阅读说明：本技术 一种聚醚醚酮及其制备方法 (Polyether-ether-ketone and preparation method thereof ) 是由 张东宝 张奇 于 2020-06-12 设计创作，主要内容包括：本发明公开了一种聚醚醚酮及其制备方法。<Image he="251" wi="700" file="DDA0002537429820000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses polyether-ether-ketone and a preparation method thereof.)

1. A polyether-ether-ketone is characterized in that the structural formula is

Wherein the content of the first and second substances,

R₁、R₂each independently selected from H, C_1-6Alkyl and C_1-6A haloalkyl group;

m＝0.3～0.6；

n＝0.3～0.6；

m+n＝1。

2. the polyetheretherketone of claim 1, which isCharacterized in that R₁Selected from the group consisting of H, methyl, ethyl, isopropyl, and trifluoromethyl.

3. The polyetheretherketone of claim 2, wherein R is₂Selected from the group consisting of H, methyl, ethyl, isopropyl, and trifluoromethyl.

4. The polyetheretherketone of claim 3, wherein R is₁、R₂Each independently selected from H, methyl, ethyl, n-propyl or isopropyl.

5. The polyetheretherketone of claim 1, having the formula

Wherein the content of the first and second substances,

m＝0.4，n＝0.6；

or m is 0.5 and n is 0.5.

6. The method for preparing polyetheretherketone according to any of claims 1 to 5, wherein the reaction comprises the steps of,

step 1: adding 4,4 '-difluorobenzophenone, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane, 3',5 '-bis (trifluoromethyl) - [1,1' -biphenyl ] -2, 5-diol and a catalyst into a reaction bottle, adding a solvent and a water-carrying agent, and heating under the protection of nitrogen, refluxing and removing water;

step 2: removing the water generated in the step 1, evaporating to remove the water-carrying agent, and continuing to heat for polymerization reaction;

and step 3: after the polymerization reaction is finished, pouring the reaction solution into deionized water, grinding the obtained solid, and boiling and washing the solid for 3-5 times by using the deionized water;

and 4, step 4: and (4) drying the product obtained in the step (3) in vacuum to obtain the target product of the polyether-ether-ketone.

7. The method for preparing polyetheretherketone according to claim 6, wherein the molar ratio of 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane to 3',5' -bis (trifluoromethyl) - [1,1' -biphenyl ] -2, 5-diol is 1:1 to 1: 1.5;

the molar ratio of the 4,4 '-difluorobenzophenone to the sum of the moles of 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane and 3',5 '-bis (trifluoromethyl) - [1,1' -biphenyl ] -2, 5-diol is 1:1.

8. The method of claim 6, wherein the catalyst is selected from potassium carbonate or sodium carbonate.

9. The method of claim 6, wherein the solvent is selected from the group consisting of sulfolane, N-methylpyrrolidone, and N, N-dimethylformamide.

10. The method for preparing polyetheretherketone according to claim 6, wherein the polymerization temperature in step 2 is 200 to 220 ℃.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to polyether-ether-ketone and a preparation method thereof.

Background

Polyether ether ketone (PEEK) is a linear aromatic semi-crystalline thermoplastic plastic, is a novel semi-crystalline aromatic thermoplastic engineering plastic successfully researched and developed in the end of the 70 s of the 20 th century, has the performances of high temperature resistance, solvent resistance, aging resistance, hydrolysis resistance, extremely high specific strength, specific modulus and the like, can still keep good comprehensive performance particularly in a severe environment with high temperature and high humidity, and has extremely small deformation amount during use. The excellent performance makes the polyether-ether-ketone become the most popular special engineering plastic following fluoroplastic. As a substitute for steel, aluminum, copper, titanium, Polytetrafluoroethylene (PTFE), and other high-performance materials, PEEK has been widely used in the fields of medicine (such as artificial joints), automobiles (including aviation), electronic information, transmission pipelines, daily necessities (such as electronic cigarette housings), and the like.

The main problems of the polyether-ether-ketone in the practical application process are as follows: 1. the surface cohesiveness is checked, the bonding force with a filler interface is not strong, the thermal conductivity is poor, and thermal expansion, thermal deformation and thermal fatigue are easily caused; 2. the wear resistance can not meet the requirements of engineering, such as bracket materials, sealing rings, valves and the like; 3. the glass transition temperature is relatively low and the use in some fields is limited.

Disclosure of Invention

The invention aims to provide polyether-ether-ketone with a novel structure, which can improve the glass transition temperature and ensure the heat resistance of the polyether-ether-ketone by introducing 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane into the polyether-ether-ketone, thereby providing a new idea for the research of the polyether-ether-ketone.

The invention provides polyether-ether-ketone which is characterized in that the structural formula is shown in the specification

Wherein the content of the first and second substances,

R₁、R₂each independently selected from H, C_1-6Alkyl and C_1-6A haloalkyl group;

m＝0.3～0.6；

n＝0.3～0.6；

m+n＝1。

in some embodiments of the invention, R is as defined above₁Selected from the group consisting of H, methyl, ethyl, isopropyl, and trifluoromethyl.

In some embodiments of the invention, R is as defined above₂Selected from the group consisting of H, methyl, ethyl, isopropyl, and trifluoromethyl.

In some embodiments of the invention, R is₁、R₂Each independently selected from H, methyl, ethyl, n-propyl or isopropyl.

In some embodiments of the present invention, the polyetheretherketone is characterized by having a structural formula

Wherein the content of the first and second substances,

m＝0.4，n＝0.6；

or, m is 0.5 and n is 0.5.

In some embodiments of the present invention, the method for preparing polyetheretherketone is characterized in that the reaction steps are as follows,

step 1: adding 4,4 '-difluorobenzophenone, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane, 3',5 '-bis (trifluoromethyl) - [1,1' -biphenyl ] -2, 5-diol and a catalyst into a reaction bottle, adding a solvent and a water-carrying agent, and heating under the protection of nitrogen, refluxing and removing water;

step 2: removing the water generated in the step 1, evaporating to remove the water-carrying agent, and continuing to heat for polymerization reaction;

and step 3: after the polymerization reaction is finished, pouring the reaction solution into deionized water, grinding the obtained solid, and boiling and washing the solid for 3-5 times by using the deionized water;

and 4, step 4: and (4) drying the product obtained in the step (3) in vacuum to obtain the target product of the polyether-ether-ketone.

In some embodiments of the present invention, the molar ratio of the 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane to the 3',5' -bis (trifluoromethyl) - [1,1' -biphenyl ] -2, 5-diol is 1:1 to 1: 1.5.

In some embodiments of the invention, the molar ratio of the 4,4 '-difluorobenzophenone to the sum of the moles of 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane and 3',5 '-bis (trifluoromethyl) - [1,1' -biphenyl ] -2, 5-diol is 1:1.

In some embodiments of the present invention, the catalyst is selected from potassium carbonate or sodium carbonate.

In some embodiments of the present invention, the solvent is selected from sulfolane, N-methylpyrrolidone, or N, N-dimethylformamide.

In some embodiments of the present invention, the water-carrying agent is selected from toluene.

In some schemes of the invention, the mass ratio of the water-carrying agent to the organic solvent is 1-2: 10.

In some embodiments of the present invention, the polymerization temperature in step 2 is 200-220 ℃.

The invention has the beneficial effects that:

the invention provides polyether-ether-ketone with a brand-new structure, the preparation method is simple, the glass transition temperature can be increased to over 240 ℃, and the polyether-ether-ketone has great potential industrial application value

Detailed Description

The following detailed description of specific embodiments of the present invention is provided to illustrate and explain the present invention and to be understood not to limit the present invention.