CN114214025A - Novel two-component silicone structural sealant and preparation method thereof - Google Patents
Novel two-component silicone structural sealant and preparation method thereof Download PDFInfo
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- CN114214025A CN114214025A CN202111528381.7A CN202111528381A CN114214025A CN 114214025 A CN114214025 A CN 114214025A CN 202111528381 A CN202111528381 A CN 202111528381A CN 114214025 A CN114214025 A CN 114214025A
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- 239000000565 sealant Substances 0.000 title claims abstract description 54
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 112
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 56
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims abstract description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 6
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940083037 simethicone Drugs 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 239000011259 mixed solution Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 abstract description 18
- 230000032683 aging Effects 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 7
- 239000004590 silicone sealant Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007787 solid 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- DDSWIYVVHBOISO-UHFFFAOYSA-N ctk0i1982 Chemical group N[SiH](N)N DDSWIYVVHBOISO-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- -1 phosphate ester Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WYSYKUDDULIZNW-UHFFFAOYSA-N trimethoxy(silyl)silane Chemical compound CO[Si]([SiH3])(OC)OC WYSYKUDDULIZNW-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The application relates to the technical field of silicone structural sealant, and particularly discloses a novel two-component silicone structural sealant and a preparation method thereof. A novel two-component silicone structural sealant comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 30-70 parts of nano calcium carbonate, 20-55 parts of base rubber and 2-35 parts of dimethyl silicone oil; the component B comprises the following raw materials in parts by weight: 10-30 parts of carbon black, 3-15 parts of fumed silica, 20-40 parts of simethicone, 10-50 parts of a first cross-linking agent, 10-45 parts of a second cross-linking agent, 10-45 parts of a coupling agent and 0.01-0.14 part of a catalyst; wherein the second crosslinking agent is propyl trimethoxy silane oligomer, and the polymerization degree is 4-6. The two-component silicone structural sealant has the advantages of excellent soaking binding performance and excellent ageing resistance.
Description
Technical Field
The application relates to the technical field of silicone structural sealants, in particular to a novel two-component silicone structural sealant and a preparation method thereof.
Background
The silicone sealant belongs to organosilicon products, a high molecular main chain mainly comprises silicon-oxygen-silicon bonds, a cross-linking agent reacts with a basic polymer to form a reticular Si-O-Si framework structure in the curing process, and the silicone sealant has the most remarkable characteristics of excellent high and low temperature resistance and weather resistance, strong cohesive force, high tensile strength and the like.
The silicone sealant can be generally divided into a single-component silicone sealant and a two-component silicone sealant, wherein the curing of the single-component silicone sealant is carried out by contacting moisture in air to generate a chemical reaction; by two-component is meant that the silicone gums are divided into A, B groups, neither group alone is capable of forming a cure, but the two groups of gums once mixed are cured.
When the two-component silicone structural sealant is used, the two components are required to be uniformly mixed firstly, and then the sealant is injected into a sealant using part within a certain time. The curing speed of the two-component silicone structural sealant can be adjusted within a certain range, so that a satisfactory curing effect is achieved.
In view of the above-mentioned related technologies, the applicant has found that the two-component silicone structural sealant has poor water-immersion adhesion after curing.
Disclosure of Invention
In order to improve the soaking bonding performance of the two-component silicone structure sealant, the application provides a novel two-component silicone structure sealant and a preparation method thereof.
In a first aspect, the application provides a novel two-component silicone structural sealant, which adopts the following technical scheme: a novel two-component silicone structural sealant comprises a component A and a component B,
the component A comprises the following raw materials in parts by weight:
30-70 parts of nano calcium carbonate, 20-55 parts of base rubber and 2-35 parts of dimethyl silicone oil;
the component B comprises the following raw materials in parts by weight:
10-30 parts of carbon black, 3-15 parts of fumed silica, 20-40 parts of simethicone, 10-50 parts of a first cross-linking agent, 10-45 parts of a second cross-linking agent, 10-45 parts of a coupling agent and 0.01-0.14 part of a catalyst;
wherein the second crosslinking agent is propyl trimethoxy silane oligomer, and the structural formula is as follows:
wherein n is 4-10.
