CN110776806A - Hyperbranched polymer-SiO 2Modified epoxy resin insulating material and preparation method thereof - Google Patents

Hyperbranched polymer-SiO 2Modified epoxy resin insulating material and preparation method thereof Download PDF

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CN110776806A
CN110776806A CN201911000179.XA CN201911000179A CN110776806A CN 110776806 A CN110776806 A CN 110776806A CN 201911000179 A CN201911000179 A CN 201911000179A CN 110776806 A CN110776806 A CN 110776806A
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hyperbranched polymer
sio
epoxy resin
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王利玲
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

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Abstract

The invention relates to the technical field of epoxy resin adhesives and discloses hyperbranched polymer-SiO 2The modified epoxy resin insulating material comprises the following raw materials in formula: hyperbranched polymer, nano silicon dioxide, silane coupling agent, catalyst, N-dodecyl succinic anhydride and epoxy resin. The three-dimensional net-shaped spherical structure of the hyperbranched polymer has high molecular branching degree, so that the nano SiO 2Uniform dispersionOn the huge specific surface of the hyperbranched polymer, the nano SiO is reduced 2Agglomerated, nano-SiO 2The hyperbranched polymer has an excellent elastic expansion structure and good structural stability, increases the crosslinking density of the epoxy resin, inhibits the mobility of molecular chain segments of the epoxy resin, and reduces the impact section generated by the stress expansion of the resin.

Description

Hyperbranched polymer-SiO 2Modified epoxy resin insulating material and preparation method thereof
Technical Field
The invention relates to the technical field of epoxy resin adhesives, in particular to hyperbranched polymer-SiO 2Modified epoxy resin insulating material and its preparation method are provided.
Background
The adhesive bonding refers to a technology of connecting surfaces of homogeneous or heterogeneous objects together by using an adhesive, has the characteristics of continuous stress distribution, light weight and the like, is suitable for connecting materials of different materials, different thicknesses and complex components, has a plurality of adhesive classification methods, generally comprises adhesive substances, curing agents, toughening agents, diluents, modifiers and the like, and mainly comprises thermoplastic adhesives such as polyacrylate, polyamide and the like, thermosetting adhesives such as urea-formaldehyde resin, epoxy resin and the like, rubber resin adhesives such as chloroprene rubber, synthetic rubber adhesives such as polyurethane rubber and the like, phenolic-nitrile rubber, epoxy-polysulfide rubber and the like.
The epoxy resin is a polymer containing a plurality of epoxy groups in the molecular structure, and due to the chemical activity of the epoxy groups, can generate ring-opening reaction with the compound containing active hydrogen, and generate a network structure by curing and crosslinking, the epoxy resin has wide application, rich products, good electrical insulation property, and is mainly provided with general adhesive, high temperature resistant adhesive, conductive adhesive, foaming adhesive, soft material bonding adhesive, sealant and the like, however, with the progress of the motor and the electrical industry and the continuous development of electrical products, the common unmodified epoxy resin coating and adhesive can not meet the application of insulating materials, in addition, the modifier is added into the insulating coating and the adhesive of the modified epoxy resin, so that the mechanical properties of the coating and the adhesive, such as tensile strength, toughness and the like, are influenced, and the practicability and the application range of the epoxy resin material are reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides hyperbranched polymer-SiO 2The modified epoxy resin insulating material and the preparation method thereof solve the problem that the electrical insulating property of the existing unmodified epoxy resin coating and adhesive is not good enough, and also solve the problem that the mechanical property of the modified epoxy resin insulating material is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: hyperbranched polymer-SiO 2The modified epoxy resin insulating material comprises the following formula raw materials in parts by weight: 3-5 parts of hyperbranched polymer, 10-15 parts of nano silicon dioxide, 0.1-0.2 part of silane coupling agent, 0.1-0.3 part of catalyst and 0.8-1.5 parts of N-dodecylSuccinic anhydride and 78-86 parts of epoxy resin.
Preferably, SiO in the nano silicon dioxide 2The average particle size is 20-40 nm.
Preferably, the silane coupling agent is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
Preferably, the catalyst is p-toluenesulfonic acid.
Preferably, the preparation method of the hyperbranched polymer comprises the following steps:
(1) a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise dimethyl 1, 4-benzenediacrylate, uniformly stirring, sequentially adding potassium carbonate and triethylamine serving as an alkali catalyst, heating a reaction bottle in a constant-temperature water bath kettle to 80-85 ℃, stirring at a constant speed, refluxing for reaction for 6-10 hours, observing the reaction process through a TLC (thin layer chromatography) thin-layer chromatography, concentrating the solution under reduced pressure to remove the solvent after the dimethyl 1, 4-benzenediacrylate completely reacts, washing a solid product with absolute ethyl ether, and drying to obtain a yellow solid Michael addition-ester exchange reaction product, namely, an amine acrylate ethylene glycol polymer.
(2) A reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding an amphetamine ethylene glycol polymer and diethyl diallylmalonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, placing a reaction bottle in an oil bath pot, heating to 165-170 ℃, uniformly stirring for carrying out transesterification reaction for 8-12h, observing the reaction process by TLC (thin layer chromatography), after the diethyl diallylmalonate completely reacts, carrying out suction filtration on the solution to remove the solvent, sequentially washing a solid product with distilled water and anhydrous ether, and drying to obtain a brown solid ester exchange product, namely, the amphetamine ethylene glycol diacrylate polymer.
