CN109651996A - High thermal conductivity flame retardant polyurethane hot melt adhesive and preparation method thereof - Google Patents
High thermal conductivity flame retardant polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109651996A CN109651996A CN201811476162.7A CN201811476162A CN109651996A CN 109651996 A CN109651996 A CN 109651996A CN 201811476162 A CN201811476162 A CN 201811476162A CN 109651996 A CN109651996 A CN 109651996A
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- CN
- China
- Prior art keywords
- parts
- flame retardant
- melt adhesive
- thermal conductivity
- polyacrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- 239000004831 Hot glue Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 34
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 34
- -1 methacryloxypropyl Chemical group 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 229920001451 polypropylene glycol Polymers 0.000 claims description 15
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 7
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 6
- YEORLXJBCPPSOC-UHFFFAOYSA-N 2-amino-5-(diaminomethylideneazaniumyl)-2-(difluoromethyl)pentanoate Chemical compound NC(N)=NCCCC(N)(C(F)F)C(O)=O YEORLXJBCPPSOC-UHFFFAOYSA-N 0.000 claims description 6
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 10
- 239000011231 conductive filler Substances 0.000 claims 4
- RUDMCWOFBGNJTR-UHFFFAOYSA-N C(C)C(C(=O)O)CCCC.C(C)(C)(CC)OOC(C)(C)CC Chemical compound C(C)C(C(=O)O)CCCC.C(C)(C)(CC)OOC(C)(C)CC RUDMCWOFBGNJTR-UHFFFAOYSA-N 0.000 claims 1
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical group NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 29
- 238000012986 modification Methods 0.000 abstract description 24
- 230000004048 modification Effects 0.000 abstract description 24
- 238000011049 filling Methods 0.000 abstract description 11
- 238000007789 sealing Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 abstract description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 150000002334 glycols Chemical class 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- 238000006757 chemical reactions by type Methods 0.000 description 7
- 239000012943 hotmelt Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229920006335 epoxy glue Polymers 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 239000004588 polyurethane sealant Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FDZUPHXVDHGJQR-UHFFFAOYSA-N 4,4-difluoroheptane Chemical compound CCCC(F)(F)CCC FDZUPHXVDHGJQR-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002083 enediols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
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- 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
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Abstract
The invention discloses a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 1~30 part, 1~60 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~60 part of crystalline polyester dihydric alcohol, 1~50 part of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object, 10~70 parts of isocyanates, 0.01~4 part of catalyst, 0.01~4 part of antioxidant, 0.1~5 part of silane coupling agent and 60~300 parts of heat filling.The present invention solves heat filling dispersion problem, hydroxyl modification polyacrylic acid fluorine-silicon copolymer object has been synthesized first, its chemical structure is: poly- (dodecafluoroheptyl methacrylate-is random-and the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of methacryloxypropyl list sealing end dimethyl polysiloxane-is random-random -4- hydroxybutyl acrylate of lauryl acrylate -), it is added base polyurethane prepolymer for use as and high efficiency dispersion is carried out to heat filling, solve the problems, such as that coating is easily precipitated in traditional dispersing agent, efficiently synergistic effect, improve oil resistance, heating conduction and flame retardant property.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive and its preparation side
Method, which are mainly applied to the electronic structures such as electronics and appliance industry, automobile industry, power battery module assembling to be bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use, environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt can be divided into thermoplastic polyurethane elastomer hot melt adhesive by cured form difference
And reactive polyurethane hot melt, reactive polyurethane hot melt can be divided into response type and enclosed type by its principle of solidification difference；
Reaction type polyurethane hot-melt adhesive PUR is a kind of one pack system hot melt adhesive, is melted after heating, and flows scatter coated in substrate surface,
It is cooled down after adherend bonding and forms excellent first adhesive property, then since substrate surface contains micro-moisture or other contain work
The compound for sprinkling hydrogen react with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate with highly cross-linked network and
A kind of big structural bonding hot melt adhesive of cohesive force.
