CN114479741B - Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof - Google Patents
Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof Download PDFInfo
- Publication number
- CN114479741B CN114479741B CN202210167533.3A CN202210167533A CN114479741B CN 114479741 B CN114479741 B CN 114479741B CN 202210167533 A CN202210167533 A CN 202210167533A CN 114479741 B CN114479741 B CN 114479741B
- Authority
- CN
- China
- Prior art keywords
- modified
- gas
- calcium oxide
- trimethoxy silane
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000565 sealant Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052710 silicon Inorganic materials 0.000 title abstract description 13
- 239000010703 silicon Substances 0.000 title abstract description 13
- 229920002396 Polyurea Polymers 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 37
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 239000003906 humectant Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 239000012767 functional filler Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000292 calcium oxide Substances 0.000 claims description 28
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 125000005442 diisocyanate group Chemical group 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- -1 titanate modified calcium oxide Chemical class 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- ZFDWSXUYIQGNHM-UHFFFAOYSA-N (6-methyl-1,1-diphenylheptyl) dihydrogen phosphate Chemical compound C=1C=CC=CC=1C(OP(O)(O)=O)(CCCCC(C)C)C1=CC=CC=C1 ZFDWSXUYIQGNHM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- KRJRKEPWQOASJN-UHFFFAOYSA-N aniline;trimethoxy(methyl)silane Chemical compound NC1=CC=CC=C1.CO[Si](C)(OC)OC KRJRKEPWQOASJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 5
- 239000012298 atmosphere Substances 0.000 claims 2
- VZVQCDBMSUPWDM-UHFFFAOYSA-L dicalcium hydrogen phosphate oxygen(2-) Chemical compound [O-2].[Ca+2].P(=O)([O-])([O-])O.[Ca+2] VZVQCDBMSUPWDM-UHFFFAOYSA-L 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical group O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims 1
- 238000001723 curing Methods 0.000 description 35
- FXMBKAAULHJRKL-UHFFFAOYSA-N [amino(dimethoxy)silyl]oxymethane Chemical compound CO[Si](N)(OC)OC FXMBKAAULHJRKL-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 12
- 239000004526 silane-modified polyether Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000004590 silicone sealant Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000013008 moisture curing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000013464 silicone adhesive Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method 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
- C09J175/02—Polyureas
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
-
- 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
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a single-component organosilicon modified sealant and a preparation method thereof. The single-component organic silicon modified sealant is prepared from the following raw materials: 15-40 parts of trimethoxy silane end-capped polyurea resin, 20-50 parts of reinforcing filler, 3-10 parts of functional filler, 10-50 parts of plasticizer, 0.2-1.5 parts of humectant, 0.1-2 parts of rheological agent, 0.5-2 parts of stabilizer, 0.5-2 parts of water removing agent, 0.5-2 parts of coupling agent and 0.1-3 parts of catalyst; the functional filler is surface modified calcium oxide. The deep curing depth of the single-component organosilicon modified sealant within 24 hours at low temperature (about 0 ℃) is more than or equal to 3mm, and the mechanical property after curing is good.
Description
Technical Field
The invention relates to the field of sealants, in particular to a low-temperature quick deep-curing single-component organosilicon modified sealant and a preparation method thereof.
Background
The traditional single-component silicone sealant and silane modified polyether sealant (MS glue) are bonded and sealed products which are in a macromolecular reticular structure and are initiated by water vapor in the air under the action of a catalyst to carry out cross-linking reaction under certain conditions. Under normal conditions, the depth (thickness) of 24h curing of the silane modified polyether adhesive is 3-4mm, while the depth of 24h curing of the silicone adhesive is only about 1-2mm, therefore, the fastest depth of 24h curing of the single-component silicone sealant is generally about 4mm, the single-component silicone sealant is cured from the outside to the inside, the single-component silicone sealant is obviously influenced by the external environment, the surface drying is slow when the temperature is low, the surface drying is fast when the temperature is high, when the temperature of the use environment is low, the activity of a catalyst is low, and the moisture curing reaction speed is very slow, so that the curing speed of the single-component silicone sealant is slow, particularly when the temperature is low in north China (about 0-5 ℃), the curing speed of the silane modified polyether adhesive is only about 1mm or even lower, if the depth (thickness) of the larger colloid is needed, the very long time is often needed, great inconvenience is brought to the construction operation, and the application of the single-component silicone sealant is limited to a certain extent.
Disclosure of Invention
Aiming at the problems, the invention provides the single-component organic silicon modified sealant which can be quickly and deeply cured at low temperature, wherein the deep curing depth of the single-component organic silicon modified sealant within 24 hours at low temperature (about 0 ℃) is more than or equal to 3mm, and the mechanical property after curing is good. The invention comprises the following technical scheme.
The single-component organic silicon modified sealant is prepared from the following raw materials in parts by weight:
the functional filler is surface modified calcium oxide.
In some embodiments, the single-component silicone modified sealant is prepared from the following raw materials:
in some embodiments, the trimethoxy silane terminated polyurea resin is obtained by reacting a polyurea prepolymer and amino trimethoxy silane, wherein the polyurea prepolymer is obtained by reacting polyether amine and diisocyanate.
In some of these embodiments, the molar ratio of amine groups in the polyetheramine to NCO groups in the diisocyanate is 1:1.2-1.5.
In some of these embodiments, the molar ratio of NCO groups to aminotrimethoxysilane in the polyurea prepolymer is from 1.
In some of these embodiments, the polyetheramine has a molecular weight of 100 to 3000.
In some of these embodiments, the polyetheramine is selected from at least one of D230, D400, and D2000 of hensme, usa.
In some of these embodiments, the diisocyanate is selected from at least one of Hexamethylene Diisocyanate (HDI), diphenylmethane 4,4' -diisocyanate (MDI), IPDI trimer, and Toluene Diisocyanate (TDI).
In some of these embodiments, the amino trimethoxysilane has a molecular weight of 100 to 2000.
In some of these embodiments, the aminotrimethoxysilane is selected from at least one of gamma-aminopropyltrimethoxysilane (KH-540), N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), and anilinomethyltrimethoxysilane (coupling agent Nanda-73).
In some of these embodiments, the method of preparing the trimethoxysilane terminated polyurea resin comprises the following steps:
(1) Adding polyether amine into a reaction kettle, adding diisocyanate, and reacting for 2-4 h under the protection of nitrogen or inert gas to obtain a polyurea prepolymer;
(2) And under the protection of nitrogen or inert gas, adding amino trimethoxy silane into the polyurea prepolymer, and stirring for reacting for 2-4 h to obtain the trimethoxy silane end-capped polyurea resin.
In some of these embodiments, the surface-modified calcium oxide is selected from at least one of stearic acid-modified calcium oxide, silane coupling agent-modified calcium oxide, and titanate-modified calcium oxide.
In some of these embodiments, the silane coupling agent modified calcium oxide is gamma-methacryloxypropyltrimethoxysilane modified calcium oxide; the titanate modified calcium oxide is calcium oxide modified by isopropyl triisostearate.
In some of these embodiments, the method of preparing the surface-modified calcium oxide comprises the steps of: reacting calcium oxide with a surface modifier in an organic solvent, filtering and drying to obtain the calcium oxide-calcium-magnesium-calcium composite material.
In some of these embodiments, the surface modifying agent is selected from at least one of stearic acid, a silane coupling agent, and a titanate ester, more preferably at least one of stearic acid, gamma-methacryloxypropyltrimethoxysilane, and isopropyl triisostearate.
In some of these embodiments, the surface modifier is 3-10% by mass of the calcium oxide.
In some of these embodiments, the organic solvent is toluene.
In some of these embodiments, the temperature of the reaction is from 30 ℃ to 40 ℃ and the time of the reaction is from 0.5 hours to 1.5 hours.
In some of these embodiments, the humectant is a polyol humectant.
In some of these embodiments, the polyhydric alcohol humectant is selected from at least one of glycerin, polyethylene glycol, and butylene glycol.
In some of these embodiments, the reinforcing filler is selected from at least one of nano-activated calcium carbonate, micro-silica powder, ground calcium carbonate, or talc.
In some of these embodiments, the plasticizer is selected from at least one of dioctyl phthalate, dioctyl adipate, diphenyl mono isooctyl phosphate, and polypropylene glycol.
In some of these embodiments, the rheological agent is selected from at least one of polyamide wax, hydrogenated castor oil, organic bentonite, and fumed silica.
In some of these embodiments, the stabilizer is a basf light stabilizer 770, a basf light stabilizer 328, and/or a basf light stabilizer 326.
In some of these embodiments, the water scavenger is a silane based water scavenger containing a vinyl functionality, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, or a mixture thereof.
In some of these embodiments, the coupling agent is an aminosilane-based coupling agent, which may be, for example, at least one of Dow Corning KH-540, KH-550, KH-792, and KH-560.
In some of these embodiments, the catalyst is selected from at least one of dibutyltin dilaurate, dioctyltin diacetate, and stannous octoate.
In some embodiments, the single-component silicone modified sealant is prepared from the following raw materials:
the trimethoxy silane end-capped polyurea resin is obtained by the reaction of a polyurea prepolymer and aniline methyl trimethoxy silane, the polyurea prepolymer is obtained by the reaction of polyether amine D2000 and IPDI tripolymer, the molar ratio of amine groups in the polyether amine D2000 to NCO groups in the IPDI tripolymer is 1:1.2-1.3, wherein the molar ratio of NCO groups in the polyurea prepolymer to amino trimethoxy silane is 0.95-1.05;
the reinforcing filler is a combination of nano active calcium carbonate and heavy calcium carbonate with the mass ratio of 1-2;
the titanate modified calcium oxide is calcium oxide modified by isopropyl triisostearate.
The invention also provides a preparation method of the single-component organic silicon modified sealant, which comprises the following technical scheme.
The preparation method of the single-component organic silicon modified sealant comprises the following steps:
kneading the trimethoxy silane terminated polyurea resin, the reinforcing filler, the functional filler, the rheological agent, the stabilizer, the humectant and part of the plasticizer for 1 to 3 hours under the conditions that the temperature is between 100 and 130 ℃ and the vacuum degree is between-0.09 and-0.1 MPa to obtain a base material;
and cooling the base material to the temperature of below 50 ℃, sequentially adding the rest of the plasticizer, the water removing agent, the coupling agent and the catalyst, stirring for 0.5 to 1 hour under the condition that the vacuum degree is-0.09 MPa to-0.1 MPa, and discharging to obtain the single-component organosilicon modified sealant.
The single-component organic silicon modified sealant which can be rapidly and deeply cured at low temperature is prepared by taking trimethoxy silane terminated polyurea resin as a basic polymer, taking a humectant, a surface modified calcium oxide filler serving as a functional filler, a rheological agent and the like as auxiliary materials and reasonably adjusting the proportion of the components, and has the following characteristics and advantages:
(1) Compared with the traditional organic silicon resin (silane modified polyether polymer, 107 glue), the silane terminated polyurea resin is trimethoxy silane terminated carbamido polymer, and the trimethoxy silane terminated polyurea resin has stronger hydrolytic activity compared with dimethoxy silane, triethoxy silane or other alkoxy silane terminated polyurea resin under similar chain end structure and is due to electron-withdrawing groups in the structure
The induction effect is strong, and the hydrolysis and polymerization activity of the alkoxy can be greatly enhanced, so that the curing speed and the crosslinking density of the sealant system can be accelerated.
