CN105504116A - Preparation method of polyfluoroethylene resin with high chain regularity - Google Patents
Preparation method of polyfluoroethylene resin with high chain regularity Download PDFInfo
- Publication number
- CN105504116A CN105504116A CN201410554669.5A CN201410554669A CN105504116A CN 105504116 A CN105504116 A CN 105504116A CN 201410554669 A CN201410554669 A CN 201410554669A CN 105504116 A CN105504116 A CN 105504116A
- Authority
- CN
- China
- Prior art keywords
- preparation
- ethylene propylene
- fluorinated ethylene
- regularity
- amylose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of polyfluoroethylene. According to the preparation method, fluoroethylene monomers are taken as the raw materials to carry out polymerization, and water and a combination of CnHxClyFz and/or CmHaClbFc are taken as the reaction medium. The provided polymerization method has the advantages of low polymerization pressure, and mild and controllable polymerization conditions. Moreover, the prepared polyfluoroethylene resin has a high chain regularity and high thermo-chemical stability.
Description
Technical field
The present invention relates to a kind of preparation method of polyfluoroethylene resin, especially relate to a kind of preparation method of high-amylose regularity polyfluoroethylene resin.
Background technology
Polyfluoroethylene resin (PVF) refers to the homopolymer of fluoride monomers, and the repeating unit of its molecular chain is-CH
2-CHF-group, PVF resin has the characteristic of fluorine resin and resins for universal use concurrently, has excellent resistance to chemical attack, high temperature resistant, weathering resistance, UV resistant.
The property of PVF resin is because its special molecular structure determines, but, because the van der Waals radius of fluorine atom is less than other halogen atoms, sterically hindered little, therefore easily there is fluoride monomers to the reverse addition increasing macromolecular chain, generate head-head or tail-tail chain joint.This abnormal structure has a significant impact the weathering resistance of fluorinated ethylene propylene, toughness, the tool such as physical strength and shock strength.Therefore the high-amylose regularity of polyfluoroethylene resin is improved, most important to improving the quality of products.
In prior art, report is rarely had to the high-amylose regularity how improving polyfluoroethylene resin, only has the report of following raising polyfluoroethylene resin over-all properties:
US Patent No. 2419008 and US2419010 report the method preparing high-performance orientation PVF resin, its polymerization pressure reaches more than 100% ~ 400% more than the elongation at break of 10MPa, resin, and the film be made up of this high-performance orientation PVF resin, at subzero 80 DEG C, still keep certain snappiness.
US Patent No. 3428618 reports and uses cyclic group azo amidine class initiator, prepares the PVF resin of high molecular, high tensile and high fracture rate elongation.
It is reaction medium that US Patent No. 3637631 reports with t-butanol solution, with peralcohol or hydrogen peroxide for the method for PVF resin is prepared in initiator polymerization, the limiting viscosity of obtained PVF resin is at more than 1.5 (100cc./g.).
CN1834124A report in reaction system, add minute quantity inorganic salt compound as auxiliary agent to prepare the method for PVF resin, the limiting viscosity of obtained PVF resin is at more than 1.35dL/g.
In above-mentioned polyfluoroethylene resin preparation method, all adopt aqueous phase emulsion polymerization or suspension polymerization preparation, i.e. " aqueous polymerization system ".When adopting " aqueous polymerization system ", the polyfluoroethylene resin end group obtained is unstable, the problems such as resin decomposition, variable color, release hydrogen fluoride gas easily occurs in following process process, and then affects outward appearance and the performance of goods; In last handling process, resin washing produces a large amount of waste water, and the resin drying at substantial energy, adds production cost; The polar monomer that some and water are had an effect cannot be used for carrying out copolymerization with vinyl fluoride, limits the exploitation of new copolymer resins product.Therefore a kind of novel method preparing fluoropolymer is needed.
Summary of the invention
The present invention is directed to " aqueous polymerization system " Problems existing, a kind of method preparing polyfluoroethylene resin is newly proposed, significantly can not only reduce the textural defect (as tail-tail and head-header structure, branching etc.) of fluorinated ethylene propylene, can also avoid producing unstable end-group, reduction production cost, the mechanical property improving product, processing characteristics and weather resistance.
For reaching goal of the invention the technical solution used in the present invention be:
A preparation method for high-amylose regularity fluorinated ethylene propylene, adopts fluoride monomers to be that raw material carries out polyreaction, with water and be selected from C
nh
xcl
yf
zand/or C
mh
acl
bf
cbe combined as reaction medium, wherein: the integer of n=1 ~ 15, x, y and z are independently selected from the integer of 0 ~ 2n+2 and x+y+z=2n+2; The integer of m=1 ~ 15, a, b and c are independently selected from the integer of 0 ~ 2n and a+b+c=2n.
Above-mentioned C
nh
xcl
yf
zin, as preferred mode, the integer of n=1 ~ 10; As further preferred mode, described C
nh
xcl
yf
zbe selected from 1,2-dichloro tetrafluoro ethane, trichlorofluoromethane, 1,1,1-Refrigerant R 113,1,1,2-Refrigerant R 113, tetracol phenixin, 1,1,1, one in 2 C2Cl4F2s, 1,1,2,2-C2Cl4F2, pentachloro-fluoroethane and hexachloroethane, more than two or three combination.
Above-mentioned C
mh
acl
bf
cin, as preferred mode, the integer of m=1 ~ 10; As further preferred mode, described C
mh
acl
bf
cbe selected from the one, two or three in chlorine seven fluorine tetramethylene, perfluoro-2-methyl cyclobutane and 1,2-dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane.
As preferred mode, above-mentioned polyreaction is preferably carried out in the presence of a free-radical initiator, and the consumption of initiator is preferably the 0.1 ~ 3wt ‰ of fluoride monomers.Described radical initiator is preferably azo compound and/or perfluor peroxidation compounds, described azo compound is preferably from 2, 2-Diisopropyl azodicarboxylate, 2, 2-azo two-2, 4, 4-trimethylammonium valeronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), one in azo-bis-iso-dimethyl and azo two cyclohexyl formonitrile HCN, more than two or three combination, described perfluor peroxidation compounds is preferably from perfluor peroxy dicarbonate diethyl ester, perfluor peroxidation two (2-positive propoxy) propionyl, one in perfluoroacyl peroxides and the perfluor oxa-ninth of the ten Heavenly Stems () acyl peroxide, more than two or three combination.
As preferred mode, above-mentioned polyreaction is carried out under reaction promoter exists, and reaction promoter is neutral inorganic compound or basic cpd, and the consumption of reaction promoter is 0.01% ~ 2.0wt% of fluoride monomers weight.The one of described inorganic salt compound preferably in potassium nitrite, Sodium Nitrite, calcium nitrite, potassium hypochlorite, clorox, potassium hypobromite and hypoiodous acid potassium, more than two or three combination.The one of described basic cpd preferably in ammoniacal liquor, sodium hydroxide, potassium hydroxide and calcium hydroxide, more than two or three combination.
In above-mentioned polyreaction, as preferred mode, described polymerization temperature-20 ~ 90 DEG C, reaction pressure 1.0 ~ 20.0MPa, reaction times 2 ~ 16 hours.
In polymerization process provided by the invention, the second comonomer can be added in the preparation of described polyfluoroethylene resin, obtain polyvinyl fluoride copolymer with fluoride monomers by copolymerization.As preferred mode, the one, more than two or three that described second comonomer is selected from vinylidene, R 1216, five fluorine propylene, tetrafluoeopropene, trifluoro propene, perfluorobuttene, hexachlorobutadiene, hexafluoro-isobutene, trifluoro-ethylene, trifluorochloroethylene, perfluoroalkyl vinyl ether and tetrafluoroethylene combines, and the mol ratio of described fluoride monomers and the second comonomer is 60/40 ~ 99.99/0.01.
Polyfluoroethylene resin prepared by polymerization process provided by the invention, its amylose regularity can reach more than 78%, and thermal weight loss 1% temperature reaches more than 370 DEG C.The polyfluoroethylene resin of preparation is suitable for sun power backboard membrane, departs from film, decorating film or corrosion protection coating.
Compared with existing polymerization process, the present invention provides a kind of high-amylose regularity PVF first time and produces polymerization process for preparing, polymerization pressure reduces greatly, polymerizing condition is gentle, easily control, and the amylose regularity of the polyfluoroethylene resin of preparation is high, thermo-chemical stability good.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
The performance of PVF resin prepared by the present invention is carried out according to following testing method:
(1) 19F-NMR test: test and carry out in VarianMercury300plus nuclear magnetic resonance analyser.Make solvent with deuterated dimethyl sulfoxide, strength of solution is about 1wt%, and probe temperature is 120 DEG C, sampling time 0.5S, pulse angle 90 degree, relaxation time 1S;
(2) DSC test: measure on Perkin-ElmerPyris1 instrument, complete under nitrogen protection.Nitrogen flow 50mL/min, amount of samples is about 4mg.Sample first rises to 220 DEG C with 10K/min speed, is incubated 5min at such a temperature to eliminate thermal history, and then drops to room temperature with-10 DEG C/min speed;
(3) TGA test: except water treatment before test, TGA/SDTA851e instrument measures, completes under nitrogen protection, sample is from 50 DEG C to 800 DEG C, and 10 DEG C/min heats up, with weightless 1% time temperature be as the criterion;
(4) intrinsic viscosity test: the DMF solution of configuration PVF resin dissolves completely at 110 DEG C, measures in 110 DEG C of glycerol oil baths with U-shaped Ubbelohde viscometer.
Embodiment 1
For 5L polymeric kettle, first by 3.0KgCCl
2fCClF
2put in polymeric kettle; inflated with nitrogen, vacuumize deoxygenation; in still, oxygen level≤20ppm is qualified, and mixing speed is transferred to 400rpm/min, and reactor temperature is adjusted to 10 DEG C; add vinyl fluoride (VF) to still pressure 2.0MPa; add 1.2g perfluor oxa-acyl peroxide and 0.1g clorox start polyreaction, keep still be pressed in 2.0MPa, reaction add VF monomer 1Kg altogether; react cooling in 6 hours, reclaim and be separated unreacted monomer and CCl
2fCClF
2, obtain white powder resin, obtain PVF resin.
Obtained PVF resin test result is as follows: intrinsic viscosity is that to record melt temperature be 195 DEG C for 1.10dl/g, DSC, and product chain regularity is 80.65%, thermal weight loss 1% temperature 385 DEG C.
Embodiment 2
For 5L polymeric kettle, first by 3.0Kg perfluoro-2-methyl cyclobutane (C
6f
12) put in polymeric kettle; inflated with nitrogen, vacuumize deoxygenation; in still, oxygen level≤20ppm is qualified, and mixing speed is transferred to 400rpm/min, and reactor temperature is adjusted to 10 DEG C; add vinyl fluoride (VF) to still pressure 2.0MPa; add 1.2g perfluor oxa-acyl peroxide and 0.1g clorox start polyreaction, keep still be pressed in 2.0MPa, reaction add VF monomer 1Kg altogether; react cooling in 5.5 hours, reclaim and be separated unreacted monomer and C
6f
12, obtain white powder resin, obtain PVF resin.
Obtained PVF resin test result is as follows: intrinsic viscosity is that to record melt temperature be 198 DEG C for 1.23dl/g, DSC, and product chain regularity is 81.23%, thermal weight loss 1% temperature 388 DEG C.
Embodiment 3
For 5L polymeric kettle, first by 3.0Kg C2Cl4F2 (CCl
3cClF
2) put in polymeric kettle; inflated with nitrogen, vacuumize deoxygenation; in still, oxygen level≤20ppm is qualified, and mixing speed is transferred to 400rpm/min, and reactor temperature is adjusted to 30 DEG C; add vinyl fluoride (VF) to still pressure 1.0MPa; add 1.0g perfluor oxa-acyl peroxide and 0.2g clorox start polyreaction, keep still be pressed in 1.0MPa, reaction add VF monomer 1Kg altogether; react cooling in 2.5 hours, reclaim and be separated unreacted monomer and CCl
3cClF
2, obtain white powder resin, obtain PVF resin.
Obtained PVF resin test result is as follows: intrinsic viscosity is that to record melt temperature be 192 DEG C for 1.20dl/g, DSC, and product chain regularity is 79.83%, thermal weight loss 1% temperature 382 DEG C.
