CN118703158B - Hot melt adhesive with high bonding strength and application thereof in silica gel and nylon composite cloth - Google Patents
Hot melt adhesive with high bonding strength and application thereof in silica gel and nylon composite cloth Download PDFInfo
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- CN118703158B CN118703158B CN202410905713.6A CN202410905713A CN118703158B CN 118703158 B CN118703158 B CN 118703158B CN 202410905713 A CN202410905713 A CN 202410905713A CN 118703158 B CN118703158 B CN 118703158B
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000004677 Nylon Substances 0.000 title claims abstract description 28
- 229920001778 nylon Polymers 0.000 title claims abstract description 28
- 239000004744 fabric Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229910002027 silica gel Inorganic materials 0.000 title abstract description 19
- 239000000741 silica gel Substances 0.000 title abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 210
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 210
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 41
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 27
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 229920001709 polysilazane Polymers 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims description 86
- 150000003077 polyols Chemical class 0.000 claims description 86
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 71
- -1 bismuth carboxylate Chemical class 0.000 claims description 71
- 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 claims description 60
- 229910052797 bismuth Inorganic materials 0.000 claims description 60
- 150000003141 primary amines Chemical class 0.000 claims description 43
- 229920002545 silicone oil Polymers 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- 229910021485 fumed silica Inorganic materials 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 24
- 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 23
- 238000002156 mixing Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 20
- 229920001296 polysiloxane Polymers 0.000 claims description 20
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 19
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 18
- 150000002009 diols Chemical class 0.000 claims description 18
- 229920005906 polyester polyol Polymers 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- 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 13
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 12
- 239000004417 polycarbonate Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000004224 protection Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000000539 dimer Substances 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 239000002981 blocking agent Substances 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims 5
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000009849 vacuum degassing Methods 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 17
- 229920002635 polyurethane Polymers 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 11
- 230000006750 UV protection Effects 0.000 abstract description 7
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 38
- 230000001070 adhesive effect Effects 0.000 description 22
- 239000000853 adhesive Substances 0.000 description 21
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 20
- 230000000903 blocking effect Effects 0.000 description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 229920000909 polytetrahydrofuran Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- HZOTTWYEWUMPPM-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCCCCCC(O)=O HZOTTWYEWUMPPM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- 235000010676 Ocimum basilicum Nutrition 0.000 description 1
- 240000007926 Ocimum gratissimum Species 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the technical field of polyurethane hot melt adhesives, in particular to a hot melt adhesive with high bonding strength and application thereof in silica gel and nylon composite cloth. The hot melt adhesive with high bonding strength is mainly prepared from the following raw materials, by mass, 10-20 parts of high-activity-NCO blocked isocyanate prepolymer A, 10-20 parts of low-activity-NCO blocked isocyanate prepolymer B, 5-10 parts of primary amine blocked isocyanate prepolymer A, 5-10 parts of primary hydroxyl blocked isocyanate prepolymer B, 5-20 parts of thermoplastic EVA resin, 1-5 parts of organic polysilazane, 0.5-2 parts of cross-linking agent, 0.5-2 parts of coupling agent, 0.5-2 parts of antioxidant, 0.5-2 parts of ultraviolet resistance agent, 0.05-0.5 part of catalyst, 4-8 parts of gas phase silicon dioxide and 1-3 parts of defoaming agent. The application has excellent bonding strength and relatively good bonding strength and bonding stability to nylon PA base materials.
Description
Technical Field
The application relates to the technical field of polyurethane hot melt adhesives, in particular to a hot melt adhesive with high bonding strength and application thereof in silica gel and nylon composite cloth.
Background
The hot melt adhesive is solid at room temperature, and after being heated to a flowable molten state, the surface of an adherend is coated and rolled, the adherend is pressed with the adherend and air-cooled, and then the adherend and the adherend are stably glued and fixed by generating cohesive force through solidification of the hot melt adhesive. The polyurethane hot melt adhesive has the advantages of low pollution, high initial viscosity, quick viscosity and the like, and is widely applied to the modern automatic assembly industry.
Polyurethane hot melt adhesives are mainly classified into thermoplastic elastic TPU hot melt adhesives with low melting point and reactive polyurethane hot melt adhesives. The thermoplastic elastic TPU hot melt adhesive with low melting point is suitable for the adherend substrate with low temperature environment and low heat sensitivity. The reactive polyurethane hot melt adhesive has relatively good temperature resistance, can be suitable for heat-sensitive adherends, can further react with active groups introduced into a molecular chain structure to realize crosslinking and curing to form a thermosetting resin form of a three-dimensional network structure, can improve heat resistance and creep resistance while improving bonding strength, effectively expands the application range, can be suitable for nonmetallic substrates such as PC, ABS, TPU and the like, but has relatively weak bonding strength and bonding stability to nylon PA substrates, and limits the development and application of the reactive polyurethane hot melt adhesive in the field of nylon composite cloth materials. Therefore, the application provides a hot melt adhesive with high bonding strength and application thereof in silica gel and nylon composite cloth.
Disclosure of Invention
In order to solve the technical problems that the bonding strength and bonding stability of the traditional reactive polyurethane hot melt adhesive to nylon PA base materials are relatively weak and limit the development and application of the reactive polyurethane hot melt adhesive in the field of nylon composite cloth fabrics, the application independently develops the hot melt adhesive with high bonding strength, has relatively good bonding strength and bonding stability to the nylon PA base materials, can be used as a bonding agent to bond and fix and glue silica gel and nylon composite cloth, and is suitable for the high bonding strength requirement of the nylon Long Fuge cloth fabrics on the hot melt adhesive.
