CN114230707A - High-performance insulating anticorrosive fluorine material ETFE and manufacturing method thereof - Google Patents

High-performance insulating anticorrosive fluorine material ETFE and manufacturing method thereof Download PDF

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CN114230707A
CN114230707A CN202210009430.4A CN202210009430A CN114230707A CN 114230707 A CN114230707 A CN 114230707A CN 202210009430 A CN202210009430 A CN 202210009430A CN 114230707 A CN114230707 A CN 114230707A
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ethylene
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糜万俊
阚大清
徐小云
陈庆
俞仁毅
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Jiangsu Huaao High Tech Development Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28

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Abstract

The invention discloses a high-performance insulating anticorrosive fluorine material ETFE and a manufacturing method thereof, wherein the method comprises the following steps of: based on the total molar weight of all the raw materials in hundred percent, the content of the tetrafluoroethylene monomer is 75-85%, the content of the ethylene is 15-25%, and the content of the perfluoroalkyl ethylene is 0.3-2%; preparing a supplementary monomer: the total molar weight of all the raw materials is calculated in percentage, the content of the tetrafluoroethylene monomer is 40-55%, the content of the ethylene is 40-55%, and the content of the perfluoroalkyl ethylene is 0.5-3%; and (3) putting the initial monomer into a polymerization kettle for polymerization reaction, and pressing the additional monomer from the additional groove by using a film press to prepare the high-performance insulating anticorrosive fluorine material ETFE. The invention can improve the tensile property at high temperature after being modified by adding the perfluorobutyl ethylene, and can maintain the tensile creep property and the heat resistance not to be reduced; the third monomer is changed into a product produced by perfluoroalkyl ethylene, and the finished product has better transparency and toughness.

Description

High-performance insulating anticorrosive fluorine material ETFE and manufacturing method thereof
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a high-performance insulating anticorrosive fluorine material ETFE and a manufacturing method thereof.
Background
Ethylene tetrafluoroethylene copolymers (ETFE) are basically composed of alternating ethylene and TFE units, and are modified by the addition of a third monomer during copolymerization to provide an ETFE resin that has good physical, chemical, mechanical and electrical properties and is easily processed by melt processing techniques.
ETFE has different advantages over other thermoplastic fluoropolymers: low creep, high tensile strength and high modulus. ETFE resins exhibit exceptional stiffness and abrasion resistance over a wide temperature range. Meanwhile, ETFE has excellent dielectric property, the dielectric constant of the ETFE is low, and the ETFE is basically not influenced by frequency; the modified ETFE has good solvent and chemical resistance; ETFE also has good thermal stability.
Because of its excellent properties, ETFE materials have become important insulating materials for aerospace cables. Therefore, the use of the aviation insulating material with low specific gravity, thin volume and high performance has great significance for improving the comprehensive performance of the aircraft.
In the rapidly growing field of the semiconductor industry, high performance ETFE is an ideal raw material for manufacturing semiconductor devices, optical fibers, optical devices, and electrical insulating materials.
At present, with the acceleration of the modern construction process and the rapid development of industries such as aviation, petrifaction, semiconductors, solar energy and the like, various industries have increasingly greater and higher requirements on high-performance fluorine material ETFE, the existing material cannot meet the requirements of the market, and the research and development of a high-performance insulating anticorrosive fluorine material is an urgent task of scientific research units and production enterprises.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of high-performance insulating anticorrosive fluorine material ETFE.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of high-performance insulating anticorrosive fluorine material ETFE comprises,
preparation of initial monomers: the content is more than or equal to 99.995 percent and O2Respectively pumping tetrafluoroethylene monomer with the concentration of less than or equal to 30ppm, ethylene with the purity of more than or equal to 99.9 percent and perfluorobutylethylene as a third monomer into an initial mixing tank, and compressing, circulating and uniformly mixing to obtain the initial monomer, wherein the total molar weight of all raw materials is hundred percent, the content of the tetrafluoroethylene monomer is 75-85 percent, the content of the ethylene is 15-25 percent, and the content of the perfluoroalkyl ethylene is 0.3-2 percent;
preparing a supplementary monomer: the content is more than or equal to 99.995 percent and O2Respectively pumping a tetrafluoroethylene monomer with the concentration of less than or equal to 30ppm, ethylene with the purity of more than or equal to 99.9 percent and a perfluoroalkyl ethylene third monomer into a replenishing mixing tank, and compressing, circulating and uniformly mixing to obtain a replenishing monomer, wherein the total molar weight of all raw materials is hundred percent, the content of the tetrafluoroethylene monomer is 40-55 percent, the content of the ethylene is 40-55 percent, and the content of the perfluoroalkyl ethylene is 0.5-3 percent;
and (3) putting the initial monomer into a polymerization kettle for polymerization reaction, and pressing the additional monomer from the additional groove by using a film press to prepare the high-performance insulating anticorrosive fluorine material ETFE.
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: the initial monomer is put into a polymerization kettle for polymerization reaction, comprising,
cleaning and replacing a polymerization kettle, removing water and oxygen, introducing a refrigerant medium into a jacket for keeping cold, adding a perfluoroalkyl alcohol solvent, starting stirring, pressing an initial monomer into the polymerization kettle from an initial tank by using a membrane press until the pressure of the polymerization kettle shows 1.0-1.2Mpa, discharging the refrigerant medium of the jacket of the polymerization kettle, introducing a heat medium for heating, continuously switching the heat medium and circulating water, and keeping the temperature at 60-70 ℃;
dissolving an initiator by perfluoroalkyl alcohol, adding the initiator into a polymerization kettle by a metering pump twice within 2 hours, observing pressure change after the initiator is added for the first time, and when the pressure in the reaction kettle begins to drop, namely the polymerization reaction begins;
and (3) along with the pressure reduction in the polymerization kettle, pressing the supplemented monomer from the supplementing groove by using a film press, maintaining the reaction pressure in the polymerization kettle at 1.0-1.2Mpa, and keeping the reaction time at 1.5-2.5 h.
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: after the polymerization reaction, the method also comprises the following steps,
pumping the generated polymer into a distillation kettle from a polymerization kettle, and distilling to recover the solvent;
putting deionized water into the distillation kettle for washing for multiple times, detecting the conductivity of the washing water, and obtaining a washed crude polymerization product, wherein the conductivity is qualified;
and (3) dishing the washed polymerization crude product into a hot air circulation drying oven, detecting that the water content is qualified, crushing or granulating, detecting, packaging and warehousing to obtain the high-performance insulating anticorrosive fluorine material ETFE.
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: the perfluoroalkyl alcohol solvent is brown yellow viscous liquid, the melting point is 65-75 ℃, the boiling point is 145-245 ℃, and the density is 1.24g/cm3。
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: the initiator comprises bis (4-tert-butylcyclohexyl) peroxydicarbonate.
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: the polymerization kettle is cleaned, replaced, dewatered and deoxygenated, wherein O is2Less than or equal to 30ppm and less than or equal to 100ppm of water.
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: the initial monomer is calculated by the total molar weight of all raw materials in percentage, the content of the tetrafluoroethylene monomer is 80.2%, the content of the ethylene is 19.1%, and the content of the perfluoroalkyl ethylene is 0.7%.
As a preferred scheme of the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, the preparation method comprises the following steps: supplementing monomers, wherein the total molar weight of all raw materials is hundred percent, the content of the tetrafluoroethylene monomer is 53%, the content of the ethylene is 46.3%, and the content of the perfluoroalkyl ethylene is 0.7%.
The invention further aims to overcome the defects in the prior art and provide a product prepared by the preparation method of the high-performance insulating anticorrosive fluorine material ETFE, wherein the TFE content in the product is 53-63%.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of high-performance insulating anticorrosive fluorine material ETFE, which can improve the tensile property at high temperature after being modified by adding perfluorobutyl ethylene and can maintain the tensile creep property and the heat resistance not to be reduced; the third monomer is changed into a product produced by perfluoroalkyl ethylene, and the finished product has better transparency and toughness;
(2) the invention has scientific material selection and proportioning, advanced process and good quality of produced and manufactured products, can be widely applied to the insulating materials of aviation and aerospace wires, radiation-resistant mould pressing materials of nuclear industry and civil use, and can be widely applied to insulating anticorrosive materials of semiconductor industry, heavy anticorrosive materials and sealing materials of large petrochemical enterprises and high-performance film materials of solar energy industry.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a process flow diagram of example 2 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The perfluoroalkyl alcohol solvent is a brown yellow viscous liquid, the melting point is 65-75 ℃, the boiling point is 145-245 ℃, and the density is 1.24g/cm3
The initiator of the invention, bis (4-tert-butylcyclohexyl) peroxydicarbonate, also known as initiator BCHPC, white solid powder, density: 1.13, theoretical active oxygen content 4.01%, easily soluble in aliphatic solvent, insoluble in water. Half-life data: activation energy Ea: 126.39KJ/ml, a 10-hour half-life temperature of 48 ℃, a 1-hour half-life temperature of 64 ℃ and a 0.1-hour half-life temperature of 82 ℃.
