CN114369440A - Single-component thermosetting sealant, preparation method thereof and thermosetting method - Google Patents
Single-component thermosetting sealant, preparation method thereof and thermosetting method Download PDFInfo
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- CN114369440A CN114369440A CN202111578050.4A CN202111578050A CN114369440A CN 114369440 A CN114369440 A CN 114369440A CN 202111578050 A CN202111578050 A CN 202111578050A CN 114369440 A CN114369440 A CN 114369440A
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- Prior art keywords
- component
- curing
- molecular sieve
- sealant
- powder
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Links
- 239000000565 sealant Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 238000003860 storage Methods 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000003707 silyl modified polymer Substances 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 238000013007 heat curing Methods 0.000 claims abstract description 6
- 238000001723 curing Methods 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 238000001029 thermal curing Methods 0.000 claims description 7
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 3
- -1 dioctyltin carboxylate Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- RAPZEAPATHNIPO-UHFFFAOYSA-N risperidone Chemical compound FC1=CC=C2C(C3CCN(CC3)CCC=3C(=O)N4CCCCC4=NC=3C)=NOC2=C1 RAPZEAPATHNIPO-UHFFFAOYSA-N 0.000 claims description 2
- 229960001534 risperidone Drugs 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 claims description 2
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000077 silane Inorganic materials 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 3
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- LACQOWNPINIUEE-PTZSQULPSA-J (z)-2,3-dioctylbut-2-enedioate;tin(4+) Chemical compound [Sn+4].CCCCCCCC\C(C([O-])=O)=C(C([O-])=O)/CCCCCCCC.CCCCCCCC\C(C([O-])=O)=C(C([O-])=O)/CCCCCCCC LACQOWNPINIUEE-PTZSQULPSA-J 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- UZFVQGTYOXJWTF-UHFFFAOYSA-L [octadecanoyloxy(dioctyl)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCCCCCCCC UZFVQGTYOXJWTF-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such 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
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides a single-component thermosetting sealant, a preparation method thereof and a thermosetting method, wherein the single-component thermosetting sealant is prepared by compounding a silane modified polymer, a catalyst, a composite antioxidant, molecular sieve activating powder, a plasticizer, a filler and a coupling agent according to a specific kind of proportion, so that the single-component sealant which is stable in storage at normal temperature can be integrally obtained, and the single-component sealant can be prevented from bulging and cracking under the thermosetting condition at 80-200 ℃. The single-component sealant is a brand-new form of heat-curing silane modified sealant and is suitable for bonding substrates needing a high-temperature baking process.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a single-component thermosetting sealant, a preparation method thereof and a thermosetting method.
Background
The silane modified sealant is prepared by taking silane modified resin as a main component. The silane modified sealant has the advantages of both silicone and polyurethane resin due to the fact that the silane modified resin has a siloxane end-capped structure and a polyether polyester main chain, has excellent weather resistance, mechanical property and wide bonding performance to a base material, has the advantages of low viscosity, long storage period, low VOC (volatile organic compounds), small odor, small damage to the base material, no bulge, paintability and the like, and is widely applied to the fields of building assembly, automobile manufacturing, rail transit and the like. However, the conventional silane modified sealant has the problems of bulging, cracking, bonding failure and the like after being baked at high temperature.
In industrial manufacturing, in order to prevent corrosion of metal as much as possible, a painting process is generally performed on the surface of a metal skeleton or a plate. With the stricter and stricter environmental policy, the traditional paint spraying process is gradually eliminated and replaced by a powder spraying or electrophoresis process. However, the baking temperature of the powder spraying or electrophoresis process is generally higher than 150 ℃, so that the application of the process can limit the application of the conventional sealant.
In addition, the existing high-temperature curing polyurethane technology uses micromolecule blocked NCO of phenol, caprolactam and the like or uses polyurea and aldimine blocked amine curing agents, and more micromolecules can be released at high temperature, so that the adhesive property and the environmental protection property of colloid are influenced. In addition, because the silane modified sealant needs water vapor to participate in the curing process, the high-temperature environment is obviously not beneficial to realizing curing. Therefore, no thermal curing technology exists in the current silane modified sealant.
