CN108239214A - A kind of method that continuous polymerization in supercritical carbon dioxide prepares polyvinyl fluoride copolymer - Google Patents
A kind of method that continuous polymerization in supercritical carbon dioxide prepares polyvinyl fluoride copolymer Download PDFInfo
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- CN108239214A CN108239214A CN201611222284.4A CN201611222284A CN108239214A CN 108239214 A CN108239214 A CN 108239214A CN 201611222284 A CN201611222284 A CN 201611222284A CN 108239214 A CN108239214 A CN 108239214A
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- Prior art keywords
- polar monomer
- polyvinyl fluoride
- fluoride copolymer
- modified polyvinyl
- monomer modified
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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
- C08F214/20—Vinyl 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
- C08F2/00—Processes of polymerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The method through polar monomer modified polyvinyl fluoride copolymer is prepared with continuity method the invention discloses a kind of, in supercritical CO2In, under radical initiator effect, fluoride monomers and the continuous copolyreaction of polar monomer is made to obtain through polar monomer modified polyvinyl fluoride copolymer.Polyvinyl fluoride copolymer prepared by the present invention, melt-processed and film bond performance are improved.
Description
Technical field
The present invention relates to a kind of polymerization of polyvinyl fluoride copolymer, more particularly, to one kind in supercritical carbon dioxide
The method that middle continuous polymerization prepares polyvinyl fluoride copolymer.
Background technology
Polyfluoroethylene resin is the resin variety that Du Pont developed in 1964, and polyvinyl fluoride thin film prepared therefrom can be used for
Solar cell backboard.In use, solar energy back veneer material is usually by polyvinyl fluoride thin film and poly terephthalic acid
The sandwich diaphragm that glycol ester (PET) is combined.Since polyvinyl fluoride surface can be relatively low so that itself and poly terephthalic acid
The adhesive property of glycol ester is poor, it is necessary to can be compound using special bonding agent.To improve polyvinyl fluoride thin film with gathering
The adhesive property of ethylene glycol terephthalate, the prior art, which is proposed, is copolymerized polyfluoroethylene resin using polar monomer
Modified method.
Preparation for polyfluoroethylene resin, generally using aqueous phase emulsion polymerization or suspension polymerization, i.e. " aqueous polymerization
System ", most polar groups easily react with water under the polymerization system, so as to which polar functionalities comonomer can not be with fluorine
Ethylene combined polymerization in aqueous systems.Therefore, it is necessary to vinyl fluoride and the copolyreaction of polar group monomer are improved.
In the research of reaction medium, the prior art is for supercritical CO2Polymer is prepared for medium to have made centainly
Contribution, such as：
(1) Baradie is in Synthesis of Fluorocarbon-Vinyl Acetate Copolymers in
Supercri tical Carbon Dioxide:Insight into Bulk Properties.Macromoleculs
(2002,35(9):3569~3575) it is disclosed in and tetrafluoroethene (TFE) and polar functionalities monomer is synthesized in supercritical CO 2
The method of novel fluorinated copolymers object.These polar monomers contain the group easily to react with water, such as vinylacetate, diformazan
Radical siloxane methacrylate etc., the copolyreaction of they and TFE cannot carry out, but in supercritical CO 2 in water, can
It is copolymerized with tetrafluoroethene；
(2) Charpentier is in Continuous precipitation polymerization of vinylidene
fluoride in supercritical carbon dioxide:Modeling the rate of
polymertization.Industrial&Engineering Chemistry Research(2000,3(12):4588~
4596) it is disclosed in supercritical CO2The middle method for preparing partial fluorine ethylene polymer (VDF), 75 DEG C of polymerization temperature, reaction pressure
Power 276bar, CO2, VDF monomers, initiator be constantly passed through the reaction kettle of high-speed stirred, product and CO2, unreacted monomer and initiation
Agent is flowed out together from reactor bottom, forms a continuous polymerization reaction system；
(3) Ahmed is in Continuous Copolymerizationg of Vinylidene Fluoride with
Hexafluoropropylene in SupercriticalCarbondioxide:High-Hexafluoropropylene-
Content Amorphous Copolymers.Macromolecule(2008,41(9):3086~3097) it is disclosed in super
Critical CO2In continuously prepare biasfluoroethylene-hexafluoropropylene (VDF-HFP) copolymerization method, CO2, VDF, HFP and initiator PBP determine
Amount is added continuously reaction kettle, and polymerization temperature is 40 DEG C, and reaction pressure is between 207-400bar.
