CN116082641B - Macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, and preparation method and application thereof - Google Patents
Macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116082641B CN116082641B CN202111310427.8A CN202111310427A CN116082641B CN 116082641 B CN116082641 B CN 116082641B CN 202111310427 A CN202111310427 A CN 202111310427A CN 116082641 B CN116082641 B CN 116082641B
- Authority
- CN
- China
- Prior art keywords
- macromolecular
- lithium
- parts
- treating agent
- symmetrical structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a macromolecular alkoxy silane treating agent with a T-shaped symmetrical structure, and a preparation method and application thereof, wherein the treating agent has a structural formula shown in a formula (I), and the preparation method comprises the following steps: A. adding an organic cyclic siloxane monomer solution and a lithium salt solution into a reaction kettle, and stirring and reacting for 1-20h at 0-40 ℃; B. adding a coupling agent, reacting for 0.5-6h at 25 ℃, purifying and drying to obtain a polysiloxane intermediate with a silicon-hydrogen or silicon-vinyl chain intermediate; C. and C, performing hydrosilylation reaction on the polysiloxane intermediate synthesized in the step B and trialkoxysilane with alkenyl or silicon-hydrogen to obtain the macromolecular alkoxysilane treating agent with the T-shaped symmetrical structure. The silane treating agent is used in the silicon rubber heat conducting material, can obviously improve the hydrophobicity of the heat conducting filler, improve the compatibility between silicone oil and the filler, improve the filling amount of the filler in the silicone oil and reduce the viscosity of a system.
Description
Technical Field
The invention belongs to the field of organic silicon materials, and particularly relates to a macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure, a preparation method thereof and application thereof in a silicon rubber heat conduction/electric conduction material.
Background
In recent years, with the development of 5G technology, the density and integration level of electronic components such as transistors, ICs, light emitting diodes are higher and higher, and when the electronic components work, a large amount of accumulated heat is generated, and if the heat cannot be timely emitted, the service life of the electronic components is reduced and the working state of the electronic components is affected. Efficient heat conduction and dissipation is particularly critical to ensure high reliability and high performance of electronic components. Therefore, there is an urgent need to develop thermal interface materials with higher thermal conductivity and better performance to meet the thermal conductivity requirements of electronic components.
The thermal interface material (THERMAL INTERFACE MATERIALS, TIM) is a material commonly used for heat dissipation of electronic components, and is mainly used for filling between a heat dissipation device and a heating device and reducing contact thermal resistance between the heat dissipation device and the heating device due to micro gaps and holes with uneven surfaces. Common thermal interface materials mainly comprise a heat conducting gasket, heat conducting grease, heat conducting gel, phase change materials and the like. Because of excellent high and low temperature resistance, weather resistance, insulation and low stress, silicone rubber is widely applied to thermal interface materials.
In general, the preparation of a high thermal conductivity silicone material is mainly achieved by using a filler with high thermal conductivity or increasing the filling amount of a thermal conductivity filler in the silicone material. However, increasing the filling amount of the heat conductive filler causes an increase in viscosity of the material and deterioration in processability. In addition, because of the large physical and chemical property difference between the surface of the organic silicon material and the surface of the heat conducting filler, the compatibility and the dispersibility between the organic silicon material and the surface of the heat conducting filler are poor, the heat conducting filler is settled and the silicone oil is separated out after long-term placement, so that the heat conductivity of the material is reduced, and other properties (such as mechanical property, hardness and the like) are also influenced.
In order to solve the above-mentioned problems, it is necessary to perform surface modification treatment on the thermally conductive filler particles to achieve a high loading amount of the thermally conductive filler, wherein the most effective surface chemical modification treatment is to perform the surface modification treatment by chemically reacting a reactive group of the surface modification treatment agent with a functional group such as hydroxyl group on the surface of the inorganic filler particles. Silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, long-chain alkylalkoxysilane (C4-C12) and the like are conventionally used for treating the surface of the filler, but these small-molecule silane coupling agents have very limited treatment effects due to weak binding force and poor coating property on the surface of inorganic filler particles. CN103224511a discloses a hydrophobic surface treating agent and a preparation method thereof, which adopts heptamethyltrisiloxane and vinyltrimethoxysilane (or vinyltriethoxysilane) to carry out hydrosilylation reaction to obtain the filler surface treating agent, and the treating agent has an unsatisfactory treating effect on filler because the treating agent has only 3 siloxane units or belongs to a micromolecule silane treating agent. At present, some preparation methods of linear single-end macromolecular silane coupling agents are reported, and U.S. Pat. No. 3, 8633276, 8912132 adopts linear single-end alkoxy dimethylpolysiloxane to treat heat-conducting filler particles, so that the surface treatment effect on the heat-conducting filler is limited, and the heat conductivity of the obtained heat-conducting material is generally below 4W/(m.K), namely, the high heat-conducting organosilicon material with the heat conductivity of 6W/(m.K) cannot be obtained.
Disclosure of Invention
The invention aims to provide a macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure and a preparation method thereof, and the silane treating agent is used in a silicon rubber heat conducting material to realize surface hydrophobization treatment of a heat conducting filler, improve the compatibility between silicone oil and filler powder, improve the filling quantity and dispersibility of the filler in the silicone oil and reduce the viscosity of the whole system.
The aim of the invention is achieved by the following technical scheme: a macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure has a structural formula shown in a formula (I):
in the formula (I), the structural formula of X is shown as the formula (II):
In the formula (I) or (II), R 1 is one of n-butyl, ethyl, propyl, isopropyl, sec-butyl, amyl, hexyl and trimethylsilyl ether;
R 2 is methyl;
R 3 is phenyl or trifluoropropyl;
r 4 is methyl or phenyl;
r 5 is one of ethylene group, propylene group, caproic group, xin Chengji, ethylene phenyl, 3- (methylpropanoyloxy) propyl and 3- (propionyloxy) propyl;
R 6 is one of methyl, ethyl and isopropyl;
In the formula (i), m=1 to 60, n=0 to 60, and p=0 to 60, and is an integer.