(2) The humectant is added, so that the moisture required in the moisture curing reaction can be provided for the organosilicon sealant system in a low-temperature environment, and the deep curing reaction speed can be maintained.
(3) Compared with the traditional organosilicon sealants such as silane modified polyether adhesive, silicone adhesive and the like, the single-component organosilicon modified sealant capable of being rapidly and deeply cured at low temperature is added with surface modified calcium oxide as functional filler, on one hand, the modified calcium oxide can be well compatible with a sealant system, on the other hand, the calcium oxide can easily react with water and emit a large amount of heat, so that the surface temperature of a sealing colloid is increased, the activity of a catalyst is further increased, the deep reaction rate of moisture curing is increased, the problem of low-temperature curing rate of the organosilicon sealant is solved, and the application range is expanded.
(4) The single-component organosilicon modified sealant disclosed by the invention is characterized in that the trimethoxy silane end-capped polyurea resin, the humectant, the surface modified calcium oxide filler serving as a functional filler and other auxiliary materials are matched with each other in a proper proportion, so that the sealant has the advantage of high low-temperature curing speed, the deep curing depth is more than or equal to 3mm within 24 hours at low temperature (about 0 ℃), and the mechanical property after curing is good.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or apparatus that comprises a list of steps is not limited to only those steps or modules recited, but may alternatively include other steps not recited, or may alternatively include other steps inherent to such process, method, article, or apparatus.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The following are specific examples.
Example 1
The single-component organosilicon modified sealant provided by the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the trimethoxy silane end-capped polyurea resin comprises the following steps:
(1) Adding polyether amine D230 (with the molecular weight of 230) into a reaction kettle, wherein the molar ratio of amine groups in the polyether amine to NCO groups in diisocyanate is 1:1.2, slowly adding diisocyanate HDI under low-speed stirring, and reacting for 3h under the condition of room temperature under the protection of nitrogen to obtain the polyurea Prepolymer (PUA).
(2) Under the protection of nitrogen, adding amino trimethoxy silane (KH-540) into the PUA prepared in the step 1 according to the molar ratio of NCO to amino trimethoxy silane being 1.8, and reacting at low speed for about 3 hours at room temperature until no isocyanate group exists in a reaction system as measured by a di-n-butylamine back titration method, so as to prepare the trimethoxy silane terminated polyurea resin.
The preparation method of the calcium oxide with the surface modified by the hard fatty acid comprises the following steps:
adding CaO and stearic acid with the mass being 3% of the CaO into a reaction kettle filled with toluene with one half of the mass of the CaO, stirring and reacting for 1.5h at the temperature of 30 ℃ at the rotating speed of 15rpm, extracting with an organic filter membrane to obtain a solid sample, drying and grinding into powder to obtain the stearic acid modified calcium oxide.
The preparation method of the single-component organosilicon modified sealant capable of being rapidly and deeply cured at low temperature comprises the following steps:
kneading the trimethoxy silane end-capped polyurea resin, a reinforcing filler (nano active calcium carbonate), a functional filler (hard fatty acid modified calcium oxide), a rheological agent (fumed silica), a stabilizer, a humectant (glycerin) and 25 parts of a plasticizer (dioctyl phthalate) for 2 hours at the temperature of 100 ℃ and the vacuum degree of-0.09 MPa to obtain a base material;
and cooling the base material to a temperature lower than 50 ℃, sequentially adding the rest of the plasticizer, the water removing agent (vinyl triethoxysilane), the coupling agent (KH-540) and the catalyst (dibutyltin dilaurate), stirring for 0.5 hour under the condition that the vacuum degree is-0.09 MPa, and discharging to obtain the low-temperature rapidly deep-cured single-component organosilicon modified sealant.
Example 2
The single-component organosilicon modified sealant provided by the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the trimethoxy silane end-capped polyurea resin comprises the following steps:
(1) Adding polyetheramine D400 (with the molecular weight of 400) into a reaction kettle, wherein the molar ratio of amine groups in the polyetheramine to NCO groups in diisocyanate is 1:1.5, slowly adding diisocyanate MDI under low-speed stirring, and reacting for 3 hours at room temperature under the protection of nitrogen to obtain the polyurea Prepolymer (PUA).
(2) Under the protection of nitrogen, adding amino trimethoxy silane (KH-792) into the PUA prepared in the step 1 according to the NCO to amino trimethoxy silane molar ratio of 1.2, and reacting at low speed for about 3 hours at room temperature until the reaction is finished when no isocyanate group exists in a reaction system as measured by a di-n-butylamine back titration method, thereby preparing the trimethoxy silane end-capped polyurea resin.
Wherein the preparation method of the silane coupling agent modified calcium oxide comprises the following steps:
adding CaO and gamma-methacryloxypropyltrimethoxysilane (KH-570) accounting for 10% of the mass of the CaO into a reaction kettle containing toluene accounting for one half of the mass of the CaO, stirring and reacting at the temperature of 40 ℃ at the rotating speed of 25rpm for 0.5h, extracting with an organic filter membrane to obtain a solid sample, drying, and grinding into powder to obtain the silane coupling agent modified calcium oxide.
The preparation method of the single-component organosilicon modified sealant capable of being rapidly and deeply cured at low temperature comprises the following steps:
kneading the trimethoxy silane terminated polyurea resin, a reinforcing filler (talcum powder), a functional filler (silane coupling agent modified calcium oxide), a rheological agent (polyamide wax), a stabilizer, a humectant (butanediol) and 15.5 parts of a plasticizer (PPG 3000) for 3 hours at the temperature of 110 ℃ and the vacuum degree of-0.1 MPa to obtain a base material;
and cooling the base material to a temperature lower than 50 ℃, sequentially adding the remaining 5 parts of plasticizer, water scavenger (vinyltrimethoxysilane), coupling agent (KH-550) and catalyst (dioctyltin diacetate), stirring for 1 hour under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the low-temperature quick deep-curing single-component organosilicon modified sealant.
Example 3
The single-component organosilicon modified sealant provided by the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the trimethoxy silane end-capped polyurea resin comprises the following steps:
(1) Adding polyether amine D2000 (with the molecular weight of 2000) into a reaction kettle, wherein the molar ratio of amine groups in the polyether amine to NCO groups in diisocyanate is 1:1.25, slowly adding diisocyanate IPDI under low-speed stirring, and reacting for 3h under the condition of room temperature under the protection of nitrogen to obtain the polyurea Prepolymer (PUA).
(2) Under the protection of nitrogen, adding amino trimethoxy silane (Nada-73) into the PUA prepared in the step 1 according to the NCO to amino trimethoxy silane molar ratio of 1, and reacting at low speed for about 3 hours at room temperature until no isocyanate group exists in a reaction system measured by a dibutyl amine back titration method, thus preparing the trimethoxy silane end-capped polyurea resin.
The titanate modified calcium oxide comprises the following steps:
adding CaO and isopropyl triisostearate accounting for 5% of CaO in mass into a reaction kettle filled with toluene accounting for one half of CaO in mass, stirring and reacting at the rotating speed of 20rpm for 1h at the temperature of 35 ℃, extracting an organic filter membrane to obtain a solid sample, drying and grinding the solid sample into powder to obtain the titanate modified calcium oxide.
The preparation method of the single-component organosilicon modified sealant capable of being rapidly and deeply cured at low temperature comprises the following steps:
kneading the trimethoxy silane end-capped polyurea resin, reinforcing fillers (nano active calcium carbonate and heavy calcium carbonate), functional fillers (titanate modified calcium oxide), a rheological agent (hydrogenated castor oil), a stabilizer, a humectant (polyethylene glycol) and 10 parts of a plasticizer (diphenyl-isooctyl phosphate) for 3 hours under the conditions that the temperature is 110 ℃ and the vacuum degree is-0.1 MPa to obtain a base material;
and cooling the base material to a temperature lower than 50 ℃, sequentially adding the rest 4.5 parts of plasticizer, dehydrator (vinyl trimethoxy silane), coupling agent (KH-792) and catalyst (stannous octoate), stirring for 1 hour under the condition that the vacuum degree is-0.09 MPa, and discharging to obtain the low-temperature quick deep-curing single-component organosilicon modified sealant.
Comparative example 1:
the difference between the single-component organosilicon modified sealant which is provided by the comparative example and can be quickly and deeply cured at a low temperature and the embodiment 1 is that triethoxysilane terminated polyurea resin is used for replacing the trimethoxysilane terminated polyurea resin in the embodiment 1, and the sealant is specifically prepared from the following raw materials in parts by weight:
the preparation method of the triethoxysilane-terminated polyurea resin comprises the following steps:
(1) Adding polyether amine D230 (with the molecular weight of 230) into a reaction kettle, wherein the molar ratio of amine groups in the polyether amine to NCO groups in diisocyanate is 1:1.2, slowly adding diisocyanate HDI under low-speed stirring, and reacting for 3 hours at room temperature under the protection of nitrogen to obtain the polyurea Prepolymer (PUA).
(2) Adding gamma-aminopropyltriethoxysilane (KH 550) into the PUA prepared in the step 1 according to the molar ratio of NCO to gamma-aminopropyltriethoxysilane being 1.8 under the protection of nitrogen, and stirring at a low speed for reaction for about 3 hours at room temperature until the reaction system is free from isocyanate groups as measured by a di-n-butylamine back titration method, so as to obtain the triethoxysilane-terminated polyurea resin.
The preparation method of the calcium oxide with the surface modified by the stearic acid comprises the following steps:
adding CaO and stearic acid accounting for 3% of the CaO in mass into a reaction kettle containing toluene accounting for one half of the CaO in mass, stirring and reacting for 1.5 hours at the temperature of 30 ℃ at the rotating speed of 15rpm, extracting with an organic filter membrane to obtain a solid sample, drying and grinding the solid sample into powder to obtain the stearic acid modified calcium oxide.
The preparation method of the single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature in the comparison example comprises the following steps:
kneading the triethoxysilane-terminated polyurea resin, a reinforcing filler (nano activated calcium carbonate), a functional filler (hard fatty acid modified calcium oxide), a rheological agent (fumed silica), a stabilizer, a humectant (glycerin) and 25 parts of a plasticizer (dioctyl phthalate) for 2 hours under the conditions that the temperature is 100 ℃ and the vacuum degree is-0.09 MPa to obtain a base material;
and cooling the base material to a temperature lower than 50 ℃, sequentially adding the rest of the plasticizer, the water removing agent (vinyl triethoxysilane), the coupling agent (KH-540) and the catalyst (dibutyltin dilaurate), stirring for 0.5 hour under the condition that the vacuum degree is-0.09 MPa, and discharging to obtain the low-temperature rapidly deep-cured single-component organosilicon modified sealant.
