CN110194943A - 抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法 - Google Patents
抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法 Download PDFInfo
- Publication number
- CN110194943A CN110194943A CN201910536517.5A CN201910536517A CN110194943A CN 110194943 A CN110194943 A CN 110194943A CN 201910536517 A CN201910536517 A CN 201910536517A CN 110194943 A CN110194943 A CN 110194943A
- Authority
- CN
- China
- Prior art keywords
- hydroxy group
- acrylic acid
- acid modified
- terminal hydroxy
- modified polyurethane
- 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
- 239000000853 adhesive Substances 0.000 title claims description 21
- 230000001070 adhesive effect Effects 0.000 title claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 20
- 229920002635 polyurethane Polymers 0.000 title claims description 20
- 239000004814 polyurethane Substances 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 239000004925 Acrylic resin Substances 0.000 claims description 15
- 229920000178 Acrylic resin Polymers 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical class N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- LDNQJFRHFLTAHA-UHFFFAOYSA-N butyl 3-hydroxy-2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=CO LDNQJFRHFLTAHA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及胶黏剂领域，具体公开了一种抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法。本发明通过将聚氨酯预聚体与端羟基丙烯酸树脂进行接枝改性，得到丙烯酸改性聚氨酯树脂；再添加纳米TiO2、偶联剂和光引发剂进行反应，制备得到所述丙烯酸改性聚氨酯胶黏剂。按照本发明所述方法制备得到的产品，在电子束或者紫外线作用下发生自由基聚合，可使胶黏剂迅速交联固化、缩短固化时间，提高生产效率；另外，紫外光固化可使能量集中在胶层上，不同于普通的热固化需要被粘物整体加热，从而会大大的提高能量的利用率。本发明所制备的产品，在提高胶黏剂耐温性能的同时，还增强了胶黏剂的抗紫外性能。
Description
技术领域
本发明涉及胶黏剂领域，具体地说，涉及一种抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂。
背景技术
光固化型丙烯酸改性聚氨酯胶黏剂通常由多异氰酸酯、聚酯/聚醚二元醇和端羟基丙烯酸树脂经两步反应而合成，在有机玻璃、聚酯薄膜与铝板的粘接上性能卓著，显示广泛的市场前景。
然而，现有技术中的聚氨酯胶黏剂常含有异氰酸基团，对人体和环境都有一定的危害。不仅如此，聚氨酯胶黏剂对玻璃、聚酯薄膜等的粘接都需用底涂剂，且具有高温时强度不够，固化速度慢，抗紫外线性能差等缺陷。
发明内容
为了解决现有技术中存在的问题，本发明的目的是提供一种抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法。
为了实现本发明目的，本发明的技术方案如下：
本发明首先提供了一种抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂的制备方法：将聚氨酯预聚体与端羟基丙烯酸树脂进行接枝改性，得到丙烯酸改性聚氨酯树脂；再添加纳米TiO2、偶联剂和光引发剂进行反应，制备得到所述丙烯酸改性聚氨酯胶黏剂。
其中，所述端羟基的丙烯酸树脂选自端羟基丙烯酸乙酯、端羟基丙烯酸丙酯、端羟基甲基丙烯酸丁酯、端羟基甲基丙烯酸乙酯、端羟基甲基丙烯酸丙酯、端羟基甲基丙烯酸丁酯中的一种或多种。
进一步地，将聚氨酯预聚体与含羟基的丙烯酸树脂进行接枝改性时，先将聚氨酯预聚体与甲基丙烯酸丁酯混合后，再与含羟基的丙烯酸树脂在40～45℃，真空度为-900MPa以下的真空条件下，进行改性反应。
作为优选，将丙烯酸改性聚氨酯树脂与纳米TiO2、偶联剂和光引发剂在60～65℃进行反应。
其中，所述偶联剂可选为KH-540、KH-550、KH-792、KH-552等，优选为KH-550。所述光引发剂可选为二苯甲酮、4-甲基二苯甲酮、2,4,6-三甲基二苯丙酮等，优选为2,4,6-三甲基二苯甲酮。
更为优选，本发明进一步提供所述方法中使用的原料及其重量份如下：
聚氨酯预聚体53～75份，甲基丙烯酸丁酯20～30份，对苯二酚0.05～0.1份，端羟基丙烯酸树脂12～30份，纳米TiO2 0.7～1份，偶联剂2～3份，光引发剂3～5份。
进一步优选地，所述端羟基丙烯酸树脂在加入前，先进行高温脱水处理。所述高温脱水处理可选为在120℃脱水2小时，之后冷却至50℃，再加入反应体系中。
本发明所述方法中的聚氨酯预聚体，是由聚醚或者聚酯多元醇与二异氰酸酯制成的NCO封端的聚氨酯预聚体，其制备方法可采用本领域常规的制备方法。
在本发明的一个具体实施方式中，所述聚氨酯预聚体的制备方法为：将聚碳酸酯二醇CD210、聚碳酸酯二醇CD205和1,4-丁二醇在120℃真空脱水2小时，冷却至50℃，在HMDI和二月桂酸二丁基锡(催化剂)的参与下，由氮气保护，在60～70℃、真空度为-900MPa以下的真空条件下反应2小时所得。
其原料及其重量份如下：
需要说明的是，由本发明所述方法制备得到的抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其相关应用或衍生产品，也属于本发明的保护范围。
本发明涉及到的原料或试剂均为普通市售产品，涉及到的操作如无特殊说明均为本领域常规操作。
在符合本领域常识的基础上，上述各优选条件，可以相互组合，得到具体实施方式。
本发明的有益效果在于：
本发明通过将聚醚或者聚酯多元醇与二异氰酸酯制成NCO封端的聚氨酯预聚体，再通过与端羟基丙烯酸树脂进行接枝改性，制得丙烯酸改性聚氨酯树脂；再添加纳米TiO2，光敏剂等助剂，制得一种环保型的单组份体系丙烯酸改性聚氨酯胶黏剂。
本发明利用纳米TiO2表面与聚氨酯基体发生了反应，并利用了TiO2可以吸收紫外线，从而在提高胶黏剂耐温性能的同时，还增强了胶黏剂的抗紫外性能。
本发明所提供的丙烯酸改性聚氨酯胶黏剂在电子束或者紫外线作用下发生自由基聚合，可使胶黏剂迅速交联固化、缩短固化时间，提高生产效率；另外，紫外光固化可使能量集中在胶层上，不同于普通的热固化需要被粘物整体加热，从而会大大的提高能量的利用率。
综上所述，本发明解决了现有聚氨酯胶黏剂不环保，不耐高温，耐候性差等缺点，符合环境卫生法规，且具有良好的耐热性、抗紫外性，且制备工艺操作简便，固化速度快，固化收缩小，不含挥发性溶剂，节约能源。
本发明所涉及的缩略语和关键术语定义如下：
聚氨酯：聚氨酯甲酸酯的简称，是主链上含有重复氨基甲酸酯基团的大分子化合物的统称。
丙烯酸树脂：丙烯酸、甲基丙烯酸及其酯类按不同的比例共聚而成的一类高分子聚合物。
二氧化钛：白色固体两性氧化物，有较好的紫外线掩蔽作用。
聚酯多元醇：端羟基聚酯。
HMDI：4，4，-二环已基甲烷二异氰酸酯。
光引发剂：一种能吸收辐射能，经激发发生光化学变化，产生具有引发聚合能力的活性中间体的物质。
附图说明
图1为本发明实施例1中所述抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂的制备工艺。
具体实施方式
下面将结合实施例对本发明的优选实施方式进行详细说明。需要理解的是以下实施例的给出仅是为了起到说明的目的，并不是用于对本发明的范围进行限制。本领域的技术人员在不背离本发明的宗旨和精神的情况下，可以对本发明进行各种修改和替换。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
1、配方：
2、采用图1所示的制备工艺，进行抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂的制备。
3、性能检测
在以下条件下，检测拉伸强度和断裂伸长率：
实施例2
配方：
3、性能检测
在以下条件下，检测拉伸强度和断裂伸长率：
对比例1
本对比例与实施例1的区别仅在于：将端羟基丙烯酸树脂替换为端羟基聚烯烃。
其余配方与制备方法同实施例1，将制备得到的产品进行性能检测，结果如下：
通过比较可知，当采用端羟基聚烯烃替换端羟基丙烯酸树脂时，耐热性相较实施例1发生变化，变得下降，不仅如此，抗紫外性能也有所下降。
对比例2
本对比例与实施例1的区别仅在于：不添加二氧化钛。
其余配方与制备方法同实施例1，将制备得到的产品进行性能检测，结果如下：
通过比较可知，当不添加二氧化钛时，抗紫外能力相较实施例1发生变化，拉伸强度变小，不仅如此，断裂伸长率也有所下降。
应当理解的是，对上述实施例所用试剂或原料的用量进行等比例扩大或者缩小后的技术方案，与上述实施例的实质相同。
