阅读说明：本技术 耐高温树脂生产方法 (Production method of high-temperature-resistant resin ) 是由 张加骏 黄智� 于 2020-12-29 设计创作，主要内容包括：本发明提供耐高温树脂生产方法,包括如下步骤：S1、向反应装置内依次加入苯酚、硼酸和氢氧化钠溶液,搅拌均匀,加热到70℃,恒温保持1h,然后加甲醛,继续加热搅拌,恒温90℃,并保持3-5h,然后减压脱水,得到硼酸改性酚醛树脂；S2、向无水乙醇中加入纳米二氧化硅和硅烷偶联剂,在超声下分散,然后进行干燥、研磨、筛分,得到改性纳米二氧化硅；S3、向硼酸改性酚醛树脂中加入改性纳米二氧化硅,然后加热到70℃,并在该温度下搅拌30min,然后继续升温,控制温度为110-130℃,搅拌2-5h,得到混合液；S4、将混合液倒入模具中,然后经固化、脱模后得到耐高温树脂。本发明有助于提高酚醛树脂的耐热性能。(The invention provides a production method of high-temperature resistant resin, which comprises the following steps: s1, sequentially adding phenol, boric acid and sodium hydroxide solution into a reaction device, uniformly stirring, heating to 70 ℃, keeping the temperature constant for 1h, then adding formaldehyde, continuously heating and stirring, keeping the temperature constant for 90 ℃, keeping the temperature for 3-5h, and then carrying out reduced pressure dehydration to obtain boric acid modified phenolic resin; s2, adding nano silicon dioxide and a silane coupling agent into absolute ethyl alcohol, dispersing under ultrasonic, and then drying, grinding and screening to obtain modified nano silicon dioxide; s3, adding modified nano silicon dioxide into the boric acid modified phenolic resin, heating to 70 ℃, stirring for 30min at the temperature, continuing to heat, controlling the temperature to be 110-130 ℃, and stirring for 2-5h to obtain a mixed solution; and S4, pouring the mixed solution into a mold, and then curing and demolding to obtain the high-temperature-resistant resin. The invention is helpful for improving the heat resistance of the phenolic resin.)

1. The production method of the high-temperature resistant resin is characterized by comprising the following steps:

s1, sequentially adding 100 parts by mass of phenol, 3-8 parts by mass of boric acid and a sodium hydroxide solution serving as an alkali catalyst into a reaction device, uniformly stirring, heating to 70 ℃, keeping the temperature constant for 1 hour, then adding 70-90 parts by mass of formaldehyde, continuously heating and stirring, keeping the temperature constant for 90 ℃, keeping the temperature constant for 3-5 hours, and then removing water and free phenol in the system through reduced pressure dehydration to obtain boric acid modified phenolic resin;

s2, adding nano silicon dioxide and a silane coupling agent into absolute ethyl alcohol, dispersing for 30min under ultrasound, then drying for 6h at 120 ℃, grinding and screening after drying to obtain modified nano silicon dioxide;

s3, adding the modified nano-silica prepared in the S2 step into the boric acid modified phenolic resin prepared in the S1 step, wherein the mass of the modified nano-silica accounts for 1-5% of the mass of the boric acid modified phenolic resin, heating to 70 ℃, stirring at the temperature for 30min, continuing to heat, controlling the temperature to be 110-130 ℃, and stirring for 2-5h to obtain a mixed solution;

and S4, pouring the mixed solution obtained in the step S3 into a mold, and then curing and demolding to obtain the high-temperature-resistant resin.

2. The method for producing a high-temperature-resistant resin according to claim 1, wherein the mass fraction of the sodium hydroxide solution is 20 to 30%, and the mass ratio of phenol to the sodium hydroxide solution in the step S1 is 100: 80-150.

3. The method for producing a high-temperature-resistant resin according to claim 1, wherein the sodium hydroxide solution is present in an amount of 25% by mass.

4. The method for producing a high-temperature resistant resin according to claim 1, wherein the mass of the nano silica accounts for 3 to 8% of the mass of the anhydrous ethanol in the step of S2, and the mass of the silane coupling agent accounts for 0.1 to 0.5% of the mass of the anhydrous ethanol.

5. The method for producing a high temperature resistant resin according to claim 1, wherein the nano silica has a particle size of 50 to 100 nm.

6. The method for producing a high temperature resistant resin according to claim 1, wherein the silane coupling agent in the step of S2 is a mixture of one or more of KH550, KH560, KH570, KH580, and KH 590.

