CN116656315A - Halogen-free flame-retardant heat-conducting organic silicon pouring sealant and preparation method and application thereof - Google Patents
Halogen-free flame-retardant heat-conducting organic silicon pouring sealant and preparation method and application thereof Download PDFInfo
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- CN116656315A CN116656315A CN202310741329.2A CN202310741329A CN116656315A CN 116656315 A CN116656315 A CN 116656315A CN 202310741329 A CN202310741329 A CN 202310741329A CN 116656315 A CN116656315 A CN 116656315A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 239000000565 sealant Substances 0.000 title claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 43
- 239000010703 silicon Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000945 filler Substances 0.000 claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 30
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- -1 polydimethylsiloxane Polymers 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- JXOOCQBAIRXOGG-UHFFFAOYSA-N [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] Chemical compound [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] JXOOCQBAIRXOGG-UHFFFAOYSA-N 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004382 potting Methods 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UJYZRMROGXVXFD-UHFFFAOYSA-N 1-hex-1-ynylcyclohexan-1-ol Chemical compound CCCCC#CC1(O)CCCCC1 UJYZRMROGXVXFD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides a halogen-free flame-retardant heat-conducting organic silicon pouring sealant, which uses a certain amount of methyl vinyl MQV type silicon resin as a reinforcing agent and a certain amount of silazane as an adhesion promoter, so that the viscosity of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant is reduced, and the filling and the dispersion of modified heat-conducting filler and modified flame retardant are facilitated; the halogen-free flame-retardant heat-conducting organic silicon pouring sealant has the advantages that the compatibility of the modified flame retardant and the modified heat-conducting filler with the base adhesive is improved, the flame retardant performance and the heat-conducting performance are obviously improved, the halogen-free flame-retardant heat-conducting organic silicon pouring sealant has good adhesive performance, the halogen-free flame-retardant heat-conducting organic silicon pouring sealant is halogen-free and environment-friendly, and the service life is long by adding a certain amount of at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by the first coupling agent and a certain amount of at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by the second coupling agent as the modified heat-conducting filler.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a halogen-free flame-retardant heat-conducting organic silicon pouring sealant, and a preparation method and application thereof.
Background
With the rapid development of electronic science and technology, electronic components increasingly tend to be integrated, miniaturized and modularized, and stricter requirements are put on the use stability of the electronic components. The encapsulation can improve the integrity of the electronic device, prevent the damage of moisture, dust and harmful gas to the electronic device, and improve the flame retardance and the heat conduction performance, thereby prolonging the service life of the electronic device.
The organic silicon material has excellent electrical insulation performance, and has ideal water resistance, ultraviolet resistance and other performances, so the organic silicon material is a common electronic potting material. The addition type organosilicon pouring sealant is free from heat release during vulcanization, has no low molecular byproducts, small shrinkage rate and deep curing, can keep elasticity for a long time within the temperature range of-65 ℃ to 200 ℃ after vulcanization, has excellent electrical property and chemical stability, and has ideal water resistance, ultraviolet resistance, weather resistance, aging resistance and the like. However, the addition type organic silicon pouring sealant has poor adhesion performance with a substrate, especially a plastic substrate, after being cured due to low molecular polarity, and meanwhile, the addition type organic silicon pouring sealant has combustibility (limiting oxygen index is about 18 percent) and cannot meet the legal requirements of China, europe and America and the like on the flame retardance of electric appliances. And the heat conduction performance of the organic silicon pouring sealant in the prior art needs to be improved. Therefore, the halogen-free flame-retardant heat-conducting organic silicon pouring sealant is a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant heat-conducting organic silicon pouring sealant, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a halogen-free flame-retardant heat-conducting organic silicon pouring sealant, which comprises a component A and a component B;
the component A is prepared from the following raw materials in parts by weight: 40 to 60 parts of base adhesive, 5 to 15 parts of modified flame retardant, 40 to 100 parts of modified heat conducting filler, 3 to 16 parts of reinforcing agent, 0.3 to 2.0 parts of catalyst and 2 to 8 parts of adhesion promoter,
the component B is prepared from the following raw materials in parts by weight: 40 to 60 parts of base adhesive, 3 to 18 parts of modified flame retardant, 30 to 80 parts of modified heat conducting filler, 5 to 10 parts of reinforcing agent, 0.05 to 0.5 part of inhibitor and 2.5 to 8 parts of hydrogen-containing cross-linking agent;
the reinforcing agent is methyl vinyl MQV type silicon resin with the vinyl content of 1-3 wt%;
the modified flame retardant is at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by a first coupling agent;
the modified heat conducting filler is at least one of aluminum oxide, aluminum nitride, aluminum boride, silicon carbide or silicon nitride which is subjected to surface modification by a second coupling agent;
the adhesion promoter is silazane.