(3) Loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding an amine ethyl acrylate dipropylene polymer and triethanolamine, uniformly stirring, adding an initiator azodiisobutyronitrile and a catalyst sodium methoxide, placing the reaction bottle into an oil bath pot, heating to 190 ℃ and 200 ℃, uniformly stirring for carrying out an ester exchange reaction for 20-25h until a large amount of brown solid is generated, slowly adding glycine while stirring, uniformly stirring for reacting for 18-24h, carrying out an amino-olefin Michael addition reaction, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using a proper amount of absolute ethyl alcohol, and obtaining the carboxyl-terminated triethanolamine-based hyperbranched polymer.
Preferably, the mass molar ratio of the diethanol amine, the dimethyl 1, 4-benzenediacrylate, the potassium carbonate and the triethylamine is 1:1.5-2:2-2.5: 2-3.
Preferably, the molar ratio of the diethyl diallylmalonate, the amphetamine ethylene glycol polymer, the 4-dimethylaminopyridine and the sodium methoxide is 1:4-8:6-10: 2-5.
Preferably, the molar ratio of the substances of the ethyl acrylate diacrylate phenylpropionate, the azodiisobutyronitrile and the sodium methoxide is 1:16-24:0.2-0.4: 2-3.
Preferably, the hyperbranched polymer-SiO 2The preparation method of the modified epoxy resin insulating material comprises the following steps:
(1) adding a proper amount of distilled water into a reaction bottle, mixing with 10-15 parts of nano silicon dioxide, stirring uniformly, adding absolute ethyl alcohol and 0.1-0.2 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:15-20, placing the reaction bottle in an ultrasonic processor, heating to 50-60 ℃, and modifying nano SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2。
(2) Adding a proper amount of N, N-dimethylformamide into a reaction bottle, then adding 3-5 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer, 0.1-0.3 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2After being stirred uniformly, the solution is transferred into a hydrothermal synthesis reaction kettle and is placed in a heating box of the reaction kettle, the solution is heated to 120-140 ℃,reacting for 6-8h, and grafting the hyperbranched polymer to modify the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2。
(3) Adding a proper amount of acetone, 78-86 parts of epoxy resin and the hyperbranched polymer graft modification nano SiO prepared in the step (2) into a reaction bottle in sequence 2Then adding 0.8-1.5 parts of N-dodecyl succinic anhydride, controlling the solid-liquid mass ratio to be 60-80%, placing the reaction bottle in an ultrasonic processor, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 2-4h at the ultrasonic frequency of 20-28KHz, and obtaining the hyperbranched polymer-SiO 2Modified epoxy resin insulating material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the hyperbranched polymer-SiO 2The modified epoxy resin insulating material is prepared through the reaction of polymer chain termination reaction between carboxyl terminated triethanolamine-base hyperbranched polymer and silane coupling agent modified SiO 2The grafting is realized, and the three-dimensional net-shaped spherical structure of the hyperbranched polymer has high molecular branching degree, so that the hyperbranched polymer has huge external specific surface area and developed and rich pore structure, and the nano SiO 2Uniformly dispersed in the network structure and abundant pores of the hyperbranched polymer, thereby avoiding the nano SiO 2Agglomeration and caking, proper amount of nano SiO 2The modified epoxy resin reduces effective charges and charge aggregation at the interface area of the coating, and when electrons generated by an external electric field enter the epoxy resin coating through conduction, the electrons are captured by the network structure and the pores of the hyperbranched polymer, so that the carriers are prevented from moving to the inside of a medium through the coating, the diffusion and transmission rates of the carriers are reduced, and the formation of a conductive path is inhibited, thereby improving the breakdown characteristic of the epoxy resin coating and enhancing the insulating property of the coating.
The hyperbranched polymer-SiO 2The hyperbranched polymer contains a large amount of hydrophobic substancesThe epoxy resin coating has the advantages that the epoxy resin coating has high hydrophobicity, the surface of the epoxy resin coating is prevented from being electrically connected, and the electric insulation performance of the coating is improved.
The hyperbranched polymer-SiO 2The hyperbranched polymer modified epoxy resin increases the cross-linking density of the epoxy resin, inhibits the activity of molecular chain segments of the epoxy resin, and reduces impact sections generated by stress expansion of the resin, thereby improving the mechanical properties of the epoxy resin, such as tensile strength, toughness and the like.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: hyperbranched polymer-SiO 2The modified epoxy resin insulating material comprises the following formula raw materials in parts by weight: 3-5 parts of hyperbranched polymer, 10-15 parts of nano-silica, 0.1-0.2 part of silane coupling agent, 0.1-0.3 part of catalyst, 0.8-1.5 parts of N-dodecyl succinic anhydride and 78-86 parts of epoxy resin, wherein SiO in the nano-silica 2The size is that the average grain diameter is 20-40nm, the silane coupling agent is N- (2-aminoethyl) -3-aminopropyl trimethoxy silane, and the catalyst is p-methyl benzene sulfonic acid.
