CN112625165B - Trifluoroethylene modified fluororesin and preparation method thereof - Google Patents

Trifluoroethylene modified fluororesin and preparation method thereof Download PDF

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CN112625165B
CN112625165B CN201910950467.5A CN201910950467A CN112625165B CN 112625165 B CN112625165 B CN 112625165B CN 201910950467 A CN201910950467 A CN 201910950467A CN 112625165 B CN112625165 B CN 112625165B
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emulsion polymerization
trifluoroethylene
perfluorooctanoate
monomer
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CN112625165A (en
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余金龙
汪仲权
张廷健
王先荣
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
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Zhonghao Chenguang Research Institute of Chemical Industry 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
    • C08F214/22—Vinylidene fluoride
    • 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
    • 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
    • C08F214/24—Trifluorochloroethene

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The invention relates to the field of fluororesins, in particular to a trifluoroethylene modified fluororesin and a preparation method thereof. The fluororesin is obtained by carrying out emulsion polymerization on a basic monomer and a modified monomer, wherein the basic monomer is vinylidene fluoride, the modified monomer comprises chlorotrifluoroethylene, and the modified monomer further comprises 1-20% of trifluoroethylene by taking the total mole number of the monomers as a reference. The dielectric constant of the fluororesin can reach 29-31 (epsilon/epsilon o), and the energy density can reach 23-25J/cm3(650MV/m), and also has ferroelectric, pressure point and other properties, thus widening the application field of the fluororesin. Meanwhile, the preparation method is simple, environment-friendly and beneficial to industrial production.

Description

Trifluoroethylene modified fluororesin and preparation method thereof
Technical Field
The invention relates to the field of fluororesins, in particular to a trifluoroethylene modified fluororesin and a preparation method thereof.
Background
Fluorine atoms are contained in fluorine resin molecules, the C-F performance formed by the fluorine atoms and carbon atoms is very high, and meanwhile, the fluorine atoms have a great adsorption effect, so that the C-C bond performance in a fluorocarbon molecular chain is enhanced and enhanced along with the improvement of the fluorination degree of the fluorocarbon molecular chain, and the fluorine atoms can shield a C-C main bond better so as to ensure the chemical inertia of the C-C bond. The special molecular structure enables the fluororesin to have various excellent specific performances such as heat resistance, chemical resistance, solvent resistance, fluoridation resistance, vacuum resistance, oil resistance, aging resistance and the like.
In recent years, fluororesin F23 (i.e., a copolymer of vinylidene fluoride and chlorotrifluoroethylene) has been widely used and studied in the field of high energy storage and low loss capacitive materials because of its excellent dielectric, ferroelectric, voltage point, and other properties. The fluororesin F23 material has a high residual polarization value, so that more stored charges cannot be effectively released, the material has high dielectric loss, the dielectric constant is only 10-15 (epsilon/epsilon o), and the application of the fluororesin F23 is influenced.
According to the information (science.1998,280,2101-2104.), a method (Macromolecules 2002,35, 7678-.
The data (appl. phys. lrtt.2009,94,052907.) report that P (VDF-CTFE) is used to graft Polystyrene (PS), although this method reduces the energy loss of the fluoropolymer, the energy storage density of the material is greatly reduced, limiting the use of the material.
CN108395503A adopts P (VDF-TrFE-CTFE) to graft Polymethacrylate (PXMA), and although the energy loss of the material can be effectively improved by grafting polymethacrylate and styrene (St), the grafting rate of the process is low, and the process is not beneficial to industrial production.
CN109810212A discloses a preparation method of high dielectric constant polyvinylidene fluoride, in the method, polymerization monomers are trifluoroethylene, chlorotrifluoroethylene, difluoroethylene, tetrafluoroethylene and vinylidene fluoride, which belong to multi-component copolymerization, and an organic initiator is used in the polymerization reaction, and the reaction activity of the organic initiator is higher, which is not beneficial to the control of the polymerization reaction rate, and is further not beneficial to the uniform distribution of each monomer in a polymer chain segment, the molecular weight of the obtained polymer is about 80 ten thousand, the molecular weight distribution is 4-6.5, the molecular weight is higher, which is not beneficial to the subsequent processing application; meanwhile, the polymerization pressure is 3.5-5.0MPa, the requirement on polymerization equipment is high, and the industrial production is not facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention firstly provides a preparation method of a fluororesin with a high dielectric constant, which is obtained by carrying out emulsion polymerization on a base monomer and a modified monomer, wherein the base monomer is vinylidene fluoride, the modified monomer comprises chlorotrifluoroethylene, and the modified monomer further comprises 1-20% of trifluoroethylene by taking the total molar number of the monomers as a reference.