The supercritical CO wherein used2Refer to the stream of temperature, pressure more than its critical point (31.1 DEG C, 72.8atm)
Body, in the supercritical state, CO2Density, dielectric constant and Conventional solvents approach；Meanwhile its viscosity is very small, with gas
It is close.Supercritical CO2Inherent compressibility, in addition the performances such as its density, viscosity can be adjusted by pressure and temperature change,
Water is being substituted as having some superiority on polymer polymerizing medium.
To sum up, the copolyreaction of vinyl fluoride and polar group monomer is also hopeful to be further improved.
Invention content
The purpose of the present invention is to provide one kind with supercritical CO2It is prepared for reaction medium, continuous polymerization through polarity list
The method of modifies polyvinyl fluoride copolymer, what is obtained has good add through polar monomer modified polyvinyl fluoride copolymer
Work performance and adhesive property.
By the present invention in that use supercritical CO2For reaction medium, overcome the shortcomings of that polyvinyl fluoride aqueous systems polymerize, reduce poly-
The ratio of unstable end-group in object, while the copolymerization units by introducing polar functionalities are closed, it is regular to destroy polyvinyl fluoride main chain
Property and increase polyvinyl fluoride surface can, improve the processing performance and adhesive property of polyvinyl fluoride copolymer.
The present invention provides following technical solution：
It is a kind of that the method through polar monomer modified polyvinyl fluoride copolymer is prepared with continuity method, the method includes：
In supercritical CO2In, under radical initiator effect, fluoride monomers and polar monomer is made continuously to be passed through instead
Kettle, fluoride monomers and polar monomer is answered to be obtained through copolyreaction through polar monomer modified polyvinyl fluoride copolymer.
Method provided by the invention, the polar monomer used, be preferably selected from unsaturated olefin and/or insatiable hunger aliphatic acid or
Ester.
Wherein unsaturated olefin, it is preferred that the unsaturated olefin is CnHxCly.Wherein：N is independently selected from 1~15
Integer, x, y and z are independently selected from the integer of 0~2n, x+y=2n.
Wherein insatiable hunger fatty acid or ester, it is preferred that the insatiable hunger fatty acid or ester is CnHxCly0z.Wherein：N is independently
Selected from 1~15 integer, x, y and z are independently selected from the integer of 0~2n, x+y=2n, x+y+z=2n.
As further preferred mode, the polar monomer is selected from ethylene, propylene, isobutene, vinyl chloride, vinyl fourth
In acid, vinyl acetate, vinyl butyrate, methyl methacrylate, vinyl crotonate, glycidyl methacrylate
It is at least one.
The dosage for the polar monomer that the present invention uses, satisfaction obtain the processing performance of polyvinyl fluoride copolymer and adhesive property
With improvement.Preferably, the mass ratio of the fluoride monomers and polar monomer is 60/40~99.999/0.001.
It may further be preferable that the mass ratio of the fluoride monomers and polar monomer is 20~1000:1.
It is even furthermore preferable that the mass ratio of the fluoride monomers and polar monomer is 40~500:1.
The radical initiator that the present invention uses, radical initiator commonly used in the art could be used for the present invention.
Preferably, the radical initiator is selected from azo compound and/or perfluor peroxidating class compound.
It may further be preferable that the azo compound be selected from 2,2- azodiisobutyronitriles, 2,2- azos two -2,4,4-
At least one of trimethyl valeronitrile, two cyclohexyl formonitrile HCN of azobisisoheptonitrile, azo-bis-iso-dimethyl and azo；It is described
Perfluor peroxidating class compound is selected from perfluor dicetyl peroxydicarbonate diethylester, perfluor peroxidating two (2- positive propoxies) propionyl, complete
At least one of fluorine acyl peroxide and perfluor oxa- nonyl () acyl peroxide.
The dosage of radical initiator of the present invention, satisfaction are smoothed out reaction.
Preferably, the dosage of the radical initiator is 0.1~3wt ‰ of fluoride monomers.
Method provided by the invention, polymerization temperature satisfaction are smoothed out reaction.
Preferably, the polymerization temperature is 40~120 DEG C.
It may further be preferable that the polymerization temperature is 70~100 DEG C.
Method provided by the invention, polymerization pressure satisfaction are smoothed out reaction.
Preferably, the polymerization pressure is 8~50MPa.
It may further be preferable that the polymerization pressure is 15~30MPa.
Method provided by the invention has following advantage compared with prior art：
(1) for the first time with supercritical CO2The continuous copolymerization of vinyl fluoride and polar monomer is carried out for reaction medium, is improved
Quality stability, the production efficiency of polymerizate reduce supplies consumption；
(2) it is prepared for for the first time through polar monomer modified polyvinyl fluoride copolymer, processing performance is than polyvinyl fluoride homopolymerization
Object is obviously improved, and due to the copolymerization units for introducing polar functionalities, is increased the surface energy of polyvinyl fluoride, be conducive to improve poly-
The bonding force of fluoroethylene film and PET material.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
The performance of polyfluoroethylene resin prepared by the present invention is carried out according to following test method：
(1) intrinsic viscosity is tested：The n,N-Dimethylformamide solution of configuration PVF resins is completely dissolved at 110 DEG C, uses U
Type Ubbelohde viscometer measures in 110 DEG C of glycerine oil baths.
(2) DSC is tested：It measures on 1 instruments of Perkin-Elmer Pyris, completes under nitrogen protection.Nitrogen flow
50mL/min, amount of samples are about 4mg.Sample first rises to 220 DEG C with 10K/min speed, keeps the temperature 5min at such a temperature to disappear
Except thermal history, room temperature is then dropped to -10 DEG C/min speed again；
Embodiment 1
The polyvinyl fluoride successive reaction carried out in polymeric kettle using supercritical carbon dioxide as medium is continuously stirred at one, instead
95 DEG C, polymerization pressure 18MPa, speed of agitator 400rpm/min of temperature is answered, is polymerize with 2,2- azodiisobutyronitriles for initiator, fluorine
Vinyl monomer continuously squeezes into polymeric kettle, the second of 2000ppm vinyl fluoride amount (wt%) after tubing heat exchanger with 22g/min flows
Vinyl acetate comonomer is continuously added to polymeric kettle, and carbon dioxide continuously squeezes into polymerization after heat exchanger with 218g/min flows
Kettle, initiator continuously squeeze into polymeric kettle with 1.00 parts/thousand parts monomer (vinyl fluoride) flows, and polyvinyl fluoride product is with 11g/min amounts
Remove polymeric kettle.
Polymerizate is detached with unreacted monomer mixtures in separator, and solid product obtains white powder after drying
Object, test result is as follows for polyvinyl fluoride copolymer resins：Intrinsic viscosity is 0.86dl/g, and it is 184.5 DEG C that DSC, which measures melting temperature,.
Embodiment 2
The polyvinyl fluoride carried out in polymeric kettle using supercritical carbon dioxide as medium is continuously stirred at one to be continuously copolymerized instead
Should, 95 DEG C, polymerization pressure 18MPa, speed of agitator 400rpm/min of reaction temperature polymerize with 2,2- azodiisobutyronitriles to cause
Agent, fluoride monomers continuously squeeze into polymeric kettle after tubing heat exchanger with 22g/min flows, and carbon dioxide is after heat exchanger
Polymeric kettle is continuously squeezed into 218g/min flows, hexafluoropropene monomer is continuously beaten after tubing heat exchanger with 1.2g/min flows
Enter polymeric kettle, initiator continuously squeezes into polymeric kettle with 1.00 parts/thousand parts monomer (vinyl fluoride) flows, polyvinyl fluoride copolymerization product with
11g/min amounts remove polymeric kettle.
Polymerizate is detached with unreacted monomer mixtures in separator, and solid product obtains white powder after drying
Object, test result is as follows for polyvinyl fluoride copolymer resins：Intrinsic viscosity is 1.01dl/g, and it is 175.8 DEG C that DSC, which measures melting temperature,.
Embodiment 3
The polyvinyl fluoride carried out in polymeric kettle using supercritical carbon dioxide as medium is continuously stirred at one to be continuously copolymerized instead
Should, 95 DEG C, polymerization pressure 25MPa, speed of agitator 400rpm/min of reaction temperature polymerize using two cyclohexyl formonitrile HCN of azo as initiation
Agent, fluoride monomers continuously squeeze into polymeric kettle, 2000ppm vinyl fluoride amounts after tubing heat exchanger with 22g/min flows
(wt%) vinyl butyric acid comonomer is continuously added to polymeric kettle, and carbon dioxide is connected after heat exchanger with 218g/min flows
Continuous to squeeze into polymeric kettle, initiator continuously squeezes into polymeric kettle, polyvinyl fluoride copolymerization production with 9.6 parts/ten thousand parts monomer (vinyl fluoride) flows
Object removes polymeric kettle with 11g/min amounts.
Polymerizate is detached with unreacted monomer mixtures in separator, and solid product obtains white powder after drying
Object, test result is as follows for polyvinyl fluoride copolymer resins：Intrinsic viscosity is 0.92dl/g, and it is 185.2 DEG C that DSC, which measures melting temperature,.
Embodiment 4
The polyvinyl fluoride carried out in polymeric kettle using supercritical carbon dioxide as medium is continuously stirred at one to be continuously copolymerized instead
Should, 95 DEG C, polymerization pressure 25MPa, speed of agitator 400rpm/min of reaction temperature polymerize using two cyclohexyl formonitrile HCN of azo as initiation
Agent, fluoride monomers continuously squeeze into polymeric kettle, 2000ppm vinyl fluoride amounts after tubing heat exchanger with 22g/min flows
(wt%) vinyl crotonate comonomer is continuously added to polymeric kettle, and carbon dioxide is after heat exchanger with 218g/min flows
Continuous to squeeze into polymeric kettle, initiator continuously squeezes into polymeric kettle with 9.6 parts/ten thousand parts flow of monomer, polyvinyl fluoride copolymerization product with
11g/min amounts remove polymeric kettle.
Polymerizate is detached with unreacted monomer mixtures in separator, and solid product obtains white powder after drying
Object, test result is as follows for polyvinyl fluoride copolymer resins：Intrinsic viscosity is 0.86dl/g, and it is 184.3 DEG C that DSC, which measures melting temperature,.
Embodiment 5
The polyvinyl fluoride carried out in polymeric kettle using supercritical carbon dioxide as medium is continuously stirred at one to be continuously copolymerized instead
Should, 95 DEG C, polymerization pressure 25MPa, speed of agitator 400rpm/min of reaction temperature polymerize with 2,2- azodiisobutyronitriles to cause
Agent, fluoride monomers continuously squeeze into polymeric kettle, 2000ppm fluoride monomers amounts after tubing heat exchanger with 22g/min flows
Glycidyl methacrylate comonomer be continuously added to polymeric kettle, carbon dioxide is flowed after heat exchanger with 218g/min
Amount continuously squeezes into polymeric kettle, and initiator continuously squeezes into polymeric kettle with 9.6 parts/ten thousand parts flow of monomer, polyvinyl fluoride copolymerization product with
11g/min amounts remove polymeric kettle.