The preparation method of the hyperbranched polymer comprises the following steps:
(1) a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise 1, 4-dimethyl phenyl diacrylate, uniformly stirring, sequentially adding additives of potassium carbonate and an alkali catalyst of triethylamine, wherein the molar ratio of the diethanol amine to the 1, 4-dimethyl phenyl diacrylate to the potassium carbonate to the triethylamine is 1:1.5-2:2-2.5:2-3, placing a reaction bottle in a constant-temperature water bath kettle, and heating to 80-8%Stirring at a constant speed for reflux reaction for 6-10h at 5 ℃, observing the reaction process through TLC (thin layer chromatography), concentrating the solution under reduced pressure to remove the solvent after the reaction of the 1, 4-benzenedimethanol diacrylate is completed, washing the solid product with anhydrous ether and drying to obtain the yellow solid Michael addition-ester exchange reaction product, namely, the cinnamic acid amine ethylene glycol polymer.
(2) A reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding an amphetamine ethylene glycol polymer and diethyl diallylmalonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, wherein the molar ratio of the diethyl diallylmalonate, the amphetamine ethylene glycol polymer, the 4-dimethylaminopyridine and the sodium methoxide is 1:4-8:6-10:2-5, placing a reaction bottle in an oil bath pot, heating to 165-170 ℃, uniformly stirring for carrying out ester exchange reaction for 8-12h, observing the reaction process by TLC chromatography, and after the diethyl diallylmalonate completely reacts, filtering the solution to remove the solvent, washing the solid product by using distilled water and anhydrous ether in sequence, and drying to obtain a brown solid ester exchange product, namely, the amphetamine ethylene diester diacrylate polymer.
(3) Loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding an amine ethyl acrylate dipropylene polymer and triethanolamine, uniformly stirring, adding an initiator azobisisobutyronitrile and a catalyst sodium methoxide, wherein the molar ratio of the substances of the amine ethyl acrylate dipropylene polymer, the azodiisobutyronitrile and the sodium methoxide is 1:16-24:0.2-0.4:2-3, placing the reaction bottle into an oil bath, heating to 190 ℃ and 200 ℃, uniformly stirring for carrying out ester exchange reaction for 20-25h until a large amount of brown solid is generated, slowly adding glycine while stirring, uniformly stirring for reacting for 18-24h, carrying out amino-olefin Michael reaction, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using a proper amount of absolute ethyl alcohol, to obtain the carboxyl-terminated triethanolamine-based hyperbranched polymer.
Hyperbranched Polymer-SiO 2Modified ringThe preparation method of the oxygen resin insulating material comprises the following steps:
(1) adding a proper amount of distilled water into a reaction bottle, mixing with 10-15 parts of nano silicon dioxide, stirring uniformly, adding absolute ethyl alcohol and 0.1-0.2 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:15-20, placing the reaction bottle in an ultrasonic processor, heating to 50-60 ℃, and modifying nano SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2。
(2) Adding a proper amount of N, N-dimethylformamide into a reaction bottle, then adding 3-5 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer, 0.1-0.3 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2After being uniformly stirred, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box to be heated to 120-140 ℃, and the reaction is carried out for 6-8h, so as to carry out hyperbranched polymer graft modification on the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2。
(3) Adding a proper amount of acetone, 78-86 parts of epoxy resin and the hyperbranched polymer graft modification nano SiO prepared in the step (2) into a reaction bottle in sequence 2Then adding 0.8-1.5 parts of N-dodecyl succinic anhydride, controlling the solid-liquid mass ratio to be 60-80%, placing the reaction bottle in an ultrasonic processor, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 2-4h at the ultrasonic frequency of 20-28KHz, and obtaining the hyperbranched polymer-SiO 2Modified epoxy resin insulating material.
Example 1:
(1) preparation of amphetamine ethylene glycol polymers: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding appropriate amount of anhydrous ethanol and diethanolamine, slowly adding dropwise 1, 4-dimethyl phenyl diacrylate, stirring, sequentially adding potassium carbonate as additive, triethylamine as base catalyst, and diethanolThe mass molar ratio of amine, 1, 4-benzenediacrylic acid dimethyl ester, potassium carbonate and triethylamine is 1:1.5:2:2, a reaction bottle is placed in a constant-temperature water bath kettle to be heated to 85 ℃, the reaction is carried out for 6 hours under uniform stirring and refluxing, the reaction process is observed through TLC thin-layer chromatography, after the 1, 4-benzenediacrylic acid dimethyl ester is completely reacted, the solution is decompressed and concentrated to remove the solvent, and then the solid product is washed by anhydrous ether and dried to obtain a yellow solid Michael addition-transesterification reaction product, namely, the cinnamic acid amine ethylene glycol polymer 1.
(2) Preparation of an amine ethylene propylene polymer: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding cinnamic acid amine ethylene glycol polymer 1 and diallyl diethyl malonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, wherein the molar ratio of the diallyl diethyl malonate to the cinnamic acid amine ethylene glycol polymer 1 to the 4-dimethylaminopyridine to the sodium methoxide is 1:4:6:2, heating the reaction bottle in an oil bath to 165 ℃, uniformly stirring for carrying out ester exchange reaction for 8h, observing the reaction process by TLC thin-layer chromatography, and after the diethyl diallylmalonate completely reacts, filtering the solution to remove the solvent, washing the solid product by using distilled water and anhydrous ether in sequence, and drying to obtain a brown solid ester exchange product, namely the amphetamine ethylene diester dipropylene polymer 1.