Preferably, the modified flame retardant has an average particle size of 2 to 8. Mu.m.
Preferably, the first coupling agent is an amino-terminated polydimethylsiloxane; the amino-terminated polydimethylsiloxane is at least one of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxysilane.
Preferably, the catalyst is an alcoholic solution of chloroplatinic acid or a vinylsiloxane complex of chloroplatinic acid.
Preferably, the second coupling agent is an epoxy silane coupling agent; the epoxy silane coupling agent is at least one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma- (2, 3-epoxypropoxy) propyl triethoxy silane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane.
The invention also provides a preparation method of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant, which comprises the following steps:
(1) Mixing a base adhesive, a modified flame retardant, a modified heat-conducting filler, a reinforcing agent, a catalyst and an adhesion promoter under a first vacuum condition, and performing first stirring heat treatment to obtain a component A;
(2) Mixing the base adhesive, the modified flame retardant, the modified heat-conducting filler and the reinforcing agent under a second vacuum condition, performing a second stirring heat treatment, adding the inhibitor and the hydrogen-containing crosslinking agent, and performing stirring treatment to obtain a component B;
(3) Mixing the component A obtained in the step (1) and the component B obtained in the step (2) with equal weight, and then sequentially carrying out defoaming stirring and curing to obtain the halogen-free flame-retardant heat-conducting organic silicon pouring sealant.
Preferably, the temperature of the first stirring heat treatment in the step (1) is 60-120 ℃, and the time of the first stirring heat treatment is 30-90 min.
Preferably, the time of defoaming and stirring in the step (3) is 3-10 min.
Preferably, the curing in the step (3) is room temperature curing or heat curing.
The invention also provides application of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant in electronic pouring sealant.
The invention provides a halogen-free flame-retardant heat-conducting organic silicon pouring sealant, which uses a certain amount of methyl vinyl MQV type silicon resin with vinyl content of 1-3wt% as a reinforcing agent, and cooperates with a certain amount of silazane as an adhesion promoter, so that the viscosity of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant is reduced, and the filling and the dispersion of modified heat-conducting filler and modified flame retardant are facilitated; the halogen-free flame-retardant heat-conducting organic silicon pouring sealant has the advantages that the compatibility of the modified flame retardant and the modified heat-conducting filler with the base adhesive is improved, the flame retardant property and the heat conducting property of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant are obviously improved, the halogen-free flame-retardant heat-conducting organic silicon pouring sealant has good bonding property, the halogen-free flame-retardant heat-conducting organic silicon pouring sealant is environment-friendly and has long service life, and a certain amount of at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by the first coupling agent is added as the modified flame retardant, and a certain amount of at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by the second coupling agent is added as the modified heat-conducting filler. The results of the examples show that the halogen-free flame-retardant heat-conducting organosilicon potting adhesive prepared by the examples of the invention has the advantages of low viscosity of 2600 mPa.s, good fluidity, flame retardant grade of V-0, high flame retardance, heat conductivity coefficient of 1.583W/m.K and excellent heat conductivity.
