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 朱谚谚 于 2020-07-24 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；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,可以降低环氧树脂的介电常数和介电损耗,而且降低了环氧树脂的吸水性,有效的解决了环氧树脂耐热性差和吸水率高的问题,扩大了环氧树脂的应用范围。(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; 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 resin can be increased, and the heat resistance of the epoxy resin is enhanced; by introducing the fluorine-containing structural group, the dielectric constant and the dielectric loss of the epoxy resin can be reduced, the water absorption of the epoxy resin is reduced, the problems of poor heat resistance and high water absorption of the epoxy resin are effectively solved, and the application range of the epoxy resin is expanded.)

1. The preparation method of the environment-friendly high temperature resistant epoxy impregnating resin is characterized by comprising the following steps: the method comprises the following steps:

step S1, preparing raw materials according to the following components and weight portions: 50-80 parts of 2, 6-dimethoxynaphthalene, 100-120 parts of p-fluorobenzoyl chloride, 60-100 parts of chloroform and anhydrous FeCl₃40 parts, 60-70 parts of hydrochloric acid, 50 parts of methanol, 40-60 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;

step S2, adding 2, 6-dimethoxynaphthalene, 30-50 parts of chloroform and p-fluorobenzoyl chloride into a reaction kettle, keeping the reaction temperature at 0-5 ℃, reacting for 0.5h under the stirring condition, and then adding anhydrous FeCl into the reaction kettle₃Reacting for 15-20 h at room temperature; 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 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 into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-diphenol 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 80-100 ℃, 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.

2. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin according to claim 1, wherein the concentration of the sodium hydroxide solution is 10-30%.

3. The method for preparing the environment-friendly high temperature resistant epoxy impregnating resin according to claim 1, wherein the concentration of boron tribromide is 10-15%.

Technical Field

The invention relates to the technical field of preparation methods of epoxy resins, in particular 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. Epoxy resins have a series of 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

In order to overcome the defects in the prior art, the invention provides a preparation method of environment-friendly high-temperature-resistant epoxy impregnating resin.

The technical scheme adopted by the invention for solving the technical problems is as follows: 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: 50-80 parts of 2, 6-dimethoxynaphthalene, 100-120 parts of p-fluorobenzoyl chloride, 60-100 parts of chloroform and anhydrous FeCl₃40 parts, 60-70 parts of hydrochloric acid, 50 parts of methanol, 40-60 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;

step S2, adding 2, 6-dimethoxynaphthalene, 30-50 parts of chloroform and p-fluorobenzoyl chloride into a reaction kettle, keeping the reaction temperature at 0-5 ℃, reacting for 0.5h under the stirring condition, and then adding anhydrous FeCl into the reaction kettle₃Reacting for 15-20 h at room temperature; 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 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 into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-diphenol 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 80-100 ℃, 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.

In the preparation method of the environment-friendly high-temperature-resistant epoxy impregnating resin, the concentration of the sodium hydroxide solution is 10-30%.

In the preparation method of the environment-friendly high-temperature-resistant epoxy impregnating resin, the concentration of boron tribromide is 10-15%.

Compared with the prior art, the invention has the following advantages and prominent effects:

the preparation method has the beneficial effects that 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 resin can be increased, and the heat resistance of the epoxy resin is enhanced; by introducing the fluorine-containing structural group, the dielectric constant and the dielectric loss of the epoxy resin can be reduced, the water absorption of the epoxy resin is reduced, the problems of poor heat resistance and high water absorption of the epoxy resin are effectively solved, and the application range of the epoxy resin is expanded.

Detailed Description

The present invention will be described in detail with reference to specific embodiments in order to make those skilled in the art better understand the technical solutions of the present invention.

[ example 1 ]

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: 50 parts of 2, 6-dimethoxynaphthalene, 100 parts of p-fluorobenzoyl chloride, 60 parts of chloroform and anhydrous FeCl₃40 parts of hydrochloric acid, 60 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, adding methanol into the reaction kettle to generate brown precipitate, filtering and washing the brown precipitate to obtain 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 into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-diphenol 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 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.

Further, the concentration of the sodium hydroxide solution is 18%.

Further, the concentration of boron tribromide is 11%.

[ 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 and 55 parts of boron tribromide solution180 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 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 into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-diphenol 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 sodium hydroxide solution into a 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.

Further, the concentration of the sodium hydroxide solution is 25%.

Further, the concentration of boron tribromide is 13%.

[ 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 and p-fluorobenzeneFormyl chloride 120 parts, chloroform 100 parts, anhydrous FeCl₃40 parts of hydrochloric acid, 70 parts of methanol, 60 parts of boron tribromide solution, 200 parts of epichlorohydrin, 50 parts of tetrabutyl ammonium 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; 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 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 into the three-neck flask, and stirring for reacting for 48 hours to obtain a yellow solid: 1, 5-di-p-fluorobenzoyl-2, 6-diphenol 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 sodium hydroxide solution 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.

Further, the concentration of the sodium hydroxide solution is 30%.

Further, the concentration of boron tribromide is 15%.

The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.