By adopting the technical scheme, the propyl trimethoxy silane oligomer is a polymer with a main chain containing polar groups and a side chain containing non-polar groups, and the propyl trimethoxy silane oligomer has more reaction crosslinking points. The propyl trimethoxy silane oligomer with a certain proportion is added into the two-component silicone structural sealant, the propyl trimethoxy silane oligomer has more surface reaction crosslinking points, high activity and high crosslinking curing speed, the surface drying time of the sealant is improved, the use amount of a catalyst can be correspondingly reduced, and the overall curing speed of the two-component silicone structural sealant is improved. In addition, the cross-linking density of the sealant can be improved, the bonding strength and the elongation of the sealant can be improved, and the ultraviolet aging resistance of the sealant with a two-component structure can be improved. Polar and nonpolar groups on the propyl trimethoxy silane oligomer can also reduce the surface tension of an object to be coated, improve the hydrophobic property and improve the soaking adhesive property of the two-component silicone structural sealant.
Preferably, the component A comprises the following raw materials in parts by weight:
40-60 parts of nano calcium carbonate, 30-50 parts of base rubber and 5-30 parts of dimethyl silicone oil;
the component B comprises the following raw materials in parts by weight:
15-20 parts of carbon black, 5-10 parts of fumed silica, 25-30 parts of simethicone, 15-40 parts of a first cross-linking agent, 15-40 parts of a second cross-linking agent, 15-40 parts of a coupling agent and 0.01-0.1 part of a catalyst.
By adopting the technical scheme, the raw material proportion is further optimized, and the overall performance of the two-component silicone structural sealant is improved.
Preferably, the preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1600-1700 parts of propyl trimethoxy silane, 200-230 parts of methanol and 18-48 parts of concentrated hydrochloric acid are uniformly mixed to obtain a mixed solution A, the mixed solution A is stirred and heated to 40-50 ℃, and the mixed solution of 88-183 parts of water and 212-400 parts of methanol is dripped into the mixed solution A to hydrolyze the propyl trimethoxy silane.
A2. After the propyl trimethoxy silane is completely hydrolyzed, heating to 110-130 ℃, carrying out polymerization reaction for 2-4h, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain a colorless and transparent propyl trimethoxy silane oligomer.
By adopting the technical scheme, the hydrolysis of the propyl trimethoxy silane is promoted under the auxiliary action of the methanol, and the hydrolyzed propyl trimethoxy silane is obtained.
Preferably, the particle size of the nano calcium carbonate is 30-100nm, and the volatile matter is less than or equal to 0.5 percent.
By adopting the technical scheme, the nano calcium carbonate has excellent tensile strength, elongation at break and aging resistance, the nano calcium carbonate is filled in a structural sealant system to improve the bonding performance and aging resistance of the structural sealant, and the nano calcium carbonate with the particle size within the range of 30-100nm and the volatile matter less than or equal to 0.5 percent can avoid the increase of hydroxyl on the surface of the calcium carbonate and the mutual condensation tendency caused by overhigh volatile matter and improve the dispersion performance of the nano calcium carbonate.
Preferably, the weight ratio of the particle size of the nano calcium carbonate between 30-60nm and 80-100nm is (1-3): 1.
by adopting the technical scheme, the grain size gradation of the nano calcium carbonate is limited, and the nano calcium carbonate in the grain size gradation range can be dispersed in a structural sealant system more uniformly and compactly, so that the anti-aging performance of the structural sealant is improved.
Preferably, the nano calcium carbonate is modified, and the processing method comprises the following steps:
and (3) carrying out surface treatment on the nano calcium carbonate by using a silane coupling agent.
By adopting the technical scheme, the nano calcium carbonate is easy to agglomerate and has poor fluidity, and the silane coupling agent is used for wrapping the nano calcium carbonate, so that the agglomeration probability of the nano calcium carbonate can be reduced, and the dispersibility of the nano calcium carbonate in a structural sealant system can be improved.
Preferably, before the modification of the silane coupling agent, the nano calcium carbonate is soaked in a phosphate solution for surface treatment, and then is filtered and dried.
The number of hydroxyl groups on the surface of the nano calcium carbonate is small, and the nano calcium carbonate is usually alkalescent, so that the silane coupling agent is poorer in combination on the surface of the calcium carbonate; the surface treatment is carried out on the nano calcium carbonate by phosphate ester, the phosphate ester group can be used as a living site for reacting with the silane coupling agent, and the silane coupling agent is coated on the surface of the nano calcium carbonate through chemical action, so that the binding force between the silane coupling agent and the nano calcium carbonate is improved.
