CN115895564A - Reaction type polyurethane hot melt adhesive for rapid deep curing car lamp and preparation method thereof - Google Patents
Reaction type polyurethane hot melt adhesive for rapid deep curing car lamp and preparation method thereof Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 239000004831 Hot glue Substances 0.000 title claims abstract description 37
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 238000006757 chemical reactions by type Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 12
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 150000003077 polyols Chemical class 0.000 claims abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- -1 polyoxypropylene Polymers 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- UPIKAIAOTXEAAZ-UHFFFAOYSA-N 2-(1,3-oxazolidin-3-yl)ethanol Chemical compound OCCN1CCOC1 UPIKAIAOTXEAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- DQSYGNJXYMAPMV-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 DQSYGNJXYMAPMV-UHFFFAOYSA-N 0.000 claims description 2
- WIBROAYAWBWRHP-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3-oxazolidin-3-yl)ethanol Chemical compound CC1(C)OCCN1CCO WIBROAYAWBWRHP-UHFFFAOYSA-N 0.000 claims description 2
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 2
- CYMHAQCMKNVHPA-UHFFFAOYSA-N 3-butyl-2-heptan-3-yl-1,3-oxazolidine Chemical compound CCCCC(CC)C1OCCN1CCCC CYMHAQCMKNVHPA-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 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 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
- 125000000160 oxazolidinyl group Chemical group 0.000 claims 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 20
- 238000004880 explosion Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000007306 turnover Effects 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000013008 moisture curing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JJZLTCPHJJAYRM-UHFFFAOYSA-N 2-(2-propan-2-yl-5h-1,3-oxazol-2-yl)ethanol Chemical compound OCCC1(C(C)C)OCC=N1 JJZLTCPHJJAYRM-UHFFFAOYSA-N 0.000 description 1
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a reactive polyurethane hot melt adhesive for rapid deep curing car lamps and a preparation method thereof, wherein the hot melt adhesive comprises 10-30 parts of crystalline polyester polyol, 15-40 parts of polyether polyol, 15-25 parts of thermoplastic resin, 5-20 parts of filler, 0.2-2 parts of carbon black, 10-28 parts of isocyanate, 1-5 parts of latent curing agent, 0.01-0.5 part of reactive catalyst, 0.5-2 parts of adhesion promoter and 1-2 parts of antioxidant. The reactive polyurethane hot melt adhesive for the fast curing car lamp is excellent in comprehensive performance, fast in deep curing speed, capable of being used from car lamp production to car lamp loading in 7 days after glue application, free of glue overflow or glue explosion, capable of greatly improving the car lamp turnover speed and improving the production efficiency, good in market prospect, simple in preparation process, easy to operate and easy to industrialize.
Description
Technical Field
The invention belongs to the technical field of high-molecular binders, and particularly relates to a reactive polyurethane hot melt adhesive for a rapid deep curing car lamp and a preparation method thereof.
Background
The reactive polyurethane hot melt adhesive (PUR) has the advantages of the traditional hot melt adhesive and the bi-component silicone adhesive, well solves the contradiction between quick positioning and high-strength bonding in the bonding of the car lamp, and enables the PUR to be quickly developed into the mainstream variety of the glue for bonding the car lamp. However, due to technical reasons, only a few enterprises in China can produce the PUR products for the car lamps at present, deep curing speed is low, the car lamps can be normally used only after being maintained for 14 days or even longer, and otherwise, the phenomena of glue overflow or glue explosion of the PUR in the lamp slot can occur in the transportation process or when the PUR is assembled on a car for high-temperature testing, so that the quality of the products is seriously influenced.
Disclosure of Invention
The invention aims to provide a reaction type polyurethane hot melt adhesive for a rapid deep curing car lamp, which has high deep curing speed, can avoid the phenomena of glue overflow or glue explosion of a lamp trough PUR, and greatly improves the production efficiency of a car lamp factory.
The invention also aims to provide a preparation method of the reaction type polyurethane hot melt adhesive for the automobile lamp with the rapid deep curing function.
The technical scheme adopted for realizing the aim of the invention is as follows:
the utility model provides a quick deep curing car light is with reaction type polyurethane hot melt adhesive, the hot melt adhesive includes the raw materials of following parts by weight: 10-30 parts of crystalline polyester polyol, 15-40 parts of polyether polyol, 15-25 parts of thermoplastic resin, 5-20 parts of filler, 0.2-2 parts of carbon black, 10-28 parts of isocyanate, 1-5 parts of latent curing agent, 0.01-0.5 part of reactive catalyst, 0.5-2 parts of adhesion promoter and 41-2 parts of antioxidant.
In some embodiments, the crystalline polyester polyol is formed by polycondensation of one or more of adipic acid, sebacic acid, terephthalic acid and dodecanedioic acid with one or more of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the hydroxyl value of the crystalline polyester polyol is between 10 and 112mgKOH/g, preferably between 18 and 60 mgKOH/g.
In some of these embodiments, the polyether polyol is a polyoxypropylene diol having a number average molecular weight of 2000.
In some of these embodiments, the thermoplastic resin is at least one of Thermoplastic Polyurethane (TPU), ethylene vinyl acetate copolymer, thermoplastic polyester, acrylic resin.
In some embodiments, the filler is at least one of white carbon black, silica powder and calcium carbonate.
In some of these embodiments, the isocyanate is one or more of 4,4' -diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate (MDI), MDI-50.
In some of the examples, the latent curing agent is a hydroxyl-containing oxazolidine, and specifically may be one or more of 3-hydroxyethyl-1, 3-oxazolidine, 3-butyl-2- (1-ethylpentyl) oxazolidine, 2- (1-methylethyl) -3-oxazolineethanol, and 2, 2-dimethyl-N-hydroxyethyl-1, 3-oxazolidine.
In some of the embodiments, the reactive catalyst is an amine reactive catalyst with hydroxyl, and specifically may be at least one of N, N ' -trimethyl-N ' -hydroxyethyl-diamino ethyl ether, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N-dimethylethanolamine, 2- (2-dimethylaminoethoxy) ethanol, and N, N ' -trimethylaminoethyl-ethanolamine.
In some embodiments, the adhesion promoter adopts a coupling agent with an isocyanate group or a mercapto group as a reactive group, and specifically may be one or more of 3-isocyanate propyl triethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane.
In some of these embodiments, the antioxidant is at least one of 2, 6-di-tert-butyl-p-methylphenol, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide.
The preparation method of the reactive polyurethane hot melt adhesive for the rapid deep curing car lamp comprises the following process steps:
1) Putting the crystallized polyester polyol, polyether polyol, thermoplastic resin, filler and carbon black into a reaction kettle, heating to 100-130 ℃, and carrying out vacuum dehydration for 60-180 minutes under stirring, wherein the vacuum degree is-0.095-0.05 MPa;
2) Charging isocyanate in N 2 Stirring and reacting for 60-120 minutes at 100-120 ℃ under protection;
3) Adding a latent curing agent and a reactive catalyst in the presence of N 2 Stirring and reacting for 20-60 minutes at 100-120 ℃ under protection;
4) Sequentially adding an adhesion promoter and an antioxidant to the mixture, adding N 2 Stirring and mixing for 20-40 minutes at 100-120 ℃ under protection;
5) Keeping the temperature at 100-120 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
