CN109609078A - Moisture-curing silicone-modified flame-retardant polyurethane hot-melt adhesive and preparation method thereof - Google Patents
Moisture-curing silicone-modified flame-retardant polyurethane hot-melt adhesive and preparation method thereof Download PDFInfo
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- CN109609078A CN109609078A CN201811475687.9A CN201811475687A CN109609078A CN 109609078 A CN109609078 A CN 109609078A CN 201811475687 A CN201811475687 A CN 201811475687A CN 109609078 A CN109609078 A CN 109609078A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 47
- 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 class 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
- 239000004831 Hot glue Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000013008 moisture curing Methods 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 methacryloxypropyl Chemical group 0.000 claims abstract description 22
- 239000003063 flame retardant Substances 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 150000002334 glycols Chemical class 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 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 23
- 229920001451 polypropylene glycol Polymers 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- 239000012943 hotmelt Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 12
- 125000004356 hydroxy functional group Chemical group O* 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- 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 8
- 239000000203 mixture Substances 0.000 claims description 8
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical group CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- BJJVDFADUDDTQK-UHFFFAOYSA-N 5-hydroxy-2-methylpentanenitrile Chemical compound N#CC(C)CCCO BJJVDFADUDDTQK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000979 retarding effect 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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- 230000003679 aging effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002009 diols Chemical class 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
- 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
- 150000002240 furans Chemical class 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
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 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
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses organic-silicon-modified flame retardant polyurethane hot melt adhesive of a kind of wet-cured type and preparation method thereof, feature is the polyether Glycols for including 5~15 parts, 1~25 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~25 part of crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer, 10~40 parts of isocyanates, 0.1~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent.Elder generation's synthesis of hydroxy of the present invention sealing end it is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of butyl acrylate -), it is then added in base polyurethane prepolymer for use as, organic silicon acrylic ester copolymer segment and reactive flame retardant are introduced, the chemicals-resistant aging and flame retardant property of polyurethane gel are further promoted.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of organic-silicon-modified flame retardant polyurethane hot melt of wet-cured type
Glue and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry, timber
Material processing and furniture industry isostructuralism are 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 and 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 is different by cured form, can be divided into thermoplastic polyurethane elastomer hot melt
Glue and reactive polyurethane hot melt；Reactive polyurethane hot melt is different by its principle of solidification, can be divided into wet-cured type and envelope
Closed form；Research of Moisture-curable Polyurethane Hot-melt Adhesive (PUR) is a kind of one pack system hot melt adhesive, is melted after heating, and flow scatter coated in
Substrate surface cools down after adherend bonding and forms excellent first adhesive property, then since substrate surface contains micro-moisture
Or other compounds containing active hydrogen, it is reacted with isocyano (- NCO) and chemical crosslink reaction occurs, so that generating has height
A kind of structural bonding hot melt adhesive of cross-linked network and cohesive force greatly.
Currently, Research of Moisture-curable Polyurethane Hot-melt Adhesive has technically obtained unprecedented development, mainly around high-adhesive-strength,
Low melt viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised." reactivity heat disclosed in Chinese patent
Melt adhesive ", application number are 201480080313.0, are prepared a kind of with the removable polyurethane-hot melt bonding reprocessed
Agent, more suitable for high-end electronic product scope application." solvent-free damp solidifying polyurethane hotmelt disclosed in Chinese patent
Composition ", application number are 201180047316.0, prepare a kind of low toxicity and quickly establish adhesive property polyacrylate and polyester
The polyurethane-hot melt viscose binder of preparation.In order to improve the cured form of Research of Moisture-curable Polyurethane Hot-melt Adhesive, Chinese patent is disclosed
" organic silicon modified polyurethane sealant ", application number is 2017102717258, and it is close to prepare a kind of organic silicon modified polyurethane
Agent is sealed, replaces isocyano (- NCO) with silane coupling agent, is more suitable for applying under high humidity environment.Currently, wet-cured type polyurethane
The research and development technology of hot melt adhesive meets different type high-end electronic product scope application in fast development.Wet-cured type polyurethane heat
Although melten gel can form highly cross-linked network after hardening, there is also solvent resistant, ageing-resistant performance and heat resistance are not
Sufficient problem.This main cause is most of Research of Moisture-curable Polyurethane Hot-melt Adhesive to improve its initial cohesiveness, be joined a large amount of
Non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction system thickening resins can not participate in solidification life
At cross-linked network, to easily reduce the chemical resistance of polyurethane hot melt adhesive coating, heat resistance and ageing-resistant performance etc..