Example 1
Firstly, 80.2 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and less than or equal to 30ppm of O2, 19.1 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.7 percent of perfluorohexylethylene as a third monomer are pressed into an initial mixing tank, are uniformly mixed by a film press to form initial monomers, and are pressed into the initial tank; pressing 53 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and O2 of less than or equal to 30ppm, 46.3 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.7 percent of perfluorohexylethylene as a third monomer into a supplementing mixing tank, uniformly mixing by using a film press, and driving into the supplementing mixing tank;
② cleaning polymerization kettle, drying, vacuum oxygen-discharging, O2Introducing a cooling medium into the jacket to keep the temperature less than or equal to 30ppm, then adding a specified amount of perfluoroalkyl alcohol solvent to stir, pressing initial monomers into the polymerization kettle from the initial tank by using a membrane press until the pressure of the polymerization kettle shows 1.0-1.2Mpa, discharging the cooling medium of the jacket of the polymerization kettle, introducing a heating medium to raise the temperature, continuously switching the heating medium and the circulating water, and keeping the temperature at 60 ℃.
The initiator with the prescribed formula amount is dissolved by a small amount of perfluoroalkyl alcohol, and then the solution is divided into two times by a metering pump and is pumped into a polymerization kettle within 2 hours. And (3) observing the pressure change after the initiator is added for the first time, and when the pressure in the reaction kettle begins to drop, namely the polymerization reaction begins. Along with the pressure reduction in the polymerization kettle, a membrane press is used for pressing in the supplemented monomer from the supplementing groove, the reaction pressure in the polymerization kettle is maintained at 1.0-1.2Mpa, and the continuous reaction time is 2-3 hours;
after the polymerization reaction, the resulting polymer was stirred into a distillation still from the polymerization still, and the solvent was recovered by distillation.
And (3) putting deionized water into the distillation kettle for repeated washing, detecting the conductivity of the washing water, and obtaining a washed polymerization crude product, wherein the conductivity is qualified.
And fourthly, the washed polymerization crude product is placed in a hot air circulation drying oven to reach the specified drying time, the water content is detected to be qualified, and the polymerization crude product is crushed or granulated, detected, packaged and put in storage.
Example 2
Firstly, 80.2 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and less than or equal to 30ppm of O2, 19.1 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.7 percent of perfluorobutylethylene, which is a third monomer, are pressed into an initial mixing tank, are uniformly mixed by a membrane press to form initial monomers, and are pressed into the initial mixing tank; pressing 53 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and O2 of less than or equal to 30ppm, 46.3 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.7 percent of perfluorobutyl ethylene as a third monomer into a supplementing mixing tank, uniformly mixing by using a membrane press, and driving into the supplementing mixing tank;
② cleaning polymerization kettle, drying, vacuum oxygen-discharging, O2Introducing a cooling medium into the jacket to keep the temperature less than or equal to 30ppm, then adding a specified amount of perfluoroalkyl alcohol solvent to stir, pressing initial monomers into the polymerization kettle from the initial tank by using a membrane press until the pressure of the polymerization kettle shows 1.0-1.2Mpa, discharging the cooling medium of the jacket of the polymerization kettle, introducing a heating medium to raise the temperature, continuously switching the heating medium and the circulating water, and keeping the temperature at 60 ℃.