(3) Preparation of hyperbranched polymers: loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding the cinnamic acid amine ethylene diester dipropylene polymer 1 and triethanolamine, stirring uniformly, adding the initiator azobisisobutyronitrile and the catalyst sodium methoxide, wherein the molar ratio of the cinnamic acid amine ethylene diester dipropylene polymer 1 to the azo diisobutyronitrile to the sodium methoxide is 1:16:0.2:2, placing the reaction bottle in an oil bath, heating to 190 ℃, carrying out ester exchange reaction for 25h under uniform stirring until a large amount of brown solid is generated, slowly adding glycine under stirring, carrying out Michael addition reaction on amino-olefin under uniform stirring for 18h, cooling the solution to room temperature, filtering to remove the solvent, and washing the solid product with a proper amount of absolute ethyl alcohol to obtain the carboxyl-terminated triethanolamine-based hyperbranched polymer 1.
(4) Preparation of modified Nano SiO 2: adding a proper amount of distilled water into a reaction bottle, mixing with 10 parts of nano-silica, stirring uniformly, adding absolute ethyl alcohol and 0.1 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:15, placing the reaction bottle into an ultrasonic processor, heating to 50 ℃, and modifying nano-SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2And (3) component 1.
(5) Preparation of hyperbranched polymer graft modified nano SiO 2: adding a proper amount of N, N-dimethylformamide into a reaction bottle, adding 3 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer 1, 0.1 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2Uniformly stirring the component 1, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 120 ℃, reacting for 6 hours, and grafting the hyperbranched polymer to modify the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2And (3) component 1.
(6) Preparation of hyperbranched Polymer-SiO 2Modified epoxy resin insulating material: adding a proper amount of acetone, 86 parts of epoxy resin and the hyperbranched polymer graft modified nano SiO prepared in the step (2) into a reaction bottle in sequence 2Adding 0.8 part of N-dodecyl succinic anhydride into the component 1, controlling the solid-liquid mass ratio to be 60%, placing a reaction bottle in an ultrasonic processor, heating to 40 ℃, performing ultrasonic dispersion treatment for 2 hours at the ultrasonic frequency of 20KHz, and obtaining the hyperbranched polymer-SiO 2Modified epoxy resin insulation material 1.
Example 2:
(1) preparation of amphetamine ethylene glycol polymers: a reflux device is mounted in the reaction bottle and communicated withInto high purity N 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise 1, 4-benzene diacrylic acid dimethyl ester, uniformly stirring, sequentially adding additives of potassium carbonate and an alkali catalyst triethylamine, wherein the molar ratio of the diethanol amine to the 1, 4-benzene diacrylic acid dimethyl ester to the potassium carbonate to the triethylamine is 1:1.6:2.1:2.2, placing a reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, uniformly stirring and refluxing for 6 hours, observing the reaction process through TLC (thin-layer chromatography), concentrating the solution under reduced pressure to remove the solvent after the 1, 4-benzene diacrylic acid dimethyl ester completely reacts, washing the solid product with anhydrous ether, and drying to obtain a yellow solid Michael addition-ester exchange reaction product, namely, the cinnamic acid amine ethylene glycol polymer 2.
(2) Preparation of an amine ethylene propylene polymer: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding cinnamic acid amine ethylene glycol polymer 2 and diallyl diethyl malonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, wherein the molar ratio of the diallyl diethyl malonate to the cinnamic acid amine ethylene glycol polymer 2 to the 4-dimethylaminopyridine to the sodium methoxide is 1:5:7:3, placing a reaction bottle in an oil bath, heating to 165 ℃, uniformly stirring for carrying out ester exchange reaction for 10 hours, observing the reaction process by TLC thin-layer chromatography, and after the diethyl diallylmalonate completely reacts, filtering the solution to remove the solvent, washing the solid product by using distilled water and anhydrous ether in sequence, and drying to obtain a brown solid ester exchange product, namely, the amphetamine ethylene diester dipropylene polymer 2.
(3) Preparation of hyperbranched polymers: loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding the cinnamic acid amine ethylene diester dipropylene polymer 2 and triethanolamine, stirring uniformly, adding an initiator azobisisobutyronitrile and a catalyst sodium methoxide, wherein the molar ratio of the cinnamic acid amine ethylene diester dipropylene polymer 2 to the azo diisobutyronitrile to the sodium methoxide is 1:18:0.2:2.2, placing the reaction bottle into an oil bath kettle, heating to 190 ℃, carrying out ester exchange reaction for 22h under uniform stirring until a large amount of brown solid is generated, slowly adding glycine under stirring, carrying out Michael addition reaction for 20h under uniform stirring, cooling the solution to room temperature, filtering to remove the solvent, and washing the solid product with a proper amount of absolute ethyl alcohol to obtain the carboxyl-terminated triethanolamine-based hyperbranched polymer 2.
(4) Preparation of modified Nano SiO 2: adding a proper amount of distilled water into a reaction bottle, mixing 11 parts of nano-silica, stirring uniformly, adding absolute ethyl alcohol and 0.1 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:16, placing the reaction bottle into an ultrasonic processor, heating to 50 ℃, and modifying nano-SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2And (3) component 2.
