CN114369440B - 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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- CN114369440B CN114369440B CN202111578050.4A CN202111578050A CN114369440B CN 114369440 B CN114369440 B CN 114369440B CN 202111578050 A CN202111578050 A CN 202111578050A CN 114369440 B CN114369440 B CN 114369440B
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- molecular sieve
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- 239000000565 sealant Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000003963 antioxidant agent Substances 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
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 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
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 27
- 238000001723 curing Methods 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000000203 mixture 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
- 238000013007 heat curing Methods 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 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
- -1 dioctyltin carboxylate Chemical class 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 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
- 150000001875 compounds 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
- 238000011049 filling Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002245 particle 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 230000003213 activating effect Effects 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
- 238000004321 preservation Methods 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000077 silane Inorganic materials 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 9
- 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 4
- 239000000084 colloidal system Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 206010042674 Swelling Diseases 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000001029 thermal curing Methods 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
- UZFVQGTYOXJWTF-UHFFFAOYSA-L [octadecanoyloxy(dioctyl)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCCCCCCCC UZFVQGTYOXJWTF-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 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
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 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
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 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
- 230000009286 beneficial effect Effects 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
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- 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
- 150000002739 metals Chemical class 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
- 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
- 238000005070 sampling 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
- 230000008719 thickening Effects 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 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 and a thermosetting method thereof, wherein the single-component thermosetting sealant is compounded by silane modified polymers, catalysts, composite antioxidants, molecular sieve activated powder, plasticizers, fillers and coupling agents in specific types of proportions, so that the single-component sealant with good normal-temperature storage stability can be obtained as a whole, and the single-component thermosetting sealant can not bulge or crack under the thermosetting condition of 80-200 ℃. The single-component sealant is a brand new type of thermosetting silane modified sealant, and is suitable for bonding substrates requiring 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 resin has the advantages of a siloxane end-capped structure and a polyether polyester main chain, so that the silane modified sealant has the advantages of both silicone and polyurethane resin, has excellent weather resistance, mechanical property and wide bonding property to a substrate, and also has the advantages of low viscosity, long storage period, low VOC, low odor, low damage to the substrate, no bulge, paintability and the like, and has wide application in the fields of building assembly, automobile manufacturing, rail transit and the like. However, conventional silane modified sealants can suffer from swelling, cracking, adhesive failure, and the like upon baking at high temperatures.
In industrial manufacturing, in order to prevent corrosion of metals as much as possible, a paint-spraying treatment is generally performed on the surface of a metal skeleton or a plate. With the increasing environmental protection policy, the traditional spray painting process is gradually eliminated, and the traditional spray painting process is replaced by the powder spraying or electrophoresis process. However, baking temperatures of powder spraying or electrophoresis processes are generally higher than 150 ℃, and therefore the use of such processes can limit the use of conventional sealants.
In addition, the existing high-temperature polyurethane curing technology uses phenol, caprolactam and other small molecules to end up NCO or polyurea and aldimine to end up amine curing agents, so that more small molecules can be released at high temperature, and the colloid bonding performance and the environmental protection performance are affected. In addition, because the silane modified sealant curing process requires water vapor to participate, the high temperature environment is obviously unfavorable for realizing the curing. Therefore, there is no heat curing technology for silane modified sealants at present.
Disclosure of Invention
Based on this, it is necessary to provide a one-component heat-curable sealant, a method for preparing the same and a heat-curable method capable of realizing high-temperature (80-200 ℃) curing without swelling, and 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 end capped polyether, the STP resin is triethoxy isocyanate silane end capped polyether polymer or methyl diethoxy isocyanate silane end capped 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, the single-component thermosetting sealant is preferably 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 at least one selected from the group consisting of dioctyl tin maleate, and dioctyl tin distearate.
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 diethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate. In some embodiments, the secondary antioxidant is selected from at least one of tri (tridecyl) phosphite, triisodecyl phosphite.
