CN108395847A - A kind of high-strength light, heat activated blocked polyurethane adhesive and preparation method thereof and application method - Google Patents
A kind of high-strength light, heat activated blocked polyurethane adhesive and preparation method thereof and application method Download PDFInfo
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- CN108395847A CN108395847A CN201810183902.1A CN201810183902A CN108395847A CN 108395847 A CN108395847 A CN 108395847A CN 201810183902 A CN201810183902 A CN 201810183902A CN 108395847 A CN108395847 A CN 108395847A
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- heat activated
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000853 adhesive Substances 0.000 title claims description 57
- 230000001070 adhesive effect Effects 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 16
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000004417 polycarbonate Substances 0.000 claims abstract description 42
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 41
- 150000003077 polyols Chemical class 0.000 claims abstract description 40
- -1 hydroxy acryl Chemical group 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 21
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002148 esters Chemical class 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 17
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000010790 dilution Methods 0.000 claims abstract description 12
- 239000012895 dilution Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000004135 Bone phosphate Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YKHNTDZZKRMCQV-UHFFFAOYSA-N 2-(phenoxymethyl)oxirane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1OC1COC1=CC=CC=C1 YKHNTDZZKRMCQV-UHFFFAOYSA-N 0.000 claims description 5
- 238000013007 heat curing Methods 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 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 4
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical compound CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004425 Makrolon Substances 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000013008 moisture curing Methods 0.000 abstract description 41
- 238000001723 curing Methods 0.000 abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 150000005846 sugar alcohols Polymers 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 127
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 8
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical class CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- SOLZAPJHTKXTOR-UHFFFAOYSA-N cyclohexane;methanol;prop-2-enoic acid Chemical class OC.OC.OC(=O)C=C.OC(=O)C=C.C1CCCCC1 SOLZAPJHTKXTOR-UHFFFAOYSA-N 0.000 description 7
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PCLLJCFJFOBGDE-UHFFFAOYSA-N (5-bromo-2-chlorophenyl)methanamine Chemical compound NCC1=CC(Br)=CC=C1Cl PCLLJCFJFOBGDE-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- QNJVYPYNVCLCBU-UHFFFAOYSA-N CCOP(=O)C(=O)c1c(C)cc(C)cc1C Chemical class CCOP(=O)C(=O)c1c(C)cc(C)cc1C QNJVYPYNVCLCBU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- FBBZJPZVRCWILD-UHFFFAOYSA-N diphenylphosphanyl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 FBBZJPZVRCWILD-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the preparation methods that a kind of high-strength light, thermogravimetric cure polyurethane binder, to polyalcohol type compounding selection in moisturecuring oligomer, enter ultraviolet curing group and end-capping reagent, the stabilization rapid curing under humidity, under high-temperature condition is realized, realizes the effect that glued construction high strength bond is had excellent performance.Specially：Polycarbonate polyol, polyether polyol and isocyanates after drying is stirred evenly, catalyst is added, 1 5h is reacted at 70 100 DEG C, it is cooled to 60 80 DEG C, 0.5 2h of chain extender reaction is added, solvent dilution is added, obtains the moisturecuring prepolymer that NCO content is about 5 10%；50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned prepolymer, and hydroxy acryl acid ester monomer and photoinitiator, polymerization inhibitor are sequentially added into prepolymer, is stirred evenly；Under the conditions of being protected from light, to step（2）Caprolactam, sodium hydrogensulfite and methyl ethyl ketone oxime are sequentially added in uniformly mixed mixture, is stirred evenly, and addition solvent is needed according to viscosity.
Description
Technical field
The present invention relates to polyurethane binder fields, and in particular to the viscoelastic polyurethane with high intensity, photo-thermal dual curable
Mixture field further relates to specific preparation method and application method.
Background technology
Polyurethane resin belongs to a kind of good macromolecule resin substance, is widely used in every field：Such as polyurethane
Artificial leather is widely used in the making of leather and fur, clothing, and polyurethane binder, polyurethane coating and polyurethane terrace material are answered
With.