Polymerizate is detached with unreacted monomer mixtures in separator, and solid product obtains white powder after drying
Object, test result is as follows for polyvinyl fluoride copolymer resins：Intrinsic viscosity is 0.82dl/g, and it is 183.8 DEG C that DSC, which measures melting temperature,.
Comparative example
By taking 5L polymeric kettles as an example, 3.0Kg pure water is put into polymeric kettle, inflated with nitrogen vacuumizes deoxygenation, oxygen content in kettle≤
20ppm is qualification, and speed of agitator is transferred to 400rpm/min, and reaction kettle temperature is adjusted to 95 DEG C, adds in vinyl fluoride to kettle and presses 18MPa, adds
Enter 1.2g2,2- azodiisobutyronitriles and 0.2g sodium hypochlorite start polymerisation, keep kettle pressure 18MPa, and reaction adds in fluorine second altogether
Alkene monomer 2.0Kg is reacted 3 hours and is cooled down, recycles unreacted monomer, obtain white powder polyfluoroethylene resin.
Test result is as follows for polyfluoroethylene resin obtained：Intrinsic viscosity is 0.72dl/g, and DSC measures melting temperature and is
181.8℃。
Claims (10)
1. a kind of prepare the method through polar monomer modified polyvinyl fluoride copolymer with continuity method, it is characterised in that the method
Including：
In supercritical CO2In, under radical initiator effect, fluoride monomers and polar monomer is made continuously to be passed through reaction kettle,
Fluoride monomers and polar monomer are obtained through copolyreaction through polar monomer modified polyvinyl fluoride copolymer.
2. described in accordance with the claim 1 prepare the method through polar monomer modified polyvinyl fluoride copolymer with continuity method,
It is characterized in that：
The polar monomer is selected from unsaturated olefin and/or insatiable hunger fatty acid or ester,
The unsaturated olefin is CnHxCly,
The insatiable hunger fatty acid or ester is CnHxCly0z,
Wherein：N is independently selected from 1~15 integer, and x, y and z are independently selected from the integer of 0~2n, x+y=2n, x+y+z=
2n。
3. described in accordance with the claim 2 prepare the method through polar monomer modified polyvinyl fluoride copolymer with continuity method,
It is characterized in that：
The polar monomer be selected from ethylene, propylene, isobutene, vinyl chloride, vinyl butyric acid, vinyl acetate, vinyl butyrate,
At least one of methyl methacrylate, vinyl crotonate, glycidyl methacrylate.
4. described in accordance with the claim 1 prepare the method through polar monomer modified polyvinyl fluoride copolymer with continuity method,
It is characterized in that：The mass ratio of fluoride monomers and polar monomer is 60/40~99.999/0.001.
5. the method through polar monomer modified polyvinyl fluoride copolymer is prepared with continuity method according to described in claim 4,
It is characterized in that：The mass ratio of fluoride monomers and polar monomer is 20~1000:1.
6. the method through polar monomer modified polyvinyl fluoride copolymer is prepared with continuity method according to described in claim 5,
It is characterized in that：The mass ratio of fluoride monomers and polar monomer is 40~500:1.
7. described in accordance with the claim 1 prepare the method through polar monomer modified polyvinyl fluoride copolymer with continuity method,
It is characterized in that the radical initiator is selected from azo compound and/or perfluor peroxidating class compound, the free radical draw
The dosage for sending out agent is 0.1~3wt ‰ of fluoride monomers.
8. the method through polar monomer modified polyvinyl fluoride copolymer is prepared with continuity method according to described in claim 7,
It is characterized in that：The azo compound is selected from 2,2- azodiisobutyronitriles, two -2,4,4- trimethyls valeronitrile of 2,2- azos, idol
At least one of two cyclohexyl formonitrile HCN of two different heptonitrile of nitrogen, azo-bis-iso-dimethyl and azo, the perfluor peroxidating class
Compound is selected from perfluor dicetyl peroxydicarbonate diethylester, perfluor peroxidating two (2- positive propoxies) propionyl, perfluoro acidyl peroxidating
At least one of object and perfluor oxa- nonyl () acyl peroxide.
9. described in accordance with the claim 1 prepare the method through polar monomer modified polyvinyl fluoride copolymer with continuity method,
It is characterized in that：Polymerization temperature is 40~120 DEG C, and polymerization pressure is 8~50MPa.
10. the method through polar monomer modified polyvinyl fluoride copolymer is prepared with continuity method according to described in claim 9,
It is characterized in that：Polymerization temperature is 70~100 DEG C, and polymerization pressure is 15~30MPa.
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| CN201611222284.4A CN108239214A (en) | 2016-12-27 | 2016-12-27 | A kind of method that continuous polymerization in supercritical carbon dioxide prepares polyvinyl fluoride copolymer |
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| CN201611222284.4A CN108239214A (en) | 2016-12-27 | 2016-12-27 | A kind of method that continuous polymerization in supercritical carbon dioxide prepares polyvinyl fluoride copolymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810213A (en) * | 2018-12-26 | 2019-05-28 | 乳源东阳光氟树脂有限公司 | Fluoropolymer and preparation method under a kind of water/supercritical carbon dioxide mixed system |
| CN113174003A (en) * | 2021-03-31 | 2021-07-27 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of vinyl chloride-vinyl acetate copolymer with uniformly distributed blocks |
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| CN1181087A (en) * | 1995-03-10 | 1998-05-06 | 查珀尔希尔北卡罗来纳大学 | Nonaqueous polymerization of fluoromonomers |
| US20010037007A1 (en) * | 2000-02-02 | 2001-11-01 | Lousenberg Robert D. | Linear copolymers of fluorocarbon-hydrocarbon monomers synthesized in carbon dioxide |
| WO2002030991A1 (en) * | 2000-10-09 | 2002-04-18 | University Of North Carolina At Chapel Hill | Methods for preparing polymers in carbon dioxide having reactive functionality |
| CN103304720A (en) * | 2012-03-14 | 2013-09-18 | 中化蓝天集团有限公司 | Preparation method of polyvinyl fluoride copolymer in supercritical carbon dioxide |
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2016
- 2016-12-27 CN CN201611222284.4A patent/CN108239214A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181087A (en) * | 1995-03-10 | 1998-05-06 | 查珀尔希尔北卡罗来纳大学 | Nonaqueous polymerization of fluoromonomers |
| US20010037007A1 (en) * | 2000-02-02 | 2001-11-01 | Lousenberg Robert D. | Linear copolymers of fluorocarbon-hydrocarbon monomers synthesized in carbon dioxide |
| WO2002030991A1 (en) * | 2000-10-09 | 2002-04-18 | University Of North Carolina At Chapel Hill | Methods for preparing polymers in carbon dioxide having reactive functionality |
| CN103304720A (en) * | 2012-03-14 | 2013-09-18 | 中化蓝天集团有限公司 | Preparation method of polyvinyl fluoride copolymer in supercritical carbon dioxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810213A (en) * | 2018-12-26 | 2019-05-28 | 乳源东阳光氟树脂有限公司 | Fluoropolymer and preparation method under a kind of water/supercritical carbon dioxide mixed system |
| CN109810213B (en) * | 2018-12-26 | 2021-05-04 | 乳源东阳光氟树脂有限公司 | Fluorine-containing polymer in water/supercritical carbon dioxide mixed system and preparation method thereof |
| CN113174003A (en) * | 2021-03-31 | 2021-07-27 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of vinyl chloride-vinyl acetate copolymer with uniformly distributed blocks |
| CN113174003B (en) * | 2021-03-31 | 2022-09-20 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of vinyl chloride-vinyl acetate copolymer with uniformly distributed blocks |
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