The hot melt adhesive with high bonding strength provided by the application is realized by the following technical scheme:
A hot melt adhesive with high bonding strength is mainly prepared from the following raw materials, by mass, 10-20 parts of high-activity-NCO blocked isocyanate prepolymer A, 10-20 parts of low-activity-NCO blocked isocyanate prepolymer B, 5-10 parts of primary amine blocked isocyanate prepolymer A, 5-10 parts of primary hydroxyl blocked isocyanate prepolymer B, 5-20 parts of thermoplastic EVA resin, 1-5 parts of organic polysilazane MY 9150, 0.5-2 parts of cross-linking agent, 0.5-2 parts of coupling agent, 0.5-2 parts of antioxidant, 0.5-2 parts of ultraviolet resistant agent, 0.05-0.5 parts of catalyst, 4-8 parts of fumed silica and 1-3 parts of defoamer, wherein the total molar amount of-NCO in the high-activity-NCO blocked isocyanate prepolymer A and the low-activity-NCO blocked isocyanate prepolymer B is 0.5-2 times the total molar amount of primary amine in the primary amine blocked isocyanate prepolymer A and the primary hydroxyl in the primary hydroxyl blocked isocyanate prepolymer B.
The high-activity-NCO-blocked isocyanate prepolymer A in the application firstly reacts with the primary amine-blocked isocyanate prepolymer A to form initial adhesion strength, the low-activity-NCO-blocked isocyanate prepolymer B and the primary hydroxyl-blocked isocyanate prepolymer B react subsequently, in the process that the high-activity-NCO-blocked isocyanate prepolymer A reacts with the primary amine-blocked isocyanate prepolymer A firstly, the low-activity-NCO-blocked isocyanate prepolymer B and the primary hydroxyl-blocked isocyanate prepolymer B can play a role of a plasticizer, the problem of environmental pollution caused by the addition of the plasticizer is overcome, meanwhile, the whole hot melt adhesive can effectively permeate the surface of a substrate to effectively improve the bonding strength and the bonding stability, the residual part of the high-activity-NCO-blocked isocyanate prepolymer A after the consumption of the subsequent primary amine-blocked isocyanate prepolymer A can react with the primary hydroxyl-blocked isocyanate prepolymer B preferentially, the method is beneficial to improving the overall permeability and improving the leveling property and the workability of the whole, the rest of the high-activity-NCO-blocked isocyanate prepolymer A and the rest of the low-activity-NCO-blocked isocyanate prepolymer B can be crosslinked with partial air moisture and/or ultraviolet light to form a three-dimensional network structure, so that excellent bonding strength and bonding stability are achieved, the organic polysilazane MY 9150 is hydrolyzed with the air moisture to generate amino or silanol groups, the rest of the high-activity-NCO-blocked isocyanate prepolymer A and the rest of the low-activity-NCO-blocked isocyanate prepolymer B can be chain-extended and crosslinked to realize solidification, the carbon dioxide gas release is reduced, the occurrence of glue line bubbles is reduced, the bubbling probability can further improve the overall bonding strength and bonding stability of the hot melt adhesive. In conclusion, the adhesive strength of the application is excellent, and the adhesive strength and the adhesive stability of the nylon PA substrate are relatively good.
Preferably, the high-activity-NCO blocked isocyanate prepolymer A comprises a polyol, bismuth carboxylate, DMF, an antioxidant 1010, m-xylylene diisocyanate and a blocking agent-diphenylmethane-4, 4' -diisocyanate, wherein the polyol consists of a high-crystallinity polyol and a dihydroxy blocked silicone oil in a mass ratio of (8-9) (1-2), the dihydroxy blocked silicone oil is at least one of hydroxy blocked methyl vinyl silicone oil, double-end hydroxypropyl silicone oil and double-end hydroxyl long-chain alkyl silicone oil, the high-crystallinity polyol is at least one of poly (1, 6-hexanediol) diol and poly (1, 6-hexanediol) diol with a molecular weight of 1000-4000 g/mol, and the blocking agent in the high-activity-NCO blocked isocyanate prepolymer A accounts for 5-20% of the high-activity-NCO blocked isocyanate prepolymer A.
Preferably, the low-activity-NCO blocked isocyanate prepolymer B comprises a polyol, bismuth carboxylate, DMF, an antioxidant 1010, m-xylylene diisocyanate and a blocking agent-isophorone diisocyanate, wherein the polyol consists of a low-crystallization polyol and a dihydroxyl blocked silicone oil in a mass ratio of (8-9) (1-2), the dihydroxyl blocked silicone oil is at least one of hydroxyl-blocked methyl vinyl silicone oil, double-end hydroxypropyl silicone oil and double-end alcohol hydroxyl long-chain alkyl silicone oil, the low-crystallization polyol is a low-crystallization linear polyester polyol PLOS-ZY1200 with a molecular weight 2200 or a low-crystallization dimer acid polyester polyol PLOS-ZY2250 with a molecular weight 2500, and the blocking agent in the low-activity-NCO blocked isocyanate prepolymer B accounts for 5-20% of the total amount of the low-activity-NCO blocked isocyanate prepolymer B.
Preferably, the primary amine blocked isocyanate prepolymer A is prepared from polyol, bismuth carboxylate, DMF, antioxidant 1010, diphenylmethane-4, 4' -diisocyanate and blocking agent-1, 6 hexamethylenediamine, wherein the polyol is prepared from high-crystallinity polyol, polyether glycol and polycarbonate glycol according to the mass ratio of (6-8) (1-2), the high-crystallinity polyol is at least one of poly (1, 6-hexanediol) diol and poly (1, 6-hexanediol) diol with the molecular weight of 1000-4000 g/mol, and the mass of primary amine in the primary amine blocked isocyanate prepolymer A accounts for 0.5-2% of the total amount of the primary amine blocked isocyanate prepolymer A.
Preferably, the primary hydroxyl-terminated isocyanate prepolymer B comprises polyol, bismuth carboxylate, DMF, antioxidant 1010, isophorone diisocyanate and a capping agent bisphenol A dihydroxyethyl ether, wherein the polyol is formed by matching low-crystallinity polyol with at least one of hydroxyl-terminated methyl vinyl silicone oil, polyether glycol and polycarbonate glycol, the low-crystallinity polyol is low-crystallinity linear polyester polyol PLOS-ZY1200 with molecular weight 2200 or low-crystallinity dimeric acid polyester polyol PLOS-ZY2250 with molecular weight 2500, and the mass of primary hydroxyl in the primary hydroxyl-terminated isocyanate prepolymer B accounts for 0.5-2% of the total amount of the primary hydroxyl-terminated isocyanate prepolymer B.
