阅读说明：本技术 一种环保型耐高温环氧浸渍树脂制备方法 (Preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin ) 是由 黄静 郑芳 杨李懿 于 2019-11-02 设计创作，主要内容包括：本发明公开了一种环保型耐高温环氧浸渍树脂制备方法,该方法采用以下步骤：步骤S1,原料准备,原材料主要是环氧氯丙烷、2,6-二甲氧基萘和对氟苯甲酰氯；步骤S2,中间产物一1,5-二对氟苯甲酰基-2,6-二甲醚萘的制备；步骤S3,中间产物二1,5-二对氟苯甲酰基-2,6-双酚萘的制备；步骤S4,环保型耐高温环氧浸渍树脂的制备。本发明通过选用2,6-二甲氧基萘和对氟苯甲酰氯,在环氧树脂分子链中引入含萘结构的刚性基团,可以提高环氧浸渍树脂的玻璃化转变温度,增强其耐热性；通过引入含氟结构基团,可以降低环氧浸渍树脂的介电常数和介电损耗,而且降低了环氧浸渍树脂的吸水性,有效的解决了环氧浸渍树脂耐热性差和吸水率高的问题,扩大了环氧浸渍树脂的应用范围。(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.)

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%.

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.