Disclosure of Invention
Based on the above, a single-component thermosetting sealant, a preparation method thereof and a thermosetting method are needed, which can realize high-temperature (80-200 ℃) curing without swelling and are suitable for bonding substrates requiring a high-temperature baking process.
The invention adopts the following technical scheme:
the invention provides a single-component thermosetting sealant which is mainly prepared from the following raw materials in parts by weight:
the silane modified polymer is selected from MS resin or STP resin, the MS resin is methyl dimethoxy silane terminated polyether, the STP resin is triethoxy isocyanate silane terminated polyether polymer or methyl diethoxy isocyanate silane terminated polyether polymer, the catalyst is selected from dioctyl tin carboxylate, the composite antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant is selected from hindered phenol antioxidants, and the secondary antioxidant is selected from phosphite antioxidants.
In some embodiments, preferably, the one-component heat-curable sealant is mainly prepared from the following raw materials in parts by weight: 20-40 parts of silane modified polymer, 10-30 parts of plasticizer, 40-50 parts of filler, 10-15 parts of molecular sieve activated powder, 0.5-2 parts of composite antioxidant, 0.3-1 part of coupling agent and 0.2-1.6 parts of catalyst.
In some of these embodiments, the catalyst is preferably selected from at least one of tin dioctylmaleate, tin dioctyldistearate.
In some embodiments, the primary antioxidant has a melting point of 60-150 ℃ and is selected from at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate. In some of these embodiments, the secondary antioxidant is selected from at least one of tri (tridecyl) phosphite, tri-isodecyl phosphite.
Preferably, the weight ratio of the primary antioxidant to the secondary antioxidant is (5-10): 1.
further, the single-component thermosetting sealant also comprises 0-0.4 part of light stabilizer and/or 0-0.4 part of ultraviolet absorber. The light stabilizer is preferably selected from hindered amine light stabilizers, and the ultraviolet absorber is preferably selected from benzotriazole ultraviolet absorbers.
In some of these embodiments, the MS resin is selected from at least one of the group consisting of the brillouin chemical SAX203, S303H, SAX 350.
In some of these embodiments, the STP resin is selected from the group consisting of risperidone 12000E.
In some of the embodiments, the filler is at least one selected from nano calcium carbonate (preferably 40-80 nm, the surface of which is treated by stearic acid or a silane coupling agent), heavy calcium carbonate (preferably 800-3000 meshes), and silica powder (preferably 800-3000 meshes).
In some embodiments, the preparation method of the molecular sieve activated powder comprises the following steps: screening 3A molecular sieve raw powder, 4A molecular sieve raw powder, 5A molecular sieve raw powder, 13X molecular sieve raw powder and/or LSX molecular sieve raw powder with the particle size of 600-3000 meshes, and activating in an environment of 120-150 ℃ in advance for 24-48 hours when the powder is used.
In some of these embodiments, the coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, N-beta-aminoethyl-gamma-aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane.
In some of these embodiments, the plasticizer is at least one of a polyether polyol and a polyester polyol. The polyether polyol is preferably a hydroxyl-terminated polyether polyol, an alkyl etherified or esterified capped polyether polyol. The polyester polyol is preferably a polyester polyol, a polycaprolactone polyol or a polycarbonate diol.
The invention also provides a preparation method of the single-component thermosetting sealant, which comprises the following steps: adding a silane modified polymer, a plasticizer, a filler, molecular sieve activated powder and a composite antioxidant into a planetary mixer, controlling the temperature to be 110-120 ℃, vacuumizing to be more than 0.94MPa, dehydrating for 25-35 min, cooling to room temperature, and controlling the water content of a base material to be 300-800 ppm; and adding the activated molecular sieve powder into a planetary stirrer, performing vacuum dispersion for 20-40 min, adding a coupling agent and a catalyst, performing vacuum stirring for 30min, controlling the temperature to be below 45 ℃, and filling the obtained composition into a single-component sealed tube for storage.
In some embodiments, the temperature range of the thermal curing is 80-200 ℃, and the time required for curing is shortened along with the increase of the curing temperature.
In some of these embodiments, the thermal curing process is a staged curing: the first stage is placed in an environment of 80 ℃ for primary curing for 20-40 min, and the second stage is placed in a environment of 140-160 ℃ for secondary curing for 50-70 min.
In some embodiments, the thermal curing method is one-step curing, and the curing is performed for 40-60 min at 170-190 ℃.
The invention has the beneficial effects that:
compared with the prior art, the single-component sealant which is good in storage stability at normal temperature can be integrally obtained by compounding the silane modified polymer, the catalyst, the composite antioxidant, the molecular sieve activating powder, the plasticizer, the filler and the coupling agent in a specific mixture ratio, and the single-component sealant can be cured at the temperature of 80-200 ℃ without swelling and cracking. The single-component sealant is a brand-new form of heat-curing silane modified sealant and is suitable for bonding substrates needing a high-temperature baking process.
Particularly, the single-component sealant disclosed by the invention is prepared by compounding and reacting low-activity resin, a low-activity catalyst, molecular sieve activated powder, a composite antioxidant and the like, so that the heating curing is conveniently realized on the premise of ensuring the storage stability, the thermosetting range is controllable, and the environmental friendliness is improved.
Detailed Description
The present invention is further described in detail below with reference to specific examples so that those skilled in the art can more clearly understand the present invention.
The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention. All other embodiments obtained by a person skilled in the art based on the specific embodiments of the present invention without any inventive step are within the scope of the present invention.
In the examples of the present invention, all the raw material components are commercially available products well known to those skilled in the art, unless otherwise specified; in the examples of the present invention, unless otherwise specified, all technical means used are conventional means well known to those skilled in the art.
Example 1
This example provides a one-part heat-curable sealant having the following raw material composition:
the preparation method of the one-component thermosetting sealant of the embodiment comprises the following steps:
s1, adding S303H, polyether polyol, nano activated calcium carbonate, tridecyl phosphite, Irganox 245, TINUVIN329 and TINUVIN 770DF into a planetary mixer, controlling the temperature to be 110-120 ℃, vacuumizing to be more than 0.94MPa, dehydrating for 30min, cooling to room temperature, sampling and testing moisture, and controlling the moisture content of the base material to be 300-800 ppm.
S2, adding 4A molecular sieve activation powder (with the particle size of 600-3000 meshes, and needs to be activated in an environment of 120-150 ℃ in advance for 24-48 h in use) into a planetary stirrer, vacuumizing and stirring for 30min, adding gamma-aminopropyl triethoxysilane, vacuumizing and stirring for 15min, adding dioctyl tin maleate, vacuumizing and stirring for 15min, controlling the temperature to be below 45 ℃, and vacuum-filling the obtained sealant into a single-component sealing rubber tube.
Example 2
This example provides a one-part heat-curable sealant having the following raw material composition:
the one-part heat curable sealant of this example was prepared in substantially the same manner as in example 1.
Example 3
This example provides a one-part heat-curable sealant having the following raw material composition:
the one-part heat curable sealant of this example was prepared in substantially the same manner as in example 1.
Example 4
This example provides a one-part heat-curable sealant having the following raw material composition:
the one-part heat curable sealant of this example was prepared in substantially the same manner as in example 1.
Comparative example 1
This comparative example provides a sealant having essentially the same raw material composition as in example 1, except that: chelated tin U-220H is used instead of dioctyl tin maleate.
The procedure for the preparation of the sealant of this comparative example was substantially the same as that of example 1.
Comparative example 2
This comparative example provides a sealant having essentially the same raw material composition as in example 1, except that: the tri (tridecyl) phosphite was replaced with an equal amount of rganox 245.
The sealant of this comparative example was prepared in substantially the same manner as in example 1.
Comparative example 3
This comparative example provides a sealant having essentially the same raw material composition as in example 1, except that: the activated 4A molecular sieve is replaced by equivalent nano calcium carbonate.