The invention relates to a preparation method of a macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure, which comprises the following steps:
A. Adding an organic cyclic siloxane monomer solution and a lithium salt solution into a reaction kettle, and stirring and reacting for 1-20h at 0-40 ℃;
B. Adding a coupling agent, reacting for 0.5-6h at 25 ℃, purifying and drying to obtain a polysiloxane intermediate with a silicon-hydrogen or silicon-vinyl chain intermediate;
C. and C, performing hydrosilylation reaction on the polysiloxane intermediate synthesized in the step B and trialkoxysilane with alkenyl or silicon-hydrogen to obtain the macromolecular alkoxysilane treating agent with the T-shaped symmetrical structure.
In the technical scheme of the invention, the organic cyclic siloxane monomer in the step A is selected from one or more of hexamethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane and 2,4, 6-trimethyl-2, 4, 6-tris (3, 3-trifluoropropyl) cyclotrisiloxane; the solvent of the organic cyclic siloxane monomer solution is one or more of toluene, benzene and tetrahydrofuran; the mass concentration of the organic cyclic siloxane monomer solution is 2g/mL.
In the technical scheme of the invention, the lithium salt solution in the step A is an organic lithium solution or a metal lithium silanol salt solution. The organic lithium is selected from one or more of n-butyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, sec-butyl lithium, amyl lithium, hexyl lithium and macromolecular alkyl lithium; the metal lithium silanol salt is selected from one or more of lithium trimethylsilanol or single-ended trimethylsilyl oligosiloxane lithium silanol salts; the solvent of the lithium salt solution is selected from one or more of normal hexane and tetrahydrofuran; the molar concentration of the lithium salt solution is 2.4mol/L.
Further, in the technical scheme of the invention, in the step A, the molar ratio of the organocyclic siloxane monomer to the organolithium or metal lithium alkoxide used as the initiator is 2:1-20:1.
In the solution of the present invention, the coupling agent in step B is selected from silane compounds containing two Si-Cl bonds and containing one Si-H bond or one Si-ch=ch 2 bond, for example from one or more of methyldichlorosilane, phenyldichlorosilane, methylvinyldichlorosilane, allylmethyldichlorosilane.
Further, in the technical scheme of the invention, in the step B, the molar ratio of the coupling agent to the organolithium or metal lithium alkoxide initiator is 1:2-1.5:2.
In the technical scheme of the invention, the reaction in the step A and the step B is carried out under an inert atmosphere, wherein the inert atmosphere is selected from nitrogen atmosphere or argon atmosphere.
In the technical scheme of the invention, the molecular weight of the polysiloxane intermediate with the silicon-hydrogen or silicon-vinyl in the chain intermediate prepared in the step A and the step B is 900-9000.
In the technical scheme of the invention, the trialkoxysilane with alkenyl or silicon-hydrogen in the step C is selected from one or more of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triisopropoxysilane, allyl trimethoxysilane, allyl triethoxysilane, 5-hexenyl trimethoxysilane, 5-hexenyl triethoxysilane, 7-octenyl trimethoxysilane, (4-vinyl phenyl) trimethoxysilane, 3- (methacryloxy) propyl trimethoxysilane, 3- (acryloxy) propyl trimethoxysilane, trimethoxy hydrosilane and triethoxy hydrosilane.
In the technical scheme of the invention, the hydrosilylation reaction in the step C is carried out under a platinum catalyst, wherein the platinum catalyst is chloroplatinic acid, a platinum-alcohol complex and a platinum-vinyl siloxane complex, and the platinum is supported on a carrier such as silicon dioxide, aluminum oxide and carbon; the mass content of platinum atoms in the reaction system of the step C is 0.1-20ppm; the hydrosilylation reaction temperature is 45-110 ℃.
The macromolecular alkoxysilane treating agent with the T-shaped symmetrical structure shown in the formula (I) is applied to surface hydrophobic treatment of the filler in the silicone rubber heat-conducting material, can obviously improve the compatibility between silicone oil and filler powder, and improves the filling amount and dispersibility of the filler in the silicone oil, so that the high-heat-conductivity organic silicon material can be prepared.
The invention also provides a heat-conductive silicone rubber material composition, which comprises the following raw materials in parts by weight: 100 parts of vinyl silicone oil, 2-8 parts of hydrogen-containing silicone oil, 700-2100 parts of heat conducting filler, 7-21 parts of macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, 0.2-4 parts of platinum catalyst and 0.2-4 parts of inhibitor.
The preparation method of the heat-conductive silicone rubber material composition comprises the following steps:
1) Adding 700-2100 parts of heat conducting filler, 50 parts of vinyl silicone oil and 7-21 parts of macromolecular alkoxy silane treating agent with a T-shaped symmetrical structure into a kneader, kneading for 0.5-3h at room temperature, heating to 130-150 ℃, vacuumizing and kneading for 1-3h, wherein the vacuum degree is-0.08 MPa, cooling to room temperature, and filling nitrogen to break vacuum to obtain base rubber;
2) Adding the kneaded base rubber into a planetary mixer, sequentially adding 50 parts of vinyl silicone oil, 2-8 parts of hydrogen-containing silicone oil, 0.2-4 parts of inhibitor and 0.2-4 parts of platinum catalyst, stirring and mixing for 15-45min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber composition.
In the technical scheme of the invention, the heat conducting filler is selected from one or more of aluminum oxide, aluminum hydroxide, magnesium oxide, zinc oxide, aluminum powder, boron nitride, silicon nitride and boron carbide, and the D50 particle size of the heat conducting filler is 1-100 mu m.
In the technical scheme of the invention, the inhibitor is 1-ethynyl-1-cyclohexanol, diallyl maleate, 2-methyl-3-butynyl-2-alcohol or 3, 5-dimethyl-1-hexyn-3-alcohol and the like.