Preferably, the silane coupling agent is a triamino silane.
By adopting the technical scheme, the triamine silane has a large number of amino functional groups, and the amino functional groups can improve the inorganic-organic interface adhesive force in a structural sealant system, so that the soaking adhesive property is improved.
Preferably, the viscosity of the base rubber at 25 ℃ is 500-80000mpa & s, and the volatile component is less than or equal to 0.5 percent.
By adopting the technical scheme, the parameters of the base rubber are limited, and the base rubber can be better matched with the cross-linking agent for curing, so that the bonding property is improved.
In a second aspect, the application provides a preparation method of a novel two-component silicone structural sealant, which adopts the following technical scheme:
a preparation method of a novel two-component silicone structural sealant comprises the following steps:
mixing nanometer calcium carbonate, base gum, and dimethyl silicone oil at 50-90 deg.C and vacuum degree (-0.09Mpa) - (-0.1Mpa), and packaging separately to obtain component A;
according to the weight portion, the carbon black is evenly stirred at the temperature of 110-150 ℃ and the vacuum degree of (-0.09Mpa) - (-0.1Mpa), then the first cross-linking agent and the second cross-linking agent are added and mixed under the condition that the vacuum degree is-0.09 Mpa to-0.1 Mp, the gas phase silicon dioxide is added and evenly mixed, finally the coupling agent and the catalyst are added and evenly mixed under the condition that the vacuum degree is-0.09 Mp to-0.1 Mp, and the mixture is packaged separately to form the component B.
By adopting the technical scheme, the scheme is simple to operate, has no special requirement on processing equipment, and is suitable for mass production.
In summary, the present application has the following beneficial effects:
1. according to the application, the propyl trimethoxy silane oligomer is adopted as a cross-linking agent to be matched with other components such as base glue and the like, so that the deep curing speed is improved, the bonding strength of the prepared structural sealant under standard conditions can reach 1.65-2.91MPa, the bonding strength after soaking can reach 1.28-2.36MPa, the bonding performance and the soaking bonding performance are excellent, the thermal weight loss after thermal aging treatment is 0.4-2.3%, and the ageing resistance is excellent.
2. In the application, the nano calcium carbonate is preferably subjected to surface modification treatment, the bonding strength of the prepared structural sealant under standard conditions can reach 2.67-2.91MPa, the bonding strength after soaking can reach 2.15-2.36MPa, and the soaking bonding performance is further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples of starting materials and intermediates
Raw materials
The base glue is 107 base glue;
the volatile component of the gas-phase silicon dioxide is less than or equal to 0.5 percent, and the specific surface area is 130-2In this example, the volatile component used was 0.2%, and the specific surface area was 150m2/g；
The first cross-linking agent is any one of methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyl orthosilicate and ethyl orthosilicate, and in the embodiment, methyltriethoxysilane is selected;
the coupling agent is any one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, and aminopropyltriethoxysilane is selected in the embodiment;
the catalyst is dibutyltin dilaurate;
the mass percentage concentration of the concentrated hydrochloric acid is 37 percent;
the phosphate is 1006P isomeric dodecyl alcohol polyoxyethylene ether phosphate;
other raw materials are all commercially available.
Preparation example
Preparation example 1
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1600g of propyl trimethoxy silane, 200g of methanol and 18g of concentrated hydrochloric acid are added into a 3000ml three-neck flask and are uniformly mixed to obtain a mixed solution A, a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the mixed solution A is stirred and heated to 50 ℃, a mixed solution of 88g of water and 212g of methanol is dropped into the mixed solution A through the constant pressure dropping funnel, and hydrolysis of the propyl trimethoxy silane is carried out;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 110 ℃, carrying out polymerization reaction for 2 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain a colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 4, and the NMR spectrum showed absorption peaks at 0.592ppm, 0.922ppm, 1.425ppm, and 3.503 ppm.
Preparation example 2
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. adding 1700g of propyl trimethoxy silane, 230g of methanol and 48g of concentrated hydrochloric acid into a 3000ml three-neck flask, uniformly mixing to obtain a mixed solution A, installing a reflux condenser, a thermometer and a constant pressure dropping funnel on the three-neck flask, stirring and heating the mixed solution A to 40 ℃, dropping a mixed solution of 186g of water and 400g of methanol into the mixed solution A through the constant pressure dropping funnel, and hydrolyzing the propyl trimethoxy silane;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 130 ℃, carrying out polymerization reaction for 4 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain a colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 6, and the NMR spectrum showed absorption peaks at 0.590ppm, 0.924ppm, 1.422ppm and 3.499 ppm.
