CN115181535B - Ultraviolet light-moisture dual-curing polyurethane hot melt adhesive and preparation method thereof - Google Patents
Ultraviolet light-moisture dual-curing polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN115181535B CN115181535B CN202210963602.1A CN202210963602A CN115181535B CN 115181535 B CN115181535 B CN 115181535B CN 202210963602 A CN202210963602 A CN 202210963602A CN 115181535 B CN115181535 B CN 115181535B
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- Prior art keywords
- polyol
- diisocyanate
- hot melt
- melt adhesive
- polyester polyol
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 65
- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 103
- 150000003077 polyols Chemical class 0.000 claims abstract description 91
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000009977 dual effect Effects 0.000 claims abstract description 15
- 125000004185 ester group Chemical group 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims description 82
- -1 acrylic ester diol Chemical class 0.000 claims description 39
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 29
- 229920000570 polyether Polymers 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 13
- 239000004359 castor oil Substances 0.000 claims description 13
- 235000019438 castor oil Nutrition 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- XOMPUFACNHSNPC-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1C XOMPUFACNHSNPC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 5
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 3
- KGGBUGLHJUGXEF-UHFFFAOYSA-N [6-hydroxy-4-(2-hydroxyethoxy)-6-methylcyclohexa-2,4-dien-1-yl]-phenylmethanone Chemical compound OC1(C(C(=O)C2=CC=CC=C2)C=CC(=C1)OCCO)C KGGBUGLHJUGXEF-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 6
- 238000001723 curing Methods 0.000 description 51
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- 238000013008 moisture curing Methods 0.000 description 17
- 125000005442 diisocyanate group Chemical group 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- FQFXYFNHFVFHPV-UHFFFAOYSA-N 2,3,4-trihydroxy-6-methylcyclohexan-1-one Chemical compound CC1CC(O)C(O)C(O)C1=O FQFXYFNHFVFHPV-UHFFFAOYSA-N 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QBQSKYIIEGLPJT-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOC(=O)C=C QBQSKYIIEGLPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
-
- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/48—Polyethers
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
In order to solve the problems of incomplete curing in a shadow area, slow positioning of the hot melt adhesive and short service life in the actual curing and bonding process of using the PUR hot melt adhesive in the prior art, the application provides an ultraviolet light-moisture dual curing polyurethane hot melt adhesive and a preparation method thereof; the hot melt adhesive comprises acrylic ester group dihydric alcohol, isocyanate, macromolecular polyol and an initiator, wherein the structural formula of the acrylic ester group dihydric alcohol is shown as the formula (I):
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to an ultraviolet light-moisture dual-curing polyurethane hot melt adhesive and a preparation method thereof.
Background
Hot melt adhesives are a relatively common adhesive and are widely used for bonding various types in various industries. In the bonding construction process, the operation can be carried out only by matching with a hot melt adhesive gun, the construction is convenient, the curing speed is high, the curing can be carried out only by about ten seconds, and the construction progress can be increased. Accordingly, hot melt adhesives have become the first choice for industrial bonding, sealing, laminating, joining, insulating, electronic protection, and assembly. Specific applications include smart phones, tablet computer screen component assembly, learning machines, GPS navigators, wearable electronics, window bonding, housing structure bonding, battery bonding, planar sealing, PCB assembly, and protection.
Along with the development and popularization of electronic products such as smart phones and intelligent wearing equipment, the application requirements of the electronic glue in the field are higher and higher. The development of the intelligent mobile phone is also towards integration, screw removal and borderless, and many traditional glues and hot melt adhesives cannot meet the development requirements of modern intelligent devices, and the moisture curing reaction type Polyurethane (PUR) hot melt adhesive is a novel electronic product adhesive which is researched and developed according to the development requirements of the intelligent devices. Compared with the common electronic adhesive, the PUR hot melt adhesive is easier to control the thickness of the adhesive, and can meet the design requirements of the current narrow-frame mobile phones and computers; the PUR hot melt adhesive has strong adhesiveness and higher strength than the common hot melt adhesive, and can meet the bonding requirements of most electronic products; in addition, the base materials are widely used, and almost all base materials such as metal, glass, plastic, ceramic and the like can be bonded.
However, in the actual curing and bonding process, the problem that the curing of a small amount of shadow areas is incomplete easily occurs, and in the process of combining ultraviolet curing and moisture curing, the problems that partial areas cannot be cured or the service life of the obtained adhesive is shorter, the curing time is longer or the positioning is slower and the like are sometimes accompanied.
Disclosure of Invention
Aiming at the problems that in the prior art, shadow area solidification is incomplete, hot melt adhesive positioning is slow and service life is short easily caused in the actual solidification and bonding process of PUR hot melt adhesive, the application provides an ultraviolet light-moisture dual-solidification polyurethane hot melt adhesive and a preparation method thereof.