(5) Preparation of hyperbranched polymer graft modified nano SiO 2: adding a proper amount of N, N-dimethylformamide into a reaction bottle, adding 3.5 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer 2, 0.2 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2And (2) uniformly stirring the component, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 120 ℃, reacting for 6 hours, and grafting the hyperbranched polymer to modify the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2And (3) component 2.
(6) Preparation of hyperbranched Polymer-SiO 2Modified epoxy resin insulating material: adding a proper amount of acetone, 84 parts of epoxy resin and the hyperbranched polymer graft modified nano SiO prepared in the step (2) into a reaction bottle in sequence 2Adding 1.2 parts of N-dodecyl succinic anhydride into the component 2, controlling the solid-liquid mass ratio to be 65%, placing a reaction bottle in an ultrasonic processor, heating to 45 ℃, carrying out ultrasonic dispersion treatment for 3 hours at the ultrasonic frequency of 20KHz, and obtaining the hyperbranched polymer-SiO 2Modified epoxy resin insulation material 2.
Example 3:
(1) preparation of amphetamine ethylene glycol polymers: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise 1, 4-benzene diacrylic acid dimethyl ester, uniformly stirring, sequentially adding additives of potassium carbonate and an alkali catalyst triethylamine, wherein the molar ratio of the diethanol amine to the 1, 4-benzene diacrylic acid dimethyl ester to the potassium carbonate to the triethylamine is 1:1.8:2.3:2.7, placing a reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, uniformly stirring and refluxing for 8 hours, observing the reaction process through TLC (thin-layer chromatography), concentrating the solution under reduced pressure to remove the solvent after the 1, 4-benzene diacrylic acid dimethyl ester completely reacts, washing the solid product with anhydrous ether, and drying to obtain a yellow solid Michael addition-ester exchange reaction product, namely, the cinnamic acid amine ethylene glycol polymer 3.
(2) Preparation of an amine ethylene propylene polymer: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding the cinnamic acid amine ethylene glycol polymer 3 and the diallyl malonic acid diethyl ester, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, wherein the molar ratio of the diallyl malonic acid diethyl ester to the cinnamic acid amine ethylene glycol polymer 3 to the 4-dimethylaminopyridine to the sodium methoxide is 1:6:8:4, placing a reaction bottle in an oil bath, heating to 170 ℃, uniformly stirring for carrying out ester exchange reaction for 10 hours, observing the reaction process by TLC thin-layer chromatography, and after the diethyl diallylmalonate completely reacts, filtering the solution to remove the solvent, washing the solid product by using distilled water and anhydrous ether in sequence, and drying to obtain a brown solid ester exchange product, namely, the amphetamine ethylene diester dipropylene polymer 3.
(3) Preparation of hyperbranched polymers: loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding the cinnamic acid amine ethylene diester dipropylene polymer 3 and triethanolamine, stirring uniformly, adding an initiator azobisisobutyronitrile and a catalyst sodium methoxide, wherein the molar ratio of the cinnamic acid amine ethylene diester dipropylene polymer 3 to the azo diisobutyronitrile to the sodium methoxide is 1:20:0.3:2.6, placing the reaction bottle into an oil bath pot, heating to 200 ℃, carrying out ester exchange reaction for 23h under uniform stirring until a large amount of brown solid is generated, slowly adding glycine under stirring, carrying out Michael addition reaction for 22h under uniform stirring, cooling the solution to room temperature, filtering to remove the solvent, and washing the solid product with a proper amount of absolute ethyl alcohol to obtain the carboxyl-terminated triethanolamine-based hyperbranched polymer 3.
(4) Preparation of modified Nano SiO 2: adding a proper amount of distilled water into a reaction bottle, mixing 12 parts of nano-silica, stirring uniformly, adding absolute ethyl alcohol and 0.2 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:18, placing the reaction bottle into an ultrasonic processor, heating to 55 ℃, and modifying nano-SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2And (3) component.
(5) Preparation of hyperbranched polymer graft modified nano SiO 2: adding a proper amount of N, N-dimethylformamide into a reaction bottle, then adding 3.6 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer 3, 0.2 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2And (3) uniformly stirring the component, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating the reaction kettle to 130 ℃, reacting for 7 hours, and grafting the hyperbranched polymer to modify the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2And (3) component.
(6) Preparation of hyperbranched Polymer-SiO 2Modified epoxy resin insulating material: adding a proper amount of acetone, 83 parts of epoxy resin and the hyperbranched polymer graft modified nano SiO prepared in the step (2) into a reaction bottle in sequence 2Adding 1 part of N-dodecyl succinic anhydride into the component 3, controlling the solid-liquid mass ratio to be 70%, placing a reaction bottle in an ultrasonic processor, heating to 45 ℃, carrying out ultrasonic dispersion treatment for 3 hours at the ultrasonic frequency of 25KHz, and obtaining the hyperbranched polymer-SiO 2A modified epoxy resin insulating material 3.
Example 4:
(1) preparation of amphetamine ethylene glycol polymers: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise 1, 4-benzene diacrylic acid dimethyl ester, uniformly stirring, sequentially adding additives of potassium carbonate and an alkali catalyst triethylamine, wherein the molar ratio of the diethanol amine to the 1, 4-benzene diacrylic acid dimethyl ester to the potassium carbonate to the triethylamine is 1:1.8:2.5:2.8, placing a reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, uniformly stirring and refluxing for 8 hours, observing the reaction process through TLC (thin-layer chromatography), concentrating the solution under reduced pressure to remove the solvent after the 1, 4-benzene diacrylic acid dimethyl ester completely reacts, washing the solid product with anhydrous ether, and drying to obtain a yellow solid Michael addition-ester exchange reaction product, namely, the cinnamic acid amine ethylene glycol polymer 4.