According to the rapid deep curing reactive polyurethane hot melt adhesive (PUR) for the automobile lamp, a proper amount of thermoplastic resin is added, so that the condensation of the hot melt adhesive can be accelerated when the hot melt adhesive is cooled, and the initial adhesion of the hot melt adhesive is favorably improved. The method is characterized in that a proper amount of hydroxyl-containing oxazolidine is added to serve as a latent curing agent, the hydroxyl groups of the hydroxyl-containing oxazolidine are introduced to a polyurethane molecular chain of the PUR system through a chemical reaction with NCO, and when the PUR is subjected to a moisture curing reaction, the oxazolidine preferentially reacts with water to generate secondary amine and hydroxyl, so that the deep curing speed of the PUR is improved. Amine reaction type catalyst with hydroxyl is selected as catalyst, the hydroxyl is introduced to polyurethane molecular chain of PUR system through chemical reaction with NCO, the catalyst is not easy to volatilize, and the catalyst has higher catalytic efficiency because the catalyst is more fully contacted with the PUR system, both of which are beneficial to improving the curing speed of PUR. In addition, a coupling agent with active groups of isocyanate groups or mercapto groups is added as an adhesion promoter, the coupling agent with mercapto groups can react with NCO, the coupling agent with isocyanate groups can participate in a moisture curing reaction during the moisture curing reaction of the PUR, both the coupling agent and the PUR can be introduced into a crosslinking curing system, and meanwhile, the attached alkoxy groups form hydrogen bonds or react with the surface of the bonded base material, so that the adhesion of the PUR to the base material and the wet-heat aging resistance after bonding can be improved.
In conclusion, the reactive polyurethane hot melt adhesive for the fast curing car lamp is prepared by reasonably matching the components according to a certain proportion, has excellent comprehensive performance and high deep curing speed, can be used from car lamp production to car lamp loading in 7 days after glue application, does not cause glue overflow or glue explosion, can greatly improve the turnover speed of the car lamp, improves the production efficiency, and has good market prospect.
The reactive polyurethane hot melt adhesive disclosed by the invention is simple in preparation process, easy to operate and easy to industrialize.
Detailed Description
The technical solution of the present invention is described in detail below with reference to specific examples, but the scope of the present invention is not limited thereto. The embodiments described below are only a part of the embodiments of the present invention, and not all embodiments, and all other similar embodiments performed by those skilled in the art without inventive work are within the scope of the present invention.
The crystalline polyester polyol used in the present invention is obtained by reacting the following alcohol and acid: the acid is at least one of adipic acid, sebacic acid, terephthalic acid and dodecanedioic acid; the alcohol is at least one of ethylene glycol, 1, 4-butanediol, and 1, 6-hexanediol. In the following examples and comparative examples, crystalline polyester polyols were purchased from Corp Ltd
7300 series, specifically as follows:
Polyether polyol: the polypropylene oxide glycol (PPG 2000) is purchased from Jiangsu Mount Belgium chemical industry Co., ltd, mn =2000, and the hydroxyl value is 54-58 mgKOH/g.
Latent curing agent: 3-hydroxyethyl-1, 3-oxazolidine, 2-dimethyl-N-hydroxyethyl-1, 3-oxazolidine are available from Incorez, UK.
The catalyst is purchased from Hensman, USA, and is specifically as follows:
the reaction type catalyst N, N, N '-trimethyl-N' -hydroxyethyl-diamino ethyl ether has the trade name: JEFFCAT @ ZF-10;
the reaction type catalyst N- (3-dimethylaminopropyl) -N, N-diisopropanolamine has the trade name of: JEFFCAT @ DPA;
the common catalyst 2,2' -dimorpholinodiethylether has the trade name: JEFFCAT @ DMDEE;
other raw material components are all commercial products.