In the technical scheme of the invention, the platinum catalyst is chloroplatinic acid, a platinum-alcohol complex or a platinum-vinyl siloxane complex and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. The macromolecular alkoxysilane treating agent with the T-shaped symmetrical structure has high purity, controllable molecular weight and low viscosity, and adopts dichlorosilane as a coupling agent during synthesis, and two Si-Cl bonds in the dichlorosilane molecule can quickly perform coupling reaction with polysiloxane lithium salt obtained by anionic polymerization, so that the prepared macromolecular alkoxysilane treating agent has a bilateral symmetrical structure, and has regular structure and low viscosity.
2. When the macromolecular alkoxysilane treating agent prepared by the invention is used for surface treatment of filler in silicone rubber heat-conducting material, because the special T-shaped symmetrical structure and the reactive alkoxy group are arranged in the middle of the polymer chain, the organopolysiloxane chain can form an umbrella-shaped structure on the surface of the filler, which is beneficial to coating of the filler particles by the silane treating agent, and the hydrophobicity of the filler particles is obviously improved, so that the compatibility between silicone oil and filler powder is greatly improved, and the filling quantity and dispersibility of the filler in the silicone oil are improved; the prepared heat-conductive silicone rubber has high heat conductivity, excellent high-temperature resistance and ageing resistance and good storage stability.
Detailed Description
The technical scheme of the present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Example 1
A. 50g (0.225 mol) of hexamethylcyclotrisiloxane and 25mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen was purged into the system while the raw material monomer was dissolved. 9.36mL of an n-butyllithium solution (2.4M in n-hexane) was added to the reaction system by syringe, and the reaction was stirred at room temperature for 12 hours.
B. 1.288mL (12.38 mmol) of methyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at 25℃for 5 hours after the completion of the dropwise addition. After the reaction, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 45g of a clear and transparent oily liquid, namely, a silicone intermediate with a silicon-hydrogen chain in the middle, which had a number average molecular weight of 4100 and a polydispersity PDI of 1.4 as measured by GPC (gel permeation chromatography).
C. 25g of the intermediate was taken in a three-necked flask, to which 1.88g of vinyltrimethoxysilane and 60mg of a platinum catalyst supported on a silica carrier (wherein the amount of platinum atoms was 3 ppm) were added, and reacted at 85℃for 7 hours. After the reaction is completed, cooling to room temperature, removing a supported platinum catalyst by suction filtration, and removing low-boiling substances by reduced pressure distillation to obtain 25.02g of macromolecular alkoxysilane treating agent 1, wherein the structural formula is as follows:
and has the following nuclear magnetic characterization data ：1H NMR (400 MHz,CDCl3),δ (ppm): 3.58 (9H,-Si-OCH3),1.31 (8H,CH3-CH2-CH2-CH2-Si-),0.89 (6H,CH3-CH2-CH2-CH2-Si-),0.57 (8H,CH3-CH2-CH2-CH2-Si-,-Si-CH2-CH2-Si-),0.06 (324H,CH3-Si-CH3).
Example 2
A. 50g (0.225 mol) of hexamethylcyclotrisiloxane and 25mL of toluene were charged into a three-necked flask, and nitrogen was purged into the system while the raw material monomer was dissolved. 16.74mL of n-butyllithium solution (2.4M in n-hexane) was taken in the reaction system by syringe, and reacted at room temperature for 12 hours.
B. 2.299mL (22.10 mmol) of methyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at 25℃for 5 hours after the completion of the dropwise addition. After the reaction, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 44g of a clear and transparent oily liquid, which was a silicone intermediate having a silicon-hydrogen chain in the middle, and the number average molecular weight was 2200 and the polydispersity PDI was 1.5 as measured by GPC (gel permeation chromatography).
C. 25g of the intermediate was placed in a three-necked flask, to which 5g of 3- (acryloyloxy) propyltrimethoxysilane and 70mg of a platinum catalyst supported on an alumina carrier (wherein the amount of platinum atoms was 5 ppm) were added, and reacted at 85℃for 7 hours. After the reaction is completed, cooling to room temperature, suction filtering to remove a supported platinum catalyst, and then removing low-boiling substances by reduced pressure distillation to obtain 26g of macromolecular alkoxysilane treating agent 2, wherein the structural formula is as follows:
and has the following nuclear magnetic characterization data:
1H NMR (400 MHz,CDCl3),δ (ppm): 4.13 (2H,-CH2-CH2-O-C(=O)-),3.58 (9H,-Si-OCH3),2.21 (2H,-CH2-CH2-C(=O)-O-),1.53 (2H,-CH2-CH2-O-C(=O)-),1.30 (8H,CH3-CH2-CH2-CH2-Si-),1.02 (2H,-CH2-CH2-C(=O)-O-),0.89(6H,CH3-CH2-CH2-CH2-Si-),0.57(6H,CH3-CH2-CH2-CH2-Si-,-Si-CH2-CH2-CH2-O-),0.06 (180H,CH3-Si-CH3).
example 3
A. 33.3g (0.15 mol) of hexamethylcyclotrisiloxane, 30.65g (0.075 mol) of 2,4, 6-trimethyl-2, 4, 6-triphenylcyclotrisiloxane and 32mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen gas was blown into the system while the raw material monomers were dissolved. 9.36mL of an n-butyllithium solution (2.4M in n-hexane) was taken in the reaction system by syringe, and reacted at room temperature for 18 hours.
B. 1.821mL (12.38 mmol) of phenyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at 25℃for 6 hours after the completion of the dropwise addition. After the reaction, the mixed solution is distilled under reduced pressure to remove tetrahydrofuran solvent, and then lithium chloride insoluble matters are removed by positive pressure filtration to obtain 56g of clear and transparent oily liquid, namely polysiloxane intermediate with silicon-hydrogen in the chain, wherein the number average molecular weight is 5100 and the polydispersity PDI is 1.3 by GPC (gel permeation chromatography).
