CN116836520A - Resin composition, electrical insulation member prepared from same, and preparation method of electrical insulation member - Google Patents

Resin composition, electrical insulation member prepared from same, and preparation method of electrical insulation member Download PDF

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Publication number
CN116836520A
CN116836520A CN202311002050.9A CN202311002050A CN116836520A CN 116836520 A CN116836520 A CN 116836520A CN 202311002050 A CN202311002050 A CN 202311002050A CN 116836520 A CN116836520 A CN 116836520A
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China
Prior art keywords
epoxy resin
resin composition
bisphenol
type epoxy
toughening agent
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Pending
Application number
CN202311002050.9A
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Chinese (zh)
Inventor
刘北军
费龙菲
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Shanghai Rox Electric Co ltd
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Shanghai Rox Electric Co ltd
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Priority to CN202311002050.9A priority Critical patent/CN116836520A/en
Publication of CN116836520A publication Critical patent/CN116836520A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a resin composition, an electrical insulating part prepared from the resin composition and a preparation method of the electrical insulating part. The resin composition for the electrical equipment insulation device comprises the following components in parts by weight: 70-90 parts of bisphenol A type epoxy resin, 10-30 parts of alicyclic epoxy resin, 45-65 parts of curing agent, 300-500 parts of heat conducting filler and 5-30 parts of toughening agent OX; the toughening agent OX is bisphenol A type epoxy resin containing oxazolidone structure. According to the invention, the special epoxy resin toughening agent containing the oxazolidone structure is added into the formula, so that the use of aliphatic epoxy resin can be reduced, and a formula with higher Tg can be obtained.

