CN108264606B - Preparation method of acrylate high-performance environment-friendly pressure-sensitive adhesive - Google Patents
Preparation method of acrylate high-performance environment-friendly pressure-sensitive adhesive Download PDFInfo
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- CN108264606B CN108264606B CN201810062833.9A CN201810062833A CN108264606B CN 108264606 B CN108264606 B CN 108264606B CN 201810062833 A CN201810062833 A CN 201810062833A CN 108264606 B CN108264606 B CN 108264606B
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- acrylate
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- monomer
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 73
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 239000000839 emulsion Substances 0.000 claims abstract description 62
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical group [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- LWUICDQVEORCSP-UHFFFAOYSA-L disodium butanoate Chemical compound [Na+].[Na+].CCCC([O-])=O.CCCC([O-])=O LWUICDQVEORCSP-UHFFFAOYSA-L 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical group CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 31
- 239000002245 particle Substances 0.000 description 22
- 230000001070 adhesive effect Effects 0.000 description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 description 15
- 239000004816 latex Substances 0.000 description 15
- 229920000126 latex Polymers 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000037351 starvation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OSOUVRPBZFTYNQ-UHFFFAOYSA-N C(CCC)(=O)OCCCCC.C(CCC)(=O)OCCCCC.[Na] Chemical compound C(CCC)(=O)OCCCCC.C(CCC)(=O)OCCCCC.[Na] OSOUVRPBZFTYNQ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000000231 Ficus thonningii Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Abstract
The invention relates to a preparation method of an acrylate high-performance environment-friendly pressure-sensitive adhesive. The method comprises the following steps: a. preparing a seed pre-emulsion; b. preparing a shell layer monomer pre-emulsion; c. and (4) preparing the core-shell emulsion. The invention uses a charging mode of continuously dropping an oxidation-reduction initiator at a constant speed to replace a one-time charging mode of a thermal initiator, and the shell layer adopts a blending crosslinking agent of divinyl benzene and bis-methacrylic acid polyglycidyl ester and takes the polypentyl acrylate as a seed. The pressure-sensitive adhesive obtained by the invention has excellent water resistance and lasting viscosity, and the polymerization temperature is reduced in the polymerization process, so that the energy is saved.
Description
Technical Field
The invention relates to the field of preparation of high-performance environment-friendly pressure-sensitive adhesives, in particular to a method for preparing a core/shell polymer emulsion polymerization and pressure-sensitive adhesive.
Background
Pressure-sensitive adhesive (PSA) is a viscoelastic material that can adhere to the surface of an adherend under a relatively low contact Pressure and a relatively short contact time, and is widely used in packaging, printing, construction, electrical appliances, and even medical hygiene. The acrylate pressure-sensitive adhesive is widely applied at present, has pressure-sensitive property and does not need to be added with other tackifiers; the polymer has no unsaturated bonds and has excellent oxidation resistance and weather resistance; the product is colorless, transparent and does not turn yellow after illumination. The influence of the soft monomer composition in the acrylate pressure-sensitive adhesive on the performance of the pressure-sensitive adhesive is researched by Luguangdu and the like. The research finds that: with the increase of the using amount of isooctyl acrylate (2-EHA), the initial adhesion and stripping performance of the pressure-sensitive adhesive are obviously improved, and when the ratio of 2-EHA to BA is 2: 1, the best performance. This is because the 2-EHA has a long hydrocarbon group, and the molecular chain is flexible and has good wettability. But when the ratio thereof exceeds 2: 1, the rigidity of the pressure-sensitive adhesive becomes insufficient, and the shear strength and the tack-holding property are seriously lowered. The synthesis and performance research of acrylate pressure-sensitive adhesives (LvGuanpu, Li Yi Jiang, Guo Yan, etc.; [ J ] bonding, 2009(9):46-49.) Yanghuanxin, etc. uses ethyl acetate as solvent, AIBN as initiator, and adopts improved solution polymerization process to research the influence of internal cross-linking agent TC, external cross-linking agent aziridine (Sac-100) and aqueous polyisocyanate (Bayhydur 3100) on the peeling strength and heat resistance of the adhesive. Researches show that the cohesive force of the colloid can be obviously increased and the residual gum removing effect is obvious by introducing the internal and external cross-linking agents. The introduction of the external cross-linking agent Sac-100 has better effects than Bayhydur3100 in the aspects of improving the colloid heat resistance and reducing the peel strength; the surface protection film prepared by adopting the internal cross-linking agent TC with the monomer content of 0.80% and the external cross-linking agent Sac-100 with the glue solution content of 1.0% has good performance, and does not have any residual glue and shadow in the heat resistance detection of the high-finish stainless steel plate. (Yanghuaxin, Rong, Xiang in forest. influence of cross-linking agent on performance of solvent type acrylate pressure-sensitive adhesive for protective film [ J ]. chemistry and adhesion, 2009, 31(1):14-17.) however, polyisocyanates and aziridine used in experiments belong to highly toxic reagents, have great harm to human body, and use of a large amount of organic solvent has great pollution to environment, and violate the concept of green environmental protection. Ficus microcarpa and the like adopt a bulk polymerization method, prepolymer of acrylic ester is prepared by changing a feeding mode of a core-shell monomer and a proper amount of chain transfer agent, and then a photoinitiator dissolved in a solvent is mixed with the prepolymer for UV curing. (Chenyanzhen, Chengrongming, Lizhongqing, and the like. preparation of UV curing polyacrylate pressure-sensitive adhesive and performance research thereof [ J ] Chinese adhesive, 2006, 15(8):28-30.) the pressure-sensitive adhesive prepared by the method has the problems of residual solvent, general pressure-sensitive performance, easy yellowing, peculiar smell and the like. Li and the like are introduced into the acrylate pressure-sensitive adhesive by a heat treatment method through a seed semi-continuous emulsion polymerization method to obtain the high-peel-strength low-residue siloxane modified polyacrylate pressure-sensitive adhesive. (Li P, Nian F, Zhang M, et al, siloxane-modified polyacrylate low-residual pressure-sensitive adhesive with high-molecular tension [ J ]. Journal of Applied Polymer Science,2016,133 (8)), but this method is cumbersome to operate, complicated in steps, and not very applicable.
At present, in order to improve or enhance the comprehensive performance of the acrylate emulsion, the acrylate emulsion is often designed into a core-shell structure. The polymer emulsion with the core-shell structure has an out-of-phase structure, so that the polymer emulsion has excellent performance which is difficult to obtain by common random copolymers and mechanical blends, can be designed according to actual requirements, and has a very high application prospect. However, in actual operation, there are still problems of low monomer conversion rate, low solid content, high energy consumption, and the like, for example, in the previous patent CN100425631C, "polyacrylate composite emulsion for pressure-sensitive adhesive and preparation and application methods thereof", the initiator one-time feeding method adopted is liable to cause too high local polymerization temperature, insufficient monomer reaction, minimum monomer conversion rate of 93.28%, and wide particle size distribution, which reaches 0.102, and does not belong to a narrow distribution range, and the adopted thermal initiation mode of potassium persulfate is relatively high in emulsion polymerization temperature. In addition, the acrylic pressure-sensitive adhesive has high water absorption, for example, in patent CN1517422A, "peelable emulsion pressure-sensitive adhesive and pressure-sensitive adhesive sheet", an external cross-linking agent of water-dispersible polyisocyanate is used to reduce the peel strength, but the water-dispersible polyisocyanate reacts with water in the emulsion to reduce the degree of cross-linking, thereby reducing the water resistance and shortening the service life of the pressure-sensitive adhesive.
Disclosure of Invention
The invention aims to conform to the current high-efficiency, environment-friendly and economic green development concept, and solves the problems of high energy consumption, large pollution and poor water resistance in the preparation process of the pressure-sensitive adhesive by replacing a solvent method with a starvation charging seed emulsion polymerization method. The one-time feeding mode of the thermal initiator is replaced by the feeding mode of continuously and uniformly dropping the oxidation-reduction initiator, the initiator solution is continuously and uniformly dropped, the extremely high monomer conversion rate can be kept and is more than 99.5 percent, the latex particles with narrow particle size distribution are obtained, the PDI is less than 0.02, the content of the coalescent is less than 0.5 weight percent, the polymerization temperature is reduced in the polymerization process, and the energy is saved. The shell layer adopts a blending crosslinking agent of divinyl benzene and diethylene glycol dimethacrylate, so that the pressure-sensitive adhesive is endowed with excellent water resistance and lasting viscosity. The composite modified emulsion with the core-shell structure is prepared by taking the amyl polyacrylate as a seed, the amyl polyacrylate and the isooctyl acrylate as shell soft monomers and acrylamide, acrylic acid or a mixture of the acrylamide and the hydroxyethyl acrylate as shell functional monomers.
The technical scheme of the invention is as follows:
a preparation method of acrylate high-performance environment-friendly pressure-sensitive adhesive comprises the following steps:
a. preparation of seed Pre-emulsion
The material composition and the proportion are as follows:
firstly, adding the emulsifier, the acrylate monomer and the deionized water with the specified mass into a reactor, and mixing and stirring for 30min under the argon atmosphere for later use;
b. preparation of Shell monomer Pre-emulsion
Adding the above components into a beaker, mixing and stirring for 20min to obtain a shell layer pre-emulsion for later use;
c. preparation of core-shell emulsions
Firstly, vacuumizing a reactor filled with the seed pre-emulsion in the step a, and then replacing the reactor with argon; then continuously introducing argon, carrying out polymerization reaction under the protection of argon, controlling the temperature at 60 +/-2 ℃, controlling the stirring speed at 170-200 revolutions per minute, introducing condensed water, and stirring and dispersing the seed pre-emulsion for 30 min; then dropping an initiator solution by a constant-pressure dropping funnel at a constant speed for 1 min, wherein the dropping is finished in 10min, and the mass ratio is that the seed pre-emulsion: and (3) continuing the reaction for 50min by using an initiator solution 1 of 153.45-158.75: 18.28, and finishing the seed stage polymerization. Then, uniformly dripping the shell monomer pre-emulsion, controlling the shell monomer pre-emulsion to be completely dripped within 180min, and continuously dripping an initiator solution 2 within 180min at the same time, wherein the mass ratio of the initiator solution to the seed pre-emulsion is as follows: pre-emulsion of shell monomer: initiator solution 2 is 153.45-158.75: 185-226.8: 30.53; after all the monomers are dripped, heating the system to 68 ℃, and preserving the heat for 120min to ensure that the reaction is full; filtering with 325 μm filter screen when the emulsion is cooled to normal temperature, collecting the filtered emulsion, and bottling;
the acrylate monomer in the step a is amyl acrylate;
the acrylate monomer in the step b is a mixture of amyl acrylate and nonyl acrylate, wherein the mass of the amyl acrylate accounts for 60-75% of the mixture;
the functional monomer mixture in the step b is two, and the formula 1 is a mixture of acrylamide and acrylic acid, or the formula 2 is a mixture of acrylamide and hydroxyethyl acrylate; wherein, the mass of the acrylamide accounts for 45-55% of the total mass of the functional monomer mixture in each formula;
the emulsifier used in the steps a and b is anionic emulsifier sodium dibutyrate;
the chain transfer agent in the step b is tetradecyl mercaptan;
the cross-linking agent in step b is a blend of divinylbenzene and polyethylene glycol dimethacrylate, wherein the molar ratio of divinylbenzene: the mass ratio of the bis-methacrylic acid polyethylene glycol ester is 3: 1;
the initiator is an oxidation-reduction initiation system, the oxidant is ammonium persulfate, the reducing agent is ferrous ammonium sulfate, and the initiator is prepared into an aqueous solution for use, wherein the specific mixture ratio is as follows:
the specific mass of the substances is not limited to the invention, and the substances are wholly enlarged or reduced according to the mass proportion in actual production according to the required products.
The invention has the beneficial effects that:
1. the method conforms to the current green development concept of high efficiency, environmental protection and economy, replaces a solvent method with a starvation charging seed emulsion polymerization method, avoids using a large amount of solvents, polyisocyanates and other toxic reagents, and solves the problems of high energy consumption, large environmental pollution and poor safety in the preparation process of the pressure-sensitive adhesive.
2. In the literature for preparing pressure-sensitive adhesives, the initiator used in the emulsion polymerization reaction is mostly a thermal decomposition initiator which is used alone and has higher polymerization initiation temperature; the initiator is added in one step, so that the concentration of instantaneous free radicals is easily too high during the polymerization of the monomers, and the emulsion polymerization is locally overheated and unstable; the invention adopts an oxidation-reduction initiation system, not only reduces the reaction temperature, but also adopts a continuous uniform dripping mode, so that the emulsion polymerization is more stable, the monomer conversion rate is higher than 99.5 percent, the content of the coalescent is lower than 0.05 percent by weight, the PDI is less than 0.02, the production cost and the difficulty of post-treatment of wastes are reduced, and the method is economical and efficient.
3. The shell layer adopts a blend of a composite crosslinking agent of divinyl benzene and bis-methacrylic acid polyethylene glycol ester, so that the crosslinking degree of the shell layer can be improved. According to the data of example 3 and comparative example 1, when the amount of the crosslinking agent added was 2.4g, the initial tack, peel strength and permanent tack of the pressure-sensitive adhesive were improved by 42.0%, 164.4% and 334.9%, respectively, compared with the pressure-sensitive adhesive without the crosslinking agent. Overcomes the problems of good initial adhesion and reduced peel strength and permanent adhesion.
4. The composite modified emulsion with the core-shell structure is prepared by taking the amyl polyacrylate as a seed, the amyl polyacrylate and the isooctyl polyacrylate as shell soft monomers and acrylamide, acrylic acid or a blend of the acrylamide and the hydroxyethyl acrylate as shell functional monomers. The addition of the functional monomer improves the system compatibility and the crosslinking degree to a certain extent. The pressure-sensitive adhesive emulsion prepared by the polymerization reaction has better initial viscosity, is green and environment-friendly and can be used in the fields of more rigorous medicine and the like.
5. Utilizes a novel core-shell seed emulsion polymerization technology to prepare latex particles with controllable morphological structure, controllable composition, controllable particle size and predesigned, and overcomes the defects that the particle morphology is fixed in the traditional emulsion polymerization polymer and the requirements of special products cannot be met
6. The heat resistance and the water absorption of the pressure-sensitive adhesive are improved along with the increase of the dosage of the cross-linking agent no matter the pressure-sensitive adhesive composed of the formula 1 or the formula 2, because the strength of the adhesive layer is increased due to the addition of the cross-linking agent, the water absorption of the pressure-sensitive adhesive can be greatly reduced due to a compact cross-linking network, and the high temperature resistance of the material is improved. As can be seen from the comparison between the example 1 and the example 5, compared with the pressure-sensitive adhesive added with 0.8g of the crosslinking agent, the heat resistance of the pressure-sensitive adhesive added with 4.0g of the crosslinking agent is improved from the evaluation grade 6 (the adhesive layer is degummed and is completely transferred to the surface of stainless steel) to the evaluation grade 1 (the surface is unchanged), and no residual adhesive is left; compared with example 6 and example 10, the water absorption of the pressure-sensitive adhesive added with 4.0g of the cross-linking agent is reduced by 120 percent compared with the pressure-sensitive adhesive added with 0.8g of the cross-linking agent.
Drawings
FIG. 1 is a graph of monomer conversion as a function of reaction time during the emulsion polymerization of example 1.
FIG. 2 is a graph showing a particle size distribution of latex particles in the emulsion polymerization process of example 1.
FIG. 3 is a graph showing the change of the particle size of the latex particles in example 1 with time.
Detailed Description
Example 1
a. Preparation of seed Pre-emulsion
Firstly, adding 0.5g of sodium dibutyl dibutyrate emulsifier, 8g of amyl acrylate monomer and 145g of deionized water into a 500ml four-neck flask, and mixing and stirring for 30min under an argon atmosphere to obtain a seed pre-emulsion for later use;
b. preparation of Shell monomer Pre-emulsion
A blend of 110.5g of the soft monomer amyl acrylate and 59.5g of nonyl acrylate, 12g of the functional monomer acrylamide, 13g of the functional monomer acrylic acid, 4g of the anionic emulsifier dipentyl dibutyrate sodium sulfonate, 2.4g of the chain transfer agent dodecyl mercaptan, 1.2g of the crosslinking agent divinylbenzene and 0.4g of the crosslinking agent diethyleneglycol dimethacrylate. Adding into a beaker, mixing and stirring for 20min to obtain a shell layer pre-emulsion for later use;
c. preparation of core-shell emulsions
Introducing argon into a 500ml four-neck flask containing the seed pre-emulsion in the step a for three times, then carrying out an experiment under the protection of argon, boiling condensed water, heating in a boiling water bath, keeping the temperature in the four-neck flask at 60 ℃, controlling the mechanical stirring speed at 170-200 revolutions per minute, and stirring and dispersing for 30 min; dropping 18.28g of initiator solution 1 at constant speed by using a constant-pressure dropping funnel, and finishing dropping within 10 min; the reaction is continued for 50min, and the polymerization at the seed stage is finished. Then, uniformly dripping the shell layer monomer pre-emulsion, controlling the shell layer pre-emulsion to be completely dripped within 180min, and simultaneously dripping 30.53g of initiator solution 2 within 180 min; after all the monomers are dripped, heating the system to 68 ℃, and preserving the heat for 120min to ensure that the reaction is full; filtering with 325 μm filter screen when the emulsion is cooled to normal temperature, collecting the filtered emulsion, and bottling;
the initiator is an oxidation-reduction initiation system, the oxidant is ammonium persulfate, the reducing agent is ammonium ferrous sulfate, deionized water with a certain proportion is added when the initiator is used, the initiator is stirred and dissolved for 20min on an electromagnetic stirrer to prepare an initiator aqueous solution for use, and the specific proportion is as follows:
and dropwise adding 2 wt% of ammonia water into the polymer emulsion while stirring, and monitoring the pH value of the polymer emulsion by using an acidimeter until the pH value is about 7.
e. Latex coating
In this experiment, a polyethylene terephthalate (PET) film with a thickness of 75 μm was selected as a substrate, SL79 silicone paper was selected as a protective paper, and an Elcometer 4360/15 coating rod with a groove depth of 60 μm was used as a coating tool. When the latex is coated on a base material, the base material must be ensured to be dry and clean so as to prevent the glue layer from generating defects during coating, and the coating process should be ensured to be smooth. The whole coating process is carried out on a clean glass plate so as to be beneficial to uniformly and continuously spreading the latex, and the specific operation steps are as follows:
firstly, cutting a PET film into B5 paper size, wiping the paper with acetone and naturally airing the paper. The latex was poured onto the fixed end of the substrate film uniformly and continuously. The coating rod was rolled several times in the latex on the substrate film so that it was completely covered with the latex, with a coating thickness of 3mm, and then at a rate of about 6 cm.s-1The coating rod was dragged over the substrate film at a rate to give a uniformly coherent coated film which was then dried in a forced air oven at 105 ℃ for 4 min. And finally, taking out the dried film, cooling for half a minute, covering the surface of the protection paper treated by the organic silicon on the adhesive layer downwards, flattening and removing air bubbles for later use.
f. Test standards and Performance characterization
The initial adhesion, the peel strength and the permanent adhesion of the pressure-sensitive adhesive prepared by the experiment are respectively determined according to the following standards:
initial adhesion: the initial adhesive performance of the pressure-sensitive adhesive is tested according to British FINAT Testing 8 standard, and the initial adhesive performance of the pressure-sensitive adhesive is tested by adopting a vertical ring initial adhesive test method, namely the force required for separating a closed circular ring of pressure-sensitive materials which are mutually contacted and have certain contact area from a certain standard surface at a specific speed. And selecting three original cut sample rubber strips for testing each sample, wherein the cut marks among the sample rubber strips are clean and straight. Stripping the release paper, folding into a ring shape, facing downwards the side coated with latex and having viscosity, and fixing the overlapped end in an upper clamping plate of a testing machine; the standard stainless steel plate was fixed to the lower jaw (horizontal), the tester was started, the upper jaw was lowered to bring the tape loop into full contact with the surface of the stainless steel plate, and then the tape was immediately separated from the stainless steel plate at 300mm/min and the maximum force was recorded. The testing temperature is 23 +/-2 ℃; each bar was placed in the test conditions for at least 24h prior to testing.
Peel strength: this test measures the 180 ° peel strength of pressure-sensitive adhesive tapes according to the FINAT Testing 1 standard in the uk. The test plate is a stainless steel plate, and is cleaned by acetone and absolute ethyl alcohol before testing, wiped by clean absorbent gauze, and cleaned repeatedly for three times until the working surface of the stainless steel plate is clean through visual inspection. The protective paper was removed from each strip, the latex-coated side of each strip was faced down, placed on the test piece and light finger pressure was applied. Using standard test rolls at approximately 10mm s-1Is rolled back and forth 2 times on each sample bar to fully contact the adhesive with the bonded surface, and the test is carried out after the adhesive is placed for 24 hours. The free end of the sample is folded in half for 180 ℃, the free end of the sample and the stainless steel plate are fixed on an upper clamp and a lower clamp of a testing machine, and the stripping surface is consistent with the force line of the testing machine. The separation speed of the jig of the testing machine was set to 300mm/min-1The peel force and maximum force were recorded. The test temperature is 23 +/-2 ℃, and the stripping rate is 300mm min-1(ii) a The test results of 180 DEG peel adhesion are expressed as the average of the peel force (N/25mm) of 3 specimens measured at 24-hour rest time.
Permanent adhesion: this experiment tests the pressure sensitive adhesive for tack-maintaining properties according to the FINAT Testing 9 standard in the UK. The stainless steel plate was first wiped clean with acetone solvent, the latex coated side of each strip was removed and carefully adhered to the next two glass plates, with light finger pressure, and then with a standard test roller at approximately 10 mm-min-1Is rolled back and forth 3 times over each bar to bring the adhesive into full contact with the surface to be bonded. The test was carried out after 20min of standing. And (3) hanging a sample under the test strip by a weight of 1kg, and recording the time required by falling to obtain the permanent adhesion of the pressure-sensitive adhesive.
The test bar dimensions are shown in table 1:
TABLE 1 dimensions of test bars in pressure sensitive adhesive Property test
And (3) characterization of heat resistance performance:
the mirror surface stainless steel plate is wiped up by soaking the absorbent cotton in absolute ethyl alcohol, the prepared protective film is uniformly stuck on the mirror surface stainless steel plate, the mirror surface stainless steel plate is placed in an oven and is placed at 80 ℃ for 4 hours, then the mirror surface stainless steel plate is taken out for cooling, the adhesive tape is peeled off, the surface condition of the mirror surface stainless steel plate is observed, and the evaluation index is shown in table 2.
TABLE 2 characterization index of heat resistance of pressure-sensitive adhesive
Measurement of Water absorption of coating film:
coating the prepared emulsion on a culture dish, forming a film at room temperature, and weighing the film (M)0) Then, the film was immersed in deionized water for 48 hours, taken out, and the water on the surface of the film was sucked off with filter paper and weighed again (M)1). And taking three test samples for each coating film, and calculating the average value of the three test samples to obtain the water absorption rate. Calculated as follows:
characterization of the pressure-sensitive adhesive emulsion:
in the preparation process of the core-shell emulsion, 2ml of the emulsion is sampled at intervals of 30 minutes, 0.05ml of the emulsion is diluted by deionized water, and the final particle size and the particle size distribution index of the emulsion particles are detected by a Malvern Zetasizer Nano-ZS90 dynamic laser particle size analyzer, wherein when the particle size distribution index is less than 0.08, the narrow distribution is specified. And detecting whether the increase and distribution of the latex particle size are qualified or not and whether the emulsion is successfully prepared or not.
The remaining 1.95ml portion was used to determine the instantaneous and total conversion of polymerized monomer, and the data are shown in tables 2 and 3. After weighing (recording the weight of the wet beaker), putting the beaker into an oven at 80 ℃ for drying for 24 hours, and weighing (recording the weight of the dry beaker) again after the mass is not changed.
Calculation of monomer conversion:
total conversion OC:
instantaneous conversion IC:
in the formula: miIs the total mass of the emulsion at the sampling of the ith time, SiIs the solid content at the sampling time of the ith time, M' is the total mass of the initiator added at the sampling time of the ith time, Δ M is the total mass of the emulsifier and the crosslinking agent added at the sampling time of the ith time, M0M is the mass of monomer added up to the ith sample.
The agglomerate content calculation formula is as follows:
in the formula: w' is the total mass of the agglomerates and beaker before drying, w is the total mass of the agglomerates and beaker after drying, w0Is the total mass of the acrylate monomers used in the formulation.
Comparative example 1: the pressure-sensitive adhesive is prepared by adopting a seed emulsion polymerization method, wherein a shell layer functional monomer is a mixture of 12g of acrylamide and 13g of acrylic acid in a formula 1, and a shell layer cross-linking agent is not added, so that the acrylate pressure-sensitive adhesive which takes the formula 1 as the functional monomer and is not added with the cross-linking agent is prepared.
Comparative example 2: the pressure-sensitive adhesive is prepared by adopting a seed emulsion polymerization method, wherein a shell layer functional monomer is a mixture of 12g of acrylamide and 13g of hydroxyethyl acrylate in a formula 2, and a shell layer cross-linking agent is not added, so that the acrylate pressure-sensitive adhesive which takes the formula 2 as the functional monomer and is not added with the cross-linking agent is prepared.
The specific steps of examples 2-5 are the same as example 1, but the total amount of the shell crosslinking agent used in examples 2-5 is different, and the amount and emulsion polymerization parameters are shown in Table 3.
The specific steps of examples 6-10 are the same as example 1, but the shell functional monomer is added according to the formula 2, the dosage of the shell cross-linking agent is changed, the dosage and the emulsion polymerization parameters are shown in table 4,
the results of testing the pressure-sensitive adhesive properties of the polymerization products of examples 1 to 10 are shown in Table 5.
TABLE 3 formulation 1 emulsion polymerization Process parameters for different crosslinker loadings
Table 4 formulation 2 emulsion polymerization process parameters for different crosslinker content
TABLE 5 test results of pressure-sensitive adhesive Properties of the polymerization products
Characterization of emulsion Properties
As can be seen from tables 3 and 4: the shell cross-linking agent dosage is changed, and the particle size of the core-shell particles is still consistent, because the emulsifier dosage at the seed stage is the same, and the particle size is determined by the emulsifier dosage at the seed stage. The total conversion rate of emulsion polymerization can be kept at a level of more than 99.5 percent, and the monomer reaction is relatively sufficient; the PDI of the latex particles is less than 0.02, and the distribution is narrow; the content of the agglomerates in the system is less than 0.5 wt%, and increases with the increase of the content of the crosslinking agent, because the molecular weight of the polymer is increased sharply and more gels are generated during the polymerization due to the participation of a part of the double bonds as branched chains. Although the amount of the agglomerates in the present invention was increased, the amounts were below 0.5 wt%, indicating that the increase in the amount of the crosslinking agent in this experiment did not affect the stability of the emulsion polymerization. The continuous uniform dropping of the initiator and the monomer ensures that the monomer reacts more fully, the added monomer grows on the surface of the seed colloidal particle, no excessive waste is generated, and the post-treatment is simple.
The same conclusion can be obtained from fig. 1 and fig. 2, the instantaneous conversion rate and the total conversion rate of the monomer are both high, the particle size distribution is narrow, the monomer reaction is sufficient, the temperature control of the polymerization is proper, and no secondary particles are generated in the system.
Measurement of pressure-sensitive adhesive Properties of Polymer products
As can be seen from the data in Table 5, the initial tack of examples 1 to 5 and 6 to 10 did not change much with the increase of the amount of the crosslinking agent, because the initial tack was mainly determined by the soft monomers amyl acrylate and nonyl acrylate, and the composition and the amount of addition thereof did not change in the present invention, so the initial tack was hardly changed; the peel strength in the embodiments 1 to 10 is reduced with the increase of the amount of the cross-linking agent, because the addition of the cross-linking agent makes the reaction monomers cross-linked to form a network structure, the compactness of the polymer is increased, the adhesive layer strength is increased, the peel strength of the pressure-sensitive adhesive is slightly reduced, but the peel strength is still stronger than that of the pressure-sensitive adhesive without the cross-linking agent, and the higher peel strength is maintained; the pressure-sensitive adhesive tack strength in the embodiments 1 to 10 shows a tendency of increasing first and then decreasing along with the increase of the crosslinking degree of the system, because the addition amount of the crosslinking agent is appropriate, the number and distribution of crosslinking points in the system, and the number of introduced polar groups is just in an optimal state, and then the amount of the crosslinking monomer is increased, so that the crosslinking degree is too large, the system generates a gel phenomenon, and the problems of brittleness and pressure-sensitive performance decrease of the material are caused.
The heat resistance and water absorption of the pressure-sensitive adhesive composed of different functional monomers in the formula 1 or the formula 2 are improved continuously with the increase of the dosage of the cross-linking agent, because the addition of the cross-linking agent increases the strength of the adhesive layer, and the increase of the cross-linking network can greatly reduce the free volume among polymer molecular chains in the pressure-sensitive adhesive, thereby reducing the water absorption of the pressure-sensitive adhesive and improving the high temperature resistance of the material. As can be seen from the comparison between example 1 and example 5, the heat resistance of the pressure-sensitive adhesive added with 4.0g of the crosslinking agent is improved from the evaluation grade 6 to the evaluation grade 1 without adhesive residue compared with the pressure-sensitive adhesive added with 0.8g of the crosslinking agent; compared with example 6 and example 10, the water absorption of the pressure-sensitive adhesive added with 4.0g of the cross-linking agent is reduced by 120 percent compared with the pressure-sensitive adhesive added with 0.8g of the cross-linking agent. The addition of the cross-linking agent can greatly improve the heat resistance and the water absorption of the acrylate pressure-sensitive adhesive.
According to the invention, acrylamide is used as a functional monomer, on one hand, the balance of adhesive force and cohesive force is maintained through interaction with a shell layer soft monomer, the movement of a shell layer chain segment is limited, on the other hand, the glass transition temperature of a polymer is increased, and the problems of glue leakage, wire drawing, poor water resistance and the like which occur when the glass transition temperature is lower are solved; in the formula 2, the functional monomer hydroxyethyl acrylate has stronger hydroxyl and ester groups and is a hydrophilic monomer with strong polarity. The hydroxyl group carried by the emulsion is easy to form hydrogen bond with water molecules, so that the association between polymer molecules and water molecules is enhanced, the acting force between molecules is increased, and finally, the viscosity and the cohesive force of the emulsion are increased, and the permanent viscosity is improved. The carboxyl group of the acrylic acid in the formula 1 can be crosslinked with the amide group of the hard monomer acrylamide, so that the permanent adhesion of the pressure-sensitive adhesive is improved, and the water absorption is improved.
As can be seen from the comparison between the examples and the comparative examples, the peel strength and the permanent adhesion of the pressure-sensitive adhesive can be effectively improved without reducing the initial adhesion of the pressure-sensitive adhesive after the mixed crosslinking agent is added. The problems that the initial adhesion is good and the permanent adhesion is reduced are solved. Looking specifically at the data of example 3 and comparative example 1, the initial tack, peel strength, and permanent tack were increased by 42.0%, 164.4%, and 334.9%, respectively, when the crosslinker was added at 2.4g, as compared to comparative example 1. In comparison with comparative example 2, in example 9, when the addition amount of the crosslinking agent is 3.2g, the initial adhesion, peel strength and permanent adhesion of the pressure-sensitive adhesive are respectively improved by 24.6%, 120.7% and 270.0% compared with comparative example 2.
The contents of the present invention are not limited to the above embodiments.
The invention is not the best known technology.
Claims (2)
1. A preparation method of acrylate high-performance environment-friendly pressure-sensitive adhesive is characterized by comprising the following steps:
a. preparation of seed Pre-emulsion
The material composition and the proportion are as follows:
firstly, adding the emulsifier, the acrylate monomer and the deionized water with the specified mass into a reactor, and mixing and stirring for 30min under the argon atmosphere for later use;
b. preparation of Shell monomer Pre-emulsion
Adding the above components into a beaker, mixing and stirring for 20min to obtain a shell layer pre-emulsion for later use;
c. preparation of core-shell emulsions
Firstly, vacuumizing a reactor filled with the seed pre-emulsion in the step a, and then replacing the reactor with argon; then continuously introducing argon, carrying out polymerization reaction under the protection of argon, controlling the temperature at 60 +/-2 ℃, controlling the stirring speed at 170-200 revolutions per minute, introducing condensed water, and stirring and dispersing the seed pre-emulsion for 30 min; then dropping an initiator solution by a constant-pressure dropping funnel at a constant speed for 1 min, wherein the dropping is finished in 10min, and the mass ratio is that the seed pre-emulsion: continuing the reaction for 50min by using an initiator solution 1 (153.45-158.75: 18.28), and finishing the seed stage polymerization; then, uniformly dripping the shell monomer pre-emulsion, controlling the shell monomer pre-emulsion to be completely dripped within 180min, and continuously dripping an initiator solution 2 within 180min at the same time, wherein the mass ratio of the initiator solution to the seed pre-emulsion is as follows: pre-emulsion of shell monomer: initiator solution 2 is 153.45-158.75: 185-226.8: 30.53; after all the monomers are dripped, heating the system to 68 ℃, and preserving the heat for 120min to ensure that the reaction is full; filtering with 325 μm filter screen when the emulsion is cooled to normal temperature, collecting the filtered emulsion, and bottling;
the acrylate monomer in the step a is amyl acrylate;
the acrylate monomer in the step b is a mixture of amyl acrylate and nonyl acrylate, wherein the mass of the amyl acrylate accounts for 60-75% of the mixture;
the functional monomer mixture in the step b is two, and the formula 1 is a mixture of acrylamide and acrylic acid, or the formula 2 is a mixture of acrylamide and hydroxyethyl acrylate; wherein, the mass of the acrylamide accounts for 45-55% of the total mass of the functional monomer mixture in each formula;
the emulsifier used in the steps a and b is anionic emulsifier sodium dibutyrate;
the cross-linking agent in step b is a blend of divinylbenzene and polyethylene glycol dimethacrylate, wherein the molar ratio of divinylbenzene: the mass ratio of the bis-methacrylic acid polyethylene glycol ester is 3: 1;
the initiator is an oxidation-reduction initiation system, the oxidant is ammonium persulfate, the reducing agent is ferrous ammonium sulfate, and the initiator is prepared into an aqueous solution for use, wherein the specific mixture ratio is as follows:
2. the method for preparing the acrylate high-performance environment-friendly pressure-sensitive adhesive according to claim 1, wherein the chain transfer agent in the step b is tetradecyl mercaptan.
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