Preferably, the preparation method of the hot melt adhesive with high bonding strength comprises the following steps:
The preparation of high-activity-NCO blocked isocyanate prepolymer A, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and m-xylylene diisocyanate, heating to 65-70 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding blocking agent-diphenylmethane-4, 4' -diisocyanate, and reacting for 0.5-2 hours at 80-85 ℃ to obtain isocyanate prepolymer A with 5-20wt% of-NCO content;
The preparation of low-activity-NCO blocked isocyanate prepolymer B, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and m-xylylene diisocyanate, heating to 65-70 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding blocking agent-isophorone diisocyanate, and reacting for 0.5-2 hours at 90-95 ℃ to obtain isocyanate prepolymer B with 5-20wt% of-NCO content;
The preparation of primary amine blocked isocyanate prepolymer A, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and diphenylmethane-4, 4' -diisocyanate, heating to 65-70 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding blocking agent-1, 6 hexamethylenediamine, and reacting for 0.5-2 hours at 75-85 ℃ to obtain primary amine blocked isocyanate prepolymer A with primary amine group content of 0.5-2 wt%;
The preparation of a primary hydroxyl-terminated isocyanate prepolymer B, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and isophorone diisocyanate, heating to 75-80 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding a capping agent bisphenol A dihydroxyethyl ether, and reacting for 0.5-2 hours at 90-95 ℃ to obtain the primary hydroxyl-terminated isocyanate prepolymer B with the primary hydroxyl content of 0.5-2 wt%;
And step two, uniformly mixing the high-activity-NCO-blocked isocyanate prepolymer A, the low-activity-NCO-blocked isocyanate prepolymer B, the primary amine-blocked isocyanate prepolymer A and the primary hydroxyl-blocked isocyanate prepolymer B in the step one under the protection of nitrogen, adding 5-20 parts of thermoplastic EVA resin, 1-5 parts of organic polysilazane MY 9150, a cross-linking agent, a coupling agent, an antioxidant, an ultraviolet resistance agent, a catalyst, fumed silica and a defoaming agent, heating to 98-100 ℃, stirring for 30-45min under vacuum of-0.09-0.08 MPa, and cooling to normal temperature after vacuum defoaming is finished, and packaging by a black sealing bag.
The double-hydroxyl end-capped silicone oil introduced into the molecular chain segments of the high-activity-NCO end-capped isocyanate prepolymer A and the low-activity-NCO end-capped isocyanate prepolymer B has Si-O bond polarity similar to that of the Si-O bond in a silica gel structure, so that the high-activity-NCO end-capped isocyanate prepolymer A and the silica gel substrate have better interface compatibility, have certain initial adhesive strength with the silica gel interface, and can enable the formed hot melt adhesive layer to have better adhesive strength with the silica gel after the subsequent low-activity-NCO end-capped isocyanate prepolymer B is subjected to final crosslinking and curing, thereby being capable of meeting the adhesive composite use of the silica gel and nylon composite cloth.
The preparation method provided by the application is relatively simple, is convenient for realizing batch production, and reduces the overall production cost.
Preferably, the cross-linking agent is at least one of trimethylolpropane triacrylate, pentaerythritol triacrylate and tris (2-hydroxyethyl) isocyanurate triacrylate.
Preferably, the coupling agent is at least one of gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1098 and antioxidant BHT and is matched with antioxidant 168, and the ultraviolet resistance agent is at least one of UV-531, UV-326, UV-320 and UV-622.
Preferably, the catalyst is at least one of stannous octoate, bismuth carboxylate and dimorpholine diethyl ether, and the defoamer is at least one of BASF Basoff Efka 2720, efka 2723 and Yingchuang TEGO Airex 963.
The hot melt adhesive with high bonding strength is applied to the field of bonding of the silica gel and nylon composite cloth, and is particularly applied to the field of bonding of the nylon composite cloth surface material.
In summary, the application has the following advantages:
1. The adhesive has excellent adhesive strength and relatively good adhesive strength and adhesive stability to nylon PA base materials, is applied to the field of nylon composite cloth fabric cementing, and is used for cementing and fixing a silica gel surface layer and nylon composite cloth through hot melt adhesive with high adhesive strength.
2. The preparation method provided by the application is relatively simple, is convenient for realizing batch production, and reduces the overall production cost.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples.
Examples
A hot melt adhesive with high bonding strength is mainly prepared from the following raw materials, by mass, 10-20 parts of an-NCO blocked isocyanate prepolymer A, 10-20 parts of an-NCO blocked isocyanate prepolymer B, 5-10 parts of a primary amine blocked isocyanate prepolymer A, 5-10 parts of a primary hydroxyl blocked isocyanate prepolymer B, 5-20 parts of a thermoplastic EVA resin, 1-5 parts of an organic polysilazane MY 9150, 0.5-2 parts of a cross-linking agent, 0.5-2 parts of a coupling agent, 0.5-2 parts of an antioxidant, 0.5-2 parts of an ultraviolet resistant agent, 0.05-0.5 part of a catalyst, 4-8 parts of fumed silica and 1-3 parts of an antifoaming agent. The hot melt adhesive with high bonding strength prepared by the application is applied to the field of nylon composite cloth fabric cementing, and the silica gel surface layer and the nylon composite cloth are cemented and fixed through the hot melt adhesive with high bonding strength.
The cross-linking agent is at least one of trimethylolpropane triacrylate, pentaerythritol triacrylate and tri (2-hydroxyethyl) isocyanuric acid triacrylate.
The coupling agent is at least one of gamma-glycidol ether oxypropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane and 3-isocyanatopropyl triethoxy silane.
The antioxidant is at least one of antioxidant 1010, antioxidant 1098 and antioxidant BHT and is matched with antioxidant 168;
The ultraviolet resistance agent is at least one of UV-531, UV-326, UV-320 and UV-622.
The catalyst is at least one of stannous octoate, bismuth carboxylate and dimorpholine diethyl ether.
