CN110746575A - Preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin - Google Patents
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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Abstract
The invention discloses a preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin, which comprises the following steps: step S1, preparing raw materials, wherein the raw materials mainly comprise epichlorohydrin, 2, 6-dimethoxynaphthalene and p-fluorobenzoyl chloride; step S2, preparing an intermediate product, namely 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene; step S3, preparing an intermediate product di-1, 5-di-p-fluorobenzoyl-2, 6-diphenol naphthalene; and step S4, preparing environment-friendly high-temperature-resistant epoxy impregnating resin. According to the invention, 2, 6-dimethoxynaphthalene and p-fluorobenzoyl chloride are selected, and a rigid group containing a naphthalene structure is introduced into a molecular chain of the epoxy resin, so that the glass transition temperature of the epoxy impregnating resin can be increased, and the heat resistance of the epoxy impregnating resin is enhanced; by introducing the fluorine-containing structural group, the dielectric constant and the dielectric loss of the epoxy impregnating resin can be reduced, the water absorption of the epoxy impregnating resin is reduced, the problems of poor heat resistance and high water absorption of the epoxy impregnating resin are effectively solved, and the application range of the epoxy impregnating resin is expanded.
Description
Technical Field
The invention belongs to the technical field of preparation methods of epoxy resins, and particularly relates to a preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin.
Background
Epoxy resin generally refers to a high molecular oligomer which contains two or more epoxy groups in its molecule, has an aliphatic, alicyclic or aromatic skeleton, and is a thermosetting product having various uses formed by the reaction of the epoxy groups with a curing agent.
The active epoxy group in the epoxy resin can generate cross-linking reaction with a plurality of organic matters. Epoxy resins can be roughly classified into glycidyl ether type, glycidyl ester type, aliphatic type, alicyclic type, and the like according to their structures. In the middle of the 20 th century, the epoxy resin technology makes a major breakthrough in the application fields of coatings, adhesives and the like, and new industries are continuously developed, so that the epoxy resin industry is rapidly developed.
The epoxy resin has the following advantages: (1) the shrinkage is low, and the curing shrinkage of the epoxy resin is generally less than 2 percent and lower than that of other polymer resins. (2) The epoxy resin coating has good film forming and leveling properties, and the coating formed after curing is relatively flat. (3) The epoxy resin has strong adhesion to metal, contains a plurality of strong polar groups in a molecular structure, can improve the adhesion of the epoxy resin, and is commonly used as a protective coating to slow down the corrosion speed of metal. (4) The self-corrosion resistance is strong, and due to the molecular structure characteristic of the self-corrosion resistance, the self-corrosion resistance and the curing agent can generate a cross-linking reaction to form a compact layer with a three-dimensional network structure, so that the acid-resistant and alkali-resistant coating has good acid resistance and alkali resistance and can be used as an isolation barrier. (5) Good mechanical property, and the epoxy resin forms a compact layer after being cured, so the property (large bending strength, good dimensional stability and the like) is superior to other resins.
As a thermosetting resin, with the progress of science and technology, new epoxy resins are continuously synthesized in recent years, and researchers begin to develop and apply epoxy resins more deeply. The composite material is widely applied due to the excellent comprehensive performance. The main application areas at present are as follows: in the aspect of adhesives, the epoxy resin is widely applied to metal and nonmetal materials due to good adhesion, and the epoxy resin is an important component in the adhesives; in the aspect of corrosion resistance, the epoxy resin is used as a coating material, so that the contact between a corrosion medium and a matrix can be well blocked, the occurrence of corrosion can be slowed down or even prevented, and the metal is protected. Epoxy resin is widely applied to offshore facilities, oil and gas pipelines and the like; the composite material is also related in the aspect of composite materials and is often used in the fields of chemical industry, aerospace, military industry and the like; in addition, epoxy resins are also used in electronics. But the heat resistance of the prior epoxy resin is poor; the cured epoxy resin has large internal stress and is easy to wear processing tools in the processing process. In addition, the epoxy resin contains structural functional groups such as hydroxyl groups and ether bonds, so that the hydrophilicity of the epoxy resin is remarkably improved, and the epoxy resin has high water absorption rate, thereby influencing the use.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin, which increases the heat resistance and the water absorption performance of the epoxy impregnating resin.