In order to solve the technical problems, the application provides an ultraviolet light-moisture dual-curing polyurethane hot melt adhesive, which comprises acrylic ester group dihydric alcohol, isocyanate, macromolecular polyol and an initiator, wherein the structural formula of the acrylic ester group dihydric alcohol is shown as formula (I):
wherein:
R 1 is the main structure of isocyanate;
R 2 is a main structure of small molecule polyalcohol;
R 3 is a hydrogen atom or a methyl group. Preferably, the mass ratio of the acrylic acid ester group dihydric alcohol to the macromolecular polyol is: 1: (4-8); the content of the initiator is 0.25-1.25% of the total weight of the acrylic ester group dihydric alcohol and the macromolecular polyol.
Preferably, the macropolyol comprises any one or more combinations of crystalline polyester polyol, amorphous polyester polyol and polyether polyol.
Preferably, the macropolyol includes crystalline polyester polyol, amorphous polyester polyol and polyether polyol;
the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol to the polyether polyol is (1.5-3): (0.7-1.3): 1.
preferably, the molecular weight of the crystalline polyester polyol is 2000-4000 g/mol, and the hydroxyl value of the crystalline polyester polyol is 20-50 mgKOH/g; the melting point of the crystalline polyester polyol is 35-90 ℃;
the molecular weight of the amorphous polyester polyol is 2000 g/mol-4000 g/mol; the hydroxyl value of the amorphous polyester polyol is 25 mgKOH/g-40 mgKOH/g;
the glass transition temperature of the amorphous polyester polyol is between minus 30 ℃ and 30 ℃;
the molecular weight of the polyether polyol is 1500 g/mol-3000 g/mol, and the viscosity of the polyether polyol is 300 cPs-500 cPs at 25 ℃.
Preferably, the amorphous polyester polyol comprises an amorphous polyester polyol 1 with a glass transition temperature of-30 ℃ to 0 ℃ and an amorphous polyester polyol 2 with a glass transition temperature of 0 ℃ to 30 ℃, and the mass ratio of the amorphous polyester polyol 1 to the amorphous polyester polyol 2 is 1: (0.65-0.85);
the initiator comprises one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, 2-dimethoxy-2-phenylacetophenone, methyl benzoate and isopropylthioxanthone;
the isocyanate comprises one or more of aliphatic diisocyanate and aromatic diisocyanate; the aromatic diisocyanate comprises one or more of ortho-xylene diisocyanate, meta-xylene diisocyanate, para-xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate and hydrogenated xylene diisocyanate; the aliphatic diisocyanate comprises one or more of hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
On the other hand, the application provides a preparation method of the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive, which comprises the following steps:
s1: heating diisocyanate to 50-75 ℃, then adding monohydroxy acrylic ester monomer and polymerization inhibitor to react for 1-3 h, and when the-NCO content is 11-16%; adding small molecular polyol, and continuing to react at 50-75 ℃ until the-NCO content is less than 1% to obtain acrylic ester diol;
s2: mixing the prepared acrylic ester-based dihydric alcohol, isocyanate and macromolecular polyol, heating to 115-145 ℃, wherein the molar ratio of-NCO/-OH is 1.5-3.0, adding an initiator for reaction, and obtaining the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive when the mass content of-NCO is 0.5-3.0%.
Preferably, the molar ratio of the diisocyanate, the monohydroxy acrylate monomer and the small molecule polyol added in the step S1 is 1: (0.8-1.2): (0.8-1.2);
the polymerization inhibitor accounts for 0.1 to 0.5 percent of the mass of the diisocyanate.
Preferably, in the step S1, the time for continuous reaction after the small molecular polyol is added is 1 to 3 hours;
in the step S2, the specific steps of mixing the prepared acrylic ester-based dihydric alcohol, isocyanate and macromolecular polyol are as follows: melting and stirring macromolecular polyol at 110-135 ℃, vacuumizing, and then adding the macromolecular polyol into a mixture of dihydric alcohol containing acrylate groups and isocyanate;
the reaction time after the initiator is added into the S2 is 1 to 3 hours.
Preferably, the monohydroxyacrylate monomer includes one or more of beta-hydroxyethyl acrylate and beta-hydroxypropyl acrylate;
the number of hydroxyl groups in a single molecule of the micromolecular polyol is more than or equal to 3; the molecular weight of the micromolecular polyol is less than or equal to 1000;
the small molecule polyalcohol comprises one or more of trimethylolpropane, glycerol, castor oil and 2,3, 4-trihydroxy-6-methylcyclohexanone;
the diisocyanate comprises one or more of aliphatic diisocyanate and aromatic diisocyanate; the aromatic diisocyanate comprises one or more of ortho-xylene diisocyanate, meta-xylene diisocyanate, para-xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate and hydrogenated xylene diisocyanate; the aliphatic diisocyanate comprises one or more of hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate;
the polymerization inhibitor comprises one or more of p-hydroxyanisole, hydroquinone and 2, 6-di-tert-butyl-4-methylphenol.
The beneficial effects are that:
the acrylic ester-based dihydric alcohol adopted by the application contains an ultraviolet curing active group and is cooperated with the macromolecular polyol, so that the acrylic ester-based dihydric alcohol is more uniformly dispersed in a molecular chain of the hot melt adhesive, the complete curing of the adhesive solution is realized, and the problem of incomplete curing of a shadow area is solved; meanwhile, the glue solution has the characteristics of improving the use stability, initial adhesion and final adhesion of the glue solution, and the prepared glue solution has the characteristics of long service life, quick positioning and complete solidification.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The ultraviolet light-moisture dual-curing polyurethane hot melt adhesive comprises acrylic ester group dihydric alcohol, isocyanate, macromolecular polyol and an initiator, wherein the structural formula of the acrylic ester group dihydric alcohol is shown as formula (I):
wherein:
R 1 is the main structure of isocyanate;
R 2 is a main structure of small molecule polyalcohol;
R 3 is a hydrogen atom or a methyl group.
Specifically, the application adopts the dihydric alcohol with the acrylate group and takes the dihydric alcohol as the raw material component of the hot melt adhesive, and the dihydric alcohol can be synergistic with macromolecular polyol while providing active groups capable of ultraviolet curing, so that the dihydric alcohol containing the acrylate group is uniformly dispersed in a molecular chain of the hot melt adhesive, the full curing of the adhesive solution is realized, the shadow area of a part of areas is reduced, the complete curing is realized, and the final adhesive force is improved.
The ultraviolet light-moisture dual-curing polyurethane hot melt adhesive prepared by the method can effectively solve the problem of incomplete curing of a shadow area of a material, can realize good stability of the obtained adhesive solution, has long service life, and also has the characteristics of good initial adhesion and final adhesion, and is fast to position and complete to cure.
In some embodiments, the macropolyol comprises any one or more combinations of crystalline polyester polyol, amorphous polyester polyol, and polyether polyol.
In some preferred embodiments, the macropolyols include crystalline polyester polyols, amorphous polyester polyols, and polyether polyols.
Specifically, the macromolecular polyol is an indispensible synthetic raw material of polyurethane, and the inventor finds through a great deal of research that in the preparation of polyurethane hot melt adhesive, the macromolecular polyol is selected from the combination of crystalline polyester polyol, amorphous polyester polyol and polyether polyol, and the combination of the crystalline polyester polyol, the amorphous polyester polyol and the polyether polyol is mutually synergistic, so that the higher or lower viscosity of the adhesive system is avoided, and the curing effect of the system is improved; the three are mutually cooperated, the long-term viscosity can be avoided, the durability of the material can be improved, and the initial adhesion and the final adhesion of the colloid can be improved.
In some embodiments, the weight ratio of the crystalline polyester polyol, the amorphous polyester polyol, the polyether polyol is (1.5-3): (0.7-1.3): 1.
in particular, in the actual development process for preparing the polyurethane hot melt adhesive, it is difficult to infer how to achieve the balance among the viscosity, water absorption, initial adhesion and final adhesion of the polyurethane hot melt adhesive, and the inventors have found through extensive studies that the weight ratio of the crystalline polyester polyol, the amorphous polyester polyol and the polyether polyol is (1.5 to 3): (0.7-1.3): 1, the colloid can be well spread and solidified, and the initial adhesion is good.
In some preferred embodiments, the weight ratio of crystalline polyester polyol, amorphous polyester polyol, polyether polyol is 2.2:1.1:1.
specifically, the preferable weight ratio can effectively prevent polyether or amorphous polyester polyol from influencing the viscosity of the colloid, lower or higher viscosity from influencing the curing effect, and prevent insufficient moisture curing, thereby realizing good curing.
In some embodiments, the crystalline polyester polyol has a molecular weight of 2000g/mol to 4000g/mol and a hydroxyl number of 20mgKOH/g to 50mgKOH/g; the melting point of the crystalline polyester polyol is 35-90 ℃.
In particular, from the viewpoint of processability, it is preferable that the crystalline polyester polyol has a melting point of between 35℃and 90℃and is solid at room temperature, which is advantageous in maintaining a good initial adhesion.
The hydroxyl value of the present application is 1g of the number of milligrams of potassium hydroxide corresponding to hydroxyl groups in the crystalline polyester polyol, expressed as mgKOH/g. The hydroxyl numbers in the amorphous polyester polyols are likewise defined.
In some preferred embodiments, the crystalline polyester polyol has a hydroxyl number of 20mgKOH/g to 35mgKOH/g.
The crystalline polyester polyol may be obtained commercially, and may be Dynacoll7360, dynacoll7380, dynacoll7330, for example.