The sealant of this comparative example was prepared in substantially the same manner as in example 1.
Comparative example 4
This comparative example provides a sealant having essentially the same raw material composition as in example 1, except that: equal amount of the secondary antioxidant, tri (tridecyl) phosphite, was used in place of the primary antioxidant, TINUVIN 329.
The sealant of this comparative example was prepared in substantially the same manner as in example 1.
Comparative example 5
This comparative example provides a sealant having essentially the same raw material composition as in example 1, except that: the 4A molecular sieve activated powder is replaced by the same amount of the 4A molecular sieve without activation treatment (the static water adsorption rate is more than 20 percent).
The sealant of this comparative example was prepared in substantially the same manner as in example 1.
Comparative example 6
This comparative example provides a sealant having essentially the same raw material composition as in example 1, except that: resin S303H was replaced with an equal amount of trimethoxy terminated polyether resin SAX 580.
The sealant of this comparative example was prepared in substantially the same manner as in example 1.
Performance testing
(1) Storage stability: the products and packages obtained in examples 1-4 and comparative examples 1-6 were stored in a forced air drying oven at 40 ℃ for 2 weeks and then taken out, and the viscosity change of the products was evaluated by using a single-component glue gun to apply a glue strip.
(2) Curing performance: the products obtained in examples 1 to 4 and comparative examples 1 to 6 were each coated with a sheet of 10cm by 10cm in length and 10cm in width and 5mm in thickness on a 6-series aluminum plate, and cured under the curing conditions shown in the following table, and the cured state of the product was evaluated using a finger touch hardness tester.
(3) Cutting and stripping: and (3) forcibly peeling the film solidified on the aluminum plate from one end of the film by a knife in a direction vertical to or greater than 90 degrees, checking whether the sealant has cohesive failure or adhesive degumming phenomenon, and recording the cohesive failure percentage.
(4) And after the shear strength test sample piece is prepared, placing the sample piece in an environment of 180 ℃ for curing for 50min, taking out the sample piece, and testing after keeping the temperature for 2 hours.
The results of the relevant tests are given in the following table:
statistical table of performance test results
Remarking: CF is cohesive failure of the colloid, AF is interfacial failure of the colloid and the substrate, "-" indicates no subsequent testing.
As can be seen from the above table, compared with comparative examples 1 to 6, the single-component heat-curable sealant of examples 1 to 4 can realize no thickening of the curing agent within 14 days of storage at 40 ℃, and can synchronously meet the adverse conditions of heat curing at 80 to 200 ℃ and no air holes and the like.
In addition, it should be noted that the above embodiments 1 to 4 only represent some preferred embodiments, and the inventor team has found through a lot of research that:
(1) the silane modified polymer is preferably methyl dimethoxy silane terminated polyether, triethoxy isocyanate silane terminated polyether polymer or methyl diethoxy isocyanate silane terminated polyether polymer, the primary antioxidant is preferably hindered phenol antioxidant, the secondary antioxidant is preferably phosphite antioxidant, the catalyst is selected from at least one of dioctyl tin carboxylate, dioctyl tin dilaurate, dioctyl tin maleate and dioctyl tin distearate, the molecular sieve activating powder is preferably 3A molecular sieve raw powder, 4A molecular sieve raw powder, 5A molecular sieve raw powder, 13X molecular sieve raw powder and/or LSX molecular sieve raw powder which are screened to have the particle size of 600-3000 meshes and are subjected to activating treatment, the plasticizer is preferably polyether polyol or polyester polyol with the molecular weight of 1000-4000, and the weight ratio of the silane modified polymer, the plasticizer, the molecular sieve activating powder and the composite antioxidant is (10-40): 10-30): 0.5-2, the single-component sealant which has good storage stability at normal temperature (can not be cured after accelerated aging for 2 weeks in the environment of 40 ℃) and has no bad conditions such as air holes during heat curing can be obtained on the whole.
(2) The temperature range of the thermal curing is preferably 80-200 ℃, and the time required for curing is shortened along with the increase of the curing temperature. After the curing temperature exceeds 180 ℃, the curing time is not longer than 1.5 h. The maximum curing temperature should not exceed 250 ℃ to avoid irreversible deterioration of the gel.
(3) The weight ratio of the primary antioxidant to the secondary antioxidant is preferably (5-10): 1.
It should be noted that the above examples are only for further illustration and description of the technical solution of the present invention, and are not intended to further limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment, and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The single-component thermosetting sealant is characterized by being mainly prepared from the following raw materials in parts by weight:
the silane modified polymer is selected from MS resin or STP resin, the MS resin is methyl dimethoxy silane terminated polyether, and the STP resin is triethoxy isocyanate silane terminated polyether polymer or methyl diethoxy isocyanate silane terminated polyether polymer;
the catalyst is selected from dioctyltin carboxylate;
the compound antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is selected from hindered phenol antioxidants, and the secondary antioxidant is selected from phosphite antioxidants.
2. The one-component heat-curable sealant according to claim 1, further comprising 0 to 0.4 parts of hindered amine light stabilizer and/or 0 to 0.4 parts of ultraviolet absorber.
3. The one-component heat-curable sealant according to claim 1, wherein said MS resin is selected from at least one of the group consisting of SAX203, S303H, SAX350 in the brillouin chemistry.
4. The one-part heat curable sealant according to claim 1 wherein the STP resin is selected from the group consisting of risperidone 12000E.
5. The one-component, heat-curable sealant according to any of claims 1 to 4, wherein the filler is at least one selected from the group consisting of nano calcium carbonate, ground calcium carbonate, and fine silica powder.
6. The one-component heat-curable sealant according to any one of claims 1 to 4, wherein the molecular sieve activating powder is prepared by a method comprising the steps of: screening 3A molecular sieve raw powder, 4A molecular sieve raw powder, 5A molecular sieve raw powder, 13X molecular sieve raw powder and/or LSX molecular sieve raw powder with the particle size of 600-3000 meshes, and activating in an environment of 120-150 ℃ in advance for 24-48 hours when the powder is used.
7. The one-component, heat-curable sealant according to any of claims 1 to 4, wherein the primary antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate; and/or
The auxiliary antioxidant is at least one of tridecyl phosphite and triisodecyl phosphite;
the coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, N-beta-aminoethyl-gamma-aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane; and/or
The plasticizer is at least one of polyether polyol and polyester polyol, and the molecular weight is 1000-4000.
8. The method for preparing a one-component heat-curable sealant according to any one of claims 1 to 7, comprising the steps of:
adding a plasticizer, a filler, molecular sieve activated powder and a composite antioxidant into a planetary stirrer, controlling the temperature to be 110-120 ℃, vacuumizing for more than 0.94MPa, dehydrating for 25-35 min, cooling to room temperature, and controlling the water content of a base material to be 300-800 ppm;
and adding the activated molecular sieve powder into a planetary stirrer, performing vacuum dispersion for 20-40 min, adding a coupling agent and a catalyst, performing vacuum stirring for 30min, controlling the temperature to be below 45 ℃, and filling the obtained composition into a single-component sealed tube for storage.
9. The method for thermally curing one-component heat-curable sealants according to any of claims 1 to 7, wherein the temperature range for thermal curing is 80 ℃ to 200 ℃.
10. The heat-curing process for one-component heat-curable sealants according to any of claims 1 to 7, characterized in that the heat-curing process is a staged curing: the first stage is placed in an environment with the temperature of 80-100 ℃ for primary curing for 20-40 min, and the second stage is placed at the temperature of 140-160 ℃ for secondary curing for 50-70 min; or
The thermal curing method is one-step curing, and curing is carried out for 40-60 min at the temperature of 170-190 ℃.
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| CN116254085A (en) * | 2023-02-15 | 2023-06-13 | 湖北回天新材料股份有限公司 | Weather-resistant MS door and window glue and preparation method thereof |
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