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the environment-friendly high-temperature-resistant epoxy impregnating resin comprises the following operation steps: step S1, preparing raw materials, wherein the raw materials mainly comprise epichlorohydrin, 2, 6-dimethoxynaphthalene and p-fluorobenzoyl chloride; step S2, preparing an intermediate product, namely 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene; step S3, preparing an intermediate product di-1, 5-di-p-fluorobenzoyl-2, 6-diphenol naphthalene; and step S4, preparing environment-friendly high-temperature-resistant epoxy impregnating resin.
Further, the chemical structural formula of the intermediate product 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene is as follows:
further, the chemical structural formula of the intermediate di-1, 5-di-p-fluorobenzoyl-2, 6-bisphenol naphthalene is as follows:
by adopting the technical scheme, 2, 6-dimethoxynaphthalene and p-fluorobenzoyl chloride are selected, and a rigid group containing a naphthalene structure is introduced into a molecular chain of the epoxy resin, so that the glass transition temperature of the epoxy impregnating resin can be increased, and the heat resistance of the epoxy impregnating resin is enhanced; meanwhile, the fluorine-containing structural group is added, so that the dielectric constant and the dielectric loss of the epoxy impregnating resin can be reduced, the water absorption of the epoxy impregnating resin is reduced, and the problems of poor heat resistance and high water absorption of the epoxy impregnating resin are effectively solved.
Further, in step S1, the specific operation steps of raw material preparation are as follows: preparing raw materials according to the following components in parts by weight: 50-80 parts of 2, 6-dimethoxynaphthalene, 100-120 parts of p-fluorobenzoyl chloride, 60-100 parts of chloroform and anhydrous FeCl340-50 parts of hydrochloric acid, 60-70 parts of methanol, 50-60 parts of boron tribromide solution, 150-200 parts of epoxy chloropropane, 40-50 parts of tetrabutyl ammonium bromide, 150-250 parts of sodium hydroxide solution and 50-80 parts of benzene.
By optimizing the dosage of the components, the cost can be saved and the performance can be optimized on the basis of ensuring the epoxy impregnating resin.
Further, in step S2, the specific operation of preparing the intermediate product, 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene, is: adding 2, 6-dimethoxynaphthalene, chloroform and p-fluorobenzoyl chloride into a reaction kettle, and then adding anhydrous FeCl into the reaction kettle3Reacting at room temperature; and then adding hydrochloric acid into the obtained mixture, stirring uniformly, adding methanol into the reaction kettle to generate brown precipitate, filtering and washing the brown precipitate to obtain the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene.
Further, the reaction conditions of step S2 are that 2, 6-dimethoxynaphthalene, 30-50 parts of chloroform and p-fluorobenzoyl chloride are added into a reaction kettle, the reaction temperature is kept at 0-5 ℃, the reaction is carried out for 0.5h under the stirring condition, and then anhydrous FeCl is added into the reaction kettle3And reacting for 15-20 h at room temperature.
By adopting the technical scheme, in the process of synthesizing the intermediate I, the 2, 6-dimethoxynaphthalene and the p-fluorobenzoyl chloride are added in chloroform and anhydrous FeCl3Under the action of (1), when the whole intermediate I is not in the reactionThe important contribution to the introduction of the above functional groups into the epoxy resin is made when the epoxy resin contains only a naphthalene structure and also has 2 equivalent of a fluorine structure.
Further, in step S3, the specific operation of preparing the intermediate di-1, 5-di-p-fluorobenzoyl-2, 6-diphenol naphthalene is as follows: and (4) putting the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene obtained in the step (S2) into a reactor, pouring the rest chloroform, stirring uniformly, dropwise adding a boron tribromide solution, and stirring for reacting for 48 hours to obtain yellow solid 1, 5-di-p-fluorobenzoyl-2, 6-bisphenol naphthalene.
Further, the concentration of boron tribromide is 10-15%.
Because the methyl ether structure is not beneficial to the addition reaction with the epoxy resin, the intermediate I is reacted under the action of chloroform and boron tribromide solution to obtain the yellow intermediate II by adopting the technical scheme, and at the moment, the preparation for the addition of the epoxy resin in the early stage is made, and the defect of high water absorption performance caused by the introduction of hydrophilic groups such as ether bonds and the like is reduced.
Further, in step S4, the preparation of the environmentally friendly high temperature resistant epoxy impregnating resin has the operations of: adding the yellow powder obtained in the step S3 into a reactor, then adding epoxy chloropropane and tetrabutyl ammonium bromide into the reactor, keeping the reaction temperature at 80-100 ℃, and reacting for 4-5 hours under the stirring condition; cooling the reaction system to room temperature, adding benzene and sodium hydroxide solution into a reactor, keeping the reaction temperature at 80-100 ℃, reacting for 3-5 h, boiling and refluxing the obtained mixture, removing water in the solution, stopping heating when no water bubbles appear, and cooling at room temperature; and then putting the cooled solution into a debenzolization pot, and performing reduced pressure debenzolization until no benzene liquid comes out, thus obtaining the environment-friendly high-temperature-resistant epoxy impregnating resin.
Further, the concentration of the sodium hydroxide solution is 10-30%.
By adopting the technical scheme, the intermediate II reacts with the epichlorohydrin and the tetrabutylammonium bromide under the action of the benzene and the sodium hydroxide solution, and the reaction temperature is optimized and controlled, so that the intermediate II can be added to the epoxy resin as much as possible, and the heat resistance and the water absorption of the epoxy impregnating resin are greatly improved.
The invention relates to an application of environment-friendly high temperature resistant epoxy impregnating resin in outdoor paint and outdoor cable protection layers.
The invention has the following beneficial effects: according to the invention, 2, 6-dimethoxynaphthalene and p-fluorobenzoyl chloride are selected, and a rigid group containing a naphthalene structure is introduced into a molecular chain of the epoxy resin, so that the glass transition temperature of the epoxy impregnating resin can be increased, and the heat resistance of the epoxy impregnating resin is enhanced; by introducing the fluorine-containing structural group, the dielectric constant and the dielectric loss of the epoxy impregnating resin can be reduced, the water absorption of the epoxy impregnating resin is reduced, the problems of poor heat resistance and high water absorption of the epoxy impregnating resin are effectively solved, and the application range of the epoxy impregnating resin is expanded.
Drawings
FIG. 1 is a process flow diagram of example 1 in a method for preparing an environmentally friendly, high temperature resistant epoxy impregnating resin.
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings.
First, an embodiment
Example 1: a preparation method of environment-friendly high temperature resistant epoxy impregnating resin, as shown in figure 1, the method comprises the following steps: step S1, preparing raw materials according to the following components and weight portions: 50 parts of 2, 6-dimethoxynaphthalene, 100 parts of p-fluorobenzoyl chloride, 60 parts of chloroform and anhydrous FeCl340 parts, 60 parts of hydrochloric acid, 50 parts of methanol, 40 parts of boron tribromide solution, 150 parts of epoxy chloropropane, 40 parts of tetrabutyl ammonium bromide, 150 parts of sodium hydroxide solution and 50 parts of benzene.
Step S2, adding 2, 6-dimethoxynaphthalene, 30 parts of chloroform and p-fluorobenzoyl chloride into a reaction kettle, keeping the reaction temperature at 0 ℃, reacting for 0.5h under the condition of stirring, and then adding anhydrous FeCl into the reaction kettle3Reacting for 15 hours at room temperature; then adding hydrochloric acid into the obtained mixture, stirring uniformly, and adding A into a reaction kettleAnd (3) generating brown precipitate by using alcohol, filtering and washing the brown precipitate to obtain the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene.
Step S3, putting the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene obtained in the step S2 into a three-neck flask, then pouring the rest chloroform into the three-neck flask, uniformly stirring, putting the three-neck flask into an ice water bath, dropwise adding a boron tribromide solution with the concentration of 11 wt% into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-bisphenol naphthalene.
Step S4, adding the yellow powder obtained in the step S3 into a reactor, then adding epoxy chloropropane and tetrabutyl ammonium bromide into the reactor, keeping the reaction temperature at 80 ℃, and reacting for 4 hours under the condition of stirring; cooling the reaction system to room temperature, adding benzene and 18 wt% sodium hydroxide solution into a reactor, keeping the reaction temperature at 80 ℃, reacting for 3 hours, boiling and refluxing the obtained mixture, removing water in the solution, stopping heating when no water bubbles appear, and cooling at room temperature; and then putting the cooled solution into a debenzolization pot, and performing reduced pressure debenzolization until no benzene liquid comes out, thus obtaining the environment-friendly high-temperature-resistant epoxy impregnating resin.