Reaction type polyurethane hot-melt adhesive has technically obtained unprecedented development at present, mainly around high-adhesive-strength, eutectic
Body viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised.Chinese patent discloses one kind entitled " one
The application for a patent for invention of kind of reactive hot melt adhesive ", application number is 201480080313.0, is prepared a kind of with reprocessing
Removable polyurethane-hot melt adhesive, more suitable for high-end electronic product scope application.Chinese patent also discloses a kind of name
Referred to as the application for a patent for invention of " solvent-free damp solidifying polyurethane hot-melt adhesive composition ", application number are
201180047316.0, prepare a kind of quick polyurethane-hot melt for establishing adhesive property polyacrylate and polyester preparation of low toxicity
Viscose binder.In order to improve the cured form of reaction type polyurethane hot-melt adhesive, it is that " one kind has that Chinese patent, which discloses a kind of title,
The application for a patent for invention of machine silicon modified polyurethane sealant ", application number are 201710271725.8, prepare a kind of organosilicon and change
Property polyurethane sealant, with silane coupling agent replace isocyano (- NCO), be more suitable for applying under high humidity environment.Currently, reaction
The research and development technology of type polyurethane hot melt adhesive meets different type high-end electronic product scope application in fast development.Response type is poly-
Although urethane hot melt adhesive can form highly cross-linked network after hardening, there is also chemicals-resistant corrosivity, heat-resisting, resistance to old
The performances deficiency problem such as change, fire-retardant.This main cause is most of reaction type polyurethane hot-melt adhesives to improve its initial cohesiveness,
It joined a large amount of non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction systems thickening resins without
Method participates in solidification and generates cross-linked network, thus easily reduce the chemicals-resistant corrosive nature of polyurethane hot melt adhesive coating, heat resistance,
Ageing-resistant performance etc..
Heat-conducting glue is exclusively used in the bonding and conductive force of electronic and electrical equipment material.Currently, mainly have heat-conducting organic silica gel,
Thermally conductive epoxy glue and heat-conduction polyurethane glue.Heat-conducting organic silica gel has excellent heat-resisting and ageing-resistant performance, but to the attached of substrate
Put forth effort compared to weaker.Thermally conductive epoxy glue is very big to the bonding force of substrate, but deposits that hardness is big after hardening and brittleness is too strong.It is thermally conductive poly-
Urethane glue has excellent adhesive force and flexibility, can reach good damping and conductive force.Heat-conduction polyurethane glue is usually set
It is calculated as two-component, using mixed process, in order to quickly defoam, a large amount of silicon class defoaming agents is added and are quickly defoamed.Defoaming agent
Because that can not participate in reacting, coating surface, polluted product is easily precipitated.
Summary of the invention
There is provided the purpose of the present invention is overcome the deficiencies in the prior art a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive and its
Preparation method can since high thermal conductivity flame retardant polyurethane hot melt adhesive introduces fluorine silicon segment, reactive flame retardant and heat filling
Further improve the oil resistivity performance of polyurethane coating, flame retardant property, heating conduction, ageing-resistant performance etc..
In order to achieve the above object, the technical solution of high thermal conductivity flame retardant polyurethane hot melt adhesive of the invention is realized in
, it is characterised in that it is poly- including 1~30 part of polyether Glycols, 1~60 part of flame retardant polyether polyol, 1~40 part of liquid
Ester dihydric alcohol, 1~60 part of crystalline polyester dihydric alcohol, 1~50 part of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object, 10~70
Part isocyanates, 0.01~4 part of catalyst, 0.01~4 part of antioxidant, 0.1~5 part of silane coupling agent and 60~
300 parts of heat filling is mass fraction above；The chemical structure of the hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is:
Poly- (dodecafluoroheptyl methacrylate-is random-random -2- first of methacryloxypropyl list sealing end dimethyl polysiloxane -
Base -2- 2-hydroxyethyl acrylate phosphate-is random-random -4- hydroxybutyl acrylate of lauryl acrylate -) i.e. P
(DFMA-r-MAPDMS-r-HMP-r-LA-r-HBA), the number-average molecular weight of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is 1000
~50000.
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
One or two kinds of any combination of PPG or polytetrahydrofuran ether glycol PTMG；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42；
The heat filling is one or more kinds of any combination of aluminium oxide, graphite, aluminium hydroxide and calcium carbonate, thermally conductive
Packing material size is 0.1~5 μm.
