CN115287036B - Organosilicon sealant and production process thereof - Google Patents
Organosilicon sealant and production process thereof Download PDFInfo
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- CN115287036B CN115287036B CN202210987069.2A CN202210987069A CN115287036B CN 115287036 B CN115287036 B CN 115287036B CN 202210987069 A CN202210987069 A CN 202210987069A CN 115287036 B CN115287036 B CN 115287036B
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- 239000000565 sealant Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000006229 carbon black Substances 0.000 claims abstract description 69
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 239000004590 silicone sealant Substances 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 241000872198 Serjania polyphylla Species 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 7
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000413 hydrolysate Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- DKGZKEKMWBGTIB-UHFFFAOYSA-N [diacetyloxy(propyl)silyl] acetate Chemical compound CCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O DKGZKEKMWBGTIB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000012974 tin catalyst Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect 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
- 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an organosilicon sealant and a production process thereof. The composite material comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 10-30 parts of silicone oil, 5-30 parts of grafted white carbon black, 0-60 parts of nano calcium carbonate, 1-8 parts of cross-linking agent, 1-8 parts of silane coupling agent and 0.01-5 parts of organotin catalyst; the grafted white carbon black is gas-phase white carbon black grafted by acrylic ester, and the gas-phase white carbon black is grafted by an aminosilane coupling agent and the acrylic ester. The organic silicon sealant for PET prepared by the invention has excellent mechanical strength, low modulus, excellent adhesive force, good damp-heat resistance and room temperature self-curing property. Solves the problems of poor adhesiveness, easy peeling due to damp and heat and the like of the traditional organic silicon sealant on polymer products, and has wide application prospect.
Description
Technical Field
The invention relates to an organic silicon sealant, in particular to an organic silicon sealant for PET and a production process thereof.
Background
The organic silicon sealant has good weather resistance, durability, ultraviolet aging resistance, excellent sealing property and thermal stability, wide use temperature range and good flexibility, and has wide application in the fields of buildings, automobiles, aerospace, ships, electric appliances and the like. Common silicone sealants can be classified into various types such as deacidification type, dealcoholization type, ketoxime type, deamination type, and the like according to the types of crosslinking agents and low-molecular byproducts. The deacidification type organic silicon sealant has high reactivity, good cohesiveness and low cost, and is one of important categories of organic silicon sealants.
The traditional organic silica gel adhesive is mainly applied to the building industry, such as hollow glass, glass curtain walls, externally hung wallboards, metal frame structures and the like, an adhesion object is mainly inorganic nonmetallic materials such as glass, cement, ceramics and the like or metal materials such as alloy, steel and the like, the adhesion object does not show good adhesion to polymer materials such as PET, PP, PC and the like, and the adhesive has the problems of easy stripping, falling off in a damp-heat state, poor flexibility, incomplete solidification and the like, so that a great amount of improvement space is still provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organosilicon sealant and a production process thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the organic silicon sealant comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 10-30 parts of silicone oil, 5-30 parts of grafted white carbon black, 0-60 parts of nano calcium carbonate, 1-8 parts of cross-linking agent, 1-8 parts of silane coupling agent and 0.01-5 parts of organotin catalyst;
the grafted white carbon black is gas-phase white carbon black grafted by acrylic ester.
The grafted white carbon black comprises the following components in parts by weight: 80-100 parts of absolute ethyl alcohol, 5-20 parts of water, 1-20 parts of an aminosilane coupling agent, 3-15 parts of gas-phase white carbon black, 3-20 parts of an acrylic ester monomer, 150-250 parts of methanol and 1-5 parts of ethylenediamine.
The aminosilane coupling agent is any one or two or more than two of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N-beta-aminoethyl-gamma-aminopropyl triethoxysilane, N-beta-aminoethyl-gamma-aminopropyl methyl diethoxysilane and N, N' -bis (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane.
The acrylic ester monomer is one or two or more of methyl acrylate, ethyl acrylate and butyl acrylate.
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 10000cs-80000cs; the viscosity of the silicone oil is 500cs-3000cs; the grain diameter of the nano calcium carbonate is less than or equal to 300nm; the grain diameter of the grafted white carbon black is less than or equal to 300nm.
The cross-linking agent is any one or two or more than two of methyl triacetoxy silane, ethyl triacetoxy silane, propyl triacetoxy silane and vinyl triacetoxy silane.