In some embodiments, the amorphous polyester polyol has a molecular weight of 2000g/mol to 4000g/mol; the hydroxyl value of the amorphous polyester polyol is 25 mgKOH/g-40 mgKOH/g;
the amorphous polyester polyol can be in a liquid state or a solid state at room temperature, and in order to keep high initial adhesion and avoid long-term adhesion, the amorphous polyester polyol with the molecular weight of 2000 g/mol-4000 g/mol, the hydroxyl value of 25 mgKOH/g-40 mgKOH/g and the glass transition temperature of-30 ℃ to 30 ℃ is selected.
Amorphous polyester polyols are commercially available and may be, for example, dynacoll7111, dynacoll7130, dynacoll7210, dynacoll7220, dynacoll7230.
In some preferred embodiments, the amorphous polyester polyol has a glass transition temperature of from-30 ℃ to 30 ℃; the amorphous polyester polyol comprises an amorphous polyester polyol 1 with a glass transition temperature of-30 ℃ to 0 ℃ and an amorphous polyester polyol 2 with a glass transition temperature of 0 ℃ to 30 ℃, wherein the mass ratio of the amorphous polyester polyol 1 to the amorphous polyester polyol 2 is 1: (0.65-0.85).
In particular, the amorphous polyester polyol preferred herein can further avoid the phenomenon of poor surface drying effect.
In some embodiments, the polyether polyol has a molecular weight of 1500g/mol to 3000g/mol and a viscosity of 300cPs to 500cPs at 25 ℃.
Specifically, the polyether polyol has certain polarity, which is beneficial to improving the moisture curing effect and the viscosity of the colloid system. Polyether polyols can be obtained commercially.
In some embodiments, to balance dual curing effects, to avoid the problem of insufficient moisture curing or insufficient internal curing of the colloid caused in the uv curing process, the mass ratio of acrylate-based diol to macromolecular polyol is 1: (4-8);
in some preferred embodiments, the mass ratio of acrylate-based diol to macropolyol is 1: (5-6.5).
In some embodiments, the isocyanate comprises one or more of an aliphatic diisocyanate, an aromatic diisocyanate; the aromatic diisocyanate comprises one or more of ortho-xylene diisocyanate, meta-xylene diisocyanate, para-xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate and hydrogenated xylene diisocyanate; the aliphatic diisocyanate comprises one or more of hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate;
the initiator comprises one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, 2-dimethoxy-2-phenylacetophenone, methyl benzoate and isopropylthioxanthone;
the content of the initiator is 0.25-1.25% of the total weight of the acrylic ester group dihydric alcohol and the macromolecular polyol.
Specifically, the initiator used in the present application is a photoinitiator that can trigger an ultraviolet curing reaction. In order to improve the curing efficiency, reduce the production cost and fully utilize resources, the initiator content of the application is 0.25-1.25% of the total weight of the acrylic ester group dihydric alcohol and the macromolecular polyhydric alcohol. In some preferred embodiments, the initiator is present in an amount of 0.5% to 0.85% of the total weight of the acrylate-based diol and the macropolyol.
On the other hand, the application provides a preparation method of the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive, which comprises the following steps:
s1: heating diisocyanate to 50-75 ℃, maintaining the temperature, adding monohydroxy acrylic ester monomer and polymerization inhibitor to react for 1-3 h, and when the-NCO content is 11-16%; adding small molecular polyol, and continuing to react at 50-75 ℃ until the-NCO content is less than 1% to obtain acrylic ester diol;
s2: mixing the prepared acrylic ester-based dihydric alcohol, isocyanate and macromolecular polyol, heating to 115-145 ℃, wherein the molar ratio of-NCO/-OH is 1.5-3.0, adding an initiator for reaction, and obtaining the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive when the mass content of-NCO is 0.5-3.0%.
Specifically, the acrylic ester group dihydric alcohol adopts diisocyanate, micromolecular polyol and monohydroxy acrylic ester monomer as raw materials, and has the advantages of easily available materials, low cost and simple preparation process.
In some embodiments, the molar ratio of diisocyanate, monohydroxyacrylate monomer, small molecule polyol added in S1 is 1: (0.8-1.2): (0.8-1.2);
the polymerization inhibitor accounts for 0.1 to 0.5 percent of the mass of the diisocyanate.
Specifically, the addition amount of the polymerization inhibitor is calculated by taking the addition amount of diisocyanate as 100%, and the mass content of the polymerization inhibitor is 0.1% -0.5%.
In some embodiments, the polymerization inhibitor includes one or more of para-hydroxyanisole, hydroquinone, and 2, 6-di-tert-butyl-4-methylphenol.
In some embodiments, in the step S1, the reaction time is continued for 1 to 3 hours after the small molecule polyol is added;
in the step S2, the specific steps of mixing the prepared acrylic ester-based dihydric alcohol, isocyanate and macromolecular polyol are as follows: melting and stirring macromolecular polyol at 110-135 ℃, vacuumizing, and then adding the macromolecular polyol into a mixture of dihydric alcohol containing acrylate groups and isocyanate; the reaction time after the initiator is added into the S2 is 1 to 3 hours.
