CN102382323A - Method for enhancing alkaline corrosion resistance of polyvinylidene fluoride - Google Patents
Method for enhancing alkaline corrosion resistance of polyvinylidene fluoride Download PDFInfo
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Abstract
The invention discloses a method for enhancing the alkaline corrosion resistance of polyvinylidene fluoride. By forming a layer of perfluoroalkylated amphiphilic molecules capable of resisting the attack of alkali on the surface of the polyvinylidene fluoride, the method realizes the purpose of enhancing the alkaline corrosion resistance of the polyvinylidene fluoride product. The method for enhancing the alkaline corrosion resistance of the polyvinylidene fluoride includes the following steps: the solution blending method is adopted to blend the perfluoroalkylated amphiphilic molecules and polyvinylidene fluoride solution, and after drying, a film is formed.
Description
Technical field
The present invention relates to a kind of method that improves the pvdf erosion resistance, more specifically to a kind of method that improves pvdf alkali corrosion resistance property.
Technical background
Pvdf is a kind of hemicrystalline, partially fluorinated polymkeric substance; It has not only inherited (per) fluoropolymer excellent thermostability, anti-oxidant and radiation resistance, also possesses certain chemical stability, outstanding mechanical property, dielectric properties, good processing properties and good solubility ability in polar solvent simultaneously.Above-mentioned excellent comprehensive performance makes pvdf become important polyalcohol stephanoporate membrane prepare material.In the preparation technology of polyvinylidene fluoride porous film, like thermally induced phase separation or immersion precipitation, need to add N, dinethylformamide, N-Methyl pyrrolidone isopolarity solvent promote the pvdf dissolving.After the film forming because crystalline structure, the percent crystallinity of polyvinylidene fluoride material changes and factor such as dissolvent residual; Make the alkali corrosion resistance ability drop of pvdf; The cleansing power of alkaline solution such as anti-sodium hydroxide is not enough in actual use to have caused polyvinylidene fluoride porous film, causes that easily the jaundice variable color of polyvinylidene fluoride film surface, degraded are aging.
Different with (per) fluoropolymer, the pvdf molecular chain contains not by the substituted β carbon of fluorine, and the hydrogen on the β carbon is because receive the influence of the electrophilic inductive effect of fluorine atom to have positive polarity, and the E2 that under the effect of alkali or nucleophilic reagent, removes HF easily eliminates reaction.In addition, N that maybe be remaining in the pvdf product, dinethylformamide, N-Methyl pyrrolidone equal solvent decompose under highly basic easily, and its degradation production amine is the nucleophilic reagent stronger than hydroxide radical nucleophilie nucleus ability, has more aggravated this defluorinating and degrading complete reaction.(Polymer such as Ross; 41; 1685-1689,2000) adopt methods analysts such as XPS, ToF-SIMS NaOH handle the chemical constitution of back polyvinylidene fluoride surface, think that polyvinylidene fluoride surface had formed the polyene hydrocarbon structure before this under the elimination effect of alkali; Then under attack hydroxy, continue defluorinate, produced structures such as oxygen containing enol, ketenes.Utilize the defluorinating and degrading complete reaction of this alkali of polyvinylidene fluoride surface just, realized the hydrophilic modifying (chemical industry progress, 23,480-485,2004) of polyvinylidene fluoride surface.Shen Juan etc. (chemical journal, 63,1187-1192,2005) adopt the ESR method also to detect the existence of radical at the polyvinylidene fluoride surface of alkaline purification, and on this basis polyvinylidene fluoride surface have been done the polystyrene graft modification.
Because the limitation of pvdf chemical structure; Caused the corrosion of alkali such as the not anti-sodium hydroxide of pvdf, amine or nucleophilic reagent; Limited the use of solution method pvdf product under severe rugged environment; Therefore be necessary polyvinylidene fluoride material is carried out modification, improve the alkali corrosion resistance performance of pvdf.
Summary of the invention
The present invention is directed to the not problem of alkali corrosion resistance of polyvinylidene fluoride material surface; A kind of method that improves pvdf product alkali corrosion resistance property has been proposed; This method realizes improving the purpose of pvdf product alkali corrosion resistance performance through form the perfluoroalkyl amphipathic molecule that one deck can alkaline-resisting attack at polyvinylidene fluoride surface.
