CN117736684B - Nano composite functional hot melt adhesive and manufacturing process thereof - Google Patents
Nano composite functional hot melt adhesive and manufacturing process thereof Download PDFInfo
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- CN117736684B CN117736684B CN202311739324.2A CN202311739324A CN117736684B CN 117736684 B CN117736684 B CN 117736684B CN 202311739324 A CN202311739324 A CN 202311739324A CN 117736684 B CN117736684 B CN 117736684B
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 89
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 54
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 42
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 33
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012964 benzotriazole Substances 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 19
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 16
- 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 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 16
- 229920001610 polycaprolactone Polymers 0.000 claims description 16
- 239000004632 polycaprolactone Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 11
- 230000004224 protection Effects 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 claims description 4
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 33
- 229920002635 polyurethane Polymers 0.000 abstract description 33
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000006750 UV protection Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000007654 immersion Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives and discloses a nano composite functional hot melt adhesive and a manufacturing process thereof, wherein the hot melt adhesive comprises polyester polyol, hexamethylene diisocyanate, tackifying resin, modified nitrile rubber, a chain extender, a catalyst A, an antioxidant and benzotriazole modified nano hydroxyapatite, and the high temperature resistance of the polyurethane hot melt adhesive is effectively improved by preparing the modified nitrile rubber crosslinked into a reticular structure, so that the reduction of the bonding strength of the hot melt adhesive under the high temperature condition is avoided; the nano hydroxyapatite is grafted and modified by the benzotriazole, so that the ultraviolet resistance of the polyurethane hot melt adhesive is effectively improved, the ageing speed of the hot melt adhesive is further slowed down, and the adhesive is applied to the adhesion of automobile parts, so that the adhesion failure of the automobile parts is not easy to cause, and the service life of an automobile is prolonged.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a nano composite functional hot melt adhesive and a manufacturing process thereof.
Background
In recent years, along with the continuous acceleration of the industrialization process in China, the hot melt adhesive is favored for having the advantages of environmental protection, stable chemical property, high curing speed, simple production process and the like, and mainly comprises polyolefin hot melt adhesive, ethylene and copolymer hot melt adhesive thereof, polyester hot melt adhesive, polyamide hot melt adhesive, polyurethane hot melt adhesive and the like, wherein the polyurethane hot melt adhesive is prepared from single-component and solvent-free isocyanate-terminated prepolymer and corresponding auxiliary agents, can be quickly cured, has good initial adhesion, is widely applied to the fields of electronic device assembly, automobile part adhesion, product packaging and the like, and is prepared by adopting crystalline polyester polyol, phthalic anhydride polyester polyol, propylene oxide polyether polyol, hydroxyl-terminated polybutadiene and diisocyanate to react and synthesize the prepolymer, then adding diacrylate-based monomers and other auxiliary agents under the light-shielding condition and stirring uniformly, and the prepared polyurethane hot melt adhesive has the characteristics of low viscosity and high initial strength, can be widely applied to the fields of electronic device assembly, automobile part adhesion, product packaging and the like, and the application number of the invention is 201611012018.9.
However, when the polyurethane hot melt adhesive is applied to the bonding field of automobile parts, the automobile can be exposed to sunlight in the using process, ultraviolet rays are strong, and the capability of the polyurethane hot melt adhesive for resisting ultraviolet rays is poor, so that the hot melt adhesive can be aged, bonding failure of the automobile parts is caused, the service life of the automobile is shortened, in addition, the automobile runs in the running process, the temperature of the automobile body is high, the bonding strength of the polyurethane hot melt adhesive can be reduced due to poor high temperature resistance, the automobile parts are easy to fall off, and the performance of the automobile is influenced, so that the development of the polyurethane hot melt adhesive which can resist ultraviolet rays and has the high temperature resistance is of great significance to the development of adhesives.
Disclosure of Invention
The invention aims to provide a nano composite functional hot melt adhesive and a manufacturing process thereof, which solve the problems of poor ultraviolet resistance and poor high temperature resistance of polyurethane hot melt adhesives.
The aim of the invention can be achieved by the following technical scheme:
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 50-70 parts of polyester polyol, 20-30 parts of hexamethylene diisocyanate, 10-20 parts of tackifying resin, 6-8 parts of modified nitrile rubber, 3-5 parts of chain extender, 0.5-1 part of catalyst A, 1-2 parts of antioxidant and 4-6 parts of benzotriazole modified nano-hydroxyapatite.
