CN101177464A - Method for preparing thermal-stable vinylidenefluoride homopolymer or copolymer - Google Patents
Method for preparing thermal-stable vinylidenefluoride homopolymer or copolymer Download PDFInfo
- Publication number
- CN101177464A CN101177464A CNA2007100709412A CN200710070941A CN101177464A CN 101177464 A CN101177464 A CN 101177464A CN A2007100709412 A CNA2007100709412 A CN A2007100709412A CN 200710070941 A CN200710070941 A CN 200710070941A CN 101177464 A CN101177464 A CN 101177464A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- vinylidenefluoride
- vinylidene fluoride
- stable
- add
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing thermostable vinylidene fluoride polymer, comprising following steps: 5.0 to 7.0Kg deionized water, 10.0 to 15.0g entilre fuorine caprylate and 0.5 to 5.0g rare-earth compounds are added in 10.0 litre polymerizing-kettle; vinylidene fluoride monomer or fluorine-containing comonomer are added as well, so as to maintain the pressure at 2.5 to 4.0 MPa; when the temperature of the reaction kettle is increased up to 70 to 90 DEG C, 0.5 to 1.0g persulfate is added to start polymerization reaction; the temperature is decreased to the ambient temperature when the reaction is finished, polyvinylidene fluorine dispersion liquid is obtained, and polyvinylidene resin with rare-earth compounds is obtained through condensating, washing and drying. The invention conducts polymerization using vinylidene fluoride (VDF) or fluorine-containing comonomer in the presence of persulfate initiator; wherein, rare-earth compounds are added in at the beginning, during or random time after the VDF polymerization. The obtained PVDF resin has high thermal stability.
Description
Technical field
The present invention relates to the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer or multipolymer
Background technology
As everyone knows, based on vinylidene fluoride CF
2=CH
2(VDF) monomeric homopolymerization or modification by copolymerization resin (PVDF), has excellent mechanical stability, good unreactiveness, ageing resistance, be applied at numerous areas, as be applied to make chemical industry or electronic industry injection moulding, extrude or moulded parts, and be used for preparing the coating of building field or film etc.
Atofina and some Japanese firms are commercialization of production polyvinylidene fluoride resin all.
Patent US4025709 discloses VDF at the Potassium Persulphate initiator, the polymerization process under sodium acetate and dispersion agent exist, and wherein dispersion agent can be Sodium perfluorooctanoate or the Rf-C with general formula
2H
4=SO
3M, M represents basic metal or ammonium in the formula.Gained PVDF is the latex form, needs just can make PVDF by centrifugation or oven drying.
Patent EP169328 disclose a kind of in the presence of tensio-active agent, initiator and trichlorofluoromethane or Virahol the method for polymerization VDF, back two kinds of compounds have alleviated the yellow variable color of this PVDF in melting process largely as chain-transfer agent.
In order to improve its thermostability, can be with salt in PVDF.Patent FR1298572 discloses the PVDF that comprises barium salt or strontium salt.Patent US6843948 (US6512032) adopts phosphorous acid ester, phenolic compound, the compound thermo-stabilizer of doing of polyester plasticizer.
Patent US5929152 discloses by adding bismuth salt, and as succinate, acrylate, terephthalate or their mixture are to improve the thermostability of PVDF.This stablizer is all effective to the stable and variable color of the polymkeric substance of initial polymer and process hot-work recovery.
JP62018457 (JP62084138) discloses interpolation dioctyl tin maleate or hexanodioic acid calcium or sebacic acid calcium as stablizer.
It is initiator that patent US3728303 discloses with persulphate, subsequently with sodium-chlor, and Repone K, sodium chlorate, Potcrate adds among the PVDF, and satisfactory stability is arranged.
Have now found that polyvinylidene fluoride resin (PVDF) can obtain the PVDF of high thermal stability by adding rare earth compound as stablizer, and the rare earth compound wide material sources, and is cheap.
Summary of the invention
Purpose of the present invention provides the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer or multipolymer.The preparation method of a kind of thermal-stable vinylidenefluoride homopolymer or multipolymer: add 5.0～7.0Kg deionized water in 10.0 liters of polymerization reaction kettles, 10.0～15.0g perfluorooctanoic acid salt, 0.5～5.0g rare earth compound, charge into interpolymerized vinylidene fluoride monomer or fluorine-containing comonomer to still internal pressure again and maintain 2.5～4.0MPa, when reactor is warmed up to 70～90 ℃, add 0.5～1.0g persulphate and begin polyreaction, after finishing, reaction reduces to room temperature, obtain the poly(vinylidene fluoride) dispersion liquid, again through cohesion, washing, drying obtains containing the polyvinylidene fluoride resin of rare earth compound.