Preferably, the weight ratio of the primary antioxidant to the secondary antioxidant is (5-10): 1.
further, the one-component heat-curing sealant further comprises 0 to 0.4 part of light stabilizer and/or 0 to 0.4 part of ultraviolet absorber. The light stabilizer is preferably selected from hindered amine light stabilizers, and the ultraviolet light absorber is preferably selected from benzotriazole ultraviolet light absorbers.
In some of these embodiments, the MS resin is selected from at least one of brillouin chemistry SAX203, S303H, SAX 350.
In some of these embodiments, the STP resin is selected from the group consisting of rayleigh Yang Antai 12000E.
In some 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 silane coupling agent), heavy calcium carbonate (preferably 800-3000 mesh), and silica micropowder (preferably 800-3000 mesh).
In some of these embodiments, the method of preparing the molecular sieve activated powder comprises the steps of: screening the 3A molecular sieve raw powder, the 4A molecular sieve raw powder, the 5A molecular sieve raw powder, the 13X molecular sieve raw powder and/or the LSX molecular sieve raw powder with the particle size of 600-3000 meshes, and activating the raw powder in an environment of 120-150 ℃ 24-48 hours in advance when the raw powder is used.
In some of these embodiments, the coupling agent is selected from at least one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane gamma- (2, 3-glycidoxy) propyl triethoxysilane, N-beta-aminoethyl-gamma-aminopropyl triethoxysilane, mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane.
In some of these embodiments, the plasticizer is at least one of a polyether polyol, 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 the silane modified polymer, the plasticizer, the filler, the molecular sieve activated powder and the compound 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 the base material to be 300-800 ppm; and adding the activated molecular sieve powder into a planetary stirrer, dispersing in vacuum for 20-40 min, adding a coupling agent and a catalyst, vacuumizing and stirring for 30min, controlling the temperature below 45 ℃, and filling the obtained composition into a single-component sealed tube for preservation.
In some of these embodiments, the temperature range of the thermal cure is 80 ℃ to 200 ℃ and the time required for curing shortens with increasing curing temperature.
In some of these embodiments, the thermal curing method is a staged curing: the first stage is placed in an environment of 80 ℃ for primary solidification for 20-40 min, and the second stage is placed in an environment of 140-160 ℃ for secondary solidification for 50-70 min.
In some of these embodiments, the thermal curing process is a one-step cure and is carried out at 170-190 ℃ for 40-60 minutes.
The invention has the beneficial effects that:
compared with the prior art, the invention can obtain the single-component sealant with good normal-temperature storage stability as a whole by compounding the silane modified polymer, the catalyst, the composite antioxidant, the molecular sieve activated powder, the plasticizer, the filler and the coupling agent in specific types of proportions, and can be cured within the range of 80-200 ℃ without swelling and cracking. The single-component sealant is a brand new type of thermosetting silane modified sealant, and is suitable for bonding substrates requiring a high-temperature baking process.
In particular, the single-component sealant of the invention is convenient to realize heating and curing under the premise of ensuring the storage stability by means of the material compounding reaction of low-activity resin, low-activity catalyst, molecular sieve activated powder, compound antioxidant and the like, the thermal curing range is controllable, and the environmental protection property is improved.
Detailed Description
The present invention will be described in further detail with reference to specific examples so as to more clearly understand the present invention by those skilled in the art.
The following examples are given for illustration of the invention only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art without creative efforts are within the protection scope of the present invention based on the specific embodiments of the present invention.
In the examples of the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise; in the embodiments of the present invention, unless specifically indicated, all technical means used are conventional means well known to those skilled in the art.
Example 1
The present example provides a single component heat curable sealant having the following raw materials composition in table:
the preparation method of the single-component thermosetting sealant comprises the following steps:
s1, adding S303H, polyether polyol, nano activated calcium carbonate, tricridecyl 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 for dehydration for 30min, cooling to the room temperature, sampling and testing the moisture, and controlling the moisture of the base material to be 300-800 ppm.