The silane coupling agent is one or two or more of KH550, KH560, KH570 and KH 792.
The organotin catalyst is any one or two or more of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate and dibutyltin dilaurate.
The production process of the organic silicon sealant comprises the following steps:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) Mixing alpha, omega-dihydroxyl polydimethylsiloxane, silicone oil, grafted white carbon black and nano calcium carbonate, and vacuum kneading for 3 hours to remove excessive water to obtain uniformly mixed base adhesive;
(3) Adding a cross-linking agent and a silane coupling agent, and stirring in vacuum for 10-30min;
(4) Adding an organotin catalyst, and stirring in vacuum for 10-30min;
(5) And stirring to obtain the organosilicon sealant.
The production process of the grafted white carbon black comprises the following steps:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) According to absolute ethyl alcohol: the water is 9:1, is used for dissolving an aminosilane coupling agent to obtain an aminosilane coupling agent hydrolysate with the mass concentration of 1-20%;
(3) Adding gas-phase white carbon black into the hydrolysate of the amino silane coupling agent, and carrying out ultrasonic reaction for 6h at 60 ℃;
(4) Filtering after ultrasonic treatment, washing with absolute ethyl alcohol, and drying at 80 ℃ for 24 hours to obtain gas-phase white carbon black with amino active groups;
(5) Mixing gas-phase white carbon black with amino active groups, acrylate monomers and methanol, and reacting for 2 hours at 50 ℃;
(6) Adding ethylenediamine, and continuing to react for 4 hours at 50 ℃;
(7) And after the reaction is finished, carrying out suction filtration, washing with absolute ethyl alcohol for 3-5 times, drying at 80 ℃ for 24 hours, and grinding to obtain the acrylate grafted gas-phase white carbon black, namely the grafted white carbon black.
The invention has the beneficial effects that:
the invention relates to an organosilicon sealant for PET plastic, which is prepared by grafting gas-phase white carbon black by using an aminosilane coupling agent and acrylic ester, and is used as a reinforcing filler to be applied to silica gel.
Because the traditional gas-phase white carbon black has high specific surface area, large oil absorption value, rich hydroxyl on the surface, high hydrophilicity, difficulty in dispersing in base rubber and high thixotropic viscosity of the product, the traditional gas-phase white carbon black is unfavorable for the mechanical strength and the curing speed of silica gel, and the prepared product is low in strength, poor in adhesiveness and poor in usability. Therefore, the invention is beneficial to the grafting treatment of the acrylic ester on the common white carbon black, on one hand, increases the dispersibility of the white carbon black in the silica gel, plays a role in reducing viscosity to a certain extent, and improves the mechanical strength of the sealant; on the other hand, the adhesion between the sealant and the PET substrate is improved, so that the adhesion is greatly improved.
The organic silicon sealant for PET prepared by the invention has excellent mechanical strength, low modulus, excellent adhesive force, good damp-heat resistance and room temperature self-curing property. Wherein, the adhesive force test can reach 5B, the tensile shear strength can reach 1.068MPa,1000h wet heat resistance test: the coating does not fall off, has good adhesion, and is tested at high temperature (heating for 60min in 180 ℃) and 180 DEG bending: the coating does not fall off, has good bending flexibility, and can reach 8 levels in salt spray corrosion resistance test. The invention solves the problems of poor adhesiveness, easy peeling due to damp and heat and the like of the traditional organic silicon sealant on polymer products, and has wide application prospect.
Drawings
FIG. 1 is a flow chart of a grafting modification process of the gas phase white carbon black.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. Unless otherwise specified, the instruments and devices involved in the embodiments are all conventional instruments and devices; the related raw materials are all conventional raw materials sold in the market; the related test methods are all conventional methods.
Example 1 production Process of grafted white carbon Black
The grafted white carbon black comprises the following components in parts by weight: 90 parts of absolute ethyl alcohol, 10 parts of water, 5 parts of gamma-aminopropyl triethoxy silane coupling agent, 12 parts of gas-phase white carbon black, 15 parts of methyl acrylate monomer, 200 parts of methanol and 2 parts of ethylenediamine.
