阅读说明：本技术 一种无机杂化改性酚醛环氧树脂及其制备方法 (Inorganic hybrid modified novolac epoxy resin and preparation method thereof ) 是由 叶俊 王三川 李效玉 邱藤 于 2021-02-01 设计创作，主要内容包括：本发明公开了一种无机杂化改性酚醛环氧树脂及其制备方法,其中,所述一种无机杂化改性酚醛环氧树脂由以下组分组成：一种无机杂化改性酚醛环氧树脂,由100重量份无机杂化改性酚醛树脂、300-600重量份环氧氯丙烷和30-40重量份碱性反应物组成；所述无机杂化改性酚醛树脂由100重量份苯酚、30-45重量份醛类物质、1-3重量份碱性催化剂、5-20重量份改性剂、1-3重量份pH缓冲剂和10-30重量份交联剂组成。通过将硼和锆等元素等引入酚醛树脂结构,提高树脂的耐热性,同时通过合成工艺的控制降低树脂的粘度。本发明在提升了酚醛环氧树脂耐热性的同时,使其在室温下有较低的粘度,在25℃下粘度小于4000mPa·s,固化物的5％热分解温度大于250℃。(The invention discloses an inorganic hybrid modified novolac epoxy resin and a preparation method thereof, wherein the inorganic hybrid modified novolac epoxy resin consists of the following components: an inorganic hybrid modified novolac epoxy resin, which consists of 100 parts by weight of inorganic hybrid modified novolac resin, 300 parts by weight of epichlorohydrin and 30-40 parts by weight of alkaline reactant; the inorganic hybrid modified phenolic resin consists of 100 parts by weight of phenol, 30-45 parts by weight of aldehyde substances, 1-3 parts by weight of alkaline catalyst, 5-20 parts by weight of modifier, 1-3 parts by weight of pH buffer and 10-30 parts by weight of cross-linking agent. The heat resistance of the resin is improved by introducing elements such as boron, zirconium and the like into the phenolic resin structure, and the viscosity of the resin is reduced by controlling the synthesis process. The invention improves the heat resistance of the novolac epoxy resin, and simultaneously leads the novolac epoxy resin to have lower viscosity at room temperature, the viscosity is less than 4000mPa & s at 25 ℃, and the 5% thermal decomposition temperature of a condensate is more than 250 ℃.)

1. An inorganic hybrid modified novolac epoxy resin is characterized by comprising 100 parts by weight of inorganic hybrid modified novolac resin, 300 parts by weight of epichlorohydrin and 30-40 parts by weight of alkaline reactant; the inorganic hybrid modified phenolic resin consists of 100 parts by weight of phenol, 30-45 parts by weight of aldehyde substances, 1-3 parts by weight of alkaline catalyst, 5-20 parts by weight of modifier, 1-3 parts by weight of pH buffer and 10-30 parts by weight of cross-linking agent.

2. The inorganic hybrid modified phenolic epoxy resin as claimed in claim 1, wherein the inorganic hybrid modified phenolic resin is prepared by the following steps:

1) preparing materials: preparing raw materials according to the following components: 100 parts of phenol, 30-45 parts of aldehyde substances, 1-3 parts of alkaline catalyst, 5-20 parts of modifier, 1-3 parts of pH buffer and 10-30 parts of cross-linking agent;

2) putting the phenol, the aldehyde substances and the alkaline catalyst prepared in the step 1) into a reaction kettle, heating to 40 ℃, keeping the temperature for 10 minutes, and then heating to 60-70 ℃ for reaction for 2-3 hours;

3) cooling to 40-50 ℃ after the reaction in the step 2) is finished, putting the modifier and the pH buffering agent prepared in the step 1) into a reaction kettle, heating to 70-80 ℃, and reacting for 1-2 h;

4) and 3) after the reaction is finished, putting the cross-linking agent prepared in the step 1) into a reaction kettle, heating to 80-90 ℃, and reacting for 1-2h to obtain the inorganic hybrid modified phenolic resin.

3. The inorganic hybrid modified novolac epoxy resin of claim 2, wherein in step 1), the aldehyde is one or more of paraformaldehyde and trioxymethylene.

4. The inorganic hybrid modified novolac epoxy resin of claim 2, wherein in step 1), the alkali catalyst is any one of sodium hydroxide, barium hydroxide, ammonia water and sodium carbonate or a plurality of sodium hydroxide, barium hydroxide and sodium carbonate; wherein, the sodium hydroxide, the barium hydroxide and the sodium carbonate are prepared into 30-50% aqueous solution for use when in use.

5. The inorganic hybrid modified novolac epoxy resin of claim 2, wherein in step 1), the modifier is any one or more of boric acid, molybdic acid and phosphoric acid.