C. 25g of the intermediate was placed in a three-necked flask, 2g of allyltrimethoxysilane and 140mg of a platinum catalyst supported on an alumina carrier (wherein the amount of platinum atoms was 10 ppm) were added thereto, and the mixture was reacted at 85℃for 5 hours. After the reaction is completed, cooling to room temperature, removing a supported platinum catalyst by suction filtration, and removing low-boiling substances by reduced pressure distillation to obtain 25.1g of macromolecular alkoxysilane treating agent 3, wherein the structural formula is as follows:
And has the following nuclear magnetic characterization data ：1H NMR (400 MHz, CDCl3), δ (ppm): 7.31-7.10 (95H, -Si-Ph), 3.58 (9H, -Si-OCH3), 1.31 (10H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-CH2-Si-), 0.89 (6H, CH3-CH2-CH2-CH2-Si-),0.66 (54H, -Si(-Ph)-CH3-), 0.57 (8H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-CH2-Si-), 0.06 (216H, CH3-Si-CH3).
Example 4
A. 33.3g (0.15 mol) of hexamethylcyclotrisiloxane, 19.83g (0.033 mol) of hexaphenylcyclotrisiloxane, 17.03g (0.042 mol) of 2,4, 6-trimethyl-2, 4, 6-triphenylcyclotrisiloxane and 35mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen gas was purged into the system while the raw material monomers were dissolved. 9.36mL of an n-butyllithium solution (2.4M in n-hexane) was taken in the reaction system by syringe, and reacted at 25℃for 20 hours.
B. 1.821mL (12.38 mmol) of phenyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at room temperature for 6 hours after the completion of the dropwise addition. After the reaction, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 60g of clear and transparent oily liquid, namely, a silicone intermediate with a silicon-hydrogen chain in the middle, which had a number average molecular weight of 5800 and a polydispersity PDI of 1.3 as measured by GPC (gel permeation chromatography).
C. 25g of the intermediate was placed in a three-necked flask, to which 1.90g of vinyltrimethoxysilane and 280mg of a platinum catalyst supported on an alumina carrier (wherein the amount of platinum atoms was 20 ppm) were added, and reacted at 85℃for 3 hours. After the reaction is completed, cooling to room temperature, removing a supported platinum catalyst by suction filtration, and removing low-boiling substances by reduced pressure distillation to obtain 25.1g of macromolecular alkoxysilane treatment agent 4, wherein the structural formula is as follows:
The nuclear magnetic data are as follows:
1H NMR (400 MHz, CDCl3), δ (ppm): 7.31-7.10 (130H, -Si-Ph), 3.58 (9H, -Si-OCH3), 1.31 (8H, CH3-CH2-CH2-CH2-Si-), 0.89 (6H, CH3-CH2-CH2-CH2-Si-), 0.66 (30H, -Si(-Ph)-CH3-), 0.57 (8H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-Si-), 0.06 (228H, CH3-Si-CH3).
Example 5
A. 50g (0.225 mol) of hexamethylcyclotrisiloxane and 25mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen was purged into the system while the raw material monomer was dissolved. 9.36mL of an n-butyllithium solution (2.4M in n-hexane) was taken in the reaction system by syringe, and reacted at room temperature for 12 hours.
B. 1.61mL (12.38 mmol) of methylvinyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at 25℃for 5 hours after the completion of the dropwise addition. After the reaction, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 45.2g of a clear and transparent oily liquid, which was a silicone intermediate having a silicon-vinyl group in the chain, having a number average molecular weight of 4150 and a polydispersity PDI of 1.4 as measured by GPC (gel permeation chromatography).
C. 25g of the intermediate was taken in a three-necked flask, to which 1.5g of trimethoxysilane and 120mg of a platinum catalyst supported on a carbon carrier (wherein the amount of platinum atoms was 10 ppm) were added, and reacted at 85℃for 6 hours. After the reaction was completed, cooling to room temperature, suction-filtering to remove the supported platinum catalyst, and then vacuum-distilling to remove the low-boiling-point substances, thereby obtaining 25g of a macromolecular alkoxysilane treatment agent 5 having the following structural formula (same as the macromolecular alkoxysilane treatment agent 1 prepared in example 1):
The nuclear magnetic data are as follows ：1H NMR (400 MHz,CDCl3),δ (ppm): 3.58 (9H,-Si-OCH3),1.31 (8H,CH3-CH2-CH2-CH2-Si-),0.89 (6H,CH3-CH2-CH2-CH2-Si-),0.57 (8H,CH3-CH2-CH2-CH2-Si-,-Si-CH2-CH2-Si-),0.06 (324H,CH3-Si-CH3).
Example 6
A. 50g (0.225 mol) of hexamethylcyclotrisiloxane and 25mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen was purged into the system while the raw material monomer was dissolved. 9.36mL of an n-butyllithium solution (2.4M in n-hexane) was taken in the reaction system by syringe, and reacted at room temperature for 12 hours.
B. 1.799mL (12.38 mmol) of allylmethyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at 25℃for 5 hours after the completion of the dropwise addition. After the reaction, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 45.2g of a clear and transparent oily liquid, which was a silicone intermediate having a silicon-vinyl group in the chain, having a number average molecular weight of 4200 and a polydispersity PDI of 1.4 as measured by GPC (gel permeation chromatography).
C. 25g of the above intermediate was taken in a three-necked flask, to which 2.04g of triethoxysilane, 3mg of a platinum-vinyl siloxane complex catalyst (in which the amount of platinum atoms was 0.1 ppm) were added, and reacted at 100℃for 12 hours. After the reaction is completed, cooling to room temperature, and distilling under reduced pressure to remove low-boiling-point substances, thereby obtaining 25.08g of macromolecular alkoxysilane treating agent 6, wherein the molecular weight of the macromolecular alkoxysilane treating agent is as follows:
And has the following nuclear magnetic characterization data ：1H NMR (400 MHz, CDCl3), δ (ppm): 3.82 (6H, -Si-OCH2CH3), 1.31 (10H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-CH2-Si-), 1.21 (9H, -Si-OCH2CH3), 0.89 (6H, CH3-CH2-CH2-CH2-Si-), 0.57 (8H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-CH2-Si-), 0.06 (324H, CH3-Si-CH3).