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
Claims (9)
1.一种抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂的制备方法，其特征在于，将聚氨酯预聚体与含羟基的丙烯酸树脂进行接枝改性，得到丙烯酸改性聚氨酯树脂；再添加纳米TiO2、偶联剂和光引发剂进行反应，制备得到所述丙烯酸改性聚氨酯胶黏剂。
2.根据权利要求1所述的方法，其特征在于，所述端羟基的丙烯酸树脂选自端羟基丙烯酸乙酯、端羟基丙烯酸丙酯、端羟基甲基丙烯酸丁酯、端羟基甲基丙烯酸乙酯、端羟基甲基丙烯酸丙酯、端羟基甲基丙烯酸丁酯中的一种或多种。
3.根据权利要求1所述的方法，其特征在于，将聚氨酯预聚体与甲基丙烯酸丁酯混合后，再与含羟基的丙烯酸树脂在40～45℃，真空度为-900MPa以下的真空条件下，进行改性反应。
4.根据权利要求3所述的方法，其特征在于，将丙烯酸改性聚氨酯树脂与纳米TiO2、偶联剂和光引发剂在60～65℃进行反应。
5.根据权利要求4所述的方法，其特征在于，所述偶联剂为KH550。
6.根据权利要求4所述的方法，其特征在于，所述光引发剂为2,4,6-三甲基二苯甲酮。
7.根据权利要求3～6任意一项所述的方法，其特征在于，所述方法中使用的原料及其重量份如下：
聚氨酯预聚体53～75份，甲基丙烯酸丁酯20～30份，对苯二酚0.05～0.1份，端羟基丙烯酸树脂12～30份，纳米TiO2 0.7～1份，偶联剂2～3份，光引发剂3～5份。
8.根据权利要求7所述的方法，其特征在于，所述端羟基丙烯酸树脂在加入前，先进行高温脱水处理。
9.权利要求1～8任一项所述方法制备得到的抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910536517.5A CN110194943A (zh) | 2019-06-20 | 2019-06-20 | 抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910536517.5A CN110194943A (zh) | 2019-06-20 | 2019-06-20 | 抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110194943A true CN110194943A (zh) | 2019-09-03 |
Family
ID=67754906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910536517.5A Pending CN110194943A (zh) | 2019-06-20 | 2019-06-20 | 抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110194943A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105840A (zh) * | 2021-04-22 | 2021-07-13 | 广东硕成科技有限公司 | 一种粘附性好的晶圆切割用保护膜及其制备方法 |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189762A (ja) * | 1997-12-26 | 1999-07-13 | Nippon Kayaku Co Ltd | 粘着シート基材用樹脂組成物、粘着シート用基材及びそれを用いた粘着シート |
| CN1844182A (zh) * | 2006-03-22 | 2006-10-11 | 中国科学技术大学 | 一种可紫外光固化水性聚氨酯树脂的制备方法 |
| CN1887972A (zh) * | 2006-07-14 | 2007-01-03 | 浙江大学 | 一种用于紫外光固化胶粘剂中的纳米SiO2改性的方法 |
| CN101372530A (zh) * | 2008-08-08 | 2009-02-25 | 中国工程物理研究院化工材料研究所 | 一种水性光固化聚氨酯树脂及其制备方法 |
| CN103374323A (zh) * | 2013-07-31 | 2013-10-30 | 深圳市安立新材料有限公司 | 一种耐黄变液态光学胶的制备方法 |
| CN104017489A (zh) * | 2014-05-29 | 2014-09-03 | 中国石油大学(华东) | 一种纳米二氧化钛改性丙烯酸聚氨酯面漆及其制备方法 |
| CN104031227A (zh) * | 2013-03-07 | 2014-09-10 | 上海恩多水性树脂有限公司 | 一种水性聚氨酯制备方法 |
| CN104086742A (zh) * | 2014-06-27 | 2014-10-08 | 广东工业大学 | 一种玻璃基材用耐酸碱紫外光固化胶膜树脂的制备方法 |
