CN116640530A - Environment-friendly pressure-sensitive adhesive tape and preparation method thereof - Google Patents
Environment-friendly pressure-sensitive adhesive tape and preparation method thereof Download PDFInfo
- Publication number
- CN116640530A CN116640530A CN202310633049.XA CN202310633049A CN116640530A CN 116640530 A CN116640530 A CN 116640530A CN 202310633049 A CN202310633049 A CN 202310633049A CN 116640530 A CN116640530 A CN 116640530A
- Authority
- CN
- China
- Prior art keywords
- sensitive adhesive
- acrylic ester
- emulsion
- environment
- adhesive tape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 triamino ethoxy phosphite Chemical compound 0.000 claims abstract description 133
- 239000000839 emulsion Substances 0.000 claims abstract description 111
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 80
- 229920002635 polyurethane Polymers 0.000 claims abstract description 78
- 239000004814 polyurethane Substances 0.000 claims abstract description 78
- 238000002156 mixing Methods 0.000 claims abstract description 65
- 241001122767 Theaceae Species 0.000 claims abstract description 54
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 52
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 51
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 49
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012948 isocyanate Substances 0.000 claims abstract description 37
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 37
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 33
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 229920006381 polylactic acid film Polymers 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003141 primary amines Chemical class 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 114
- 238000003756 stirring Methods 0.000 claims description 105
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000007864 aqueous solution Substances 0.000 claims description 59
- 239000008367 deionised water Substances 0.000 claims description 56
- 229910021641 deionized water Inorganic materials 0.000 claims description 56
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 49
- 238000004321 preservation Methods 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 46
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 41
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 40
- 150000002148 esters Chemical class 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 23
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 23
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 23
- 238000002390 rotary evaporation Methods 0.000 claims description 22
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 21
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 21
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 21
- 125000005456 glyceride group Chemical group 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 235000011187 glycerol Nutrition 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 238000010008 shearing Methods 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 13
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 9
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 6
- 125000005336 allyloxy group Chemical group 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- WKALCYAZQNVDNE-UHFFFAOYSA-N triethoxy phosphite Chemical compound CCOOP(OOCC)OOCC WKALCYAZQNVDNE-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- 239000012074 organic phase Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930003935 flavonoid Natural products 0.000 description 2
- 235000017173 flavonoids Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- KLRKLHFSVZZHDE-UHFFFAOYSA-N triethyl phosphite trimethyl phosphite Chemical compound COP(OC)OC.CCOP(OCC)OCC KLRKLHFSVZZHDE-UHFFFAOYSA-N 0.000 description 2
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 241000862513 Kandelia Species 0.000 description 1
- VFTKIWJJPDJBKD-UHFFFAOYSA-N OCCC[Na] Chemical compound OCCC[Na] VFTKIWJJPDJBKD-UHFFFAOYSA-N 0.000 description 1
- 241001184198 Orthosiphon Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001765 catechin Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
- C09J2451/00—Presence of graft polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, and discloses an environment-friendly pressure-sensitive adhesive tape and a preparation method thereof. The method comprises the following steps: modifying the tea polyphenol by using cinnamoyl chloride to obtain modified tea polyphenol; reacting trialkyl phosphite with ethanolamine to obtain triamino ethoxy phosphite; preparing five-membered ring carbonate by using glycidyl acrylate to react with carbon dioxide, preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer by using five-membered ring carbonate to react with polybasic primary amine, emulsifying, and reacting with acrylate mixed monomer solution, modified tea polyphenol, triethoxy phosphite ester, emulsifier and the like to obtain polyurethane modified acrylate emulsion; and mixing the polyurethane modified acrylic ester emulsion with a tackifier and a plasticizer, coating the mixture on a polylactic acid film, and performing processes such as drying, coating release paper and the like to obtain the environment-friendly pressure-sensitive adhesive tape.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an environment-friendly pressure-sensitive adhesive tape and a preparation method thereof.
Background
Pressure-sensitive adhesive tapes are a new type of adhesive tape that can bond the tape to an adherend by applying pressure for only a short period of time. The adhesive has the characteristics of easy use, repeated use and no damage to an adherend during peeling, so that the adhesive has wide application in various fields. However, the common pressure-sensitive adhesive tape is not easy to degrade in natural environment, and the solvent in the production process is difficult to recycle, so that the ecological environment is greatly damaged.
Chinese patent application CN114517063a discloses a preparation method of a PET pressure-sensitive adhesive tape, the performance of the prepared pressure-sensitive adhesive tape is excellent, the initial adhesion is similar to that of normal temperature at-5 ℃, and there is no residual adhesive when peeling, but the solvent ethyl acetate used in the production process is difficult to recover, and is easy to pollute the environment, the substrate used in the pressure-sensitive adhesive tape is a PET film, although the substrate cannot directly damage the natural environment, the pressure-sensitive adhesive tape has strong resistance to the atmosphere and microorganisms, and is difficult to decompose; chinese patent CN112391131B discloses a preparation method of an environment-friendly water-soluble acrylate pressure-sensitive adhesive, the prepared pressure-sensitive adhesive is soluble in water and easy to recycle, but isocyanate is required to be used as an external cross-linking agent for curing the pressure-sensitive adhesive in the production process, the isocyanate is a highly toxic reagent, the harm to human bodies is large, a large amount of organic solvents are still required in the synthesis process, and the environment-friendly idea is not met.
Disclosure of Invention
In order to solve the technical problems, the invention provides an environment-friendly pressure-sensitive adhesive tape and a preparation method thereof, and solves the problems that raw materials are toxic, solvents are difficult to recycle and treat in the synthesis process of the pressure-sensitive adhesive tape, and the pressure-sensitive adhesive tape is not ageing-resistant and difficult to recycle.
In order to achieve the above object, the present invention provides a method for preparing an environment-friendly pressure-sensitive adhesive tape, comprising the steps of:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
mixing glycidyl methacrylate and tetrabutylammonium bromide, introducing carbon dioxide, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, and purifying after the reaction to obtain methacrylic acid five-membered ring carbonate;
mixing methacrylic acid five-membered ring carbonic ester, poly primary amine and N, N' -dimethylformamide, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, and purifying after the reaction to obtain methacrylic acid five-membered ring carbonic ester end-capped non-isocyanate polyurethane prepolymer;
and (2) preparing polyurethane modified acrylic ester emulsion:
mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer with deionized water, shearing and emulsifying, and filtering to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triamino ethoxy phosphite, an emulsifier, an ammonium persulfate aqueous solution and a sodium bicarbonate aqueous solution into a polyurethane prepolymer emulsion, stirring and heating to a set temperature under the inert gas atmosphere, and carrying out heat preservation reaction at the set temperature to obtain a polyurethane modified acrylic ester emulsion;
Wherein the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, cooling and purifying after the reaction to obtain cinnamoyl chloride modified tea polyphenol;
the triamino ethoxy phosphite is prepared by the following steps:
mixing trialkyl phosphite, ethanolamine and dibutyltin dilaurate, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, and carrying out rotary evaporation after the reaction to obtain triamino ethoxy phosphite;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
mixing an emulsifier and deionized water, stirring to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring to obtain an acrylic ester pre-emulsion;
respectively dripping the acrylic ester pre-emulsion and the ammonium persulfate aqueous solution into the polyurethane modified acrylic ester emulsion, carrying out heat preservation reaction, and filtering after the reaction to obtain polyurethane modified acrylic ester composite emulsion;
step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylic ester composite emulsion, adjusting the pH value, adding tackifier rosin glyceride and plasticizer glycerol, mixing and stirring to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film, drying, covering release paper, flattening, cutting and rolling to obtain the environment-friendly pressure-sensitive adhesive tape.