In order to achieve the above object, the technical solution of the preparation method of high thermal conductivity flame retardant polyurethane hot melt adhesive of the invention is
It is achieved, it is characterised in that preparation step is as follows:
Step 1: synthesis of hydroxy modified polyacrylic acid fluorine-silicon copolymer object
1~30 part of dodecafluoroheptyl methacrylate DFMA, 1~30 part of methacryloxypropyl list are blocked into dimethyl
Polysiloxanes MAPDMS, 1~40 part of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP, 1~60 part of acrylic acid
Lauryl LA and 1~20 part of 4- hydroxybutyl acrylate HBA are dissolved in 50~300 parts of toluene, are controlled in 40~110
DEG C, under nitrogen protection, 0.1~5 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 2~50 is small
When, after rotary evaporation removes toluene, obtain hydroxyl modification polyacrylic acid fluorine-silicon copolymer object, hydroxyl modification polyacrylic acid fluorine-silicon copolymer
The number-average molecular weight of object is 1000~50000；
Step 2: synthesis high thermal conductivity flame retardant polyurethane hot melt adhesive
By 1~30 part of polyether Glycols, 1~60 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~
60 parts of crystalline polyester dihydric alcohol, 1~50 part of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object, 0.01~4 part of catalyst,
After 60~300 parts of heat filling and the mixing of 0.01~4 part of antioxidant, 120~150 DEG C are calorified, mechanical dispersion is carried out, is taken out
Vaccum dewatering about 1~3 hour, until the water content of mixture is lower than 280ppm, cool down in 70~100 DEG C, in nitrogen protection
Under, 10~70 parts of isocyanates is added, carries out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% content reaches
1%~3%, viscosity reaches 5000~60000 mPa.s, and 0.1~5 part of silane coupling agent is added, and obtains the fire-retardant poly- ammonia of high thermal conductivity
Ester hot melt adhesive is mass fraction above.
In the technical scheme, in step 1 methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number
Average molecular weight is 1000, No. CAS: 146632-07-7.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
1, the present invention solves heat filling dispersion problem, and the low surface energy fluorine silicon that may participate in polyurethane reaction of synthesis closes altogether
Object has excellent dispersibility to heat filling, and thermal conductivity can carry out Effective Regulation (thermal coefficient by adjusting heat filling amount
1.0~2.0 W/(mK)), solve the problems, such as that coating is easily precipitated in traditional dispersing agent；
2, the present invention solves traditional reaction type polyurethane hot-melt adhesive oil resistance, flame retardant property, heating conduction and resistance to ag(e)ing
The defect of the deficiencies of energy is mentioned by introducing fluorine silicon segment, reactive flame retardant and heat filling in base polyurethane prepolymer for use as
Its high comprehensive performance；
3, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, is improved thickening resin and is gathered
The compatibility of urethane further solves the problems, such as reaction type polyurethane hot-melt adhesive oil resistance and ageing-resistant performance deficiency；
4, the present invention solves the problems, such as that traditional reaction type polyurethane hot-melt adhesive is poor to substrate wet performance, improves hot melt adhesive and applies
The flow leveling of glue, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy modified polyacrylic acid fluorine-silicon copolymer object
10 parts of dodecafluoroheptyl methacrylate DFMA, 15 parts of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 10 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP, 40 parts of lauryl acrylate LA and 1 part
4- hydroxybutyl acrylate HBA be dissolved in 100 parts of toluene, be controlled in 85 DEG C, under nitrogen protection, be added 4 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 7 hours, after rotary evaporation removes toluene, obtains hydroxyl modification
The chemical structure of polyacrylic acid fluorine-silicon copolymer object, hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is: poly- (ten difluoro of methacrylic acid
Heptyl ester-is random-random -2- methyl -2- acrylic acid -2- ethoxy of methacryloxypropyl list sealing end dimethyl polysiloxane -
Ester phosphate-is random-random -4- hydroxybutyl acrylate of lauryl acrylate -) i.e. P(DFMA-r-MAPDMS-r-HMP-r-
LA-r-HBA), the number-average molecular weight of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is 4400；Methacryloxypropyl list sealing end
The number-average molecular weight of dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis high thermal conductivity flame retardant polyurethane hot melt adhesive
15 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 25 parts of flame retarding polyether is more
The hydroxyl modification polyacrylic acid that first alcohol WANOL FR-130,40 parts of 7320,20 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After fluorine-silicon copolymer object, 100 parts of aluminium oxide, 0.2 part of phosphoric acid and the mixing of 0.5 part of irgasfos 168,150 DEG C are calorified, is carried out
Mechanical dispersion vacuumizes water removal 1 hour, until the water content of mixture is lower than 280ppm, cools down in 70 DEG C, in nitrogen protection
Under, 50 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), polymerize anti-
It answers 4 hours, sampling analysis polymerizate NCO% content reaches 2.3%, and viscosity reaches 12500 mPa.s, it is even that 2 parts of silane is added
Join agent ND-42, obtains high thermal conductivity flame retardant polyurethane hot melt adhesive, be above mass fraction.The number of polyoxypropyleneglycol PPG is equal
Molecular weight is 1000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 500, viscous with Brookfield DV-C number
Viscosity measurement is spent, test setting temperature is 100 DEG C.