From nineteen thirty-seven, after polyurethane material synthesizes for the first time, development is very fast, and the polyurethane of each category emerges one after another, 20 years
For the middle period, there is thermoplastic polyurethane adhesive, nineteen sixty-eight solvent-free polyurethane adhesive occurs, occurs within 1978 wet solid
Change polyurethane binder, reaction type hot-fusible polyurethane binder occurs within 1984.Foundation class polyurethane binder is in 20th century
It has been be basically completed that, the research of recent two decades is concentrated mainly on high-performance, compound polyurethane binder, both for specifically answering
The research difficulty of adhesive category, general adhesive gradually increases.
High molecular material is used, inventor has carried out details for the curing mode of photo-thermal, damp and hot and wet light and ground
Study carefully, and has carried out patent application respectively.For how to obtain using under a kind of suitable light and heat condition in actual use high intensity,
Heat safe polyurethane binder is product category leaved for development.
In view of the above technical problems, inventor enterprise is studied for a long period of time, obtains the present invention.
Invention content
Goal of the invention：The technical issues of for being introduced in background technology, the present invention by the selection to polyurethane component, with
Based on holding NCO urethane oligomers, a kind of design by light rapid curing, multi-stage curing is obtained, is realized under high temperature
Quickly, stable curing, curing degree increases under high temperature, and glued construction high strength bond, high temperature resistance and quickly may be implemented
Cure excellent effect.
There is provided the preparation methods of high-strength light, heat activated blocked polyurethane adhesive for another object of the present invention.
Another object of the present invention is to provide the application method of high-strength light, heat activated blocked polyurethane adhesive.
In order to realize above-mentioned technique effect, the following technical solution is used.
The preparation method of a kind of high-strength light, heat activated blocked polyurethane adhesive, includes the following steps：
(1) NCO polyurethane prepolymers are held
Polycarbonate polyol, polyether polyol and isocyanates are dried in vacuo respectively；
Polycarbonate polyol, polyether polyol and isocyanates after drying is stirred evenly, catalyst is added,
1-5h is reacted at 70-100 DEG C, is cooled to 60-80 DEG C, chain extender reaction 0.5-2h is added, solvent dilution is added, obtains NCO and contains
Amount is about the end NCO polyurethane prepolymers of 5-10%.
(2) light-cured components are added
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned prepolymer, and hydroxyl propylene is sequentially added into prepolymer
Acid ester monomer and photoinitiator, polymerization inhibitor, stir evenly.
(3) addition of sealer
Under the conditions of being protected from light, to step (2) be uniformly mixed mixture in sequentially add caprolactam, sodium hydrogensulfite and
Methyl ethyl ketone oxime stirs evenly, and needs to be added solvent according to viscosity to get product.
As optimal technical scheme, the polyether polyol is polyether-tribasic alcohol, and molecular weight is described poly- in 1000-5000
Carbonate polyol is polycarbonate glycol, and molecular weight is in 1000-2000.
As optimal technical scheme, the molar ratio of the polycarbonate polyol and polyether polyol is 3-5：1.
As optimal technical scheme, the total moles ratio of the polycarbonate polyol and polyether polyol rubs with isocyanates
You are than being 1：(1.2-2.3).
As optimal technical scheme, the isocyanates be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or
Isophorone diisocyanate.
As optimal technical scheme, the solvent is toluene, dimethylbenzene or acetone.
Preferably, the chain extender is 1,4-butanediol, diethylene glycol (DEG), 1,6- hexylene glycols, trimethylolpropane, castor
Sesame oil etc..
As optimal technical scheme, the photoinitiator be 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxides or 2,
4,6- trimethylbenzoyl phosphinic acid ethyl esters.
As optimal technical scheme, the polymerization inhibitor is hydroquinone or 1,4-benzoquinone.
As optimal technical scheme, the gross mass of the caprolactam, sodium hydrogensulfite and methyl ethyl ketone oxime accounts for bonding
The weight ratio of the 3-10wt% of agent solid constituent, caprolactam, sodium hydrogensulfite and methyl ethyl ketone oxime are 1：(2-3)：1.
As optimal technical scheme, the hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, phenyl glycidyl ether
Acrylate and hexamethylene dimethoxy diacrylate ratio are 1:(0.8-1.5)：The mixing of (0.2-0.5) (molar ratio)
Object, above-mentioned monomer gross mass account for the 10-25% of adhesive solids ingredient, can further preferred 11%, 13%, 15%, 17%,
19%, 21%, 23%.
A kind of high-strength light, heat activated blocked polyurethane adhesive preparation method to obtain high-strength light, heat activated blocked polyurethane viscous
Mixture.
The application method of a kind of high-strength light, heat activated blocked polyurethane adhesive, one surface of adherend is coated on by adhesive,
By the compacting of adherend two on one surface of adherend that adhesive is coated, it is clamped and connected portion using clip, ultraviolet light 3-
10min, and then it is placed in 60-80 DEG C of solidification 1-3h of temperature, you can.
At least one material that can pass through for ultraviolet lights is made in the adherend one and adherend two.As preferably being glued
Object one and adherend two are glass or high-temperature resistance plastice, and high-temperature resistance plastice is preferably PMMA, PC, PS, PPS etc..
Specific implementation mode
In order to make technical staff and the public be more fully understood from technical scheme of the present invention, below to the mechanism of reaction and
Way of example is described.
The present invention prepares the dual solid cured polyurethane binder of high-strength light, heat by the method for fractional steps, separately below to two
Focus technology point in a step is introduced.
Hold NCO polyurethane prepolymers
It is by the polycarbonate polyol after drying, polyether polyol and isocyanates to hold the preparation of NCO polyurethane prepolymers
It stirs evenly, reacts 1-5h at 70-100 DEG C, be cooled to 60-80 DEG C, chain extender reaction 0.5-2h is added, it is dilute that solvent is added
It releases, obtains the moisturecuring prepolymer of NCO content about 5-10%, relative to from the point of view of the present inventor other patents, endgroup content
Low, mainly due to not needing moisture curable, end group significantly reduces, but the present invention is not excluded for containing NCO in final products
Group makes it have moisture cure characteristics.
Polycarbonate polyol and polyether polyol are used cooperatively, and polyether polyol has preferable flexibility, poly- carbonic acid
There is ester polyol preferable rigidity, the two to be coordinated by suitable molar ratio, and obtained adhesive has preferable intensity, compared with
Good flexibility ensure that the stickiness and adhesiveness of adhesive.
Due to invention adhesives use when be bonded high intensity material, after solidification will have larger mechanical strength and
Adhesive strength, wherein the molar ratio of the polycarbonate polyol and polyether polyol is 3-5:1, polycarbonate polyol accounts for master
Body, use ensure that mechanical strength, if not in the range, after polyether polyol amount increases, adhesive strength is promoted,
But mechanical strength significantly declines；If without using polyether polyol or usage amount it is too small, mechanical strength increase but due to
The affinity of base material is too low, and adhesive strength reduces, and is easily broken in connector when transverse shifting or bending occurs.
The polyether polyol is polyether-tribasic alcohol, and molecular weight is in 1000-5000, and molecular weight preferred 2500-3500 is described
Polycarbonate polyol is polycarbonate glycol, and molecular weight is in 1000-2000.Above-mentioned selection molecular weight should not be too large, molecule
Measure excessive, hydroxyl value is relatively low, and later stage crosslinking degree is low, and mechanical strength reduces, if molecular weight is too small, crosslinking degree is excessive, bonding
Intensity has the tendency that reduction.
Polyalcohol selects：Polycarbonate polyol is polycarbonate glycol (PCDL), and Asahi Chemical Industry's trade mark may be selected
For L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas (55 DEG C)；L5651,
Molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity 1200-2400mPas (55 DEG C)；Polyether polyol is poly-
Ether trihydroxylic alcohol, can select N330, molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, and viscosity 500 ±
75mPas。
Isocyanates does not limit explicitly, can be common any isocyanates, preferably, the isocyanide
Acid esters is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or isophorone diisocyanate, further preferably first
Phenylene diisocyanate or methyl diphenylene diisocyanate or mixture with isophorone diisocyanate, it is further preferably
For the compounding of aromatic isocyanates and non-aromatic isocyanates, balance strength and flexibility.
In the reaction of polyalcohol and isocyanates, the total moles ratio of the polycarbonate polyol and polyether polyol with
Isocyanates molar ratio is 1：(1.2-2.3), the end NCO polyurethane prepolymers that the NCO content being intended to is about 5-10%,
The NCO content can ensure carry out with the ultraviolet curing group containing active hydrogen and end-capping reagent used in next step below anti-
It answers.
The introducing of ultraviolet curing group
It is that there are a large amount of terminal isocyanate groups in above-mentioned end NCO polyurethane prepolymers, it can be by containing hydroxyl
Acrylate or sealer are reacted with isocyanates.
Hydroxy acryl acid ester monomer and photoinitiator, polymerization inhibitor are sequentially added in prepolymer, is stirred evenly, and according to viscous
Degree needs to be added solvent to get product.
It is related to monomer selection, hydroxy-ethyl acrylate is as main monomer, as most common basic type hydroxy acryl acid
Ester, excellent combination property；Phenyl glycidyl ether acrylate contains phenyl, can provide intensity, meanwhile, hydroxyl can be with ring
Oxygroup slow reaction, solidification improve later stage crosslinking degree；Due to moisturecuring early period and containing benezene acrylate cures, not
It is disconnected to improve intensity, but adhesion strength decline is more apparent；The pungent hexane dimethoxy diacrylate of ring is as Adhesion enhancement type
SR406 may be used in monomer, and with quick solidifying, strong adhesive force, anti-light solution, high temperature resistant is strong to the adhesive ability of plastics, resistance to
Chemical attack, the selection of the monomer is making up above-mentioned difference.
As optimal technical scheme, the hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, phenyl glycidyl ether
Acrylate and hexamethylene dimethoxy diacrylate ratio are 1:(0.8-1.5)：The mixing of (0.2-0.5) (molar ratio)
Object.Due to the present invention targetedly use aspect be high-strength material bonding, therefore phenyl glycidyl ether acrylate makes
Dosage is larger, can increase substantially the self-strength of adhesive, if usage amount is too small, intensity enhancing is insufficient；But due to
The above-mentioned influence to adhesion property, the invention have selected hexamethylene dimethoxy diacrylate, have compensated for
Above-mentioned deficiency, but also should not be too large, excessive then strength reduction, if be added without or addition is minimum, adhesive adhesiveness
It can decline.Its gross mass is to ensure final hydroxyl monomer and sealer can the reaction was complete all NCO, however not excluded that final production
Situation containing NCO group in product.
The addition of sealer
An important inventive point is that the selection of sealer in the present invention, and obtaining one kind by the selection of sealer can
To realize the adhesive of segmentation heat cure, it is divided into low-temperature zone, middle-temperature section and high temperature section sealer, wherein low-temperature zone sealer is
It is just cured reaction in primary solidification, ensures the intensity in adhesion process, the sealer of middle-temperature section and high temperature section is in high temperature
Lower deblocking is cured reaction, improves crosslinking degree, improves high temperature resistance.
Middle-end NCO polyurethane prepolymers of the present invention under the conditions of being protected from light, sequentially add in oneself after ultraviolet curing group is added
Amide, sodium hydrogensulfite and methyl ethyl ketone oxime, stir evenly, and need to be added solvent according to viscosity to get product.It is wherein low
Temperature section sealer is the dissociation temperature of sodium hydrogensulfite at 60 DEG C, and middle-temperature section sealer is that the dissociation temperature of methyl ethyl ketone oxime exists
125-130 DEG C, high temperature section sealer is caprolactam, and dissociation temperature is 160 DEG C.Above-mentioned three's sealer is at different temperatures
Deblocking, after realize the stage curing effect of the present invention.
The weight ratio of the caprolactam, sodium hydrogensulfite and methyl ethyl ketone oxime is 1：(2-3)：1, wherein bisulfite
The usage amount of sodium is maximum, ensure that preliminary basic bonding force, meanwhile, also ensure mechanical strength, subsequent methyl ethyl ketone
The mole of oxime and caprolactam gradually decreases.The gross mass of the caprolactam, sodium hydrogensulfite and methyl ethyl ketone oxime accounts for
The 3-10wt% of adhesive solids ingredient, dosage are selected according to using the intensity requirement of product.
Due to the dosage of the photo-curing monomer and end-capping reagent that are added in subsequent step, there is remaining NCO under partial picture,
But residual quantity is little, does not influence overall performance.Substantially the present invention at high temperature, also depends on the crosslinking of part water realization again.
Meanwhile in the present invention in embodiment light-cured components and stage curing embodiment and comparative example on the same day
It is documented in detail in other patents, it was demonstrated that effect is not repeating in the application.
Application method
The present invention provides a kind of specific application methods, select to obtain according to the basic performance of adhesive, specially：
Since the solidification of the adhesive needs one section of longer time, therefore adhesive is coated on one surface of adherend, by adherend two
On one surface of adherend that adhesive is coated, need to be clamped and connected portion using clip, ensure that it will not shift for compacting.
For photo curing condition, usage time is more conventional, ultraviolet light 3-10min, subsequent free radical polymerization crosslinking
It can be in subsequent heat curing middle completion.For heat cure condition, due to needing moisturecuring and ensureing preliminary heat cure (low-temperature zone
Sealer is the dissociation temperature of sodium hydrogensulfite at 60 DEG C), select 60-80 DEG C of solidification 1-3h of temperature.
Selection for adherend, it can be UV transmission material to glue object one and adherend two, as preferred adherend
One and adherend two be glass or high-temperature resistance plastice, high-temperature resistance plastice is preferably PMMA, PC, PS, PPS etc..
Beneficial technique effect
The structure design main body of the present invention is to introduce hydroxyl photo-curing monomer and sealing end by the prepolymer that NCO is blocked
Agent makes it have photocuring and stage curing adhesive, and the two cooperates, and rapid curing may be implemented in photocuring, blocks
The hot setting of segmentation may be implemented in solidification, improves high temperature resistance.
Middle-end NCO moisturecuring prepolymers of the present invention have selected the polycarbonate polyol of specific dosage and molecular weight, polyethers
Polyalcohol realizes mechanical strength and the balance of adhesive force；Ultraviolet curing group is introduced, the acrylic acid of special ratios has mainly been selected
Monomeric acrylic hydroxyl ethyl ester, phenyl glycidyl ether acrylate and cyclohexane dimethanol diacrylate, further balance
Mechanical strength and adhesive force；End-capping reagent is introduced, selects under the conditions of being protected from light, sequentially adds caprolactam, sodium hydrogensulfite and first
Base ethyl ketoxime realizes three sections of solidifications.The present invention further preferably provides the application method for coordinating above-mentioned composition simultaneously, makes it more
That has got well realizes said effect.
In order to make technical staff's more intuitive understanding technical scheme of the present invention, exemplary embodiments and comparison are selected below
Example is introduced, these embodiments do not constitute limiting the scope of the invention, any from now on without departing substantially from the basic structure of the present invention
The embodiment of think of is all in the scope of the present invention.
Specific embodiment and comparative example are as follows：
Embodiment 1
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 40g polycarbonate glycol L6001,30g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the mass content of prepolymer, similarly hereinafter).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 8g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 20g phenyl glycidyl ethers acrylate and 7g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
Sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light 3.5g caprolactams, 7g sodium hydrogensulfites and
3.5g methyl ethyl ketone oximes, stir evenly, and the polyurethane for according to viscosity needing that dimethylbenzene is added to get high intensity multi-curing
Adhesive.
Comparative example 1
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas) it is dried in vacuo respectively with methyl diphenylene diisocyanate；
62g polycarbonate glycol L6001 and 40g methyl diphenylene diisocyanates after drying are stirred evenly, are added
Catalyst dibutyltin dilaurylate 0.5g, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, and chain extender 1,4-butanediol 4g is added
1h is reacted, dimethylbenzene dilution is added, obtaining the moisturecuring prepolymer that NCO content is about 8%, (NCO content is to account for containing for prepolymer
Amount).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 8g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 20g phenyl glycidyl ethers acrylate and 7g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
Sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light 3.5g caprolactams, 7g sodium hydrogensulfites and
3.5g methyl ethyl ketone oximes, stir evenly, and the polyurethane for according to viscosity needing that dimethylbenzene is added to get high intensity multi-curing
Adhesive.
Comparative example 2
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 30g polycarbonate glycol L6001,43g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the content of prepolymer).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 8g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 20g phenyl glycidyl ethers acrylate and 7g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
Sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light 3.5g caprolactams, 7g sodium hydrogensulfites and
3.5g methyl ethyl ketone oximes, stir evenly, and the polyurethane for according to viscosity needing that dimethylbenzene is added to get high intensity multi-curing
Adhesive.
Comparative example 3
(1) moisturecuring prepolymer is by polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value
0.05mgKOH/g, viscosity 1100-2300mPas), polyether Glycols VORANOL3010 (molecular weight 3000) and diphenyl methane
Diisocyanate is dried in vacuo respectively；
By 40g polycarbonate glycol L6001,35g polyether Glycols VORANOL3010 and the 40g diphenylmethyls after drying
Alkane diisocyanate stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60
DEG C, chain extender 1,4-butanediol 4g is added and reacts 1h, dimethylbenzene dilution is added, obtains the moisturecuring pre-polymerization that NCO content is about 8%
Object (NCO content is the content for accounting for prepolymer).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 8g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 20g phenyl glycidyl ethers acrylate and 7g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
Sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light 3.5g caprolactams, 7g sodium hydrogensulfites and
3.5g methyl ethyl ketone oximes, stir evenly, and the polyurethane for according to viscosity needing that dimethylbenzene is added to get high intensity multi-curing
Adhesive.
Comparative example 4
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 40g polycarbonate glycol L6001,30g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the content of prepolymer).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 10g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 23g phenyl glycidyl ethers acrylate and the oxidation of photoinitiator 2,4,6 (trimethylbenzoyl) diphenyl
Phosphine 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
Sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light 3.5g caprolactams, 7g sodium hydrogensulfites and
3.5g methyl ethyl ketone oximes, stir evenly, and the polyurethane for according to viscosity needing that dimethylbenzene is added to get high intensity multi-curing
Adhesive.
Comparative example 5
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 40g polycarbonate glycol L6001,30g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the content of prepolymer).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 20g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 5g phenyl glycidyl ethers acrylate and 10g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
Sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light 3.5g caprolactams, 7g sodium hydrogensulfites and
3.5g methyl ethyl ketone oximes, stir evenly, and the polyurethane for according to viscosity needing that dimethylbenzene is added to get high intensity multi-curing
Adhesive.
Comparative example 6
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 40g polycarbonate glycol L6001,30g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the content of prepolymer).
(2) light-initiated group is added
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 8g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 20g phenyl glycidyl ethers acrylate and 7g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly, and need to add according to viscosity
Enter dimethylbenzene to get polyurethane binder of the damp and hot dual cure of high intensity.