The initiator with the prescribed formula amount is dissolved by a small amount of perfluoroalkyl alcohol, and then the solution is divided into two times by a metering pump and is pumped into a polymerization kettle within 2 hours. And (3) observing the pressure change after the initiator is added for the first time, and when the pressure in the reaction kettle begins to drop, namely the polymerization reaction begins. Along with the pressure reduction in the polymerization kettle, a membrane press is used for pressing in the supplemented monomer from the supplementing groove, the reaction pressure in the polymerization kettle is maintained at 1.0-1.2Mpa, and the continuous reaction time is 1.5-2.5 hours;
after the polymerization reaction, the resulting polymer was stirred into a distillation still from the polymerization still, and the solvent was recovered by distillation.
And (3) putting deionized water into the distillation kettle for repeated washing, detecting the conductivity of the washing water, and obtaining a washed polymerization crude product, wherein the conductivity is qualified.
And fourthly, the washed polymerization crude product is placed in a hot air circulation drying oven to reach the specified drying time, the water content is detected to be qualified, and the polymerization crude product is crushed or granulated, detected, packaged and put in storage.
The process flow diagram is shown in FIG. 1.
Example 3
Firstly, 80.4 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and O2 of less than or equal to 30ppm, 19.1 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.5 percent of perfluorobutylethylene as a third monomer are pressed into an initial mixing tank, are uniformly mixed by a membrane press to form initial monomers, and are pressed into the initial tank;
pressing 53 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and O2 of less than or equal to 30ppm, 46.5 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.5 percent of perfluorobutyl ethylene as a third monomer into a supplementing mixing tank, uniformly mixing by using a film press, and driving into the supplementing mixing tank;
cleaning a polymerization kettle, drying, vacuum oxygen discharge, introducing a refrigerant medium into a jacket for keeping the temperature of the polymerization kettle at less than or equal to 30ppm, adding a specified amount of perfluoroalkyl alcohol solvent for stirring, pressing an initial monomer into the polymerization kettle from an initial tank by using a membrane press until the pressure of the polymerization kettle shows 1.0-1.2Mpa, discharging the refrigerant medium of the jacket of the polymerization kettle, introducing a heating medium for heating, continuously switching the heating medium and circulating water, and keeping the temperature at 60 ℃.
The initiator with the prescribed formula amount is dissolved by a small amount of perfluoroalkyl alcohol, and then the solution is divided into two times by a metering pump and is pumped into a polymerization kettle within 2 hours. And (3) observing the pressure change after the initiator is added for the first time, and when the pressure in the reaction kettle begins to drop, namely the polymerization reaction begins. Along with the pressure reduction in the polymerization kettle, a membrane press is used for pressing in the supplemented monomer from the supplementing groove, the reaction pressure in the polymerization kettle is maintained at 1.0-1.2Mpa, and the continuous reaction time is 1.5-2.5 hours;
after the polymerization reaction, the resulting polymer was stirred into a distillation still from the polymerization still, and the solvent was recovered by distillation.
And (3) putting deionized water into the distillation kettle for repeated washing, detecting the conductivity of the washing water, and obtaining a washed polymerization crude product, wherein the conductivity is qualified.
And fourthly, the washed polymerization crude product is placed in a hot air circulation drying oven to reach the specified drying time, the water content is detected to be qualified, and the polymerization crude product is crushed or granulated, detected, packaged and put in storage.
Example 4
Firstly, pressing 79.9 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and O2 of less than or equal to 30ppm, 19.1 percent of ethylene with the purity of more than or equal to 99.9 percent and 1 percent of perfluorobutylethylene as a third monomer into an initial mixing tank, uniformly mixing the initial monomers by using a membrane press to form initial monomers, and driving the initial monomers into the initial mixing tank; pressing 53 percent of tetrafluoroethylene monomer (TFE) with the content of more than or equal to 99.995 percent and O2 of less than or equal to 30ppm, 46.3 percent of ethylene with the purity of more than or equal to 99.9 percent and 0.7 percent of perfluorobutyl ethylene as a third monomer into a supplementing mixing tank, uniformly mixing by using a membrane press, and driving into the supplementing mixing tank;
cleaning a polymerization kettle, drying, vacuum oxygen discharge, introducing a refrigerant medium into a jacket for keeping the temperature of the polymerization kettle at less than or equal to 30ppm, adding a specified amount of perfluoroalkyl alcohol solvent for stirring, pressing an initial monomer into the polymerization kettle from an initial tank by using a membrane press until the pressure of the polymerization kettle shows 1.0-1.2Mpa, discharging the refrigerant medium of the jacket of the polymerization kettle, introducing a heating medium for heating, continuously switching the heating medium and circulating water, and keeping the temperature at 60 ℃.