Technical Field

The invention belongs to the technical field of resin materials, and particularly relates to a production method of high-temperature-resistant resin.

Background

Phenolic resin belongs to a high-molecular synthetic material, has excellent mechanical property, heat resistance, corrosion resistance and flame retardant property, and is widely applied to the fields of airplanes and aviation, military equipment, automobiles, transportation industry, building industry and the like. However, phenolic hydroxyl and methylene groups in the structure of the phenolic resin are easily oxidized, so that the heat resistance of the phenolic resin is affected, for example, a common phenolic resin can be stably used for a long time at the temperature of below 200 ℃, and if the temperature exceeds 200 ℃, the oxidation obviously occurs. With the development of the industry, higher requirements are also put on the performance of the phenolic resin material, such as the requirement of better high temperature resistance.

Disclosure of Invention

The invention aims to provide a method for producing high-temperature-resistant resin aiming at the defects of the prior art.

The invention provides the following technical scheme:

the production method of the high-temperature resistant resin comprises the following steps:

s1, sequentially adding 100 parts by mass of phenol, 3-8 parts by mass of boric acid and a sodium hydroxide solution serving as an alkali catalyst into a reaction device, uniformly stirring, heating to 70 ℃, keeping the temperature constant for 1 hour, then adding 70-90 parts by mass of formaldehyde, continuously heating and stirring, keeping the temperature constant for 90 ℃, keeping the temperature constant for 3-5 hours, and then removing water and free phenol in the system through reduced pressure dehydration to obtain boric acid modified phenolic resin;

s2, adding nano silicon dioxide and a silane coupling agent into absolute ethyl alcohol, dispersing for 30min under ultrasound, then drying for 6h at 120 ℃, grinding and screening after drying to obtain modified nano silicon dioxide;

s3, adding the modified nano-silica prepared in the S2 step into the boric acid modified phenolic resin prepared in the S1 step, wherein the mass of the modified nano-silica accounts for 1-5% of the mass of the boric acid modified phenolic resin, heating to 70 ℃, stirring at the temperature for 30min, continuing to heat, controlling the temperature to be 110-130 ℃, and stirring for 2-5h to obtain a mixed solution;

and S4, pouring the mixed solution obtained in the step S3 into a mold, and then curing and demolding to obtain the high-temperature-resistant resin.

Preferably, the mass fraction of the sodium hydroxide solution is 25-30%, and the mass ratio of phenol to sodium hydroxide solution in the step S1 is 100: 80-150.

Preferably, the mass fraction of the sodium hydroxide solution is 25%.

Preferably, the mass of the nano silicon dioxide accounts for 3-8% of the mass of the absolute ethyl alcohol in the S2 step, and the mass of the silane coupling agent accounts for 0.1-0.5% of the mass of the absolute ethyl alcohol.

Preferably, the particle size of the nano-silica is 50 to 100 nm.

Preferably, the silane coupling agent in the step S2 is a mixture of one or more of KH550, KH560, KH570, KH580 and KH 590.

The invention has the beneficial effects that:

in the process of preparing the high-temperature resistant resin, the phenolic resin is modified by boric acid, boron is introduced into the structure of the modified phenolic resin, and can replace hydrogen in phenolic hydroxyl, so that the heat resistance of the phenolic resin is improved.

Detailed Description

Example 1

The production method of the high-temperature resistant resin comprises the following steps:

s1, sequentially adding 100 parts by mass of phenol, 4 parts by mass of boric acid and a sodium hydroxide solution serving as an alkali catalyst into a reaction device, uniformly stirring, heating to 70 ℃, keeping the temperature constant for 1h, then adding 70 parts by mass of formaldehyde, continuing heating and stirring, keeping the temperature constant for 90 ℃, keeping the temperature constant for 4h, and then removing moisture and free phenol in a system through reduced pressure dehydration to obtain the boric acid modified phenolic resin, wherein the mass fraction of the sodium hydroxide solution is 25%, and the mass ratio of the phenol to the sodium hydroxide solution is 100: 110;

s2, adding nano-silica and a silane coupling agent into absolute ethyl alcohol, dispersing for 30min under ultrasound, drying for 6h at 120 ℃, grinding and screening after drying to obtain modified nano-silica, wherein the particle size of the nano-silica is 50-100nm, the mass of the nano-silica accounts for 5% of the mass of the absolute ethyl alcohol, the mass of the silane coupling agent is KH550, and the mass of the silane coupling agent accounts for 0.2% of the mass of the absolute ethyl alcohol;

s3, adding the modified nano-silica prepared in the S2 step into the boric acid modified phenolic resin prepared in the S1 step, wherein the mass of the modified nano-silica accounts for 1.5% of the mass of the boric acid modified phenolic resin, heating to 70 ℃, stirring at the temperature for 30min, continuing to heat, controlling the temperature to be 110 ℃, and stirring for 3h to obtain a mixed solution;

and S4, pouring the mixed solution obtained in the step S3 into a mold, and then curing and demolding to obtain the high-temperature-resistant resin.

Example 2

The production method of the high-temperature resistant resin comprises the following steps:

s1, sequentially adding 100 parts by mass of phenol, 6 parts by mass of boric acid and a sodium hydroxide solution serving as an alkali catalyst into a reaction device, uniformly stirring, heating to 70 ℃, keeping the temperature constant for 1h, then adding 75 parts by mass of formaldehyde, continuing heating and stirring, keeping the temperature constant for 90 ℃, keeping the temperature constant for 4h, and then removing moisture and free phenol in a system through reduced pressure dehydration to obtain the boric acid modified phenolic resin, wherein the mass fraction of the sodium hydroxide solution is 25%, and the mass ratio of the phenol to the sodium hydroxide solution is 100: 120 of a solvent;

s2, adding nano-silica and a silane coupling agent into absolute ethyl alcohol, dispersing for 30min under ultrasound, drying for 6h at 120 ℃, grinding and screening after drying to obtain modified nano-silica, wherein the particle size of the nano-silica is 50-100nm, the mass of the nano-silica accounts for 5% of the mass of the absolute ethyl alcohol, the mass of the silane coupling agent is KH550, and the mass of the silane coupling agent accounts for 0.3% of the mass of the absolute ethyl alcohol;

s3, adding the modified nano-silica prepared in the S2 step into the boric acid modified phenolic resin prepared in the S1 step, wherein the mass of the modified nano-silica accounts for 2% of that of the boric acid modified phenolic resin, heating to 70 ℃, stirring at the temperature for 30min, continuing to heat, controlling the temperature to be 120 ℃, and stirring for 3h to obtain a mixed solution;

and S4, pouring the mixed solution obtained in the step S3 into a mold, and then curing and demolding to obtain the high-temperature-resistant resin.

Example 3

The production method of the high-temperature resistant resin comprises the following steps:

s1, sequentially adding 100 parts by mass of phenol, 6 parts by mass of boric acid and a sodium hydroxide solution serving as an alkali catalyst into a reaction device, uniformly stirring, heating to 70 ℃, keeping the temperature constant for 1h, then adding 80 parts by mass of formaldehyde, continuing heating and stirring, keeping the temperature constant for 90 ℃, keeping the temperature constant for 4h, and then removing moisture and free phenol in a system through reduced pressure dehydration to obtain the boric acid modified phenolic resin, wherein the mass fraction of the sodium hydroxide solution is 25%, and the mass ratio of the phenol to the sodium hydroxide solution is 100: 120 of a solvent;

s2, adding nano-silica and a silane coupling agent into absolute ethyl alcohol, dispersing for 30min under ultrasound, drying for 6h at 120 ℃, grinding and screening after drying to obtain modified nano-silica, wherein the particle size of the nano-silica is 50-100nm, the mass of the nano-silica accounts for 3% of the mass of the absolute ethyl alcohol, the mass of the silane coupling agent is KH580, and the mass of the silane coupling agent accounts for 0.2% of the mass of the absolute ethyl alcohol;

s3, adding the modified nano-silica prepared in the S2 step into the boric acid modified phenolic resin prepared in the S1 step, wherein the mass of the modified nano-silica accounts for 3% of that of the boric acid modified phenolic resin, heating to 70 ℃, stirring at the temperature for 30min, continuing to heat, controlling the temperature to be 120 ℃, and stirring for 3h to obtain a mixed solution;

and S4, pouring the mixed solution obtained in the step S3 into a mold, and then curing and demolding to obtain the high-temperature-resistant resin.

In the process of preparing the high-temperature resistant resin, the phenolic resin is modified by boric acid, boron is introduced into the structure of the modified phenolic resin, and can replace hydrogen in phenolic hydroxyl, so that the heat resistance of the phenolic resin is improved.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.