Summary of the invention
A kind of organic-silicon-modified fire-retardant poly- ammonia of wet-cured type is provided the purpose of the present invention is overcome the deficiencies in the prior art
Ester hot melt adhesive and preparation method thereof, since the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type passes through organic-silicon-modified and draws
Enter reactive flame retardant, improves chemical resistance, flame retardant property, heat resistance, waterproof performance of polyurethane coating etc..
In order to achieve the above object, the organic-silicon-modified flame retardant polyurethane hot melt adhesive technical solution of wet-cured type of the invention is
It is achieved, it is characterised in that including 5~15 parts of polyether Glycols, 1~25 part of liquid polyesters dihydric alcohol, 1~40 part
Flame retardant polyether polyol, 1~25 part of crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped phosphor-containing flame-proof poly-organosilicon
Acrylate copolymer, 10~40 parts of isocyanates, 0.1~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2
The silane coupling agent of part；It is above mass fraction；The hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer
Chemical structure is: it is hydroxy-end capped it is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate
Ester-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of butyl acrylate -) i.e. P(MAPDMS-r-MMA-r-
BA-r- HMP), average each macromolecular chain end is contained in hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer
1~2 hydroxy functional group, the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer 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 and 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 and polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
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 and 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.
In order to achieve the above object, wet-cured type of the invention organic-silicon-modified flame retardant polyurethane hot melt adhesive preparation method
Technical solution is achieved in that it is characterized in that preparation step is as follows:
Step 1 synthesis of hydroxy blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~30 part of methacrylic acid
Methyl esters MMA, 1~30 part of butyl acrylate BA and 5~25 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are molten
Solution is controlled in 40~100 DEG C in 50~100 parts of toluene, under nitrogen protection, 0.1~3 part of thermal initiator 4 is added,
4'- azo is bis- (4- cyano amylalcohol), polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtains hydroxy-end capped phosphorous
Fire-retardant poly-organosilicon acrylate copolymer, the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer
It is 1000~50000；The number-average molecular weight of methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is
1000；
Step 2 synthesizes the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type
By 5~15 parts of polyether Glycols, 1~25 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~
The hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate that the step of 25 parts of crystalline polyester dihydric alcohol, 5~40 parts one synthesizes
After copolymer, 0.1~1 part of catalyst and the mixing of 0.01~1 part of antioxidant, 120~150 DEG C are calorified, water removal is vacuumized
About 1~3 hour, until the water content of mixture is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, be added 10
~40 parts of isocyanates carries out polymerization reaction 1~5 hour, and sampling analysis polymerizate NCO% content reaches 1%~3%, 100
Tested viscosity reaches 3000~15000 mPa.s at DEG C, and 0.1~2 part of silane coupling agent is added, and obtains wet-cured type organosilicon
Modified flame-retardant polyurethane hot melt is mass fraction above.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
1, in the technical solution of the present invention, hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer is free using hydroxyl
Base initiator by organic silicon monomer (MAPDMS), acrylic ester monomer (MMA and BA) and fire-proof phosphorus-containing monomer (HMP) be copolymerized and
At hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer.Organic silicon monomer can promote the chemical-resistant of hot melt adhesive
Energy, heat resistance and ageing-resistant performance.Acrylic ester monomer can promote hot melt adhesive tack and cooling velocity.Fire-proof phosphorus-containing list
Body (HMP) can promote the flame retardant property and adhesive force of hot melt adhesive.Hydroxyl blocks phosphor-containing flame-proof poly-organosilicon acrylic ester copolymer
Object subparticipation is formulated efficiently synergistic effect to base polyurethane prepolymer for use as synthetic reaction, shows preferable compatibility, and further
Other raw material compositions and content are adjusted, chemical resistance, flame retardant property and adhesive force are improved.
2, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, improves thickening resin
With the compatibility of polyurethane, Research of Moisture-curable Polyurethane Hot-melt Adhesive solvent resistance is further solved；
3, the present invention solves the problems, such as that traditional Research of Moisture-curable Polyurethane Hot-melt Adhesive is poor to substrate wet performance, improves hot melt adhesive
The flow leveling of 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 organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer
7 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 10 parts of methyl methacrylate
MMA, 20 parts of butyl acrylate BA and 8 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 50 parts
In toluene, 60 DEG C are controlled in, under nitrogen protection, 2.4 parts of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), gathers
It closes reaction 5 hours and obtains hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer, hydroxyl after rotary evaporation removes toluene
The number-average molecular weight that base blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer is 11000, and chemical structure is: hydroxy-end capped
It is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-butyl acrylate-
Randomly -2- methyl -2- 2-hydroxyethyl acrylate phosphate) i.e. P(MAPDMS-r-MMA-r-BA-r-HMP), hydroxy-end capped
1~2 hydroxy functional group is contained in average each macromolecular chain end in phosphor-containing flame-proof poly-organosilicon acrylate copolymer；The first
The number-average molecular weight that base acryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type
5 parts of polyoxypropyleneglycol PPG, 25 parts of polyethylene glycol adipate glycol PEA, 15 parts of flame retarding polyether is polynary
The hydroxy-end capped phosphor-containing flame-proof that the step of alcohol WANOL FR-130,7360,15 parts of crystalline polyester dihydric alcohol of 15 parts one synthesizes
After poly-organosilicon acrylate copolymer, 0.2 part of phosphoric acid and the mixing of 0.08 part of irgasfos 168,120 DEG C are calorified, is taken out true
Sky water removal 2 hours cools down until the water content of mixture is lower than 280ppm in 80 DEG C, under nitrogen protection, is added 20 parts
4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane -), it carries out polymerization reaction 2 hours, sampling
Analysis polymerizate NCO% content reaches 1.5%, and viscosity reaches 4100 mPa.s, 0.5 part of silane coupling agent ND-42 is added,
The organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type is obtained, is above mass fraction；The polyoxypropyleneglycol PPG
Number-average molecular weight be 1000, the number-average molecular weight of the polyethylene glycol adipate glycol PEA is 500, uses Brookfield
DV-C digital viscometer viscosity, setting test temperature are 100 DEG C.
Embodiment two
It is a kind of organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer
13 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 25 parts of methyl methacrylate
MMA, 10 parts of butyl acrylate BA and 15 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 80 parts of first
In benzene, 65 DEG C are controlled in, under nitrogen protection, 1.5 parts of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), polymerization
Reaction 14 hours obtains hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer, hydroxyl after rotary evaporation removes toluene
The number-average molecular weight for blocking phosphor-containing flame-proof poly-organosilicon acrylate copolymer is 23000, and chemical structure is: hydroxy-end capped poly-
(methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-butyl acrylate-nothing
Rule -2- methyl -2- 2-hydroxyethyl acrylate phosphate) i.e. P(MAPDMS-r-MMA-r-BA-r-HMP), contain hydroxy-end capped
1~2 hydroxy functional group is contained in average each macromolecular chain end in the fire-retardant poly-organosilicon acrylate copolymer of phosphorus；The methyl
The number-average molecular weight that acryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type
By 10 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 25 parts of resistance
The hydroxyl envelope that the step of combustible polyether glycol WANOL FR-130,7380,20 parts of crystalline polyester dihydric alcohol of 20 parts one synthesizes
After holding phosphor-containing flame-proof poly-organosilicon acrylate copolymer, 0.3 part of triethanolamine and the mixing of 0.2 part of irgasfos 168, heating
In 130 DEG C, water removal 2.5 hours is vacuumized, until the water content of mixture is lower than 280ppm, cools down in 70 DEG C, is protected in nitrogen
Under shield, 27 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), it is polymerize
Reaction 4 hours, sampling analysis polymerizate NCO% content reach 1.9%, and viscosity reaches 5900 mPa.s, and 0.7 part of silane is added
Coupling agent ND-42 obtains the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, is above mass fraction；Described poly- four
The number-average molecular weight of hydrogen furans ether glycol PTMG is 2000, the equal molecule of number of polyadipate -1,6- hexylene glycol esterdiol PHA
Amount is 1000, and with Brookfield DV-C digital viscometer viscosity, it is 100 DEG C that test temperature, which is arranged,.