Comparative example 7
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 40g polycarbonate glycol L6001,30g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the content of prepolymer).
(2) addition of ultraviolet curing group
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned moisturecuring prepolymer, and 8g third is sequentially added into prepolymer
Olefin(e) acid hydroxyl ethyl ester, 20g phenyl glycidyl ethers acrylate and 7g cyclohexane dimethanol diacrylates and photoinitiator 2,4,6
(trimethylbenzoyl) diphenyl phosphine oxide 0.5g, hydroquinone of polymerization retarder 0.3g, stir evenly.
(3) addition of end-capping reagent
14g sodium hydrogensulfites are sequentially added into above-mentioned moisturecuring prepolymer under the conditions of being protected from light, are stirred evenly, and according to
Viscosity needs polyurethane binder that dimethylbenzene is added to get high intensity multi-curing.
Comparative example 8
(1) moisturecuring prepolymer
By polycarbonate glycol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 ± 10, acid value 0.05mgKOH/g, viscosity
1100-2300mPas), polyether-tribasic alcohol N330 (molecular weight 3000 ± 200, hydroxyl value 56 ± 3, acid value≤0.1mgKOH/g, viscosity
500 ± 75mPas) and methyl diphenylene diisocyanate be dried in vacuo respectively；
By two isocyanide of 40g polycarbonate glycol L6001,30g polyether-tribasic alcohol N330 and 40g diphenyl methane after drying
Acid esters stirs evenly, and catalyst dibutyltin dilaurylate 0.5g is added, reacts 1-5h at 80 DEG C, is cooled to 60 DEG C, is added
Chain extender 1,4-butanediol 4g reacts 1h, and dimethylbenzene dilution is added, obtains the moisturecuring prepolymer (NCO that NCO content is about 8%
Content is to account for the content of prepolymer).
(2) addition of sealer
3.5g caprolactams, 7g sodium hydrogensulfites and 3.5g methyl ethyl ketones are sequentially added in above-mentioned moisturecuring prepolymer
Oxime stirs evenly, and the polyurethane binder for according to viscosity needing that dimethylbenzene is added to get the wet smooth dual cure of high intensity.
【Test method】
1. tensile shear strength
Testing standard is carried out with reference to GB/T13936-92, and sheet metal is replaced with PMMA testing pieces, with the embodiment of the present invention and
The adhesive of comparative example replaces vulcanized rubber, the same GB/T13936-92 of other conditions, and records the failure mode of the plane of fracture.
Sample curing 1：Adhesive is coated on PMMA testing pieces, by another PMMA testing pieces compacting be coated it is viscous
The PMMA testing pieces surface of mixture is clamped and connected portion using clip, and ultraviolet illumination 10min is placed at 50,65 DEG C of humidity, Gu
Change 2h, you can tested according to the method described above, obtain cryogenic tensile shear strength and record rupture event.
Sample curing 2：Adhesive is coated on PMMA testing pieces, adhesive is being coated in the compacting of adherend two
PMMA testing pieces surface is clamped and connected portion using clip, and ultraviolet illumination 10min is placed at 50,65 DEG C of humidity, cures 2h, into
And it is again placed in humidity 50, cure 30 minutes at 160 DEG C, you can tested according to the method described above, obtain drawing by high temperature shearing
Intensity.
2. 3 plastics bend tests
3 points of test testing standards are carried out with reference to GB/T9341-2000, and testing piece is prepared via a method which：By adhesive
It is coated on release film, other side covering release film obtains thick 4mm, wide 10mm, the sample of long 80mm using above-mentioned curing
Product.Record bending modulus (MPa) and bending strength (MPa).
【Test result】
Remarks：Comparative example 8 early period of slow curing, intensity rise very slow.
Demonstrate the content of specification by above-mentioned experimental data, the ratio of polycarbonate polyol and polyether polyol,
The type of photo-curing monomer selects and the selection of sealer type can all have a major impact the performance of final products, if not
Within the technical scope of the present invention, it is difficult to equilibrium shear intensity, modulus, intensity and solidification rate, it is difficult to adapt to high intensity, fast
The cured demand of speed.
Claims (10)
1. the preparation method of a kind of high-strength light, heat activated blocked polyurethane adhesive, it is characterised in that：Include the following steps：
（1）Hold NCO polyurethane prepolymers：
Polycarbonate polyol, polyether polyol and isocyanates are dried in vacuo respectively, for use；
Polycarbonate polyol, polyether polyol and isocyanates after drying is stirred evenly, catalyst is added, in 70-100
1-5h is reacted at DEG C, is cooled to 60-80 DEG C, chain extender reaction 0.5-2h is added, and solvent dilution is added, obtaining NCO content is about
The end NCO polyurethane prepolymers of 5-10%；
（2）Light-cured components are added：
50 DEG C are cooled to hereinafter, under the conditions of being protected from light in above-mentioned prepolymer, and hydroxy acryl acid ester is sequentially added into prepolymer
Monomer and photoinitiator, polymerization inhibitor, stir evenly；
（3）The addition of sealer：
Under the conditions of being protected from light, to step（2）Caprolactam, sodium hydrogensulfite and methyl are sequentially added in uniformly mixed mixture
Ethyl ketoxime stirs evenly, and needs to be added solvent according to viscosity to get product.
2. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
It is polyether-tribasic alcohol to state polyether polyol, and for molecular weight in 1000-5000, the polycarbonate polyol is makrolon binary
Alcohol, molecular weight is in 1000-2000.
3. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
The molar ratio for stating polycarbonate polyol and polyether polyol is 3-5：1.
4. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
The total moles ratio and isocyanates molar ratio for stating polycarbonate polyol and polyether polyol are 1：（1.2-2.3）.
5. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
It is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or isophorone diisocyanate to state isocyanates.
6. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
It is toluene, dimethylbenzene or acetone to state solvent.
7. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
The gross mass for stating caprolactam, sodium hydrogensulfite and methyl ethyl ketone oxime accounts for the 3-10wt% of adhesive solids ingredient, acyl in oneself
The weight ratio of amine, sodium hydrogensulfite and methyl ethyl ketone oxime is 1：（2-3）：1.
8. the preparation method of high-strength light according to claim 1, heat activated blocked polyurethane adhesive, it is characterised in that：Institute
It is hydroxy-ethyl acrylate, phenyl glycidyl ether acrylate and hexamethylene dimethoxy dipropyl to state hydroxy acryl acid ester monomer
Olefin(e) acid ester ratio is 1:（0.8-1.5）：（0.2-0.5）（Molar ratio）Mixture, above-mentioned monomer gross mass accounts for adhesive solids
The 10-25% of ingredient.
9. the preparation method of high-strength light, heat activated blocked polyurethane adhesive described in claim 1-8 obtains high-strength light, heat cure
Polyurethane binder.
10. the application method of high-strength light described in claim 9, heat activated blocked polyurethane adhesive, it is characterised in that：By adhesive
It is coated on one surface of adherend, by the compacting of adherend two on one surface of adherend that adhesive is coated, is clamped and is connected using clip
Socket part, ultraviolet light 3-10min, and then it is placed in 60-80 DEG C of solidification 1-3h of temperature, you can.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN113234199A (en) * | 2021-06-10 | 2021-08-10 | 淄博华天橡塑科技有限公司 | High-toughness 3D printing photosensitive resin composition and 3D printing method |
| CN114716964A (en) * | 2021-12-30 | 2022-07-08 | 无锡市万力粘合材料股份有限公司 | UV curing glue for bonding solar backboard material and preparation method thereof |
| CN116651715A (en) * | 2023-05-12 | 2023-08-29 | 佛山市奥川顺新材料实业有限公司 | Polyurethane adhesive coating film forming process |
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