Specifically, macromolecular polyol is melted and stirred at 110-135 ℃, water is required to be removed in vacuum, then the macromolecular polyol is added into a mixture of dihydric alcohol containing acrylate groups and isocyanate, the molar ratio of-NCO/-OH in a reaction system is controlled to be 1.5-3.0, an initiator is added, then the reaction is carried out for 1-3 hours at 115-145 ℃, the mass content of-NCO is controlled to be 0.5-3.0%, and the reaction is finished, so that the ultraviolet-moisture dual-curing polyurethane hot melt adhesive is prepared. It is noted that the test for the-NCO content is obtained according to the national standard 12009.4-89.
In some embodiments, the monohydroxyacrylate monomer includes one or more of beta-hydroxyethyl acrylate and beta-hydroxypropyl acrylate.
In some embodiments, the number of hydroxyl groups in a single molecule of the small molecule polyol is greater than or equal to 3; i.e., 1 mole of small molecule polyol contains at least 3 moles of hydroxyl groups.
The molecular weight of the micromolecular polyol is less than or equal to 1000;
specifically, in the preparation of the acrylic ester-based diol, the small molecule polyol preferably has 3 hydroxyl groups in a single molecule thereof, i.e., 1mol of the small molecule polyol contains 3mol of hydroxyl groups. The small molecular polyol with 3 hydroxyl groups in single molecule comprises one or more of trimethylolpropane, glycerol, castor oil and 2,3, 4-trihydroxy-6-methylcyclohexanone.
In some preferred embodiments, the small molecule polyols are trimethylolpropane and castor oil.
Specifically, the inventor finds that when the small molecular polyol is selected from trimethylolpropane and castor oil, the service life of the prepared polyurethane hot melt adhesive is longer, and the dual curing effect is better; especially when the molar ratio of trimethylolpropane to castor oil is 1: in the range of (3.3-4.2), the reaction between the micromolecular polyol and one end of isocyanate can be realized under the action of steric hindrance and radical activity, and the formation of the dihydric alcohol containing the acrylate group can be better promoted.
In some embodiments, the diisocyanate comprises one or more of an aliphatic diisocyanate, an aromatic diisocyanate; the aromatic diisocyanate comprises one or more of ortho-xylene diisocyanate, meta-xylene diisocyanate, para-xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate and hydrogenated xylene diisocyanate; the aliphatic diisocyanate comprises one or more of hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
On the other hand, the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive is applied to electronic products.
Specific embodiments of the present invention will be further illustrated by the following examples, but it is not intended that the scope of the invention be limited to the examples.
The various reagents used in the examples and comparative examples are all commercially available products.
Example 1
(1) The preparation method of the acrylic ester diol comprises the following steps:
heating o-xylene diisocyanate to 65 ℃, maintaining the temperature, adding acrylic acid-beta-hydroxyethyl acrylate, mixing, adding a polymerization inhibitor, reacting for 2.5 hours, when the-NCO content is 14.5%, adding small-molecule polyol, and when the-NCO content is less than 1%, preparing liquid acrylic ester-based dihydric alcohol;
wherein the polymerization inhibitor is 2, 6-di-tert-butyl-4-methylphenol; the micromolecular polyol is selected from trimethylolpropane and castor oil, and the molar ratio of the trimethylolpropane to the castor oil is 1:3.7;
the molar ratio of the o-xylene diisocyanate to the acrylic acid-beta-hydroxyethyl ester to the small molecular polyol is 1:1.1:1.1;
(2) The preparation method of the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive comprises the following steps:
melting and stirring macromolecular polyol at 120 ℃, vacuumizing to remove water, adding the macromolecular polyol into a mixture of dihydric alcohol containing acrylate groups and m-xylene diisocyanate, controlling the molar ratio of-NCO/-OH in the system to be 2.5, adding an initiator to react at 125 ℃, and controlling the content of-NCO to be 2.2wt%. Wherein the weight ratio of the dihydric alcohol containing the acrylic ester group to the macromolecular polyol is 1:5.8; the initiator content was 0.65wt% of the total amount of the acrylate group-containing diol and the macropolyol.
The initiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.
The macromolecular polyol is selected from crystalline polyester polyol, amorphous polyester polyol and polyether polyol, and the mass ratio of the macromolecular polyol to the amorphous polyester polyol is 2.2:1.1:1.
the crystalline polyester polyol is Dynacoll7380 (molecular weight: 3500g/mol, hydroxyl value: 27-34 mgKOH/g, melting point: 70 ℃ C.).
The amorphous polyester polyols are Dynacoll7130 and Dynacoll7220 with the mass ratio of 0.72:1.
wherein Dynacoll7130 has a molecular weight of 3000g/mol, a hydroxyl value of 31-39 mgKOH/g and a glass transition temperature of 30 ℃.
Dynacoll7220 has a molecular weight of 3500g/mol, a hydroxyl value of 27-34 mgKOH/g, a glass transition temperature of-20 ℃, and a weight ratio of 0.72:1.
the polyether polyol was L62 (molecular weight 2500g/mol, viscosity 25 ℃ C. 400 cPs) and was purchased from Nantong Jiuze chemical Co., ltd.
Example 2
Example 2 provides an ultraviolet light-moisture dual curing polyurethane hot melt adhesive, the specific implementation mode of which is similar to example 1, except that trimethylolpropane is selected as the small molecule polyol.
Example 3
Example 3 provides an ultraviolet light-moisture dual curing polyurethane hot melt adhesive, the specific implementation mode of which is similar to that of example 1, and the difference is that only amorphous polyester polyol and polyether polyol are selected as macromolecular polyol, the amorphous polyester polyol and the polyether polyol are selected from the same class as in example 1, and the mass ratio of the amorphous polyester polyol to the polyether polyol is still 1.1:1.
Example 4
Example 4 provides an ultraviolet light-moisture dual cure polyurethane hot melt adhesive, the specific embodiment of which is similar to example 1, except that the crystalline polyester polyol Dynacoll7380 is replaced with Dynacoll7361 (molecular weight 8500g/mol, hydroxyl number 10mgKOH/g to 16mgKOH/g, melting point 57 ℃).
Example 5
Example 5 provides an ultraviolet light-moisture dual cure polyurethane hot melt adhesive, the specific embodiment of which is similar to example 1, except that the amorphous polyester polyol Dynacoll7220 is replaced with Dynacoll7131 (molecular weight of 3000g/mol, hydroxyl number of 31mgKOH/g to 39mgKOH/g, glass transition temperature of 30 ℃).
Example 6
Example 6 provides an ultraviolet light-moisture dual cure polyurethane hot melt adhesive, the specific embodiment of which is similar to example 1, except that polyether polyol L62 is replaced with F38 (molecular weight 5000g/mol, solid state), available from Nantong Jiuze chemical Co., ltd.
Comparative example 1
Comparative example 1 was substantially the same as the embodiment of example 1, except that the content of the acrylic acid ester-based diol was 0.
Comparative example 2
Comparative example 2 provides an ultraviolet light-moisture dual curing polyurethane hot melt adhesive, the concrete implementation mode of which is similar to that of example 1, except that o-xylene diisocyanate is heated to 65 ℃, the temperature is kept, and small molecular polyol is added for mixing, meanwhile, polymerization inhibitor accounting for 0.25 weight percent of the xylene diisocyanate is added for 2.5 hours for reaction, when the-NCO content is 4.4%, acrylic acid-beta-hydroxyethyl ester is added, and when the-NCO content is less than 1%, acrylic ester-based dihydric alcohol is obtained; wherein, the mole ratio of the micromolecular polyol, diisocyanate and monohydroxy acrylic ester monomer is the same as that of the example 1, the types of the micromolecular polyol are the same as those of the example 1, and the dihydric alcohol of the acrylic ester group prepared by the reaction is gel substance.
Comparative example 3
Comparative example 3 is different from example 1 in that:
(1) The preparation method of the acrylic ester diol comprises the following steps: heating o-xylene diisocyanate to 65 ℃, maintaining the temperature, adding acrylic acid-beta-hydroxyethyl ester for mixing, simultaneously adding a polymerization inhibitor accounting for 0.25 weight percent of the xylene diisocyanate, reacting for 2.5 hours, and adding polyethylene glycol when the content of the obtained-NCO is 14.5%, so as to prepare polyurethane acrylate prepolymer; wherein, the mol ratio of polyethylene glycol, diisocyanate and monohydroxyacrylate is the same as that of example 1.
(2) The preparation method of the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive comprises the following steps:
melting and stirring macromolecular polyol at 120 ℃, vacuumizing to remove water, adding the macromolecular polyol into a mixture of polyurethane acrylic ester prepolymer and m-xylene diisocyanate, controlling the molar ratio of-NCO/-OH in the system to be 2.5, adding an initiator to react at 125 ℃, and controlling the content of-NCO to be 2.2wt%. Wherein, the weight ratio of the polyurethane acrylic ester prepolymer to the macromolecular polyol is 1:5.8; the initiator content was 0.65wt% of the total amount of urethane acrylate prepolymer and macropolyol.
Wherein the macropolyol was the same as in example 1.