Example 7
A. 50g (0.225 mol) of hexamethylcyclotrisiloxane and 25mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen was purged into the system while the raw material monomer was dissolved. 2.16g of lithium trimethylsilanol was weighed and added to the reaction system, and reacted at room temperature for 16 hours.
B. 1.288mL (12.38 mmol) of methyldichlorosilane was slowly added dropwise to the reaction system, and the mixture was reacted at 25℃for 5 hours after the completion of the dropwise addition. After the reaction was completed, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 44.6g of a clear and transparent oily liquid, which was a silicone intermediate having a silicon-hydrogen chain in the middle, having a number average molecular weight of 4350 and a polydispersity PDI of 1.4 as measured by GPC (gel permeation chromatography).
C. 25g of the above intermediate was taken in a three-necked flask, to which 1.89g of vinyltrimethoxysilane and 12mg of a platinum-alcohol complex catalyst (wherein the amount of platinum atom was 2 ppm) were added, and reacted at 85℃for 8 hours. After the reaction was completed, cooling to room temperature, and distilling off low boiling point substances under reduced pressure to obtain 25.02g of a macromolecular alkoxysilane treating agent 7 having the following structural formula:
And has the following nuclear magnetic characterization data ：1H NMR (400 MHz, CDCl3), δ (ppm): 3.58 (9H, -Si-OCH3), 1.31 (8H, CH3-CH2-CH2-CH2-Si-), 0.89 (6H, CH3-CH2-CH2-CH2-Si-), 0.57 (8H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-Si-), 0.21 (18H, (CH3)3-Si-), 0.06 (324H, CH3-Si-CH3).
Example 8
A. 50g (0.225 mol) of hexamethylcyclotrisiloxane and 25mL of tetrahydrofuran were charged into a three-necked flask, and nitrogen was purged into the system while the raw material monomer was dissolved. 6.25mL of an n-butyllithium solution (2.4M in n-hexane) was taken in the reaction system by syringe, and reacted at room temperature for 12 hours.
B. To the reaction system, 0.858mL (8.25 mmol) of methyldichlorosilane was slowly added dropwise, and after the completion of the addition, the mixture was reacted at room temperature for 5 hours. After the reaction was completed, the mixed solution was distilled under reduced pressure to remove the tetrahydrofuran solvent, and then the lithium chloride insoluble matter was removed by filtration under positive pressure to obtain 44.6g of a clear and transparent oily liquid, which was a silicone intermediate having a silicon-hydrogen chain in the middle, having a number average molecular weight of 6300 and a polydispersity PDI of 1.3 as measured by GPC (gel permeation chromatography).
C. 25g of the intermediate was placed in a three-necked flask, to which 1.23g of vinyltrimethoxysilane and 13mg of chloroplatinic acid catalyst (the amount of platinum atom used was 2 ppm) were added, and reacted at 85℃for 8 hours. After the reaction is completed, cooling to room temperature, and distilling under reduced pressure to remove low-boiling-point substances, thereby obtaining 25g of macromolecular alkoxysilane treating agent 8, wherein the structural formula is as follows:
And has the following nuclear magnetic characterization data ：1H NMR (400 MHz, CDCl3), δ (ppm): 3.58 (9H, -Si-OCH3), 1.31 (8H, CH3-CH2-CH2-CH2-Si-), 0.89 (6H, CH3-CH2-CH2-CH2-Si-), 0.57 (8H, CH3-CH2-CH2-CH2-Si-, -Si-CH2-CH2-Si-), 0.06 (504H, CH3-Si-CH3).
Example 9
800 Parts of spherical alumina powder having a median particle diameter (D50) of 60 μm, 600 parts of spherical alumina powder having a median particle diameter (D50) of 20 μm, 400 parts of spherical alumina powder having a median particle diameter (D50) of 1 μm, 300 parts of aluminum hydroxide powder having a median particle diameter (D50) of 1 μm, 50 parts of vinyl silicone oil having a viscosity of 1200 mPas and 21 parts of the macromolecular alkoxysilane treatment agent prepared in example 1 were added to a kneader, kneaded at room temperature for 2 hours, then heated to 150℃and vacuum kneaded for 2 hours under vacuum of-0.08 MPa, and then cooled to room temperature and then nitrogen-filled for vacuum breaking to obtain a base rubber. Taking the kneaded base rubber, adding 50 parts of vinyl silicone oil with the viscosity of 1200 mPas, 4 parts of side hydrogen silicone oil with the hydrogen content of 0.2wt%, 2 parts of terminal hydrogen silicone oil, 1 part of diallyl maleate inhibitor and 1 part of platinum-vinyl siloxane complex catalyst into a planetary stirrer in sequence, stirring and mixing for 30min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
Example 10
400 Parts of spherical alumina powder having a median particle diameter (D50) of 60 μm, 200 parts of spherical alumina powder having a median particle diameter (D50) of 30 μm, 100 parts of spherical alumina powder having a median particle diameter (D50) of 2 μm, 50 parts of vinyl silicone oil having a viscosity of 1500 mPas and 7 parts of the macromolecular alkoxysilane treatment agent prepared in example 3 were added to a kneader, kneaded at room temperature for 0.5h, then heated to 130℃and vacuum-kneaded for 1h under vacuum of-0.08 MPa, and cooled to room temperature and then nitrogen-filled to break the vacuum to obtain a base rubber. Taking the kneaded base rubber, adding 50 parts of vinyl silicone oil with the viscosity of 1500 mPas, 3 parts of side hydrogen silicone oil with the hydrogen content of 0.3wt%, 0.2 part of 2-methyl-3-butynyl-2-ol inhibitor and 0.2 part of chloroplatinic acid catalyst into a planetary stirrer in sequence, stirring and mixing for 15min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
Example 11
600 Parts of spherical alumina powder having a median particle diameter (D50) of 60 μm, 400 parts of spherical alumina powder having a median particle diameter (D50) of 30 μm, 300 parts of spherical alumina powder having a median particle diameter (D50) of 5 μm, 200 parts of aluminum hydroxide powder having a median particle diameter (D50) of 1 μm, 50 parts of vinyl silicone oil having a viscosity of 1200 mPas and 15 parts of the macromolecular alkoxysilane treating agent prepared in example 7 were added to a kneader, kneaded at room temperature for 3 hours, then heated to 140℃and vacuum kneaded for 3 hours at a vacuum of-0.08 MPa, and then cooled to room temperature and then nitrogen-filled for vacuum breaking to obtain a base rubber. Taking the kneaded base rubber, putting the base rubber into a planetary stirrer, sequentially adding 50 parts of vinyl silicone oil with the viscosity of 1200 mPas, 4 parts of side hydrogen silicone oil with the hydrogen content of 0.2wt%, 4 parts of terminal hydrogen silicone oil, 4 parts of 2-methyl-3-butynyl-2-ol inhibitor and 4 parts of platinum-alcohol complex catalyst, stirring and mixing for 45min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
Comparative example 1
800 Parts of spherical alumina powder having a median particle diameter (D50) of 60 μm, 600 parts of spherical alumina powder having a median particle diameter (D50) of 20 μm, 400 parts of spherical alumina powder having a median particle diameter (D50) of 1 μm, 300 parts of aluminum hydroxide powder having a median particle diameter (D50) of 1 μm, 50 parts of vinyl silicone oil having a viscosity of 1200 mPas and 21 parts of dodecyl trimethoxysilane were added to a kneader, kneaded at room temperature for 2 hours, then heated to 150℃and vacuum-kneaded for 2 hours under vacuum, the degree of vacuum was about-0.08 MPa, and then cooled to room temperature and then nitrogen-filled for vacuum breaking to obtain a base rubber. Taking the kneaded base rubber, adding 50 parts of vinyl silicone oil with the viscosity of 1200 mPas, 4 parts of side hydrogen silicone oil with the hydrogen content of 0.2wt%, 2 parts of terminal hydrogen silicone oil, 1 part of diallyl maleate inhibitor and 1 part of platinum-vinyl siloxane complex catalyst (wherein the platinum content is 5000 ppm) into a planetary stirrer in sequence, stirring and mixing for 30min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
Comparative example 2
400 Parts of spherical alumina powder having a median particle diameter (D50) of 60 μm, 200 parts of spherical alumina powder having a median particle diameter (D50) of 30 μm, 100 parts of spherical alumina powder having a median particle diameter (D50) of 2 μm, 50 parts of vinyl silicone oil having a viscosity of 1500 mPas and 7 parts of hexamethyldisilazane were added to a kneader, kneaded at room temperature for 0.5 hours, then heated to 130℃and vacuum-kneaded at-0.08 MPa, and cooled to room temperature and then nitrogen-filled for vacuum breaking to obtain a base rubber. Taking the kneaded base rubber, adding 50 parts of vinyl silicone oil with the viscosity of 1500 mPas, 3 parts of side hydrogen silicone oil with the hydrogen content of 0.3wt%, 0.2 part of 2-methyl-3-butynyl-2-ol inhibitor and 0.2 part of chloroplatinic acid catalyst into a planetary stirrer in sequence, stirring and mixing for 15min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
Comparative example 3
600 Parts of spherical alumina powder having a median particle diameter (D50) of 60 μm, 400 parts of spherical alumina powder having a median particle diameter (D50) of 30 μm, 300 parts of spherical alumina powder having a median particle diameter (D50) of 5 μm, 200 parts of aluminum hydroxide powder having a median particle diameter (D50) of 1 μm, 50 parts of vinyl silicone oil having a viscosity of 1200 mPas and 15 parts of gamma- (2, 3-glycidoxypropyl) trimethoxysilane were added to a kneader, kneaded at room temperature for 3 hours, then heated to 140℃and subjected to vacuum kneading for 3 hours at a vacuum of-0.08 MPa, and cooled to room temperature and then subjected to nitrogen-filled vacuum breaking to obtain a base rubber. Taking the kneaded base rubber, putting the base rubber into a planetary stirrer, sequentially adding 50 parts of vinyl silicone oil with the viscosity of 1200 mPas, 4 parts of side hydrogen silicone oil with the hydrogen content of 0.2wt%, 4 parts of terminal hydrogen silicone oil, 4 parts of 2-methyl-3-butynyl-2-ol inhibitor and 4 parts of platinum-alcohol complex catalyst, stirring and mixing for 45min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
The thermally conductive silicone rubber material compositions obtained in examples 9 to 11 and comparative examples were subjected to product performance test, and the results are shown in Table 1.
As can be seen from the data in Table 1, the heat conductive silicone rubber material composition prepared by using the macromolecular alkoxysilane treatment agent of T-type symmetrical structure of the present invention (only the treatment agents prepared in examples 1 to 8, example 3 and example 7 are selected as an example), has lower viscosity, lower hardness and higher heat conductivity, and has lower fluctuation in hardness and heat conductivity after heat aging at 150 ℃ and shows excellent high temperature and aging resistance compared with the heat conductive silicone rubber material composition prepared by using silane coupling agents (such as dodecyl trimethoxysilane, hexamethyldisilazane and gamma- (2, 3-glycidoxy) propyl trimethoxysilane) in the prior art.
The embodiments described above are only preferred embodiments of the present invention, and the embodiments of the present invention are not limited by the embodiments described above, so that any other modifications, adaptations, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be considered as equivalent substitutions and are included in the scope of the present invention.
Claims (15)
1. A macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure is characterized in that: has a structural formula shown as a formula (I):
in the formula (I), the structural formula of X is shown as the formula (II):
In the formula (I) or (II), R 1 is one of n-butyl, ethyl, propyl, isopropyl, sec-butyl, amyl, hexyl and trimethylsilyl ether;
R 2 is methyl;
R 3 is phenyl or trifluoropropyl;
r 4 is methyl or phenyl;
r 5 is one of ethylene group, propylene group, caproic group, xin Chengji, ethylene phenyl, 3- (methylpropanoyloxy) propyl and 3- (propionyloxy) propyl;
R 6 is one of methyl, ethyl and isopropyl;
in the formula (I), m=1-60, n=0-60, and p=0-60, and is an integer;
The preparation method of the macromolecular alkoxysilane treating agent with the T-shaped symmetrical structure comprises the following steps:
A. Adding an organic cyclic siloxane monomer solution and a lithium salt solution into a reaction kettle, and stirring and reacting for 1-20h at 0-40 ℃;
B. adding a coupling agent, reacting for 0.5-6h at 25 ℃, purifying and drying to obtain a polysiloxane intermediate with a chain intermediate of silicon-hydrogen or silicon-vinyl, wherein the molecular weight of the intermediate is 900-9000.
2. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
A. Adding an organic cyclic siloxane monomer solution and a lithium salt solution into a reaction kettle, and stirring and reacting for 1-20h at 0-40 ℃;
the mass concentration of the organic cyclic siloxane monomer solution is 2g/mL;
the molar concentration of the lithium salt solution is 2.4mol/L; the lithium salt solution is an organic lithium solution or a metal silicon alcohol lithium salt solution;
the molar ratio of the organic cyclic siloxane monomer to the organic lithium or metal lithium alkoxide used as an initiator is 2:1-20:1;
B. Adding a coupling agent, reacting for 0.5-6h at 25 ℃, purifying and drying to obtain a polysiloxane intermediate with a silicon-hydrogen or silicon-vinyl chain intermediate;
the molar ratio of the coupling agent to the organic lithium or metal lithium alkoxide initiator is 1:2-1.5:2;
C. and C, performing hydrosilylation reaction on the polysiloxane intermediate synthesized in the step B and trialkoxysilane with alkenyl or silicon-hydrogen to obtain the macromolecular alkoxysilane treating agent with the T-shaped symmetrical structure.
3. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2, wherein the method comprises the following steps: the organic cyclic siloxane monomer in the step A is selected from one or more of hexamethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane and 2,4, 6-trimethyl-2, 4, 6-tris (3, 3-trifluoropropyl) cyclotrisiloxane; the solvent of the organic cyclic siloxane monomer solution is one or more of toluene, benzene and tetrahydrofuran.
4. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2, wherein the method comprises the following steps: in the step A, the organic lithium is selected from one or more of n-butyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, sec-butyl lithium, amyl lithium, hexyl lithium and macromolecular alkyl lithium; the metal lithium silanol salt is selected from one or more of lithium trimethylsilanol or single-ended trimethylsilyl oligosiloxane lithium silanol salts; the solvent of the lithium salt solution is selected from one or more of normal hexane and tetrahydrofuran.
5. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2, wherein the method comprises the following steps: in step B, the coupling agent is selected from silane compounds containing two si—cl bonds and containing one si—h bond or one si—ch=ch 2 bond.
6. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2 or 5, wherein the method comprises the following steps: in the step B, the coupling agent is selected from one or more of methyldichlorosilane, phenyldichlorosilane, methylvinyldichlorosilane and allylmethyldichlorosilane.
7. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2, wherein the method comprises the following steps: the reaction in the step A and the step B is carried out under an inert atmosphere, wherein the inert atmosphere is selected from nitrogen atmosphere or argon atmosphere.
8. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2, wherein the method comprises the following steps: in step C, the trialkoxysilane with alkenyl or silicon-hydrogen is selected from one or more of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triisopropoxysilane, allyl trimethoxysilane, allyl triethoxysilane, 5-hexenyl trimethoxysilane, 5-hexenyl triethoxysilane, 7-octenyl trimethoxysilane, (4-vinylphenyl) trimethoxysilane, 3- (methacryloxy) propyl trimethoxysilane, 3- (acryloxy) propyl trimethoxysilane, trimethoxyhydrosilane, triethoxysilane.
9. The method for preparing the macromolecular alkoxysilane treating agent with a T-shaped symmetrical structure according to claim 2, wherein the method comprises the following steps: the hydrosilylation reaction in the step C is carried out under a platinum catalyst, wherein the platinum catalyst is chloroplatinic acid, a platinum-alcohol complex, a platinum-vinyl siloxane complex or platinum loaded on a silicon dioxide, aluminum oxide or carbon carrier; the mass content of platinum atoms in the reaction system of the step C is 0.1-20ppm; the hydrosilylation reaction temperature is 45-110 ℃.
10. Use of the macromolecular alkoxysilane treatment agent of a T-type symmetrical structure according to claim 1 in thermally conductive silicone rubber materials.
11. The use according to claim 10, wherein: the heat-conducting silicone rubber material composition comprises the following raw materials in parts by weight: 100 parts of vinyl silicone oil, 2-8 parts of hydrogen-containing silicone oil, 700-2100 parts of heat conducting filler, 7-21 parts of macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, 0.2-4 parts of platinum catalyst and 0.2-4 parts of inhibitor.
12. The use according to claim 11, wherein: the preparation method of the heat-conductive silicone rubber material composition comprises the following steps:
1) Adding 700-2100 parts of heat conducting filler, 50 parts of vinyl silicone oil and 7-21 parts of macromolecular alkoxy silane treating agent with a T-shaped symmetrical structure into a kneader, kneading for 0.5-3h at room temperature, heating to 130-150 ℃, vacuumizing and kneading for 1-3h, wherein the vacuum degree is-0.08 MPa, cooling to room temperature, and filling nitrogen to break vacuum to obtain base rubber;
2) Adding the kneaded base rubber into a planetary mixer, sequentially adding 50 parts of vinyl silicone oil, 2-8 parts of hydrogen-containing silicone oil, 0.2-4 parts of inhibitor and 0.2-4 parts of platinum catalyst, stirring and mixing for 15-45min at room temperature, defoaming, and discharging to obtain the heat-conductive silicone rubber material composition.
