CN109679565A - Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof - Google Patents
Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109679565A CN109679565A CN201811476166.5A CN201811476166A CN109679565A CN 109679565 A CN109679565 A CN 109679565A CN 201811476166 A CN201811476166 A CN 201811476166A CN 109679565 A CN109679565 A CN 109679565A
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- China
- Prior art keywords
- flame retardant
- hot melt
- parts
- melt adhesive
- thermally conductive
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 49
- 239000004831 Hot glue Substances 0.000 title claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 47
- 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 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 34
- 239000011737 fluorine Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 32
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 31
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- -1 hexafluorobutyl Chemical group 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 150000002334 glycols 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
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 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 24
- 229920001451 polypropylene glycol Polymers 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical group CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 6
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims 1
- 239000012943 hotmelt Substances 0.000 abstract description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 8
- 238000006757 chemical reactions by type Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 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
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 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
- 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
- 206010054949 Metaplasia Diseases 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000499 gel Substances 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
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000003921 oil Substances 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
- 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
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid 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
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
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- 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
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- 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
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- 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
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7862—Nitrogen containing cyano groups or aldimine or ketimine groups
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention discloses a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof, feature be the polyether Glycols for including 1~30 part, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~60 part containing isocyanate-modified polyacrylic acid fluorinated copolymer, 1~60 part of isocyanates, 0.01~3 part of catalyst, 0.01~3 part of antioxidant, 0.1~4 part of silane coupling agent and 40~200 parts of heat filling.The present invention first synthesizes poly- (hexafluorobutyl acrylate-is random-acrylonitrile-is random-butyl acrylate-is random-isocyanatoethyl), it is added in polyurethane prepolymer precursor reactant, heat filling is further added, low-surface-energy fluoro-acrylate copolymer plays peptizaiton for heat filling high efficiency dispersion in base polyurethane prepolymer for use as, fluoro-acrylate copolymer segment and reactive flame retardant are introduced in base polyurethane prepolymer for use as simultaneously, formula efficiently acts synergistically, and improves the comprehensive chemical resistance of polyurethane hot melt, heating conduction and flame retardant property.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and its system
Preparation Method, which are mainly applied to electronics and appliance industry, power battery assembling, automobile industry isostructuralism 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 table
Face cools down after adherend bonding and forms excellent first adhesive property, then due to substrate surface contain micro-moisture or other
Compound containing active hydrogen reacts with isocyano (- NCO) and chemical crosslink reaction occurs, so that generating has highly cross-linked net
A kind of structural bonding hot melt adhesive of network and cohesive force greatly.
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, it is thermally conductive, fire-retardant etc. that there is also chemicals-resistant burn intos
Performance deficiency problem.This main cause is most of reaction type polyurethane hot-melt adhesives to improve its initial cohesiveness, be joined big
The non-reacted thermoplasticity thickening resin of amount or polynary acrylic copolymer.These non-reaction system thickening resins can not participate in solid
Metaplasia is at cross-linked network, to easily reduce chemicals-resistant corrosive nature, heat resistance, the resistance to ag(e)ing of polyurethane hot melt adhesive coating
Energy is equal.
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
A kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is provided the purpose of the present invention is overcome the deficiencies in the prior art
And preparation method thereof, since thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive introduces fluorine-containing groups, reactive flame retardant and thermally conductive
Filler can further promote chemicals-resistant corrosive nature, flame retardant property, heating conduction of polyurethane coating etc..