Embodiment two
It is a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy modified polyacrylic acid fluorine-silicon copolymer object
10 parts of dodecafluoroheptyl methacrylate DFMA, 20 parts of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 20 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP, 50 parts of lauryl acrylate LA and 5 parts
4- hydroxybutyl acrylate HBA be dissolved in 80 parts of toluene, be controlled in 90 DEG C, under nitrogen protection, 3 parts of heat be added
Polymerization reaction 8 hours, after rotary evaporation removes toluene, it is poly- to obtain hydroxyl modification for initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester
The chemical structure of acrylic acid fluorine-silicon copolymer object, hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is: poly- (ten difluoro heptan of methacrylic acid
Ester-is random-random -2- methyl -2- 2-hydroxyethyl acrylate of methacryloxypropyl list sealing end dimethyl polysiloxane -
Phosphate-is random-random -4- hydroxybutyl acrylate of lauryl acrylate -) i.e. P(DFMA-r-MAPDMS-r-HMP-r-
LA-r-HBA), the number-average molecular weight of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is 9200；Methacryloxypropyl list sealing end
The number-average molecular weight of dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis high thermal conductivity flame retardant polyurethane hot melt adhesive
By 10 parts of polytetrahydrofuran ether glycol PTMG, 30 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 35 parts of resistance
The hydroxyl modification that combustible polyether glycol WANOL FR-212,40 parts of 7360,35 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After polyacrylic acid fluorine-silicon copolymer object, 120 parts of calcium carbonate, 0.4 part of triethanolamine and the mixing of 0.8 part of irgasfos 168, heating
In 140 DEG C, carry out mechanical dispersion, vacuumize water removal 2.5 hours, until mixture water content be lower than 280ppm, cooling in
80 DEG C, under nitrogen protection, it is pre- that 45 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI of modified diphenylmethane-is added
Aggressiveness), it carries out polymerization reaction 6 hours, sampling analysis polymerizate NCO% content reaches 2.4%, and viscosity reaches 15490 mPa.s,
3.0 parts of silane coupling agent ND-42 is added, obtains high thermal conductivity flame retardant polyurethane hot melt adhesive, is above mass fraction.Poly- tetrahydro
The number-average molecular weight of furans ether glycol PTMG is 2000, and the number-average molecular weight of polyadipate -1,6- hexylene glycol esterdiol PHA is
1000, with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Embodiment three
It is a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy modified polyacrylic acid fluorine-silicon copolymer object
25 parts of dodecafluoroheptyl methacrylate DFMA, 10 parts of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 30 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP, 55 parts of lauryl acrylate LA and 5 parts
4- hydroxybutyl acrylate HBA be dissolved in 150 parts of toluene, be controlled in 95 DEG C, under nitrogen protection, be added 2 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 8 hours, after rotary evaporation removes toluene, obtains hydroxyl modification
The chemical structure of polyacrylic acid fluorine-silicon copolymer object, hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is: poly- (ten difluoro of methacrylic acid
Heptyl ester-is random-random -2- methyl -2- acrylic acid -2- ethoxy of methacryloxypropyl list sealing end dimethyl polysiloxane -
Ester phosphate-is random-random -4- hydroxybutyl acrylate of lauryl acrylate -) i.e. P(DFMA-r-MAPDMS-r-HMP-r-
LA-r-HBA), the number-average molecular weight of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is 14200；Methacryloxypropyl list envelope
The number-average molecular weight for holding dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis high thermal conductivity flame retardant polyurethane hot melt adhesive
20 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 45 parts of flame retarding polyether is more
The hydroxyl modification polyacrylic acid that first alcohol WANOL FR-312,40 parts of 7360,40 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After fluorine-silicon copolymer object, 120 parts of graphite, 0.5 part of 2,2- dimorpholine base Anaesthetie Ether and the mixing of 1 part of antioxidant 1010, add
Heat in 150 DEG C, carry out mechanical dispersion, vacuumize water removal 3 hours, until mixture water content be lower than 280ppm, cooling in
80 DEG C, under nitrogen protection, it is pre- that 60 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI of modified diphenylmethane-is added
Aggressiveness), it carries out polymerization reaction 3 hours, sampling analysis polymerizate NCO% content reaches 2.5%, and viscosity reaches 19500 mPa.s,
2 parts of silane coupling agent ND-42 is added, obtains high thermal conductivity flame retardant polyurethane hot melt adhesive, is above mass fraction.Polyoxygenated third
The number-average molecular weight of enediol PPG is 3000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 1500, is used
Brookfield DV-C digital viscometer viscosity, test setting temperature are 100 DEG C.
Example IV
It is a kind of high thermal conductivity flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy modified polyacrylic acid fluorine-silicon copolymer object
10 parts of dodecafluoroheptyl methacrylate DFMA, 30 parts of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 20 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP, 55 parts of lauryl acrylate LA and 10
The 4- hydroxybutyl acrylate HBA of part is dissolved in 200 parts of toluene, is controlled in 100 DEG C, under nitrogen protection, is added 1 part
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization reaction 7 hours, rotary evaporation remove toluene after, obtain hydroxyl change
Property polyacrylic acid fluorine-silicon copolymer object, the chemical structure of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is: poly- (methacrylic acid 12
Fluorine heptyl ester-is random-random -2- methyl -2- acrylic acid -2- hydroxyl second of methacryloxypropyl list sealing end dimethyl polysiloxane -
Base ester phosphate-is random-random -4- hydroxybutyl acrylate of lauryl acrylate -) i.e. P(DFMA-r-MAPDMS-r-HMP-
R-LA-r-HBA), the number-average molecular weight of hydroxyl modification polyacrylic acid fluorine-silicon copolymer object is 21200；Methacryloxypropyl list
The number-average molecular weight for blocking dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis high thermal conductivity flame retardant polyurethane hot melt adhesive
By 20 parts of polyoxypropyleneglycol PPG, 15 parts of polyadipate -1,4-butanediol esterdiol PBA, 55 parts fire-retardant poly-
The hydroxyl modification poly- third that ethoxylated polyhydric alcohol WANOL FR-312,50 parts of 7380,45 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After olefin(e) acid fluorine-silicon copolymer object, 170 parts of aluminium hydroxide, 0.8 part of triethanolamine and the mixing of 1 part of irgasfos 168, calorify
150 DEG C, mechanical dispersion is carried out, vacuumizes water removal 2 hours, until the water content of mixture is lower than 280ppm, is cooled down in 90 DEG C,
Under nitrogen protection, 65 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added),
It carries out polymerization reaction 5 hours, sampling analysis polymerizate NCO% content reaches 2.7%, and viscosity reaches 25430 mPa.s, is added 1
The silane coupling agent ND-42 of part obtains high thermal conductivity flame retardant polyurethane hot melt adhesive, is above mass fraction.Polypropylene oxide two
The number-average molecular weight of alcohol PPG is 4000, and polyadipate -1,4-butanediol esterdiol PBA number-average molecular weight is 2000, is used
Brookfield DV-C digital viscometer viscosity, test setting temperature are 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the high thermal conductivity flame retardant polyurethane heat that the four kinds of above embodiments are obtained
Melten gel carries out melt viscosity, open hour, shore hardness, elongation at break, shear strength, oxygen index (OI) and can refer to resistance to acidity of oil
Mapping examination.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, is arranged 100 DEG C.Open hour
It is tested referring to ASTM D4497-1994 (2004) method.Shore hardness is tested referring to GB-T2411-2008 standard.
Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is surveyed referring to GB/T7124-2004 standard
Examination.Oxygen index (OI) is measured using GB/T5454-1997 " textile combustion performance test-oxygen index method ".Chemical resistance refers to
Marking specific test method is to prepare sample after sample places solidification in 72 hours with reference to test shear strength method to soak sample
It steeps in oleic acid (purity 98%) solution 24 hours, takes out sample, be placed under 85 DEG C and 85% relative humidity conditions, progress aging
After 1000 hours, then carry out shear strength test.Thermal coefficient is tested with reference to ASTMD5470 standard.All test datas
Comparative situation is see the following table 1.
Each embodiment specific performance of table 1 tests control case
From the data of table 1 can be seen that the high thermal conductivity flame retardant polyurethane hot melt adhesive that synthesizes of the present invention have excellent oil resistance,
Heating conduction and flame retardant property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (4)
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| CN113372868A (en) * | 2021-05-20 | 2021-09-10 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| CN115926713A (en) * | 2022-11-01 | 2023-04-07 | 无锡博锦高分子研究发展有限公司 | Single-component heat-conducting hot-melt polyurethane adhesive and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372868A (en) * | 2021-05-20 | 2021-09-10 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| CN115926713A (en) * | 2022-11-01 | 2023-04-07 | 无锡博锦高分子研究发展有限公司 | Single-component heat-conducting hot-melt polyurethane adhesive and preparation method and application thereof |
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