Embodiment three
It is a kind of organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer
15 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 25 parts of methyl methacrylate
MMA, 15 parts of butyl acrylate BA and 20 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 90 parts of first
In benzene, 75 DEG C are controlled in, under nitrogen protection, 0.5 part of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), polymerization
Reaction 10 hours obtains hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer, hydroxyl after rotary evaporation removes toluene
The number-average molecular weight for blocking phosphor-containing flame-proof poly-organosilicon acrylate copolymer is 33000, and chemical structure is: hydroxy-end capped poly-
(methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-butyl acrylate-nothing
Rule -2- methyl -2- 2-hydroxyethyl acrylate phosphate) i.e. P(MAPDMS-r-MMA-r-BA-r-HMP), contain hydroxy-end capped
1~2 hydroxy functional group is contained in average each macromolecular chain end in the fire-retardant poly-organosilicon acrylate copolymer of phosphorus；The methyl
The number-average molecular weight that acryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type
12 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 30 parts of flame retarding polyether is more
The hydroxy-end capped phosphor-containing flame-proof that first alcohol WANOL FR-312,20 parts of 7320,30 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After poly-organosilicon acrylate copolymer, 0.5 part of 2,2- dimorpholine base Anaesthetie Ether and the mixing of 0.7 part of antioxidant 1010,
150 DEG C are calorified, water removal 3 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 80 DEG C, in nitrogen
Under protection, 35 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), gathered
Reaction 4 hours is closed, sampling analysis polymerizate NCO% content reaches 2.4%, and viscosity reaches 7200 mPa.s, and 0.7 part of silicon is added
Alkane coupling agent ND-42 obtains the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, is above mass fraction；It is described poly-
The number-average molecular weight of propylene oxide glycol PPG is 3000, and the number-average molecular weight of the polyethylene glycol adipate glycol PEA is
1500, with Brookfield DV-C digital viscometer viscosity, it is 100 DEG C that test temperature, which is arranged,.
Example IV
It is a kind of organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer
20 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 15 parts of methyl methacrylate
MMA, 20 parts of butyl acrylate BA and 25 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 100 parts
In toluene, 75 DEG C are controlled in, under nitrogen protection, 0.3 part of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), gathers
It closes reaction 20 hours and obtains hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer, hydroxyl after rotary evaporation removes toluene
The number-average molecular weight that base blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer is 43000, and chemical structure is: hydroxy-end capped
It is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-butyl acrylate-
Randomly -2- methyl -2- 2-hydroxyethyl acrylate phosphate) i.e. P(MAPDMS-r-MMA-r-BA-r-HMP), hydroxy-end capped
1~2 hydroxy functional group is contained in average each macromolecular chain end in phosphor-containing flame-proof poly-organosilicon acrylate copolymer；The first
The number-average molecular weight that base acryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type
By 15 parts of polyoxypropyleneglycol PPG, 20 parts of polyadipate -1,4-butanediol esterdiol PBA, 35 parts fire-retardant poly-
Hydroxy-end capped the containing of the synthesis of the step of ethoxylated polyhydric alcohol WANOL FR-312,7360,35 parts of crystalline polyester dihydric alcohol of 25 parts one
After the fire-retardant poly-organosilicon acrylate copolymer of phosphorus, 1.0 parts of triethanolamine and the mixing of 0.8 part of irgasfos 168, calorify
150 DEG C, water removal 2 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 90 DEG C, under nitrogen protection,
40 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), carry out polymerization reaction 5
Hour, sampling analysis polymerizate NCO% content reaches 2.6%, and (100 DEG C of mPa.s@, Brookfield DV-C number is viscous for viscosity
Degree meter) 8700 mPa.s, 1.8 parts of silane coupling agent ND-42 is added, obtains the organic-silicon-modified flame retardant polyurethane heat of wet-cured type
Melten gel is mass fraction above；The number-average molecular weight of the polyoxypropyleneglycol PPG is 4000, the polyadipate -1,
The number-average molecular weight of 4- butyl glycol ester diol PBA is 2000, with Brookfield DV-C digital viscometer viscosity, setting
Test temperature is 100 DEG C.