In order to achieve the above object, the technical solution of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive of the invention is such reality
It is existing, it is characterised in that including 1~30 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part fire-retardant
Polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~60 part of the fluorine-containing copolymerization containing isocyanate-modified polyacrylic acid
Object, 1~60 part of isocyanates, 0.01~3 part of catalyst, 0.01~3 part of antioxidant, 0.1~4 part of silane coupling agent
It is above mass fraction with 40~200 parts of heat filling；It is described containing isocyanate-modified polyacrylic acid fluorinated copolymer
Chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-and butyl acrylate-is random-methacrylic acid isocyanide
Base ethyl ester) i.e. P(HFMA-r-AN-r-BA-r-ICEMA), the equal molecule of number containing isocyanate-modified polyacrylic acid fluorinated copolymer
Amount 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 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 PMA one or more any combination；
The flame retardant polyether polyol is the WANOL FR-130, WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
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 thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive preparation method of the invention
It is achieved in that preparation method is characterized in that:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 1~40 part of hexafluorobutyl acrylate HFMA, 1~50 part of acrylonitrile AN, 1~50 part of butyl acrylate BA and 1
~20 parts of isocyanatoethyl ICEMA is dissolved in 50~200 parts of toluene, 40~110 DEG C is controlled in, in nitrogen
Under gas shielded, 0.1~4 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 2~50 hours, rotates
After evaporation removes toluene, obtains and contain isocyanate-modified polyacrylic acid fluorinated copolymer, contain containing isocyanate-modified polyacrylic acid
The number-average molecular weight of fluo-copolymer is 1000~50000；
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 1~30 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~
60 parts of crystalline polyester dihydric alcohol, 40~200 parts of heat filling, 0.01~3 part of catalyst and 0.01~3 part of antioxygen
After agent mixing, 120~150 DEG C are calorified, carries out mechanical dispersion, vacuumizes water removal about 1~3 hour, until the moisture content of mixture
Content is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, be added 1~60 part isocyanates and 1~60 part
Containing isocyanate-modified polyacrylic acid fluorinated copolymer, carry out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% contains
Amount reaches 1%~3%, and tested viscosity reaches 5000~50000 mPa.s at 100 DEG C, and 0.1~4 part of silane coupling agent is added, obtains
Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is obtained, is above mass fraction.
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 work of dispersing agent can be played due to the low-surface-energy of fluorine element containing isocyanate-modified polyacrylic acid fluorinated copolymer
With promotion heat filling dispersibility in hot melt colloid reduces the Viscosity of colloid, improves the thermal conductivity of heat filling；
2, the present invention is improved by introducing fluorine-containing groups, reactive flame retardant and heat filling in base polyurethane prepolymer for use as
Reaction type polyurethane hot-melt adhesive chemical resistance, flame retardant property, heating conduction and ageing-resistant 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 the deficiencies of solving the problems, such as reaction type polyurethane hot-melt adhesive chemical resistance.
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
The flow leveling of glue sizing, 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 thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 10 parts of hexafluorobutyl acrylate HFMA, 30 parts of acrylonitrile AN, 10 parts of butyl acrylate BA and 5 parts of methyl-prop
Olefin(e) acid isocyano group ethyl ester ICEMA is dissolved in 70 parts of toluene, is controlled in 95 DEG C, under nitrogen protection, 2.5 parts of heat is added and draws
Agent peroxidating 2 ethyl hexanoic acid tert-pentyl ester is sent out, polymerization reaction 15 hours, after rotary evaporation removes toluene, acquisition changed containing isocyanates
Property polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer be 6200, change
Learning structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-and butyl acrylate-is random-methacrylic acid isocyano group
Ethyl ester) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
10 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 25 parts of flame retarding polyether is more
First alcohol WANOL FR-130,30 parts of 7320,50 parts of crystalline polyester dihydric alcohol of heat filling aluminium oxide, 0.3 part of phosphoric acid
After 0.5 part of irgasfos 168 mixing, 150 DEG C are calorified, mechanical dispersion is carried out, vacuumizes water removal 1 hour, until mixture
Water content be lower than 280ppm, cool down in 75 DEG C, under nitrogen protection, 35 parts of modified diphenylmethane -4 be added, 4 '-two is different
Cyanate Desmodur CD-C(MDI performed polymer) and the synthesis of 25 parts of step 1 is fluorine-containing total containing isocyanate-modified polyacrylic acid
Polymers carries out polymerization reaction 5 hours, and sampling analysis polymerizate NCO% content reaches 1.4%, and viscosity reaches 12400 mPa.s,
1.5 parts of silane coupling agent ND-42 is added, obtains thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is above mass fraction.It is poly-
The number-average molecular weight of propylene oxide glycol PPG is 1000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 500, is used
Brookfield DV-C digital viscometer viscosity, test temperature are set as 100 DEG C.