Example 2: a preparation method of environment-friendly high temperature resistant epoxy impregnating resin comprises the following steps:
step S1, preparing raw materials according to the following components and weight portions: 70 parts of 2, 6-dimethoxynaphthalene, 110 parts of p-fluorobenzoyl chloride, 85 parts of chloroform and anhydrous FeCl340 parts, 65 parts of hydrochloric acid, 50 parts of methanol, 55 parts of boron tribromide solution, 180 parts of epichlorohydrin, 43 parts of tetrabutylammonium bromide, 190 parts of sodium hydroxide solution and 60 parts of benzene.
Step S2, adding 2, 6-dimethoxynaphthalene, 40 parts of chloroform and p-fluorobenzoyl chloride into a reaction kettle, keeping the reaction temperature at 2 ℃, reacting for 0.5h under the condition of stirring, and then adding anhydrous FeCl into the reaction kettle3Reacting at room temperature for 18 h; then adding hydrochloric acid into the obtained mixture, stirring uniformly, adding methanol into the reaction kettle to generate brown precipitate, filtering and washing the brown precipitate to obtain the 1, 5-two pairsFluorobenzoyl-2, 6-dimethyl ether naphthalene.
Step S3, putting the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene obtained in the step S2 into a three-neck flask, then pouring the rest chloroform into the three-neck flask, uniformly stirring, putting the three-neck flask into an ice water bath, dropwise adding a boron tribromide solution with the concentration of 13 wt% into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-bisphenol naphthalene.
Step S4, adding the yellow powder obtained in the step S3 into a reactor, then adding epoxy chloropropane and tetrabutyl ammonium bromide into the reactor, keeping the reaction temperature at 90 ℃, and reacting for 4.5 hours under the condition of stirring; cooling the reaction system to room temperature, adding benzene and 25 wt% sodium hydroxide solution into the reactor, keeping the reaction temperature at 95 ℃, reacting for 3.5h, boiling and refluxing the obtained mixture, removing water in the solution, stopping heating when no water bubbles appear, and cooling at room temperature; and then putting the cooled solution into a debenzolization pot, and performing reduced pressure debenzolization until no benzene liquid comes out, thus obtaining the environment-friendly high-temperature-resistant epoxy impregnating resin.
Example 3: a preparation method of environment-friendly high temperature resistant epoxy impregnating resin comprises the following steps:
step S1, preparing raw materials according to the following components and weight portions: 80 parts of 2, 6-dimethoxynaphthalene, 120 parts of p-fluorobenzoyl chloride, 100 parts of chloroform and anhydrous FeCl340 parts, 70 parts of hydrochloric acid, 50 parts of methanol, 60 parts of boron tribromide solution, 200 parts of epichlorohydrin, 50 parts of tetrabutylammonium bromide, 250 parts of sodium hydroxide solution and 80 parts of benzene.
Step S2, adding 2, 6-dimethoxynaphthalene, 50 parts of chloroform and p-fluorobenzoyl chloride into a reaction kettle, keeping the reaction temperature at 4 ℃, reacting for 0.5h under the condition of stirring, and then adding anhydrous FeCl into the reaction kettle3Reacting at room temperature for 20 h; and then adding hydrochloric acid into the obtained mixture, stirring uniformly, adding methanol into the reaction kettle to generate brown precipitate, filtering and washing the brown precipitate to obtain the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene.
Step S3, putting the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene obtained in the step S2 into a three-neck flask, then pouring the rest chloroform into the three-neck flask, uniformly stirring, putting the three-neck flask into an ice water bath, dropwise adding a boron tribromide solution with the concentration of 15 wt% into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-bisphenol naphthalene.
Step S4, adding the yellow powder obtained in the step S3 into a reactor, then adding epoxy chloropropane and tetrabutyl ammonium bromide into the reactor, keeping the reaction temperature at 100 ℃, and reacting for 5 hours under the condition of stirring; cooling the reaction system to room temperature, adding benzene and a sodium hydroxide solution with the concentration of 30 wt% into a reactor, keeping the reaction temperature at 100 ℃, reacting for 5 hours, boiling and refluxing the obtained mixture, removing water in the solution, stopping heating when no water bubbles appear, and cooling at room temperature; and then putting the cooled solution into a debenzolization pot, and performing reduced pressure debenzolization until no benzene liquid comes out, thus obtaining the environment-friendly high-temperature-resistant epoxy impregnating resin.