Description

Resin composition, electrical insulation member prepared from same, and preparation method of electrical insulation member
Technical Field
The invention relates to the field of insulating materials, in particular to a resin composition for an electrical insulating part, an electrical insulating part prepared from the resin composition and a preparation method of the electrical insulating part.
Background
The epoxy insulating part produced by the epoxy resin formula material has good mechanical property and excellent electrical property, and is widely applied to the fields of power systems, rail transit, new energy sources and the like. However, in practical use, in many cases, epoxy insulating materials with high glass transition temperature (Tg) are required to be used due to excessive local temperature rise, but the toughness of the epoxy insulating materials with high Tg is relatively poor, and the epoxy insulating materials are easy to crack in application scenes.
Epoxy resin toughening modes are numerous, such as rubber toughening, inorganic nanoparticle toughening, shell-core structure particle toughening and the like, but all have corresponding problems: the modulus of the material can be greatly reduced by toughening the rubber, so that the rigidity of the material is reduced, and the material is easy to deform; the inorganic nano particles and the shell-core structure particles are difficult to disperse in the resin, special equipment is often needed, the use is relatively difficult, and the processability is poor.
Disclosure of Invention
In order to solve the problem that an epoxy insulating material cannot have high Tg and high toughness at the same time, bisphenol A epoxy resin and alicyclic epoxy resin are used as matrixes to provide insulation, high Tg and fixing functions, but the inventor discovers that the introduction of the alicyclic epoxy resin can improve the brittleness of a system, and the heat resistance of the material can be reduced while the common toughening agent plays a toughening role. According to the invention, the special epoxy resin toughening agent containing the oxazolidone structure is added into the formula, so that the use of aliphatic epoxy resin can be reduced, and a formula with higher Tg can be obtained.
Based on this, in a first aspect of the present invention, there is provided a resin composition for an electrical insulating device, which is composed of the following components in parts by weight:
the toughening agent OX is bisphenol A type epoxy resin containing oxazolidone structure.
In a specific embodiment, the resin composition consists of the following components in parts by weight:
the general structure of bisphenol a type epoxy resin main body is as follows:
wherein n represents the degree of polymerization.
The bisphenol a type epoxy resin product may further contain conventional auxiliary materials, and the specific auxiliary materials may vary from product to product.
In a specific embodiment, the bisphenol a type epoxy resin has an epoxy value of 0.09 to 0.22eq/100g, the main body of which can be selected from one or more of E20, E12 or E14, and the bisphenol a type epoxy resin is preferably CT5531CI of hendsmei company, and the main body of the resin is E20.
In a specific embodiment, the cycloaliphatic epoxy resin is selected from CY179 of huntsmai, or one or more combinations of TTA182, TTA26 or TTA21 of tetter, preferably CY179. The invention utilizes the advantage of high Tg of the alicyclic epoxy resin condensate, and improves the Tg of bisphenol A epoxy resin, thereby meeting the requirement of high temperature resistance of the system.
In a specific embodiment, the toughening agent OX forms bisphenol A epoxy resin containing oxazolidone structure from bisphenol A epoxy resin and diphenylmethane diisocyanate (MDI) under the catalysis of imidazole catalyst.
Preferably, the preparation method of the toughening agent OX comprises the following steps:
heating bisphenol A epoxy resin at 100-140 ℃ for dehydration, cooling to 70-90 ℃, adding imidazole catalyst, dropwise adding diphenylmethane diisocyanate in the stirring process, and reacting for 3-5h after the dropwise adding is finished, thus obtaining the bisphenol A epoxy resin containing oxazolidone structure.
In a specific embodiment, in the method for preparing OX, the bisphenol a epoxy resin is one or more selected from E51, E54 and E44, and is preferably form E51 because the prepared OX has higher rigidity and does not lower Tg.
In a specific embodiment, in the preparation method of OX, the imidazole catalyst is selected from one or more of 2-methylimidazole, imidazole, 2-ethylimidazole and 2-phenylimidazole, and preferably is 2-methylimidazole.
In a specific embodiment, in the preparation method of the OX, the mass ratio of the bisphenol A type epoxy resin to the diphenylmethane diisocyanate to the imidazole catalyst is 190-220:115-125:0.18-0.22; preferably 200:120:0.2.
In a specific embodiment, the toughening agent OX has the following structure:
in a specific embodiment, the curing agent is selected from one or more of solid modified hexahydrophthalic anhydride, solid modified tetrahydrophthalic anhydride or methylnadic anhydride, preferably solid modified hexahydrophthalic anhydride. The solid modified hexahydrophthalic anhydride, solid modified tetrahydrophthalic anhydride or methyl nadic anhydride may be commercially available products such as solid modified tetrahydrophthalic anhydride curing agent HT5535CI supplied by Henschel advanced chemical materials (Guangdong) Inc.
In a specific embodiment, the heat-conducting filler is selected from one or more of alumina, silica micropowder, wollastonite and glass fiber, preferably alumina; which is primarily intended to provide reinforcement and heat conduction.
In a second aspect of the present invention, there is provided a method for producing an electrical insulating member by the above-mentioned resin composition for an electrical insulating member, comprising the steps of:
(1) After the epoxy resin and the toughening agent OX are melted at 110-130 ℃, adding the heat conducting filler, and stirring for 2-4 hours at the temperature to fully infiltrate the epoxy resin and the heat conducting filler;
(2) Adding the melted curing agent into the mixture obtained in the step (1), vacuumizing, wherein the vacuum degree is 0.3-0.5MPa, the stirring speed is 30-100r/min, and vacuumizing is carried out for 10-20min while stirring;
(3) And (3) pouring the mixture obtained in the step (2) into a mold under vacuum, and demolding after curing to obtain the electrical insulation part.
The electric insulating device prepared by the resin composition for electric insulating device according to the present invention has both high Tg and high toughness. For example, tg may be above 130℃and preferably above 135℃and toughness may be 13kJ/m below 150℃and in particular below 146.5 ℃ 2 Above, preferably 15kJ/m 2 Above, and 20kJ/m 2 Below, in particular 19.5kJ/m 2 The following is given.