15 lanthanon that described rare earth compound comprises ordination number from 57 to 71 are main single and compound mixture at interior rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt.
The rare earth compound add-on is contained poly(vinylidene fluoride) dried resin total amount 0.01%～1.0%, and preferable amount is 0.05～0.5%.
The preparation method of another kind of thermal-stable vinylidenefluoride homopolymer or multipolymer: add 5.0～7.0Kg deionized water in 10.0 liters of polymerization reaction kettles, 10.0～15.0g perfluorooctanoic acid salt, charge into interpolymerized vinylidene fluoride monomer or fluorine-containing comonomer to still internal pressure again and maintain 3.0～4.0MPa, when reactor is warmed up to 70～90 ℃, add 0.5～1.0g persulphate and begin polyreaction, after finishing, reaction reduces to room temperature, obtain the poly(vinylidene fluoride) dispersion liquid, in dispersion liquid, add 0.5～5.0g rare earth compound, again through cohesion, washing, drying obtains containing the polyvinylidene fluoride resin of rare earth compound.
15 lanthanon that described rare earth compound comprises ordination number from 57 to 71 are main single and compound mixture at interior rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt.
The rare earth compound add-on is contained poly(vinylidene fluoride) dried resin total amount 0.01%～1.0%, and preferable amount is 0.05～0.5%.
The preparation method of another kind of thermal-stable vinylidenefluoride homopolymer or multipolymer: poly(vinylidene fluoride) dispersion liquid, after cohesion, separation, drying, obtain powder, in the poly(vinylidene fluoride) powder, add rare earth compound, uniform mixing under 500～3000 rev/mins of rotating speeds obtains containing the polyvinylidene fluoride resin of rare earth compound.
15 lanthanon that described rare earth compound comprises ordination number from 57 to 71 are main single and compound mixture at interior rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt.
9. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 7 or multipolymer, it is characterized in that described rare earth compound add-on is contained poly(vinylidene fluoride) dried resin total amount 0.01%～2.0%, preferable amount is 0.1～1.0%.
Advantage of the present invention
The thermostability of the polyvinylidene fluoride resin (PVDF) of interpolation rare earth compound stablizer is very good.The PVDF that contains a certain amount of rare earth compound can improve the heat-resistant stability of resin.But as pvdf membrane sheet original color and luster of the maintenance of long period still under 260 ℃.And do not add the pvdf membrane sheet of rare earth compound, have yellowing metachromatism in various degree.When the rare earth compound add-on less than 0.01% the time, because of the less heat stabilization of addition not obvious; Add-on can produce certain influence greater than 2.0% o'clock to other performance of PVDF.The rare earth compound preferable amount is 0.05～0.5% of a polyvinylidene fluoride resin total amount.
Embodiment
A kind of method for preparing the thermal-stable vinylidenefluoride polymkeric substance.This method is utilized vinylidene fluoride (VDF) or is reached optional fluorine-containing comonomer, in the presence of persulfate initiator and chain-transfer agent, dispersion agent and paraffin stablizer, and polymerization in aqueous dispersions; The PVDF aqueous dispersions that obtains obtains the PVDF resin after centrifugal cohesion, drying.Wherein, begin in the VDF polymerization, between polymerization period or optional polyreaction in the PVDF powder, add rare earth compound after finishing.
The present invention adopts in the aqueous polymerization medium of batchwise polymerization technology in the presence of a kind of dispersion agent and paraffin, wherein also comprises chain-transfer agent, initiator and adds the method that rare earth compound prepares heat-staple PVDF.The vinyl comonomer that can carry out free radical or ionic copolyreaction with it is a fluorochemical monomer, if any vinyl fluoride, and trifluoro-ethylene (TRFE), chloro trifluoro-ethylene (CTFE), 1,2-difluoroethylene, tetrafluoroethylene (TFE), hexafluoroethylene (HFP), perfluorobutyl ethylene (PFBE), and perfluoroalkyl vinyl ether are if any perfluoro methyl vinyl ether (PEVE), perfluoroethylvinyl ether (PMVE), perfluoro propyl vinyl ether (PPVE).More than can be simultaneously with a kind of or some kinds of monomers.With regard to the PVDF multipolymer, the monomeric ratio of VDF and copolymerization is 70%-99% weight/30%-1% weight, and preferred proportion is 80%-90% weight/20%-10% weight.
Described initiator is water-soluble or oil-soluble initiator.The preferred persulphate of water soluble starter, as ammonium persulphate, Sodium Persulfate or Potassium Persulphate.Oil-soluble initiator is a hydrocarbon peroxides, as selects ditertiary butyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate diethyl ester, di-isopropyl superoxide or benzoyl peroxide for use.
Described dispersion agent is an ionogenic surfactant, can be dispersed in monomer in the water and make its easier polymerization, and be ZCnF as general formula
2The fluoride ion tensio-active agent of nCOOM, wherein Z is the fluorine or chlorine atom, and n is 6 to 13 integer, and M is hydrogen atom or alkali metal atom or ammonium or the ammonium that at least one low alkyl group replacement is arranged.
Described rare earth thermal stabilizer comprises 15 lanthanon of ordination number from 57 to 71 at the interior single and compound mixture based on rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt, as rare-earth stearate, fatty acid rare earth, carboxylicesters rare earth, toxilic acid monoester rare earth.Rare earth thermal stabilizer begins at the VDF monomer polymerization, polymerization process or reaction add in the PVDF powder after finishing, and add-on is used fluorine resin total amount 0.01%～1.0%, and preferable amount is 0.05～0.5%.
The present invention realizes in the following manner:
1. in polymeric kettle, add entry, dispersion agent and optional paraffin.Then, polymeric kettle vacuumizes for several times repeatedly, inflated with nitrogen to be to get rid of oxygen.
2. polymeric kettle is warming up to design temperature, feeds VDF monomer or optional fluorine-containing comonomer to required pressure.
3. whole disposable adding rare-earth stabilizers, chain-transfer agent and initiator begin initiated polymerization, or introduce a part when polymerization begins, and divide several times or add remainder continuously between polymerization period.
4. the reduction of reaction pressure can compensate by adding VDF monomer or fluorine-containing comonomer in the polymerization process, and the monomer add-on finishes reaction after reaching preset value, reclaims residual monomer in the reactor, obtains the PVDF aqueous dispersions.
5. the PVDF aqueous dispersions obtains the PVDF powder through separation, drying.
6. with the dry part PVDF powder that does not add stablizer, add rare earth compound, pre-mixing is 1～3 minute under 500～1500 rev/mins of rotating speeds; Then, Preblend is all added in remaining PVDF powder under 2500～3000 rev/mins of rotating speeds uniform mixing 5～10 minutes, obtain containing the PVDF resin of rare earth compound.
Assess thermal stability: the PVDF powder is by vulcanizing press compression moulding 5min under 230 ℃ and 5MPa, and cooling makes the sheet material of a 100mm * 100mm * 4mm in 25 ℃ of water then.260 ℃ of following reheat 15 minutes to 1 hour, the sheet material after this thermal treatment more or less was colored with baking oven for this sheet material.The painted of sheet material estimated sheet material variable color degree with visual colorimetry under ordinary ray, appearance luster is divided into 5 ranks respectively and characterizes from a (white) to e (yellow).
Below will the present invention be described in further detail by specific embodiment (polymerization reactor 10.0L reactor).
Embodiment 1
In reactor, add following material: 5.0 liters of deoxidation deionized waters, 3.0g paraffin, 10g perfluoro ammonium caprylate solution, 0.5g rare-earth stearate compound.Be warmed up to 70 ℃ after the reactor exhaust deoxygenation, charge into the VDF monomer to 3.0MPa, add the 15.0g weight concentration again and be 5% ammonium persulfate solution, polyreaction begins.Keep reaction pressure by continuing to add the VDF monomer.After amounting to adding 1.75KgVDF, lower the temperature, and reaction pressure is reduced to below the 0.5MPa, remove residual monomer.The dispersion liquid that obtains is through isolating paraffin, and cohesion, washing are with the removal tensio-active agent, and drying is 6 hours under 110 ℃, obtains the PVDF resin that 1.55Kg contains rare-earth stabilizer.