Performance evaluation
1. Adhesive strength test: the hot melt adhesives obtained in examples 1 to 6 and comparative examples 1 to 3 were coated between two substrates, which were respectively stainless steel test pieces and PET substrates, and tensile shear strength was measured according to GB/T7124-2008; the test point conditions are respectively as follows: (1) Firstly, ultraviolet curing is utilized, the wavelength is 200 nm-400 nm, the radiation intensity is 120mW/cm < 2 >, and the time is 35s; (2) Then placing the mixture in a constant temperature and humidity box with the temperature of 25+/-2 ℃ and the RH of 45+/-5 percent for 6 hours and 24 hours respectively. Tensile shear strength is respectively tested, the unit of the obtained mechanical property is MPa, and the specific test results are shown in Table 1; meanwhile, whether the surface of the adhesive layer is dried after 35s of ultraviolet irradiation is also measured, namely, the adhesive layer is not sticky;
2. service life test: the material obtained after moisture curing for 24 hours in test 1 was left for 12 months at 25.+ -. 2 ℃ and then tested for tensile shear strength according to GB/T7124-2008, with the following evaluation criteria: the tensile shear strength after 12 months is reduced by 0-5%% to grade A, reduced by 5% -15% to not 5% to grade B, reduced by 15% -30% to not 5% to grade C, reduced by more than 30% to grade D, wherein W= (E0-E1)/E0X 100%, E0 is the tensile shear strength after 24 hours of moisture curing, and E1 is the tensile shear strength after 12 months of standing.
Table 1 table of examples and comparative examples performance test data
As shown in Table 1, the content of the acrylic acid ester diol in the hot melt adhesive prepared in the comparative example 1 is 0, and the prepared hot melt adhesive has very low tensile shear strength after ultraviolet curing, is not completely cured, has poor moisture curing strength and service life test grade, and shows that the ultraviolet curing strength of the adhesive can be improved by adding the acrylic acid ester diol in the preparation process of the hot melt adhesive, and meanwhile, the hot melt adhesive can also cooperate with macromolecular polyol to improve the moisture curing strength of the adhesive and also has the effect of improving the service life. In comparative example 2, the order of addition of the small-molecular polyol was changed, and although the acrylate-based diol was finally obtained, the small-molecular polyol added first was subjected to a bulk crosslinking reaction with diisocyanate to obtain a gel substance, which could not be used for the next preparation of the polyurethane hot melt adhesive. In the embodiment 1, compared with the comparative example 3, polyether alcohols, namely polyethylene glycol, are added, the tensile shear strength is reduced by half before moisture curing after ultraviolet curing, the surface condition after ultraviolet curing is not dried, the shear strength and the service life after moisture curing are lower than those of the embodiment 1, and the condition that the acrylate-based dihydric alcohol obtained by the reaction of micromolecular polyol, diisocyanate and monohydroxyacrylate monomers is used for preparing the polyurethane hot melt adhesive, so that the polyurethane hot melt adhesive can be uniformly dispersed in the molecular chain of the hot melt adhesive, the complete curing of the adhesive solution is realized, and the final adhesive force and the service life are improved.
In the embodiment 2, the small-molecular polyol has no castor oil, the ultraviolet curing tensile shear strength is reduced by more than half, and the ultraviolet curing tensile shear strength is not completely cured, which indicates that the small-molecular polyol adopts trimethylolpropane and castor oil, and the prepared hot melt adhesive has better ultraviolet curing performance, moisture curing performance and service life grade. The macropolyol of example 3, the non-crystalline polyester polyol, was not fully cured; the crystalline polyester polyol of example 4 has a molecular weight higher than 4000g/mol, a hydroxyl value content lower than 20mgKOH/g, a moisture cure shear strength and a life grade lower than that of example 3; presuming that the macromolecular polyol is a non-crystalline polyester polyol, and affecting the curing effect; the molecular weight of the crystalline polyester polyol is higher than 4000g/mol, the hydroxyl value is lower than 20mgKOH/g, the initial adhesion is reduced, and the service life is prolonged. In example 5, only the amorphous polyester polyol with the glass transition temperature between 0 ℃ and 30 ℃ is selected, the adhesive is not completely cured, the ultraviolet curing performance and the moisture curing performance are reduced, the service life grade is reduced, and the amorphous polyester polyol 1 with the glass transition temperature between-30 ℃ and 0 ℃ and the amorphous polyester polyol 2 with the glass transition temperature between 0 ℃ and 30 ℃ are selected, so that the surface drying effect of the adhesive is improved, the ultraviolet curing and moisture curing shear strength of the prepared hot melt adhesive is higher, the service life is longer, and the complete curing can be realized. In the same way, the molecular weight of the polyether polyol in the embodiment 6 is not in the range of 1500g/mol to 3000g/mol, and the moisture curing effect is poor, which indicates that the molecular weight of the polyether polyol is in the range of 1500g/mol to 3000g/mol, and the moisture curing effect of the adhesive can be improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. An ultraviolet light-moisture dual-curing polyurethane hot melt adhesive is characterized by comprising acrylic ester group dihydric alcohol, isocyanate, macromolecular polyol and an initiator,
the preparation method of the acrylic ester diol comprises the following steps:
heating o-xylene diisocyanate to 65 ℃, maintaining the temperature, adding acrylic acid-beta-hydroxyethyl, mixing, adding a polymerization inhibitor, reacting for 2.5 hours, when the-NCO content is 14.5%, adding small-molecule polyol, and when the-NCO content is less than 1%, preparing liquid acrylic ester-based dihydric alcohol;
the micromolecular polyol is selected from trimethylolpropane and castor oil, and the molar ratio of the trimethylolpropane to the castor oil is 1:3.7;
the molar ratio of the o-xylene diisocyanate to the acrylic acid-beta-hydroxyethyl ester to the small molecular polyol is 1:1.1:1.1;
the macromolecular polyol comprises crystalline polyester polyol, amorphous polyester polyol and polyether polyol;
the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol to the polyether polyol is (1.5-3): (0.7 to 1.3): 1.
