阅读说明：本技术 一种合成装置及其用途和生产热致性液晶聚合物的方法 (Synthesis device and application thereof, and method for producing thermotropic liquid crystal polymer ) 是由 高敬民 吴煜 金纪阳 于 2020-05-09 设计创作，主要内容包括：本发明提供一种合成装置及其用途和生产热致性液晶聚合物的方法；所述合成装置包括反应釜(1)、冷凝器(2)和储液罐(3)；所述反应釜(1)与所述冷凝器(2)的进液口通过第一管道连通；所述储液罐3与所述冷凝器(2)的出液口通过第二管道连通；所述反应釜(1)内设有搅拌器(11)、喷淋器(12)和温度传感器；所述储液罐(3)通过第三管道与所述喷淋器(12)连通；所述的第三管道上设有计量泵(4)和第一温控开关(5)；所述第一温控开关(5)与所述温度传感器电信号连接。本申请中的反应装置结构紧凑,能够实现反应釜内反应物料温度的精准控制,非常适合用于生产热致性液晶聚合物。(The present invention provides a synthesis apparatus and use thereof and a method for producing a thermotropic liquid crystalline polymer; the synthesis device comprises a reaction kettle (1), a condenser (2) and a liquid storage tank (3); the reaction kettle (1) is communicated with a liquid inlet of the condenser (2) through a first pipeline; the liquid storage tank 3 is communicated with a liquid outlet of the condenser (2) through a second pipeline; a stirrer (11), a sprayer (12) and a temperature sensor are arranged in the reaction kettle (1); the liquid storage tank (3) is communicated with the sprayer (12) through a third pipeline; a metering pump (4) and a first temperature control switch (5) are arranged on the third pipeline; the first temperature control switch (5) is in electrical signal connection with the temperature sensor. The reaction device in the application has a compact structure, can realize the accurate control of the temperature of reaction materials in the reaction kettle, and is very suitable for producing thermotropic liquid crystal polymers.)

1. A synthesis device is characterized by comprising a reaction kettle (1), a condenser (2) and a liquid storage tank (3); the reaction kettle (1) is communicated with a liquid inlet of the condenser (2) through a first pipeline; the liquid storage tank (3) is communicated with a liquid outlet of the condenser (2) through a second pipeline; a stirrer (11), a sprayer (12) and a temperature sensor are arranged in the reaction kettle (1); the liquid storage tank (3) is communicated with the sprayer (12) through a third pipeline; a metering pump (4) and a first temperature control switch (5) are arranged on the third pipeline; the first temperature control switch (5) is in electrical signal connection with the temperature sensor.

2. The synthesis device according to claim 1, characterized in that the condenser (2) is arranged at the upper part of the reaction vessel (1); and/or the outer side wall of the reaction kettle (1) is also provided with a plurality of heat exchange interlayers (13) in a winding manner, and circulating heat conduction oil is arranged in the heat exchange interlayers (13).

3. A synthesis unit according to claim 2, characterized in that the heat exchange sandwich (13) is further provided with a cooling module (14); the cooling assembly (14) comprises a cooling tube that spirals around the reactor vessel (1); and/or the heat exchange interlayer(s) (13) is/are one or more; and/or an ultrasonic generator is also arranged in the heat exchange interlayer (13); and/or the average molecular weight of the heat conduction oil is 200-400; the kinematic viscosity at 40 ℃ is 25-32 mm²(s) kinematic viscosity at 100 ℃ of 2 to 5mm²/s。

4. The synthesizer according to claim 3, wherein a second temperature control switch is disposed on the cooling tube, and the second temperature control switch is electrically connected to the temperature sensor; and/or a plurality of heat exchange interlayers (13) are distributed in sequence along the height direction of the reaction kettle (1).

5. The synthesis device according to claim 1, characterized in that the temperature sensor is arranged in the middle or at the bottom of the reaction kettle (1); and/or the sprayer (12) is arranged at the top of the reaction kettle (1); and/or the side surface of the reaction kettle (1) is also provided with an inner window; and/or along the flowing direction of liquid on the third pipeline, the third pipeline is divided into a manual switch communicating channel and an automatic switch communicating channel after passing through the first temperature control switch (5).

6. Use of a synthesis device according to any one of claims 1 to 5 for the production of thermotropic liquid crystalline polymers.

7. A method for producing a thermotropic liquid crystalline polymer, comprising the steps of: 1) adding a monomer into a reaction kettle, dissolving the monomer with a solvent, adding a certain amount of catalyst, and heating until the temperature of reaction materials reaches 80-150 ℃ and keeping the temperature for acetylation; 2) after the acetylation reaction is finished, heating the reaction materials in the reaction kettle to reach and keep the temperature at 200-350 ℃ for polymerization deacidification reaction; and in the steps 1) and 2), the produced fraction is extracted and condensed, and then is refluxed and sprayed back to the reaction kettle and/or the temperature is regulated and controlled by a heat exchange interlayer arranged on the wall of the reaction kettle, so that the temperature is kept at 80-150 ℃ or 200-350 ℃.

8. The method of claim 7, wherein the monomer is one or more selected from the group consisting of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, hydroquinone, biphenol, p-hydroxyaniline and derivatives thereof; the catalyst is acetate of any one or more of calcium, iron, zinc and selenium.

9. The method of claim 7, wherein the condensed distillate is automatically controlled to flow back and spray to the reaction kettle or the temperature of the heat exchange interlayer is automatically controlled by a temperature switch and a temperature sensor arranged in the reaction kettle; and/or observing the condition of a reaction system in the reaction kettle through an inner window arranged on the reaction kettle, and manually controlling the temperature of the condensed fraction reflux spray back to the reaction kettle or the heat exchange interlayer when white monomers are sublimated and adhered to the kettle wall in the reaction kettle.

10. A method according to any one of claims 7 to 9, wherein a synthesis apparatus according to any one of claims 1 to 5 is used.

Technical Field

The invention relates to the field of synthesis of liquid crystal polyester, in particular to a synthesis method and a synthesis device of liquid crystal polyester.

Background

Thermotropic liquid crystal polymer (T L CP) as an engineering plastic with special performance has a series of excellent performances, such as high strength, high modulus, short molding period, heat and chemical resistance, small linear expansion coefficient, low hygroscopicity, low dielectric constant, excellent electric insulation and the like, so that the thermotropic liquid crystal polymer has wide application in the fields of electronic appliances, fiber optical fibers, flexible circuit boards, 5G mobile phone antennas and the like at present.

The melt-process synthesis of thermotropic liquid crystalline polyesters generally comprises the following steps: (1) performing acetylation reaction on the mixed monomers in the reaction kettle; (2) after the acetylation is finished, raising the temperature to carry out polycondensation reaction, and distilling off acetic acid and excessive acetic anhydride; (3) when the reaction system has a certain viscosity, the polymer is discharged from the bottom of the kettle in a strip shape.

The whole reaction process is accompanied with strong heat absorption and release phenomena, which can cause the temperature change of a reaction system in the kettle to be larger, deviate from the set temperature and even generate temperature runaway phenomena. In addition, the excessive temperature causes sublimation and crystallization of reaction monomers, and the reaction monomers are separated out and adhered to the wall of the kettle and the stirring paddle, so that the determined monomer molar ratio is influenced, and the performance of the liquid crystal polymer is finally influenced.

Therefore, how to inhibit the temperature runaway phenomenon and avoid the influence of monomer sublimation crystallization on the molar ratio is a key process for preparing the high-performance liquid crystal polyester.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a synthesis apparatus, its use and a method for producing thermotropic liquid crystalline polymers, which are used to solve the problems of the prior art that the temperature of materials is too high during the reaction of liquid crystalline polymers, and the sublimation of monomers affects the precise molar ratio of the reactants and thus the final properties of the liquid crystalline polymers.

To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.

The invention provides a synthesis device, which comprises a reaction kettle, a condenser and a liquid storage tank, wherein the reaction kettle is connected with the condenser; the reaction kettle is communicated with a liquid inlet of the condenser through a first pipeline; the liquid storage tank is communicated with a liquid outlet of the condenser through a second pipeline; a stirrer, a sprayer and a temperature sensor are arranged in the reaction kettle; the liquid storage tank is communicated with the sprayer through a third pipeline; a metering pump and a first temperature control switch are arranged on the third pipeline; the first temperature control switch is in electrical signal connection with the temperature sensor.