In a third aspect of the present invention, there is provided an electrical insulation member made from the epoxy resin composition of the first aspect or prepared by the method of the second aspect.
The beneficial effects are that:
the special bisphenol A type epoxy resin toughening agent containing the oxazolidone structure is added in the formula, so that the use of aliphatic epoxy resin can be reduced, and a formula with higher Tg can be obtained. The epoxy resin with the special structure is added into a common epoxy resin system to reduce the crosslinking density compared with the common epoxy resin, so that the toughness of the epoxy resin formula is improved, and on the other hand, the epoxy resin with the special structure is provided with rigidity due to the fact that the molecular chain contains the oxazolidone structure, so that the crosslinking density is reduced, but Tg is not excessively reduced.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Reagent:
bisphenol a epoxy resin: model CT5531CI, available from the company Style advanced chemical (Guangdong) Co.
Aliphatic epoxy resin: model CY179, available from smith advanced chemical materials (guangdong).
Solid modified hexahydrophthalic anhydride: model HT5535CI, available from the company Style advanced chemical (Guangdong).
Alumina: model RF-2, available from thaumatin source powder limited.
DY040: purchased from the company of the chemical industry advanced by smith.
OX: the epoxy resin E51 (purchased from Kunshan Nanya epoxy resin Co., ltd.) and modified liquid MDI (diphenylmethane diisocyanate, purchased from Shandong Wanhua group Co., ltd.) were used as main materials for synthesis. The specific synthesis process is as follows:
200g of E51 epoxy resin is dehydrated by heating and vacuumizing for 4 hours, then cooled to 70 ℃, and 0.2g of catalyst 2-methylimidazole is added. After mechanical stirring for 1h, about 120g of liquid MDI was dropped by dropping, with a dropping rate of 40mL/min. After the dripping is finished, the reaction is carried out for 4 hours under the heat preservation, and the required product OX is obtained.
Table 1 lists the epoxy material formulations of the examples and comparative examples of the present invention.
Table 1 epoxy resin composition formulation table for electric insulation parts (unit: parts by weight)
The following epoxy compositions for high Tg and high toughness electrical insulation provided in examples 1-4 and comparative examples 1-5 were used to prepare high Tg and high toughness electrical insulation. The method comprises the following specific steps:
(1) After melting 110 trees, adding an alumina filler into the epoxy resin and the toughening agent, and stirring for 4 hours at the temperature to fully infiltrate the resin and the filler;
(2) Adding the melted curing agent into the mixture obtained in the step (1), vacuumizing, wherein the vacuum degree is 0.4MPa, and vacuumizing for 10min while stirring at the stirring speed of 60 r/min;
(3) And (3) pouring the mixture obtained in the step (2) into a mold under vacuum, and demolding after curing to obtain the high Tg and high toughness electrical insulation part.
A conventional epoxy insulator was prepared with the material formulation provided in comparative example 1, comprising:
(1) After the epoxy resin is melted in a 110-tree, adding an alumina filler, and stirring for 4 hours at the temperature to fully infiltrate the resin and the filler;
(2) Adding the melted curing agent into the mixture obtained in the step (1), vacuumizing, wherein the vacuum degree is 0.4MPa, and vacuumizing for 10min while stirring at the stirring speed of 60 r/min;
(3) And (3) pouring the mixture obtained in the step (2) into a mold under vacuum, and demolding after curing to obtain the conventional epoxy insulating spline.
The insulation pieces prepared according to the formulations provided in examples 1-4 and comparative examples 1-5 were subjected to performance tests, the test results are shown in table 2, and the performance evaluation methods and test criteria are:
tg: ISO 11357-2:1999 plastic-Differential Scanning Calorimetry (DSC) -part 2: and (3) measuring the glass transition temperature.
Tensile strength: ISO 527-1:2012 determination of plastic-tensile properties-part 1: general rule.
Flexural strength: ISO 178:2001 determination of Plastic-bending Properties.
Impact strength: ISO 179-1: determination of impact Properties of 2000 Plastic-simply supported beams-part 1: non-instrumented impact testing.
Breakdown field strength: IEC 60243-1:2013 solid insulation electrical strength test method-part 1: and (5) testing at the power frequency.
Volume resistance: EC 62631-3-1: dielectric and resistive properties of 2016 solid insulation-section 3-1: measurement of resistance characteristics (direct current method) -volume resistance and volume resistivity-general method.
TABLE 2 Performance test data sheet
From the above results, the toughness of comparative example 1 is far inferior to that of examples 1 to 4 and comparative examples 2 to 5 to which a toughening agent was added. DY040 (polyhydroxy polyether compound) is a conventional toughening agent, and the toughness of a cured product is improved mainly by reducing the crosslinking density of the system, but the premise is that the heat resistance of a product is always sacrificed. For example, in comparative examples 1 to 5, as the amount of DY040 added increases, the Tg of the cured product was significantly lowered.
In a mixed epoxy resin system, the Tg of a bisphenol a epoxy resin is generally increased by utilizing the advantage of a high Tg of a cured alicyclic epoxy resin, wherein the smaller the amount of alicyclic epoxy resin is, the lower the Tg is (which is determined by the structure of alicyclic epoxy) and the toughness is deteriorated by using alicyclic epoxy, so that it is impossible to combine high toughness and high Tg for a general toughening system. In the examples 1-4 using OX as the toughening agent, the Tg is higher than that of the comparative examples 2-5 under the conditions that the aliphatic epoxy dosage is much lower than that of the comparative examples and the toughening agent dosage is more, so that the effect of reducing the aliphatic epoxy dosage to obtain higher Tg is achieved, and the characteristics of high toughness and high Tg of the formula are reflected. This may be that the addition of OX on the one hand does not itself significantly reduce Tg and on the other hand may promote curing of the system, so that the structure of the molecular chain of the cured product is more perfect under the same curing process, resulting in excellent overall properties.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.