| CN104910852A (zh) * | 2015-06-26 | 2015-09-16 | 福建师范大学 | 一种纳米TiO2改性碳酸酯聚氨酯胶黏剂的制备方法 |
| CN105331324A (zh) * | 2015-11-20 | 2016-02-17 | 烟台信友新材料股份有限公司 | 一种用于光学定位的自由基型紫外光固化胶及制备方法 |
| CN105482766A (zh) * | 2015-12-31 | 2016-04-13 | 广西科技大学 | 聚氨酯丙烯酸酯型uv固化材料及其制备方法 |
| CN106497499A (zh) * | 2016-10-28 | 2017-03-15 | 南京汇鑫光电材料有限公司 | 一种uv固化光学胶 |
| CN107384242A (zh) * | 2017-06-15 | 2017-11-24 | 烟台信友新材料股份有限公司 | 一种紫外光双固化导电胶黏剂的制备方法 |
| CN107502271A (zh) * | 2017-08-04 | 2017-12-22 | 烟台信友新材料股份有限公司 | 一种紫外光固化胶黏剂及其制备方法 |
| CN108034399A (zh) * | 2017-12-26 | 2018-05-15 | 芜湖市长江起重设备制造有限公司 | 一种抗紫外线交联改性聚碳酸酯型水性聚氨酯胶黏剂的制备方法 |
| CN109294512A (zh) * | 2018-10-11 | 2019-02-01 | 扬州市祥华新材料科技有限公司 | 高转移性uv光固化胶黏剂及其制备方法和应用 |
-
2019
- 2019-06-20 CN CN201910536517.5A patent/CN110194943A/zh active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189762A (ja) * | 1997-12-26 | 1999-07-13 | Nippon Kayaku Co Ltd | 粘着シート基材用樹脂組成物、粘着シート用基材及びそれを用いた粘着シート |
| CN1844182A (zh) * | 2006-03-22 | 2006-10-11 | 中国科学技术大学 | 一种可紫外光固化水性聚氨酯树脂的制备方法 |
| CN1887972A (zh) * | 2006-07-14 | 2007-01-03 | 浙江大学 | 一种用于紫外光固化胶粘剂中的纳米SiO2改性的方法 |
| CN101372530A (zh) * | 2008-08-08 | 2009-02-25 | 中国工程物理研究院化工材料研究所 | 一种水性光固化聚氨酯树脂及其制备方法 |
| CN104031227A (zh) * | 2013-03-07 | 2014-09-10 | 上海恩多水性树脂有限公司 | 一种水性聚氨酯制备方法 |
| CN103374323A (zh) * | 2013-07-31 | 2013-10-30 | 深圳市安立新材料有限公司 | 一种耐黄变液态光学胶的制备方法 |
| CN104017489A (zh) * | 2014-05-29 | 2014-09-03 | 中国石油大学(华东) | 一种纳米二氧化钛改性丙烯酸聚氨酯面漆及其制备方法 |
| CN104086742A (zh) * | 2014-06-27 | 2014-10-08 | 广东工业大学 | 一种玻璃基材用耐酸碱紫外光固化胶膜树脂的制备方法 |
| CN104910852A (zh) * | 2015-06-26 | 2015-09-16 | 福建师范大学 | 一种纳米TiO2改性碳酸酯聚氨酯胶黏剂的制备方法 |
| CN105331324A (zh) * | 2015-11-20 | 2016-02-17 | 烟台信友新材料股份有限公司 | 一种用于光学定位的自由基型紫外光固化胶及制备方法 |
| CN105482766A (zh) * | 2015-12-31 | 2016-04-13 | 广西科技大学 | 聚氨酯丙烯酸酯型uv固化材料及其制备方法 |
| CN106497499A (zh) * | 2016-10-28 | 2017-03-15 | 南京汇鑫光电材料有限公司 | 一种uv固化光学胶 |
| CN107384242A (zh) * | 2017-06-15 | 2017-11-24 | 烟台信友新材料股份有限公司 | 一种紫外光双固化导电胶黏剂的制备方法 |
| CN107502271A (zh) * | 2017-08-04 | 2017-12-22 | 烟台信友新材料股份有限公司 | 一种紫外光固化胶黏剂及其制备方法 |
| CN108034399A (zh) * | 2017-12-26 | 2018-05-15 | 芜湖市长江起重设备制造有限公司 | 一种抗紫外线交联改性聚碳酸酯型水性聚氨酯胶黏剂的制备方法 |
| CN109294512A (zh) * | 2018-10-11 | 2019-02-01 | 扬州市祥华新材料科技有限公司 | 高转移性uv光固化胶黏剂及其制备方法和应用 |
Non-Patent Citations (3)