Embodiment two
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 20 parts of hexafluorobutyl acrylate HFMA, 10 parts of acrylonitrile AN, 35 parts of butyl acrylate BA and 10 parts of methyl
Acrylic acid isocyano group ethyl ester ICEMA is dissolved in 100 parts of toluene, is controlled in 100 DEG C, under nitrogen protection, is added 1.8 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 15 hours, after rotary evaporation removes toluene, obtains and contains isocyanic acid
Ester modified polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer are 11300,
Its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-butyl acrylate-is random-and methacrylic acid is different
Cyanaoethyl methacrylate) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 10 parts of polytetrahydrofuran ether glycol PTMG, 15 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 40 parts of resistance
Combustible polyether glycol WANOL FR-312,30 parts of 7360,70 parts of crystalline polyester dihydric alcohol of heat filling graphite, 0.5 part
Triethanolamine and the mixing of 0.9 part of irgasfos 168 after, calorify 140 DEG C, carry out mechanical dispersion, it is small to vacuumize water removal 2.5
When, until the water content of mixture is lower than 280ppm, cool down in 70 DEG C, under nitrogen protection, 35 parts of modification hexichol is added
Methane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and the synthesis of 30 parts of step 1 containing isocyanate-modified
Polyacrylic acid fluorinated copolymer carries out polymerization reaction 4 hours, and sampling analysis polymerizate NCO% content reaches 2.1%, and viscosity reaches
To 17540 mPa.s, 3 parts of silane coupling agent ND-42 is added, obtains thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, it is above equal
For mass fraction.The number-average molecular weight of polytetrahydrofuran ether glycol PTMG is 2000, polyadipate -1,6- hexylene glycol esterdiol
The number-average molecular weight of PHA is 1000, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as 100
℃。
Embodiment three
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 30 parts of hexafluorobutyl acrylate HFMA, 40 parts of acrylonitrile AN, 20 parts of butyl acrylate BA and 10 parts of methyl
Acrylic acid isocyano group ethyl ester ICEMA is dissolved in 140 parts of toluene, is controlled in 95 DEG C, under nitrogen protection, is added 1.2 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 12 hours, after rotary evaporation removes toluene, obtains and contains isocyanic acid
Ester modified polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer are 16850,
Its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-butyl acrylate-is random-and methacrylic acid is different
Cyanaoethyl methacrylate) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
25 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 40 parts of flame retarding polyether is more
First alcohol WANOL FR-212,50 parts of 7360,110 parts of crystalline polyester dihydric alcohol of heat filling aluminium hydroxide, 0.4 part
After 2,2- dimorpholine base Anaesthetie Ethers and the mixing of 1.2 parts of antioxidant 1010,150 DEG C are calorified, mechanical dispersion is carried out, taken out true
Sky water removal 3 hours cools down until the water content of mixture is lower than 280ppm in 80 DEG C, under nitrogen protection, is added 40 parts
Modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and 35 parts of step 1 synthesis contain isocyanide
Acid esters modified polyacrylic acid fluorinated copolymer carries out polymerization reaction 6 hours, and sampling analysis polymerizate NCO% content reaches
2.3%, viscosity reaches 31230 mPa.s, and 3.5 parts of silane coupling agent ND-42 is added, obtains thermally conductive fluorine richness flame retardant polyurethane
Hot melt adhesive is mass fraction above.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, polyethylene glycol adipate
The number-average molecular weight of glycol PEA is 1500, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as
100℃。
Example IV
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 40 parts of hexafluorobutyl acrylate HFMA, 10 parts of acrylonitrile AN, 40 parts of butyl acrylate BA and 15 parts of methyl
Acrylic acid isocyano group ethyl ester ICEMA is dissolved in 180 parts of toluene, is controlled in 100 DEG C, under nitrogen protection, is added 1.0 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 7 hours, after rotary evaporation removes toluene, obtains and contains isocyanic acid
Ester modified polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer are 24000,
Its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-butyl acrylate-is random-and methacrylic acid is different
Cyanaoethyl methacrylate) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 10 parts of polyoxypropyleneglycol PPG, 20 parts of polyadipate -1,4-butanediol esterdiol PMA, 45 parts fire-retardant poly-
Ethoxylated polyhydric alcohol WANOL FR-312,45 parts of 7380,150 parts of crystalline polyester dihydric alcohol of heat filling calcium carbonate, 0.8 part
Triethanolamine and the mixing of 1.5 parts of irgasfos 168 after, calorify 150 DEG C, carry out mechanical dispersion, vacuumize water removal 2 hours,
Until the water content of mixture is lower than 280ppm, cool down in 90 DEG C, under nitrogen protection, 50 parts of modification hexichol first is added
Alkane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and the synthesis of 50 parts of step 1 containing isocyanate-modified poly-
Acrylic acid fluorinated copolymer carries out polymerization reaction 3 hours, and sampling analysis polymerizate NCO% content reaches 2.3%, and viscosity reaches
3.5 parts of silane coupling agent ND-42 is added in 43520 mPa.s, obtains thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, above equal