The defoamer is at least one of BASF Bafska 2720, efska 2723 and Yingchuang TEGO Airex 963.
The total molar quantity of-NCO in the-NCO blocked isocyanate prepolymer A and the-NCO blocked isocyanate prepolymer B is 0.5-2 times of the total molar quantity of primary amine in the primary amine blocked isocyanate prepolymer A and primary hydroxyl in the primary hydroxyl blocked isocyanate prepolymer B, and the reactive groups in the prepared high-bonding-strength hot melt adhesive are high-low-activity-NCO groups and active groups contained in a crosslinking agent.
The high-activity-NCO blocked isocyanate prepolymer A comprises polyol, bismuth carboxylate, DMF, antioxidant 1010, m-xylylene diisocyanate and a blocking agent-diphenylmethane-4, 4' -diisocyanate. The mass of the end-capping agent in the high-activity-NCO end-capped isocyanate prepolymer A accounts for 5-20% of that of the high-activity-NCO end-capped isocyanate prepolymer A.
The polyol consists of high-crystallinity polyol and dihydroxyl end-capped silicone oil in the mass ratio of (8-9) (1-2). The dihydroxyl end-capped silicone oil is at least one of hydroxyl end-capped methyl vinyl silicone oil, double-end hydroxypropyl silicone oil and double-end alcohol hydroxyl long-chain alkyl silicone oil. The high-crystallinity polyol is at least one of poly (1, 6-hexanediol adipate) glycol and poly (1, 6-hexanediol sebacate) glycol with the molecular weight of 1000-4000 g/mol.
The low-reactivity-NCO blocked isocyanate prepolymer B comprises polyol, bismuth carboxylate, DMF, antioxidant 1010, m-xylylene diisocyanate and a blocking agent-isophorone diisocyanate. The mass of the blocking agent in the low-reactivity-NCO blocked isocyanate prepolymer B accounts for 5-20% of the total amount of the low-reactivity-NCO blocked isocyanate prepolymer B.
The polyol consists of low-crystallization polyol and dihydroxy terminated silicone oil in the mass ratio of (8-9) (1-2).
The dihydroxyl end-capped silicone oil is at least one of hydroxyl end-capped methyl vinyl silicone oil, double-end hydroxypropyl silicone oil and double-end alcohol hydroxyl long-chain alkyl silicone oil. The low crystalline polyol is low crystalline linear polyester polyol PLOS-ZY1200 with molecular weight 2200 or low crystalline dimer acid polyester polyol PLOS-ZY2250 with molecular weight 2500. The mass of primary amine in the primary amine-terminated isocyanate prepolymer A is 0.5 to 2% of the total amount of the primary amine-terminated isocyanate prepolymer A.
The primary amine blocked isocyanate prepolymer A comprises polyalcohol, carboxylic acid bismuth, DMF, antioxidant 1010, diphenylmethane-4, 4' -diisocyanate and blocking agent-1, 6 hexamethylenediamine. The polyol is high-crystallinity polyol, polyether glycol and polycarbonate glycol, and the mass ratio of the polyol to the polycarbonate glycol is (6-8) (1-2). The high-crystallinity polyol is at least one of poly (1, 6-hexanediol adipate) glycol and poly (1, 6-hexanediol sebacate) glycol with the molecular weight of 1000-4000 g/mol.
The primary hydroxyl-terminated isocyanate prepolymer B is prepared from polyalcohol, bismuth carboxylate, DMF, antioxidant 1010, isophorone diisocyanate and a blocking agent bisphenol A dihydroxyethyl ether. The primary hydroxyl group mass in the primary hydroxyl group-blocked isocyanate prepolymer B is 0.5 to 2% of the total amount of the primary hydroxyl group-blocked isocyanate prepolymer B.
The polyol is at least one of low-crystallinity polyol, hydroxyl-terminated methyl vinyl silicone oil, polyether glycol and polycarbonate glycol. Preferably, the polyol is low-crystalline polyol, hydroxyl-terminated methyl vinyl silicone oil and polyether glycol, and the mass ratio of the polyol to the polyether glycol is (6-8) (0.5-1) (1-3).
The low crystalline polyol is low crystalline linear polyester polyol PLOS-ZY1200 with molecular weight 2200 or low crystalline dimer acid polyester polyol PLOS-ZY2250 with molecular weight 2500.
The preparation method of the hot melt adhesive with high bonding strength comprises the following steps:
The preparation of high-activity-NCO blocked isocyanate prepolymer A, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and m-xylylene diisocyanate, heating to 65-70 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding blocking agent-diphenylmethane-4, 4' -diisocyanate, and reacting for 0.5-2 hours at 80-85 ℃ to obtain isocyanate prepolymer A with 5-20wt% of-NCO content;
The preparation of low-activity-NCO blocked isocyanate prepolymer B, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and m-xylylene diisocyanate, heating to 65-70 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding blocking agent-isophorone diisocyanate, and reacting for 0.5-2 hours at 90-95 ℃ to obtain isocyanate prepolymer B with 5-20wt% of-NCO content;
The preparation of primary amine blocked isocyanate prepolymer A, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and diphenylmethane-4, 4' -diisocyanate, heating to 65-70 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding blocking agent-1, 6 hexamethylenediamine, and reacting for 0.5-2 hours at 75-85 ℃ to obtain primary amine blocked isocyanate prepolymer A with primary amine group content of 0.5-2 wt%;
The preparation of a primary hydroxyl-terminated isocyanate prepolymer B, namely, heating polyol to 100-110 ℃ and dehydrating for 1-4 hours under vacuum condition, uniformly mixing the obtained polyol with bismuth carboxylate, DMF, antioxidant 1010 and isophorone diisocyanate, heating to 75-80 ℃ and reacting until the system viscosity is 3000-12000 mPa.s/25 ℃, adding a capping agent bisphenol A dihydroxyethyl ether, and reacting for 0.5-2 hours at 90-95 ℃ to obtain the primary hydroxyl-terminated isocyanate prepolymer B with the primary hydroxyl content of 0.5-2 wt%;
And step two, uniformly mixing the high-activity-NCO-blocked isocyanate prepolymer A, the low-activity-NCO-blocked isocyanate prepolymer B, the primary amine-blocked isocyanate prepolymer A and the primary hydroxyl-blocked isocyanate prepolymer B in the step one under the protection of nitrogen, adding a cross-linking agent, a coupling agent, an antioxidant, an ultraviolet resistance agent, a catalyst, fumed silica and a defoaming agent, heating to 98-100 ℃, stirring for 30-45min under vacuum of-0.09-0.08 MPa, cooling to normal temperature after vacuum defoaming, and packaging by a black sealing bag to obtain the hot melt adhesive with high adhesive strength.
Example 1A high adhesive strength hot melt adhesive was prepared from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts by mass of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts by mass of a primary amine blocked isocyanate prepolymer A, 8 parts by mass of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts by mass of a thermoplastic EVA resin, 4 parts by mass of an organopolysiloxane MY 9150 (Angming silicon Co., ltd.), 1 part by mass of trimethylolpropane triacrylate, 1 part by mass of 3-isocyanatopropyl triethoxysilane, 0.6 part by mass of antioxidant 1010, 0.2 part by mass of antioxidant 168, 0.5 part by mass of UV-622, 0.05 part by mass of bismuth carboxylate, 0.25 part by mass of catalyst dimorpholine diethyl ether, 5 parts by mass of fumed silica (German Waxg fumed silica N20), 2 parts by mass of defoamer Basil Efka.
The high-activity-NCO-blocked isocyanate prepolymer A is prepared from 400g of poly (1, 6-hexanediol adipate) glycol with a number average molecular weight of 2000 (manufactured by Zhejiang Seenchen technology Co., ltd.), 71g of double-end-alcohol hydroxyl long-chain alkyl silicone oil IOTA-8865H (average molecular weight 3550, hydroxyl value 25.0 KOHmg/g), 0.5g of bismuth carboxylate, 20g of DMF, 0.8g of antioxidant 1010, 38.3g of m-xylylene diisocyanate and 125.2g of blocking agent-diphenylmethane-4, 4' -diisocyanate.
The preparation method of the high-activity-NCO-blocked isocyanate prepolymer A comprises the following steps of heating 400g of poly adipic acid-1, 6-hexanediol ester diol with the number average molecular weight of 2000 and 71g of double-end alcohol hydroxyl long-chain alkyl silicone oil IOTA-8865H to 105 ℃ and dehydrating for 2 hours under vacuum condition to obtain mixed polyol, uniformly mixing the obtained mixed polyol with 0.5g of bismuth carboxylate, 20g of DMF, 0.8g of antioxidant 1010 and 38.3g of m-xylylene diisocyanate, heating to 65 ℃ and reacting for 2 hours, testing the viscosity of the system every 10 minutes, adding 125.2g of diphenylmethane-4, 4' -diisocyanate MDI when the system viscosity is 6000-8000 mPa.s/25 ℃, and reacting for 1.0 hour under the protection of nitrogen at 80 ℃ to obtain the isocyanate prepolymer A with the-NCO content of 6.62 wt%.
The low-reactivity-NCO blocked isocyanate prepolymer B is prepared from 396g of low-crystallization type linear polyester polyol PLOS-ZY1200 with a number average molecular weight of 2200, 71g of double-end alcohol hydroxyl long-chain alkyl silicone oil IOTA-8865H, 0.8g of bismuth carboxylate, 16g of DMF, 0.8g of antioxidant 1010, 34.8g of m-xylylene diisocyanate and 151.2g of blocking agent-isophorone diisocyanate.
The preparation method of the low-activity-NCO blocked isocyanate prepolymer B comprises the steps of heating 396g of low-crystallization type linear polyester polyol PLOS-ZY1200 with the number average molecular weight 2200 and 71g of double-end alcohol hydroxyl long-chain alkyl silicone oil IOTA-8865H to 105 ℃ and dehydrating for 2 hours under vacuum condition to obtain mixed polyol, uniformly mixing the obtained mixed polyol with 0.8g of bismuth carboxylate, 16g of DMF, 0.8g of antioxidant 1010 and 34.8g of m-xylylene diisocyanate, heating to 70 ℃ and reacting for 3 hours, testing the viscosity of the system every 10 minutes, adding 151.2g of blocking agent-isophorone diisocyanate when the system viscosity is 6000-8000 mPa.s/25 ℃, and reacting for 100 minutes under the protection of nitrogen at 90 ℃ to obtain the isocyanate prepolymer B with the-NCO content of 8.75 wt%.
The primary amine blocked isocyanate prepolymer A was prepared from 200g of 1, 6-hexanediol polyadipate diol having a number average molecular weight of 2000, 50g of polytetramethylene ether glycol PTMEG (BASF Bus PolyTHF) having a number average molecular weight of 1000, 100g of polycarbonate diol PCDL 1012 having a number average molecular weight of 2000 (Guangzhou Hayata, new Material technology Co., ltd.), 0.88g of bismuth carboxylate, 18gDMF, 0.8g of antioxidant 1010, 55.1g of diphenylmethane-4, 4' -diisocyanate, and 8.15g of blocking agent-1, 6 hexamethylenediamine.
The preparation method of the primary amine blocked isocyanate prepolymer A comprises the steps of uniformly mixing 200g of poly adipic acid-1, 6-hexanediol ester glycol with the number average molecular weight of 2000, 50g of polytetramethylene ether glycol PTMEG with the number average molecular weight of 1000, 100g of polycarbonate diol PCDL 1012 with the number average molecular weight of 2000, heating to 105 ℃ and dehydrating under vacuum for 2 hours to obtain mixed polyol, uniformly mixing the obtained mixed polyol with 0.88g of bismuth carboxylate, 18gDMF, 0.8g of antioxidant 1010 and 55.1g of diphenylmethane-4, 4' -diisocyanate, heating to 65 ℃ and reacting for 1 hour, testing the viscosity of the system every 10 minutes, adding 8.15g of blocking agent-1, 6 hexamethylenediamine when the measured viscosity of the system is 6000-8000 mPa.s/25 ℃, and reacting for 1.0 hour under the protection of nitrogen at 80 ℃ to obtain the primary amine blocked isocyanate prepolymer A with the primary amine group of which weight percent is 0.77.
The primary hydroxyl-terminated isocyanate prepolymer B is prepared from 200g of low-crystalline dimer acid polyester polyol PLOS-ZY2250 with a number average molecular weight of 2500, 50g of polytetramethylene ether glycol PTMEG with a number average molecular weight of 1000, 30g of HX-209 hydroxyl-terminated methyl vinyl silicone oil (WUH Hua Xiangke Jiete Biotechnology Co., ltd., hydroxyl content: 6.+ -. 0.5mol%, vinyl content: 6.+ -. 0.5 mol%), 0.94g of bismuth carboxylate, 20. 20gDMF, 0.8g of antioxidant 1010, 44.45g of isophorone diisocyanate, and 13.7g of blocking agent bisphenol A dihydroxyethyl ether.
The preparation method of the primary hydroxyl-terminated isocyanate prepolymer B comprises the steps of uniformly mixing 200g of low-crystallization dimer acid polyester polyol PLOS-ZY2250 with the number average molecular weight 2500, 50g of polytetramethylene ether glycol PTMEG with the number average molecular weight 1000 and 30g of HX-209 hydroxyl-terminated methyl vinyl silicone oil, heating to 105 ℃ and dehydrating for 2 hours under vacuum condition to obtain mixed polyol, uniformly mixing the obtained mixed polyol with 0.94g of bismuth carboxylate, 20gDMF, 0.8g of antioxidant 1010 and 44.45g of isophorone diisocyanate, heating to 70 ℃ and reacting for 1.5 hours, and then testing the viscosity of the system every 10 minutes, wherein when the viscosity of the system is measured to be 6000-8000 mPa.s/25 ℃, 13.7g of blocking agent bisphenol A dihydroxyethyl ether is added, reacting for 1.5 hours under the protection of nitrogen, and obtaining the primary hydroxyl-terminated isocyanate prepolymer B with the primary hydroxyl content of 0.76 wt%.
The preparation method of the hot melt adhesive with high bonding strength comprises the steps of uniformly mixing 12 parts of prepared high-activity-NCO blocked isocyanate prepolymer A, 18 parts of low-activity-NCO blocked isocyanate prepolymer B, 6 parts of primary amine blocked isocyanate prepolymer A and 8 parts of primary hydroxyl blocked isocyanate prepolymer B under the protection of nitrogen, adding 8 parts of thermoplastic EVA resin, 4 parts of organic polysilazane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.5 part of ultraviolet resistant agent UV-622, 0.05 part of bismuth carboxylate, 0.25 part of catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20 and 2 parts of defoamer-Basoff Efka 2720, heating to 100 ℃, stirring for 30-45min under vacuum-0.09 MPa, and cooling to normal temperature after vacuum defoaming, and packaging the hot melt adhesive with black sealing bags.
Example 2 differs from example 1 in that the high bond strength hot melt adhesive is made from 18 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 12 parts by mass of a low reactive-NCO blocked isocyanate prepolymer B, 8 parts by mass of a primary amine blocked isocyanate prepolymer A, 6 parts by mass of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts by mass of a thermoplastic EVA resin, 3.2 parts by mass of an organopolysiloxane MY 9150, 1.2 parts by mass of trimethylolpropane triacrylate, 0.8 parts by mass of 3-isocyanatopropyl triethoxysilane, 0.6 parts by mass of an antioxidant 1010, 0.2 parts by mass of an antioxidant 168, 0.5 parts by mass of an ultraviolet inhibitor UV-622, 0.05 parts by mass of bismuth carboxylate, 0.25 parts by mass of a catalyst dimorpholine diethyl ether, 4 parts by mass of fumed silica N20, 1.278 parts by mass of an antifoaming agent Basoff Efka 20.
Example 3 differs from example 1 in that the high bond strength hot melt adhesive is made from 15 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 15 parts of a low reactive-NCO blocked isocyanate prepolymer B, 8 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts of a thermoplastic EVA resin, 3 parts of an organopolysiloxane MY 9150, 1.2 parts of trimethylolpropane triacrylate, 0.8 parts of 3-isocyanatopropyl triethoxysilane, 0.6 parts of an antioxidant 1010, 0.2 parts of an antioxidant 168, 0.5 parts of an ultraviolet inhibitor UV-622, 0.05 parts of bismuth carboxylate, 0.25 parts of a catalyst dimorpholine diethyl ether, 6 parts of fumed silica N20, 2.4 parts of an antifoaming agent Basoff Efka 20.
Example 4 differs from example 1 in that a high bond strength hot melt adhesive is made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 5 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of an ultraviolet inhibitor UV-622, 0.05 part of bismuth carboxylate, 0.25 part of a catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of a defoamer Basoff Efka.
Example 5 differs from example 1 in that a high bond strength hot melt adhesive is made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 12 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of an ultraviolet inhibitor UV-622, 0.05 part of bismuth carboxylate, 0.25 part of a catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of a defoamer Basoff Efka.
Example 6 differs from example 1 in that a high bond strength hot melt adhesive is made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 20 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of an ultraviolet inhibitor UV-622, 0.05 part of bismuth carboxylate, 0.25 part of a catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of a defoamer Basoff Efka.
Example 7 differs from example 1 in that a high bond strength hot melt adhesive is made from the following raw materials, by mass, 18 parts of a high reactive-NCO blocked isocyanate prepolymer A, 12 parts of a low reactive-NCO blocked isocyanate prepolymer B, 8 parts of a primary amine blocked isocyanate prepolymer A, 6 parts of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1.2 parts of tris (2-hydroxyethyl) isocyanurate triacrylate, 0.8 parts of gamma-glycidoxypropyl trimethoxysilane, 0.6 parts of an antioxidant 1010, 0.2 parts of an antioxidant 168, 0.5 parts of an ultraviolet inhibitor UV-622, 0.05 parts of bismuth carboxylate, 0.25 parts of a catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20, and 2 parts of an antifoaming agent-BafsEfka 2723.
Example 8 differs from example 1 in that a high bond strength hot melt adhesive is made from the following raw materials, by mass, 18 parts of a high reactive-NCO blocked isocyanate prepolymer A, 12 parts of a low reactive-NCO blocked isocyanate prepolymer B, 8 parts of a primary amine blocked isocyanate prepolymer A, 6 parts of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of pentaerythritol triacrylate, 1 part of gamma-methacryloxypropyl trimethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of an ultraviolet inhibitor UV-622, 0.05 part of bismuth carboxylate, 0.25 part of a catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of winning TEGO Airex 963.
Example 9 differs from example 1 in that the primary hydroxyl-terminated isocyanate prepolymer B is prepared from 200g of a low-crystalline dimer acid polyester polyol PLOS-ZY2250 having a number average molecular weight of 2500, 50g of a polytetramethylene ether glycol PTMEG having a number average molecular weight of 1000, 100g of a polycarbonate diol PCDL 1012 having a number average molecular weight of 2000, 0.94g of bismuth carboxylate, 20gDMF, 0.8g of an antioxidant 1010, 44.45g of isophorone diisocyanate, 13.7g of a capping agent bisphenol A dihydroxyethyl ether.
The preparation method of the primary hydroxyl-terminated isocyanate prepolymer B comprises the steps of uniformly mixing 200g of low-crystallization dimer acid polyester polyol PLOS-ZY2250 with the number average molecular weight 2500, 50g of polytetramethylene ether glycol PTMEG with the number average molecular weight 1000 and 100g of polycarbonate diol PCDL 1012 with the number average molecular weight 2000, heating to 105 ℃ and dehydrating for 2 hours under vacuum condition to obtain mixed polyol, uniformly mixing the obtained mixed polyol with 0.94g of bismuth carboxylate, 20gDMF, 0.8g of antioxidant 1010 and 44.45g of isophorone diisocyanate, heating to 70 ℃ and reacting for 1.5 hours, testing the viscosity of the system every 10 minutes, and adding 13.7g of blocking agent-bisphenol A dihydroxyethyl ether when the measured viscosity of the system is 6000-8000 mPa/25 ℃, and reacting for 1.5 hours under the protection of nitrogen at 85 ℃ to obtain the primary hydroxyl-terminated isocyanate prepolymer B with the primary hydroxyl content of 0.63 wt%.
Example 10 differs from example 1 in that the high bond strength hot melt adhesive is made from 20 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 10 parts of a low reactive-NCO blocked isocyanate prepolymer B, 5 parts of a primary amine blocked isocyanate prepolymer A, 10 parts of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1.2 parts of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 4 parts of fumed silica N20, 1.8 parts of Basoff Efka 2720.
The high-activity-NCO blocked isocyanate prepolymer A is prepared from 400g of poly (1, 6-hexanediol) glycol with a number average molecular weight of 2000, 71g of double-end alcohol hydroxyl long-chain alkyl silicone oil IOTA-8865H, 0.5g of bismuth carboxylate, 20g of DMF, 0.8g of antioxidant 1010, 38.3g of m-xylylene diisocyanate and 220.2g of blocking agent-diphenylmethane-4, 4' -diisocyanate. The NCO content of the highly reactive-NCO-blocked isocyanate prepolymer A was 10.1% by weight.
Comparative example
Comparative example 1 differs from example 1 in that a high bond strength hot melt adhesive was made from 44 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of Basoff Efka 2720.
Comparative example 2 differs from example 1 in that a high adhesive strength hot melt adhesive was prepared from the following raw materials, by mass, 30 parts of a high reactive-NCO blocked isocyanate prepolymer A, 14 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 5 parts of fumed silica N20, and 2 parts of Basoff Efka 2720.
Comparative example 3 differs from example 1 in that a high adhesive strength hot melt adhesive was made from the following raw materials, by mass, 30 parts of a high reactive-NCO blocked isocyanate prepolymer A, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of Basoff Efka 2720.
Comparative example 4 differs from example 1 in that a high bond strength hot melt adhesive was made from 44 parts by mass of an-NCO blocked isocyanate prepolymer, 4 parts of an organopolysiloxane MY 9150, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of Basoff Efka 2720.
The NCO-blocked isocyanate prepolymer was prepared from 300g of 1, 6-hexanediol polyadipate diol having a number average molecular weight of 2000, 90g of polytetramethylene ether glycol PTMEG having a number average molecular weight of 1000, 0.58g of bismuth carboxylate, 25g of DMF, 1g of antioxidant 1010, 38.3g of m-xylylene diisocyanate, 220.2g of diphenylmethane-4, 4' -diisocyanate MDI.
The preparation method of the high-activity-NCO-blocked isocyanate prepolymer A comprises the following steps of heating 300g of poly adipic acid-1, 6-hexanediol ester glycol with the number average molecular weight of 2000 and 90g of polytetramethylene ether glycol PTMEG with the number average molecular weight of 1000 to 105 ℃ and dehydrating for 2 hours under vacuum condition to obtain mixed polyol, uniformly mixing the obtained mixed polyol with 0.58g of bismuth carboxylate, 250g of DMF, 1g of antioxidant 1010 and 38.3g of m-xylylene diisocyanate, heating to 65 ℃ and reacting for 1.5 hours, testing the viscosity of the system every 10 minutes, adding 220.2g of diphenylmethane-4, 4' -diisocyanate when the viscosity of the system is 6000-8000 mPa.s/25 ℃, and reacting for 1.0 hour under the protection of nitrogen at 80 ℃ to obtain the isocyanate prepolymer with the-NCO content of 11.4 wt%.