Further preferably, the polyester polyol has a molecular weight of 2000 to 4000; the polyester polyol is any one of polycarbonate diol or polycaprolactone diol; the tackifying resin is any one of petroleum resin, rosin resin or terpene resin; the chain extender is any one of ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol; the catalyst A is any one of dibutyl tin dilaurate, stannous octoate, triethylenediamine or dimorpholinodiethyl ether; the antioxidant is any one of an antioxidant 168 or an antioxidant 1076.
Further preferably, the preparation method of the modified nitrile rubber specifically comprises the following steps:
Adding carboxyl-terminated nitrile rubber and dimethylbenzene into a reaction bottle with a thermometer, uniformly stirring, raising the temperature to 90-100 ℃, adding tri (4-hydroxyphenyl) methane triglycidyl ether and tetrabutylammonium bromide, carrying out heat preservation reaction for 2-3h, and carrying out reduced pressure distillation to remove the solvent after the reaction is completed, thus obtaining the modified nitrile rubber.
Further preferably, the average molecular weight of the carboxyl terminated nitrile rubber is 2000.
Through the catalysis of tetrabutylammonium bromide, carboxyl groups at two ends of a molecular chain of the carboxyl-terminated nitrile rubber can carry out ring opening esterification reaction with epoxy groups in a tri (4-hydroxyphenyl) methane triglycidyl ether structure, active hydroxyl is introduced, and the carboxyl groups are crosslinked to form a network structure, so that the modified nitrile rubber is obtained.
Further preferably, the preparation method of the benzotriazole modified nano hydroxyapatite comprises the following steps:
S1: adding nano hydroxyapatite and toluene into a reaction bottle with a thermometer, raising the temperature to 90-100 ℃, adding thioglycollic acid and p-toluenesulfonic acid, uniformly stirring, carrying out heat preservation reaction for 6-8h, and filtering, washing and vacuum drying after the reaction is finished to obtain modified nano hydroxyapatite;
S2: adding modified nano hydroxyapatite and ethanol into a reaction bottle, uniformly stirring, adding 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole and a catalyst B, reacting for 16-20H at room temperature, filtering, washing and drying in vacuum after the reaction is finished, thus obtaining the benzotriazole modified nano hydroxyapatite.
Further preferably, in step S1, the average particle size of the nano hydroxyapatite is 60nm.
Further preferably, in step S2, the catalyst B is triethylamine.
Through the catalysis of paratoluenesulfonic acid, hydroxyl in nano hydroxyapatite can perform esterification reaction with carboxyl in thioglycollic acid, so that sulfydryl is introduced into the structure of nano hydroxyapatite to obtain modified nano hydroxyapatite, and under the action of triethylamine, sulfydryl in the structure can perform click reaction with alkenyl in the 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole structure to obtain benzotriazole modified nano hydroxyapatite.
A manufacturing process of nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polyester polyol, tackifying resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 2-3h at 110-120 ℃;
step two: cooling to 60-70 ℃, adding hexamethylene diisocyanate, raising the temperature to 80-90 ℃ under the protection of nitrogen, and stirring for reaction for 1-2h;
step three: adding a chain extender into the system to continue the reaction for 0.5-1h;
step four: then adding the catalyst A, the antioxidant and the benzotriazole modified nano hydroxyapatite, stirring and reacting for 1.5-2 hours under the vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
The invention has the beneficial effects that:
(1) According to the invention, the modified nitrile rubber which is crosslinked into the network structure is prepared and added into the preparation process of the polyurethane hot melt adhesive, the nitrile rubber can improve the oil resistance of the polyurethane hot melt adhesive, so that the pollution of oil stains in a vehicle to automobile parts is avoided, the adhesive effect of the polyurethane hot melt adhesive is influenced, the network structure of the modified nitrile rubber can effectively improve the high temperature resistance of the hot melt adhesive, and the generated active hydroxyl can interact with isocyanate groups in the preparation process of the polyurethane hot melt adhesive, so that the high temperature resistance of the hot melt adhesive is further improved, the reduction of the adhesive strength of the hot melt adhesive under the high temperature condition is avoided, the automobile parts are not easy to fall off, and the influence on the performance of an automobile is avoided.