For mass fraction.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, and the number of polyethylene glycol adipate glycol PEA is equal
Molecular weight is 1500, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the fire-retardant poly- ammonia of thermally conductive fluorine richness that the four kinds of above embodiments are obtained
Ester hot melt adhesive carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength, oxygen index (OI) and with resistance to acidity of oil
It can index test.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, is arranged 100 DEG C.It is open
Time is tested referring to ASTM D4497-1994 (2004) method.Shore hardness is surveyed referring to GB-T2411-2008 standard
Examination.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is carried out referring to GB/T7124-2004 standard
Test.Oxygen index (OI) is measured using GB/T5454-1997 " textile combustion performance test-oxygen index method ".Chemical resistance
The specific test method of index is that sample is prepared with reference to test shear strength method, after sample places solidification in 72 hours, by sample
It is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, be placed under 85 DEG C and 85% relative humidity conditions, carry out 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
Can be seen that the thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive that the present invention synthesizes from the data of table 1 has excellent resistance toization
Product ageing properties, 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 (3)
1. a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, it is characterised in that including 1~30 part of polyether Glycols, 1~40
Liquid polyesters dihydric alcohol, 1~50 part of the flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~60 part of part
Containing isocyanate-modified polyacrylic acid fluorinated copolymer, 1~60 part of isocyanates, 0.01~3 part of catalyst, 0.01~
3 parts of antioxidant, 0.1~4 part of silane coupling agent and 40~200 parts of heat filling, are mass fraction above；It is described to contain
The chemical structure of isocyanate-modified polyacrylic acid fluorinated copolymer is: poly- (hexafluorobutyl acrylate-is random-acrylonitrile-nothing
Rule-butyl acrylate-is random-isocyanatoethyl) i.e. P(HFMA-r-AN-r-BA-r-ICEMA) and, contain isocyanic acid
The number-average molecular weight of ester modified polyacrylic acid fluorinated copolymer is 1000~50000.
2. thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG or polytetrahydrofuran ether two of the number-average molecular weight 500~4000
One or two kinds of any combination of alcohol PTMG；
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 PMA one or more any combination；
The flame retardant polyether polyol is the WANOL FR-130, WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
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.
3. a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive preparation method, preparation method are characterized in that:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 1~40 part of hexafluorobutyl acrylate HFMA, 1~50 part of acrylonitrile AN, 1~50 part of butyl acrylate BA and 1
~20 parts of isocyanatoethyl ICEMA is dissolved in 50~200 parts of toluene, 40~110 DEG C is controlled in, in nitrogen
Under gas shielded, 0.1~4 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 2~50 hours, rotates
After evaporation removes toluene, obtains and contain isocyanate-modified polyacrylic acid fluorinated copolymer, contain containing isocyanate-modified polyacrylic acid
The number-average molecular weight of fluo-copolymer is 1000~50000；
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 1~30 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~
60 parts of crystalline polyester dihydric alcohol, 40~200 parts of heat filling, 0.01~3 part of catalyst and 0.01~3 part of antioxygen
After agent mixing, 120~150 DEG C are calorified, carries out mechanical dispersion, vacuumizes water removal about 1~3 hour, until the moisture content of mixture
Content is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, be added 1~60 part isocyanates and 1~60 part
Containing isocyanate-modified polyacrylic acid fluorinated copolymer, carry out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% contains
Amount reaches 1%~3%, and tested viscosity reaches 5000~50000 mPa.s at 100 DEG C, and 0.1~4 part of silane coupling agent is added, obtains
Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is obtained, is above mass fraction.
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| CN201811476166.5A CN109679565A (en) | 2018-12-04 | 2018-12-04 | Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334226A (en) * | 2019-12-31 | 2020-06-26 | 武汉长盈鑫科技有限公司 | Heat-conducting adhesive with low glass transition temperature and preparation method thereof |
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| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
| CN105670550A (en) * | 2016-03-31 | 2016-06-15 | 东莞新能源科技有限公司 | A thermally conductive adhesive and a secondary battery containing the thermally conductive adhesive |
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2018
- 2018-12-04 CN CN201811476166.5A patent/CN109679565A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
| CN105670550A (en) * | 2016-03-31 | 2016-06-15 | 东莞新能源科技有限公司 | A thermally conductive adhesive and a secondary battery containing the thermally conductive adhesive |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111334226A (en) * | 2019-12-31 | 2020-06-26 | 武汉长盈鑫科技有限公司 | Heat-conducting adhesive with low glass transition temperature and preparation method thereof |
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