Comparative example 2:
the single-component organosilicon modified sealant which is provided by the comparative example and can be quickly and deeply cured at low temperature is different from the sealant in the example 2 in that the silane coupling agent modified calcium oxide is not added, and the sealant is specifically prepared from the following raw materials in parts by weight:
the preparation method of the trimethoxy silane end-capped polyurea resin comprises the following steps:
(1) Adding polyetheramine D400 (with the molecular weight of 400) into a reaction kettle, wherein the molar ratio of amine groups in the polyetheramine to NCO groups in diisocyanate is 1:1.5, slowly adding diisocyanate MDI under low-speed stirring, and reacting for 3h under the condition of room temperature under the protection of nitrogen to obtain the polyurea Prepolymer (PUA).
(2) Under the protection of nitrogen, adding amino trimethoxy silane (KH-792) into the PUA prepared in the step 1 according to the NCO to amino trimethoxy silane molar ratio of 1.2, and reacting at low speed for about 3 hours at room temperature until the reaction is finished when no isocyanate group exists in a reaction system as measured by a di-n-butylamine back titration method, thereby preparing the trimethoxy silane end-capped polyurea resin.
The preparation method of the single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature in the comparison example comprises the following steps:
kneading the trimethoxy silane terminated polyurea resin, a reinforcing filler (talcum powder), a rheological agent (polyamide wax), a stabilizer, a humectant (butanediol) and 15.5 parts of a plasticizer (PPG 3000) for 3 hours at the temperature of 110 ℃ and the vacuum degree of-0.1 MPa to obtain a base material;
and cooling the base material to a temperature lower than 50 ℃, sequentially adding the remaining 5 parts of plasticizer, water scavenger (vinyltrimethoxysilane), coupling agent (KH-550) and catalyst (dioctyltin diacetate), stirring for 1 hour under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the low-temperature quick deep-curing single-component organosilicon modified sealant.
Comparative example 3
The difference between the single-component organosilicon modified sealant which is provided by the comparative example and can be quickly and deeply cured at low temperature and is prepared from the following raw materials in parts by weight without adding a humectant:
the preparation method of the trimethoxy silane end-capped polyurea resin comprises the following steps:
(1) Adding polyether amine D2000 (with the molecular weight of 2000) into a reaction kettle, wherein the molar ratio of amine groups in the polyether amine to NCO groups in diisocyanate is 1:1.25, slowly adding diisocyanate IPDI under low-speed stirring, and reacting for 3h under the condition of room temperature under the protection of nitrogen to obtain the polyurea Prepolymer (PUA).
(2) Under the protection of nitrogen, adding amino trimethoxy silane (Nada-73) into the PUA prepared in the step 1 according to the molar ratio of NCO to amino trimethoxy silane being 1, stirring at a low speed at room temperature for reacting for about 3 hours until no isocyanate group exists in a reaction system measured by a di-n-butylamine back titration method, and finishing the reaction to prepare the trimethoxy silane end-capped polyurea resin.
The titanate-modified calcium oxide comprises the following steps:
adding CaO and 5% isopropyl triisostearate of CaO in mass into a reaction kettle containing toluene with one half of CaO in mass, stirring and reacting at the rotation speed of 20rpm for 1h at the temperature of 35 ℃, extracting an organic filter membrane to obtain a solid sample, drying, and grinding into powder to obtain the titanate modified calcium oxide.
The preparation method of the single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature in the comparison example comprises the following steps:
kneading the trimethoxy silane end-capped polyurea resin, reinforcing fillers (nano active calcium carbonate and heavy calcium carbonate), functional fillers (titanate modified calcium oxide), a rheological agent (hydrogenated castor oil), a stabilizer and 10 parts of a plasticizer (diphenyl-isooctyl phosphate) for 3 hours at the temperature of 110 ℃ and the vacuum degree of-0.1 MPa to obtain a base material;
and cooling the base material to a temperature lower than 50 ℃, sequentially adding the rest 4.5 parts of plasticizer, dehydrator (vinyl trimethoxy silane), coupling agent (KH-792) and catalyst (stannous octoate), stirring for 1 hour under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the low-temperature quick deep-curing single-component organosilicon modified sealant.
Comparative example 4
The silane modified polyether adhesive 331 which is sold on the market and is produced by a certain product with better curing depth is selected.
The single-component organosilicon modified sealant prepared in the examples 1-3 and the comparative examples 1-4 and capable of being rapidly and deeply cured at low temperature is subjected to the following performance tests, and the test method is as follows:
deep curing: the samples prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to 24-hour curing depth test in three conditions of 23 ℃ RH, 50% RH, (2) 0 ℃ and (3) 10 ℃ according to GB/T32369-2015 "determination of sealant curing degree" appendix A curing cup method.
Surface drying time: testing according to GB/T13477.5-2003. Under the conditions of (23 +/-2) DEG C and (50 +/-10) percent RH, the adhesive tape is extruded on a clean glass plate, the surface of the adhesive tape is lightly touched by fingers every 1min until the adhesive tape is not sticky, namely the surface drying time.
Hardness: tested according to GB/T531-1999.
Tensile strength and elongation at break: tested according to GB/T528-2009. Placing a mould on a PE film, injecting the sealant into the mould by using a glue gun, scraping by using a scraper, removing the redundant sealant, taking the mould from the film, curing and curing for 7 days at the glue layer thickness of 2.5-3.0mm under the conditions of the temperature of (23 +/-2) DEG C and (50 +/-10)% RH, taking out the film, cutting the film into dumbbell-shaped test pieces with specified sizes, and testing the tensile strength and the elongation at normal temperature at the tensile speed of 500 mm/min.
Tensile shear strength: tested according to GB/T7124-2008. The lap length of the standard sample is (10.0 +/-0.5) mm, and the thickness of the adhesive glue layer is 0.2mm. The bonding base material is anodic aluminum oxide, the anodic aluminum oxide is wiped by ethyl acetate, the anodic aluminum oxide is dried at the temperature of 105-110 ℃, and the anodic aluminum oxide is put into a dryer for standby. After the test pieces were bonded with an adhesive, they were cured at (23. + -. 2) ° C and (50. + -. 10)% RH for 7 days and then tested, and the failure type (CF: cohesive failure, AF: interfacial failure) was recorded as specified in GB/T169997.
Table 1:24h sealant deep layer solidification test result (mm/24 h)
Table 2: basic mechanical property test results
As can be seen from the experimental results in Table 1, the sealants prepared in examples 1-3 and comparative examples 1-4 all had better curing rates and 24h curing depths of 4mm or more at 23 ℃ and 50% RH, but the one-component silicone modified sealants prepared in examples 1-3 all had 24h curing depths of 3.3mm or more and better than the 24h curing depths (all < 3 mm) of comparative examples 1-4 at 0 ℃, and the conventional silane modified polyether gum commercially available in comparative example 4 was only 1.27mm and had slow curing rates compared to examples 1-3 and comparative examples 1-3, thus limiting the use thereof, which also indicates that the silane terminated polyurea polymer prepared by using the present invention has higher activity. Under the condition of-10 ℃, the curing depth of the single-component organosilicon modified sealant prepared in the examples 1-3 can still reach more than 1.2mm after 24 hours, and the curing depth of the single-component organosilicon modified sealant prepared in the example 3 can still approach 2mm after 24 hours, which shows that the sealant still has better deep curing capability in a low-temperature environment of-10 ℃; the single-component organosilicon modified sealants prepared in comparative examples 1 to 4 have curing depths of less than 1mm after 24 hours, and the conventional silane modified polyether adhesive sold on the market is only 0.38mm.
The mechanical results in table 2 show that compared with the conventional silane modified polyether adhesive in the market, the organosilicon modified sealant prepared by the invention also has better mechanical properties. Therefore, the single-component silicone sealant capable of being rapidly and deeply cured prepared by the invention has the curing depth of more than 3mm within 24h at normal temperature or low temperature (0 ℃), has better mechanical property after being completely cured, and even has the curing depth of more than 1.2mm within 24h at-10 ℃ (equivalent to the curing depth of silicone adhesive within 24h under the common condition), thereby expanding the use of the silicone sealant in the low-temperature environment.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (19)
1. The single-component organosilicon modified sealant is characterized by being prepared from the following raw materials in parts by weight:
the functional filler is surface modified calcium oxide;
the trimethoxy silane terminated polyurea resin is obtained by the reaction of polyurea prepolymer and amino-containing trimethoxy silane, and the polyurea prepolymer is obtained by the reaction of polyether amine and diisocyanate.
2. The single-component organosilicon modified sealant as claimed in claim 1, is prepared from raw materials comprising:
3. the one-component silicone modified sealant according to claim 1, wherein the molar ratio of amine groups in the polyether amine to NCO groups in the diisocyanate is 1: 1.2-1.5; and/or the presence of a gas in the gas,
the molar ratio of NCO group in the polyurea prepolymer to amino-containing trimethoxy silane is 1: 0.8-1.2; and/or the presence of a gas in the gas,
the molecular weight of the polyether amine is 100-3000; and/or the presence of a gas in the atmosphere,
the molecular weight of the amino-containing trimethoxy silane is 100-2000.
4. The one-part silicone modified sealant according to claim 3, wherein said polyetheramine is selected from at least one of D230, D400 and D2000 from Hensmai corporation, USA.
5. The one-component silicone modified sealant according to claim 3, wherein said diisocyanate is at least one member selected from the group consisting of hexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, IPDI trimer and toluene diisocyanate.
6. The one-part silicone modified sealant according to claim 3, wherein the amino group-containing trimethoxysilane is at least one member selected from the group consisting of γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane and anilinomethyltrimethoxysilane.
7. The one-component silicone modified sealant according to claim 1, wherein the preparation method of the trimethoxysilane terminated polyurea resin comprises the following steps:
(1) Adding polyether amine into a reaction kettle, adding diisocyanate, and reacting for 2-4 h under the protection of nitrogen or inert gas to obtain a polyurea prepolymer;
(2) Under the protection of nitrogen or inert gas, adding amino-containing trimethoxy silane into the polyurea prepolymer, and stirring for reaction for 2-4 h to obtain the trimethoxy silane end-capped polyurea resin.
8. The one-component silicone modified sealant according to any of claims 1 to 7, wherein the surface-modified calcium oxide is selected from at least one of stearic acid-modified calcium oxide, silane coupling agent-modified calcium oxide, and titanate-modified calcium oxide;
the calcium oxide modified by the silane coupling agent is calcium oxide modified by gamma-methacryloxypropyltrimethoxysilane;
the titanate modified calcium oxide is calcium oxide modified by isopropyl triisostearate.
9. The one-component silicone-modified sealant according to any one of claims 1 to 7, wherein the surface-modified calcium oxide is prepared by a method comprising the steps of:
reacting calcium oxide with a surface modifier in an organic solvent, filtering and drying to obtain the calcium oxide-calcium phosphate.
10. The one-part silicone modified sealant according to claim 9, wherein the surface modifying agent is at least one selected from stearic acid, silane coupling agents and titanates.
11. The one-part silicone modified sealant according to claim 10, wherein said surface modifier is at least one member selected from the group consisting of stearic acid, gamma-methacryloxypropyltrimethoxysilane, and isopropyl triisostearate.
12. The one-component silicone modified sealant according to claim 9, wherein the surface modifier is 3-10% by mass of calcium oxide.
13. The one-component silicone modified sealant according to claim 9, wherein the organic solvent is toluene; the reaction temperature is 30-40 ℃, and the reaction time is 0.5-1.5 hours.
14. The one-component silicone modified sealant according to any one of claims 1 to 7, characterized in that,
the humectant is a polyalcohol humectant; and/or the presence of a gas in the gas,
the reinforcing filler is selected from at least one of nano active calcium carbonate, silica micropowder, ground calcium carbonate or talcum powder; and/or the presence of a gas in the atmosphere,
the plasticizer is selected from at least one of dioctyl phthalate, dioctyl adipate, diphenyl-isooctyl phosphate and polypropylene glycol; and/or the presence of a gas in the gas,
the rheological agent is selected from at least one of polyamide wax, hydrogenated castor oil, organic bentonite and fumed silica; and/or the presence of a gas in the gas,
the stabilizer is a basf light stabilizer 770, a basf light stabilizer 328, and/or a basf light stabilizer 326; and/or the presence of a gas in the gas,
the water removing agent is a silane water removing agent containing vinyl functional groups; and/or the presence of a gas in the gas,
the coupling agent is an amino silane coupling agent; and/or the presence of a gas in the gas,
the catalyst is at least one of dibutyltin dilaurate, dioctyltin diacetate and stannous octoate.
15. The one-part silicone modified sealant of claim 14, wherein said humectant is selected from at least one of glycerin, polyethylene glycol, and butylene glycol.
16. The one-part silicone modified sealant according to claim 14, wherein the water scavenger is at least one member selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldimethoxysilane.
17. The one-part silicone modified sealant according to claim 14, wherein said coupling agent is selected from the group consisting of KH-540, KH-550, KH-792.
18. The single-component organosilicon modified sealant as claimed in claim 1, is prepared from raw materials comprising:
the trimethoxy silane end-capped polyurea resin is obtained by the reaction of polyurea prepolymer and aniline methyl trimethoxy silane, the polyurea prepolymer is obtained by the reaction of polyether amine D2000 and IPDI tripolymer, the molar ratio of amine group in the polyether amine D2000 to NCO group in the IPDI tripolymer is 1:1.2-1.3, and the molar ratio of NCO group in the polyurea prepolymer to amino-containing trimethoxy silane is 1: 0.95-1.05;
the reinforcing filler is a combination of nano active calcium carbonate and heavy calcium carbonate with the mass ratio of 1-2: 1;
the titanate modified calcium oxide is calcium oxide modified by isopropyl triisostearate.
19. A method of preparing the one-component silicone modified sealant according to any one of claims 1 to 18, comprising the steps of:
kneading the trimethoxy silane terminated polyurea resin, the reinforcing filler, the functional filler, the rheological agent, the stabilizer, the humectant and part of the plasticizer for 1 to 3 hours under the conditions that the temperature is between 100 and 130 ℃ and the vacuum degree is between-0.09 and-0.1 MPa to obtain a base material;
and cooling the base material to the temperature of below 50 ℃, sequentially adding the rest of the plasticizer, the water removing agent, the coupling agent and the catalyst, stirring for 0.5 to 1 hour under the condition that the vacuum degree is-0.09 MPa to-0.1 MPa, and discharging to obtain the single-component organosilicon modified sealant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210167533.3A CN114479741B (en) | 2022-02-23 | 2022-02-23 | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof |
| PCT/CN2022/141393 WO2023160197A1 (en) | 2022-02-23 | 2022-12-23 | Single-component organic silicon-modified sealant capable of being rapidly deep-layer cured at low temperature, and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210167533.3A CN114479741B (en) | 2022-02-23 | 2022-02-23 | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114479741A CN114479741A (en) | 2022-05-13 |
| CN114479741B true CN114479741B (en) | 2023-03-31 |
Family
ID=81481780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210167533.3A Active CN114479741B (en) | 2022-02-23 | 2022-02-23 | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114479741B (en) |
| WO (1) | WO2023160197A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479741B (en) * | 2022-02-23 | 2023-03-31 | 广州市白云化工实业有限公司 | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998018843A1 (en) * | 1996-10-31 | 1998-05-07 | Minnesota Mining And Manufacturing Company | Moisture curable alkoxysilane functional poly(ether-urethane) based sealants |
| EP1462500A1 (en) * | 2003-03-28 | 2004-09-29 | Le Joint Francais | Single component, chemically curing warm applied sealant for durable insulating glazing units |
| ATE540065T1 (en) * | 2006-04-18 | 2012-01-15 | Henkel Ag & Co Kgaa | ORGANOSILICONE POLYUREA BASED POLYMERS, ELASTOMERS PRODUCED THEREOF AND THEIR USE |
| US7781513B2 (en) * | 2007-11-14 | 2010-08-24 | Momentive Performance Materials Inc. | Two-part moisture-curable resin composition and adhesive, sealant and coating compositions based thereon |
| US8378037B2 (en) * | 2007-12-26 | 2013-02-19 | Momentive Performance Materials Inc. | Moisture-curable silylated polyurea and adhesive, sealant and coating compositions containing same |
| US8138297B2 (en) * | 2009-02-09 | 2012-03-20 | Momentive Performance Materials Inc. | Moisture-curable silylated polymer possessing improved storage stability |
| BR112012009910A2 (en) * | 2009-10-30 | 2016-03-08 | Henkel Ag & Co Kgaa | moisture-curable formulations with time-modified phases |
| DE102009046269A1 (en) * | 2009-10-30 | 2011-05-05 | Henkel Ag & Co. Kgaa | Urea-bound alkoxysilanes for use in sealants and adhesives |
| CN102408870B (en) * | 2011-08-16 | 2014-06-11 | 北京天山新材料技术股份有限公司 | Sealant of silane-terminated polymer and preparation method thereof |
| US9156981B2 (en) * | 2013-07-24 | 2015-10-13 | Momentive Performance Materials Inc. | Moisture curable compositions with enhanced elongation and tear strength properties |
| AU2016328372B2 (en) * | 2015-09-23 | 2021-01-14 | Sika Technology Ag | Two-component composition |
| CN105968285A (en) * | 2016-06-02 | 2016-09-28 | 深圳市深赛尔股份有限公司 | Waterborne silane polyurea resin and preparation method thereof |
| CN111269679B (en) * | 2019-12-17 | 2021-10-22 | 湖北回天新材料股份有限公司 | Environment-friendly silane modified adhesive and preparation method and application thereof |
| CN111471155B (en) * | 2020-05-08 | 2022-08-30 | 湖南耐渗塑胶工程材料有限公司 | Silane-terminated modified polyurethane resin, high-strength low-modulus modified polyurethane sealant and preparation method thereof |
| CN112094616A (en) * | 2020-09-24 | 2020-12-18 | 杭州之江新材料有限公司 | High-thixotropy and fast-curing single-component low-modulus polyurethane sealant and preparation method thereof |
| CN113667086A (en) * | 2021-08-26 | 2021-11-19 | 贵州理工学院 | Siloxane modified polyurea material and preparation method and application thereof |
| CN113603717A (en) * | 2021-09-07 | 2021-11-05 | 衡阳拓创聚合新材料有限公司 | Preparation method of silicon modified asparagus polyurea resin and asparagus polyurea resin |
| CN114479741B (en) * | 2022-02-23 | 2023-03-31 | 广州市白云化工实业有限公司 | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof |
-
2022
- 2022-02-23 CN CN202210167533.3A patent/CN114479741B/en active Active
- 2022-12-23 WO PCT/CN2022/141393 patent/WO2023160197A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023160197A1 (en) | 2023-08-31 |
| CN114479741A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107841277B (en) | Preparation method of fast-curing and high-strength single-component silane modified polyurethane sealant | |
| KR100660662B1 (en) | Compositions of silylated polymer and aminosilane adhesion promoters | |
| EP2220163B1 (en) | Two-part moisture-curable resin composition and adhesive, sealant and coating compositions based thereon | |
| EP0819749B1 (en) | Adhesive composition | |
| CN108034352B (en) | Primer for modified silicone sealant suitable for PC (polycarbonate) building and preparation method of primer | |
| CN102816549B (en) | Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof | |
| CN109575870B (en) | Modified siloxane-terminated polyurethane sealant and preparation method thereof | |
| JP5512529B2 (en) | Polyurethane adhesive composition with high filler level | |
| CN1715356A (en) | Novel adhesive composition | |
| CN110637051B (en) | Low modulus silylated adhesive compositions | |
| CN112608444B (en) | Polyurethane resin, MS sealant and preparation method | |
| CN103897652A (en) | Environment-friendly high-strength polyurethane adhesive sealant and preparation method thereof | |
| CN114479741B (en) | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof | |
| JP7333314B2 (en) | Isocyanate-functional adhesive for primerless bonding to coatings based on silanized acrylic polyols | |
| CN101245182B (en) | Fire resistant water resistant polyurethane composition for fluid sealant and manufacture method thereof | |
| CN111378413B (en) | Primer-free single-component polyurethane sealant and preparation method thereof | |
| CN113980563A (en) | Method for preparing one-component semi-polyurea waterproof coating composition and one-component semi-polyurea waterproof coating composition | |
| CN111117549B (en) | Single-component polyurethane sealant prepared by using PAPI (polymethylacrylate polyimide) | |
| CN114292574B (en) | Single-component polyurethane waterproof paint and preparation method thereof | |
| CN111892901A (en) | Fast-curing two-component polyurethane sealant for hollow glass and preparation method thereof | |
| CN114667305B (en) | Moisture crosslinkable sealant composition for high temperature joint exposure | |
| KR102375885B1 (en) | Sealant | |
| CN110951381B (en) | High-weather-resistance exposed single-component polyurethane waterproof coating and preparation method thereof | |
| JPH11263965A (en) | Agent for imparting thixotropic properties and moisture-curable polyurethane composition | |
| JPH07196913A (en) | Moisture-setting urethane sealant composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Guangzhou private science and Technology Park Yunan road Baiyun District of Guangzhou City, Guangdong Province, No. 1 510540 Patentee after: Guangzhou Baiyun Technology Co.,Ltd. Patentee after: Guangdong Baiyun Technology Co.,Ltd. Address before: Guangzhou private science and Technology Park Yunan road Baiyun District of Guangzhou City, Guangdong Province, No. 1 510540 Patentee before: GUANGZHOU BAIYUN CHEMICAL INDUSTRY Co.,Ltd. Patentee before: Guangdong Baiyun Technology Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |