WO2022188268A1 - (meth)acrylic acid polymer containing crosslinkable functional group at terminal position - Google Patents
(meth)acrylic acid polymer containing crosslinkable functional group at terminal position Download PDFInfo
- Publication number
- WO2022188268A1 WO2022188268A1 PCT/CN2021/095174 CN2021095174W WO2022188268A1 WO 2022188268 A1 WO2022188268 A1 WO 2022188268A1 CN 2021095174 W CN2021095174 W CN 2021095174W WO 2022188268 A1 WO2022188268 A1 WO 2022188268A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- functional group
- acrylate
- crosslinkable functional
- terminal position
- Prior art date
Links
- 125000000524 functional group Chemical group 0.000 title claims abstract description 41
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title abstract description 6
- 229920002125 Sokalan® Polymers 0.000 title abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 150000003254 radicals Chemical class 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 12
- -1 poly(methyl) Polymers 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000976 ink Substances 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
- FIWNTOUHYJJODB-UHFFFAOYSA-N 4-[(4-butylphenyl)diazenyl]phenol Chemical compound CCCCc1ccc(cc1)N=Nc1ccc(O)cc1 FIWNTOUHYJJODB-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003926 acrylamides Chemical class 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 claims description 2
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 claims description 2
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-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
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- IWTIJBANDVIHPX-UHFFFAOYSA-N 2-[(2-cyano-5-hydroxypentan-2-yl)diazenyl]-5-hydroxy-2-methylpentanenitrile Chemical compound OCCCC(C)(C#N)N=NC(C)(CCCO)C#N IWTIJBANDVIHPX-UHFFFAOYSA-N 0.000 claims 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 238000005538 encapsulation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 36
- 239000007787 solid Substances 0.000 abstract description 26
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 23
- 238000004132 cross linking Methods 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 29
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 239000012456 homogeneous solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- IMQBXFQPBALLJP-UHFFFAOYSA-N 2-(4-benzoylphenoxy)ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 IMQBXFQPBALLJP-UHFFFAOYSA-N 0.000 description 2
- FQYZFXMURPITPH-UHFFFAOYSA-N 2-cyano-2-[(1,3-dicarboxy-1-cyanopropyl)diazenyl]pentanedioic acid Chemical compound OC(=O)CCC(C(O)=O)(C#N)N=NC(C(O)=O)(C#N)CCC(O)=O FQYZFXMURPITPH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- BJJVDFADUDDTQK-UHFFFAOYSA-N 5-hydroxy-2-methylpentanenitrile Chemical compound N#CC(C)CCCO BJJVDFADUDDTQK-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002023 wood Substances 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
- C08F220/12—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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
Definitions
- the invention belongs to the technical field of new polymer materials, in particular to a (meth)acrylic polymer containing a crosslinkable functional group at a terminal position and an application thereof.
- Acrylic pressure sensitive adhesives are widely used in industrial tapes due to a number of important performance advantages. These important performance advantages include excellent temperature resistance, weather resistance, water resistance, oil resistance, high clarity, and a wide temperature range. Acrylic PSAs are typically polymerized in solution by free radical polymerization, and then solution coated onto the tape substrate and dried to remove the solvent to form the final tape product.
- acrylic PSAs especially high performance acrylic PSAs, typically have very low solids content. Since acrylic PSAs require a high linear molecular weight to achieve the high adhesion and cohesion required for high performance applications, such high molecular weight PSA solutions are too viscous and require dilution with a large amount of solvent to meet production and coating process requirements .
- acrylic PSAs used in polarizing films typically have molecular weights in excess of one million, and their solution solids must be reduced to 20% to suit the viscosity requirements of the coating process.
- the molecular weight of acrylic PSAs used in the production of solar films for glass windows is also very high, and usually the solids content needs to be diluted to around 10% to obtain a smooth coating surface and excellent optical properties.
- solvent-based PSA with low solid content has many shortcomings that need to be solved urgently: (1) the viscosity of high molecular weight polymers is high, and the production process control is relatively difficult; (2) the use of a large amount of solvent leads to high raw material costs and low production efficiency; (3) ) Low solid content solvent-based PSA causes slow coating speed and high drying energy consumption; (4) Coating quality control is more difficult, especially for products with thicker adhesive layers; (5) The production and use of low solid content solvent-based PSA The process produces a large amount of carbon dioxide, which is not conducive to environmental protection, energy saving and production sustainability.
- the purpose of the present invention is to provide a solvent-based pressure-sensitive adhesive, in which the functional groups at the terminal positions can be cross-linked and chain-extended during the curing process, so as to effectively increase the linear length of the polymer chain, thereby not only improving the performance of the product, but also enabling Greatly reducing the initial viscosity of the polymer and increasing the solids content of the pressure-sensitive adhesive are used to prepare (meth)acrylate copolymers containing crosslinkable functional groups at the terminal positions.
- a (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is mainly prepared by the polymerization of the following components:
- the weight average molecular weight of the (meth)acrylic polymer containing crosslinkable functional groups at the terminal positions is about 2,000 to about 2,000,000 g/mol, more preferably 50,000 to about 500,000 g/mol.
- the cross-linkable functional group-containing free radical initiator described in the (meth)acrylic polymer containing a cross-linkable functional group at the terminal position is one of azo-based or peroxide-based thermal initiators, or random combination.
- the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position, the described free radical initiator containing a crosslinkable functional group is azobenzene-4,4-dibenzoic acid (CAS No.: 586-91-4), 4,4'-azobis(4-cyanoacrylic acid)(CAS:2638-94-0), 4.4'azobis(4-cyanopentanol)(CAS:4693- 47-4), 4-(4-butylphenylazo)phenol (CAS:2496-21-1), 2,2-azo(2-methyl-N-(2-hydroxyethyl)propane) amide) (CAS: 61551-69-7) or any combination.
- the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position the copolymerizable monomers include 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate, acrylic acid Lauryl ester, n-butyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Esters, acrylamides, mono- or di-N-alkyl substituted acrylamides, tert-butyl acrylamide, dimethylaminoethyl acrylamide, N-octyl acrylamide, poly(meth)acrylate alkoxyalkanes base ester, 2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (me)acrylate, 2-me
- the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is characterized in that, the copolymerizable monomer further includes a monomer containing an ultraviolet functional group.
- the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is characterized in that, the monomer containing the ultraviolet light functional group is benzophenone, benzophenone bio, One or any combination of epoxy group, acid anhydride, caprolactam, pyrrolidone, ethylene oxide and tetrahydrofuran.
- the second technical solution provided by the present invention is that the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is used to prepare adhesives, coatings, packaging materials and inks.
- the present invention provides a new polymerization production technology for preparing a (meth)acrylate copolymer containing a crosslinkable functional group at the terminal position, and a solvent-based polymer produced by using the novel polymer provided in the present application.
- Pressure-sensitive adhesive, the functional group on its terminal position can be cross-linked and chain-extended during the curing process, which can effectively increase the linear length of the polymer chain, which can not only improve the performance of the product, but also greatly reduce the initial viscosity of the polymer and improve the The solids content of the pressure sensitive adhesive.
- This new polymer production technology is beneficial for reducing production costs and improving production sustainability.
- the novel (meth)acrylate copolymer provided by the present invention is particularly suitable for preparing various adhesives, coatings, packaging materials or inks.
- the functional groups at the terminal positions can be cross-linked and chain-extended, effectively Increasing the linear length of the polymer chain can not only meet the performance requirements of high-end tapes, but also reduce the initial viscosity of the polymer, which is beneficial to the construction of coating or printing processes, and at the same time, it can increase the solid content of the product formulation, reduce production costs, Improve production sustainability.
- the technical solutions provided in this application are particularly suitable for preparing various adhesives, coatings, packaging materials, or inks. Because during the curing process of these products, the functional groups at their terminal positions can cross-link and extend the chain, effectively increasing the linear length of the polymer chain, which can not only meet the performance requirements of high-end tapes, but also reduce the initial viscosity of the polymer. It is beneficial to the construction of coating or printing process, and at the same time, it can increase the solid content of the product formula, reduce the production cost and improve the production sustainability.
- Example 1 (meth)acrylic polymer containing carboxylic acid on end groups
- the final solventless hot melt adhesive sample had a melt viscosity of 49500 cps at 150°C and a solids content of >99.7%.
- the melt viscosity results show that the polymer of this example also meets the viscosity requirements of the hot melt adhesive production and coating process.
- Example 2 Using metal chelate to extend the molecular chain of (meth)acrylic acid polymer containing carboxylic acid on the end group
- the polymer solution of Example 1 100 g of the polymer solution prepared in Example 1, 0.12 g of aluminum acetylacetonate and 5 g of isopropanol were mixed to form a homogeneous solution.
- the relative viscosity of the homogeneous solution diluted to 2% solids in ethyl acetate was about 2.14, similar to the relative viscosity value of the polymer solution prepared in Example 1.
- the polymer solution of this example has a viscosity similar to the relative viscosity value of the polymer solution prepared in Example 1, which is suitable for the requirements of high-speed coating process.
- the results of this example show that the pressure-sensitive adhesive formulation prepared by using the (meth)acrylic polymer containing carboxylic acid at the end group can not only significantly reduce the amount of solvent used, but also meet the viscosity requirements of production and coating processes and the product performance requirements.
- Example 4 Using metal chelate to extend the molecular chain of (meth)acrylic acid polymer containing carboxylic acid on the end group
- Example 3 100 g of the polymer solution prepared in Example 3, 0.041 g of aluminum acetylacetonate and 5 g of isopropanol were mixed to form a homogeneous solution. After the polymer solution of this example was coated on the polyester release film, it was dried at 135° C. for about 5 minutes. After the dried polymer is separated from the polyester release film, it can be completely dissolved in ethyl acetate to form a homogeneous solution. However, the relative viscosity increased to 5.5 when diluted to 2% solids in ethyl acetate.
- Example 5 Using metal chelate to extend the molecular chain of (meth)acrylic acid polymer containing carboxylic acid on the end group
- Example 3 100 g of the polymer solution prepared in Example 3, 0.51 g of aluminum acetylacetonate, and 5 g of isopropanol were mixed to form a homogeneous solution. After the polymer solution of this example was coated on the polyester release film, it was dried at 135° C. for about 5 minutes. After the dried polymer is separated from the polyester release film, it can be completely dissolved in ethyl acetate to form a homogeneous solution. However, the relative viscosity increased to 6.4 when diluted to 2% solids in ethyl acetate.
- the polymer solution samples prepared in Examples 3 to 6 were uniformly coated on a polyester film with a thickness of 50 ⁇ m, respectively, and then dried at 135° C. for about 5 minutes.
- the coating weight of the dried sample was controlled at 25 g/square meter.
- the dried samples were subjected to ultraviolet (UV) curing using a desktop UV curing machine (medium pressure mercury column, H lamp, 120 W/cm), and the UVC curing dose was controlled at 0.03 J/cm 2 .
- UV ultraviolet
- the performance of the sample for high temperature protective film is evaluated by the peeling force and the degree of residual glue on the steel plate after being baked at different temperatures after being attached to the stainless steel plate.
- the protective film with excellent performance will show small peeling and climbing after high baking, and there will be no adhesive residue on the steel plate during peeling.
- Table 1 lists the peel force of 1800 and the degree of adhesive residue on the steel plate when the samples are baked at high temperature.
- Example 3 Example 4
- Example 5 Example 6 Relative viscosity 4.3 5.5 6.4 6.7 Peel force after baking at 70°C for 1 hour (N/25mm) 8.9(CM) 7.7(CM) 7.2(CM) 6.9(CM)
- CM no glue residue on the steel plate
- SM slight glue residue on the steel plate
- HM high glue residue on the steel plate
- the results in Table 1 show that the (meth)acrylic polymer prepared in Example 6 has excellent high temperature protective film performance, but the solid content of the polymer solution is extremely low, and more than 80% of the weight is organic solvent.
- the (meth)acrylic polymer containing terminal carboxylic acid prepared in Example 5 has the same excellent high temperature protective film performance as Example 6, but the usage amount of organic solution is reduced by 50%.
- Coated substrates can be in the form of films, tapes, sheets, boards, foams, and the like; and can be made of various substances such as paper, fabric, plastics (polyester, PE, PP, BOPP, and PVC), nonwoven fibers , metal, foil, glass, natural rubber, synthetic rubber, wood or plywood. The enumeration here is not limiting.
- the backside of the substrate is typically coated with a release coating to prevent the adhesive from adhering to the backside of the substrate. If the substrate is to be coated with adhesive on both sides and rolled up, cover the adhesive with a peelable paper or other protector on one side to prevent the adhesive from sticking to the adhesive on the other side mixture.
- UV crosslinking compounds may include polyfunctional (meth)acrylate crosslinkers, eg, difunctional (meth)acrylates or trifunctional (meth)acrylates, polyfunctional (meth)acrylates Acrylates, and other difunctional or polyfunctional compounds capable of crosslinking (meth)acrylate polymers.
- cross-linking compounds examples include aziridine cross-linking agents, isocyanate cross-linking agents, epoxy cross-linking agents, and metal chelates; it is also possible to further add antioxidants, light stabilizers, adhesion promoters, or enhancers. Adhesives to improve product heat resistance, weather resistance, or adhesive properties.
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Abstract
The present invention relates to a (meth)acrylic acid polymer containing a crosslinkable functional group at a terminal position and an application thereof, and aims at providing a (meth)acrylate copolymer containing a crosslinkable functional group at a terminal position, in which the functional group at the terminal position can be subjected to crosslinking and chain extension during curing to effectively increase the linear length of a polymer chain, so that not only the product performance can be improved, but also the initial viscosity of the polymer can be greatly reduced, and the solid content of a pressure-sensitive adhesive can be increased. The (meth)acrylic acid polymer is mainly prepared from the following components by polymerization: a) 95% to 99.9% by weight of copolymerizable monomer, comprising at least one (meth)acrylate monomer, b) 0.01% to 5% by weight of free radical initiator, comprising at least one free radical initiator containing a crosslinkable functional group, and c) 0% to 5% by weight of free radical chain transfer agent, comprising at least one free radical chain transfer agent containing a crosslinkable functional group; and the sum of the weight ratios of the components of the polymerization reactant is 100%.
Description
本发明属于高分子新材料技术领域，具体涉及一种终端位置含可交联官能团的(甲基)丙烯酸聚合物及应用。The invention belongs to the technical field of new polymer materials, in particular to a (meth)acrylic polymer containing a crosslinkable functional group at a terminal position and an application thereof.
丙烯酸类压敏胶(PSA)由于许多重要性能优势而被广泛应用于工业胶带。这些重要的性能优势包括优异的耐温性、耐候性、耐水性、耐油性，高透明度，和使用温度范围广。丙烯酸类PSA通常通过自由基聚合在溶液中聚合，然后在胶带基材上实施溶液涂布，干燥走除溶剂，形成最终胶带产品。Acrylic pressure sensitive adhesives (PSAs) are widely used in industrial tapes due to a number of important performance advantages. These important performance advantages include excellent temperature resistance, weather resistance, water resistance, oil resistance, high clarity, and a wide temperature range. Acrylic PSAs are typically polymerized in solution by free radical polymerization, and then solution coated onto the tape substrate and dried to remove the solvent to form the final tape product.
大多数溶剂型的丙烯酸类PSA，特别是高性能的丙烯酸类PSA，通常都只有很低的固体含量。由于丙烯酸类PSA需要有很高的线性分子量才能获得高性能应用所需要的高附着力和内聚力，但这种高分子量的PSA溶液粘度太大，需要用大量溶剂稀释来满足生产和涂布工艺要求。例如，用于偏光膜的丙烯酸PSA的分子量通常超过一百万，其溶液固体含量必须降至20％时才能适合涂布工艺的粘度要求。另外，用于生产玻璃窗户的太阳膜的丙烯酸PSA的分子量也非常高，通常固体含量需稀释到10％左右，才能获得光滑涂层表面和优异的光学性能。Most solventborne acrylic PSAs, especially high performance acrylic PSAs, typically have very low solids content. Since acrylic PSAs require a high linear molecular weight to achieve the high adhesion and cohesion required for high performance applications, such high molecular weight PSA solutions are too viscous and require dilution with a large amount of solvent to meet production and coating process requirements . For example, acrylic PSAs used in polarizing films typically have molecular weights in excess of one million, and their solution solids must be reduced to 20% to suit the viscosity requirements of the coating process. In addition, the molecular weight of acrylic PSAs used in the production of solar films for glass windows is also very high, and usually the solids content needs to be diluted to around 10% to obtain a smooth coating surface and excellent optical properties.
但是低固含量溶剂型PSA的生产存在许多急需解决的缺点：(1)高分子量聚合物的粘度高，生产过程控制比较困难；(2)大量溶剂使用导致原料成本高和生产效率低；(3)低固含量溶剂型PSA造成涂布速度慢和烘干能耗高；(4)涂布质量控制更困难、特别较厚胶层的产品；(5)低固含量溶剂型PSA的生产和使用过程产生大量二氧化碳，不利于环保节能和生产可持续性。However, the production of solvent-based PSA with low solid content has many shortcomings that need to be solved urgently: (1) the viscosity of high molecular weight polymers is high, and the production process control is relatively difficult; (2) the use of a large amount of solvent leads to high raw material costs and low production efficiency; (3) ) Low solid content solvent-based PSA causes slow coating speed and high drying energy consumption; (4) Coating quality control is more difficult, especially for products with thicker adhesive layers; (5) The production and use of low solid content solvent-based PSA The process produces a large amount of carbon dioxide, which is not conducive to environmental protection, energy saving and production sustainability.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种溶剂型压敏胶，其终端位置上的官能团在固化过程中能夠交联扩链，有效地提高聚合物链的线性长度，从而不仅能够提高产品的性能，而且能夠较大地降低聚合物的初始粘度和提高压敏胶的固体含量用于制备终端位置上含有可交联官能团的(甲基)丙烯酸酯共聚物。The purpose of the present invention is to provide a solvent-based pressure-sensitive adhesive, in which the functional groups at the terminal positions can be cross-linked and chain-extended during the curing process, so as to effectively increase the linear length of the polymer chain, thereby not only improving the performance of the product, but also enabling Greatly reducing the initial viscosity of the polymer and increasing the solids content of the pressure-sensitive adhesive are used to prepare (meth)acrylate copolymers containing crosslinkable functional groups at the terminal positions.
一种在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，主要由下述组分聚合制备：A (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is mainly prepared by the polymerization of the following components:
a)95％至99.9％重量的可共聚单体，且其中至少有一种(甲基)丙烯酸酯单体,a) 95% to 99.9% by weight of copolymerizable monomers with at least one (meth)acrylate monomer,
b)0.01％至5％重量的自由基引发剂，且其中至少一种含有可交联官能团的自由基引发剂，b) 0.01% to 5% by weight of free-radical initiators, and at least one of which contains a cross-linkable functional group of free-radical initiators,
c)0％至5％重量的自由基链转移剂，且其中至少一种含有可交联官能团的自由基链转移c) 0% to 5% by weight of a free radical chain transfer agent, and at least one of which contains a crosslinkable functional group free radical chain transfer agent
剂，agent,
且上述聚合反应物的各组分重量比之和为100％。And the sum of the weight ratio of each component of the above-mentioned polymerization reactant is 100%.
作为进一步优选，所述终端位置上含有可交联官能团的(甲基)丙烯酸聚合物重量平均分子量约为2000至约2000000g/摩尔，更优选地为50000至约500000g/摩尔。As a further preference, the weight average molecular weight of the (meth)acrylic polymer containing crosslinkable functional groups at the terminal positions is about 2,000 to about 2,000,000 g/mol, more preferably 50,000 to about 500,000 g/mol.
作为进一步优选，上述在终端位置含有可交联官能团的(甲基)丙烯酸聚合物所述的含可交联官能团自由基引发剂为偶氮类或过氧化物类热引发剂的其中之一或者任意组合。As a further preference, the cross-linkable functional group-containing free radical initiator described in the (meth)acrylic polymer containing a cross-linkable functional group at the terminal position is one of azo-based or peroxide-based thermal initiators, or random combination.
作为进一步优选，上述在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，所述的含可交联官能团自由基引发剂为偶氮苯-4,4-二苯甲酸(CAS号:586-91-4)，4,4'-偶氮双(4-氰基丙烯酸)(CAS:2638-94-0)，4.4’偶氮双(4-氰基戊醇)(CAS：4693-47-4)，4-(4-丁基苯基偶氮)苯酚(CAS:2496-21-1)，2,2-偶氮(2-甲基-N-(2-羟基乙基)丙酰胺)(CAS：61551-69-7)的其中之一或者任意组合。As a further preference, the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position, the described free radical initiator containing a crosslinkable functional group is azobenzene-4,4-dibenzoic acid (CAS No.: 586-91-4), 4,4'-azobis(4-cyanoacrylic acid)(CAS:2638-94-0), 4.4'azobis(4-cyanopentanol)(CAS:4693- 47-4), 4-(4-butylphenylazo)phenol (CAS:2496-21-1), 2,2-azo(2-methyl-N-(2-hydroxyethyl)propane) amide) (CAS: 61551-69-7) or any combination.
作为进一步优选，上述在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，所述的可共聚单体包括为丙烯酸2-乙基己酯、丙烯酸异辛酯、丙烯酸异癸酯、丙烯酸十二烷基酯、丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基)丙烯酸，(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸4-羟基丁酯、丙烯酰胺、单或二-N-烷基取代的丙烯酰胺、叔丁基丙烯酰胺、二甲基氨基乙基丙烯酰胺、N-辛基丙烯酰胺、聚(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基乙氧基乙酯、甲基丙烯酸2-甲氧基乙酯)、聚乙二醇单(甲基)丙烯酸酯,苯乙烯、醋酸乙烯酯的其中之一或者任意组合。As a further preference, the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position, the copolymerizable monomers include 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate, acrylic acid Lauryl ester, n-butyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Esters, acrylamides, mono- or di-N-alkyl substituted acrylamides, tert-butyl acrylamide, dimethylaminoethyl acrylamide, N-octyl acrylamide, poly(meth)acrylate alkoxyalkanes base ester, 2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-methoxyethyl methacrylate), polyethylene glycol mono ( Meth)acrylate, one of styrene, vinyl acetate or any combination.
作为进一步优选，上述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的可共聚单体还包括含有紫外光官能团的单体。As a further preference, the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is characterized in that, the copolymerizable monomer further includes a monomer containing an ultraviolet functional group.
作为进一步优选，上述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的含有紫外光官能团的单体为二苯甲酮、二苯甲酮洐生物、环氧基团、酸酐、己内酰胺、吡咯烷酮、环氧乙烷和四氢呋喃的其中之一或者任意组合。As a further preference, the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is characterized in that, the monomer containing the ultraviolet light functional group is benzophenone, benzophenone bio, One or any combination of epoxy group, acid anhydride, caprolactam, pyrrolidone, ethylene oxide and tetrahydrofuran.
本发明提供的第二个技术方案是上述在终端位置含有可交联官能团的(甲基)丙烯酸聚合物用于制备胶粘剂、涂料、封装材材料、油墨。The second technical solution provided by the present invention is that the above-mentioned (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is used to prepare adhesives, coatings, packaging materials and inks.
与现有技术相比，本发明提供一种新聚合产生技术，用于制备终端位置上含有可交联官 能团的(甲基)丙烯酸酯共聚物，采用本申请提供的新型聚合物生产的溶剂型压敏胶，其终端位置上的官能团在固化过程中能夠交联扩链，有效地提高聚合物链的线性长度，从而不仅能够提高产品的性能，而且能夠较大地降低聚合物的初始粘度和提高压敏胶的固体含量。这种新聚合产生技术有利于降低生产成本和提高生产可持续性。Compared with the prior art, the present invention provides a new polymerization production technology for preparing a (meth)acrylate copolymer containing a crosslinkable functional group at the terminal position, and a solvent-based polymer produced by using the novel polymer provided in the present application. Pressure-sensitive adhesive, the functional group on its terminal position can be cross-linked and chain-extended during the curing process, which can effectively increase the linear length of the polymer chain, which can not only improve the performance of the product, but also greatly reduce the initial viscosity of the polymer and improve the The solids content of the pressure sensitive adhesive. This new polymer production technology is beneficial for reducing production costs and improving production sustainability.
本发明提供的新型(甲基)丙烯酸酯共聚物特别适用于制备各种胶粘剂，涂料，封装材材料或油墨，在这些产品固化过程中，其终端位置上的官能团能夠交联扩链，有效地提高聚合物链的线性长度，从而不仅能够满足高端胶带的性能要求，而且能夠降低聚合物的初始粘度，有利于涂布或印刷工艺施工，同时又能提高产品配方的固体含量，降低生产成本、提高生产可持续性。The novel (meth)acrylate copolymer provided by the present invention is particularly suitable for preparing various adhesives, coatings, packaging materials or inks. During the curing process of these products, the functional groups at the terminal positions can be cross-linked and chain-extended, effectively Increasing the linear length of the polymer chain can not only meet the performance requirements of high-end tapes, but also reduce the initial viscosity of the polymer, which is beneficial to the construction of coating or printing processes, and at the same time, it can increase the solid content of the product formulation, reduce production costs, Improve production sustainability.
总而言之，本申请提供的技术方案特别适用于制备各种胶粘剂，涂料，封装材材料，或油墨。因为在这些产品固化过程中，其终端位置上的官能团能夠交联扩链，有效地提高聚合物链的线性长度，从而不仅能够满足高端胶带的性能要求，而且能夠降低聚合物的初始粘度，有利于涂布或印刷工艺施工，同时又能提高产品配方的固体含量，降低生产成本、提高生产可持续性。All in all, the technical solutions provided in this application are particularly suitable for preparing various adhesives, coatings, packaging materials, or inks. Because during the curing process of these products, the functional groups at their terminal positions can cross-link and extend the chain, effectively increasing the linear length of the polymer chain, which can not only meet the performance requirements of high-end tapes, but also reduce the initial viscosity of the polymer. It is beneficial to the construction of coating or printing process, and at the same time, it can increase the solid content of the product formula, reduce the production cost and improve the production sustainability.
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例对本发明的具体实施方式做详细的说明。In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention will be described in detail below with reference to specific embodiments.
实施例1端基上含羧酸的(甲基)丙烯酸聚合物Example 1 (meth)acrylic polymer containing carboxylic acid on end groups
将780g丙烯酸丁酯、140g甲基丙烯酸甲酯、80g丙烯酸羟乙酯、1.5 g4-[2-(甲基丙烯酰氧基)乙氧基]二苯甲酮(4-[2-(methacryloyloxy)ethoxy]benzophenone)和500 g2-丁酮(MEK)加入配有不锈钢搅拌器、温度计、冷凝器、水浴和慢加漏斗的3升的4颈圆底烧瓶中。搅拌加热至回流温度后，在30分钟内将2g 4,4'-偶氮双(4-氰基丙烯酸)和60g2-丁酮的混合溶液缓慢加入烧瓶中。继续回流240分钟后，向烧瓶中添加100g 2-丁酮，将烧瓶中的固体含量降低至约60％左右(按重量计)。继续回流下保持2小时后，聚合物溶液冷却至室温。本实施例制备的聚合物溶液最终固体含量约为58.5％，溶液粘度为3800cps。在乙酸乙酯稀中释至2％的固含量时相对粘度约为2.15。虽然本实施例的聚合物溶液固含量远远高于普遍的溶剂型压敏胶(固含量约为40％)，但其溶液粘度却与普遍的溶剂型压敏胶类似，适合各种传统的涂布工艺。780 g of butyl acrylate, 140 g of methyl methacrylate, 80 g of hydroxyethyl acrylate, 1.5 g of 4-[2-(methacryloyloxy) ethoxy] benzophenone (4-[2-(methacryloyloxy) ethoxy]benzophenone) and 500 g of 2-butanone (MEK) were added to a 3-liter 4-neck round bottom flask equipped with a stainless steel stirrer, thermometer, condenser, water bath and slow addition funnel. After stirring and heating to reflux temperature, a mixed solution of 2 g of 4,4'-azobis(4-cyanoacrylic acid) and 60 g of 2-butanone was slowly added to the flask within 30 minutes. After continued reflux for 240 minutes, 100 g of 2-butanone was added to the flask to reduce the solids content in the flask to about 60% by weight. After a further 2 hours at reflux, the polymer solution was cooled to room temperature. The final solid content of the polymer solution prepared in this example is about 58.5%, and the solution viscosity is 3800cps. The relative viscosity was about 2.15 when diluted to 2% solids in ethyl acetate. Although the solid content of the polymer solution in this example is much higher than that of common solvent-based pressure-sensitive adhesives (the solid content is about 40%), its solution viscosity is similar to that of common solvent-based pressure-sensitive adhesives, which is suitable for various traditional pressure-sensitive adhesives. coating process.
将500g上述聚合物溶液与0.3g抗氧剂(Irganox 1010，BASF)混合，然后在减压下加热至130℃除去溶剂和其它残余挥发物。最终的无溶剂热熔胶样品在150℃时的熔体粘度为49500cps，固体含量>99.7％。熔体粘度结果表明，本实施例的聚合物也满足热熔胶生产和涂布工艺对粘度的要求。500 g of the above polymer solution was mixed with 0.3 g of antioxidant (Irganox 1010, BASF), then heated to 130°C under reduced pressure to remove solvent and other residual volatiles. The final solventless hot melt adhesive sample had a melt viscosity of 49500 cps at 150°C and a solids content of >99.7%. The melt viscosity results show that the polymer of this example also meets the viscosity requirements of the hot melt adhesive production and coating process.
实施例2使用金属螯合物扩展端基上含羧酸的(甲基)丙烯酸聚合物分子链Example 2 Using metal chelate to extend the molecular chain of (meth)acrylic acid polymer containing carboxylic acid on the end group
将100g实施例1制备的聚合物溶液，0.12g乙酰丙酮酸铝和5g异丙醇混合形成均相溶液。该均相溶液在乙酸乙酯稀中释至2％的固含量时相对粘度约为2.14，与实施例1制备的聚合物溶液的相对粘度值相似。换而言之，本实施例的聚合物溶液有与实施例1制备的聚合物溶液的相对粘度值相似低的粘度，适合高速涂布工艺的要求。100 g of the polymer solution prepared in Example 1, 0.12 g of aluminum acetylacetonate and 5 g of isopropanol were mixed to form a homogeneous solution. The relative viscosity of the homogeneous solution diluted to 2% solids in ethyl acetate was about 2.14, similar to the relative viscosity value of the polymer solution prepared in Example 1. In other words, the polymer solution of this example has a viscosity similar to the relative viscosity value of the polymer solution prepared in Example 1, which is suitable for the requirements of high-speed coating process.
将本实施例的聚合物溶液涂在聚酯离型膜后，在135℃下干燥约5分钟。干燥后的聚合物从聚酯离型膜分离后，能夠完全溶解在乙酸乙酯中形成均相溶液。但在乙酸乙酯稀中释至2％的固含量时相对粘度增加至3.60。结果表明，高温烘烤后，乙酰丙酮铝与聚合物链的末端羧酸基团形成有效交联，显著地扩展了聚合物链的长度，达到与普遍的溶剂型压敏胶类似其的相对粘度值。本实施例结果表明采用端基上含羧酸的(甲基)丙烯酸聚合物制备的压敏胶配方，既可以明显地减少溶剂的使用量，又可以满足生产和涂布工艺的粘度要求以及产品的性能要求。After the polymer solution of this example was coated on the polyester release film, it was dried at 135° C. for about 5 minutes. After the dried polymer is separated from the polyester release film, it can be completely dissolved in ethyl acetate to form a homogeneous solution. But the relative viscosity increased to 3.60 when diluted to 2% solids in ethyl acetate. The results show that after high temperature baking, aluminum acetylacetonate forms effective cross-linking with the terminal carboxylic acid group of the polymer chain, which significantly extends the length of the polymer chain and achieves a relative viscosity similar to that of common solvent-based pressure-sensitive adhesives. value. The results of this example show that the pressure-sensitive adhesive formulation prepared by using the (meth)acrylic polymer containing carboxylic acid at the end group can not only significantly reduce the amount of solvent used, but also meet the viscosity requirements of production and coating processes and the product performance requirements.
实施例3高分子量的含端基羧酸的(甲基)丙烯酸聚合物Example 3 High molecular weight (meth)acrylic polymer containing terminal carboxylic acid
将630g丙烯酸丁酯、20g丙烯酸2-羟乙基乙酯、1.1g 4-[2-(甲基丙烯酰氧基)乙氧基]二苯甲酮和500g乙酸乙酯加入配有不锈钢搅拌器、温度计、冷凝器、水浴和慢加漏斗的3升四颈圆底烧瓶中。将初始添加料搅拌至均相溶液并加热至回流温度后，在2分钟内将1.3g4,4'-偶氮双(4-氰基戊二酸)和60g乙酸乙酯的混合液添加到烧瓶中。继续回流120分钟后，在240分钟内将600g乙酸乙酯均速加入烧瓶中。聚合物溶液冷却至室温，其溶液固体含量约为34.5％，在乙酸乙酯中为固体含量2％时的相对粘度约为4.3。630 g of butyl acrylate, 20 g of 2-hydroxyethyl acrylate, 1.1 g of 4-[2-(methacryloyloxy)ethoxy]benzophenone, and 500 g of ethyl acetate were added with a stainless steel stirrer , thermometer, condenser, water bath, and slow addition funnel in a 3-liter four-neck round-bottomed flask. After the initial charge was stirred to a homogeneous solution and heated to reflux temperature, a mixture of 1.3 g of 4,4'-azobis(4-cyanoglutaric acid) and 60 g of ethyl acetate was added to the flask over 2 minutes middle. After continuing to reflux for 120 minutes, 600 g of ethyl acetate was added to the flask at a uniform rate over 240 minutes. The polymer solution was cooled to room temperature and had a solution solids content of about 34.5% and a relative viscosity of about 4.3 at 2% solids in ethyl acetate.
实施例4使用金属螯合物扩展端基上含羧酸的(甲基)丙烯酸聚合物分子链Example 4 Using metal chelate to extend the molecular chain of (meth)acrylic acid polymer containing carboxylic acid on the end group
将100g实施例3制备的聚合物溶液，0.041g乙酰丙酮酸铝和5g异丙醇混合形成均相溶液。将本实施例的聚合物溶液涂在聚酯离型膜后，在135℃下干燥约5分钟。干燥后的聚合物从聚酯离型膜分离后，能夠完全溶解在乙酸乙酯中形成均相溶液。但在乙酸乙酯稀中释至 2％的固含量时相对粘度增加至5.5。100 g of the polymer solution prepared in Example 3, 0.041 g of aluminum acetylacetonate and 5 g of isopropanol were mixed to form a homogeneous solution. After the polymer solution of this example was coated on the polyester release film, it was dried at 135° C. for about 5 minutes. After the dried polymer is separated from the polyester release film, it can be completely dissolved in ethyl acetate to form a homogeneous solution. However, the relative viscosity increased to 5.5 when diluted to 2% solids in ethyl acetate.
实施例5使用金属螯合物扩展端基上含羧酸的(甲基)丙烯酸聚合物分子链Example 5 Using metal chelate to extend the molecular chain of (meth)acrylic acid polymer containing carboxylic acid on the end group
将100g实施例3制备的聚合物溶液，0.51g乙酰丙酮酸铝，和5g异丙醇混合形成均相溶液。将本实施例的聚合物溶液涂在聚酯离型膜后，在135℃下干燥约5分钟。干燥后的聚合物从聚酯离型膜分离后，能夠完全溶解在乙酸乙酯中形成均相溶液。但在乙酸乙酯稀中释至2％的固含量时相对粘度增加至6.4。100 g of the polymer solution prepared in Example 3, 0.51 g of aluminum acetylacetonate, and 5 g of isopropanol were mixed to form a homogeneous solution. After the polymer solution of this example was coated on the polyester release film, it was dried at 135° C. for about 5 minutes. After the dried polymer is separated from the polyester release film, it can be completely dissolved in ethyl acetate to form a homogeneous solution. However, the relative viscosity increased to 6.4 when diluted to 2% solids in ethyl acetate.
实施例6极高分子量的(甲基)丙烯酸聚合物Example 6 Very high molecular weight (meth)acrylic polymer
将630g丙烯酸丁酯、20g丙烯酸2-羟乙基乙酯、1.1g4-[2-(甲基丙烯酰氧基)乙氧基]二苯甲酮和360g乙酸乙酯加入配有不锈钢搅拌器、温度计、冷凝器、水浴和慢加漏斗的3升四颈圆底烧瓶中。将初始添加料搅拌至均相溶液并加热至回流温度后，在2分钟内将0.8g4,4'-偶氮双(4-氰基戊二酸)和60g乙酸乙酯的混合液添加到烧瓶中。继续回流120分钟后，在240分钟内将2000g乙酸乙酯均速加入烧瓶中。聚合物溶液冷却至室温，其溶液固体含量约为19.5％，在乙酸乙酯中为固体含量2％时的相对粘度约为6.7。630 g of butyl acrylate, 20 g of 2-hydroxyethyl acrylate, 1.1 g of 4-[2-(methacryloyloxy)ethoxy]benzophenone, and 360 g of ethyl acetate were added to a stainless steel stirrer, Thermometer, condenser, water bath, and slow addition funnel in a 3-liter four-neck round bottom flask. After the initial charge was stirred to a homogeneous solution and heated to reflux temperature, a mixture of 0.8 g of 4,4'-azobis(4-cyanoglutaric acid) and 60 g of ethyl acetate was added to the flask over 2 minutes middle. After continuing to reflux for 120 minutes, 2000 g of ethyl acetate was added to the flask at a uniform rate over 240 minutes. The polymer solution was cooled to room temperature and had a solution solids content of about 19.5% and a relative viscosity of about 6.7 at 2% solids in ethyl acetate.
实施例7高温保护膜性能的测试Example 7 Test of high temperature protective film performance
将实施例3至6制备的聚合物溶液样品分别均匀地涂在50微米厚的聚酯薄膜上，然后在135℃下干燥约5分钟。干燥后的样品的涂布量控制在25g/平方米。采用台式紫外线固化机(中压汞柱，H灯，120瓦/厘米)对干燥后的样品进行紫外(UV)固化，其UVC固化剂量控制在0.03焦耳/平方厘米。样品用于高温保护膜的性能通过贴合在不锈钢板上后，经不同温度烘烤后的剥离力和在钢板上残胶的程度来评定。性能优异的保护膜在高烘烤后，会表现出剥离爬升小，剥离时在钢板无残胶。表1列出了样品经高温度烘烤后的180
0剥离力和剥离时钢板上残胶程度。
The polymer solution samples prepared in Examples 3 to 6 were uniformly coated on a polyester film with a thickness of 50 μm, respectively, and then dried at 135° C. for about 5 minutes. The coating weight of the dried sample was controlled at 25 g/square meter. The dried samples were subjected to ultraviolet (UV) curing using a desktop UV curing machine (medium pressure mercury column, H lamp, 120 W/cm), and the UVC curing dose was controlled at 0.03 J/cm 2 . The performance of the sample for high temperature protective film is evaluated by the peeling force and the degree of residual glue on the steel plate after being baked at different temperatures after being attached to the stainless steel plate. The protective film with excellent performance will show small peeling and climbing after high baking, and there will be no adhesive residue on the steel plate during peeling. Table 1 lists the peel force of 1800 and the degree of adhesive residue on the steel plate when the samples are baked at high temperature.
表1Table 1
| 实施例3Example 3 | 实施例4Example 4 | 实施例5Example 5 | 实施例6Example 6 | |
| 相对粘度Relative viscosity | 4.34.3 | 5.55.5 | 6.46.4 | 6.76.7 |
| 70℃烘烤1小时后的剥离力(牛顿/25毫米)Peel force after baking at 70°C for 1 hour (N/25mm) | 8.9(CM)8.9(CM) | 7.7(CM)7.7(CM) | 7.2(CM)7.2(CM) | 6.9(CM)6.9(CM) |
| 90℃烘烤1小时后的剥离力(牛顿/25毫米)Peel force after baking at 90℃ for 1 hour (N/25mm) | 20.5(SM)20.5 (SM) | 10.5(CM)10.5(CM) | 8.5(CM)8.5(CM) | 7.8(CM)7.8(CM) |
| 120℃烘烤1小时后的剥离力(牛顿/25毫米)Peel force after baking at 120℃ for 1 hour (N/25mm) | 25.7HM)25.7HM) | 20.7(SM)20.7(SM) | 13.7(CM)13.7(CM) | 12.8(CM)12.8(CM) |
| 130℃烘烤1小时后的剥离力(牛顿/25毫米)Peel force after baking at 130℃ for 1 hour (N/25mm) | 29.9(HM)29.9 (HM) | 27.5(HM)27.5(HM) | 16.9(CM)16.9(CM) | 15.0(CM)15.0(CM) |
CM＝钢板上无残胶；SM＝钢板上轻微残胶；HM＝钢板上高度残胶CM = no glue residue on the steel plate; SM = slight glue residue on the steel plate; HM = high glue residue on the steel plate
表1结果表明实施例6所制备的(甲基)丙烯酸聚合物具有优异的高温度保护膜性能，但其聚合物溶液固含量极低，超过80％的重量都是有机溶剂。而实施例5制备的含端基羧酸的(甲基)丙烯酸聚合物具有与实施例6同样优异的高温度保护膜性能，但有机溶液的使用量减少了50％。The results in Table 1 show that the (meth)acrylic polymer prepared in Example 6 has excellent high temperature protective film performance, but the solid content of the polymer solution is extremely low, and more than 80% of the weight is organic solvent. The (meth)acrylic polymer containing terminal carboxylic acid prepared in Example 5 has the same excellent high temperature protective film performance as Example 6, but the usage amount of organic solution is reduced by 50%.
本申请提供的技术方案特别适用于溶剂型压敏胶或无溶剂热熔压敏胶。可采用各种常规涂布方法来制备压敏胶胶带，压敏胶标签，或其它压敏胶产品。常规涂布方法包括但不限于挤出涂布，窄口涂布，凹版涂布、窗帘涂布、开槽涂布、旋转涂布、丝网涂布。被涂布的基材可以是膜、带、片、板、泡沫，和类似形式；并且可以由各种物质如纸、织物、塑料(聚酯、PE、PP、BOPP和PVC)、无纺纤维、金属、箔、玻璃、天然橡胶、合成橡胶、木材或胶合板制成。这里的列举并不是限制性的。如果带涂层的基材欲以卷状物的形式应用，那么基材的背面通常用防粘涂料来涂覆，以防止粘合剂粘合到基材的背面。如果基材欲在两面均涂布上粘合剂并卷起，那么在一侧将可剥离纸或其它保护物覆盖到粘合剂上，以防止粘合剂粘合于另一侧上的粘合剂。The technical solutions provided in this application are particularly suitable for solvent-based pressure-sensitive adhesives or solvent-free hot-melt pressure-sensitive adhesives. Various conventional coating methods can be employed to prepare pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, or other pressure-sensitive adhesive products. Conventional coating methods include, but are not limited to extrusion coating, narrow opening coating, gravure coating, curtain coating, slot coating, spin coating, screen coating. Coated substrates can be in the form of films, tapes, sheets, boards, foams, and the like; and can be made of various substances such as paper, fabric, plastics (polyester, PE, PP, BOPP, and PVC), nonwoven fibers , metal, foil, glass, natural rubber, synthetic rubber, wood or plywood. The enumeration here is not limiting. If the coated substrate is to be applied in roll form, the backside of the substrate is typically coated with a release coating to prevent the adhesive from adhering to the backside of the substrate. If the substrate is to be coated with adhesive on both sides and rolled up, cover the adhesive with a peelable paper or other protector on one side to prevent the adhesive from sticking to the adhesive on the other side mixture.
需要说明的是：本领域技术人员根据产品的实际需要，可以在反应进一步添加本领域常用的丙烯酸聚合物、热交联剂或UV交联剂来进一步有提高产品的性能。合适的UV交联化合物的例子可以包括多官能团的(甲基)丙烯酸酯交联剂，例如，双官能团(甲基)丙烯酸酯或三官能团(甲基)丙烯酸酯，多官团(甲基)丙烯酸酯，和其它的能够交联(甲基)丙烯酸酯聚合物的双官能或多官能化合物。合适的交联化合物的例子包括氮丙啶交联剂，异氰酸酯交联剂，环氧交联剂和金属螯合物等；也可以进一步添加抗氧化剂，光稳定剂、粘接促进剂，或增粘剂，以提高产品的耐热性，耐候性，或粘接性能。It should be noted that those skilled in the art can further add acrylic polymer, thermal crosslinking agent or UV crosslinking agent commonly used in the field in the reaction to further improve the performance of the product according to the actual needs of the product. Examples of suitable UV crosslinking compounds may include polyfunctional (meth)acrylate crosslinkers, eg, difunctional (meth)acrylates or trifunctional (meth)acrylates, polyfunctional (meth)acrylates Acrylates, and other difunctional or polyfunctional compounds capable of crosslinking (meth)acrylate polymers. Examples of suitable cross-linking compounds include aziridine cross-linking agents, isocyanate cross-linking agents, epoxy cross-linking agents, and metal chelates; it is also possible to further add antioxidants, light stabilizers, adhesion promoters, or enhancers. Adhesives to improve product heat resistance, weather resistance, or adhesive properties.
对本发明可以进行许多修改和变化，而不背离其精神和范围，这对于本领域的技术人员将是显而易见的。这里所述的具体实施方案仅仅是通过实施例加以提供，而本发明仅由权利要求以及与之等效的整个范围来限定。Many modifications and variations can be made in the present invention without departing from its spirit and scope, as will be apparent to those skilled in the art. The specific embodiments described herein are provided by way of example only, and the invention is to be limited only by the claims along with their full scope of equivalents.
Claims (9)
- 一种在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，主要由下述组分聚合制备：A (meth)acrylic polymer containing a crosslinkable functional group at the terminal position is characterized in that it is mainly prepared by the polymerization of the following components:a)95％至99.9％重量的可共聚单体，且其中至少有一种(甲基)丙烯酸酯单体,a) 95% to 99.9% by weight of copolymerizable monomers with at least one (meth)acrylate monomer,b)0.01％至5％重量的自由基引发剂，且其中至少一种含有可交联官能团的自由基引发剂，b) 0.01% to 5% by weight of free-radical initiators, and at least one of which contains a cross-linkable functional group of free-radical initiators,c)0％至5％重量的自由基链转移剂，且其中至少一种含有可交联官能团的自由基链转移剂，c) 0% to 5% by weight of a free radical chain transfer agent, and at least one of which contains a crosslinkable functional group of a free radical chain transfer agent,且上述聚合反应物的各组分重量比之和为100％。And the sum of the weight ratio of each component of the above-mentioned polymerization reactant is 100%.
- 根据权利要求1所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，其重量平均分子量约为2000至约2000000g/摩尔。The (meth)acrylic polymer containing crosslinkable functional groups at terminal positions according to claim 1, wherein the weight average molecular weight is about 2000 to about 2000000 g/mol.
- 根据权利要求1所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的含可交联官能团自由基引发剂为偶氮类或过氧化物类热引发剂的其中之一或者任意组合。The (meth)acrylic polymer containing a crosslinkable functional group at the terminal position according to claim 1, wherein the free radical initiator containing a crosslinkable functional group is an azo type or a peroxide type heat One of the initiators or any combination.
- 根据权利要求1所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的含可交联官能团自由基引发剂为偶氮苯-4,4-二苯甲酸，4,4'-偶氮双(4-氰基丙烯酸)、4,4’偶氮双(4-氰基戊醇)、4-(4-丁基苯基偶氮)苯酚、2,2-偶氮(2-甲基-N-(2-羟基乙基)丙酰胺)的其中之一。The (meth)acrylic polymer containing a crosslinkable functional group at the terminal position according to claim 1, wherein the free radical initiator containing a crosslinkable functional group is azobenzene-4,4-di Benzoic acid, 4,4'-azobis(4-cyanoacrylic acid), 4,4'azobis(4-cyanopentanol), 4-(4-butylphenylazo)phenol, 2 , One of 2-azo (2-methyl-N-(2-hydroxyethyl) propionamide).
- 根据权利要求1所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的可共聚单体为丙烯酸2-乙基己酯、丙烯酸异辛酯、丙烯酸异癸酯、丙烯酸十二烷基酯、丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基)丙烯酸，(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸4-羟基丁酯、丙烯酰胺、单或二-N-烷基取代的丙烯酰胺、叔丁基丙烯酰胺、二甲基氨基乙基丙烯酰胺、N-辛基丙烯酰胺、聚(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基乙氧基乙酯、甲基丙烯酸2-甲氧基乙酯)、聚乙二醇单(甲基)丙烯酸酯,苯乙烯、醋酸乙烯酯的其中之一或者任意组合。The (meth)acrylic polymer containing a crosslinkable functional group at the terminal position according to claim 1, wherein the copolymerizable monomer is 2-ethylhexyl acrylate, isooctyl acrylate, acrylic acid Isodecyl acrylate, dodecyl acrylate, n-butyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, (meth)acrylate 4-Hydroxybutyl acrylate, acrylamide, mono- or di-N-alkyl substituted acrylamide, tert-butyl acrylamide, dimethylaminoethyl acrylamide, N-octyl acrylamide, poly(methyl) Alkoxyalkyl acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-methoxyethyl methacrylate), poly Ethylene glycol mono(meth)acrylate, one of styrene, vinyl acetate or any combination.
- 根据权利要求4所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的可共聚单体还包括含有紫外光官能团的单体。The (meth)acrylic polymer containing a crosslinkable functional group at the terminal position according to claim 4, wherein the copolymerizable monomer further comprises a monomer containing an ultraviolet functional group.
- 根据权利要求5所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物，其特征在于，所述的含有紫外光官能团的单体为二苯甲酮、二苯甲酮洐生物、环氧基团、酸酐、己内酰胺、吡咯烷酮、环氧乙烷和四氢呋喃的其中之一或者任意组合。The (meth)acrylic polymer containing a crosslinkable functional group at the terminal position according to claim 5, wherein the monomer containing the ultraviolet light functional group is benzophenone, benzophenone oxidative , epoxy group, acid anhydride, caprolactam, pyrrolidone, ethylene oxide and tetrahydrofuran, or any combination thereof.
- 权利要求1所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物作为制 备胶粘剂的应用。The application of the (meth)acrylic polymer containing a crosslinkable functional group at the terminal position as claimed in claim 1 for preparing an adhesive.
- 权利要求1所述的在终端位置含有可交联官能团的(甲基)丙烯酸聚合物用于制备涂料，封装材料或油墨。The (meth)acrylic polymer containing a crosslinkable functional group at the terminal position according to claim 1 is used for the preparation of coatings, encapsulation materials or inks.
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