2. the ultraviolet light-moisture dual curing polyurethane hot melt adhesive according to claim 1, wherein the amorphous polyester polyol comprises an amorphous polyester polyol 1 having a glass transition temperature of-30 ℃ to 0 ℃ and an amorphous polyester polyol 2 having a glass transition temperature of 0 ℃ to 30 ℃, and the mass ratio of the amorphous polyester polyol 1 to the amorphous polyester polyol 2 is 1: (0.65 to 0.85).
3. The uv-moisture dual cure polyurethane hot melt adhesive of claim 1, wherein the initiator comprises one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, 2-dimethoxy-2-phenylacetophenone, methyl benzoate, and isopropylthioxanthone.
4. The ultraviolet light-moisture dual cure polyurethane hot melt adhesive of claim 1, wherein the isocyanate comprises one or more of an aliphatic diisocyanate and an aromatic diisocyanate; the aromatic diisocyanate comprises one or more of ortho-xylene diisocyanate, meta-xylene diisocyanate and para-xylene diisocyanate; the aliphatic diisocyanate includes one or more of hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, and cyclohexyl diisocyanate.
5. The ultraviolet light-moisture dual curing polyurethane hot melt adhesive according to claim 1, wherein the mass ratio of the acrylate-based diol and the macromolecular polyol is: 1: (4-8); the content of the initiator is 0.25-1.25% of the total weight of the acrylic ester group dihydric alcohol and the macromolecular polyol.
6. The ultraviolet light-moisture dual curing polyurethane hot melt adhesive according to claim 1, wherein the molecular weight of the crystalline polyester polyol is 2000g/mol to 4000g/mol, and the hydroxyl value of the crystalline polyester polyol is 20mgKOH/g to 50mgKOH/g; the melting point of the crystalline polyester polyol is 35-90 ℃;
the molecular weight of the amorphous polyester polyol is 2000 g/mol-4000 g/mol; the hydroxyl value of the amorphous polyester polyol is 25 mgKOH/g-40 mgKOH/g;
the molecular weight of the polyether polyol is 1500 g/mol-3000 g/mol, and the viscosity of the polyether polyol is 300 cPs-500 cPs at 25 ℃.
7. A method for preparing the ultraviolet light-moisture dual curing polyurethane hot melt adhesive as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
s1: heating o-xylene diisocyanate to 65 ℃, maintaining the temperature, adding acrylic acid-beta-hydroxyethyl, mixing, adding a polymerization inhibitor, reacting for 2.5 hours, when the-NCO content is 14.5%, adding small-molecule polyol, and when the-NCO content is less than 1%, preparing liquid acrylic ester-based dihydric alcohol;
the micromolecular polyol is selected from trimethylolpropane and castor oil, and the molar ratio of the trimethylolpropane to the castor oil is 1:3.7;
the molar ratio of the o-xylene diisocyanate to the acrylic acid-beta-hydroxyethyl ester to the small molecular polyol is 1:1.1:1.1;
s2: mixing the prepared acrylic ester-based dihydric alcohol, isocyanate and macromolecular polyol, heating to 115-145 ℃, wherein the molar ratio of-NCO/-OH is 1.5-3.0, adding an initiator for reaction, and obtaining the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive when the mass content of-NCO is 0.5-3.0%.
8. The method for preparing the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive according to claim 7, wherein,
in the step S2, the specific steps of mixing the prepared acrylic ester-based dihydric alcohol, isocyanate and macromolecular polyol are as follows: melting and stirring macromolecular polyol at 110-135 ℃, vacuumizing, and then adding the macromolecular polyol into a mixture of dihydric alcohol containing acrylate groups and isocyanate;
and the reaction time after the initiator is added in the S2 is 1-3 h.
9. The method for preparing the ultraviolet light-moisture dual-curing polyurethane hot melt adhesive according to claim 7, wherein,
the polymerization inhibitor comprises one or more of p-hydroxyanisole, hydroquinone and 2, 6-di-tert-butyl-4-methylphenol.
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| CN115851208B (en) * | 2022-12-06 | 2024-10-15 | 烟台德邦科技股份有限公司 | UV (ultraviolet) moisture dual-curing reaction type polyurethane hot melt adhesive and preparation method thereof |
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