Claims (10)

1. The resin composition for the electrical appliance insulating device is characterized by comprising the following components in parts by weight:
the toughening agent OX is bisphenol A type epoxy resin containing oxazolidone structure.
2. The resin composition for electrical insulation devices according to claim 1, which is composed of the following components in parts by weight:
3. the resin composition for electric appliance insulation member according to claim 1 or 2, wherein the bisphenol a type epoxy resin has an epoxy value of 0.09 to 0.22eq/100g; preferably, the main body of the bisphenol a type epoxy resin is selected from one or more of E20, E12 or E14, preferably CT5531CI.
4. The resin composition for electrical insulation according to claim 1 or 2, wherein the cycloaliphatic epoxy resin is selected from one or more combinations of CY179, TTA182, TTA26 or TTA21, preferably CY179.
5. The resin composition for electric appliance insulation parts according to claim 1 or 2, wherein the toughening agent OX is a bisphenol a type epoxy resin containing an oxazolidone structure formed by bisphenol a type epoxy resin and diphenylmethane diisocyanate under the catalysis of an imidazole type catalyst;
preferably, the preparation method of the toughening agent OX comprises the following steps:
heating bisphenol A epoxy resin at 100-140 ℃ for dehydration, cooling to 70-90 ℃, adding imidazole catalyst, dropwise adding diphenylmethane diisocyanate in the stirring process, and reacting for 3-5h after the dropwise adding is finished, thus obtaining the bisphenol A epoxy resin containing oxazolidone structure.
6. The resin composition for electrical insulation of claim 5, wherein in the method for producing OX, the bisphenol a type epoxy resin is selected from one or more combinations of E51, E54 or E44, preferably E51 type;
the imidazole catalyst is selected from one or more of 2-methylimidazole, imidazole, 2-ethylimidazole and 2-phenylimidazole, and is preferably 2-methylimidazole;
the mass ratio of the bisphenol A type epoxy resin to the diphenylmethane diisocyanate to the imidazole catalyst is 190-220:115-125:0.18-0.22; preferably 200:120:0.2.
7. The resin composition for an electrical insulating device according to claim 5, wherein the toughening agent OX has the following structure:
8. the resin composition for an electrical insulating device according to claim 1 or 2, wherein the curing agent is selected from one or more combinations of solid modified hexahydrophthalic anhydride, solid modified tetrahydrophthalic anhydride or methylnadic anhydride, preferably solid modified hexahydrophthalic anhydride; and/or
The heat conducting filler is one or more selected from alumina, silica micropowder, wollastonite and glass fiber, preferably alumina.
9. A method for producing an electrical insulating device by the resin composition for an electrical insulating device according to any one of claims 1 to 8, comprising the steps of:
(1) After the epoxy resin and the toughening agent OX are melted at 110 ℃, adding the heat conducting filler, and stirring for 2-4 hours at the temperature to fully infiltrate the epoxy resin and the heat conducting filler;
(2) Adding the melted curing agent into the mixture obtained in the step (1), vacuumizing, wherein the vacuum degree is 0.3-0.5MPa, the stirring speed is 30-100r/min, and vacuumizing is carried out for 10-20min while stirring;
(3) And (3) pouring the mixture obtained in the step (2) into a mold under vacuum, and demolding after curing to obtain the electrical insulation part.
10. An electrical insulating device made of the resin composition for electrical insulating device according to any one of claims 1 to 8 or made by the method according to claim 9.
CN202311002050.9A 2023-08-09 2023-08-09 Resin composition, electrical insulation member prepared from same, and preparation method of electrical insulation member Pending CN116836520A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311002050.9A CN116836520A (en) 2023-08-09 2023-08-09 Resin composition, electrical insulation member prepared from same, and preparation method of electrical insulation member

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311002050.9A CN116836520A (en) 2023-08-09 2023-08-09 Resin composition, electrical insulation member prepared from same, and preparation method of electrical insulation member

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Publication Number Publication Date
CN116836520A true CN116836520A (en) 2023-10-03

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