The present invention realizes through following technical scheme:
The method of raising pvdf alkali corrosion resistance property of the present invention the steps include: to adopt solution blended process that the perfluoroalkyl amphipathic molecule is mixed with pvdf solution, then drying and forming-film.Because polar perfluoroalkyl amphipathic molecule is compatible with the pvdf part; The perfluoroalkyl amphipathic molecule moves to polyvinylidene fluoride surface under phase separation; Its perfluoroalkyl moieties and pvdf consistency are good and combine with surperficial pvdf molecular chain, and its negatively charged ion or non-ionic polar end and pvdf consistency are bad and at surface enrichment.Because fluoridized alkyl structure has excellent alkali corrosion resistance performance; The amphipathic molecule anionic polar end of surface enrichment is because electrical charge rejection can stop the attack of hydroxide radical anion or nucleophilic reagent again, and perfluoroalkyl amphipathic molecule surface enrichment layer has realized improving the purpose of polyvinylidene fluoride surface alkali corrosion resistance property.
The method of raising pvdf alkali corrosion resistance property of the present invention, its further technical scheme is: taking by weighing quality is the perfluoroalkyl amphipathic molecule of pvdf raw material 2%～5%, dissolves in pvdf solution, dry back film forming.
The method of raising pvdf alkali corrosion resistance property of the present invention, its technical scheme further are that described perfluoroalkyl amphipathic molecule is perfluoro octyl sulfonic acid salt, perfluoro capryl carboxylate salt, perfluorinated sulfonic resin or perfluoroalkyl nonionogenic tenside; Wherein said perfluoro octyl sulfonic acid salt is preferably perfluoro octyl sulfonic acid amine, perfluoro octyl sulfonic acid sodium or perfluoro octyl sulfonic acid potassium; Described perfluoro capryl carboxylate salt is preferably perfluoro capryl carboxylic acid amine, perfluoro capryl carboxylic acid sodium or perfluoro capryl carboxylic acid potassium; Described perfluorinated sulfonic resin is the PFSA perfluorinated sulfonic resin that Donggue Shenzhou New Material Co., Ltd., Shandong produces, and described perfluoroalkyl nonionogenic tenside is the non-ion fluorin carbon surface active agent of FC-4430 for the model that 3M company produces.
The method of raising pvdf alkali corrosion resistance property of the present invention; Its technical scheme further is that solvent for use is N in the described pvdf solution; Dinethylformamide (DMF), DMAC N,N (DMAc), N-Methyl pyrrolidone (NMP), methyl-sulphoxide (DMSO) or pimelinketone.Because of solvents most behind the drying and forming-film is removed; Solvent load does not exert an influence to the alkali corrosion resistance performance of pvdf sample, for the used quantity of solvent of handled easily pvdf solution is generally the 30%～70% better of pvdf solution quality.
Method of the present invention in addition also is adapted to the polyvinylidene fluoride porous film for thermally induced phase separation or immersion precipitation preparation fully.
The present invention has following beneficial effect:
1) adopt solution blended process that a spot of perfluoroalkyl amphipathic molecule is mixed with pvdf solution; Pvdf product for adopting the solution process preparation need not increase extra technological process; Such as the thermally induced phase separation or the immersion precipitation preparation technology of polyvinylidene fluoride porous film, so modified technique is very simple.
2) for the pvdf product of high added value, such as polyvinylidene fluoride porous film, add a spot of perfluoroalkyl amphipathic molecule, cost increases not obvious.
3) polar perfluoroalkyl amphipathic molecule nature under phase separation moves and enrichment to polyvinylidene fluoride surface; Need not can form on the top layer of pvdf product through special processing the alkali corrosion resistance blocking layer of perfluoroalkyl amphipathic molecule, modified effect is remarkable.
4) the perfluoroalkyl amphipathic molecule of surface enrichment makes the hydrophobicity of pvdf product surface improve, and hydrophilicity improves.
