, comprising the following steps:
(1) 0.04-0.15 part of water-soluble initiator is mixed with the following components in percentage by weight: 70% -90% of the mixture is divided into a first initiator and a second initiator for standby;
(2) Uniformly mixing 5-20 parts of pure water, 0.15-0.6 part of mixed emulsifier and a second initiator, and slowly adding 15-40 parts of mixed polymerization monomer to obtain a pre-emulsion;
(3) Adding 45-75 parts of aqueous neoprene latex, 0.6-1.2 parts of pH value regulator and a first initiator into a reactor, and uniformly mixing to obtain kettle bottom liquid;
(4) Heating the kettle bottom liquid in the step (3) to 80-90 ℃, dropwise adding the pre-emulsion in the step (2) into the kettle bottom liquid in a stirring state, controlling the dropwise adding time to be 150-210 min, and keeping the temperature for continuous reaction for 60-90 min after the dropwise adding is finished;
(5) And cooling to room temperature, adding 0.08-0.4 part of external cross-linking agent and 1-5 parts of cosolvent, and uniformly stirring to obtain the high-solid-content quick setting adhesive.
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