Embodiment 2
In reactor, add following material: 7.0 liters of deoxidation deionized waters, 3.0g paraffin, 15g perfluoro ammonium caprylate solution, 3.5g rare-earth stearate compound.Be warmed up to 85 ℃ after the reactor exhaust deoxygenation, charge into the VDF monomer to 4.0MPa, add the 20.0g weight concentration again and be 5% ammonium persulfate solution, polyreaction begins.Keep reaction pressure by continuing to add the VDF monomer.After amounting to adding 1.5KgVDF, lower the temperature, remove residual monomer.The dispersion liquid that obtains is through isolating paraffin, and cohesion, washing are with the removal tensio-active agent, and drying is 6 hours under 110 ℃, obtains the PVDF resin that 1.35Kg contains rare-earth stabilizer.
Embodiment 3
With example 2, what added is the rare-earth stearate compound, add-on 5.0g.
Above-mentioned gained PVDF resin powder is hot pressed into sheet material under 230 ℃.This sheet material sees Table 1 with the thermostability experimental result of baking oven under 260 ℃.
Embodiment 4
In reactor, add following material: 6.0 liters of deoxidation deionized waters, 5.0g paraffin, 12g perfluoro ammonium caprylate solution.Be warmed up to 88 ℃ after the reactor exhaust deoxygenation, add the 20.0g weight concentration when introducing the VDF monomer and be 5% ammonium persulfate solution and begin polyreaction to 4.0MPa.After amounting to adding 2.2KgVDF, lower the temperature, and reaction pressure is reduced to below the 0.5MPa, remove residual monomer.In the dispersion liquid that obtains, add 0.5g carboxylicesters rare earth compound, and, obtain containing the PVDF resin of carboxylicesters rare earth compound through cohesion, washing, drying.
Embodiment 5
With example 4, to add the carboxylicesters rare earth compound be 3.0g.
Embodiment 6
With example 4, to add the carboxylicesters rare earth compound be 5.0g.
Above-mentioned gained PVDF resin powder is hot pressed into sheet material under 230 ℃.This sheet material sees Table 1 with the thermostability experimental result of baking oven under 260 ℃.
Embodiment 7
Press the PVDF aqueous dispersions of embodiment 3 gained, after agglomeration separation, drying, obtain powder 2.0Kg.Get above-mentioned PVDF powder 0.1Kg, join in the high speed kneader, add rare-earth stearate compound 0.4g simultaneously, 500 rev/mins of pre-mixings 2 minutes; Then, in Preblend, add all the other 1.90Kg PVDF powders,, obtain containing the PVDF resin of 0.02% weight rare-earth stearate compound 3000 rev/mins of following high-speed mixing 5 minutes.
Embodiment 8
Press embodiment 7 methods, the amount of the rare-earth stearate compound that different is adds is 2.0g.
Embodiment 9
Press embodiment 7 methods, the amount of the rare-earth stearate compound that different is adds is 7.0g.
Embodiment 10
Getting PVDF powder 2.0Kg joins in the high speed kneader, start and be stirred to 100 rev/mins of rotating speeds, slowly add carboxylicesters rare earth compound 2.0g again, treat that all adding the back stirred 1 minute in advance under 500～1000 rev/mins of rotating speeds, then rotating speed is brought up to 3000 rev/mins of high-speed mixing 5 minutes, obtained containing the PVDF resin of 0.1% weight carboxylic acid ester rare earth compound.
Embodiment 11
Press embodiment 10 methods, the amount of the carboxylicesters rare earth compound that different is adds is 10.0g.
Embodiment 12
Press embodiment 10 methods, the amount of the carboxylicesters rare earth compound that different is adds is 20.0g.
Comparative Examples a-c:
Comparative Examples a does not add any stablizer, and what Comparative Examples b added is the agent of sebacic acid calcium stable, and what Comparative Examples c added is the Potcrate stablizer.
The heat stability test of embodiment 7-12PVDF resin the results are shown in Table 2.