The invention discovers that when the mol ratio of the modified monomer trifluoroethylene is added and effectively controlled to be 1-20% in the polymerization process, the dielectric constant of the material can be greatly improved.
In the emulsion polymerization process, monomers including vinylidene fluoride, chlorotrifluoroethylene, and trifluoroethylene are used as an initial mixed monomer and a post-mixed monomer.
Preferably, the trifluoroethylene content in the initial mixed monomers is 10 to 20% based on the total number of moles of the monomers.
Preferably, the trifluoroethylene content in the post-makeup mixed monomer is 1 to 10% based on the total molar number of the monomers.
In order to achieve the excellent properties of fluororesin F23, the molar ratio of the base monomer to the modifying monomer in the initial mixed monomer is preferably 60:40 to 80:20, wherein the modifying monomer comprises the following components in the molar ratio of (10 to 20): (10-20) trifluoroethylene and chlorotrifluoroethylene. In the post-compensation mixed monomer, the molar ratio of the base monomer to the modified monomer is preferably 70: 30-89: 11, wherein the modified monomer comprises the following components in a molar ratio of (1-10): (10-20) trifluoroethylene and chlorotrifluoroethylene.
In order to improve the performance of the material, the invention further screens and prefers other influencing factors.
Preferably, the reaction temperature of the emulsion polymerization is 70-100 ℃; preferably 80 to 90 ℃. At this temperature, the reaction rate is moderate, which is favorable for the uniform distribution of the comonomer (especially the monomer with small reactivity ratio) in the polymer chain segment.
Preferably, the pressure of the emulsion polymerization is 1.6-4.0 MPa; preferably 1.6 to 3.0 MPa; more preferably 2.0. + -. 0.02 MPa.
When the polymerization pressure is higher than 3.0MPa, the requirement on equipment is higher, and the method is not beneficial to industrial production.
Preferably, in the emulsion polymerization, the initiator is ammonium persulfate and/or potassium persulfate; preferably, the initiator is used in an amount of 0.1 to 10wt% based on the total weight of the aqueous medium.
Preferably, the reducing agent is sodium metabisulfite when the emulsion polymerization is carried out; preferably, the reducing agent is used in an amount of 0.05 to 5wt% based on the total weight of the aqueous medium.
Preferably, when the emulsion polymerization is carried out, the chain transfer agent is one or more of methanol, diethyl malonate and chloroform; preferably, the amount of the chain transfer agent is 0.01-5 wt% of the total weight of the monomers.
Preferably, the dispersing agent is perfluorooctanoate when the emulsion polymerization is carried out; preferably one or more of ammonium perfluorooctanoate, sodium perfluorooctanoate and potassium perfluorooctanoate; preferably, the dispersant is used in an amount of 0.01 to 5wt% based on the total weight of the aqueous medium.
When the solid content of the emulsion reaches about 30 percent (mass percent), the polymerization reaction is finished, and in the invention, the reaction time is about 2-4 hours.
In one embodiment, the preparation method specifically comprises the following operations: controlling the oxygen content of a reaction environment to be less than or equal to 30ppm, adding a dispersing agent, setting the temperature to be 70-100 ℃, adding an initial mixed monomer, setting the pressure to be 1.6-4.0 MPa, adding an initiator, a reducing agent and a chain transfer agent, carrying out polymerization reaction, adding a post-mixed monomer in the reaction process, and finishing the polymerization reaction when the solid content of the emulsion reaches about 30% (mass percentage).
In some embodiments, the monomer may be recovered after the polymerization reaction.
The emulsion obtained by the polymerization reaction is coagulated, washed, dried, etc. to obtain a purified polymer according to the conventional understanding of the skilled person, and is not further limited herein.
The preferred embodiments of the present invention can be obtained by combining the above-described preferred embodiments as conventionally understood by those skilled in the art.
The invention further provides trifluoroethylene modified fluororesin prepared by the preparation method.
The invention has the following beneficial effects:
(1) the invention provides a fluororesin, the dielectric constant of which can reach 29-31 (epsilon/epsilon o), and the energy density of which reaches 23-25J/cm3(650MV/m), and also has ferroelectric, pressure point and other properties, thus widening the application field of the fluororesin.
(2) The preparation method is simple, environment-friendly and beneficial to industrial production.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a trifluoroethylene modified fluororesin, which is prepared by the following specific steps:
the emulsion polymerization of the invention is carried out in a 50L reactor. 32L of deionized water was added to the reactor. Evacuating the reactor, adding 35g of perfluorooctanoate when the oxygen content is less than or equal to 30ppm, heating the contents in the reactor to 85 ℃, and adding an initial mixed monomer, wherein the molar ratio of trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride is 12: 15:73, the reactor pressure was increased to 2.0 MPa. Adding 25g of potassium persulfate, 15g of sodium metabisulfite and 35g of diethyl malonate to start reaction, after the polymerization reaction is carried out, supplementing and supplementing mixed monomers to maintain the absolute pressure in the reactor to be 2.0 +/-0.02 MPa, wherein the mol ratio of trifluoroethylene, chlorotrifluoroethylene to vinylidene fluoride in the supplemented mixed gas is 2: and 21:77, wherein the reaction time is about 3 hours, the solid content of the emulsion reaches about 30 percent (mass percent), the polymerization reaction is finished, the reaction monomer is recovered, and the emulsion is placed into a plastic barrel. The emulsion was coagulated in an environment at-35 ℃ and dried under vacuum at about 120 ℃ to give about 8Kg of polymer.
The modified fluororesin F23 was sampled and examined, and found to have a chlorine content of 9.9%, a tensile strength of 25.3MPa, an elongation at break of 320%, an intrinsic viscosity of 1.2g/100ml, a dielectric constant of 29 (. epsilon./ε o), and an energy density of 23J/cm3(650MV/m)。
Example 2
This example provides a trifluoroethylene modified fluororesin, which differs from example 1 in that: in the initial mixed monomer, the mol ratio of trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride is 20:20: 60; in the post-compensation mixed monomer, the molar ratio of trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride is 1:10: 89.
The modified fluororesin F23 was sampled and detected, and chlorine was addedThe content of the polymer was 5.2%, the tensile strength was 27.8MPa, the elongation at break was 310%, the intrinsic viscosity was 1.1g/100ml, the dielectric constant was 31 (. epsilon./ε o), and the energy density was 23.7J/cm3(650MV/m)。
Example 3
This example provides a trifluoroethylene modified fluororesin, which differs from example 1 in that: in the initial mixed monomer, the mol ratio of trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride is 10:10: 80; in the post-compensation mixed monomer, the molar ratio of the trifluoroethylene to the chlorotrifluoroethylene to the vinylidene fluoride is 10:20: 70.
The modified fluororesin F23 was sampled and examined, and found to have a chlorine content of 9.6%, a tensile strength of 24.5MPa, an elongation at break of 330%, an intrinsic viscosity of 1.3g/100ml, a dielectric constant of 30 (. epsilon./ε o), and an energy density of 22.8J/cm3(650MV/m)。
Example 4
This example provides a trifluoroethylene modified fluororesin, which differs from example 1 in that: the reaction temperature was 100 ℃.
The modified fluororesin F23 was sampled and examined, and found to have a chlorine content of 8.7%, a tensile strength of 23.0MPa, an elongation at break of 290%, an intrinsic viscosity of 0.9g/100ml, a dielectric constant of 29.6 (. epsilon./ε o), and an energy density of 22.7J/cm3(650MV/m)。
Example 5
This example provides a trifluoroethylene modified fluororesin, which differs from example 1 in that: the reaction pressure was controlled to 4.0 MPa.
The modified fluororesin F23 was sampled and examined, and found to have a chlorine content of 10.6%, a tensile strength of 29.0MPa, an elongation at break of 280%, an intrinsic viscosity of 1.4g/100ml, a dielectric constant of 29.7 (. epsilon./ε o), and an energy density of 23.9J/cm3(650MV/m)。
Comparative example 1
This comparative example differs from example 1 in that: trifluoroethylene was replaced with an equimolar amount of chlorotrifluoroethylene.
The modified fluororesin F23 was sampled and tested, and had a chlorine content of 12.6%, a tensile strength of 21.4MPa, an elongation at break of 420%, an intrinsic viscosity of 0.9g/100ml and a viscosity index ofAn electric constant of 17 (. epsilon./ε o) and an energy density of 11.6J/cm3(650MV/m)。
Comparative example 2
This comparative example differs from example 1 in that: the molar ratio of trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride in the initial mixed monomers was 25:15: 60.
The modified fluororesin F23 was sampled and examined, and found to have a chlorine content of 8.3%, a tensile strength of 11.5MPa, an elongation at break of 520%, an intrinsic viscosity of 0.9g/100ml, a dielectric constant of 31 (. epsilon./ε o), and an energy density of 8.7J/cm3(650MV/m)。
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (31)

1. A method for producing a trifluoroethylene-modified fluororesin, comprising:
carrying out emulsion polymerization on a basic monomer and a modified monomer to obtain the modified polyvinylidene fluoride-vinylidene fluoride copolymer, wherein the modified monomer comprises chlorotrifluoroethylene and trifluoroethylene;
in the emulsion polymerization process, monomers including vinylidene fluoride, chlorotrifluoroethylene and trifluoroethylene are used as an initial mixed monomer and a post-compensation mixed monomer; when emulsion polymerization is carried out, the used reagents also comprise an initiator, a reducing agent, a chain transfer agent, a dispersing agent and water;
in the initial mixed monomer, the content of trifluoroethylene is 10-20% by taking the total mole number of the initial mixed monomer as a reference; the molar ratio of the basic monomer to the modified monomer is 60: 40-80: 20, wherein the modified monomer comprises the following components in a molar ratio of (10-20): (10-20) trifluoroethylene and chlorotrifluoroethylene;
in the post-compensation mixed monomer, the total mole number of the post-compensation mixed monomer is taken as a reference, and the content of trifluoroethylene is 1-10%; the molar ratio of the basic monomer to the modified monomer is 70: 30-89: 11, wherein the modified monomer comprises the following components in a molar ratio of (1-10): (10-20) trifluoroethylene and chlorotrifluoroethylene;
the reaction temperature of the emulsion polymerization is 70-100 ℃, and the pressure is 1.6-4.0 MPa.
2. The method according to claim 1, wherein the emulsion polymerization is carried out at a reaction temperature of 80 to 90 ℃.
3. The method according to claim 1 or 2, wherein the emulsion polymerization pressure is 1.6 to 3.0 MPa.
4. The production method according to claim 1 or 2, wherein an initiator is ammonium persulfate and/or potassium persulfate at the time of the emulsion polymerization.
5. The production method according to claim 3, wherein an initiator is ammonium persulfate and/or potassium persulfate at the time of the emulsion polymerization.
6. The method according to claim 4, wherein the initiator is used in an amount of 0.1 to 10wt% based on the total weight of the aqueous medium.
7. The method according to claim 5, wherein the initiator is used in an amount of 0.1 to 10wt% based on the total weight of the aqueous medium.
8. The production method according to any one of claims 1 to 2 and 5 to 7, wherein a reducing agent is sodium metabisulfite when the emulsion polymerization is carried out.
9. The method according to claim 3, wherein the reducing agent is sodium metabisulfite when the emulsion polymerization is carried out.
10. The method according to claim 4, wherein the reducing agent is sodium metabisulfite when the emulsion polymerization is carried out.
11. The method according to claim 8, wherein the reducing agent is used in an amount of 0.05 to 5wt% based on the total weight of the aqueous medium.
12. The method according to claim 9 or 10, wherein the reducing agent is used in an amount of 0.05 to 5wt% based on the total weight of the aqueous medium.
13. The method according to any one of claims 1 to 2, 5 to 7, and 9 to 11, wherein the chain transfer agent is one or more selected from methanol, diethyl malonate, and chloroform during the emulsion polymerization.
14. The method according to claim 3, wherein the chain transfer agent is one or more selected from methanol, diethyl malonate and chloroform during the emulsion polymerization.
15. The method according to claim 4, wherein the chain transfer agent is one or more selected from methanol, diethyl malonate and chloroform during the emulsion polymerization.
16. The method according to claim 8, wherein the chain transfer agent is one or more selected from methanol, diethyl malonate and chloroform during the emulsion polymerization.
17. The method according to claim 12, wherein the chain transfer agent is one or more selected from methanol, diethyl malonate and chloroform during the emulsion polymerization.
18. The method as claimed in claim 13, wherein the chain transfer agent is used in an amount of 0.01 to 5wt% based on the total weight of the monomers.
19. The method of any one of claims 14 to 17, wherein the chain transfer agent is used in an amount of 0.01 to 5wt% based on the total weight of the monomers.
20. The method according to any one of claims 1 to 2, 5 to 7, 9 to 11, and 14 to 18, wherein a dispersing agent is a perfluorooctanoate in the emulsion polymerization.
21. The method according to claim 3, wherein a dispersing agent is perfluorooctanoate in carrying out the emulsion polymerization.
22. The method according to claim 4, wherein a dispersing agent is perfluorooctanoate in the emulsion polymerization.
23. The method according to claim 8, wherein a dispersing agent is perfluorooctanoate in carrying out the emulsion polymerization.
24. The method according to claim 12, wherein a dispersing agent is perfluorooctanoate in carrying out the emulsion polymerization.
25. The method according to claim 13, wherein a dispersing agent is perfluorooctanoate in carrying out the emulsion polymerization.
26. The method according to claim 19, wherein a dispersing agent is perfluorooctanoate in carrying out the emulsion polymerization.
27. The method according to claim 20, wherein the dispersant is one or more selected from the group consisting of ammonium perfluorooctanoate, sodium perfluorooctanoate and potassium perfluorooctanoate.
28. The method according to any one of claims 21 to 26, wherein the dispersant is one or more selected from the group consisting of ammonium perfluorooctanoate, sodium perfluorooctanoate and potassium perfluorooctanoate.
29. The method according to claim 27, wherein the dispersant is used in an amount of 0.01 to 5wt% based on the total weight of the aqueous medium.
30. The method according to claim 28, wherein the dispersant is used in an amount of 0.01 to 5wt% based on the total weight of the aqueous medium.
31. A trifluoroethylene-modified fluororesin characterized by being produced by the production method according to any one of claims 1 to 30.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087679A (en) * 1989-04-07 1992-02-11 Daikin Industries Ltd. Polymeric dielectrics
CN103588922A (en) * 2012-08-14 2014-02-19 中化蓝天集团有限公司 Vinylidene fluoride copolymer, and preparation method and application thereof
CN106674406A (en) * 2016-12-31 2017-05-17 山东华夏神舟新材料有限公司 Preparation method and modification method of flexible low-melting point vinylidene fluoride copolymer
CN109810212A (en) * 2017-11-20 2019-05-28 中昊晨光化工研究院有限公司 A kind of high dielectric constant Kynoar and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087679A (en) * 1989-04-07 1992-02-11 Daikin Industries Ltd. Polymeric dielectrics
CN103588922A (en) * 2012-08-14 2014-02-19 中化蓝天集团有限公司 Vinylidene fluoride copolymer, and preparation method and application thereof
CN106674406A (en) * 2016-12-31 2017-05-17 山东华夏神舟新材料有限公司 Preparation method and modification method of flexible low-melting point vinylidene fluoride copolymer
CN109810212A (en) * 2017-11-20 2019-05-28 中昊晨光化工研究院有限公司 A kind of high dielectric constant Kynoar and its preparation method and application

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