(2) Preparation of an amine ethylene propylene polymer: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding the cinnamic acid amine ethylene glycol polymer 4 and the diallyl diethyl malonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, wherein the molar ratio of the diallyl diethyl malonate to the cinnamic acid amine ethylene glycol polymer 4 to the 4-dimethylaminopyridine to the sodium methoxide is 1:7:9:4, heating the reaction bottle in an oil bath to 170 ℃, uniformly stirring for carrying out ester exchange reaction for 10 hours, observing the reaction process by TLC thin-layer chromatography, and after the diethyl diallylmalonate completely reacts, filtering the solution to remove the solvent, washing the solid product by using distilled water and anhydrous ether in sequence, and drying to obtain a brown solid ester exchange product, namely, the amphetamine ethylene diester dipropylene polymer 4.
(3) Preparation of hyperbranched polymers: loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding the cinnamic acid amine ethylene diester dipropylene polymer 4 and triethanolamine, stirring uniformly, adding the initiator azobisisobutyronitrile and the catalyst sodium methoxide, wherein the molar ratio of the cinnamic acid amine ethylene diester dipropylene polymer 4 to the azo diisobutyronitrile to the sodium methoxide is 1:22:0.4:3, placing the reaction bottle into an oil bath kettle, heating to 200 ℃, carrying out ester exchange reaction for 25h under uniform stirring until a large amount of brown solid is generated, slowly adding glycine under stirring, carrying out Michael addition reaction for 24h under uniform stirring, cooling the solution to room temperature, filtering to remove the solvent, and washing the solid product with a proper amount of absolute ethyl alcohol to obtain the carboxyl-terminated triethanolamine-based hyperbranched polymer 4.
(4) Preparation of modified Nano SiO 2: adding a proper amount of distilled water into a reaction bottle, mixing 13 parts of nano-silica, stirring uniformly, adding absolute ethyl alcohol and 0.2 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:20, placing the reaction bottle into an ultrasonic processor, heating to 60 ℃, and modifying nano-SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2And (4) component.
(5) Preparation of hyperbranched polymer graft modified nano SiO 2: adding a proper amount of N, N-dimethylformamide into a reaction bottle, adding 4.3 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer 4, 0.3 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2And (4) uniformly stirring the component, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating the reaction kettle to 135 ℃, reacting for 8 hours, and grafting the hyperbranched polymer to modify the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2And (4) component.
(6) Preparation of hyperbranched Polymer-SiO 2Modified epoxy resin insulating material: adding a proper amount of acetone, 81 parts of epoxy resin and the hyperbranched polymer graft modified nano SiO prepared in the step (2) into a reaction bottle in sequence 2Adding 1.2 parts of N-dodecyl succinic anhydride into the component 4, controlling the solid-liquid mass ratio to be 75%, placing a reaction bottle in an ultrasonic processor, heating to 50 ℃, carrying out ultrasonic dispersion treatment for 4 hours at the ultrasonic frequency of 28KHz, and obtaining the hyperbranched polymer-SiO 2A modified epoxy resin insulating material 4.
Example 5:
(1) preparation of amphetamine ethylene glycol polymers: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise 1, 4-dimethyl benzene diacrylate, uniformly stirring, sequentially adding additives of potassium carbonate and an alkali catalyst of triethylamine, wherein the molar ratio of the diethanol amine to the 1, 4-dimethyl benzene diacrylate to the potassium carbonate to the triethylamine is 1:2:2.5:3, placing a reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, uniformly stirring and refluxing for 10 hours, observing the reaction process through TLC (thin-layer chromatography), when the 1, 4-dimethyl benzene diacrylate completely reacts, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with anhydrous ethyl ether, and drying to obtain a yellow solid Michael addition-ester exchange reaction product, namely, the cinnamic acid amine ethylene glycol polymer 5.
(2) Preparation of an amine ethylene propylene polymer: a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding an allylamine ethylene glycol polymer 5 and diethyl diallylmalonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, wherein the molar ratio of the diethyl diallylmalonate to the allylamine ethylene glycol polymer 5 to the 4-dimethylaminopyridine to the sodium methoxide is 1:8:10:5, placing a reaction bottle in an oil bath, heating to 170 ℃, uniformly stirring to perform ester exchange reaction for 12 hours, observing the reaction process by TLC thin-layer chromatography, and when the diallylmalonic acid is detected, adding N, N-dimethylformamide, and performing ester exchange reaction on the mixtureAnd after the diethyl ester completely reacts, filtering the solution to remove the solvent, washing the solid product by using distilled water and anhydrous ether in sequence, and drying to obtain a brown solid ester exchange product, namely, the cinnamic acid amine ethylene diester dipropylene polymer 5.
(3) Preparation of hyperbranched polymers: loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding the cinnamic acid amine ethylene glycol dipropylene polymer 5 and triethanolamine, stirring uniformly, adding the initiator azobisisobutyronitrile and the catalyst sodium methoxide, wherein the molar ratio of the cinnamic acid amine ethylene glycol dipropylene polymer 5 to the azo diisobutyronitrile to the sodium methoxide is 1:24:0.4:3, placing the reaction bottle into an oil bath kettle, heating to 200 ℃, carrying out ester exchange reaction for 25h under uniform stirring until a large amount of brown solid is generated, slowly adding glycine under stirring, carrying out Michael addition reaction for 24h under uniform stirring, cooling the solution to room temperature, filtering to remove the solvent, and washing the solid product with a proper amount of absolute ethyl alcohol to obtain the carboxyl-terminated triethanolamine-based hyperbranched polymer 5.
(4) Preparation of modified Nano SiO 2: adding a proper amount of distilled water and 15 parts of nano-silica into a reaction bottle, uniformly stirring, adding absolute ethyl alcohol and 0.2 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:20, placing the reaction bottle into an ultrasonic processor, heating to 60 ℃, and modifying nano-SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2And (5) component.
(5) Preparation of hyperbranched polymer graft modified nano SiO 2: adding a proper amount of N, N-dimethylformamide into a reaction bottle, then adding 5 parts of carboxyl-terminated triethanolamine-based hyperbranched polymer 5, 0.3 part of catalyst p-toluenesulfonic acid and the silane coupling agent modified nano SiO prepared in the step (1) 2And (5) uniformly stirring the components, transferring the solution into a hydrothermal synthesis reaction kettle, placing the solution into a reaction kettle heating box, heating the solution to 140 ℃, reacting for 8 hours, and grafting the hyperbranched polymer to modify the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2And (5) component.
(6) Preparation of hyperbranched Polymer-SiO 2Modified epoxy resin insulating material: adding a proper amount of acetone, 78 parts of epoxy resin and the hyperbranched polymer graft modified nano SiO prepared in the step (2) into a reaction bottle in sequence 2Adding 1.5 parts of N-dodecyl succinic anhydride into the component 5, controlling the solid-liquid mass ratio to be 80%, placing a reaction bottle in an ultrasonic processor, heating to 50 ℃, performing ultrasonic dispersion treatment for 4 hours at the ultrasonic frequency of 28KHz, and obtaining the hyperbranched polymer-SiO 2Modified epoxy resin insulation material 5.
In summary, the hyperbranched polymer-SiO 2The modified epoxy resin insulating material is prepared through the reaction of polymer chain termination reaction between carboxyl terminated triethanolamine-base hyperbranched polymer and silane coupling agent modified SiO 2The grafting is realized, and the three-dimensional net-shaped spherical structure of the hyperbranched polymer has high molecular branching degree, so that the hyperbranched polymer has huge external specific surface area and developed and rich pore structure, and the nano SiO 2Uniformly dispersed in the network structure and abundant pores of the hyperbranched polymer, thereby avoiding the nano SiO 2Agglomeration and caking, proper amount of nano SiO 2The modified epoxy resin reduces effective charges and charge aggregation at the interface area of the coating, and when electrons generated by an external electric field enter the epoxy resin coating through conduction, the electrons are captured by the network structure and the pores of the hyperbranched polymer, so that the carriers are prevented from moving to the inside of a medium through the coating, the diffusion and transmission rates of the carriers are reduced, and the formation of a conductive path is inhibited, thereby improving the breakdown characteristic of the epoxy resin coating and enhancing the insulating property of the coating.
The hyperbranched polymer contains a large number of hydrophobic group ester groups, the carboxyl group at the chain end is condensed with the amino group on the silane coupling agent to form a hydrophobic amide group, and the curing agent N-dodecyl succinic anhydride contains a long alkyl chain with strong hydrophobic property, so that the hydrophobic property of the epoxy resin is greatly improved, the adhesion of water molecules on the surface of the epoxy resin coating is inhibited, the formation of an electric path on the surface of the epoxy resin coating is hindered, and the electric insulation property of the coating is achieved.
The hyperbranched polymer modifies the epoxy resin, increases the crosslinking density of the epoxy resin, inhibits the mobility of molecular chain segments of the epoxy resin, and reduces impact sections generated by stress expansion of the resin, thereby improving the mechanical properties of the epoxy resin, such as tensile strength, toughness and the like.

Claims (9)

1. Hyperbranched polymer-SiO 2The modified epoxy resin insulating material comprises the following formula raw materials in parts by weight, and is characterized in that: 3-5 parts of hyperbranched polymer, 10-15 parts of nano silicon dioxide, 0.1-0.2 part of silane coupling agent, 0.1-0.3 part of catalyst, 0.8-1.5 parts of N-dodecyl succinic anhydride and 78-86 parts of epoxy resin.
2. The hyperbranched polymer-SiO of claim 1 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: SiO in the nano silicon dioxide 2The average particle size is 20-40 nm.
3. The hyperbranched polymer-SiO of claim 1 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: the silane coupling agent is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
4. The hyperbranched polymer-SiO of claim 1 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: the catalyst is p-toluenesulfonic acid.