According to the above synthesis device, the condenser is arranged at the upper part of the reaction kettle.

According to the synthesizer, the outer side wall of the reaction kettle is further wound with a plurality of heat exchange interlayers, and circulating heat conduction oil is arranged in the heat exchange interlayers.

According to the synthesis device, the heat exchange interlayer is also provided with a cooling assembly; the cooling assembly includes a cooling tube that spirals around the reactor.

According to the synthesis device, one or more heat exchange interlayers are provided. More preferably, a plurality of heat exchange interlayers are distributed along the height direction of the reaction kettle in sequence.

According to the synthesis device, the heat exchange interlayer is also internally provided with an ultrasonic generator.

According to the synthesis device, the average molecular weight of the heat conduction oil is 200-400; the kinematic viscosity at 40 ℃ is 25-32 mm²(s) kinematic viscosity at 100 ℃ of 2 to 5mm²/s。

According to the synthesizer, the cooling pipe is provided with a second temperature control switch, and the second temperature control switch is in electrical signal connection with the temperature sensor.

According to the synthesis device, the temperature sensor is arranged in the middle or at the bottom of the reaction kettle; and/or the sprayer is arranged at the top of the reaction kettle; and/or the side surface of the reaction kettle is also provided with an inner window.

According to the synthesis device, along the flowing direction of liquid on the third pipeline, the third pipeline is divided into a manual switch communication channel and an automatic switch communication channel after passing through the first temperature control switch.

The invention also discloses the application of the synthesis device for producing the thermotropic liquid crystal polymer.

The invention also discloses a method for producing the thermotropic liquid crystal polymer, which comprises the following steps: 1) adding a monomer into a reaction kettle, dissolving the monomer with a solvent, adding a certain amount of catalyst, and heating until the temperature of reaction materials reaches 80-150 ℃ and keeping the temperature for acetylation; 2) after the acetylation reaction is finished, heating the reaction materials in the reaction kettle to 200-350 ℃ and keeping the temperature for polymerization deacidification reaction; and in the steps 1) and 2), the produced fraction is extracted and condensed, and then is refluxed and sprayed back to the reaction kettle and/or the temperature is regulated and controlled by a heat exchange interlayer arranged on the wall of the reaction kettle, so that the temperature is kept at 80-150 ℃ or 200-350 ℃.

According to the method, the monomer is one or more of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, hydroquinone, biphenol, p-hydroxyamine and derivatives thereof; the catalyst is acetate of any one or more of calcium, iron, zinc and selenium.

According to the method, the condensed fraction is automatically controlled to flow back and spray back to the reaction kettle or the temperature of the heat exchange interlayer is automatically controlled through the temperature switch and the temperature sensor arranged in the reaction kettle.

According to the method, the condition of a reaction system in the reaction kettle is observed through the inner window arranged on the reaction kettle, and when white monomers are sublimated and adhered to the kettle wall in the reaction kettle, the distillate after condensation is manually controlled to flow back and spray back to the reaction kettle or the temperature of the heat exchange interlayer is controlled.

According to the method described above, it employs a synthesis apparatus as described above in the present application.

The invention has the beneficial effects that:

reaction unit compact structure in this application can realize the accurate control of reation kettle interior reaction material temperature. Specifically, through the design of spray set and heat transfer intermediate layer in this application, effectively restrained acetylation in-process monomer and appeared the phenomenon, solved simultaneously that high temperature polymerization in-process system is exothermic in a large number, lead to the emergence that the interior actual temperature of cauldron drifted away the settlement temperature, ensure that the reaction is mild controllable, be particularly suitable for producing thermotropic liquid crystal polymer.

Drawings

FIG. 1 is a schematic diagram of the synthesis apparatus of the present invention.

Description of the drawings in FIG. 1

1	Reaction kettle
		11	Stirrer
12	Spray thrower
		13	Heat exchange interlayer
14	Cooling assembly
		2	Condenser
3	Liquid storage tank
		4	Metering pump
5	First temperature control switch

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.

Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.