6. The inorganic hybrid modified novolac epoxy resin of claim 2, wherein in the step 1), the cross-linking agent is one or more of zirconium oxychloride, tungsten hexachloride, tungsten tetrachloride oxide and tungsten dichloride oxide.

7. The inorganic hybrid modified novolac epoxy resin of claim 2, wherein in step 1), the pH buffer is any one or more of triethanolamine, diethanolamine and AMP-95.

8. The inorganic hybrid modified novolac epoxy resin of claim 1, wherein the alkaline reactant is solid sodium hydroxide.

9. The preparation method of the inorganic hybrid modified novolac epoxy resin of any one of claims 1 to 8, comprising the following steps:

I) preparing materials: preparing raw materials according to the following components: 100 parts by weight of inorganic hybrid modified phenolic resin, 300-600 parts by weight of epichlorohydrin and 30-40 parts by weight of alkaline reactant;

II) mixing, stirring and dissolving the inorganic hybrid modified phenolic resin prepared in the step I) and epoxy chloropropane;

III) adding the alkaline reactant prepared in the step I), heating to 80-100 ℃, and reacting for 3-5 h;

IV) filtering, washing the filtrate with water, separating the liquid to remove a water phase, and distilling under reduced pressure to obtain the inorganic hybrid modified novolac epoxy resin.

10. The preparation method of claim 9, wherein the inorganic hybrid modified phenolic resin is prepared by the following steps:

1) preparing materials: preparing raw materials according to the following components: 100 parts of phenol, 30-45 parts of aldehyde substances, 1-3 parts of alkaline catalyst, 5-20 parts of modifier, 1-3 parts of pH buffer and 10-30 parts of cross-linking agent;

2) putting the phenol, the aldehyde substances and the alkaline catalyst prepared in the step 1) into a reaction kettle, heating to 40 ℃, keeping the temperature for 10 minutes, and then heating to 60-70 ℃ for reaction for 2-3 hours;

3) after the reaction in the step 2) is finished, cooling to 40-50 ℃, adding the modifier and the pH buffer prepared in the step 1), heating to 70-80 ℃, and reacting for 1-2 h;

4) and 3) after the reaction is finished, adding the cross-linking agent prepared in the step 1), heating to 80-90 ℃, and reacting for 1-2h to obtain the inorganic hybrid modified phenolic resin.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to inorganic hybrid modified novolac epoxy resin and a preparation method thereof.

Background

The phenolic epoxy resin is obtained by epoxidizing thermoplastic linear low molecular weight phenolic resin with epichlorohydrin under the action of a catalyst. The novolac epoxy resin is one of polyfunctional epoxy resins, can improve the crosslinking density of a cured product during curing, has the characteristics of the novolac epoxy resin and the epoxy resin, and has excellent heat resistance, corrosion resistance and the like. With the miniaturization and high performance of electronic equipment, higher requirements on the heat resistance of novolac epoxy resin are put forward in the fields of electronic industry and the like.

The main approaches for improving the high temperature resistance of the epoxy resin system are as follows: modifying the main body structure of the epoxy resin matrix, developing a novel high-temperature-resistant curing agent, and modifying by a copolymerization and blending method. The modification of the main body structure of the epoxy resin matrix also comprises methods of introducing multifunctionality, rigid group, heteroatom and the like. At present, in order to improve the heat resistance of novolac epoxy resins, many researches have selected a method of introducing a large rigid group into a molecular skeleton, but this generally increases the viscosity of the resin while improving the heat resistance, and is not favorable for processing. In patent CN101070372, rosin is introduced in the preparation process of phenolic resin, so as to prepare rosin modified phenolic epoxy resin. Patent CN103012743 adopts cardanol as a phenol source to prepare a cardanol epoxy resin containing both benzene ring and long alkyl chain. Patent CN101450936 adopts naphthol as one of the monomer raw materials to prepare a naphthalene novolac epoxy resin. Patent CN102167799 uses 4, 4' -biphenyl dimethyl ether and p-hydroxyphenol as raw materials to prepare a diphenol aldehyde resin, performs epoxidation, and reacts with a phosphorus-containing active monomer to prepare a phosphorus-containing diphenol aldehyde epoxy resin.

Disclosure of Invention

Therefore, the invention provides the inorganic hybrid modified novolac epoxy resin and the preparation method thereof, which not only have better heat resistance, but also have lower viscosity at room temperature.

In order to solve the technical problems, the invention provides the following technical scheme:

an inorganic hybrid modified novolac epoxy resin, which consists of 100 parts by weight of inorganic hybrid modified novolac resin, 300 parts by weight of epichlorohydrin and 30-40 parts by weight of alkaline reactant; the inorganic hybrid modified phenolic resin consists of 100 parts by weight of phenol, 30-45 parts by weight of aldehyde substances, 1-3 parts by weight of alkaline catalyst, 5-20 parts by weight of modifier, 1-3 parts by weight of pH buffer and 10-30 parts by weight of cross-linking agent.

The inorganic hybrid modified phenolic epoxy resin is prepared by the following steps:

1) preparing materials: preparing raw materials according to the following components: 100 parts of phenol, 30-45 parts of aldehyde substances, 1-3 parts of alkaline catalyst, 5-20 parts of modifier, 1-3 parts of pH buffer and 10-30 parts of cross-linking agent;

2) putting the phenol, the aldehyde substances and the alkaline catalyst prepared in the step 1) into a reaction kettle, heating to 40 ℃, keeping the temperature for 10 minutes, and then heating to 60-70 ℃ for reaction for 2-3 hours;

3) cooling to 40-50 ℃ after the reaction in the step 2) is finished, putting the modifier and the pH buffering agent prepared in the step 1) into a reaction kettle, heating to 70-80 ℃, and reacting for 1-2 h;

4) and 3) after the reaction is finished, putting the cross-linking agent prepared in the step 1) into a reaction kettle, heating to 80-90 ℃, and reacting for 1-2h to obtain the inorganic hybrid modified phenolic resin.

In the inorganic hybrid modified novolac epoxy resin, in the step 1), the aldehyde substance is any one or more of paraformaldehyde and trioxymethylene.

In the inorganic hybrid modified novolac epoxy resin, in the step 1), the alkali catalyst is any one of sodium hydroxide, barium hydroxide, ammonia water and sodium carbonate or a plurality of sodium hydroxide, barium hydroxide and sodium carbonate; wherein, the sodium hydroxide, the barium hydroxide and the sodium carbonate are prepared into 30-50% aqueous solution for use when in use.

In the inorganic hybrid modified novolac epoxy resin, in the step 1), the modifier is any one or more of boric acid, molybdic acid and phosphoric acid.

In the step 1), the crosslinking agent is any one or more of zirconium oxychloride, tungsten hexachloride, tungsten tetrachloride oxide and tungsten dichloride oxide.

In the inorganic hybrid modified novolac epoxy resin, in the step 1), the pH buffer is any one or more of triethanolamine, diethanolamine and AMP-95.

In the inorganic hybrid modified novolac epoxy resin, the alkaline reactant is solid sodium hydroxide.

The preparation method of the inorganic hybrid modified novolac epoxy resin comprises the following steps:

I) preparing materials: preparing raw materials according to the following components: 100 parts by weight of inorganic hybrid modified phenolic resin, 300-600 parts by weight of epichlorohydrin and 30-40 parts by weight of alkaline reactant;

II) mixing, stirring and dissolving the inorganic hybrid modified phenolic resin prepared in the step I) and epoxy chloropropane;

III) adding the alkaline reactant prepared in the step I), heating to 80-100 ℃, and reacting for 3-5 h;

IV) filtering, washing the filtrate with water, separating the liquid to remove a water phase, and distilling under reduced pressure to obtain the inorganic hybrid modified novolac epoxy resin.

In the preparation method, the inorganic hybrid modified phenolic resin is prepared by the following steps:

1) preparing materials: preparing raw materials according to the following components: 100 parts of phenol, 30-45 parts of aldehyde substances, 1-3 parts of alkaline catalyst, 5-20 parts of modifier, 1-3 parts of pH buffer and 10-30 parts of cross-linking agent;

2) putting the phenol, the aldehyde substances and the alkaline catalyst prepared in the step 1) into a reaction kettle, heating to 40 ℃, keeping the temperature for 10 minutes, and then heating to 60-70 ℃ for reaction for 2-3 hours;

3) after the reaction in the step 2) is finished, cooling to 40-50 ℃, adding the modifier and the pH buffer prepared in the step 1), heating to 70-80 ℃, and reacting for 1-2 h;

4) and 3) after the reaction is finished, adding the cross-linking agent prepared in the step 1), heating to 80-90 ℃, and reacting for 1-2h to obtain the inorganic hybrid modified phenolic resin.

The technical scheme of the invention achieves the following beneficial technical effects:

the invention improves the heat resistance of the novolac epoxy resin, and simultaneously leads the novolac epoxy resin to have lower viscosity at room temperature, the viscosity is less than 4000mPa & s at 25 ℃, and the 5% thermal decomposition temperature of a condensate is more than 250 ℃.

Drawings

FIG. 1 is an infrared spectrum of the inorganic hybrid modified novolac epoxy resin prepared in specific example 1.

FIG. 2 is a graph showing the thermogravimetric loss of the inorganic hybrid modified novolac epoxy resin prepared in the specific example 1.

Detailed Description

Example 1

In this example, the inorganic hybrid modified novolac epoxy resin is composed of 100g of inorganic hybrid novolac resin, 500g of epichlorohydrin, and 40g of sodium hydroxide.

Wherein the inorganic hybrid phenolic resin is prepared by the following steps:

1) preparing materials: preparing raw materials according to the following components: 100g phenol, 30g paraformaldehyde, 2g sodium hydroxide, 5g boric acid, 1g triethanolamine and 10g zirconium oxychloride;

2) putting the phenol, the paraformaldehyde and the sodium hydroxide prepared in the step 1) into a reaction kettle, heating to 40 ℃, keeping the temperature for 10 minutes, and then heating to 60 ℃ for reaction for 2 hours;

3) cooling to 40 ℃ after the reaction in the step 2) is finished, putting the boric acid and the triethanolamine prepared in the step 1) into a reaction kettle, heating to 70 ℃, and reacting for 1 h;

4) and 3) after the reaction is finished, putting the zirconium oxychloride prepared in the step 1) into a reaction kettle, heating to 80 ℃, and reacting for 1h to obtain the inorganic hybrid modified phenolic resin.

Example 2

The difference between the inorganic hybrid modified novolac epoxy resin in the present embodiment and the inorganic hybrid modified novolac epoxy resin in embodiment 1 is as follows: the amount of paraformaldehyde used to prepare the inorganic hybrid modified novolac epoxy resin used in this example was 40 g.

Example 3

The difference between the inorganic hybrid modified novolac epoxy resin in the present embodiment and the inorganic hybrid modified novolac epoxy resin in embodiment 1 is as follows: the boric acid amount of the inorganic modified phenolic resin used for preparing the inorganic hybrid modified phenolic epoxy resin in this example was 10 g.

Example 4

The difference between the inorganic hybrid modified novolac epoxy resin in the present embodiment and the inorganic hybrid modified novolac epoxy resin in embodiment 1 is as follows: the pH buffering agent in the inorganic modified phenolic resin used to prepare the inorganic hybrid modified novolac epoxy resin in this example is diethanolamine.

Example 5

The difference between the inorganic hybrid modified novolac epoxy resin in the present embodiment and the inorganic hybrid modified novolac epoxy resin in embodiment 2 is that: the amount of epichlorohydrin used for preparing the inorganic hybrid modified novolac epoxy resin in this example was 300 g.

Example 6

The difference between the inorganic hybrid modified novolac epoxy resin in the present embodiment and the inorganic hybrid modified novolac epoxy resin in embodiment 2 is that: the amount of sodium hydroxide used to prepare the inorganic hybrid modified novolac epoxy resin in this example was 40 g.

The preparation method of the inorganic hybrid modified novolac epoxy resin in the embodiments 1 to 6 comprises the following steps:

I) preparing materials: preparing raw materials according to the following components: 100 parts by weight of inorganic hybrid modified phenolic resin, 300-600 parts by weight of epichlorohydrin and 30-40 parts by weight of alkaline reactant;

II) mixing, stirring and dissolving the inorganic hybrid modified phenolic resin prepared in the step I) and epoxy chloropropane;

III) adding the alkaline reactant prepared in the step I), heating to 80-100 ℃, and reacting for 3-5 h;

IV) filtering, washing the filtrate with water, separating the liquid to remove a water phase, and distilling under reduced pressure to obtain the inorganic hybrid modified novolac epoxy resin. .

Comparative example

The inorganic hybrid modified novolac epoxy resin in the embodiment consists of the following components: 100g of thermoplastic phenolic resin, 500g of epichlorohydrin and 40g of sodium hydroxide, the preparation method is the same as that of the inorganic hybrid modified phenolic epoxy resin in the examples 1 to 4, and the prepared inorganic hybrid modified phenolic epoxy resin is recorded as a phenolic epoxy resin for comparison.

The results of epoxy value, 25 ℃ viscosity and cured product heat resistance of inorganic hybrid modified novolac epoxy resins 1-6 and comparative novolac epoxy resins are shown in table 1.

TABLE 1 results of epoxy value, viscosity and heat resistance of cured product of inorganic hybrid modified novolac epoxy resins 1-6 and comparative novolac epoxy resins

As can be seen from the data shown in table 1, the inorganic hybrid modified novolac epoxy resin prepared in the present invention has a low viscosity at room temperature and sufficient heat resistance.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.