(2) According to the invention, the benzotriazole modified nano-hydroxyapatite is added in the preparation process of the polyurethane hot melt adhesive, so that the mechanical property of the polyurethane hot melt adhesive can be improved, the ultraviolet resistance of the polyurethane hot melt adhesive can be effectively improved after the nano-hydroxyapatite is subjected to grafting modification, the ageing speed of the hot melt adhesive is slowed down, the adhesion failure of automobile parts is not easy to cause, and the service life of an automobile is prolonged.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of the modified nitrile rubber of example 1 of the present invention;
FIG. 2 is a thermogravimetric plot of nano-hydroxyapatite, modified nano-hydroxyapatite and benzotriazole modified nano-hydroxyapatite according to example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of modified nitrile rubber
In a reaction flask equipped with a thermometer, 8.5g of carboxyl terminated nitrile rubber with an average molecular weight of 2000 and 100mL of xylene are added, stirred uniformly, the temperature is raised to 100 ℃, 1.3g of tri (4-hydroxyphenyl) methane triglycidyl ether and 0.8g of tetrabutylammonium bromide are added, the reaction is carried out for 3 hours under heat preservation, and after the reaction is completed, the solvent is distilled off under reduced pressure, so that the modified nitrile rubber is obtained.
The infrared characterization of carboxylated nitrile rubber and modified nitrile rubber resulted in the disappearance of the absorption peak of c=o in the carboxyl group at 1713cm -1 and the absorption peak of C-O-C at 1232cm -1 compared to carboxylated nitrile rubber, as shown in fig. 1, with the absorption peak of hydroxyl group at 3325cm -1, the absorption peak of C-H in the benzene ring at 3027cm -1, the absorption peak of c=o in the ester group at 1741cm -1.
2. Preparation of benzotriazole modified nano hydroxyapatite
S1: adding 5g of nano hydroxyapatite with the average particle size of 60nm and 50mL of toluene into a reaction bottle with a thermometer, raising the temperature to 90 ℃, adding 6.4g of thioglycollic acid and 0.5g of p-toluenesulfonic acid, uniformly stirring, preserving heat, reacting for 8 hours, and filtering, washing and vacuum drying after the reaction is completed to obtain modified nano hydroxyapatite;
S2: adding 3.6g of modified nano hydroxyapatite and 50mL of ethanol into a reaction bottle, uniformly stirring, adding 5.8g of 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole and 1.2g of triethylamine, reacting for 18H at room temperature, filtering, washing and drying in vacuum after the reaction is finished, thus obtaining the benzotriazole modified nano hydroxyapatite.
Thermogravimetric analysis was performed on the nano-hydroxyapatite, the modified nano-hydroxyapatite and the benzotriazole modified nano-hydroxyapatite, and as shown in fig. 2, the final weight retention rate of the nano-hydroxyapatite was 95.2%, the final weight retention rate of the modified nano-hydroxyapatite was 87.3%, and the final weight retention rate of the benzotriazole modified nano-hydroxyapatite was 64.5%, indicating that benzotriazole was successfully modified to the nano-hydroxyapatite.
3. Preparation of nano composite functional hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 50 parts of polycaprolactone diol with molecular weight of 3000, 20 parts of hexamethylene diisocyanate, 10 parts of C 5 petroleum resin, 6 parts of modified nitrile rubber, 3 parts of ethylene glycol, 0.5 part of dibutyltin dilaurate, 1 part of antioxidant 1076 and 4 parts of benzotriazole modified nano hydroxyapatite.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000, C 5 petroleum resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 2 hours at the temperature of 110 ℃;
Step two: cooling to 60 ℃, adding hexamethylene diisocyanate, raising the temperature to 80 ℃ under the protection of nitrogen, and stirring for reaction for 1h;
step three: adding glycol into the system to continue the reaction for 0.5h;
Step four: and adding dibutyl tin dilaurate, an antioxidant 1076 and benzotriazole modified nano hydroxyapatite, stirring and reacting for 1.5 hours under vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
The modified nitrile rubber and benzotriazole modified nano-hydroxyapatite prepared in this example were applied to the following examples and comparative examples.
Example 2
Preparation of nano composite functional hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 60 parts of polycaprolactone diol with molecular weight of 3000, 25 parts of hexamethylene diisocyanate, 15 parts of C 5 petroleum resin, 7 parts of modified nitrile rubber, 4 parts of ethylene glycol, 0.8 part of dibutyltin dilaurate, 1.5 parts of antioxidant 1076 and 5 parts of benzotriazole modified nano hydroxyapatite.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000, C 5 petroleum resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 2.5h at 120 ℃;
Step two: cooling to 65 ℃, adding hexamethylene diisocyanate, raising the temperature to 85 ℃ under the protection of nitrogen, and stirring for reaction for 1.5h;
Step three: adding glycol into the system to continue the reaction for 1h;
step four: and adding dibutyl tin dilaurate, an antioxidant 1076 and benzotriazole modified nano hydroxyapatite, stirring and reacting for 2 hours under vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
Example 3
Preparation of nano composite functional hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 70 parts of polycaprolactone diol with molecular weight of 3000, 30 parts of hexamethylene diisocyanate, 20 parts of C 5 petroleum resin, 8 parts of modified nitrile rubber, 5 parts of ethylene glycol, 1 part of dibutyltin dilaurate, 2 parts of antioxidant 1076 and 6 parts of benzotriazole modified nano-hydroxyapatite.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000, C 5 petroleum resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 3 hours at the temperature of 120 ℃;
Step two: cooling to 70 ℃, adding hexamethylene diisocyanate, raising the temperature to 90 ℃ under the protection of nitrogen, and stirring for reaction for 2h;
Step three: adding glycol into the system to continue the reaction for 1h;
step four: and adding dibutyl tin dilaurate, an antioxidant 1076 and benzotriazole modified nano hydroxyapatite, stirring and reacting for 2 hours under vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
Comparative example 1
Preparation of polyurethane hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 70 parts of polycaprolactone diol with molecular weight of 3000, 30 parts of hexamethylene diisocyanate, 20 parts of C 5 petroleum resin, 5 parts of ethylene glycol, 1 part of dibutyltin dilaurate, 2 parts of antioxidant 1076 and 6 parts of benzotriazole modified nano-hydroxyapatite.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000 and C 5 petroleum resin into a reaction kettle, and vacuum dehydrating for 3h at 120 ℃;
Step two: cooling to 70 ℃, adding hexamethylene diisocyanate, raising the temperature to 90 ℃ under the protection of nitrogen, and stirring for reaction for 2h;
Step three: adding glycol into the system to continue the reaction for 1h;
step four: and adding dibutyl tin dilaurate, an antioxidant 1076 and benzotriazole modified nano hydroxyapatite, stirring and reacting for 2 hours under vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
Comparative example 2
Preparation of polyurethane hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 70 parts of polycaprolactone diol with molecular weight of 3000, 30 parts of hexamethylene diisocyanate, 20 parts of C 5 petroleum resin, 8 parts of modified nitrile rubber, 5 parts of ethylene glycol, 1 part of dibutyl tin dilaurate and 2 parts of antioxidant 1076.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000, C 5 petroleum resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 3 hours at the temperature of 120 ℃;
Step two: cooling to 70 ℃, adding hexamethylene diisocyanate, raising the temperature to 90 ℃ under the protection of nitrogen, and stirring for reaction for 2h;
Step three: adding glycol into the system to continue the reaction for 1h;
step four: and adding dibutyl tin dilaurate and an antioxidant 1076, stirring and reacting for 2 hours under vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
Comparative example 3
Preparation of polyurethane hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 70 parts of polycaprolactone diol with molecular weight of 3000, 30 parts of hexamethylene diisocyanate, 20 parts of C 5 petroleum resin, 8 parts of carboxyl terminated nitrile rubber, 5 parts of ethylene glycol, 1 part of dibutyltin dilaurate, 2 parts of antioxidant 1076 and 6 parts of benzotriazole modified nano-hydroxyapatite.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000, C 5 petroleum resin and carboxyl-terminated nitrile rubber into a reaction kettle, and vacuum dehydrating for 3 hours at the temperature of 120 ℃;
Step two: cooling to 70 ℃, adding hexamethylene diisocyanate, raising the temperature to 90 ℃ under the protection of nitrogen, and stirring for reaction for 2h;
Step three: adding glycol into the system to continue the reaction for 1h;
step four: and adding dibutyl tin dilaurate, an antioxidant 1076 and benzotriazole modified nano hydroxyapatite, stirring and reacting for 2 hours under vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
Comparative example 4
Preparation of polyurethane hot melt adhesive
A nano composite functional hot melt adhesive comprises the following raw materials in parts by weight: 70 parts of polycaprolactone diol with molecular weight of 3000, 30 parts of hexamethylene diisocyanate, 20 parts of C 5 petroleum resin, 8 parts of modified nitrile rubber, 5 parts of ethylene glycol, 1 part of dibutyltin dilaurate, 2 parts of antioxidant 1076 and 6 parts of nano hydroxyapatite.
The manufacturing process of the nano composite functional hot melt adhesive comprises the following steps:
Step one: putting polycaprolactone dihydric alcohol with molecular weight of 3000, C 5 petroleum resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 3 hours at the temperature of 120 ℃;
Step two: cooling to 70 ℃, adding hexamethylene diisocyanate, raising the temperature to 90 ℃ under the protection of nitrogen, and stirring for reaction for 2h;
Step three: adding glycol into the system to continue the reaction for 1h;
Step four: and adding dibutyl tin dilaurate, an antioxidant 1076 and nano hydroxyapatite, stirring under vacuum condition for reacting for 2 hours, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
Performance detection
The polyurethane hot melt adhesives prepared in examples 1 to 3 and comparative examples 1 to 4 were placed on glass panels, respectively, and 10 mm. Times.10 mm. Times.5 mm adhesive tapes were applied thereto, and cured for 48 hours, and the glass panels were removed to obtain test pieces.
I, referring to national standard GB/T2792-2014, test the peel strength of adhesive tape, and then, immersing the test sample in gasoline at constant temperature of 25 ℃ for 72 hours, taking out and testing the peel strength again, and calculating the peel strength reduction rate before and after oil immersion according to the formula [ (peel strength before oil immersion-peel strength after oil immersion)/peel strength before oil immersion multiplied by 100% ], wherein the smaller the peel strength reduction rate is, the better the oil resistance of the hot melt adhesive is shown, and the test results are shown in the following table:
As is clear from the above table, the samples prepared in examples 1 to 3 have a smaller decrease in peel strength, indicating that the polyurethane hot melt adhesives all have good oil resistance, the samples prepared in comparative examples 2,3 and 4 have a smaller decrease in peel strength, and the oil resistance of the prepared polyurethane hot melt adhesives is better due to the addition of the nitrile rubber, while the sample prepared in comparative example 1 has a larger decrease in peel strength, and the oil resistance is worse due to the fact that the nitrile rubber is not added during the preparation of the polyurethane hot melt adhesives.
II, referring to national standard GB/T7124-2008 "determination of adhesive tensile shear Strength", a tensile strength test is carried out on a sample, the sample is used for representing the mechanical properties of polyurethane hot melt adhesive, and the test results are shown in the following table:
As is apparent from the above table, the tensile strength of the samples prepared in examples 1 to 3 and comparative examples 1, 3 and 4 is higher as compared with example 2, and the tensile strength is lower because example 2 does not add nano-hydroxyapatite capable of improving the mechanical properties of the polyurethane hot melt adhesive to the preparation process of the hot melt adhesive.
III, carrying out thermal weightlessness analysis on the sample by using a thermogravimetric analyzer under the test conditions of nitrogen atmosphere, wherein the temperature rising range is 10-800 ℃, the temperature rising rate is 10 ℃/min, recording the temperature when the polyurethane hot melt adhesive loss is 5%, evaluating the high temperature resistance, and the test results are shown in the following table:
As can be seen from the above table, the temperature of the samples prepared in examples 1 to 3 was higher when the mass loss was 5%, which indicates that the high temperature resistance of the polyurethane hot melt adhesives was better, the temperature of the samples prepared in comparative examples 2 and 4 was also higher when the mass loss was 5%, and the high temperature resistance of the hot melt adhesives was better because the modified nitrile rubber having a network structure was added during the preparation of the polyurethane hot melt adhesives, while the temperature of the samples prepared in comparative examples 1 and 3 was relatively lower when the mass loss was 5%, which indicates that the high temperature resistance of the hot melt adhesives was poor.
IV, illuminating the sample for 48 hours under a 20W ultraviolet lamp, testing the yellow index of the sample before and after illumination by using a color difference meter, calculating the change value of the yellow index, and testing the result shown in the following table:
As can be seen from the above table, the samples prepared in examples 1 to 3 of the present invention have smaller yellow index change values, which indicates that the polyurethane hot melt adhesives have excellent anti-ultraviolet properties, the samples prepared in comparative examples 1 and 3 have relatively smaller yellow index change values, which indicates that the polyurethane hot melt adhesives have stronger anti-ultraviolet properties, and the samples prepared in comparative examples 2 and 4 have larger yellow index change values, so that the anti-ultraviolet properties are poor because the benzotriazole modified nano-hydroxyapatite is not added into the preparation process of the polyurethane hot melt adhesives.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (6)
1. The nano composite functional hot melt adhesive is characterized by comprising the following raw materials in parts by weight: 50-70 parts of polyester polyol, 20-30 parts of hexamethylene diisocyanate, 10-20 parts of tackifying resin, 6-8 parts of modified nitrile rubber, 3-5 parts of chain extender, 0.5-1 part of catalyst A, 1-2 parts of antioxidant and 4-6 parts of benzotriazole modified nano-hydroxyapatite;
the preparation method of the modified nitrile rubber specifically comprises the following steps:
adding carboxyl-terminated nitrile rubber and dimethylbenzene into a reaction bottle with a thermometer, uniformly stirring, raising the temperature to 90-100 ℃, adding tri (4-hydroxyphenyl) methane triglycidyl ether and tetrabutylammonium bromide, carrying out heat preservation reaction for 2-3h, and carrying out reduced pressure distillation to remove a solvent after the reaction is completed, thereby obtaining modified nitrile rubber;
the preparation method of the benzotriazole modified nano hydroxyapatite comprises the following steps:
S1: adding nano hydroxyapatite and toluene into a reaction bottle with a thermometer, raising the temperature to 90-100 ℃, adding thioglycollic acid and p-toluenesulfonic acid, uniformly stirring, carrying out heat preservation reaction for 6-8h, and filtering, washing and vacuum drying after the reaction is finished to obtain modified nano hydroxyapatite;
S2: adding modified nano hydroxyapatite and ethanol into a reaction bottle, uniformly stirring, adding 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole and a catalyst B, reacting for 16-20H at room temperature, filtering, washing and drying in vacuum after the reaction is finished, thus obtaining the benzotriazole modified nano hydroxyapatite.
2. The nanocomposite functional hot melt adhesive according to claim 1, wherein the polyester polyol has a molecular weight of 2000 to 4000; the polyester polyol is any one of polycarbonate diol or polycaprolactone diol; the tackifying resin is any one of petroleum resin, rosin resin or terpene resin; the chain extender is any one of ethylene glycol, 1, 3-propylene glycol or1, 4-butanediol; the catalyst A is any one of dibutyl tin dilaurate, stannous octoate, triethylenediamine or dimorpholinodiethyl ether; the antioxidant is any one of an antioxidant 168 or an antioxidant 1076.
3. The nanocomposite functional hot melt adhesive according to claim 1, wherein the carboxyl terminated nitrile rubber has an average molecular weight of 2000.
4. The nanocomposite functional hot melt adhesive according to claim 1, wherein in step S1, the average particle size of the nano-hydroxyapatite is 60nm.
5. The nanocomposite functional hot melt adhesive according to claim 1, wherein in step S2, the catalyst B is triethylamine.
6. A process for manufacturing a nanocomposite functional hot melt adhesive according to claim 1, comprising the steps of:
Step one: putting polyester polyol, tackifying resin and modified nitrile rubber into a reaction kettle, and vacuum dehydrating for 2-3h at 110-120 ℃;
step two: cooling to 60-70 ℃, adding hexamethylene diisocyanate, raising the temperature to 80-90 ℃ under the protection of nitrogen, and stirring for reaction for 1-2h;
step three: adding a chain extender into the system to continue the reaction for 0.5-1h;
step four: then adding the catalyst A, the antioxidant and the benzotriazole modified nano hydroxyapatite, stirring and reacting for 1.5-2 hours under the vacuum condition, stopping heating, and discharging to obtain the nano composite functional hot melt adhesive.
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