S2, adding 4A molecular sieve activated powder (the particle size is 600-3000 meshes, and the activation is performed in an environment of 120-150 ℃ in advance for 24-48 hours when the sealant is used) into a planetary mixer, 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 below 45 ℃, and vacuum-filling the obtained sealant into a single-component sealant tube.
Example 2
The present example provides a single component heat curable sealant having the following raw materials composition in table:
the preparation method of the one-component heat-curable sealant of this example was substantially the same as that of example 1.
Example 3
The present example provides a single component heat curable sealant having the following raw materials composition in table:
the preparation method of the one-component heat-curable sealant of this example was substantially the same as that of example 1.
Example 4
The present example provides a single component heat curable sealant having the following raw materials composition in table:
the preparation method of the one-component heat-curable sealant of this example was substantially the same as that of example 1.
Comparative example 1
This comparative example provides a sealant having substantially the same composition as in example 1 except that: tin chelate U-220H was used instead of dioctyl tin maleate.
The preparation method 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 substantially the same composition as in example 1 except that: equivalent amounts of rganox245 were used instead of tris (tridecyl) phosphite.
The preparation method of the sealant of this comparative example was substantially the same as that of example 1.
Comparative example 3
This comparative example provides a sealant having substantially the same composition as in example 1 except that: an equivalent amount of nano calcium carbonate is used to replace the activated 4A molecular sieve.
The preparation method of the sealant of this comparative example was substantially the same as that of example 1.
Comparative example 4
This comparative example provides a sealant having substantially the same composition as in example 1 except that: an equivalent amount of tris (tridecyl) phosphite as a secondary antioxidant was used in place of the primary antioxidant TINUVIN329.
The preparation method of the sealant of this comparative example was substantially the same as that of example 1.
Comparative example 5
This comparative example provides a sealant having substantially the same composition as in example 1 except that: equal amount of 4A molecular sieve which is not activated (static water adsorption rate is more than 20%) is adopted to replace 4A molecular sieve activated powder.
The preparation method of the sealant of this comparative example was substantially the same as that of example 1.
Comparative example 6
This comparative example provides a sealant having substantially the same composition as in example 1 except that: resin S303H was replaced with an equivalent amount of trimethoxy-terminated polyether resin SAX 580.
The preparation method of the sealant of this comparative example was substantially the same as that of example 1.
Performance testing
(1) Storage stability: the products and packages obtained in examples 1 to 4 and comparative examples 1 to 6 were placed in a forced air drying oven at 40℃for 2 weeks, and then taken out, and a single-component glue gun was used for applying a glue strip to evaluate the viscosity change of the products.
(2) Curing performance: the products obtained in examples 1 to 4 and comparative examples 1 to 6 were each subjected to a doctor blade having a length and width of 10 cm.times.10 cm and a thickness of 5mm on a 6-series aluminum plate, and were each placed in the curing conditions of the following table to be cured, and the curing conditions of the products were evaluated using a finger touch durometer.
(3) Cutting and stripping: and (3) forcibly peeling the film solidified on the aluminum plate by using a knife from one end of the film in a direction vertical to or greater than 90 degrees, checking that the sealant is cohesive failure or adhesive degumming, and recording the cohesive failure percentage.
(4) And after the preparation of the shear strength test sample, placing the test sample in an environment of 180 ℃ for curing for 50min, taking out the test sample, and testing the test sample after keeping the temperature for 2 hours.
The relevant test results are shown in the following table:
performance test result statistics
Remarks: CF is cohesive failure of the colloid, AF is interfacial failure of the colloid and the substrate, "-" indicates that no subsequent testing was performed.
As can be seen from the above table, the single-component heat-curable sealants of examples 1 to 4 can achieve the occurrence of no thickening of the curing agent within 14 days of storage at 40 ℃ and can simultaneously satisfy the heat-curing at 80 to 200 ℃ and no defects such as air holes, as compared with comparative examples 1 to 6.
In addition, it should be noted that the above examples 1 to 4 represent only a few preferred examples, and the inventors have found through extensive studies that:
(1) The silane modified polymer is preferably methyl dimethoxy silane end capped polyether, triethoxy isocyanate silane end capped polyether polymer or methyl diethoxy isocyanate silane end capped 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 dioctyltin carboxylate, dioctyltin dilaurate, dioctyltin maleate and dioctyltin distearate, the molecular sieve activated 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 subjected to activation treatment, the plasticizer is preferably polyether polyol or polyester polyol with molecular weight of 1000-4000, the weight ratio of the silane modified polymer, the plasticizer, the molecular sieve activated powder and the composite antioxidant is (10-40): (0.5-2), and the single-component sealant with good normal temperature storage stability (accelerated aging for 2 weeks at 40 ℃ and no solidification) and no bad air holes and the like can be obtained in the whole.
(2) The temperature range of the heat curing is preferably 80 to 200 ℃, and the time required for the curing is shortened with the increase of the curing temperature. After the curing temperature exceeds 180 ℃, the curing time is not more than 1.5 hours. The maximum curing temperature should not exceed 250℃in order to avoid irreversible degradation of the colloid.
(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 illustrating and describing the technical solution of the present invention, and are not intended to 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 scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The single-component thermosetting sealant is characterized by being prepared from the following raw materials in parts by weight:
the silane modified polymer is selected from MS resin or STP resin, wherein the MS resin is methyl dimethoxy silane end capped polyether and is selected from at least one of Brillouin chemistry SAX203 and S303H, SAX 350; the STP resin is triethoxy isocyanate silane end-capped polyether polymer or methyl diethoxy isocyanate silane end-capped polyether polymer, and is selected from the group consisting of Rayleigh Yang Antai 12000E;
the catalyst is selected from dioctyltin carboxylate;
the preparation method of the molecular sieve activated powder comprises the following steps: screening a 3A molecular sieve raw powder, a 4A molecular sieve raw powder, a 5A molecular sieve raw powder, a 13X molecular sieve raw powder and/or an LSX molecular sieve raw powder with the particle size of 600-3000 meshes, and activating the raw powder in an environment of 120-150 ℃ 24-48 hours in advance when the raw powder is used;
the composite antioxidant comprises the following components in percentage by weight (5-10): 1 and a secondary antioxidant selected from the group consisting of hindered phenolic antioxidants and phosphite antioxidants.
2. The one-component heat-curable sealant according to claim 1, wherein the filler is at least one selected from the group consisting of nano calcium carbonate, heavy calcium carbonate, and fine silica powder.
3. The one-part heat-curable sealant according to claim 1, wherein the primary antioxidant is at least one selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], ethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate; and/or
The auxiliary antioxidant is selected from at least one of tri (tridecyl) phosphite and triisodecyl phosphite;
the coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, N-beta-aminoethyl-gamma-aminopropyl triethoxysilane, mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane; and/or
The plasticizer is at least one of polyether polyol and polyester polyol, and has a molecular weight of 1000-4000.
4. A method of preparing a one-component heat-curable sealant according to any one of claims 1 to 3, comprising the steps of:
adding a plasticizer, a filler, molecular sieve activated powder and a compound 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, dispersing in vacuum for 20-40 min, adding a coupling agent and a catalyst, vacuumizing and stirring for 30min, controlling the temperature below 45 ℃, and filling the obtained composition into a single-component sealed tube for preservation.
5. A method of heat curing a one-component heat-curable sealant according to any one of claims 1 to 3, characterized in that the temperature of heat curing is in the range of 80 ℃ to 200 ℃.
6. A method of heat curing a one-component heat-curable sealant according to any one of claims 1 to 3, characterized in that the heat curing method is a staged curing: the first stage is placed in an environment of 80-100 ℃ for primary solidification for 20-40 min, and the second stage is placed in an environment of 140-160 ℃ for secondary solidification for 50-70 min; or alternatively
The heat curing method is one-step curing, and the heat curing is carried out for 40-60 min in an environment of 170-190 ℃.
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