Preferably, in the step (1), the mass ratio of the glycidyl methacrylate to the tetrabutylammonium bromide is 100 (1.2-2.4); setting the temperature to be 130-150 ℃; the reaction time is 2-8h.
Preferably, the carbon dioxide is introduced, comprising two processes:
firstly, introducing carbon dioxide to exhaust air;
and step two, introducing carbon dioxide to pressurize the reaction system to 0.4-0.6MPa.
Preferably, the purification comprises extraction, dehydration, filtration.
Preferably, in the step (1), the mass ratio of the methacrylic acid five-membered ring carbonate to the poly primary amine to the N, N' -dimethylformamide is (1850-1900): (240-1020): (800-1000); setting the temperature to 140-160 ℃; the reaction time is 2-4h;
the primary polyamine comprises at least one of isophorone diamine, hexamethylene diamine and ethylenediamine.
Preferably, the purification comprises rotary evaporation.
Preferably, in the step (2), the mass ratio of the methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite, the emulsifier, the ammonium persulfate aqueous solution, the sodium bicarbonate aqueous solution and the deionized water is (80-240): (232-365): (12-30): (12-30): (3-15): (20-400): (18-48): (270-390); the inert gas includes nitrogen; setting the temperature to 75-95 ℃; the reaction time is 1-1.5h.
Preferably, the inert gas comprises nitrogen.
Preferably, the mass fraction of the sodium bicarbonate aqueous solution is 10%, i.e. the mass percentage of sodium bicarbonate in the sodium bicarbonate aqueous solution is 10%; the mass fraction of the ammonium persulfate aqueous solution is 5%, namely the mass percentage of the ammonium persulfate in the ammonium persulfate aqueous solution is 5%.
Preferably, the acrylate blend monomer includes a hard monomer, a soft monomer, and a functional monomer;
the hard monomer comprises methyl methacrylate;
soft monomers include isooctyl acrylate, butyl acrylate;
functional monomers include hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide, rosin acrylate, N-methylolacrylamide;
the emulsifier comprises a composite emulsifier composed of at least two of sodium allyloxy hydroxypropyl sulfonate, allyl polyethylene glycol, alkyl alcohol alkoxylated sodium sulfate and sodium alkylbenzenesulfonate.
Preferably, in the step (2), when the cinnamoyl chloride modified tea polyphenol is prepared, the mass ratio of the tea polyphenol to the cinnamoyl chloride to the ethyl acetate is (400-500): 150-180): 700-860; setting the temperature to be 45-65 ℃ and the reaction time to be 1.5-3.5h;
preferably, triethylamine is added while the reaction is kept warm to control the pH value of the reaction system to 7-8.
Preferably, the purification comprises extraction, washing, spin-steaming.
Preferably, in the step (2), when the triethoxy phosphite ester is prepared, the mass ratio of trialkyl phosphite, ethanolamine and dibutyl tin dilaurate is (230-270): 255-315): 2.5-4.5; setting the temperature to be 130-150 ℃ and the reaction time to be 2-4h; the trialkyl phosphite is at least one of trimethyl phosphite and triethyl phosphite.
Preferably, the purification comprises rotary evaporation.
Preferably, in the step (3), the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is (610-928), 7-56, 250-630, 40-156 and 754-984; the reaction conditions are 90-100 ℃ and the reaction time is 2-4h;
the acrylate mixed monomer comprises a hard monomer, a soft monomer and a functional monomer;
the hard monomer comprises methyl methacrylate;
soft monomers include isooctyl acrylate, butyl acrylate;
functional monomers include hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide, rosin acrylate, N-methylolacrylamide;
The emulsifier comprises a composite emulsifier composed of at least two of sodium allyloxy hydroxypropyl sulfonate, allyl polyethylene glycol, alkyl alcohol alkoxylated sodium sulfate and sodium alkylbenzenesulfonate.
Preferably, in the step (4), the mass ratio of the rosin glyceride, the adipic acid dihydrazide, the glycerol and the polyurethane modified acrylic emulsion is (80-160): (12-28): (20-80): (1800-2000);
the pH value is adjusted to 7.5-8.5 by adding ammonia water.
Preferably, the invention provides an environment-friendly pressure-sensitive adhesive tape prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the acrylic ester is modified by polyurethane to prepare the pressure-sensitive adhesive, so that on one hand, the polyurethane improves the water resistance, low temperature resistance and flexibility of the acrylic ester; on the other hand, the two are connected through chemical bonds, so that the compatibility between the two is improved, the phase separation problem of a blending system is avoided, and the emulsion system is more stable; the polyurethane of the invention adopts non-isocyanate polyurethane, meets the requirements of environmental protection, and the beta position of the carbamate group generated by the reaction of the polyurethane simultaneously generates a hydroxyl, and the hydroxyl is an active group and can form a crosslinking system with functional monomers through chemical bonds and hydrogen bonds.
The polyurethane modified acrylic pressure-sensitive adhesive is prepared by an emulsion polymerization method, so that the problems that solvents generated by conventional solution polymerization are difficult to recover, and the environment is easy to pollute are avoided, and isocyanate and aziridine high-toxicity crosslinking agents are not required; tea polyphenol is an all-natural antioxidant substance extracted from tea, and the main component of the tea is flavonoid substances, namely catechin compounds, which have polyphenol structures, and the tea polyphenol has excellent antioxidant effect when being compounded with phosphite compounds, and is modified by cinnamoyl chloride, double bonds are introduced to participate in polymerization, so that the compatibility of the flavonoid compounds and the phosphite compounds is increased, and the migration of the tea in colloid is also inhibited; the emulsifier selected in the production process is a composite emulsifier which does not contain a nonylphenol structure and is easy to decompose; the invention selects the polylactic acid film as the substrate film, the polylactic acid is a polymer material which can be degraded in natural environment, and the degraded final product is carbon dioxide and water, has no secondary pollution and meets the requirements of green environmental protection.
Drawings
FIG. 1 is a flow chart of a process for preparing an environmentally friendly pressure sensitive adhesive tape of the present invention;
FIG. 2 is a schematic representation of the synthesis of the triaminoethyl phosphate in the present invention;
FIG. 3 is a schematic diagram of the synthesis of five-membered ring carbonates of methacrylic acid according to the invention;
FIG. 4 is a diagram showing the reaction mechanism of a five-membered ring carbonate and a primary amine in the present invention;
FIG. 5 is a schematic representation of the crosslinking of diacetone acrylamide with adipic acid dihydrazide in the present invention;
FIG. 6 is a graph comparing 180 peel strength of a pressure sensitive adhesive tape of the present invention before and after aging.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
uniformly mixing glycidyl methacrylate and tetrabutylammonium bromide according to the mass ratio of 100:1.2, introducing carbon dioxide, exhausting air, continuously introducing carbon dioxide to pressurize a reaction system to 0.4MPa, stirring and heating to 130 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 8 hours at the temperature of 130 ℃, adding deionized water for mixing, standing for layering, taking an organic phase, adding anhydrous magnesium sulfate for dehydration, and filtering to remove the anhydrous magnesium sulfate to obtain the methacrylic acid five-membered ring carbonate;
Uniformly mixing methacrylic acid five-membered ring carbonic ester, hexamethylenediamine and N, N' -dimethylformamide according to the mass ratio of 1850:240:800, stirring and heating to 140 ℃ at the stirring speed of 180r/min, preserving heat at the temperature of 140 ℃ for 4 hours, and performing rotary evaporation at 135 ℃ after the reaction to obtain methacrylic acid five-membered ring carbonic ester end-capped non-isocyanate polyurethane prepolymer;
and (2) preparing polyurethane modified acrylic ester emulsion:
uniformly mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer and deionized water, shearing and emulsifying for 30min at a shearing speed of 1500r/min, and filtering by using a 200-mesh screen to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite, an emulsifier, 5% ammonium persulfate aqueous solution and 10% sodium bicarbonate aqueous solution into polyurethane prepolymer emulsion, stirring and heating to 75 ℃ under nitrogen atmosphere, and carrying out heat preservation reaction for 1.5 hours at 75 ℃ to obtain polyurethane modified acrylic ester emulsion;
wherein, the mass ratio of methacrylic acid five-membered ring carbonic ester blocked non-isocyanate polyurethane prepolymer, acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite ester, emulsifier, 5% ammonium persulfate aqueous solution, 10% sodium bicarbonate aqueous solution and deionized water is 80:310:12:12:3:20:18:390;
The acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 184:184:368:74:46:46:46:9:9;
the emulsifier is a composite emulsifier composed of alkyl alcohol alkoxylated sodium sulfate and allyl polyethylene glycol according to a mass ratio of 7:3;
the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate according to a mass ratio of 400:150:700, stirring and heating to 45 ℃ at a stirring speed of 180r/min, carrying out heat preservation reaction for 3.5h at the temperature of 45 ℃, adding triethylamine to control the pH value of a reaction system to be 7 while carrying out heat preservation reaction, cooling to room temperature after reaction, adding deionized water to uniformly mix, standing for layering, taking an organic phase, washing the organic phase with deionized water until the pH value of a separated water phase is 7, and removing ethyl acetate by rotary evaporation to obtain cinnamoyl chloride modified tea polyphenol;
the triamino ethoxy phosphite is prepared by the following steps:
mixing trimethyl phosphite, ethanolamine and dibutyltin dilaurate according to the mass ratio of 230:255:2.5, heating to 130 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 4 hours at the temperature of 130 ℃, and removing ethanol serving as a reaction byproduct by rotary evaporation after the reaction to obtain the triethoxy phosphite;
Step (3) preparing polyurethane modified acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
simultaneously and respectively dripping acrylic ester pre-emulsion and ammonium persulfate aqueous solution into polyurethane modified acrylic ester emulsion from two feed inlets, finishing dripping within 3 hours, carrying out heat preservation reaction for 4 hours at 90 ℃, and filtering after the reaction to obtain polyurethane modified acrylic ester composite emulsion;
wherein the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is 610:7:610:40:845;
step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylate composite emulsion, adding ammonia water to adjust the pH value to 7.5, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film with the thickness of 10 mu m, drying for 3min at the temperature of 100 ℃, covering release paper, flattening, cutting and winding to obtain the environment-friendly pressure-sensitive adhesive tape;
The thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride, adipic acid dihydrazide, glycerin and polyurethane acrylic ester composite emulsion is 80:28:20:1800.
Example 2
The embodiment discloses a preparation method of an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
uniformly mixing glycidyl methacrylate and tetrabutylammonium bromide according to the mass ratio of 100:1.5, introducing carbon dioxide, exhausting air, continuously introducing carbon dioxide to pressurize a reaction system to 0.45MPa, stirring and heating to 135 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 6.5 hours at the temperature of 135 ℃, adding deionized water after the reaction, mixing, standing for layering, taking an organic phase, adding anhydrous magnesium sulfate for dehydration, and filtering to remove the anhydrous magnesium sulfate to obtain the methacrylic acid five-membered cyclic carbonate;
uniformly mixing methacrylic acid five-membered ring carbonic ester, isophorone diamine and N, N' -dimethylformamide according to the mass ratio of 1860:440:850, stirring and heating to 145 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 3.5h at the temperature of 145 ℃, and carrying out rotary evaporation at the temperature of 135 ℃ after the reaction to obtain methacrylic acid five-membered ring carbonic ester end-capped non-isocyanate polyurethane prepolymer;
And (2) preparing polyurethane modified acrylic ester emulsion:
uniformly mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer and deionized water, shearing and emulsifying for 28min at a shearing speed of 1600r/min, and filtering by using a 200-mesh screen to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite, an emulsifier, 5% ammonium persulfate aqueous solution and 10% sodium bicarbonate aqueous solution into polyurethane prepolymer emulsion, stirring and heating to 80 ℃ under nitrogen atmosphere, and carrying out heat preservation reaction for 1.4 hours at 80 ℃ to obtain polyurethane modified acrylic ester emulsion;
wherein, the mass ratio of the methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite ester, the emulsifier, the ammonium persulfate aqueous solution with the mass fraction of 5 percent, the sodium bicarbonate aqueous solution with the mass fraction of 10 percent and the deionized water is 120:245:16:16:8:28:21:270;
the acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 176:216:421:59:39:39:15:15;
The emulsifier is a composite emulsifier composed of sodium alkylbenzenesulfonate and allyl polyethylene glycol according to a mass ratio of 16:6;
the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate according to a mass ratio of 430:160:750, stirring and heating to 50 ℃ at a stirring speed of 180r/min, carrying out heat preservation reaction for 3 hours at a temperature of 50 ℃, adding triethylamine to control the pH value of a reaction system to be 7 while carrying out heat preservation reaction, cooling to room temperature after reaction, adding deionized water to uniformly mix, standing for layering, taking an organic phase, washing the organic phase with deionized water until the pH value of a separated water phase is 7, and removing ethyl acetate by rotary evaporation to obtain cinnamoyl chloride modified tea polyphenol;
the triamino ethoxy phosphite is prepared by the following steps:
mixing trimethyl phosphite, ethanolamine and dibutyltin dilaurate according to the mass ratio of 240:270:3.0, heating to 135 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 3.5 hours at the temperature of 135 ℃, and removing ethanol serving as a reaction byproduct by rotary evaporation after the reaction to obtain the triethoxy phosphite;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
The acrylic ester pre-emulsion and ammonium persulfate aqueous solution are simultaneously and respectively dripped into the polyurethane modified acrylic ester emulsion from two feed inlets, dripping is completed within 3 hours, the temperature is kept at 92 ℃ for reaction for 3.5 hours, and after the reaction, the polyurethane modified acrylic ester composite emulsion is obtained by filtering;
wherein, the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is 735:17:630:66:754;
step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylate composite emulsion, adding ammonia water to adjust the pH value to 8, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film with the thickness of 10 mu m, drying for 3min at 105 ℃, covering release paper, flattening, cutting and winding to obtain the environment-friendly pressure-sensitive adhesive tape;
the thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride, adipic acid dihydrazide, glycerin and polyurethane acrylic ester composite emulsion is 100:24:35:1850.
Example 3
The embodiment discloses a preparation method of an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
uniformly mixing glycidyl methacrylate and tetrabutylammonium bromide according to the mass ratio of 100:1.8, introducing carbon dioxide, exhausting air, continuously introducing carbon dioxide to pressurize a reaction system to 0.5MPa, stirring and heating to 140 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 5 hours at the temperature of 140 ℃, adding deionized water to mix, standing for layering, taking an organic phase, adding anhydrous magnesium sulfate for dehydration, and filtering to remove the anhydrous magnesium sulfate to obtain the methacrylic acid five-membered ring carbonate;
uniformly mixing methacrylic acid five-membered ring carbonic ester, ethylenediamine and N, N' -dimethylformamide according to the mass ratio of 1870:640:900, stirring and heating to 150 ℃ at the stirring speed of 180r/min, preserving heat at the temperature of 150 ℃ for 3 hours, and performing rotary evaporation at 135 ℃ after the reaction to obtain methacrylic acid five-membered ring carbonic ester end-capped non-isocyanate polyurethane prepolymer;
and (2) preparing polyurethane modified acrylic ester emulsion:
uniformly mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer and deionized water, shearing and emulsifying for 26min at a shearing speed of 1750r/min, and filtering with a 200-mesh screen to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite, an emulsifier, 5% ammonium persulfate aqueous solution and 10% sodium bicarbonate aqueous solution into polyurethane prepolymer emulsion, stirring and heating to 85 ℃ under nitrogen atmosphere, and carrying out heat preservation reaction for 1.3h at 85 ℃ to obtain polyurethane modified acrylic ester emulsion;
Wherein, the mass ratio of the methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite ester, the emulsifier, the ammonium persulfate aqueous solution with the mass fraction of 5 percent, the sodium bicarbonate aqueous solution with the mass fraction of 10 percent and the deionized water is 160:260:20:20:9:38:32:300;
the acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 156:239:489:52:31:31:21:21;
the emulsifier is a composite emulsifier composed of alkyl alcohol alkoxylated sodium sulfate, allyloxy hydroxypropyl sodium sulfonate and allyl polyethylene glycol according to a mass ratio of 24:6:6;
the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate according to a mass ratio of 450:165:780, stirring and heating to 55 ℃ at a stirring speed of 180r/min, carrying out heat preservation reaction for 2.5h at a temperature of 55 ℃, adding triethylamine to control the pH value of a reaction system to be 7 while carrying out heat preservation reaction, cooling to room temperature after reaction, adding deionized water to uniformly mix, standing for layering, taking an organic phase, washing the organic phase with deionized water until the pH value of a separated water phase is 7, and removing ethyl acetate by rotary evaporation to obtain cinnamoyl chloride modified tea polyphenol;
The triamino ethoxy phosphite is prepared by the following steps:
mixing triethyl phosphite, ethanolamine and dibutyltin dilaurate according to the mass ratio of 250:285:3.5, heating to 140 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 3 hours at the temperature of 140 ℃, and removing ethanol serving as a reaction byproduct by rotary evaporation after the reaction to obtain the triethoxy phosphite;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
simultaneously and respectively dripping acrylic ester pre-emulsion and ammonium persulfate aqueous solution into polyurethane modified acrylic ester emulsion from two feed inlets, finishing dripping within 3 hours, carrying out heat preservation reaction for 3 hours at 95 ℃, and filtering after the reaction to obtain polyurethane modified acrylic ester composite emulsion;
wherein the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is 780:31:500:90:831;
step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
Adding adipic dihydrazide into the polyurethane modified acrylate composite emulsion, adding ammonia water to adjust the pH value to 8.5, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, and coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film with the thickness of 15 mu m; drying at 110deg.C for 2min, covering release paper, leveling, cutting, and winding to obtain environment-friendly pressure-sensitive adhesive tape;
the thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride to the adipic acid dihydrazide to the glycerol to the polyurethane acrylate composite emulsion is 120:20:50:1900.
Example 4
The embodiment discloses a preparation method of an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
uniformly mixing glycidyl methacrylate and tetrabutylammonium bromide according to the mass ratio of 100:2.1, introducing carbon dioxide, exhausting air, continuously introducing carbon dioxide to pressurize a reaction system to 0.55MPa, stirring and heating to 145 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 3.5 hours at the temperature of 145 ℃, adding deionized water after the reaction, mixing, standing for layering, taking an organic phase, adding anhydrous magnesium sulfate for dehydration, and filtering to remove the anhydrous magnesium sulfate to obtain the methacrylic acid five-membered cyclic carbonate;
Uniformly mixing methacrylic acid five-membered ring carbonic ester, hexamethylenediamine-isophorone diamine mixed amine and N, N' -dimethylformamide according to the mass ratio of 1880:840:960, stirring and heating to 155 ℃ at the stirring speed of 180r/min, preserving heat at the temperature of 155 ℃ for 2.5 hours, and performing rotary evaporation at 135 ℃ after the reaction to obtain methacrylic acid five-membered ring carbonic ester blocked non-isocyanate polyurethane prepolymer;
wherein, in the hexamethylenediamine-isophorone diamine mixed amine, the mass ratio of hexamethylenediamine to isophorone diamine is 160:680;
and (2) preparing polyurethane modified acrylic ester emulsion:
uniformly mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer and deionized water, shearing and emulsifying for 23min at a shearing speed of 1900r/min, and filtering by using a 200-mesh screen to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite, an emulsifier, 5% ammonium persulfate aqueous solution and 10% sodium bicarbonate aqueous solution into polyurethane prepolymer emulsion, stirring and heating to 90 ℃ under nitrogen atmosphere, and carrying out heat preservation reaction for 1.2h at 90 ℃ to obtain polyurethane modified acrylic ester emulsion;
Wherein, the mass ratio of the methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite ester, the emulsifier, the ammonium persulfate aqueous solution with the mass fraction of 5 percent, the sodium bicarbonate aqueous solution with the mass fraction of 10 percent and the deionized water is 200:275:25:25:15:39:40:350;
the acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 132:264:561:44:22:22:28:28;
the emulsifier is a composite emulsifier composed of alkyl alcohol alkoxylated sodium sulfate and allyl polyethylene glycol according to a mass ratio of 39:13;
the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate according to a mass ratio of 470:170:810, stirring and heating to 60 ℃ at a stirring speed of 180r/min, carrying out heat preservation reaction for 2 hours at the temperature of 60 ℃, adding triethylamine to control the pH value of a reaction system to be 7 while carrying out heat preservation reaction, cooling to room temperature after reaction, adding deionized water to uniformly mix, standing for layering, taking an organic phase, washing the organic phase with deionized water until the pH value of a separated water phase is 7, and removing ethyl acetate by rotary evaporation to obtain cinnamoyl chloride modified tea polyphenol;
The triamino ethoxy phosphite is prepared by the following steps:
mixing triethyl phosphite, ethanolamine and dibutyltin dilaurate according to the mass ratio of 260:300:4.0, heating to 145 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 2.5 hours at the temperature of 145 ℃, and removing ethanol serving as a reaction byproduct by rotary evaporation after the reaction to obtain the triethoxy-triamine phosphite;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
simultaneously and respectively dripping acrylic ester pre-emulsion and ammonium persulfate aqueous solution into polyurethane modified acrylic ester emulsion from two feed inlets, finishing dripping within 3 hours, carrying out heat preservation reaction at 98 ℃ for 2.5 hours, and filtering after the reaction to obtain polyurethane modified acrylic ester composite emulsion;
wherein the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is 825:40:350:123:969;
Step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylic ester composite emulsion, adding ammonia water to adjust the pH value to 8, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film with the thickness of 15 mu m, drying for 3min at 105 ℃, covering release paper, flattening, cutting and winding to obtain the environment-friendly pressure-sensitive adhesive tape;
the thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride, adipic acid dihydrazide, glycerol and polyurethane acrylate composite emulsion is 140:16:65:1950.
Example 5
The embodiment discloses a preparation method of an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
uniformly mixing glycidyl methacrylate and tetrabutylammonium bromide according to the mass ratio of 100:2.4, introducing carbon dioxide, exhausting air, continuously introducing carbon dioxide to pressurize a reaction system to 0.6MPa, stirring and heating to 150 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 2 hours at the temperature of 150 ℃, adding deionized water to react, mixing, standing for layering, taking an organic phase, adding anhydrous magnesium sulfate for dehydration, and filtering to remove the anhydrous magnesium sulfate to obtain the methacrylic acid five-membered ring carbonate;
Uniformly mixing methacrylic acid five-membered ring carbonic ester, ethylenediamine-isophorone diamine mixed amine and N, N' -dimethylformamide according to the mass ratio of 1890:1020:1000, stirring and heating to 160 ℃ at the stirring speed of 180r/min, preserving heat at 160 ℃ for 2 hours, and performing rotary evaporation at 135 ℃ after the reaction to obtain methacrylic acid five-membered ring carbonic ester capped non-isocyanate polyurethane prepolymer;
wherein, in the ethylenediamine-isophorone diamine mixed amine, the mass ratio of ethylenediamine to isophorone diamine is 60:960;
and (2) preparing polyurethane modified acrylic ester emulsion:
uniformly mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer and deionized water, shearing and emulsifying for 20min at a shearing speed of 2000r/min, and filtering by a 200-mesh screen to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite, an emulsifier, 5% ammonium persulfate aqueous solution and 10% sodium bicarbonate aqueous solution into polyurethane prepolymer emulsion, stirring and heating to 95 ℃ under nitrogen atmosphere, and carrying out heat preservation reaction for 1h at 95 ℃ to obtain polyurethane modified acrylic ester emulsion;
Wherein, the mass ratio of the methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite ester, the emulsifier, the ammonium persulfate aqueous solution with the mass fraction of 5 percent, the sodium bicarbonate aqueous solution with the mass fraction of 10 percent and the deionized water is 240:232:30:30:14:40:48:350;
the acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 116:290:638:23:12:12:35:35;
the emulsifier is a composite emulsifier composed of sodium alkylbenzenesulfonate, alkyl alcohol alkoxylated sodium sulfate and allyl polyethylene glycol according to a mass ratio of 25:25:20;
the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate according to a mass ratio of 500:180:860, stirring and heating to 65 ℃ at a stirring speed of 180r/min, carrying out heat preservation reaction for 1.5h at a temperature of 65 ℃, adding triethylamine to control the pH value of a reaction system to be 7 while carrying out heat preservation reaction, cooling to room temperature after reaction, adding deionized water to uniformly mix, standing for layering, taking an organic phase, washing the organic phase with deionized water until the pH value of a separated water phase is 7, and removing ethyl acetate by rotary evaporation to obtain cinnamoyl chloride modified tea polyphenol;
The triamino ethoxy phosphite is prepared by the following steps:
mixing trimethyl phosphite-triethyl phosphite mixture, ethanolamine and dibutyl tin dilaurate according to the mass ratio of 270:300:4.5, heating to 150 ℃ at the stirring speed of 180r/min, preserving heat at the temperature of 150 ℃ for 2 hours, and removing ethanol as a reaction byproduct by rotary evaporation after the reaction to obtain the triaminoethoxyphosphite;
wherein, in the trimethyl phosphite-triethyl phosphite mixture, the mass ratio of trimethyl phosphite to triethyl phosphite is 110:160;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
simultaneously and respectively dripping acrylic ester pre-emulsion and ammonium persulfate aqueous solution into polyurethane modified acrylic ester emulsion from two feed inlets, finishing dripping within 3 hours, carrying out heat preservation reaction for 2 hours at 100 ℃, and filtering after the reaction to obtain polyurethane modified acrylic ester composite emulsion;
wherein, the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is 928:56:250:156:984;
Step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylic ester composite emulsion, adding ammonia water to adjust the pH value to 7.5, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film with the thickness of 15 mu m, drying for 3min at 105 ℃, covering release paper, flattening, cutting and winding to obtain the environment-friendly pressure-sensitive adhesive tape;
the thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride, adipic acid dihydrazide, glycerin and polyurethane acrylic ester composite emulsion is 160:12:80:2000.
Comparative example 1
The comparative example discloses a method for preparing an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
uniformly mixing glycidyl methacrylate and tetrabutylammonium bromide according to the mass ratio of 100:1.5, introducing carbon dioxide, exhausting air, continuously introducing carbon dioxide to pressurize a reaction system to 0.45MPa, stirring and heating to 135 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 6.5 hours at the temperature of 135 ℃, adding deionized water after the reaction, mixing, standing for layering, taking an organic phase, adding anhydrous magnesium sulfate for dehydration, and filtering to remove the anhydrous magnesium sulfate to obtain the methacrylic acid five-membered cyclic carbonate;
Uniformly mixing methacrylic acid five-membered ring carbonic ester, isophorone diamine and N, N' -dimethylformamide according to the mass ratio of 1860:440:850, stirring and heating to 145 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 3.5h at the temperature of 145 ℃, and carrying out rotary evaporation at the temperature of 135 ℃ after the reaction to obtain methacrylic acid five-membered ring carbonic ester end-capped non-isocyanate polyurethane prepolymer;
and (2) preparing polyurethane modified acrylic ester emulsion:
uniformly mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer and deionized water, shearing and emulsifying for 28min at a shearing speed of 1600r/min, and filtering by using a 200-mesh screen to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, an emulsifier, an ammonium persulfate aqueous solution with the mass fraction of 5% and a sodium bicarbonate aqueous solution with the mass fraction of 10% into the polyurethane prepolymer emulsion, stirring and heating to 80 ℃ under the nitrogen atmosphere, and carrying out heat preservation reaction for 1.4h at the temperature of 80 ℃ to obtain polyurethane modified acrylic ester emulsion;
wherein, the mass ratio of the methacrylic acid five-membered ring carbonic ester blocked non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the emulsifier, the ammonium persulfate aqueous solution with the mass fraction of 5 percent, the sodium bicarbonate aqueous solution with the mass fraction of 10 percent and the deionized water is 120:245:8:28:21:302;
The acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 176:216:421:59:39:39:15:15;
the emulsifier is a composite emulsifier composed of sodium alkylbenzenesulfonate and allyl polyethylene glycol according to a mass ratio of 16:6;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
the acrylic ester pre-emulsion and ammonium persulfate aqueous solution are simultaneously and respectively dripped into the polyurethane modified acrylic ester emulsion from two feed inlets, dripping is completed within 3 hours, the temperature is kept at 92 ℃ for reaction for 3.5 hours, and after the reaction, the polyurethane modified acrylic ester composite emulsion is obtained by filtering;
wherein, the mass ratio of the acrylate mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent to the polyurethane modified acrylate emulsion is 735:17:630:66:754;
Step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylic ester composite emulsion, adding ammonia water to adjust the pH value to 8, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film with the thickness of 10 mu m, drying for 3min at 105 ℃, covering release paper, flattening, cutting and winding to obtain the environment-friendly pressure-sensitive adhesive tape;
the thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride, adipic acid dihydrazide, glycerol, tea polyphenol, trimethyl phosphite and polyurethane acrylate composite emulsion is 100:24:35:16:16:1850.
Comparative example 2
The comparative example discloses a method for preparing an environment-friendly pressure-sensitive adhesive tape, which comprises the following steps:
step (1) preparing an acrylic ester emulsion:
uniformly mixing an acrylic ester mixed monomer, deionized water and an emulsifier, shearing and emulsifying for 28min at a shearing speed of 1600r/min, adding cinnamoyl chloride modified tea polyphenol, triaminoethoxyphosphite ester, 5% ammonium persulfate aqueous solution and 10% sodium bicarbonate aqueous solution, stirring and heating to 80 ℃ in a nitrogen atmosphere, and carrying out heat preservation reaction for 1.4h at the temperature of 80 ℃ to obtain an acrylic ester emulsion;
The mass ratio of the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite, the emulsifier, the ammonium persulfate aqueous solution with the mass fraction of 5 percent, the sodium bicarbonate aqueous solution with the mass fraction of 10 percent and the deionized water is 365:16:16:8:28:21:270;
the acrylic ester mixed monomer comprises methyl methacrylate, isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide and N-methylol acrylamide according to the mass ratio of 176:216:421:59:39:39:15:15;
the emulsifier is a composite emulsifier composed of sodium alkylbenzenesulfonate and allyl polyethylene glycol according to a mass ratio of 16:6;
the cinnamoyl chloride modified tea polyphenol is prepared by the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate according to a mass ratio of 430:160:750, stirring and heating to 50 ℃ at a stirring speed of 180r/min, carrying out heat preservation reaction for 3 hours at a temperature of 50 ℃, adding triethylamine to control the pH value of a reaction system to be 7 while carrying out heat preservation reaction, cooling to room temperature after reaction, adding deionized water to uniformly mix, standing for layering, taking an organic phase, washing the organic phase with deionized water until the pH value of a separated water phase is 7, and removing ethyl acetate by rotary evaporation to obtain cinnamoyl chloride modified tea polyphenol;
The triamino ethoxy phosphite is prepared by the following steps:
mixing trimethyl phosphite, ethanolamine and dibutyltin dilaurate according to the mass ratio of 240:270:3.0, heating to 135 ℃ at the stirring speed of 180r/min, carrying out heat preservation reaction for 3.5 hours at the temperature of 135 ℃, and removing ethanol serving as a reaction byproduct by rotary evaporation after the reaction to obtain the triethoxy phosphite;
and (2) preparing an acrylic ester composite emulsion:
uniformly mixing an emulsifier and deionized water, stirring for 0.5h at a stirring speed of 500r/min to obtain an emulsifier solution, adding an acrylic ester mixed monomer into the emulsifier solution, and stirring for 1h at a stirring speed of 500r/min to obtain an acrylic ester pre-emulsion;
simultaneously and respectively dripping acrylic ester pre-emulsion and ammonium persulfate aqueous solution into acrylic ester emulsion from two feed inlets, finishing dripping within 3 hours, carrying out heat preservation reaction for 3.5 hours at 92 ℃, and filtering after the reaction to obtain acrylic ester composite emulsion;
wherein, the mass ratio of the acrylic ester mixed monomer, the emulsifier, the deionized water, the ammonium persulfate aqueous solution with the mass fraction of 5 percent and the acrylic ester emulsion is 735:17:630:66:754;
step (3) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the acrylic ester composite emulsion, adding ammonia water to adjust the pH value to 8, adding rosin glyceride and glycerol, mixing and stirring for 1h at the stirring speed of 180r/min to obtain environment-friendly pressure-sensitive adhesive liquid, and coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film; drying for 3min at 105 ℃, covering release paper, flattening, cutting and rolling to obtain the environment-friendly pressure-sensitive adhesive tape;
The thickness of the pressure-sensitive adhesive layer of the environment-friendly pressure-sensitive adhesive tape is 30 mu m;
wherein the mass ratio of the rosin glyceride, adipic acid dihydrazide, glycerin and polyurethane acrylic ester composite emulsion is 100:24:35:1850.
In all of the above examples, comparative examples, tea polyphenols were obtained from Baister Productivity supplier with CAS number 84650-62-2 (C 22 H 18 O 11 ) The method comprises the steps of carrying out a first treatment on the surface of the Cinnamoyl chloride is from Shandong Orthosiphon chemical Co., ltd, with CAS number 102-92-1; trimethyl phosphite is available from Wuhan Carnot, inc., CAS number 121-45-9; triethyl phosphite was obtained from Shanghai Jizhui Biochemical technology Co., ltd, under the product number T98350; the ethanolamine is from Jinan ren chemical industry Co., ltd, and the CAS number is 141-43-5; glycidyl methacrylate is from Shandong middle air technology services Co., ltd, CAS number 106-91-2; isophoronediamine is from Jinan Bai evolutionary engineering Co., ltd, with CAS number 2855-13-2; hexamethylenediamine from Shanghai Gao Ming chemical Co., ltd., product number 16516; the ethylenediamine is from Jinan chemical industry Co., ltd, and the CAS number is 107-15-3; methyl methacrylate is from Nantong Runfeng petrochemical Co., ltd, with CAS number of 80-62-6; isooctyl acrylate is from Asparagus chemical Co., ltd, CAS number 103-11-7; butyl acrylate comes from Jinan Kai technology development Co., ltd, with CAS number 14-32-2; hydroxyethyl acrylate is from Hubei Jusheng technology Co., ltd, CAS number 818-61-1; carboxyethyl acrylate is from Sanwang chemical materials Co., ltd., guangzhou, with CAS number 24615-84-7; acrylic acid is from Shanghai Jizhui Biochemical technology Co., ltd, CAS number 79-10-7; diacetone acrylamide is from Shanghai Michael Biochemical technology Co., ltd, with CAS number 2873-97-4; n-methylolacrylamide is from the Mian Kandelia Mian Chemicals vendor with CAS number 924-42-5; allyl polyethylene glycol is available from Haian Hua En surfactant Inc., under the product number APEG-700; sodium alkylbenzenesulfonate is available from Shanghai Seiyaka Biotechnology Co., ltd., product number S28696; rosin glyceride is from Jiangsu Miao biosciences, inc., CAS number 8050-31-5; adipic acid dihydrazide from Shanghai sources Leaf Biotechnology Co., ltd., CAS number 1071-93-8.
Test one: initial tack test: the environment-friendly pressure-sensitive adhesives prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to primary tackiness test according to GB/T4852-2002 method for primary tackiness test of pressure-sensitive adhesive tapes (ball method), and the test results are shown in Table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Primary adhesion (Steel ball size) | 12 | 13 | 14 | 15 | 15 | 13 | 12 |
As can be seen from Table 1, the environment-friendly pressure-sensitive adhesive tape prepared by the invention has excellent initial tackiness, and as can be seen from example 2 and comparative example 2, the initial tackiness of the polyurethane-modified acrylate pressure-sensitive adhesive tape is better, and as can be seen from examples 1 to 5, the initial tackiness of the pressure-sensitive adhesive tape is gradually increased as the polyurethane content is increased and the ratio of soft and hard monomers in the acrylate monomers is increased.
And II, testing: hold tack test: the environment-friendly pressure-sensitive adhesive tapes prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to a holding power test according to GB/T4851-2014 test method for holding power of adhesive tapes, and the test results are shown in Table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Hold adhesive (h) | 138 | 113 | 91 | 67 | 45 | 111 | 106 |
As can be seen from Table 2, the environment-friendly pressure-sensitive adhesive tape prepared by the invention has better holding power, and as can be seen from example 2 and comparative example 2, the pressure-sensitive adhesive tape modified by polyurethane has relatively better holding power; it can be seen from examples 1 to 5 that as the ratio of the soft and hard monomers in the acrylate mixed monomer is larger, the content of the functional monomer is reduced, the degree of crosslinking in the polymer system is reduced, and the holding power of the pressure-sensitive adhesive tape is also reduced.
And (3) testing: test of 180 ° peel strength: the environment-friendly pressure-sensitive adhesive tapes prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to 180 ° peel strength test according to GB/T2792-2014 test method for adhesive tape peel strength, and the test results are shown in table 3:
TABLE 3 Table 3
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| 180 degree peel strength (N/25 mm) | 3.21 | 3.52 | 3.73 | 3.64 | 3.53 | 3.51 | 3.61 |
| With or without residual glue | Without any means for | Without any means for | Without any means for | Without any means for | Without any means for | Without any means for | Without any means for |
As can be seen from Table 3, the environment-friendly pressure-sensitive adhesive tape prepared by the invention has excellent 180 DEG peel strength performance, small peel strength and no residual adhesive during peeling; as can be seen from example 2 and comparative example 2, the peel strength of the polyurethane modified acrylate pressure sensitive adhesive was slightly higher relative to the unmodified acrylate pressure sensitive adhesive; as can be seen from examples 1 to 5, as the ratio of the soft and hard monomers in the acrylate monomer is larger, the content of the functional monomer is reduced, the degree of crosslinking in the polymer system is reduced, and the 180 DEG peel strength of the pressure-sensitive adhesive tape tends to be increased and then decreased.
And (4) testing: aging performance test: the environment-friendly pressure-sensitive adhesive tapes prepared in examples 1 to 5 and comparative examples 1 to 2 were tested for high temperature and high humidity aging resistance according to GB/T32368-2015 test method for high temperature and high humidity aging resistance of adhesive tapes, and the test results are shown in Table 4:
TABLE 4 Table 4
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| 180 degree peel strength (N/25 mm) | 3.05 | 3.42 | 3.62 | 3.51 | 3.41 | 3.28 | 3.47 |
As can be seen from the test results in Table 4, the 180 DEG peel strength of the environment-friendly pressure-sensitive adhesive tape prepared by the invention after aging is slightly reduced compared with that of the environment-friendly pressure-sensitive adhesive tape without aging, and as can be seen from example 2 and comparative example 1, the compatibility between the environment-friendly pressure-sensitive adhesive tape prepared by the invention and the pressure-sensitive adhesive is improved by grafting tea polyphenol and phosphite ester compounds on acrylic ester through chemical bonding, and migration of the environment-friendly pressure-sensitive adhesive tape in colloid is inhibited, so that the 180 DEG peel strength of the pressure-sensitive adhesive obtained through physical blending after aging is obviously reduced.
Test five: testing of the biodegradation rate: the determination of the final aerobic biological decomposition capacity of materials under controlled composting conditions was carried out according to GB/T19277.1-2011, part 1 of the method for determining carbon dioxide release: general methods, determination of the final aerobic biological decomposition Capacity of materials under controlled composting conditions, section 2 of the method for determination of carbon dioxide release, GB/T19277.2-2013: the environment-friendly pressure-sensitive adhesive tapes prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to a biodegradation rate test by gravimetric analysis of carbon dioxide release amount under laboratory conditions, and the test results are shown in table 5:
TABLE 5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Biological decomposition Rate/% | 78% | 82% | 85% | 89% | 93% | 83% | 81% |
As can be seen from Table 5, the biological decomposition rate of the environment-friendly pressure-sensitive adhesive tape prepared by the invention is higher than 75%, and examples 1 to 5 show that as the proportion of the soft and hard monomers in the acrylate mixed monomer is larger, the content of the functional monomers is reduced, the crosslinking degree in the polymer system is reduced, the attack of microorganisms is easier, and the biological decomposition rate is gradually increased, which can be higher than 90% at most.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the environment-friendly pressure-sensitive adhesive tape is characterized by comprising the following steps of:
step (1) preparing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer:
mixing glycidyl methacrylate and tetrabutylammonium bromide, introducing carbon dioxide, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, and purifying after the reaction to obtain methacrylic acid five-membered ring carbonate;
Mixing methacrylic acid five-membered ring carbonic ester, poly primary amine and N, N' -dimethylformamide, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, and purifying after the reaction to obtain methacrylic acid five-membered ring carbonic ester end-capped non-isocyanate polyurethane prepolymer;
and (2) preparing polyurethane modified acrylic ester emulsion:
mixing methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer with deionized water, shearing and emulsifying, and filtering to obtain polyurethane prepolymer emulsion; adding an acrylic ester mixed monomer, cinnamoyl chloride modified tea polyphenol, triamino ethoxy phosphite, an emulsifier, an ammonium persulfate aqueous solution and a sodium bicarbonate aqueous solution into a polyurethane prepolymer emulsion, stirring and heating to a set temperature under the inert gas atmosphere, and carrying out heat preservation reaction at the set temperature to obtain a polyurethane modified acrylic ester emulsion;
step (3) preparing polyurethane modified acrylic ester composite emulsion:
step (4) preparing an environment-friendly pressure-sensitive adhesive tape:
adding adipic acid dihydrazide into the polyurethane modified acrylic ester composite emulsion, adjusting the pH value, adding tackifier rosin glyceride and plasticizer glycerol, mixing and stirring to obtain environment-friendly pressure-sensitive adhesive liquid, coating the environment-friendly pressure-sensitive adhesive liquid on a polylactic acid film, drying, covering release paper, flattening, cutting and rolling to obtain the environment-friendly pressure-sensitive adhesive tape.
2. The method for preparing the environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (1), the mass ratio of glycidyl methacrylate to tetrabutylammonium bromide is 100 (1.2-2.4); setting the temperature to be 130-150 ℃; the reaction time is 2-8h.
3. The method for preparing the environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (1), the mass ratio of methacrylic acid five-membered ring carbonate, poly primary amine and N, N' -dimethylformamide is (1850-1900): 240-1020): 800-1000; setting the temperature to 140-160 ℃; the reaction time is 2-4h;
the primary polyamine comprises at least one of isophorone diamine, hexamethylene diamine and ethylenediamine.
4. The method for preparing the environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (2), the mass ratio of the methacrylic acid five-membered ring carbonate end-capped non-isocyanate polyurethane prepolymer, the acrylic ester mixed monomer, the cinnamoyl chloride modified tea polyphenol, the triaminoethoxyphosphite, the emulsifier, the ammonium persulfate aqueous solution, the sodium bicarbonate aqueous solution and the deionized water is (80-240): 232-365): 12-30): 3-15): 20-400: 18-48: (270-390); the speed of shearing emulsification is 1500-2000r/min; the inert gas includes nitrogen; setting the temperature to 75-95 ℃; the reaction time is 1-1.5h.
5. The method for preparing an environmentally friendly pressure sensitive adhesive tape according to claim 4, wherein the acrylate mixed monomer comprises a hard monomer, a soft monomer and a functional monomer;
the hard monomer comprises methyl methacrylate;
soft monomers include isooctyl acrylate, butyl acrylate;
functional monomers include hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide, rosin acrylate, N-methylolacrylamide;
the emulsifier comprises a composite emulsifier composed of at least two of sodium allyloxy hydroxypropyl sulfonate, allyl polyethylene glycol, alkyl alcohol alkoxylated sodium sulfate and sodium alkylbenzenesulfonate.
6. The method for preparing the environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (2), the cinnamoyl chloride modified tea polyphenol comprises the following steps:
mixing tea polyphenol, cinnamoyl chloride and ethyl acetate, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, cooling and purifying after the reaction to obtain cinnamoyl chloride modified tea polyphenol;
the mass ratio of tea polyphenol to cinnamoyl chloride to ethyl acetate is (400-500) (150-180) (700-860); setting the temperature to be 45-65 ℃ and the reaction time to be 1.5-3.5h.
7. The method for preparing an environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (2), the triethoxy-triamine phosphite ester comprises the following steps:
mixing trialkyl phosphite, ethanolamine and dibutyltin dilaurate, stirring and heating to a set temperature, carrying out heat preservation reaction at the set temperature, and carrying out rotary evaporation after the reaction to obtain triamino ethoxy phosphite;
the mass ratio of the trialkyl phosphite to the ethanolamine to the dibutyl tin dilaurate is (230-270): 255-315): 2.5-4.5; setting the temperature to be 130-150 ℃ and the reaction time to be 2-4h; the trialkyl phosphite is at least one of trimethyl phosphite and triethyl phosphite.
8. The method for preparing an environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (3), an emulsifier and deionized water are mixed and stirred to prepare an emulsifier solution, an acrylic ester mixed monomer is added into the emulsifier solution and stirred to obtain an acrylic ester pre-emulsion;
respectively dripping the acrylic ester pre-emulsion and the ammonium persulfate aqueous solution into the polyurethane modified acrylic ester emulsion, carrying out heat preservation reaction, and filtering after the reaction to obtain polyurethane modified acrylic ester composite emulsion;
The mass ratio of the acrylic ester mixed monomer to the emulsifier to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent is (610-928), the mass ratio of the polyurethane modified acrylic ester emulsion to the polyurethane modified acrylic ester emulsion is (7-56), the mass ratio of the acrylic ester mixed monomer to the emulsifier to the deionized water to the polyurethane modified acrylic ester emulsion is (250-630), the mass ratio of the acrylic ester mixed monomer to the deionized water to the ammonium persulfate aqueous solution with the mass fraction of 5 percent is (754-984); the reaction conditions are 90-100 ℃ and the reaction time is 2-4h;
the acrylate mixed monomer comprises a hard monomer, a soft monomer and a functional monomer;
the hard monomer comprises methyl methacrylate;
soft monomers include isooctyl acrylate, butyl acrylate;
functional monomers include hydroxyethyl acrylate, carboxyethyl acrylate, acrylic acid, diacetone acrylamide, rosin acrylate, N-methylolacrylamide;
the emulsifier comprises a composite emulsifier composed of at least two of sodium allyloxy hydroxypropyl sulfonate, allyl polyethylene glycol, alkyl alcohol alkoxylated sodium sulfate and sodium alkylbenzenesulfonate.
9. The method for preparing the environment-friendly pressure-sensitive adhesive tape according to claim 1, wherein in the step (4), the mass ratio of rosin glyceride, adipic dihydrazide, glycerin and polyurethane modified acrylic emulsion is (80-160): 12-28): 20-80): 1800-2000;
the pH value is adjusted to 7.5-8.5 by adding ammonia water.
10. An environmental-friendly pressure-sensitive adhesive tape prepared by the method for preparing an environmental-friendly pressure-sensitive adhesive tape according to any one of claims 1 to 9.
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