Second, comparative example
Comparative example 1: an epoxy impregnating resin preparation method is different from the embodiment 1 in that: in step S1, p-fluorobenzoyl chloride was not added.
Comparative example 2: an epoxy impregnating resin preparation method is different from the embodiment 1 in that: in step S4, adding epichlorohydrin and tetrabutylammonium bromide into a reactor, keeping the reaction temperature at 80 ℃, and reacting for 4 hours under the condition of stirring; cooling the reaction system to room temperature, adding benzene and 18 wt% sodium hydroxide solution into a reactor, keeping the reaction temperature at 80 ℃, reacting for 3 hours, boiling and refluxing the obtained mixture, removing water in the solution, stopping heating when no water bubbles appear, and cooling at room temperature; and then putting the cooled solution into a debenzolization pot, and performing reduced pressure debenzolization until no benzene liquid comes out, thereby obtaining the epoxy impregnating resin.
Third, test performance test
Test one: basic Performance test
Test subjects: the environment-friendly high temperature resistant epoxy impregnating resin prepared in the examples 1-3 is used as a test sample 1-3, and the epoxy impregnating resin prepared in the comparison sample 1-2 is used as a comparison sample 1-2.
The test method comprises the following steps: the reference standard for the detection of the glass transition temperature is as follows: detection standards of astm e 1356-2008; the reference standard for the bending strength test is as follows: the detection standard of GB/T9341-2008; the reference standards for tensile strength testing were: the detection standard of GB/T1040.2-2006; the reference standards for adhesion detection are: GB/T11028-1999.
And (3) test results: as shown in Table 1, the glass transition temperatures of the test samples 1 to 3 were higher than those of the control samples 1 to 2, and the higher the glass transition temperature of the test samples 1 to 3 was, the better the heat resistance thereof was. Meanwhile, the bending strength, tensile strength and adhesion of the test samples 1-3 were superior to those of the control samples 1-2.
TABLE 1 basic Performance test results of test samples 1-3 and control samples 1-2
And (2) test II: water absorption test
Test subjects: the environment-friendly high temperature resistant epoxy impregnating resin prepared in the examples 1-3 is used as a test sample 1-3, and the epoxy impregnating resin prepared in the comparison sample 1-2 is used as a comparison sample 1-2.
The test method comprises the following steps: 5 parts of 100g of each of the test samples 1 to 3 and the control samples 1 to 2 were weighed, and 25 parts of 100g of each of the samples were weighed in total and clearly indicated. Then, respectively enclosing 25 samples into a circle, placing the sample in the same laboratory, then placing a humidifier (Philips HU4803/00) in the middle of the circle, enabling a sprayer opening of the humidifier to spray air towards the ceiling, then closing the laboratory, periodically supplementing water to the humidifier by an operator during the period, ensuring that the humidifier can continuously work within a week, closing the humidifier after 1 week, respectively weighing the weight of 25 samples, and calculating the average value.
And (3) test results: as can be seen in Table 2, the average weight gains after 1-3 weeks for the control samples were all less than the average weight gains for the control samples 1-2, while the average weight gain for the control sample 2 was the highest and the average weight gain for the sample 1 was the lowest. Thus, it can be seen that: the water absorption of the control sample 2 was the best, and the water absorption of the test sample 1 was the worst; and the water absorbances of the test samples 1 to 3 were all smaller than those of the test samples 1 to 2.
TABLE 2 test results of Water absorption Properties of test samples 1 to 3 and control samples 1 to 2
The specific embodiments are only for explaining the present invention, and the present invention is not limited thereto, and those skilled in the art can make modifications without inventive contribution to the present embodiments as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. The preparation method of the environment-friendly high-temperature-resistant epoxy impregnating resin is characterized by comprising the following operation steps of: step S1, preparing raw materials, wherein the raw materials mainly comprise epichlorohydrin, 2, 6-dimethoxynaphthalene and p-fluorobenzoyl chloride; step S2, preparing an intermediate product, namely 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene; step S3, preparing an intermediate product di-1, 5-di-p-fluorobenzoyl-2, 6-diphenol naphthalene; and step S4, preparing environment-friendly high-temperature-resistant epoxy impregnating resin.
2. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin according to claim 1, wherein in the step S1, the specific operation steps of raw material preparation are as follows: preparing raw materials according to the following components in parts by weight: 50-80 parts of 2, 6-dimethoxynaphthalene, 100-120 parts of p-fluorobenzoyl chloride, 60-100 parts of chloroform and anhydrous FeCl340-50 parts of hydrochloric acid, 60-70 parts of methanol, 50-60 parts of boron tribromide solution, 150-200 parts of epoxy chloropropane, 40-50 parts of tetrabutyl ammonium bromide and 150 parts of sodium hydroxide solution250 parts of benzene and 50-80 parts of benzene.
3. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin as claimed in claim 1, wherein in step S2, the preparation of the intermediate product 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene is carried out by the following steps: adding 2, 6-dimethoxynaphthalene, chloroform and p-fluorobenzoyl chloride into a reaction kettle, and then adding anhydrous FeCl into the reaction kettle3Reacting at room temperature; and then adding hydrochloric acid into the obtained mixture, stirring uniformly, adding methanol into the reaction kettle to generate brown precipitate, filtering and washing the brown precipitate to obtain the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene.
4. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin as claimed in claim 3, wherein the reaction conditions of the step S2 are that 2, 6-dimethoxynaphthalene, 30-50 parts of chloroform and p-fluorobenzoyl chloride are added into a reaction kettle, the reaction temperature is kept at 0-5 ℃, the reaction is carried out for 0.5h under the stirring condition, and then anhydrous FeCl is added into the reaction kettle3And reacting for 15-20 h at room temperature.
5. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin according to claim 1, wherein in step S3, the preparation of the intermediate product di-1, 5-di-p-fluorobenzoyl-2, 6-diphenol naphthalene comprises the following specific operations: and (4) putting the 1, 5-di-p-fluorobenzoyl-2, 6-dimethyl ether naphthalene obtained in the step (S2) into a reactor, pouring the rest chloroform, stirring uniformly, dropwise adding a boron tribromide solution, and stirring for reacting for 48 hours to obtain yellow solid 1, 5-di-p-fluorobenzoyl-2, 6-bisphenol naphthalene.
6. The preparation method of the environment-friendly high temperature resistant epoxy impregnating resin as claimed in claim 5, wherein the concentration of boron tribromide is 10-15%.
7. The method as claimed in claim 1, wherein the step S4 is performed by: adding the yellow powder obtained in the step S3 into a reactor, then adding epoxy chloropropane and tetrabutyl ammonium bromide into the reactor, keeping the reaction temperature at 80-100 ℃, and reacting for 4-5 hours under the stirring condition; cooling the reaction system to room temperature, adding benzene and sodium hydroxide solution into a reactor, keeping the reaction temperature at 80-100 ℃, reacting for 3-5 h, boiling and refluxing the obtained mixture, removing water in the solution, stopping heating when no water bubbles appear, and cooling at room temperature; and then putting the cooled solution into a debenzolization pot, and performing reduced pressure debenzolization until no benzene liquid comes out, thus obtaining the environment-friendly high-temperature-resistant epoxy impregnating resin.
8. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin according to claim 7, wherein the concentration of the sodium hydroxide solution is 10-30%.
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Cited By (3)
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| CN111808048A (en) * | 2020-07-24 | 2020-10-23 | 绍兴柯桥拟泰科技有限公司 | Preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin |
| CN115340818A (en) * | 2021-05-14 | 2022-11-15 | 丹阳市沃德立电工材料有限公司 | High-performance high-temperature-resistant impregnating resin and preparation method thereof |
| CN116041669A (en) * | 2022-12-29 | 2023-05-02 | 中国建筑材料科学研究总院有限公司 | Epoxy resin monomer and preparation method and application thereof |
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| EP2669308A1 (en) * | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808048A (en) * | 2020-07-24 | 2020-10-23 | 绍兴柯桥拟泰科技有限公司 | Preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin |
| CN115340818A (en) * | 2021-05-14 | 2022-11-15 | 丹阳市沃德立电工材料有限公司 | High-performance high-temperature-resistant impregnating resin and preparation method thereof |
| CN116041669A (en) * | 2022-12-29 | 2023-05-02 | 中国建筑材料科学研究总院有限公司 | Epoxy resin monomer and preparation method and application thereof |
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