Detailed Description
The invention provides a halogen-free flame-retardant heat-conducting organic silicon pouring sealant, which comprises a component A and a component B;
the component A is prepared from the following raw materials in parts by weight: 40 to 60 parts of base adhesive, 5 to 15 parts of modified flame retardant, 40 to 100 parts of modified heat conducting filler, 3 to 16 parts of reinforcing agent, 0.3 to 2.0 parts of catalyst and 2 to 8 parts of adhesion promoter;
the component B is prepared from the following raw materials in parts by weight: 40 to 60 parts of base adhesive, 3 to 18 parts of modified flame retardant, 30 to 80 parts of modified heat conducting filler, 5 to 10 parts of reinforcing agent, 0.05 to 0.5 part of inhibitor and 2.5 to 8 parts of hydrogen-containing cross-linking agent;
the reinforcing agent is methyl vinyl MQV type silicon resin with the vinyl content of 1-3 wt%;
the modified flame retardant is at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by a first coupling agent;
the modified heat conducting filler is at least one of aluminum oxide, aluminum nitride, aluminum boride, silicon carbide or silicon nitride which is subjected to surface modification by a second coupling agent;
the adhesion promoter is silazane.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
In the invention, the halogen-free flame-retardant heat-conducting organosilicon pouring sealant is preferably prepared from a component A and a component B in a mass ratio of 1:1.
In the invention, the A component is preferably prepared from the following raw materials in parts by weight: 45-56 parts of base adhesive, 7-13 parts of modified flame retardant, 50-90 parts of modified heat conducting filler, 6-14 parts of reinforcing agent, 0.4-1.5 parts of catalyst and 3-7 parts of adhesion promoter.
In the invention, the component B is prepared from the following raw materials in parts by weight: 43-54 parts of base adhesive, 4-15 parts of modified flame retardant, 40-70 parts of modified heat conducting filler, 6-9 parts of reinforcing agent, 0.07-0.4 part of inhibitor and 3-7 parts of hydrogen-containing crosslinking agent.
In the present invention, the base gum is preferably vinyl polydimethylsiloxane; the vinyl polydimethylsiloxane is preferably at least one of linear vinyl polydimethylsiloxane or branched vinyl polydimethylsiloxane. In the invention, the vinyl content of the vinyl polydimethylsiloxane is 0.3 to 3.0 weight percent; the viscosity of the vinyl polydimethylsiloxane at 25℃is preferably 600 to 2500 mPas.
In the invention, the modified flame retardant is at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by the first coupling agent. In the present invention, the average particle diameter of the modified flame retardant is preferably 2 to 8. Mu.m.
In the present invention, the first coupling agent is an amino-terminated polydimethylsiloxane; the amino-terminated polydimethylsiloxane is at least one of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxysilane. The method for modifying the surface of the first coupling agent is not particularly limited, and any surface treatment method commonly used in the technical field can be adopted. In the present invention, the surface modification method of the first coupling agent is preferably to dilute the first coupling agent with a solvent, uniformly mix the diluted first coupling agent with an inorganic flame retardant including at least one of aluminum hydroxide and magnesium hydroxide, and then heat and dry the mixture to obtain the modified flame retardant. In the invention, the mass ratio of the first coupling agent to the inorganic flame retardant is (1-6): 100, more preferably (2 to 5): 100.
in the present invention, the catalyst is preferably an alcoholic solution of chloroplatinic acid or a vinyl siloxane complex of chloroplatinic acid.
In the invention, the modified heat conducting filler is at least one of aluminum oxide, aluminum nitride, aluminum boride, silicon carbide or silicon nitride which is subjected to surface modification by the second coupling agent. In the present invention, the modified heat conductive filler preferably has an average particle diameter of 2 to 8. Mu.m.
In the present invention, the second coupling agent is preferably an epoxy silane coupling agent; the epoxy silane coupling agent is preferably at least one of gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma- (2, 3-epoxypropoxy) propyl triethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane. The method for modifying the surface of the second coupling agent is not particularly limited, and any surface treatment method commonly used in the technical field can be adopted. In the present invention, the surface modification method of the second coupling agent is preferably to dilute the second coupling agent with a solvent, uniformly mix the diluted second coupling agent with an inorganic filler including at least one of aluminum oxide, aluminum nitride, aluminum boride, silicon carbide or silicon nitride, and then heat and dry the mixture to obtain the modified heat conductive filler. In the present invention, the mass ratio of the second coupling agent to the inorganic filler is preferably (1 to 6): 100, more preferably (2 to 5): 100.
in the present invention, the inhibitor is at least one of 3, 5-dimethyl-1-hexynyl-3-ol, 1-hexynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, 2-phenyl-3-butynyl-2-ol and vinyl ring.
In the invention, the hydrogen-containing cross-linking agent is hydrogen-containing silicone oil with the active hydrogen content of 0.1-1.6wt%.
The invention also provides a preparation method of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant, which comprises the following steps:
(1) Mixing a base adhesive, a modified flame retardant, a modified heat-conducting filler, a reinforcing agent, a catalyst and an adhesion promoter under a first vacuum condition, and performing first stirring heat treatment to obtain a component A;
(2) Mixing the base adhesive, the modified flame retardant, the modified heat-conducting filler and the reinforcing agent under a second vacuum condition, performing a second stirring heat treatment, adding the inhibitor and the hydrogen-containing crosslinking agent, and performing stirring treatment to obtain a component B;
(3) Mixing the component A obtained in the step (1) and the component B obtained in the step (2) with equal weight, and then sequentially carrying out defoaming stirring and curing to obtain the halogen-free flame-retardant heat-conducting organic silicon pouring sealant.
Under a first vacuum condition, the invention mixes the base adhesive, the modified flame retardant, the modified heat-conducting filler, the reinforcing agent, the catalyst and the adhesion promoter, and then carries out first stirring heat treatment to obtain the component A.
The first vacuum condition is not particularly limited in the present invention, and vacuum conditions conventional in the art may be used. The stirring rotation speed of the first stirring heat treatment is not particularly limited, and a rotation speed conventional in the art is adopted. In the present invention, the temperature of the first stirring heat treatment is preferably 60 to 120 ℃, more preferably 70 to 110 ℃; the time of the first stirring heat treatment is preferably 40 to 70 minutes. The invention controls the temperature and time of the first stirring heat treatment in the range, promotes the uniform mixing of the components, fully reacts to obtain the component A with better performance, and thus obtains the halogen-free flame-retardant heat-conducting organic silicon pouring sealant with better comprehensive performance.
Under the second vacuum condition, the invention mixes the base adhesive, the modified flame retardant, the modified heat-conducting filler and the reinforcing agent, carries out second stirring heat treatment, then adds the inhibitor and the hydrogen-containing cross-linking agent, and obtains the component B through stirring treatment.
The second vacuum condition is not particularly limited, and vacuum conditions conventional in the art may be used. The stirring rotation speed of the second stirring heat treatment is not particularly limited, and a rotation speed conventional in the art is adopted. In the present invention, the temperature of the second stirring heat treatment is preferably 60 to 90 ℃, more preferably 70 to 85 ℃; the time of the second stirring heat treatment is preferably 30 to 60 minutes, more preferably 40 to 55 minutes. The invention controls the temperature and time of the second stirring heat treatment in the range, promotes the uniform mixing of the components, fully reacts to obtain the component B with better performance, and thus obtains the halogen-free flame-retardant heat-conducting organic silicon pouring sealant with better comprehensive performance.
After the component A and the component B are obtained, the invention mixes the component A and the component B with equal weight, and then carries out defoaming stirring and curing in sequence to obtain the halogen-free flame-retardant heat-conducting organic silicon pouring sealant
In the present invention, the time for the deaeration and stirring is preferably 3 to 10 minutes, more preferably 5 to 8 minutes. The invention promotes the component A and the component B to be uniformly mixed and fully reacted by defoaming and stirring.
In the present invention, the curing is room temperature curing or heat curing.
The preparation method of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The invention also provides application of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant in electronic pouring sealant.
The halogen-free flame-retardant heat-conducting organic silicon pouring sealant provided by the invention has excellent flame retardance and heat conductivity, is halogen-free and environment-friendly, has long service life, and can be used as an electronic pouring sealant.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Halogen-free flame-retardant heat-conducting organosilicon pouring sealant comprises the following components in percentage by mass: the component A and the component B of the component 1 are prepared;
the component A is prepared from the following raw materials in parts by weight: 60 parts of base adhesive, 10 parts of modified flame retardant, 80 parts of modified heat conducting filler, 5 parts of reinforcing agent, 0.5 part of catalyst and 6 parts of adhesion promoter;
the component B is prepared from the following raw materials in parts by weight: 50 parts of base adhesive, 8 parts of modified flame retardant, 70 parts of modified heat conducting filler, 7 parts of reinforcing agent, 0.3 part of inhibitor and 5 parts of hydrogen-containing crosslinking agent;
the base adhesive is branched vinyl polydimethylsiloxane with the viscosity of 1000 mPas and the vinyl content of 1 wt%;
the reinforcing agent is methyl vinyl MQV type silicon resin with the vinyl content of 2.5 weight percent;
the modified flame retardant is aluminum hydroxide subjected to surface modification by a first coupling agent N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, specifically, after mixing N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane with ethanol, adding aluminum hydroxide, then carrying out high-speed blending, and removing a solvent through heating and drying to obtain the modified flame retardant, wherein the mass ratio of the N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane to the aluminum hydroxide is 3:100; the average particle diameter of the modified flame retardant is 7 mu m;
the modified heat-conducting filler is silicon carbide subjected to surface modification by a second coupling agent gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, specifically, after mixing gamma- (2, 3-epoxypropoxy) propyltriethoxysilane and ethanol, adding silicon carbide, then carrying out high-speed blending, and removing a solvent through heating and drying to obtain the modified heat-conducting filler, wherein the mass ratio of the gamma- (2, 3-epoxypropoxy) propyltriethoxysilane to the silicon carbide is 3:100; the modified heat conducting filler has an average particle size of 4 mu m;
the adhesion promoter is silazane; the inhibitor is 2-methyl-3-butynyl-2-ol; the hydrogen-containing cross-linking agent is hydrogen-containing silicone oil with the active hydrogen content of 1.2 weight percent;
the preparation method of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant comprises the following steps:
(1) Mixing a base adhesive, a modified flame retardant, a modified heat-conducting filler, a reinforcing agent, a catalyst and an adhesion promoter under a first vacuum condition, and performing first stirring heat treatment at 80 ℃ for 70min to obtain a component A;
(2) Mixing the base adhesive, the modified flame retardant, the modified heat-conducting filler and the reinforcing agent under a second vacuum condition, performing second stirring heat treatment for 50min at 65, adding the inhibitor and the hydrogen-containing crosslinking agent, and performing stirring treatment to obtain a component B;
(3) Mixing the component A obtained in the step (1) and the component B obtained in the step (2) by equal weight, and then sequentially defoaming and stirring for 5min and curing for 4 days at room temperature to obtain the halogen-free flame-retardant heat-conducting organic silicon pouring sealant.
Example 2
A halogen-free flame-retardant heat-conducting organosilicon pouring sealant was prepared according to the method of example 1, except that 7 parts of reinforcing agent was used for preparing the component A, 7 parts of adhesion promoter was used for preparing the component B, and 7 parts of reinforcing agent was used for preparing the component B.
Example 3
A halogen-free flame-retardant heat-conducting organosilicon pouring sealant was prepared according to the method of example 1, except that 10 parts of reinforcing agent and 8 parts of adhesion promoter were used for preparing the component A and 10 parts of reinforcing agent were used for preparing the component B, respectively, as in example 1.
Viscosity is tested according to GB/T10247-2008, heat conductivity coefficient is tested according to GB/T11205-2009, flame retardance is tested according to UL94, and viscosity, flame retardance and heat conductivity coefficients of the halogen-free flame retardant heat conductive organosilicon pouring sealant prepared in examples 1-3 are detected and obtained, and are specifically shown in Table 1.
Table 1 statistics of performance of halogen-free flame retardant heat conductive silicone potting gums prepared in examples 1-3
As can be seen from Table 1, the halogen-free flame-retardant heat-conducting silicone potting adhesive prepared in the embodiment of the invention has the advantages of low viscosity of 2600 mPa.s, good fluidity, flame retardant grade of V-0, high flame retardance, high heat conductivity coefficient of 1.583W/m.K and excellent heat conductivity.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The halogen-free flame-retardant heat-conducting organic silicon pouring sealant is characterized by comprising a component A and a component B;
the component A is prepared from the following raw materials in parts by weight: 40 to 60 parts of base adhesive, 5 to 15 parts of modified flame retardant, 40 to 100 parts of modified heat conducting filler, 3 to 16 parts of reinforcing agent, 0.3 to 2.0 parts of catalyst and 2 to 8 parts of adhesion promoter;
the component B is prepared from the following raw materials in parts by weight: 40 to 60 parts of base adhesive, 3 to 18 parts of modified flame retardant, 30 to 80 parts of modified heat conducting filler, 5 to 10 parts of reinforcing agent, 0.05 to 0.5 part of inhibitor and 2.5 to 8 parts of hydrogen-containing cross-linking agent;
the reinforcing agent is methyl vinyl MQV type silicon resin with the vinyl content of 1-3 wt%;
the modified flame retardant is at least one of aluminum hydroxide and magnesium hydroxide which are subjected to surface modification by a first coupling agent;
the modified heat conducting filler is at least one of aluminum oxide, aluminum nitride, aluminum boride, silicon carbide or silicon nitride which is subjected to surface modification by a second coupling agent;
the adhesion promoter is silazane.
2. The halogen-free flame retardant heat conductive silicone pouring sealant according to claim 1, wherein the average particle size of the modified flame retardant is 2-8 μm.
3. The halogen-free flame retardant heat conductive silicone pouring sealant of claim 1 wherein the first coupling agent is an amino terminated polydimethylsiloxane; the amino-terminated polydimethylsiloxane is at least one of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxysilane.
4. The halogen-free flame retardant, thermally conductive silicone potting adhesive of claim 1, wherein the catalyst is an alcoholic solution of chloroplatinic acid or a vinyl siloxane complex of chloroplatinic acid.
5. The halogen-free flame retardant heat conductive silicone pouring sealant according to claim 1, wherein the second coupling agent is an epoxy silane coupling agent; the epoxy silane coupling agent is at least one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma- (2, 3-epoxypropoxy) propyl triethoxy silane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane.
6. The preparation method of the halogen-free flame-retardant heat-conducting organic silicon pouring sealant according to any one of claims 1 to 5, which comprises the following steps:
(1) Mixing a base adhesive, a modified flame retardant, a modified heat-conducting filler, a reinforcing agent, a catalyst and an adhesion promoter under a first vacuum condition, and performing first stirring heat treatment to obtain a component A;
(2) Mixing the base adhesive, the modified flame retardant, the modified heat-conducting filler and the reinforcing agent under a second vacuum condition, performing a second stirring heat treatment, adding the inhibitor and the hydrogen-containing crosslinking agent, and performing stirring treatment to obtain a component B;
(3) Mixing the component A obtained in the step (1) and the component B obtained in the step (2) with equal weight, and then sequentially carrying out defoaming stirring and curing to obtain the halogen-free flame-retardant heat-conducting organic silicon pouring sealant.
7. The method according to claim 6, wherein the temperature of the first stirring heat treatment in the step (1) is 60 to 120 ℃, and the time of the first stirring heat treatment is 30 to 90 minutes.
8. The method according to claim 6, wherein the time for deaeration and stirring in the step (3) is 3 to 10 minutes.
9. The method according to claim 6, wherein the curing in the step (3) is room temperature curing or heat curing.
10. Use of the halogen-free flame-retardant heat-conducting organosilicon pouring sealant according to any one of claims 1 to 5 as an electronic pouring sealant.
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| CN202310741329.2A CN116656315A (en) | 2023-06-21 | 2023-06-21 | Halogen-free flame-retardant heat-conducting organic silicon pouring sealant and preparation method and application thereof |
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