Table 1
| Embodiment | Rare earth compound | Adition process | Thermostability | ||
| Title | Consumption g | 260℃，30min | 260℃，45min， | ||
| 1 | Rare-earth stearate | 0.5 | Before the polymerization | B | D |
| 2 | Rare-earth stearate | 3.5 | Before the polymerization | A | B |
| 3 | Rare-earth stearate | 5.0 | Before the polymerization | A | C |
| 4 | The carboxylicesters rare earth | 0.5 | In the dispersion liquid | B | D |
| 5 | The carboxylicesters rare earth | 3.0 | In the dispersion liquid | A | B |
| 6 | The carboxylicesters rare earth | 5.0 | In the dispersion liquid | A | C |
| Comparative Examples a | Do not add | -- | -- | D | E |
Annotate: A-is white, and B-is whiter, the little Huang of C-, and D-is yellowish, the E-yellow
Table 2
| Embodiment | Rare earth compound | Thermostability | ||||
| Title | Adition process | Content % | 260℃， 30min | 260℃， 45min | 260℃， 1h | |
| 7 | Rare-earth stearate | Powder is sneaked into | 0.02 | |||
| 8 | Rare-earth stearate | Powder is sneaked into | 0.10 | A | B-C | E |
| 9 | Rare-earth stearate | Powder is sneaked into | 0.35 | A | B | D |
| 10 | The carboxylicesters rare earth | Powder is sneaked into | 0.1 | A | B-C | E |
| 11 | The carboxylicesters rare earth | Powder is sneaked into | 0.50 | A | B | D |
| 12 | The carboxylicesters rare earth | Powder is sneaked into | 1.0 | A | B-C | D |
| Comparative Examples a | Do not add | -- | -- | D | E | E |
| Comparative Examples b | Sebacic acid calcium | Powder is sneaked into | 0.25 | B | D-C | E |
| Comparative Examples c | Potcrate | Powder is sneaked into | 0.25 | C | D | E |
Annotate: A is white, and B-is whiter, the little Huang of C-, and D-is yellowish, the E-yellow
Claims (9)
1. the preparation method of thermal-stable vinylidenefluoride homopolymer or multipolymer, it is characterized in that adding 5.0～7.0Kg deionized water in 10.0 liters of polymerization reaction kettles, 10.0～15.0g perfluorooctanoic acid salt, 0.5～5.0g rare earth compound, charge into interpolymerized vinylidene fluoride monomer or fluorine-containing comonomer to still internal pressure again and maintain 2.5～4.0MPa, when reactor is warmed up to 70～90 ℃, add 0.5～1.0g persulphate and begin polyreaction, after finishing, reaction reduces to room temperature, obtain the poly(vinylidene fluoride) dispersion liquid, again through cohesion, washing, drying obtains containing the polyvinylidene fluoride resin of rare earth compound.
2. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 1 or multipolymer is characterized in that 15 lanthanon that described rare earth compound comprises ordination number from 57 to 71 are main single and compound mixture at interior rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt.
3. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 1 or multipolymer, it is characterized in that described rare earth compound add-on is contained poly(vinylidene fluoride) dried resin total amount 0.01%～1.0%, preferable amount is 0.05～0.5%.
4. the preparation method of thermal-stable vinylidenefluoride homopolymer or multipolymer, it is characterized in that adding 5.0～7.0Kg deionized water in 10.0 liters of polymerization reaction kettles, 10.0～15.0g perfluorooctanoic acid salt, charge into interpolymerized vinylidene fluoride monomer or fluorine-containing comonomer to still internal pressure again and maintain 3.0～4.0MPa, when reactor is warmed up to 70～90 ℃, add 0.5～1.0g persulphate and begin polyreaction, after finishing, reaction reduces to room temperature, obtain the poly(vinylidene fluoride) dispersion liquid, in dispersion liquid, add 0.5～5.0g rare earth compound, again through cohesion, washing, drying obtains containing the polyvinylidene fluoride resin of rare earth compound.
5. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 4 or multipolymer is characterized in that 15 lanthanon that described rare earth compound comprises ordination number from 57 to 71 are main single and compound mixture at interior rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt.
6. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 4 or multipolymer, it is characterized in that described rare earth compound add-on is contained poly(vinylidene fluoride) dried resin total amount 0.01%～1.0%, preferable amount is 0.05～0.5%.
7. the preparation method of thermal-stable vinylidenefluoride homopolymer or multipolymer, it is characterized in that not poly(vinylidene fluoride) dispersion liquid, after cohesion, separation, drying, obtain powder, in the poly(vinylidene fluoride) powder, add rare earth compound, uniform mixing under 500～3000 rev/mins of rotating speeds obtains containing the polyvinylidene fluoride resin of rare earth compound.
8. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 7 or multipolymer is characterized in that 15 lanthanon that described rare earth compound comprises ordination number from 57 to 71 are main single and compound mixture at interior rare earth oxide, oxyhydroxide, halogenide and rare earth organic monoacid salt.
9. the preparation method of a kind of thermal-stable vinylidenefluoride homopolymer according to claim 7 or multipolymer, it is characterized in that described rare earth compound add-on is contained poly(vinylidene fluoride) dried resin total amount 0.01%～2.0%, preferable amount is 0.1～1.0%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100709412A CN101177464A (en) | 2007-08-21 | 2007-08-21 | Method for preparing thermal-stable vinylidenefluoride homopolymer or copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100709412A CN101177464A (en) | 2007-08-21 | 2007-08-21 | Method for preparing thermal-stable vinylidenefluoride homopolymer or copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101177464A true CN101177464A (en) | 2008-05-14 |
Family
ID=39403902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100709412A Pending CN101177464A (en) | 2007-08-21 | 2007-08-21 | Method for preparing thermal-stable vinylidenefluoride homopolymer or copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101177464A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744859A (en) * | 2013-12-30 | 2015-07-01 | 江苏昊华光伏科技有限公司 | Solar backboard membrane |
| CN109065811A (en) * | 2018-08-20 | 2018-12-21 | 湖南烁普新材料有限公司 | Aqueous PVDF coating diaphragm and its preparation method and application |
-
2007
- 2007-08-21 CN CNA2007100709412A patent/CN101177464A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744859A (en) * | 2013-12-30 | 2015-07-01 | 江苏昊华光伏科技有限公司 | Solar backboard membrane |
| CN109065811A (en) * | 2018-08-20 | 2018-12-21 | 湖南烁普新材料有限公司 | Aqueous PVDF coating diaphragm and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2054474B1 (en) | Ultra-high molecular weight poly(vinylidene fluoride) | |
| US9388257B2 (en) | Azide-containing fluoropolymers and their preparation | |
| CN102336854B (en) | Preparation method for high heat resistance polyvinylidene fluoride | |
| CN105924554B (en) | A kind of preparation method of polyvinylidene fluoride resin | |
| CN103739756B (en) | A kind of polyvinylidene fluoride polymer preparation method improving heat stability | |
| CN103588922A (en) | Vinylidene fluoride copolymer, and preparation method and application thereof | |
| CN104926979A (en) | Ethylene/tetrafluoroethylene copolymer powder and method for preparing same | |
| CN101195669B (en) | Method for producing partial fluorine ethylene polymer | |
| US7863384B2 (en) | Fluoropolymers having improved whiteness | |
| CN115677936A (en) | Preparation method of perfluoropolymer emulsion, perfluoroelastomer and preparation method of perfluoroelastomer | |
| CN101177464A (en) | Method for preparing thermal-stable vinylidenefluoride homopolymer or copolymer | |
| CN104558363A (en) | Method for preparing fluorine-containing copolymer used for water treatment film | |
| CN103665238A (en) | Synthesis method of fluororubber with wide molecular weight distribution | |
| CN103755850B (en) | A kind of preparation method of the polyvinylidene fluoride resin for sun power backboard membrane | |
| JP2003165802A (en) | Method for producing fluorine-containing copolymer | |
| CN106715484B (en) | Product for synthesizing the method for the stabilization of polymers of chlorotrifluoroethylene and being manufactured using this quasi polymer | |
| CN103524647A (en) | Method for preparing polyvinylidene fluoride resin | |
| CN110627942B (en) | Fluorine-containing thermoplastic elastomer, preparation method and application thereof | |
| KR101550954B1 (en) | Method of preparing polyvinyl chloride resin | |
| JPH07292033A (en) | Peroxide-curable fluororubber without containing curing-site monomer | |
| US20010021756A1 (en) | Process for preparing fluoropolymer | |
| KR101366953B1 (en) | A Method for producing vinyl chloride based polymer | |
| CN101186662B (en) | Initiator for ultra-low Mooney fluororubber production and polymerization, and preparation method thereof | |
| CN108003265B (en) | Method for improving solubility of polyvinylidene fluoride resin | |
| KR20190046326A (en) | preparation method for Vinyl chloride polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080514 |