Performance test
The ageing-resistant performance excellent flame that the present invention obtains the four kinds of above embodiments referring to the universal method of current hot melt adhesive
Damp solidifying polyurethane hot melt adhesive carries out melt viscosity, open hour, shore hardness, elongation at break, shear strength, oxygen index (OI)
With with the energy of resistance to acidity of oil index test.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, if
Set 100 DEG C.Open hour are tested referring to ASTM D4497-1994 (2004) method.Shore hardness is referring to GB-T2411-
2008 standards are tested.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is referring to GB/
T7124-2004 standard is tested.Oxygen index (OI) uses GB/T5454-1997 " textile combustion performance test-oxygen index method "
Measurement.The specific test method of chemical resistance index is to prepare sample with reference to test shear strength method, and it is small that sample places 72
When solidification after, sample is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, is placed in 85 DEG C and 85% relatively wet
It spends under environment, after carrying out aging 1000 hours, then carries out shear strength test.Water contact angle is marked with reference to GB/T 30693-2014
Standard is tested.All test data comparative situations are see the following table 1.
Each embodiment specific performance of table 1 tests control case
It can be seen that the wet-cured type organic-silicon-modified flame retardant polyurethane hot melt adhesive of the invention synthesized with excellent from the data of table 1
Good chemicals-resistant ageing properties 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 organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type, it is characterised in that including 5~15 parts of polyethers binary
Alcohol, 1~25 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~25 part of crystalline polyester dihydric alcohol,
5~40 parts of hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer, 10~40 parts of isocyanates, 0.1~1 part
Catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent；It is above mass fraction；It is described hydroxy-end capped
The chemical structure of phosphor-containing flame-proof poly-organosilicon acrylate copolymer is: hydroxy-end capped poly- (methacryloxypropyl list sealing end
Dimethyl polysiloxane-is random-and methyl methacrylate-is random-random -2- methyl -2- acrylic acid -2- hydroxyl of butyl acrylate -
Ethyl ester phosphate) i.e. P(MAPDMS-r-MMA-r-BA-r-HMP), in hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate
1~2 hydroxy functional group, hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylic acid are contained in average each macromolecular chain end in copolymer
The number-average molecular weight of ester copolymer is 1000~50000.
2. the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG and 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 and polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
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 and 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.
3. a kind of organic-silicon-modified flame retardant polyurethane hot melt adhesive preparation method of wet-cured type, it is characterised in that preparation step is as follows:
Step 1 synthesis of hydroxy blocks phosphor-containing flame-proof poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~30 part of methacrylic acid
Methyl esters MMA, 1~30 part of butyl acrylate BA and 5~25 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are molten
Solution is controlled in 40~100 DEG C in 50~100 parts of toluene, under nitrogen protection, 0.1~3 part of thermal initiator 4 is added,
4'- azo is bis- (4- cyano amylalcohol), polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtains hydroxy-end capped phosphorous
Fire-retardant poly-organosilicon acrylate copolymer, the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate copolymer
It is 1000~50000；The number-average molecular weight of methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is
1000；
Step 2 synthesizes the organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type
By 5~15 parts of polyether Glycols, 1~25 part of liquid polyesters dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~
The hydroxy-end capped phosphor-containing flame-proof poly-organosilicon acrylate that the step of 25 parts of crystalline polyester dihydric alcohol, 5~40 parts one synthesizes
After copolymer, 0.1~1 part of catalyst and the mixing of 0.01~1 part of antioxidant, 120~150 DEG C are calorified, water removal is vacuumized
About 1~3 hour, until the water content of mixture is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, be added 10
~40 parts of isocyanates carries out polymerization reaction 1~5 hour, and sampling analysis polymerizate NCO% content reaches 1%~3%, 100
Tested viscosity reaches 3000~15000 mPa.s at DEG C, and 0.1~2 part of silane coupling agent is added, and obtains wet-cured type organosilicon
Modified flame-retardant polyurethane hot melt is mass fraction above.
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| CN110746570A (en) * | 2019-10-30 | 2020-02-04 | 武汉港川科技有限公司 | Preparation method of multi-silicon modified waterborne light-cured resin and gloss oil application thereof |
| CN114774061A (en) * | 2022-06-07 | 2022-07-22 | 广州市盛邦康体场地材料有限公司 | Adhesive for prefabricated rubber track |
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| 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 |
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| CN104262553A (en) * | 2014-09-19 | 2015-01-07 | 厦门大学 | Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof |
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| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
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| CN114774061A (en) * | 2022-06-07 | 2022-07-22 | 广州市盛邦康体场地材料有限公司 | Adhesive for prefabricated rubber track |
| CN114774061B (en) * | 2022-06-07 | 2023-09-22 | 广州市盛邦康体场地材料有限公司 | A kind of adhesive for prefabricated rubber track bonding |
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Application publication date: 20190412 |
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