阅读说明：本技术 一种二元醇改性酸酐增韧剂 (Dihydric alcohol modified anhydride toughening agent ) 是由 高文超 钱文娟 姚其胜 于 2020-06-10 设计创作，主要内容包括：本发明涉及一种二元醇改性酸酐增韧剂,其特征在于,由如下方法制备而得：将二元醇在100℃下真空脱水,脱水完毕后通氮气；加入等摩尔酸酐官能团的酸酐,在100℃-150℃温度范围内反应,反应完成后得所述二元醇改性酸酐增韧剂。本发明的二元醇改性酸酐增韧剂能够提高断裂伸长率,使树脂固化后更加有韧性,且拉伸强度也复合要求。对高温固化体系的玻璃化温度影响较小,应用前景广泛。(The invention relates to a dihydric alcohol modified anhydride toughening agent, which is characterized by being prepared by the following method: dehydrating the dihydric alcohol at 100 ℃ in vacuum, and introducing nitrogen after dehydration is finished; adding acid anhydride with an equal mole of acid anhydride functional group, reacting at the temperature of 100-150 ℃, and obtaining the dihydric alcohol modified acid anhydride toughening agent after the reaction is finished. The dihydric alcohol modified anhydride toughening agent can improve the elongation at break, so that the cured resin has higher toughness and the tensile strength meets the requirement. Has little influence on the glass transition temperature of a high-temperature curing system and has wide application prospect.)

1. The glycol modified anhydride toughening agent is characterized by being prepared by the following method:

dehydrating the dihydric alcohol at 100 ℃ in vacuum, and introducing nitrogen after dehydration is finished;

adding acid anhydride with an equal mole of acid anhydride functional group, reacting at the temperature of 100-150 ℃, and obtaining the dihydric alcohol modified acid anhydride toughening agent after the reaction is finished.

2. The glycol-modified anhydride toughening agent of claim 1, wherein the glycol comprises any one or more of ethylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, or 1, 2-propanediol.

3. The glycol-modified anhydride toughening agent of claim 1, wherein the anhydride comprises any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, maleic anhydride, or phthalic anhydride.

4. The glycol-modified anhydride toughening agent of claim 1, wherein the glycol-modified anhydride toughening agent is prepared by the reaction method of formula 1:

5. the glycol-modified anhydride toughening agent of claim 1, wherein the glycol-modified anhydride toughening agent is prepared by a reaction method of formula 2:

6. the glycol-modified anhydride toughening agent of claim 1, wherein the glycol-modified anhydride toughening agent is prepared by the reaction method of formula 3 as follows:

7. the glycol-modified anhydride toughening agent of claim 1, wherein the glycol-modified anhydride toughening agent is prepared by the reaction method of formula 4 as follows:

Technical Field

The invention relates to the field of toughening agent preparation, in particular to a diol modified anhydride toughening agent.

Background

In the epoxy curing system, bisphenol A epoxy resin or bisphenol F epoxy resin is generally reacted with amine or anhydride curing agents, so that the application is wide. However, the brittleness of the epoxy resin directly influences the further use of the epoxy resin, and the problems of high brittleness and easy cracking are often encountered in many use occasions. Most formulations require toughening modifications to improve impact resistance and elongation at break of the article.

Generally, the strength and glass transition temperature of a cured product are sacrificed during toughening, so that a toughening agent which has small influence on the bulk strength and the glass transition temperature is necessary.

At present, most of toughening agents are epoxy resin modified products or rubber modified products, and the toughening agents need to be added into a main agent during application, so that the flexibility of the overall formula product is limited.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a diol modified anhydride toughening agent, which is added into a curing agent system during application, so that the flexibility of the system is greatly improved, the toughening effect is excellent, and the influence on the body strength and the glass transition temperature is small.

A diol modified anhydride toughening agent is prepared by the following method:

dehydrating the dihydric alcohol at 100 ℃ in vacuum, and introducing nitrogen after dehydration is finished;

adding acid anhydride with an equal mole of acid anhydride functional group, reacting at the temperature of 100-150 ℃, and obtaining the dihydric alcohol modified acid anhydride toughening agent after the reaction is finished.

In a preferred embodiment of the present invention, the diol comprises any one or more of ethylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol or 1, 2-propanediol.

Preferably 1, 4-butanediol, 1, 6-hexanediol or 2-methyl-2, 4-pentanediol.

In a preferred embodiment of the invention, the acid anhydride comprises any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, maleic anhydride or phthalic anhydride.

Preferably any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride or methyl nadic anhydride.

In a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 1:

in a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 2:

in a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 3:

in a preferred embodiment of the present invention, the glycol-modified anhydride toughening agent is prepared by the following reaction method of formula 4:

the invention has the beneficial effects that:

the dihydric alcohol modified anhydride toughening agent can improve the elongation at break, so that the cured resin has higher toughness and the tensile strength meets the requirement. Has little influence on the glass transition temperature of a high-temperature curing system and has wide application prospect.

Detailed Description

The design principle of the invention is as follows:

the product of the invention is modified anhydride, is added into a curing agent system when being applied, greatly improves the flexibility of the system, has excellent toughening effect and has small influence on the body strength and the glass transition temperature.

In the research process, the invention finds that the selection and control of the temperature have larger influence on the performance of the product, and the higher the temperature is, the more violent the polymerization reaction is.

Therefore, the toughening effect can meet the requirement by adjusting within the standard range. The products obtained by the same raw materials at different reaction temperatures are different, so the reaction temperature is set well in the synthesis process and controlled strictly.

When the reaction temperature is lower than 100 ℃, the ring opening of the anhydride is not easy, the reaction is weaker, and a brown yellow liquid is obtained. The toughening effect was not significant after addition to the curative system (as in comparative example 1). When the reaction temperature is higher than 150 ℃, the synthesis reaction is violent, the obtained product has higher crosslinking degree and can play a toughening effect, but the loss of the bulk strength is caused, and the loss of the glass transition temperature is larger (as a comparative example 2).

The invention is explained below with reference to specific embodiments: