CN110078856A - A kind of tetrafluoroethene modified polyvinilidene fluoride resin and preparation method thereof - Google Patents
A kind of tetrafluoroethene modified polyvinilidene fluoride resin and preparation method thereof Download PDFInfo
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- CN110078856A CN110078856A CN201910323549.7A CN201910323549A CN110078856A CN 110078856 A CN110078856 A CN 110078856A CN 201910323549 A CN201910323549 A CN 201910323549A CN 110078856 A CN110078856 A CN 110078856A
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- tetrafluoroethene
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
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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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
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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
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Abstract
The present invention relates to a kind of preparation method of tetrafluoroethene modified polyvinilidene fluoride resin, this method carries out polymerization reaction using tetrafluoroethene and vinylidene as raw material monomer；Wherein, the molar ratio that the tetrafluoroethene and vinylidene gather is (1~60): (40~99).The present invention further optimizes polymerizing condition, dispersing agent, initiator and the chain-transferring agent etc. in resin preparation process, to ensure the preparation process using environmental protection, obtains the excellent naval stores of high-temperature stability.Tetrafluoroethene modified polyvinilidene fluoride melting point resin provided by the invention is 180~235 DEG C, the fusing point of more conventional polyvinylidene fluoride resin is higher, it can ensure that resin has good high temperature resistance, to improve the high temperature stability performance of resin, the application field for improving resin, is conducive to following process.
Description
Technical field
The present invention relates to the field of industrial production of resin, and in particular to a kind of tetrafluoroethene modified polyvinilidene fluoride resin and
Preparation method.
Background technique
Kynoar (PVDF) has excellent fatigue resistance, processability, resistance to as a kind of important fluoropolymer
Hou Xing, chemical-resistant and excellent optics, electric property, and it is widely used in aviation, electronics, the energy, automobile, chemistry
The fields such as industry, but since conventional PVDF is bad in high high-temp stability, usually when being greater than 180 DEG C, just there is part to wave
It sends out object to remove, to limit the processing and application of the product, therefore prepares the modification PVDF resin with high high-temp stability
Have great importance.
Patent document CN108047383A discloses a kind of preparation method of polyvinylidene fluoride copolymer, i.e., by polyvinylidene fluoride
Alkene is dissolved in solvent, with the processing of organic base Hybrid Heating, obtains the Kynoar solution of alkali process；It again will be after alkali process
Kynoar carries out graft reaction under the action of ultraviolet absorbing agent and initiator, obtains polyvinylidene fluoride copolymer；But
It is that the Kynoar joined ultraviolet absorbing agent in the course of the polymerization process, reduces the high temperature resistance of product, be unfavorable for material
The processing of high Warm Melt and use of material.
Patent document CN102642358A discloses a kind of polyvinylidene difluoride film, i.e. polyvinylidene difluoride film includes two
Polyvinylidene fluoride layer and the middle layer being arranged between described two polyvinylidene fluoride layers, but it is that the middle layer joined
Ethylene-vinyl acetate copolymer or (and) polymethyl methacrylate, be unfavorable for environmentally friendly close friend, reduce PVDF hot-workability
Can, showing in PVDF product process has more sour gas and volatile matter to remove, and it is resistance to reduce polyvinylidene fluoride resin
High-temperature behavior.
Summary of the invention
It is an object of the invention to the synthetic method of polyvinylidene fluoride resin in view of the prior art not enough environmental protection, closed
At polyvinylidene fluoride resin fusing point low the defects of making its poor high temperature stability, a kind of tetrafluoroethene modified polyvinilidene fluoride is provided
Resin.
Specifically, the preparation method of tetrafluoroethene modified polyvinilidene fluoride resin provided by the invention, is with tetrafluoro second
Alkene and vinylidene are raw material monomer, carry out polymerization reaction.
Wherein, the molar ratio that the tetrafluoroethene and vinylidene gather is (1~60): (40~99), more preferably (5~
30): (70~95), further preferably (20~25): (75~80).
As a preferred solution of the present invention, the molal quantity of the vinylidene account for polymerized monomer total moles 40~
99% (surplus is tetrafluoroethene), more preferably 70~95% (surplus is tetrafluoroethene), further preferably 75~80% is (remaining
Amount is tetrafluoroethene).
The present invention in the raw material monomer of Kynoar by being added a certain amount of tetrafluoroethylene monomer, available heat
The modified polyvinilidene fluoride resin of excellent in stability keeps its processed to improve the processing performance of polyvinylidene fluoride resin
The high-temperature stability of journey and use process.
Polymerization reaction of the present invention is emulsion polymerization, using water as medium, preferably 70~95 DEG C of temperature, pressure 2.0~
It carries out under conditions of 4.0MPa, is more preferably carried out under conditions of 80~90 DEG C of temperature, 2.0~4.0MPa of pressure.Above-mentioned anti-
It is carried out polymerization reaction 2~4 hours under the conditions of answering, can be obtained that yield is good, the modified polyvinilidene fluorine second with superior heat-stability
Olefine resin.
Preparation method provided by the invention needs to be added dispersing agent (i.e. emulsifier) in an aqueous medium, then is passed through monomer original
Material, in order to react abundant progress.Also, for the generation for causing polymerization reaction, need that initiator and chain-transferring agent is added.
Specifically, perfluorooctanoic acid salt can be added in the system of polymerization reaction of the present invention as dispersing agent, it is described complete
Fluorine caprylate may include its ammonium salt, sodium salt or sylvite.The dosage of the dispersing agent is preferred are as follows: every 100 parts by weight aqueous medium
More preferably 0.1~0.5 parts per weight dispersing agent is added in every 100 parts by weight aqueous medium in 0.01~5 parts per weight dispersing agent of middle addition.
Ammonium persulfate, potassium peroxydisulfate or dicetyl peroxydicarbonate diisopropyl can be added in the system of polymerization reaction of the present invention
Ester is as initiator.The dosage of the initiator is preferred are as follows: 0.01~10 parts by weight are added in every 100 parts by weight aqueous medium and cause
Agent, more preferably 0.01~0.1 parts by weight initiator of addition.
Methanol or diethyl malonate can be added in the system of polymerization reaction of the present invention as chain-transferring agent.The chain
The dosage of transfer agent is preferably the 0.01~5% of raw material monomer total weight.
As a kind of specific embodiment of the invention, the method includes following specific steps:
(1) deionized water is added in polymer reactor, dispersing agent is added when being evacuated to oxygen content≤30ppm, heats
To 80~90 DEG C；
(2) tetrafluoroethene and vinylidene fluoride monomers raw material is added, reactor pressure is risen into 2.0~4.0Mpa；
(3) initiator is added and chain-transferring agent carries out polymerization reaction, reactor is made by continuous supplementation mix monomer raw material
Interior absolute pressure maintains 2.0~4.0Mpa；
(4) reaction was completed after polymerization reaction 2~4 hours, and raw material monomer is separately recovered and contains tetrafluoroethene modified polyvinilidene
The lotion of fluoroethylene resin.
For the lotion containing tetrafluoroethene modified polyvinilidene fluoride resin, walked by cohesion, washing, drying etc.
Suddenly, it can be obtained tetrafluoroethene modified polyvinilidene fluoride resin finished product.Wherein, the flocculating agent preferably uses magnesium chloride.
The tetrafluoroethene modified polyvinilidene fluoride resin that the present invention protects the above method to be prepared simultaneously.The resin
Fusing point is preferably 180~235 DEG C.
Compared with prior art, scheme provided by the invention is in polymerization process using a certain amount of tetrafluoroethene list of addition
The fusing point of body, the more conventional polyvinylidene fluoride resin of the tetrafluoroethene modified polyvinilidene fluoride resin being prepared is higher, can be with
Ensure that there is resin good high temperature resistance to improve the application field of resin to improve the high temperature stability performance of resin,
Be conducive to following process.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
A kind of tetrafluoroethene modified polyvinilidene fluoride resin is present embodiments provided, as follows in the polymerization of 50L
It is prepared in reactor:
(1) 32L deionized water is added in the reactor, perfluorooctanoic acid salt is added when being evacuated to oxygen content≤30ppm
Content in reactor is heated to 85 DEG C by 35g；
(2) tetrafluoroethene and vinylidene fluoride monomers raw material is added, the molar ratio of the two is 22:78, by reactor pressure
Rise to 3.0Mpa；
(3) initiator potassium persulfate 15g and chain-transferring agent diethyl malonate 25g is added, carries out polymerization reaction, passes through company
Continuous supplement mix monomer raw material makes absolute pressure in reactor maintain 3.0 ± 0.02MPa；
(4) reaction was completed after polymerization reaction 2 hours, and the solid content in gained lotion reaches 30% (mass percent) at this time
Left and right, is separately recovered raw material monomer and the lotion containing tetrafluoroethene modified polyvinilidene fluoride resin；
The lotion is put to cohesion bucket, a certain amount of MgCl is added2Be condensed, collect hard resin, after washing
120 DEG C or so vacuum drying.
The present embodiment obtains tetrafluoroethene modified polyvinilidene fluoride naval stores 8Kg, is granulated transparent, particle through twin-screw
Shape, about 195 DEG C of melting temperature, melt index 10g/10min, tensile strength 38MPa, elongation 300%, volatile matter
0.1%.
Embodiment 2
A kind of tetrafluoroethene modified polyvinilidene fluoride resin is present embodiments provided, as follows in the polymerization of 50L
It is prepared in reactor:
(1) 32L deionized water is added in the reactor, perfluorooctanoic acid salt is added when being evacuated to oxygen content≤30ppm
Content in reactor is heated to 88 DEG C by 45g；
(2) tetrafluoroethene and vinylidene fluoride monomers raw material is added, the molar ratio of the two is 5:95, by reactor pressure liter
To 3.1Mpa；
(3) initiator potassium persulfate 12g and chain-transferring agent diethyl malonate 20g is added, carries out polymerization reaction, passes through company
Continuous supplement mix monomer raw material makes absolute pressure in reactor maintain 3.1MPa；
(4) reaction was completed after polymerization reaction 1.8 hours, and the solid content in gained lotion reaches 28% (quality percentage at this time
Number) left and right, raw material monomer and the lotion containing tetrafluoroethene modified polyvinilidene fluoride resin is separately recovered；
The lotion is put to cohesion bucket, a certain amount of MgCl is added2Be condensed, collect hard resin, after washing
120 DEG C or so vacuum drying.
The present embodiment obtains tetrafluoroethene modified polyvinilidene fluoride naval stores 10Kg, through twin-screw be granulated it is transparent,
It is granular, about 182 DEG C of melting temperature, melt index 3.4g/10min, tensile strength 40MPa, elongation 330%, volatilization
Divide 0.1%.
Embodiment 3
A kind of tetrafluoroethene modified polyvinilidene fluoride resin is present embodiments provided, as follows in the polymerization of 50L
It is prepared in reactor:
(1) 30L deionized water is added in the reactor, perfluorooctanoic acid salt is added when being evacuated to oxygen content≤30ppm
Content in reactor is heated to 83 DEG C by 40g；
(2) tetrafluoroethene and vinylidene fluoride monomers raw material is added, the molar ratio of the two is 10:90, by reactor pressure
Rise to 2.8Mpa；
(3) initiator potassium persulfate 20g and chain-transferring agent diethyl malonate 10g is added, carries out polymerization reaction, passes through company
Continuous supplement mix monomer raw material makes absolute pressure in reactor maintain 2.8MPa；
(4) reaction was completed after polymerization reaction 2.5 hours, and the solid content in gained lotion reaches 27% (quality percentage at this time
Number) left and right, raw material monomer and the lotion containing tetrafluoroethene modified polyvinilidene fluoride resin is separately recovered；
The lotion is put to cohesion bucket, a certain amount of MgCl is added2Be condensed, collect hard resin, after washing
120 DEG C or so vacuum drying.
The present embodiment obtains tetrafluoroethene modified polyvinilidene fluoride naval stores 8.8Kg, through twin-screw be granulated it is transparent,
Granular, about 187 DEG C of melting temperature, melt index 2.3g/10min, tensile strength 39.5MPa, elongation 320% are waved
Hair point 0.1%.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of preparation method of tetrafluoroethene modified polyvinilidene fluoride resin, which is characterized in that with tetrafluoroethene and inclined fluorine second
Alkene is raw material monomer, carries out polymerization reaction；
Wherein, the molar ratio that the tetrafluoroethene and vinylidene gather is (1~60): (40~99), preferably (5~30): (70
~95), more preferably (20~25): (75~80).
2. the method according to claim 1, wherein the molal quantity of the vinylidene accounts for raw material monomer mole always
Several 40~99%, more preferably 70~95%, further preferably 75~80%.
3. method according to claim 1 or 2, which is characterized in that the polymerization reaction using water as medium, temperature 70~
95 DEG C, carry out under conditions of 2.0~4.0MPa of pressure, preferably under conditions of 80~90 DEG C of temperature, 2.0~4.0MPa of pressure into
Row.
4. according to the method described in claim 3, it is characterized in that, the time of the polymerization reaction is 2~4 hours.
5. the method according to claim 3 or 4, which is characterized in that perfluoro caprylic acid is added in the system of the polymerization reaction
Salt is as dispersing agent；
Preferably, the dosage of the dispersing agent are as follows: 0.01~5 parts per weight dispersing agent is added in every 100 parts by weight aqueous medium, it is more excellent
0.1~0.5 parts per weight dispersing agent is added in choosing.
6. the method according to claim 3 or 4, which is characterized in that in the system of the polymerization reaction be added ammonium persulfate,
Potassium peroxydisulfate or di-isopropyl peroxydicarbonate are as initiator；
Preferably, the dosage of the initiator are as follows: 0.01~10 parts by weight initiator is added in every 100 parts by weight aqueous medium, more
It is preferably added to 0.01~0.1 parts by weight initiator.
7. the method according to claim 3 or 4, which is characterized in that methanol or third is added in the system of the polymerization reaction
Diethyl adipate is as chain-transferring agent；
Preferably, the dosage of the chain-transferring agent is the 0.01~5% of raw material monomer total weight.
8. method described in any one according to claim 1~7, which is characterized in that comprise the following specific steps that:
(1) deionized water is added in polymer reactor, dispersing agent is added when being evacuated to oxygen content≤30ppm, is heated to 80
~90 DEG C；
(2) tetrafluoroethene and vinylidene fluoride monomers raw material is added, reactor pressure is risen into 2.0~4.0Mpa；
(3) initiator is added and chain-transferring agent carries out polymerization reaction, is made in reactor absolutely by continuous supplementation mix monomer raw material
2.0~4.0Mpa is maintained to pressure；
(4) reaction was completed after polymerization reaction 2~4 hours, and raw material monomer is separately recovered and contains tetrafluoroethene modified polyvinilidene fluorine second
The lotion of olefine resin.
9. according to the method described in claim 8, it is characterized in that, further including following steps: in the resulting lotion of polymerization reaction
Middle addition flocculating agent is condensed, and collects hard resin；Preferably, the flocculating agent is magnesium chloride.
10. the tetrafluoroethene modified polyvinilidene fluoride resin that claim 1~9 any one the method is prepared；
Preferably, the fusing point of the tetrafluoroethene modified polyvinilidene fluoride resin is 180~235 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4544720A (en) * | 1983-09-21 | 1985-10-01 | Daikin Kogyo Co., Ltd. | Fluorine-containing copolymer |
| CN101357964A (en) * | 2007-07-31 | 2009-02-04 | 大金工业株式会社 | Method for producing a fluoroelastomer |
| CN103709304A (en) * | 2013-12-26 | 2014-04-09 | 中昊晨光化工研究院有限公司 | Preparation method of high-strength fluorine-containing polymer |
| CN104350635A (en) * | 2012-05-21 | 2015-02-11 | 大金工业株式会社 | Electrode mixture |
-
2019
- 2019-04-22 CN CN201910323549.7A patent/CN110078856A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4544720A (en) * | 1983-09-21 | 1985-10-01 | Daikin Kogyo Co., Ltd. | Fluorine-containing copolymer |
| CN101357964A (en) * | 2007-07-31 | 2009-02-04 | 大金工业株式会社 | Method for producing a fluoroelastomer |
| CN104350635A (en) * | 2012-05-21 | 2015-02-11 | 大金工业株式会社 | Electrode mixture |
| CN103709304A (en) * | 2013-12-26 | 2014-04-09 | 中昊晨光化工研究院有限公司 | Preparation method of high-strength fluorine-containing polymer |
Non-Patent Citations (3)
| Title |
|---|
| 罗河胜: "《塑料材料手册（第三版）》", 30 March 2010 * |
| 罗河胜: "《塑料材料手册》", 30 March 1988 * |
| 袁才根等: "四氟乙烯/偏氟乙烯乳液共聚反应的竞聚率测定", 《高分子学报》 * |
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