Comparative example 5 differs from example 1 in that a high bond strength hot melt adhesive is made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts by mass of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts by mass of a primary amine blocked isocyanate prepolymer A, 8 parts by mass of a primary hydroxyl blocked isocyanate prepolymer B, 4 parts by mass of an organopolysiloxane MY 9150, 1 part by mass of trimethylolpropane triacrylate, 1 part by mass of 3-isocyanatopropyltriethoxysilane, 0.6 part by mass of an antioxidant 1010, 0.2 part by mass of an antioxidant 168, 0.5 part by mass of an ultraviolet inhibitor UV-622, 0.05 part by mass of bismuth carboxylate, 0.25 part by mass of dimorpholine diethyl ether, 5 parts by mass of fumed silica N20, 2 parts by mass of Basoff Efka 2720.
Comparative example 6 differs from example 1 in that a high adhesive strength hot melt adhesive was made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 2 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of Basoff Efka 2720.
Comparative example 7 is different from example 1 in that a hot melt adhesive of high adhesive strength is made of, by mass, 12 parts of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 22 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of Basoff Efka 2720.
Comparative example 8 differs from example 1 in that a high adhesive strength hot melt adhesive was made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 5 parts of a thermoplastic EVA resin, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of an ultraviolet resistance agent UV-622, 0.05 part of bismuth carboxylate, 0.25 part of a catalyst dimorpholine diethyl ether, 5 parts of fumed silica N20, 2 parts of Basoff Efka 2720.
Comparative example 9 differs from example 1 in that a high bond strength hot melt adhesive was made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 5 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyl triethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of an ultraviolet resistance agent UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether N20, 2 parts of Basoff Efka 2720.
Comparative example 10 differs from example 1 in that a high bond strength hot melt adhesive was made from 12 parts by mass of a high reactive-NCO blocked isocyanate prepolymer A, 18 parts of a low reactive-NCO blocked isocyanate prepolymer B, 6 parts of a primary amine blocked isocyanate prepolymer A, 8 parts of a primary hydroxyl blocked isocyanate prepolymer B, 8 parts of a thermoplastic EVA resin, 4 parts of an organopolysiloxane MY 9150, 1 part of trimethylolpropane triacrylate, 1 part of 3-isocyanatopropyltriethoxysilane, 0.6 part of an antioxidant 1010, 0.2 part of an antioxidant 168, 0.5 part of UV-622, 0.05 part of bismuth carboxylate, 0.25 part of dimorpholine diethyl ether, 10 parts of fumed silica N20, 2 parts of an antifoaming agent-Basoff Efka 2720.
Performance test
1. The appearance test method is that the appearance change of the hot melt adhesive is observed after 14day storage at room temperature and 60% RH.
2. Storage stability test the reactive polyurethane hot melt adhesives prepared in examples 1 to 10 and comparative examples 1 to 9 were placed in a sealed manner using a stainless steel packaging can (inner wall coated with a polytetrafluoroethylene non-stick coating), and the stainless steel packaging can was placed in an electric hot blast drying oven and was stored at 50℃for 14day, and after 14day, the hot melt adhesive was examined for occurrence of skinning and delamination.
3. The method for testing the bonding performance of the PA base material comprises the steps of melting and dispensing the PA base material at 150 ℃, shearing a sample, controlling the thickness of a glue layer to be 0.25mm, standing and solidifying the sample for 3day at 25 ℃ and 60% RH, and testing the shearing strength of the sample. Shear Strength test tensile shear Strength of adhesives according to GB/T7124-2008.
4. The method for testing the adhesive property of the silica gel base material comprises the steps of melting and dispensing the silica gel base material at 150 ℃, shearing a sample, controlling the thickness of the adhesive layer to be 0.25mm, standing and solidifying the sample at 25 ℃ under the humidity of 60% RH for 3day, and testing the shearing strength of the sample.
5. Weather resistance test after the reactive polyurethane hot melt adhesive was cured at 85 ℃/85% RH for 14d, the resulting test specimens were placed in a 120 ℃ oven environment for 24h, and then the tensile shear strength of the test specimens was tested at 120 ℃.
6. 180 DEG peel Strength test according to GB/T2790-1995 adhesive 180 DEG peel strength test method, the bonding object of the reactive polyurethane hot melt adhesive is GS0102 silica gel plate (breaking force: 6MPa; elongation: 300%; hardness: 55 DEG + -5 ℃).
Data analysis
TABLE 1 test parameters of reactive polyurethane Hot melt adhesives in examples 1-10 and comparative examples 1-10
As can be seen from the analysis of the table 1 in the examples 1-3 and the comparative examples 1-4, the high bonding strength hot melt adhesive prepared by adopting the reactive polyurethane hot melt adhesive formula provided by the application has good bonding strength to the PA substrate and good bonding strength to the silica gel substrate, has relatively good bonding strength and bonding stability to the nylon PA substrate when being applied to the field of nylon composite cloth fabric bonding, and bonds and fixes the silica gel surface layer and the nylon composite cloth by the high bonding strength hot melt adhesive, thereby expanding the application of the hot melt adhesive.
As is evident from the analysis of Table 1 in examples 1 and examples 4 to 6 and comparative examples 5 to 7, the addition of the thermoplastic EVA resin improves the overall adhesive strength but also affects the weather resistance of the final adhesive layer, so that the amount of thermoplastic EVA resin added in the reactive polyurethane hot melt adhesive formulation is preferably controlled to 5 to 20 parts, and preferably the range of addition is controlled to 8 to 10 parts.
As can be seen from the analysis of the table 1 in the example 1 and the comparative example 8, the organic polysilazane MY 9150 can improve the bonding stability and weather resistance of the reactive polyurethane hot melt adhesive, and avoid poor permeability and lower pinhole of the adhesive layer caused by the reaction speed.
As can be seen from the analysis of Table 1 in example 1 and comparative examples 9-10, the fumed silica N20 used in the present application can improve the adhesion property of the prepared reactive polyurethane hot melt adhesive to the silica gel substrate and can provide the overall weather resistance and service life, but too much fumed silica N20 can cause the overall adhesion strength to be greatly reduced, and the controller addition amount is required to be between 4 and 6 parts.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (6)
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| CN109609076A (en) * | 2018-12-04 | 2019-04-12 | 顺德职业技术学院 | Fire-retardant polyurethane hot-melt adhesive with excellent waterproof performance and preparation method thereof |
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