The initiator with the prescribed formula amount is dissolved by a small amount of perfluoroalkyl alcohol, and then the solution is divided into two times by a metering pump and is pumped into a polymerization kettle within 2 hours. And (3) observing the pressure change after the initiator is added for the first time, and when the pressure in the reaction kettle begins to drop, namely the polymerization reaction begins. Along with the pressure reduction in the polymerization kettle, a membrane press is used for pressing in the supplemented monomer from the supplementing groove, the reaction pressure in the polymerization kettle is maintained at 1.0-1.2Mpa, and the continuous reaction time is 1.5-2.5 hours;
after the polymerization reaction, the resulting polymer was stirred into a distillation still from the polymerization still, and the solvent was recovered by distillation.
And (3) putting deionized water into the distillation kettle for repeated washing, detecting the conductivity of the washing water, and obtaining a washed polymerization crude product, wherein the conductivity is qualified.
And fourthly, the washed polymerization crude product is placed in a hot air circulation drying oven to reach the specified drying time, the water content is detected to be qualified, and the polymerization crude product is crushed or granulated, detected, packaged and put in storage.
TABLE 1 Effect of the third monomer on reaction time and ETFE copolymer Properties
Figure BDA0003458408330000071
It can be seen that the addition of perfluorobutyl ethylene as the third monomer results in a faster polymerization rate than perfluorohexyl ethylene;
the invention can improve the tensile property at high temperature after being modified by adding the perfluorobutyl ethylene, and can maintain the tensile creep property and the heat resistance not to be reduced; the third monomer is changed into a product produced by perfluoroalkyl ethylene, and the finished product has better transparency and toughness.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (9)

1. A preparation method of high-performance insulating anticorrosive fluorine material ETFE is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparation of initial monomers: the content is more than or equal to 99.995 percent and O2Respectively pumping tetrafluoroethylene monomer with the concentration of less than or equal to 30ppm, ethylene with the purity of more than or equal to 99.9 percent and perfluorobutylethylene as a third monomer into an initial mixing tank, and compressing, circulating and uniformly mixing to obtain the initial monomer, wherein the total molar weight of all raw materials is hundred percent, the content of the tetrafluoroethylene monomer is 75-85 percent, the content of the ethylene is 15-25 percent, and the content of the perfluoroalkyl ethylene is 0.3-2 percent;
preparing a supplementary monomer: the content is more than or equal to 99.995 percent and O2Respectively pumping a tetrafluoroethylene monomer with the concentration of less than or equal to 30ppm, ethylene with the purity of more than or equal to 99.9 percent and a perfluoroalkyl ethylene third monomer into a replenishing mixing tank, and compressing, circulating and uniformly mixing to obtain a replenishing monomer, wherein the total molar weight of all raw materials is hundred percent, the content of the tetrafluoroethylene monomer is 40-55 percent, the content of the ethylene is 40-55 percent, and the content of the perfluoroalkyl ethylene is 0.5-3 percent;
and (3) putting the initial monomer into a polymerization kettle for polymerization reaction, and pressing the additional monomer from the additional groove by using a film press to prepare the high-performance insulating anticorrosive fluorine material ETFE.
2. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1, characterized in that: the initial monomer is put into a polymerization kettle for polymerization reaction, comprising,
cleaning and replacing a polymerization kettle, removing water and oxygen, introducing a refrigerant medium into a jacket for keeping cold, adding a perfluoroalkyl alcohol solvent, starting stirring, pressing an initial monomer into the polymerization kettle from an initial tank by using a membrane press until the pressure of the polymerization kettle shows 1.0-1.2Mpa, discharging the refrigerant medium of the jacket of the polymerization kettle, introducing a heat medium for heating, continuously switching the heat medium and circulating water, and keeping the temperature at 60-70 ℃;
dissolving an initiator by perfluoroalkyl alcohol, adding the initiator into a polymerization kettle by a metering pump twice within 2 hours, observing pressure change after the initiator is added for the first time, and when the pressure in the reaction kettle begins to drop, namely the polymerization reaction begins;
and (3) along with the pressure reduction in the polymerization kettle, pressing the supplemented monomer from the supplementing groove by using a film press, maintaining the reaction pressure in the polymerization kettle at 1.0-1.2Mpa, and keeping the reaction time at 1.5-2.5 h.
3. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1 or 2, characterized in that: after the polymerization reaction, the method also comprises the following steps,
pumping the generated polymer into a distillation kettle from a polymerization kettle, and distilling to recover the solvent;
putting deionized water into the distillation kettle for washing for multiple times, detecting the conductivity of the washing water, and obtaining a washed crude polymerization product, wherein the conductivity is qualified;
and (3) dishing the washed polymerization crude product into a hot air circulation drying oven, detecting that the water content is qualified, crushing or granulating, detecting, packaging and warehousing to obtain the high-performance insulating anticorrosive fluorine material ETFE.
4. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1 or 2, characterized in that: the perfluoroalkyl alcohol solvent is brown yellow viscous liquid, the melting point is 65-75 ℃, the boiling point is 145-245 ℃, and the density is 1.24g/cm3。
5. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1 or 2, characterized in that: the initiator comprises bis (4-tert-butylcyclohexyl) peroxydicarbonate.
6. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1, characterized in that: said polymerization is carried outCleaning, replacing, dewatering and discharging oxygen in the kettle, wherein O is2Less than or equal to 30ppm and less than or equal to 100ppm of water.
7. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1, characterized in that: the initial monomer is calculated by the total molar weight of all raw materials in percentage, the content of the tetrafluoroethylene monomer is 80.2%, the content of the ethylene is 19.1%, and the content of the perfluoroalkyl ethylene is 0.7%.
8. The preparation method of high-performance insulating anticorrosive fluorine material ETFE according to claim 1, characterized in that: supplementing monomers, wherein the total molar weight of all raw materials is hundred percent, the content of the tetrafluoroethylene monomer is 53%, the content of the ethylene is 46.3%, and the content of the perfluoroalkyl ethylene is 0.7%.
9. The product prepared by the preparation method of the high-performance insulating anticorrosive fluorine material ETFE in any one of claims 1 to 8, is characterized in that: the TFE content of the tetrafluoroethylene monomer in the product is 53-63%.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2836296A1 (en) * 1977-08-19 1979-03-01 Asahi Glass Co Ltd TFE-ethylene! copolymers - contg. per-fluoroalkyl-vinyl units, with improved tensile properties at high temps., for coating wires
GB2084593A (en) * 1980-09-25 1982-04-15 Du Pont Copolymers of tetrafluoroethylene
CN101597354A (en) * 2009-06-12 2009-12-09 江苏华奥高科技发展有限公司 High-performance insulating corrosion-resistance fluorine materials and manufacture method thereof
CN105294915A (en) * 2015-12-01 2016-02-03 上海三爱富新材料股份有限公司 Transparent ethylene-tetrafluoroethylene quadripolymer
CN107141397A (en) * 2017-05-09 2017-09-08 巨化集团技术中心 A kind of preparation method of ethylene tetrafluoroethylene copolymer
CN108440702A (en) * 2018-03-19 2018-08-24 浙江巨化技术中心有限公司 A kind of preparation method of high thermal stability ethylene-tetrafluoroethylene copolymer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2836296A1 (en) * 1977-08-19 1979-03-01 Asahi Glass Co Ltd TFE-ethylene! copolymers - contg. per-fluoroalkyl-vinyl units, with improved tensile properties at high temps., for coating wires
GB2084593A (en) * 1980-09-25 1982-04-15 Du Pont Copolymers of tetrafluoroethylene
CN101597354A (en) * 2009-06-12 2009-12-09 江苏华奥高科技发展有限公司 High-performance insulating corrosion-resistance fluorine materials and manufacture method thereof
CN105294915A (en) * 2015-12-01 2016-02-03 上海三爱富新材料股份有限公司 Transparent ethylene-tetrafluoroethylene quadripolymer
CN107141397A (en) * 2017-05-09 2017-09-08 巨化集团技术中心 A kind of preparation method of ethylene tetrafluoroethylene copolymer
CN108440702A (en) * 2018-03-19 2018-08-24 浙江巨化技术中心有限公司 A kind of preparation method of high thermal stability ethylene-tetrafluoroethylene copolymer

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