Embodiment
Below further specify the present invention through embodiment:
Embodiment 1
1) takes by weighing pvdf quality 10 grams, perfluoro octyl sulfonic acid amine quality 0.2 gram, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 2
1) takes by weighing pvdf quality 10 grams, perfluoro octyl sulfonic acid sodium quality 0.5 gram, DMF quality 4.5 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 3
1) takes by weighing pvdf quality 10 grams, perfluoro octyl sulfonic acid amine quality 0.3 gram, NMP quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the KOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 4
1) takes by weighing pvdf quality 10 grams, perfluoro octyl sulfonic acid potassium quality 0.5 gram, pimelinketone quality 24.5 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 5
1) takes by weighing pvdf quality 10 grams, perfluoro octyl sulfonic acid amine quality 0.5 gram, DMF quality 6.5 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the ethylamine solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 6
1) takes by weighing pvdf quality 10 grams, perfluoro octyl sulfonic acid sodium quality 0.5 gram, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the diethylamine aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 7
1) takes by weighing pvdf quality 10 grams, perfluorinated sulfonic resin PFSA quality 0.2 gram, DMF quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 8
1) takes by weighing pvdf quality 10 grams, perfluorinated sulfonic resin PFSA quality 0.5 gram, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 9
1) takes by weighing pvdf quality 10 grams, perfluorinated sulfonic resin PFSA quality 0.3 gram, DMAc quality 4.5 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 10
1) takes by weighing pvdf quality 10 grams, perfluorinated sulfonic resin PFSA quality 0.5 gram, DMSO quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 11
1) takes by weighing pvdf quality 10 grams, perfluorinated sulfonic resin PFSA quality 0.5 gram, DMF quality 7 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the ethylamine solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 12
1) takes by weighing pvdf quality 10 grams, perfluorinated sulfonic resin PFSA quality 0.5 gram, DMF quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the diethylamine aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 13
1) takes by weighing pvdf quality 10 grams, perfluoro capryl carboxylic acid amine quality 0.3 gram, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 14
1) takes by weighing pvdf quality 10 grams, perfluoro capryl carboxylic acid sodium quality 0.5 gram, DMF quality 24.5 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the KOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 15
1) takes by weighing pvdf quality 10 grams, perfluoro capryl carboxylic acid amine quality 0.2 gram, pimelinketone quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 16
1) takes by weighing pvdf quality 10 grams, perfluoro capryl carboxylic acid potassium quality 0.5 gram, DMSO quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the ethylamine solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 17
1) takes by weighing pvdf quality 10 grams, perfluoroalkyl nonionogenic tenside FC-4430 quality 0.3 gram, DMF quality 6 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the KOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 18
1) takes by weighing pvdf quality 10 grams, perfluoroalkyl nonionogenic tenside FC-4430 quality 0.5 gram, DMF quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 19
1) takes by weighing pvdf quality 10 grams, perfluoroalkyl nonionogenic tenside FC-4430 quality 0.5 gram, DMAc quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Embodiment 20
1) takes by weighing pvdf quality 10 grams, perfluoroalkyl nonionogenic tenside FC-4430 quality 0.5 gram, DMSO quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the diethylamine aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 1
Take by weighing pvdf quality 10 gram, DMF quality 10 grams, preparation solution, dry back film forming is used the color on color difference meter analytic sample surface then, and the result sees table 1.
Comparative Examples 2
1) takes by weighing pvdf quality 10 grams, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 3
1) takes by weighing pvdf quality 10 grams, pimelinketone quality 23 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the KOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 4
1) takes by weighing pvdf quality 10 grams, DMSO quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 5
1) takes by weighing pvdf quality 10 grams, DMF quality 6.5 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the ethylamine solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 6
1) takes by weighing pvdf quality 10 grams, sodium laurylsulfonate AS quality 0.5 gram, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 7
1) takes by weighing pvdf quality 10 grams, X 2073 AS quality 0.5 gram, DMF quality 10 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 8
1) takes by weighing pvdf quality 10 grams, stearyl alcohol polyglycol ether (AEO-8) nonionogenic tenside quality 0.5 gram, DMF quality 15 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Comparative Examples 9
1) takes by weighing pvdf quality 10 grams, cetyl trimethylammonium bromide cats product quality 0.5 gram, DMF quality 24 grams, preparation solution, dry back film forming;
2) the pvdf sample being inserted temperature is that 80 ℃, concentration are corrosion 10 hours in the NaOH aqueous solution of 1mol/L, takes out the pvdf sample, and with washed with de-ionized water and dry, with the surperficial colour-change of color difference meter analytic sample, the result sees table 1.
Table 1
Can find out that from table 1 compound with perfluoroalkyl amphipathic molecule structure all can improve the alkali corrosion resistance performance of pvdf sample surfaces effectively, be good with the modified effect of perfluoroalkyl anionic compound especially wherein.Common alkyl anionic compound (like sodium laurylsulfonate and X 2073) is also helpful to the alkali corrosion resistance property of improving the pvdf sample surfaces; But effect is not as the modified effect of perfluoroalkyl anionic compound, and the modified effect of common alkyl nonionogenic tenside stearyl alcohol polyglycol ether (AEO-8) is more not obvious.The cats product cetyl trimethylammonium bromide has then played the effect of phase-transfer catalyst, has aggravated the corrosion of alkali to polyvinylidene fluoride surface.Above result shows that the perfluoroalkyl structure of properties-correcting agent or its anionic property are the principal elements that improves polyvinylidene fluoride surface alkali corrosion resistance property.
Claims (4)
1. a method that improves pvdf alkali corrosion resistance property is characterized in that step is following: adopt solution blended process that the perfluoroalkyl amphipathic molecule is mixed with pvdf solution, then drying and forming-film.
2. the method for raising pvdf alkali corrosion resistance property according to claim 1; It is characterized in that may further comprise the steps: taking by weighing quality is the perfluoroalkyl amphipathic molecule of pvdf raw material 2%～5%; Dissolve in pvdf solution, dry back film forming.
3. the method for raising pvdf alkali corrosion resistance property according to claim 1 and 2 is characterized in that described perfluoroalkyl amphipathic molecule is perfluoro octyl sulfonic acid salt, perfluoro capryl carboxylate salt, perfluorinated sulfonic resin or perfluoroalkyl nonionogenic tenside.
4. the method for raising pvdf alkali corrosion resistance property according to claim 1 and 2; Its characteristic solvent for use in described pvdf solution is N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, methyl-sulphoxide or pimelinketone.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484639A (en) * | 2020-05-20 | 2020-08-04 | 四川大学 | Method for modifying alkali-resistant PVDF (polyvinylidene fluoride) material |
| EP3858871A1 (en) * | 2017-03-31 | 2021-08-04 | Daikin Industries, Ltd. | Composition comprising a fluoropolymer |
| CN114076779A (en) * | 2020-08-14 | 2022-02-22 | 浙江蓝天环保高科技股份有限公司 | Alkali resistance test method of vinylidene fluoride polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101108313A (en) * | 2007-04-28 | 2008-01-23 | 浙江大学 | Method of amphipathic nature fluorine-contained copolymer modifying surface of polytetrafluoroethylene porous membrane |
| CN101837251A (en) * | 2010-04-07 | 2010-09-22 | 南京工业大学 | Method for hydrophilic modification on polyvinylidene fluoride porous film surface by amphipathic molecule |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101108313A (en) * | 2007-04-28 | 2008-01-23 | 浙江大学 | Method of amphipathic nature fluorine-contained copolymer modifying surface of polytetrafluoroethylene porous membrane |
| CN101837251A (en) * | 2010-04-07 | 2010-09-22 | 南京工业大学 | Method for hydrophilic modification on polyvinylidene fluoride porous film surface by amphipathic molecule |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3858871A1 (en) * | 2017-03-31 | 2021-08-04 | Daikin Industries, Ltd. | Composition comprising a fluoropolymer |
| US11279814B2 (en) | 2017-03-31 | 2022-03-22 | Daikin Industries, Ltd. | Production method for fluoropolymer, surfactant for polymerization, and use of surfactant |
| CN111484639A (en) * | 2020-05-20 | 2020-08-04 | 四川大学 | Method for modifying alkali-resistant PVDF (polyvinylidene fluoride) material |
| CN111484639B (en) * | 2020-05-20 | 2021-08-17 | 四川大学 | Method for modifying alkali-resistant PVDF (polyvinylidene fluoride) material |
| CN114076779A (en) * | 2020-08-14 | 2022-02-22 | 浙江蓝天环保高科技股份有限公司 | Alkali resistance test method of vinylidene fluoride polymer |
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Application publication date: 20120321 |