5. The hyperbranched polymer-SiO of claim 1 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: what is needed isThe preparation method of the hyperbranched polymer comprises the following steps:
(1) a reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of absolute ethyl alcohol and diethanol amine, slowly adding dropwise dimethyl 1, 4-benzenediacrylate, uniformly stirring, sequentially adding potassium carbonate and triethylamine serving as an alkali catalyst, heating a reaction bottle in a constant-temperature water bath kettle to 80-85 ℃, stirring at a constant speed, refluxing for reaction for 6-10 hours, observing the reaction process through a TLC (thin layer chromatography) thin-layer chromatography, concentrating the solution under reduced pressure to remove the solvent after the dimethyl 1, 4-benzenediacrylate completely reacts, washing a solid product with absolute ethyl ether, and drying to obtain a yellow solid Michael addition-ester exchange reaction product, namely, an amine acrylate ethylene glycol polymer.
(2) A reflux device is carried in the reaction bottle, and high-purity N is introduced 2Discharging air, adding a proper amount of N, N-dimethylformamide, sequentially adding an amphetamine ethylene glycol polymer and diethyl diallylmalonate, uniformly stirring, sequentially adding 4-dimethylaminopyridine and sodium methoxide serving as composite base catalysts, placing a reaction bottle in an oil bath pot, heating to 165-170 ℃, uniformly stirring for carrying out transesterification reaction for 8-12h, observing the reaction process by TLC (thin layer chromatography), after the diethyl diallylmalonate completely reacts, carrying out suction filtration on the solution to remove the solvent, sequentially washing a solid product with distilled water and anhydrous ether, and drying to obtain a brown solid ester exchange product, namely, the amphetamine ethylene glycol diacrylate polymer.
(3) Loading a reflux device into a reaction bottle, adding a proper amount of dimethyl sulfoxide solvent, sequentially adding an amine ethyl acrylate dipropylene polymer and triethanolamine, uniformly stirring, adding an initiator azodiisobutyronitrile and a catalyst sodium methoxide, placing the reaction bottle into an oil bath pot, heating to 190 ℃ and 200 ℃, uniformly stirring for carrying out an ester exchange reaction for 20-25h until a large amount of brown solid is generated, slowly adding glycine while stirring, uniformly stirring for reacting for 18-24h, carrying out an amino-olefin Michael addition reaction, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using a proper amount of absolute ethyl alcohol, and obtaining the carboxyl-terminated triethanolamine-based hyperbranched polymer.
6. The hyperbranched polymer-SiO of claim 5 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: the mass molar ratio of the diethanol amine, the dimethyl 1, 4-benzenediacrylate, the potassium carbonate and the triethylamine is 1:1.5-2:2-2.5: 2-3.
7. The hyperbranched polymer-SiO of claim 5 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: the weight molar ratio of the diethyl diallylmalonate, the phenylpropenoic acid amine ethylene glycol polymer, the 4-dimethylaminopyridine and the sodium methoxide is 1:4-8:6-10: 2-5.
8. The hyperbranched polymer-SiO of claim 5 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: the weight molar ratio of the substances of the ethylene propylene acrylate diester dipropylene polymer, the azodiisobutyronitrile and the sodium methoxide is 1:16-24:0.2-0.4: 2-3.
9. The hyperbranched polymer-SiO of claim 1 2The modified epoxy resin insulating material and the preparation method thereof are characterized in that: the hyperbranched polymer-SiO 2The preparation method of the modified epoxy resin insulating material comprises the following steps:
(1) adding a proper amount of distilled water into a reaction bottle, mixing with 10-15 parts of nano silicon dioxide, stirring uniformly, adding absolute ethyl alcohol and 0.1-0.2 part of silane coupling agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane according to the volume ratio of 1:15-20, placing the reaction bottle in an ultrasonic processor, heating to 50-60 ℃, and modifying nano SiO by using the silane coupling agent 2Filtering to remove the solvent, washing the product with a proper amount of absolute ethyl alcohol, and fully drying to obtain the silane coupling agent modified nano SiO 2。
(2) Adding a proper amount of N, N-dimethylformamide into a reaction bottle, and then adding 3-5 parts of carboxyl-terminated triethyl amineAlcohol amine hyperbranched polymer, 0.1-0.3 part of catalyst p-toluenesulfonic acid and silane coupling agent modified nano SiO prepared in step (1) 2After being uniformly stirred, the solution is transferred into a hydrothermal synthesis reaction kettle and placed in a reaction kettle heating box to be heated to 120-140 ℃, and the reaction is carried out for 6-8h, so as to carry out hyperbranched polymer graft modification on the nano SiO 2Filtering the material after the reaction to remove the solvent, washing the product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the hyperbranched polymer grafted modified nano SiO 2。
(3) Adding a proper amount of acetone, 78-86 parts of epoxy resin and the hyperbranched polymer graft modification nano SiO prepared in the step (2) into a reaction bottle in sequence 2Then adding 0.8-1.5 parts of N-dodecyl succinic anhydride, controlling the solid-liquid mass ratio to be 60-80%, placing the reaction bottle in an ultrasonic processor, heating to 40-50 ℃, carrying out ultrasonic dispersion treatment for 2-4h at the ultrasonic frequency of 20-28KHz, and obtaining the hyperbranched polymer-SiO 2Modified epoxy resin insulating material.
CN201911000179.XA 2019-10-21 2019-10-21 Hyperbranched polymer-SiO 2Modified epoxy resin insulating material and preparation method thereof Pending CN110776806A (en)

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CN115011294A (en) * 2022-06-07 2022-09-06 道尔化成电子材料(上海)有限公司 Sintered nano silver conductive adhesive for chip packaging and preparation method thereof
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Application publication date: 20200211