The examples of the invention and the comparative examples used the following raw materials:
table 1: the proportion of each component in each example is (in parts by weight)
The above examples 1 to 3 and comparative examples 1 to 4 were prepared by the following preparation methods, differing only in the raw materials and the amount of the raw materials:
1) Putting the crystallized polyester polyol, polyether polyol, thermoplastic resin, filler and carbon black into a reaction kettle, heating to 120 ℃, and carrying out vacuum dehydration for 120 minutes under stirring, wherein the vacuum degree is-0.095 MPa;
2) Charging of isocyanate in N 2 Stirring and reacting for 90 minutes at the temperature of 120 ℃ under protection;
3) Adding a latent curing agent and a reactive catalyst in the presence of N 2 Stirring and reacting for 40 minutes at the temperature of 120 ℃ under protection;
4) Sequentially adding adhesion promoter and antioxidant in the presence of N 2 Stirring and mixing for 30 minutes at the temperature of 120 ℃ under protection;
5) Keeping the temperature at 120 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
And (3) effect testing:
the reactive polyurethane hot melt adhesives prepared in examples 1-3 and comparative examples 1-4 were subjected to an effect test, wherein the adhesion and aging properties were tested according to the technical requirements for bonding exterior parts of vehicle lamps in the general GMW 16506-2015 standard; the deep curing speed test is as follows, the prepared PUR is respectively glued on different car lights with the same model, after being maintained for 7 days under the standard condition, the car lights are placed in a 90 ℃ oven to be baked for 48 hours, then the car lights are taken out, and whether the glue overflow or glue explosion phenomenon occurs near the gluing part of the car lights is observed.
The test results are shown in table 2.
Table 2 results of performance tests related to the reactive polyurethane hot melt adhesives for quick curing vehicle lamps of examples 1 to 3 and comparative examples 1 to 4.
As can be seen from the examples 1, 2 and 3 in the table 2, the reactive polyurethane hot melt adhesive for the fast curing car lamp prepared by the invention has better comprehensive performance, completely meets the technical requirements of bonding of the outer decoration of the car lamp in the GMW 16506-2015 standard, and after the constructed car lamp is maintained for 7 days and is baked at a high temperature of 90 ℃, the phenomenon of glue overflow or glue explosion does not occur, which indicates that the deep curing speed of the hot melt adhesive is higher. After the latent curing agent is removed in the comparative example 1 and the reactive catalyst is replaced by the common catalyst in the comparative example 2, the car lamp has the glue overflow phenomenon, and the latent curing agent and the reactive catalyst are removed at the same time, so that the car lamp has the glue explosion phenomenon, which is obviously caused by the fact that the deep curing speed of the hot melt adhesive is deteriorated; comparative example 4 has little effect on the deep-cure rate after removal of the adhesion promoter, but the aging properties are reduced to a different extent, especially the adhesion is reduced significantly after humid aging.
Therefore, the reactive polyurethane hot melt adhesive for the rapid deep curing car lamp prepared in the embodiments 1 to 3 of the invention has excellent comprehensive performance and high deep curing speed, can be used from car lamp production to car lamp loading in 7 days after glue application, does not cause glue overflow or glue explosion, can greatly improve the turnover speed of the car lamp, improves the production efficiency, and has good market prospect. Among them, the reactive polyurethane hot melt adhesive of example 3 is most excellent in overall properties.
Claims (11)
1. The utility model provides a quick deep curing car light is with reaction type polyurethane hot melt adhesive which characterized in that, includes the raw materials of following parts by weight:
10 to 30 parts of crystalline polyester polyol,
15-40 parts of polyether polyol,
15-25 parts of thermoplastic resin,
5-20 parts of a filler,
0.2 to 2 portions of carbon black,
10-28 parts of isocyanate,
1 to 5 parts of latent curing agent,
0.01 to 0.5 portion of reaction type catalyst,
0.5 to 2 parts of an adhesion promoter,
1-2 parts of antioxidant.
2. The reactive polyurethane hot melt adhesive for the fast deep curing car lamp according to claim 1, wherein the crystalline polyester polyol is formed by polycondensation of one or more of adipic acid, sebacic acid, terephthalic acid and dodecanedioic acid with one or more of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, and the hydroxyl value of the crystalline polyester polyol is 10-112mgKOH/g, preferably 18-60 mgKOH/g.
3. The rapid deep curing reactive polyurethane hot melt adhesive for automotive lamps according to claim 1, wherein the polyether polyol is a polyoxypropylene diol having a number average molecular weight of 2000.