The production process of the grafted white carbon black comprises the following steps:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) According to absolute ethyl alcohol: the water is 9:1, is used for dissolving gamma-aminopropyl triethoxysilane coupling agent to obtain gamma-aminopropyl triethoxysilane hydrolysate with mass concentration of 5%;
(3) Adding gas-phase white carbon black into gamma-aminopropyl triethoxysilane hydrolysate, and performing ultrasonic reaction at 60 ℃ for 6h at 30-80 KHz;
(4) Filtering after ultrasonic treatment, washing with absolute ethyl alcohol for 3-5 times, and drying at 80 ℃ for 24 hours to obtain gas-phase white carbon black with amino active groups;
(5) Mixing gas-phase white carbon black with amino active groups, methyl acrylate monomer and methanol, and reacting for 2 hours at 50 ℃;
(6) Adding ethylenediamine, and continuing to react for 4 hours at 50 ℃;
(7) And after the reaction is finished, carrying out suction filtration, washing 3-5 times by using absolute ethyl alcohol, drying at 80 ℃ for 24 hours, and grinding to obtain the acrylate grafted gas-phase white carbon black, namely the grafted white carbon black.
Example 2 production Process of grafted white carbon Black
The grafted white carbon black comprises the following components in parts by weight: 85 parts of absolute ethyl alcohol, 15 parts of water, 5 parts of gamma-aminopropyl trimethoxy silane coupling agent, 12 parts of gas-phase white carbon black, 15 parts of butyl acrylate monomer, 200 parts of methanol and 2.5 parts of ethylenediamine.
The production process of the grafted white carbon black is the same as in example 1.
Example 3
The grafted white carbon black comprises the following components in parts by weight: 95 parts of absolute ethyl alcohol, 5 parts of water, 4 parts of N-beta-aminoethyl-gamma-aminopropyl triethoxysilane coupling agent, 10 parts of gas-phase white carbon black, 13 parts of ethyl acrylate monomer, 200 parts of methanol and 1.5 parts of ethylenediamine.
The production process of the grafted white carbon black is the same as in example 1.
Example 4 production Process of Silicone sealants
The organic silicon sealant comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue), 20 parts of silicone oil, 10 parts of grafted white carbon black, 40 parts of nano calcium carbonate, 3 parts of methyl triacetoxy silane, 2 parts of vinyl triacetoxy silane, 2 parts of KH570 silane coupling agent and 1.5 parts of dibutyltin diacetate.
Wherein the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 10000cs-80000cs; the viscosity of the silicone oil is 500cs-3000cs; the grafted white carbon black is prepared in example 1; the grain diameter of the grafted white carbon black is less than or equal to 300nm; the grain diameter of the nano calcium carbonate is less than or equal to 300nm.
The production process of the organic silicon sealant comprises the following steps:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) Firstly, mixing 107 glue, silicone oil, grafted white carbon black and nano calcium carbonate, and vacuum kneading for 3 hours in a kneader to remove excessive water to obtain evenly mixed base glue;
(3) Adding methyltriacetoxysilane, vinyltriacetoxysilane and KH570 silane coupling agent, and vacuum mixing for 30min;
(4) Adding dibutyl tin diacetate, and vacuum mixing for 15min;
(5) Extruding and bottling to obtain the organic silicon sealant for PET.
Example 5 production Process of Silicone sealants
The organic silicon sealant comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue), 20 parts of silicone oil, 8 parts of grafted white carbon black, 50 parts of nano calcium carbonate, 4 parts of methyl triacetoxy silane, 4 parts of propyl triacetoxy silane, 2 parts of KH560 silane coupling agent and 1.5 parts of dibutyltin diacetate.
The grafted white carbon black is prepared in example 2; the performance parameters of the raw materials and the production process of the organosilicon sealant are the same as in example 4.
Example 6 production Process of Silicone sealants
The organic silicon sealant comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue), 30 parts of silicone oil, 12 parts of grafted white carbon black, 30 parts of nano calcium carbonate, 2 parts of propyl triacetoxy silane, 4 parts of vinyl triacetoxy silane, 5 parts of KH560 silane coupling agent and 1.5 parts of dibutyl tin dilaurate.
The grafted white carbon black is prepared in example 1; the performance parameters of the raw materials and the production process of the organosilicon sealant are the same as in example 4.
Example 7 production Process of Silicone sealants
The organic silicon sealant comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue), 30 parts of silicone oil, 5 parts of grafted white carbon black, 60 parts of nano calcium carbonate, 4 parts of methyltriacetoxysilane, 3 parts of vinyl triacetoxysilane, 4 parts of KH560 silane coupling agent and 1.5 parts of dibutyltin dilaurate.
The grafted white carbon black is prepared in example 3; the performance parameters of the raw materials and the production process of the organosilicon sealant are the same as in example 4.
Production process of organosilicon sealant of comparative example 1
The comparative example used a conventional fumed silica which had not been subjected to a grafting treatment.
The organic silicon sealant comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue), 20 parts of silicone oil, 10 parts of gas-phase white carbon black, 40 parts of nano calcium carbonate, 3 parts of methyl triacetoxy silane, 3 parts of vinyl triacetoxy silane, 5 parts of KH570 silane coupling agent and 1.5 parts of dibutyltin diacetate.
The performance parameters of the raw materials and the production process of the organosilicon sealant are the same as in example 4.
Performance measurement
The products obtained in examples 4 to 7 and comparative example 1 were subjected to performance test, and the results are shown in Table 1 below.
TABLE 1
Claims (9)
1. The organic silicon sealant is characterized by comprising the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 10-30 parts of silicone oil, 5-30 parts of grafted white carbon black, 0-60 parts of nano calcium carbonate, 1-8 parts of cross-linking agent, 1-8 parts of silane coupling agent and 0.01-5 parts of organotin catalyst;
the grafted white carbon black is gas-phase white carbon black grafted by acrylic ester;
the grafted white carbon black comprises the following components in parts by weight: 80-100 parts of absolute ethyl alcohol, 5-20 parts of water, 1-20 parts of an aminosilane coupling agent, 3-15 parts of gas-phase white carbon black, 3-20 parts of an acrylic ester monomer, 150-250 parts of methanol and 1-5 parts of ethylenediamine;
the production process of the grafted white carbon black comprises the following steps:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) According to absolute ethyl alcohol: the water is 9:1, is used for dissolving an aminosilane coupling agent to obtain an aminosilane coupling agent hydrolysate with the mass concentration of 1-20%;
(3) Adding gas-phase white carbon black into the hydrolysate of the amino silane coupling agent, and carrying out ultrasonic reaction for 6h at 60 ℃;
(4) Filtering after ultrasonic treatment, washing with absolute ethyl alcohol, and drying at 80 ℃ for 24 hours to obtain gas-phase white carbon black with amino active groups;
(5) Mixing gas-phase white carbon black with amino active groups, acrylate monomers and methanol, and reacting for 2 hours at 50 ℃;
(6) Adding ethylenediamine, and continuing to react for 4 hours at 50 ℃;
(7) And after the reaction is finished, carrying out suction filtration, washing with absolute ethyl alcohol for 3-5 times, drying at 80 ℃ for 24 hours, and grinding to obtain the acrylate grafted gas-phase white carbon black, namely the grafted white carbon black.
2. The silicone sealant of claim 1, wherein the aminosilane coupling agent is a combination of any one or two or more of γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, N- β -aminoethyl- γ -aminopropyl triethoxysilane, N- β -aminoethyl- γ -aminopropyl methyldiethoxysilane, N' -bis (β -aminoethyl) - γ -aminopropyl trimethoxysilane.
3. The silicone sealant of claim 1, wherein the acrylate monomer is a compound of one or two or more of methyl acrylate, ethyl acrylate, and butyl acrylate.
4. The silicone sealant of claim 1, wherein the α, ω -dihydroxy polydimethylsiloxane has a viscosity of 10000cs-80000cs; the viscosity of the silicone oil is 500cs-3000cs; the grain diameter of the nano calcium carbonate is less than or equal to 300nm; the grain diameter of the grafted white carbon black is less than or equal to 300nm.
5. The silicone sealant of claim 1, wherein the cross-linking agent is a combination of one or two or more of methyltriacetoxysilane, ethyltriacetoxysilane, propyltriacetoxysilane, and vinyltriacetoxysilane.
6. The silicone sealant of claim 1, wherein the silane coupling agent is a compound of any one or two or more of KH550, KH560, KH570, KH 792.
7. The organic silicon sealant according to claim 1, wherein the organic tin catalyst is a compound of any one or two or more of dibutyl tin dilaurate, dibutyl tin diacetate, stannous octoate and dibutyl tin dilaurate.
8. The process for producing the silicone sealant according to any one of claims 1 to 7, comprising the steps of:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) Mixing alpha, omega-dihydroxyl polydimethylsiloxane, silicone oil, grafted white carbon black and nano calcium carbonate, and vacuum kneading for 3 hours to remove excessive water to obtain uniformly mixed base adhesive;
(3) Adding a cross-linking agent and a silane coupling agent, and stirring in vacuum for 10-30min;
(4) Adding an organotin catalyst, and stirring in vacuum for 10-30min;
(5) And stirring to obtain the organosilicon sealant.
9. The process according to claim 8, wherein the process for producing grafted white carbon black comprises the steps of:
(1) Weighing the components according to the proportion of the raw materials for standby;
(2) According to absolute ethyl alcohol: the water is 9:1, is used for dissolving an aminosilane coupling agent to obtain an aminosilane coupling agent hydrolysate with the mass concentration of 1-20%;
(3) Adding gas-phase white carbon black into the hydrolysate of the amino silane coupling agent, and carrying out ultrasonic reaction for 6h at 60 ℃;
(4) Filtering after ultrasonic treatment, washing with absolute ethyl alcohol, and drying at 80 ℃ for 24 hours to obtain gas-phase white carbon black with amino active groups;
(5) Mixing gas-phase white carbon black with amino active groups, acrylate monomers and methanol, and reacting for 2 hours at 50 ℃;
(6) Adding ethylenediamine, and continuing to react for 4 hours at 50 ℃;
(7) And after the reaction is finished, carrying out suction filtration, washing with absolute ethyl alcohol for 3-5 times, drying at 80 ℃ for 24 hours, and grinding to obtain the acrylate grafted gas-phase white carbon black, namely the grafted white carbon black.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106940A (en) * | 1999-10-04 | 2001-04-17 | Nippon Aerosil Co Ltd | Method for producing dendrimer-grafted fine powder |
| JP2003064281A (en) * | 2001-08-27 | 2003-03-05 | Nippon Aerosil Co Ltd | Highly water-absorbing inorganic oxide powder and its production method |
| CN101792653A (en) * | 2010-03-19 | 2010-08-04 | 江苏明昊新材料科技有限公司 | Sealant for acrylic ester modified solar photovoltaic module and preparation method thereof |
| CN102382615A (en) * | 2010-09-03 | 2012-03-21 | 广州市白云化工实业有限公司 | Organosilicon sealant for solar photovoltaic modules and preparation method for organosilicon sealant |
| CN107353869A (en) * | 2017-07-17 | 2017-11-17 | 四川建筑职业技术学院 | It is a kind of to be used to emulate acid silicone adhesive of dinosaurs handicraft and preparation method thereof |
| CN109251720A (en) * | 2018-07-13 | 2019-01-22 | 中国航发北京航空材料研究院 | High-temperature resistant one-component depickling type room temperature vulcanized organosilicon sealant and preparation method thereof |
-
2022
- 2022-08-17 CN CN202210987069.2A patent/CN115287036B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106940A (en) * | 1999-10-04 | 2001-04-17 | Nippon Aerosil Co Ltd | Method for producing dendrimer-grafted fine powder |
| JP2003064281A (en) * | 2001-08-27 | 2003-03-05 | Nippon Aerosil Co Ltd | Highly water-absorbing inorganic oxide powder and its production method |
| CN101792653A (en) * | 2010-03-19 | 2010-08-04 | 江苏明昊新材料科技有限公司 | Sealant for acrylic ester modified solar photovoltaic module and preparation method thereof |
| CN102382615A (en) * | 2010-09-03 | 2012-03-21 | 广州市白云化工实业有限公司 | Organosilicon sealant for solar photovoltaic modules and preparation method for organosilicon sealant |
| CN107353869A (en) * | 2017-07-17 | 2017-11-17 | 四川建筑职业技术学院 | It is a kind of to be used to emulate acid silicone adhesive of dinosaurs handicraft and preparation method thereof |
| CN109251720A (en) * | 2018-07-13 | 2019-01-22 | 中国航发北京航空材料研究院 | High-temperature resistant one-component depickling type room temperature vulcanized organosilicon sealant and preparation method thereof |
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