| Title |
|---|
| SAMANE MEHRAVAR等: "Toward a Green Synthesis of Polyurethane/(Meth)acrylic", 《LANGMUIR》 * |
| 时国珍: "丙烯酸醋改性聚氨醋胶粘剂", 《中国聚氨酯工业协会第十次年会论文集》 * |
| 王杏等: "《纳米二氧化钛的生产与应用》", 31 July 2014, 贵州科技出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105840A (zh) * | 2021-04-22 | 2021-07-13 | 广东硕成科技有限公司 | 一种粘附性好的晶圆切割用保护膜及其制备方法 |
| CN113105840B (zh) * | 2021-04-22 | 2022-03-15 | 广东硕成科技股份有限公司 | 一种粘附性好的晶圆切割用保护膜及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5426166A (en) | Urethane adhesive compositions | |
| KR101380850B1 (ko) | 보호 점착 필름, 스크린 패널 및 휴대 전자단말 | |
| KR101142804B1 (ko) | 자외선 경화형 폴리우레탄 접착제의 제조방법 | |
| CN102337099B (zh) | 单组分可光热双重固化的胶粘剂及其制备方法 | |
| JP5470957B2 (ja) | フィルム保護層用活性エネルギー線硬化型樹脂組成物 | |
| EP2770000B1 (en) | Active-energy-ray-curable resin composition, adhesive, and laminate film | |
| CN101974307B (zh) | 一种含离子基团的聚氨酯丙烯酸酯胶粘剂及其制备方法 | |
| CN101906284A (zh) | 一种塑料用紫外光固化胶粘剂及其制备方法 | |
| EP1878776A1 (en) | Adhesive composition curable with actinic energy ray | |
| CN103554393B (zh) | 一种天然高分子基光固化树脂的制备方法 | |
| JP2003155455A (ja) | 活性エネルギー線硬化型粘着剤組成物 | |
| CN115521437A (zh) | 一种水溶性紫外光固化超支化聚氨酯丙烯酸树脂的制备方法 | |
| CN115433482A (zh) | 一种水性聚氨酯耐水涂层的制备方法 | |
| US8048979B2 (en) | Process for synthesis of telechelic urethane acrylate UV curable pre-polymeric materials | |
| US4659788A (en) | Radiation curable adhesive composition for surface protective film | |
| KR102048981B1 (ko) | 태양 전지 보호 시트용 용이 접착제, 태양 전지 보호 시트 및 태양 전지 모듈 | |
| CN110194943A (zh) | 抗紫外线耐高温的丙烯酸改性聚氨酯胶黏剂及其制备方法 | |
| CN108341922B (zh) | 低Tg聚氨酯丙烯酸酯预聚物的制备方法及其应用 | |
| US20220403095A1 (en) | Acrylate oligomer and preparation method and application method thereof | |
| KR102353598B1 (ko) | 폴리(메타)아크릴레이트 공중합체 및 이를 기반으로 하는 광섬유 클래딩용 수지 조성물 | |
| JP4441870B2 (ja) | 活性エネルギー線硬化性樹脂組成物および当該組成物から得られる硬化フィルム | |
| EP4047067A1 (en) | Curable composition | |
| TWI663471B (zh) | Active energy ray-curable resin composition, cured product, adhesive, and laminated film | |
| KR102545923B1 (ko) | 이중 경화형 점착제 조성물, 그 제조방법 및 이를 이용한 점착 보호 테이프, 피착재 표면 보호방법 | |
| JP2000219850A (ja) | 接着剤用組成物及びその硬化物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190903 |
|
| RJ01 | Rejection of invention patent application after publication |