4. The rapid deep curing reactive polyurethane hot melt adhesive for vehicle lamps according to claim 1, wherein the thermoplastic resin is at least one of thermoplastic polyurethane, ethylene vinyl acetate copolymer, thermoplastic polyester and acrylic resin.
5. The reactive polyurethane hot melt adhesive for rapid deep curing car lamps as claimed in claim 1, wherein the filler is at least one of white carbon black, silica micropowder and calcium carbonate.
6. The reactive polyurethane hot melt adhesive for rapid deep curing car lamps according to claim 1, wherein the isocyanate is one or more of 4,4' -diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and MDI-50.
7. The reactive polyurethane hot melt adhesive for rapid deep curing car lights according to claim 1, characterized in that the latent curing agent is oxazolidine containing hydroxyl group, which may be one or more of 3-hydroxyethyl-1, 3-oxazolidine, 3-butyl-2- (1-ethylpentyl) oxazolidine, 2- (1-methylethyl) -3-oxazoline ethanol, and 2, 2-dimethyl-N-hydroxyethyl-1, 3-oxazolidine.
8. The reactive polyurethane hot melt adhesive for fast deep curing car lights according to claim 1, wherein the reactive catalyst is amine reactive catalyst with hydroxyl, and specifically can be at least one of N, N, N ' -trimethyl-N ' -hydroxyethyl-diamino ethyl ether, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N, N-dimethylethanolamine, 2- (2-dimethylaminoethoxy) ethanol, and N, N, N ' -trimethylaminoethyl-monoethanolamine.
9. The reactive polyurethane hot melt adhesive for the rapid deep curing car lamp according to claim 1, wherein the adhesion promoter is a coupling agent with an active group of isocyanate group or mercapto group, and specifically can be one or more of 3-isocyanate propyl triethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane.
10. The reactive polyurethane hot melt adhesive for a rapid deep curing car lamp according to claim 1, wherein the antioxidant is at least one of 2, 6-di-t-butyl-p-methylphenol, pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-t-butylphenyl) phosphite, and bis (3, 5-di-t-butyl-4-hydroxyphenyl) sulfide.
11. A method for preparing the reactive polyurethane hot melt adhesive for the rapid deep curing car lamp according to any one of claims 1 to 10, which is characterized by comprising the following steps:
1) Putting the crystallized polyester polyol, polyether polyol, thermoplastic resin, filler and carbon black into a reaction kettle, heating to 100-130 ℃, and carrying out vacuum dehydration for 60-180 minutes under stirring, wherein the vacuum degree is-0.095-0.05 MPa;
2) Charging of isocyanate in N 2 Stirring and reacting for 60-120 minutes at the temperature of 100-120 ℃ under protection;
3) Adding a latent curing agent and a reactive catalyst in the presence of N 2 Stirring and reacting for 20-60 minutes at the temperature of 100-120 ℃ under protection;
4) Sequentially adding an adhesion promoter and an antioxidant to the mixture, adding N 2 Stirring and mixing for 20-40 minutes at the temperature of 100-120 ℃ under protection;
5) Keeping the temperature at 100-120 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020013406A1 (en) * | 2000-05-02 | 2002-01-31 | Yingjie Li | Moisture-curable polyurethane hot melt adhesives containing reactive amine catalysts |
| CN114045143A (en) * | 2021-11-23 | 2022-02-15 | 广州市白云化工实业有限公司 | High-transparency reactive polyurethane hot melt adhesive and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020013406A1 (en) * | 2000-05-02 | 2002-01-31 | Yingjie Li | Moisture-curable polyurethane hot melt adhesives containing reactive amine catalysts |
| CN114045143A (en) * | 2021-11-23 | 2022-02-15 | 广州市白云化工实业有限公司 | High-transparency reactive polyurethane hot melt adhesive and preparation method thereof |
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