Preparation example 3
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1700g of propyl trimethoxy silane, 200g of methanol and 48g of concentrated hydrochloric acid are added into a 3000ml three-neck flask and are uniformly mixed to obtain a mixed solution A, a reflux condenser tube, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the mixed solution A is stirred and heated to 50 ℃, the mixed solution of 746g of water and 700g of methanol is dropped into the mixed solution A through the constant pressure dropping funnel, and hydrolysis of the propyl trimethoxy silane is carried out;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 130 ℃, carrying out polymerization reaction for 4 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain a colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 24, and the NMR spectrum showed absorption peaks at 0.591ppm, 0.920ppm, 1.420ppm, and 3.501 ppm.
Preparation example 4
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. adding 1700g of propyl trimethoxy silane, 200g of methanol and 48g of concentrated hydrochloric acid into a 3000ml three-neck flask, uniformly mixing to obtain a mixed solution A, installing a reflux condenser, a thermometer and a constant pressure dropping funnel on the three-neck flask, stirring and heating the mixed solution A to 50 ℃, dropping 932g of mixed solution of water and 970g of methanol into the mixed solution A through the constant pressure dropping funnel, and hydrolyzing the propyl trimethoxy silane;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 130 ℃, carrying out polymerization reaction for 4 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain a colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 30, and the hydrogen nuclear magnetic resonance spectrum showed absorption peaks at 0.592ppm, 0.923ppm, 1.421ppm, and 3.499 ppm.
Preparation example 5
The preparation method of the modified nano calcium carbonate comprises the following steps:
weighing 1000g of nano calcium carbonate, soaking the nano calcium carbonate in a silane coupling agent KH570 solution, filtering the solution after 30min, and drying solid matters at 85 ℃ to obtain the modified nano calcium carbonate.
Preparation example 6
Unlike preparation example 4, the silane coupling agent in preparation example 5 was triaminosilane YC-618.
Preparation example 7
The preparation method of the modified nano calcium carbonate comprises the following steps:
B1. weighing 1000g of nano calcium carbonate, soaking in a phosphate solution, filtering after 30min, and drying solid at 85 ℃ to obtain primary modified nano calcium carbonate;
B2. and (3) soaking the primarily modified nano calcium carbonate obtained from B1 in a triamino silane YC-618 solution for 30min, filtering, and drying the solid at 85 ℃ to obtain the modified nano calcium carbonate.
Examples
Examples 1 to 5
The novel two-component silicone structural sealant is prepared by the following steps:
s1, adding nano calcium carbonate, base rubber and dimethyl silicone oil into a reaction kettle according to the raw material proportion in Table 1, stirring for 1.5 hours in a planetary dispersion machine at 50 ℃, and under the condition that the vacuumizing vacuum degree is-0.09 Mpa, and independently packaging the obtained mixture to be a component A;
wherein the weight ratio of the particle size of the nano calcium carbonate to the particle size of the nano calcium carbonate is 1:1, the weight of the nano calcium carbonate is 30-60nm, the weight of the nano calcium carbonate is 60-70nm, and the volatile matter is 0.2 percent; the viscosity of the base rubber at 25 ℃ is 12000mpa & s, and the volatile matter is 0.2 percent;
adding carbon black into a reaction kettle according to the raw material ratio in the table 1, stirring for 10min in a planetary dispersion machine at the temperature of 110 ℃, under the condition of vacuumizing vacuum degree of-0.09 Mpa, then adding a first cross-linking agent and a second cross-linking agent of propyl trimethoxy silane oligomer, stirring for 30min under the vacuum degree of-0.09 Mpa, adding fumed silica, stirring for 30min, finally adding a coupling agent and a catalyst, stirring for 60min under the vacuum degree of-0.09 Mpa, and independently packaging the obtained mixture to be a component B;
wherein the propyltrimethoxysilane oligomer was obtained from preparation example 1.
TABLE 1 EXAMPLES 1-5 raw materials proportioning Table (100g)
Example 2 in step S1, the temperature was 90 ℃ and the vacuum was-0.1 MPa; in step S2, the temperature is 150 deg.C and the vacuum degree is-0.1 Mpa.
Example 6
In contrast to example 3, the propyltrimethoxysilane oligomer of example 6 was obtained from preparation 2.
Examples 7 to 11
Unlike example 3, examples 7-11 differ in the grading of the nano calcium carbonate particle size, as detailed in table 2.
TABLE 2 grading table of the particle size of the nano calcium carbonate in example 3 and examples 7-11 (100g)
| Example 3 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| 30-60nm | 25.0 | 0 | 25.0 | 34.0 | 37.5 | 16.0 |
| 80-100nm | 0 | 25.0 | 25.0 | 16.0 | 12.5 | 34.0 |
| 60-70nm | 25.0 | 25.0 | 0 | 0 | 0 | 0 |
Examples 12 to 14
Unlike example 9, examples 12-14 each replaced the same amount of modified nanocalcium carbonate from preparations 5-7 instead of nanocalcium carbonate.
Comparative example
Comparative example 1
In contrast to example 1, the methyltrimethoxysilane oligomer of comparative example 1 was obtained from preparation example 3.
Comparative example 2
In contrast to example 1, the trimethoxysilylsilane oligomer of comparative example 2 was obtained from preparation 4.
Comparative example 3
Unlike example 1, the second crosslinking agent in comparative example 3 was methyl orthosilicate.
Performance test
Detection method
According to the method and requirements in GB16776-2005, the thermal weight loss, the elongation at 23 ℃ and the maximum tensile bond strength, and the tensile bond strength after soaking of the novel two-component silicone structure sealant in examples 1-14 and comparative examples 1-3 were tested, and the test results are shown in Table 3, wherein the weight ratio of the component A to the component B is 9: 1 and mixing.
TABLE 3 Performance test results
Combining examples 1-14 and comparative examples 1-3, and combining Table 3, it can be seen that the tensile strength under the standard conditions in examples 1-14, as well as the elongation at which the maximum tensile strength is reached, and the bonding strength after soaking are all superior to those in comparative examples 1-3, which indicates that the two-component silicone structural sealant prepared by the application has better bonding performance and soaking bonding performance; in addition, the thermal weight loss after the thermal aging treatment in examples 1-14 is less than that in comparative examples 1-3, which shows that the two-component silicone structural sealant prepared by the method has better aging resistance.
By combining example 1 with comparative examples 1-3 and table 3, it can be seen that the tensile strength under the standard conditions and the elongation at which the maximum tensile strength is achieved, the bonding strength after soaking in water, and the thermal weight loss in example 1 are all superior to those in comparative examples 1-3, which indicates that the structural sealant prepared by using the propyltrimethoxysilane oligomer prepared by the method as the second crosslinking agent has better bonding performance, soaking bonding performance, and aging resistance, while the structural sealant prepared by using other crosslinking agents or prepared propyltrimethoxysilane polymers with polymerization degrees beyond the polymerization degrees defined by the method has significantly reduced bonding performance, soaking bonding performance, and aging resistance, probably because the propyltrimethoxysilane oligomer prepared by the method can generate better matching effect with other components such as base glue and the like to improve the deep curing effect, the adhesive property, the soaking adhesive property and the ageing resistance are improved.
By combining the examples 3 with the examples 7-11 and by combining the table 3, it can be seen that the adhesive property, the water-soaked adhesive property and the anti-aging property of the structural sealant are changed along with the change of the nano calcium carbonate particle size grading, wherein the examples 8-10 are more excellent, which shows that the adhesive property, the water-soaked adhesive property and the anti-aging property of the prepared structural sealant are more excellent within the nano calcium carbonate grading range of the application.
By combining example 9 with examples 12-14 and by combining table 3, it can be seen that the adhesive property, the water-soaked adhesive property and the anti-aging property of examples 12-14 are better than those of example 9, probably because the nano calcium carbonate is modified to improve the dispersibility of the nano calcium carbonate, so that the nano calcium carbonate is more uniformly dispersed in the structural sealant system.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A novel two-component silicone structural sealant comprises a component A and a component B, and is characterized in that:
the component A comprises the following raw materials in parts by weight:
30-70 parts of nano calcium carbonate, 20-55 parts of base rubber and 2-35 parts of dimethyl silicone oil;
the component B comprises the following raw materials in parts by weight:
10-30 parts of carbon black, 3-15 parts of fumed silica, 20-40 parts of simethicone, 10-50 parts of a first cross-linking agent, 10-45 parts of a second cross-linking agent, 10-45 parts of a coupling agent and 0.01-0.14 part of a catalyst;
wherein the second crosslinking agent is propyl trimethoxy silane oligomer, and the structural formula is as follows:
wherein n = 4-6.
2. The novel two-component silicone structural sealant as claimed in claim 1, wherein: the component A comprises the following raw materials in parts by weight:
40-60 parts of nano calcium carbonate, 30-50 parts of base rubber and 5-30 parts of dimethyl silicone oil;
the component B comprises the following raw materials in parts by weight:
15-20 parts of carbon black, 5-10 parts of fumed silica, 25-30 parts of simethicone, 15-40 parts of a first cross-linking agent, 15-40 parts of a second cross-linking agent, 15-40 parts of a coupling agent and 0.01-0.1 part of a catalyst.
3. The novel two-component silicone structural sealant as claimed in claim 1, wherein: the preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. uniformly mixing 1600-1700 parts of propyl trimethoxy silane, 200-230 parts of methanol and 18-48 parts of concentrated hydrochloric acid to obtain a mixed solution A, stirring the mixed solution A, heating to 40-50 ℃, and dropwise adding the mixed solution of 88-183 parts of water and 212-400 parts of methanol into the mixed solution A to hydrolyze the propyl trimethoxy silane;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 110-130 ℃, carrying out polymerization reaction for 2-4h, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain a colorless and transparent propyl trimethoxy silane oligomer.
4. The novel two-component silicone structural sealant as claimed in claim 1, wherein: the grain size of the nano calcium carbonate is 30-100nm, and the volatile matter is less than or equal to 0.5 percent.
5. The novel two-component silicone structural sealant as claimed in claim 4, wherein: the weight ratio of the particle size of the nano calcium carbonate between 30-60nm and 80-100nm is (1-3): 1.
6. the novel two-component silicone structural sealant as claimed in claim 1, wherein:
the nano calcium carbonate is subjected to modification treatment, and the treatment method comprises the following steps:
and (3) carrying out surface treatment on the nano calcium carbonate by using a silane coupling agent.
7. The novel two-component silicone structural sealant as claimed in claim 6, wherein: before modification of the silane coupling agent, the nano calcium carbonate is soaked in a phosphate solution for surface treatment, and then is filtered and dried.
8. The novel two-component silicone structural sealant as claimed in claim 6, wherein: the silane coupling agent is triamine silane.
9. The novel two-component silicone structural sealant as claimed in claim 1, wherein: the viscosity of the base adhesive at 25 ℃ is 500-80000mpa & s, and the volatile component is less than or equal to 0.5 percent.
10. A method of preparing a novel two-component silicone construction sealant as claimed in any one of claims 1 to 9 which comprises the steps of:
mixing nanometer calcium carbonate, base gum, and dimethyl silicone oil at 50-90 deg.C and vacuum degree (-0.09Mpa) - (-0.1Mpa), and packaging separately to obtain component A;
according to the weight portion, the carbon black is stirred uniformly under the conditions of 110-150 ℃ and vacuum degree (-0.09Mpa) - (-0.1Mpa), then the first cross-linking agent and the second cross-linking agent are added and stirred and mixed under the condition of vacuum degree (-0.09Mpa) -0.1Mp, then the gas phase silicon dioxide is added and mixed uniformly, finally the coupling agent and the catalyst are added and mixed uniformly under the condition of vacuum degree (-0.09Mpa) - (-0.1Mpa), and the mixture is packaged separately to be the component B.
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Effective date of registration: 20240618 Address after: 311203 Huang Jiahe, Shushan street, Xiaoshan District, Zhejiang, Hangzhou Patentee after: HANGZHOU ZHIJIANG SILICONE CHEMICALS Co.,Ltd. Country or region after: China Patentee after: HANGZHOU ZHIJIANG SILICONE Co.,Ltd. Patentee after: Fenotek New Materials (Hangzhou) Co.,Ltd. Address before: 311200 Huangjiahe, Shushan street, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: HANGZHOU ZHIJIANG SILICONE CHEMICALS Co.,Ltd. Country or region before: China Patentee before: HANGZHOU ZHIJIANG SILICONE Co.,Ltd. |