Embodiment 4
For 5L polymeric kettle, first by 3.0Kg1.1.2.2-C2Cl4F2 (CCl
2fCCl
2f) put in polymeric kettle, inflated with nitrogen, vacuumize deoxygenation, in still, oxygen level≤20ppm is qualified, and mixing speed is transferred to 400rpm/min, and reactor temperature is adjusted to 70 DEG C, add vinyl fluoride (VF) to still pressure 10.0MPa, add 1.5g azo two cyclohexyl formonitrile HCN and 0.1g clorox starts polyreaction, keep still to be pressed in 10.0MPa, reaction adds VF monomer 1Kg altogether, react cooling in 8.5 hours, reclaim and be separated unreacted monomer and CCl
2fCCl
2f, obtains white powder resin, obtains PVF resin.
Obtained PVF resin test result is as follows: intrinsic viscosity is that to record melt temperature be 185 DEG C for 1.02dl/g, DSC, and product chain regularity is 79.01%, thermal weight loss 1% temperature 378 DEG C.
Embodiment 5
For 5L polymeric kettle, first by 3.0Kg1.1.2.2-C2Cl4F2 (CCl
2fCCl
2f) put in polymeric kettle, inflated with nitrogen, vacuumize deoxygenation, in still, oxygen level≤20ppm is qualified, and mixing speed is transferred to 400rpm/min, and reactor temperature is adjusted to 70 DEG C, add vinyl fluoride (VF) to still pressure 5.0MPa, add 1.5g azo two cyclohexyl formonitrile HCN and 0.1g clorox starts polyreaction, keep still to be pressed in 5.0MPa, reaction adds VF monomer 1Kg altogether, react cooling in 12.5 hours, reclaim and be separated unreacted monomer and CCl
2fCC
2lF, obtains white powder resin, obtains PVF resin.
Obtained PVF resin test result is as follows: PVF intrinsic viscosity is that to record melt temperature be 180 DEG C for 0.85dl/g, DSC, and product chain regularity is 78.59%, thermal weight loss 1% temperature 376 DEG C.
Comparative example 1
For 5L polymeric kettle, first 3.0Kg pure water is put in polymeric kettle, inflated with nitrogen, vacuumize deoxygenation, in still, oxygen level≤20ppm is qualified, mixing speed is transferred to 400rpm/min, reactor temperature is adjusted to 70 DEG C, add vinyl fluoride (VF) to still pressure 15.0MPa, add 1.5g azo two cyclohexyl formonitrile HCN and 0.1g clorox starts polyreaction, keep still to be pressed in 15.0MPa, reaction adds VF monomer 1Kg altogether, react cooling in 15.5 hours, reclaim and be separated unreacted monomer, obtain white powder resin, obtain PVF resin.
Obtained PVF resin test result is as follows: PVF intrinsic viscosity is that to record melt temperature be 172 DEG C for 0.65dl/g, DSC, and product chain regularity is 77.12%, thermal weight loss 1% temperature 370 DEG C.
Under the different polymerization technique of table 1., resin property compares
| Numbering | Amylose regularity/% | Intrinsic viscosity/dl/g | Melt temperature/DEG C | Thermal weight loss 1% temperature/DEG C |
| Embodiment 1 | 80.65 | 1.10 | 195 | 385 |
| Embodiment 2 | 81.23 | 1.23 | 198 | 388 |
| Embodiment 3 | 79.83 | 1.20 | 192 | 382 |
| Embodiment 4 | 79.01 | 1.02 | 185 | 378 |
| Embodiment 5 | 78.59 | 0.85 | 180 | 376 |
| Comparative example 1 | 77.12 | 0.65 | 172 | 370 |
Claims (11)
1. a preparation method for high-amylose regularity fluorinated ethylene propylene, adopts fluoride monomers to be that raw material carries out polyreaction, it is characterized in that with water and is selected from C
nh
xcl
yf
zand/or C
mh
acl
bf
cbe combined as reaction medium, wherein: the integer of n=1 ~ 15, x, y and z are independently selected from the integer of 0 ~ 2n+2 and x+y+z=2n+2; The integer of m=1 ~ 15, a, b and c are independently selected from the integer of 0 ~ 2n and a+b+c=2n.
2. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 1, it is characterized in that the integer of described n=1 ~ 10, the integer of m=1 ~ 10.
3., according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 1, it is characterized in that described C
nh
xcl
yf
zbe selected from 1,2-dichloro tetrafluoro ethane, trichlorofluoromethane, 1,1,1-Refrigerant R 113,1,1,2-Refrigerant R 113, tetracol phenixin, 1,1,1,2 C2Cl4F2s, 1,1,2, one in 2-C2Cl4F2, pentachloro-fluoroethane and hexachloroethane, more than two or three combination, described C
mh
acl
bf
cbe selected from the one, two or three in chlorine seven fluorine tetramethylene, perfluoro-2-methyl cyclobutane and 1,2-dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane.
4. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 1, it is characterized in that described polyreaction is carried out in the presence of a free-radical initiator, the consumption of initiator is the 0.1 ~ 3wt ‰ of fluoride monomers.
5. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 4, it is characterized in that described radical initiator is azo compound and/or perfluor peroxidation compounds, described azo compound is selected from 2, 2-Diisopropyl azodicarboxylate, 2, 2-azo two-2, 4, 4-trimethylammonium valeronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), one in azo-bis-iso-dimethyl and azo two cyclohexyl formonitrile HCN, more than two or three combination, described perfluor peroxidation compounds is selected from perfluor peroxy dicarbonate diethyl ester, perfluor peroxidation two (2-positive propoxy) propionyl, one in perfluoroacyl peroxides and the perfluor oxa-ninth of the ten Heavenly Stems () acyl peroxide, more than two or three combination.
6. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 1, it is characterized in that described polyreaction is carried out under reaction promoter exists, reaction promoter is neutral inorganic compound or basic cpd, and the consumption of reaction promoter is 0.01% ~ 2.0wt% of fluoride monomers weight.
7. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 6, it is characterized in that the one, more than two or three that described inorganic salt compound is selected from potassium nitrite, Sodium Nitrite, calcium nitrite, potassium hypochlorite, clorox, potassium hypobromite and hypoiodous acid potassium combines, the one, more than two or three that described basic cpd is selected from ammoniacal liquor, sodium hydroxide, potassium hydroxide and calcium hydroxide combines.
8. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 1, it is characterized in that polymerization temperature-20 ~ 90 DEG C, reaction pressure 1.0 ~ 20.0MPa, 2 ~ 16 hours reaction times.
9. the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 1, it is characterized in that adding the second comonomer in the preparation of described polyfluoroethylene resin, polyvinyl fluoride copolymer is obtained by copolymerization with fluoride monomers, described second comonomer is selected from vinylidene, R 1216, five fluorine propylene, tetrafluoeopropene, trifluoro propene, perfluorobuttene, hexachlorobutadiene, hexafluoro-isobutene, trifluoro-ethylene, trifluorochloroethylene, one in perfluoroalkyl vinyl ether and tetrafluoroethylene, more than two or three combination, the mol ratio of described fluoride monomers and the second comonomer is 60/40 ~ 99.99/0.01.
10., according to the preparation method of the high-amylose regularity fluorinated ethylene propylene one of claim 1 to 9 Suo Shu, it is characterized in that the amylose regularity of described fluorinated ethylene propylene is more than 78%.
11. according to the preparation method of high-amylose regularity fluorinated ethylene propylene according to claim 10, it is characterized in that described fluorinated ethylene propylene for sun power backboard membrane, depart from film, decorating film or corrosion protection coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410554669.5A CN105504116A (en) | 2014-10-20 | 2014-10-20 | Preparation method of polyfluoroethylene resin with high chain regularity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410554669.5A CN105504116A (en) | 2014-10-20 | 2014-10-20 | Preparation method of polyfluoroethylene resin with high chain regularity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105504116A true CN105504116A (en) | 2016-04-20 |
Family
ID=55712459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410554669.5A Pending CN105504116A (en) | 2014-10-20 | 2014-10-20 | Preparation method of polyfluoroethylene resin with high chain regularity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105504116A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979847A (en) * | 2019-12-17 | 2021-06-18 | 浙江蓝天环保高科技股份有限公司 | Preparation method of polyvinyl fluoride resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834124A (en) * | 2006-04-17 | 2006-09-20 | 浙江蓝天环保高科技股份有限公司 | Prepn. of PVF |
| CN102807645A (en) * | 2012-08-27 | 2012-12-05 | 中昊晨光化工研究院有限公司 | Method for preparing low molecular weight polyvinylidene fluoride |
| CN103694395A (en) * | 2013-12-09 | 2014-04-02 | 中昊晨光化工研究院有限公司 | Vinylidene fluoride copolymer and preparation method thereof |
| CN103755851A (en) * | 2013-12-30 | 2014-04-30 | 山东华夏神舟新材料有限公司 | Soap-free emulsion polymerization method of polyvinylidene fluoride for lithium battery electrode binding agent |
-
2014
- 2014-10-20 CN CN201410554669.5A patent/CN105504116A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834124A (en) * | 2006-04-17 | 2006-09-20 | 浙江蓝天环保高科技股份有限公司 | Prepn. of PVF |
| CN102807645A (en) * | 2012-08-27 | 2012-12-05 | 中昊晨光化工研究院有限公司 | Method for preparing low molecular weight polyvinylidene fluoride |
| CN103694395A (en) * | 2013-12-09 | 2014-04-02 | 中昊晨光化工研究院有限公司 | Vinylidene fluoride copolymer and preparation method thereof |
| CN103755851A (en) * | 2013-12-30 | 2014-04-30 | 山东华夏神舟新材料有限公司 | Soap-free emulsion polymerization method of polyvinylidene fluoride for lithium battery electrode binding agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979847A (en) * | 2019-12-17 | 2021-06-18 | 浙江蓝天环保高科技股份有限公司 | Preparation method of polyvinyl fluoride resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10259899B2 (en) | Vinylidene fluoride / 2,3,3,3-tetrafluoropropene copolymers | |
| JP6212542B2 (en) | Controlled free radical copolymerization of trifluoroethylene. | |
| CN103694395B (en) | Vinylidene fluoride copolymers and preparation method thereof | |
| CN102558719B (en) | Low-temperature-resistant elastic body containing fluorine and preparation method thereof | |
| US9745398B2 (en) | Method of preparing fluoroelastomer capable of being vulcanized by using peroxide | |
| JP2010539295A5 (en) | ||
| CN105085753B (en) | Preparation method for polyvinylidene difluoride resin with high thermal stability and copolymer of polyvinylidene difluoride resin | |
| CN104558364B (en) | Fluoroelastomer and preparation method thereof | |
| WO2014099508A1 (en) | Improved synthesis of 2,3,3,3-tetrafluoropropene/vinylidene fluoride copolymers | |
| CN102516438B (en) | Method for preparing fluorine-containing rubber for automobile rubber pipe | |
| JP4883756B2 (en) | Radiation-crosslinked fluorine-containing copolymer | |
| CN105504116A (en) | Preparation method of polyfluoroethylene resin with high chain regularity | |
| JP6135084B2 (en) | Method for producing fluorine-containing block copolymer | |
| CN105246925B (en) | The manufacture method of fluoropolymer | |
| CN106380533A (en) | Polyvinylidene fluoride polymer and preparation method thereof | |
| CN109810212B (en) | High-dielectric-constant polyvinylidene fluoride and preparation method and application thereof | |
| JP2005529205A (en) | Process for producing perfluorosulfonate polymers containing sulfonyl functional groups | |
| JP2012241128A (en) | Method for producing fluoropolymer | |
| CN112830993B (en) | Soap-free preparation method of fluorine-containing polymer | |
| CN103304720B (en) | The preparation method of polyvinyl fluoride copolymer in supercritical carbon dioxide | |
| CN110760026B (en) | Synthesis method of tetrafluoroethylene-propylene rubber and tetrafluoroethylene-propylene rubber thereof | |
| CN104893189A (en) | Preparation method of enhanced polyvinylidene fluoride resin | |
| CN106432565A (en) | Anticorrosive polyfluoroethylene resin, and preparation method and application thereof | |
| CN102603953A (en) | Fluorinated ethylene propylene preparation method | |
| CN112979847A (en) | Preparation method of polyvinyl fluoride resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160420 |