13. The use according to claim 11, wherein: the heat conducting filler is one or more selected from aluminum oxide, aluminum hydroxide, magnesium oxide, zinc oxide, aluminum powder, boron nitride, silicon nitride and boron carbide, and the D50 particle size of the heat conducting filler is 1-100 mu m.
14. The use according to claim 11, wherein: the inhibitor is 1-ethynyl-1-cyclohexanol, diallyl maleate, 2-methyl-3-butynyl-2-ol or 3, 5-dimethyl-1-hexyn-3-ol.
15. The use according to claim 11, wherein: the platinum catalyst is chloroplatinic acid, a platinum-alcohol complex or a platinum-vinyl siloxane complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111310427.8A CN116082641B (en) | 2021-11-08 | 2021-11-08 | Macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111310427.8A CN116082641B (en) | 2021-11-08 | 2021-11-08 | Macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116082641A CN116082641A (en) | 2023-05-09 |
| CN116082641B true CN116082641B (en) | 2024-07-09 |
Family
ID=86206875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111310427.8A Active CN116082641B (en) | 2021-11-08 | 2021-11-08 | Macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116082641B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119039792A (en) * | 2024-09-30 | 2024-11-29 | 东莞市万觅新材料科技有限公司 | Low-temperature quick-vulcanization liquid silicone rubber and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01294738A (en) * | 1988-05-23 | 1989-11-28 | Toshiba Silicone Co Ltd | Production of linear polyorganosiloxane |
| CN102796264A (en) * | 2012-07-27 | 2012-11-28 | 华南理工大学 | Macromolecular organic silicon modifier as well as preparation method and application thereof in surface treatment of hydroxide flame retardant |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2296010A1 (en) * | 1997-07-11 | 1999-01-21 | Compagnie Generale Des Etablissements Michelin - Michelin & Cie | Diene rubber composition reinforced with white filler, comprising as coupling agent (white filler/elastomer) a multifunctionalized polyorganosiloxane |
| CN101260190B (en) * | 2008-04-28 | 2011-04-27 | 华南理工大学 | Multifunctional polysiloxane coupling agent and preparation method thereof |
| CN101298498A (en) * | 2008-06-20 | 2008-11-05 | 华南理工大学 | Alkoxy end-capped linear polysiloxane resin acceptor and synthetic method thereof |
| WO2017146652A1 (en) * | 2016-02-24 | 2017-08-31 | Agency For Science, Technology And Research | Durable hydrophobic coating composition |
| EP3744754B1 (en) * | 2019-05-28 | 2024-10-02 | Evonik Operations GmbH | Method for producing siloxanes bearing acetoxy groups |
| CN112608480B (en) * | 2020-12-15 | 2022-08-02 | 万华化学集团股份有限公司 | Asymmetric silicone oil and preparation method and application thereof |
| CN113174048A (en) * | 2021-04-25 | 2021-07-27 | 深圳先进电子材料国际创新研究院 | Macromolecular silane coupling agent and preparation method thereof |
-
2021
- 2021-11-08 CN CN202111310427.8A patent/CN116082641B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01294738A (en) * | 1988-05-23 | 1989-11-28 | Toshiba Silicone Co Ltd | Production of linear polyorganosiloxane |
| CN102796264A (en) * | 2012-07-27 | 2012-11-28 | 华南理工大学 | Macromolecular organic silicon modifier as well as preparation method and application thereof in surface treatment of hydroxide flame retardant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116082641A (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112608480B (en) | Asymmetric silicone oil and preparation method and application thereof | |
| JP6082267B2 (en) | Branched polysiloxanes and their use | |
| WO2022126383A1 (en) | Asymmetric silicone oil, preparation method therefor, and application thereof | |
| EP3543304B1 (en) | Organofunctional siloxanes, method for its preparation and use for the treatment of fillers and surfaces | |
| JP6024839B2 (en) | Organopolysiloxane compound, method for producing the same, and addition-curable silicone composition | |
| JPWO2011145638A1 (en) | Novel organosilicon compound, thermosetting resin composition containing the organosilicon compound, cured resin, and sealing material for optical semiconductor | |
| CN112694757A (en) | Novel organic silicon surface treating agent composition and preparation method thereof | |
| CN115612446B (en) | Heat-conducting addition type organic silicon composition for encapsulation | |
| JPH06172536A (en) | Room temperature curing silicone sealant and its preparation | |
| US5424384A (en) | Curable organosiloxane compositions containing low temperature reactive adhesion additives | |
| JP6264307B2 (en) | Addition-curing silicone composition | |
| CN116082641B (en) | Macromolecular alkoxy silane treating agent with T-shaped symmetrical structure, and preparation method and application thereof | |
| EP2276794A1 (en) | Silicon-containing polymer, method of manufacturing thereof, and curable polymer composition | |
| CN115386087B (en) | Hydrosilylation self-crosslinking self-chain-extension linear polysiloxane and preparation method thereof | |
| JP2005298606A (en) | Curable siloxane composition | |
| CN113999647B (en) | Organic silicon pouring sealant and preparation method thereof | |
| US20230057557A1 (en) | Silirane compounds as stable silylene precursors and their use in the catalyst-free preparation of siloxanes | |
| TWI860145B (en) | Polysiloxane composition and uses of the same | |
| CN118027413A (en) | Inorganic filler surface treating agent and preparation method and application thereof | |
| CN117701234A (en) | Heat-conducting organic silicon composite material for chip packaging and preparation method thereof | |
| KR20220111311A (en) | Silirane-functionalized compounds for preparing siloxanes, especially organosilicon compounds | |
| JP3047877B2 (en) | Epoxy resin modifier and resin composition for semiconductor encapsulation | |
| WO2023101767A1 (en) | Conductive silicone composition containing carboxylic acid-functional polyorganosiloxane thixotropic agents | |
| CN119684964A (en) | Self-adhesive high thermal conductivity self-leveling flame retardant organic silicon potting glue and preparation method thereof | |
| CN119684606A (en) | A heterogeneous asymmetric organic silicon filler surface treatment agent, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |