CN103087251A - Copolymerization telomer preparation method - Google Patents
Copolymerization telomer preparation method Download PDFInfo
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- CN103087251A CN103087251A CN2011103352899A CN201110335289A CN103087251A CN 103087251 A CN103087251 A CN 103087251A CN 2011103352899 A CN2011103352899 A CN 2011103352899A CN 201110335289 A CN201110335289 A CN 201110335289A CN 103087251 A CN103087251 A CN 103087251A
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- vinyl ether
- perfluor sulfonyl
- telomer
- halogen
- trifluorochloroethylene
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a method for preparing a double halogen end capping chlorotrifluoroethene and perfluoro(sulfonyl vinyl)ether (a general formula of CF2=CF-(O-CF2-CF(CF3))m-O-(CF2)nSO2F), wherein m is 0-2, and n is 1-3) copolymerization telomer, wherein the method comprises a double halogen end capping chlorotrifluoroethene and perfluoro(sulfonyl vinyl)ether copolymerization telomer preparation step, and is characterized in that double halogen tetrafluoroethane is adopted as a telomerization agent to prepare chlorotrifluoroethene and a perfluoro(sulfonyl vinyl)ether monomer into a telomer precursor under an effect of an initiator, wherein a structure and a molecular weight of the telomer precursor meet requirements for preparing a fuel cell proton exchange membrane.
Description
Technical field
The present invention relates to the preparation method of two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer, the raw materials that the two halogen end-blocking trifluorochloroethylenes that make with the inventive method and perfluor sulfonyl base vinyl ether copolymerization telomer can be used for novel fluorine block fuel cell membranes.
Background technology
Along with the progress of social productive forces, the eco-friendly new forms of energy supply mode of development and utilization is one of hot issue of countries in the world research.Proton Exchange Membrane Fuel Cells (PEMFC) is that a kind of chemical energy that will be stored in fuel and oxygenant is directly changed into the device of electric energy by electrochemical reaction, have environmental friendliness and energy transformation ratio advantages of higher, make it to become rapidly the focus of world today's energy and field of traffic exploitation.Perfluorinated sulfonic acid type ion exchange resin (Poly (perfluorosulfonic acid), PFSA) main raw of preparation fuel cell membranes, the most representative is the Nafion of Du Pont film, it is the multipolymer of tetrafluoroethylene and perfluorinated sulfonic acid, have good chemical stability and physical strength, the advantages such as proton conductivity is high under high humidity, and ionic conduction resistance is little.The content that yet the Nafion film has, and cost is high, proton conductivity seriously relies on water in film, temperature rising can cause that conductivity descends, the easy deficiency such as poisoning of catalyzer.
Aspect the efficient proton exchange membrane of exploitation novel type, Canada Ballard company makes multipolymer with the trifluorostyrene and the trifluorostyrene copolymerization that replace, obtain the BAM3G film through sulfonation again, the principal feature of this film is to have low-down sulfonic group content, high current efficiency, and make the life-span of monocell bring up to 15000h, cost is also much lower than Nafion film and Dow film, more easily be accepted (Kikukawa and Sanui, Progress in polymer science, 2000,25:1463).But by the film that random copolymerization obtains often have again bad mechanical property, the problem such as proton conductivity is low and stability to hydrolysis is poor.
Fluorinated block copolymer possesses the distinctive chemical stability of fluoropolymer, thermotolerance, good hydrophobicity and good mechanical property, its thermotolerance can with the fine coupling of " fragrance " block, effectively improve the Integrated using performance of material; " fragrance " block of sulfonation provides good wetting ability, utilizes the proton exchange membrane of this based block copolymer preparation under low IEC condition, still has higher proton conduction efficient.
In order further to improve the proton conduction efficient of this proton exchange membrane; the present invention prepares two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer; as the telomer raw material for the synthesis of segmented copolymer; " fragrance " block except sulfonation can provide proton conductivity like this; perfluor sulfonyl base vinyl ether group in multipolymer also can provide proton conductivity, finally uses the fuel battery proton exchange film of the block polymer preparation of this structure to have more outstanding proton conductivity.
The telomer of two halogen end-blockings of fluorochemical monomer tetrafluoroethylene (TFE), trifluorochloroethylene (CTFE), vinylidene (VDF), R 1216 (HFP) is purposes chemical industry, the especially intermediate of medicine very widely, usually end group is bromine or iodine, both be easy under proper condition be transformed into functional end group, with this active site (Tortelli as chemical reaction, V.and Tonelli, C.J.Fluorine Chem., 47 (1990), 199-217 and US4808760).
For example, can remove end group by hydrolysis reaction and obtain the perfluor fat diacid, for the synthesis of fluorine-containing polyester material.For another example two halogen end-blocking telomers can and Addition on ethylene, dehydrohalogenation generates two olefin groups at the two ends of molecular chain again, for the synthesis of fluorinated block copolymer, improve heat-resisting or surface property (the Zhaobing Zhang of material, etc.Polymer 40 (1999) 1341-1345 and Yu Qiqing, organic fluorine industry, 1 (2002) 3-6).
Homopolymerization and the copolymerization telomerization method of above-mentioned simple fluorinated olefin monomers have report more, main initiating method has UV-light to cause (Dedek, V.Z.J.Fluorine Chem., 31 (1986), 363-379.), thermal initiation (Baum, K.J.Org.Chem., 59 (1994), 6804-6807), superoxide causes (US3818064) and redox initiator German Patent 3820934) several modes.Wherein the research of the TFE telomer of two iodine end-blockings the earliest.
For example, Bedford is at J.Org.Chem., and 45 (1980), 347-348. discloses and has utilized iodine and TFE monomer heat to telomerize to have prepared I (C2F4)
nI, wherein n=1～5.
Modena, S. at J.Fluorine Chem., 43 (1989), 15-25. middle employing ditertiary butyl peroxide causes, dibromotetrafluoroethane is telogen, has prepared the vinylidene telomer of two bromine end-blockings, and the method telomerizes temperature over 130 ℃, the telomer molecular weight is higher than 2000, and purity is relatively poor.
Manseri, A. be at J.Fluorine Chem., and 78 (1996), in 145-153., segmentation telomerizes the two iodine end-blocking copolymerization telomers that successfully prepared TFE, VDF and HFP.
Although prior art has been reported the preparation method of many two halogen end-blocking telomers about fluorinated olefin monomers; and the method has been carried out comparatively deep research; yet the preparation method about two halogen end-blocking telomers of fluoroolefin and fluorine ether monomer (especially two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer) but seldom has research, there are no document or patent report.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of preparation method of fluorine-containing copolymerization telomer of synthetic two halogen end-blockings, the two bromines that make in this way or the fluorine-containing telomer of two iodine end-blockings are connected with fragrant monomer fluorine-containing telomer by condensation polymerization or atom transfer living radical (ATRP) polymerization technique according to the mode of setting, prepare a series of structurally ordered, the segmented copolymer that molecular weight is controlled is with this block polymer fuel made battery proton exchange membrane.
Therefore, the invention provides a kind of method for preparing two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer, described perfluor sulfonyl base vinyl ether has following general formula:
CF
2＝CF-(O-CF
2-CF{CF
3})
m-O-(CF
2)
nSO
2F
Wherein, m=0～2,
n＝1～3，
Described method comprises the steps:
(a) the two halogen Tetrafluoroethanes of perfluor sulfonyl vinyl ether, radical initiator and telogen are added in reactor;
(b) pass into the trifluorochloroethylene monomer, simultaneously with temperature regulation to 70-150 ℃;
(c) regulate the add-on of trifluorochloroethylene in order to make pressure remain on 300-1500kPa;
(d) reacted 2-12 hour under this reaction conditions.
The inventive method uses two halogen Tetrafluoroethanes to make telogen, and the polymerization under the effect of initiator with trifluorochloroethylene and perfluor sulfonyl base vinyl ether monomers obtains the telomer precursor that structure and molecular weight satisfy the preparation fuel battery proton exchange film.
Embodiment
The method that the present invention prepares two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer comprises that (general formula is: CF with trifluorochloroethylene and perfluor sulfonyl base vinyl ether
2=CF-(O-CF
2-CF{CF
3)
m-O-(CF
2)
nSO
2F), m=0～2 wherein, n=1～3) be prepared as the copolymerization telomer of two halogen end-blockings by telomerization.As the perfluor sulfonyl vinyl ether of raw material, satisfy general formula CF in polymerization process of the present invention
2=CF-(O-CF
2-CF{CF
3)
m-O-(CF
2)
nSO
2F), m=0～2 wherein, n=1～3.In the present invention, trifluorochloroethylene and perfluor sulfonyl base vinyl ether monomers purity are greater than 99.9%.
In the preparation method of copolymerization telomer of the present invention, the add-on of perfluor sulfonyl vinyl ether and trifluorochloroethylene material is without particular limitation, and it can be the consumption of any routine known in the art.The add-on of perfluor sulfonyl vinyl ether and trifluorochloroethylene material depends primarily on the required performance of copolymerization telomer of the two halogen end-blockings that finally make.
In an example of the present invention, by weight, the add-on of described perfluor sulfonyl vinyl ether and trifluorochloroethylene material is 0.5-2: 1 to 1: 0.5-2, preferably 0.8-1.5: 1 to 1: 0.8-1.5, more preferably 0.9-1.1: 1 to 1: 0.9-1.1.
The present invention prepares in the method for two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer and uses two halogen Tetrafluoroethanes as telogen, and described pair of halogen Tetrafluoroethane can be pair tefluranes or two iodine Tetrafluoroethane.In 2 liters of polymerization reaction mixtures, the add-on of described pair of halogen Tetrafluoroethane is 150～700 milliliters, preferably 200～600 milliliters, and more preferably 300～450 milliliters.
In an example of the present invention, the purity of described telogen is greater than 98 % by weight, better greater than 98.5 % by weight, more preferably greater than 99 % by weight.
The present invention prepares the method for two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer and uses radical initiator; described radical initiator can be the polymerization starter of any routine for Raolical polymerizable known in the art, preferably organo-peroxide initiator system.The add-on of described initiator can be the consumption of any routine known in the art.In a better example of the present invention, the amount of this initiator is the 0.05-5 % by weight of perfluor sulfonyl vinyl ether monomers, preferably 0.1-1 % by weight.
In an example of the present invention, use radical initiator as polymerization starter, described radical initiator is selected from and is similar to FeCl
3/ Ni oxidation-reduction system, peroxy dicarbonate isopropyl ester (IPP), benzoyl peroxide (BPO), dimethyl formamide (AIBN) or di-t-butyl peroxide (DTBP).
Prepare in the method for two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer in the present invention, the proportioning of the polymerization temperature of employing, polymerization pressure and monomer is without particular limitation.Those of ordinary skill in the art can easily determine suitable reaction conditions according to the exchange capacity of final perfluor sulfonyl resin.At one preferably in example of the present invention, the polyreaction of described preparation perfluor sulfonyl resin is at 70-150 ℃, better at the temperature of 90-130 ℃, at 300-2000kPa, better carries out 2-12 hour better 3-10 hour under the pressure of 500-1200kPa.
In a better example of the present invention, the manufacture method of described perfluor sulfonyl resin comprises the steps:
(a) the two halogen Tetrafluoroethanes of perfluor sulfonyl vinyl ether, radical initiator and telogen are added in still;
(b) pass into the trifluorochloroethylene monomer, simultaneously with temperature regulation to 70-150 ℃;
(c) regulate the add-on of trifluorochloroethylene in order to make pressure remain on 300-1500kPa;
(d) reacted 2-12 hour under this reaction conditions.
The two halogen end-blocking trifluorochloroethylenes that make with the inventive method and the number-average molecular weight of perfluor sulfonyl base vinyl ether copolymerization telomer resin are 1000～10000, better 1200～3000.
Further illustrate the present invention below in conjunction with embodiment.
Embodiment
In the following embodiments, use the performance of the fluoropolymer resin that following determination of test method makes:
1. number-average molecular weight
The present invention adopts number-average molecular weight to characterize the molecular-weight average of resin, and number-average molecular weight: measure with gel permeation chromatography GPC, solvent is tetrahydrofuran (THF) (THF);
2. multipolymer forms
The present invention adopts
19In F NMR measure and calculation resin, the product copolymerization forms;
Embodiment 1
Room temperature adds 350mL dibromotetrafluoroethane and 300mL perfluor sulfonyl vinyl ether CF in the 2L stainless steel cauldron
2=CF-O-CF
2-CF (CF
3)-O-(CF
2)
2SO
2F (PSVE) and 10g benzoyl peroxide.With replacing with CTFE again after nitrogen replacement, then pass into the CTFE pressurization, be warming up to 90 ℃, pressure regulation makes pressure CTFE remain on 1000kPa, reacts cooling after 5 hours, the exhaust discharging.The mixture that obtains uses sherwood oil to precipitate, remove the telogen dibromotetrafluoroethane, then product is dissolved in acetone, and precipitation is 2 times in sherwood oil, 40 ℃ of vacuum-drying 24h after suction filtration.
With the performance of the described powdery resin of determination of test method recited above, the resin number-average molecular weight that result obtains is 2500, trifluorochloroethylene in polymkeric substance: PSVE=22.4: 8.2.
Embodiment 2
Room temperature adds 350mL dibromotetrafluoroethane and 300mL perfluor sulfonyl vinyl ether CF in the 2L stainless steel cauldron
2=CF-O-CF
2-CF (CF
3)-O-(CF
2)
2SO
2F (PSVE) and 10g benzoyl peroxide.With replacing with CTFE again after nitrogen replacement, then pass into the CTFE pressurization, be warming up to 90 ℃, pressure regulation makes pressure CTFE remain on 800kPa, reacts cooling after 5 hours, the exhaust discharging.The mixture that obtains uses sherwood oil to precipitate, remove the telogen dibromotetrafluoroethane, then product is dissolved in acetone, and precipitation is 2 times in sherwood oil, 40 ℃ of vacuum-drying 24h after suction filtration.
With the performance of the described powdery resin of determination of test method recited above, the resin number-average molecular weight that result obtains is 1800, trifluorochloroethylene in polymkeric substance: perfluor sulfonyl vinyl ether (PSVE)=13.5: 6.75.
Embodiment 3
Room temperature adds 550mL dibromotetrafluoroethane and 200mL perfluor sulfonyl vinyl ether CF in the 2L stainless steel cauldron
2=CF-O-CF
2-CF (CF
3)-O-(CF
2)
2SO
2F (PSVE) and 15g ditertiary butyl peroxide (DTBP).With replacing with CTFE again after nitrogen replacement, then pass into the CTFE pressurization, be warming up to 120 ℃, pressure regulation makes pressure CTFE remain on 700kPa, reacts cooling after 12 hours, the exhaust discharging.The mixture that obtains uses sherwood oil to precipitate, remove telogen dibromotetrafluoroethane and ether monomer, then product is dissolved in acetone, and precipitation is 2 times in sherwood oil, 40 ℃ of vacuum-drying 24h after suction filtration.
With the performance of the described powdery resin of determination of test method recited above, the resin number-average molecular weight that result obtains is 2800, trifluorochloroethylene in polymkeric substance: perfluor sulfonyl vinyl ether (PSVE)=14.8: 4.35.
Embodiment 4
Room temperature adds 250mL dibromotetrafluoroethane, 200mL perfluor sulfonyl vinyl ether (PSVE) and 400ml acetonitrile as solvent in the 2L stainless steel cauldron, the 20g nickel powder, and the 2.5g iron trichloride is as telomerizing catalyzer.With replacing with CTFE again after nitrogen replacement, then pass into the CTFE pressurization, be warming up to 112 ℃, pressure regulation makes pressure CTFE remain on 1000kPa, reacts cooling after 7.5 hours, the exhaust discharging.At first the mixture that obtains removes by filter solid-phase catalyst, then uses sherwood oil to precipitate, remove telogen and solvent, then product is dissolved in acetone, and precipitation is 2 times in sherwood oil, 40 ℃ of vacuum-drying 24h after suction filtration.
With the performance of the described powdery resin of determination of test method recited above, the resin number-average molecular weight that result obtains is 1600, trifluorochloroethylene in polymkeric substance: perfluor sulfonyl vinyl ether (PSVE)=23.7: 3.5.
Embodiment 5
Room temperature adds 250mL dibromotetrafluoroethane, 200mL perfluor sulfonyl vinyl ether (PSVE) and 400ml acetonitrile as solvent in the 2L stainless steel cauldron, the 20g nickel powder, and the 7.5g iron trichloride is as telomerizing catalyzer.With replacing with CTFE again after nitrogen replacement, then pass into the CTFE pressurization, be warming up to 112 ℃, pressure regulation makes pressure CTFE remain on 1000kPa, reacts cooling after 7.5 hours, the exhaust discharging.At first the mixture that obtains removes by filter solid-phase catalyst, then uses sherwood oil to precipitate, remove telogen and solvent, then product is dissolved in acetone, and precipitation is 2 times in sherwood oil, 40 ℃ of vacuum-drying 24h after suction filtration.
With the performance of the described powdery resin of determination of test method recited above, the resin number-average molecular weight that result obtains is 1200, trifluorochloroethylene in polymkeric substance: perfluor sulfonyl vinyl ether (PSVE)=18.7: 3.7.
Embodiment 6
Room temperature adds 700g diiodo-Tetrafluoroethane I (C in the 2L stainless steel cauldron
2F
4) I, 300mL perfluor sulfonyl vinyl ether (PSVE) and 20g copper powder be as telomerizing catalyzer.With replacing with CTFE again after nitrogen replacement, then pass into the CTFE pressurization, be warming up to 100 ℃, pressure regulation makes pressure CTFE remain on 700kPa, reacts cooling after 7.5 hours, the exhaust discharging.At first the mixture that obtains removes by filter solid-phase catalyst, then uses sherwood oil to precipitate, remove telogen and solvent, then product is dissolved in acetone, and precipitation is 2 times in sherwood oil, 40 ℃ of vacuum-drying 24h after suction filtration.
With the performance of the described powdery resin of determination of test method recited above, the resin number-average molecular weight that result obtains is 2200, trifluorochloroethylene in polymkeric substance: perfluor sulfonyl vinyl ether (PSVE)=16.1: 3.0.
The present invention utilizes condensation polymerization or atom transfer living radical (ATRP) polymerization technique that fluorine-containing telomer is connected according to the mode of setting with fragrant monomer, obtains the fluorine-containing copolymerization telomer of two halogen end-blockings.That the two bromines that make in this way or the fluorine-containing telomer of two iodine end-blockings have advantages of is structurally ordered, molecular weight is controlled, therefore, especially is fit to make fuel battery proton exchange film.
Claims (10)
1. the preparation method of two halogen end-blocking trifluorochloroethylenes and perfluor sulfonyl base vinyl ether copolymerization telomer, described perfluor sulfonyl base vinyl ether has following general formula:
CF
2＝CF-(O-CF
2-CF{CF
3})
m-O-(CF
2)
nSO
2F)
Wherein
m＝0～2，
n＝1～3；
Described method comprises the steps:
(a) the two halogen Tetrafluoroethanes of perfluor sulfonyl vinyl ether, radical initiator and telogen are added in still;
(b) pass into the trifluorochloroethylene monomer, simultaneously with temperature regulation to 70-150 ℃;
(c) regulate the add-on of trifluorochloroethylene in order to make pressure remain on 300-1500kPa;
(d) reacted 2-12 hour under this reaction conditions.
2. the method for claim 1, is characterized in that described pair of halogen Tetrafluoroethane is selected from dibromotetrafluoroethane or diiodo-Tetrafluoroethane.
3. the method for claim 1, is characterized in that, in 2L trifluorochloroethylene and perfluor sulfonyl base vinyl ether polymerization reaction mixture, the add-on of described pair of halogen Tetrafluoroethane is 150～700 milliliters.
4. method as claimed in claim 3, is characterized in that the add-on of described pair of halogen Tetrafluoroethane is 200～600 milliliters in 2L trifluorochloroethylene and perfluor sulfonyl base vinyl ether polymerization reaction mixture.
5. method as claimed in claim 4, is characterized in that in 2L trifluorochloroethylene and perfluor sulfonyl base vinyl ether polymerization reaction mixture, and the add-on of described pair of halogen Tetrafluoroethane is for being 300～500 milliliters.
6. the method for claim 1 is characterized in that it also uses the free radical initiator system as polymerization starter, and the add-on of described polymerization starter is the 0.05-5 % by weight of perfluor sulfonyl vinyl ether monomers.
7. method as claimed in claim 6, the add-on that it is characterized in that described polymerization starter is the 0.1-1 % by weight of perfluor sulfonyl vinyl ether monomers.
8. method as claimed in claim 6, is characterized in that described free radical type initiator is selected from FeCl
3/ Ni oxidation-reduction system, copper powder metal-powder, peroxy dicarbonate isopropyl ester (IPP), benzoyl peroxide (BPO), dimethyl formamide (AIBN) or di-t-butyl peroxide (DTBP).
9. the method for claim 1, is characterized in that it is to carry out 3-10 hour under the pressure at the temperature of 90-120 ℃, at 500-1200kPa.
10. the method for claim 1, is characterized in that the number-average molecular weight of described pair of halogen end-blocking trifluorochloroethylene and perfluor sulfonyl base vinyl ether copolymerization telomer resin is 1000～10000, better 1200～3000.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246925A (en) * | 2013-05-27 | 2016-01-13 | 大金工业株式会社 | Fluoropolymer production method |
| WO2018192368A1 (en) * | 2017-04-18 | 2018-10-25 | 浙江汉丞科技有限公司 | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
-
2011
- 2011-10-28 CN CN2011103352899A patent/CN103087251A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246925A (en) * | 2013-05-27 | 2016-01-13 | 大金工业株式会社 | Fluoropolymer production method |
| CN105246925B (en) * | 2013-05-27 | 2017-08-25 | 大金工业株式会社 | The manufacture method of fluoropolymer |
| WO2018192368A1 (en) * | 2017-04-18 | 2018-10-25 | 浙江汉丞科技有限公司 | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
| GB2575951A (en) * | 2017-04-18 | 2020-01-29 | Zhejiang Hyproof Tech Co Ltd | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same |
| US11136424B2 (en) | 2017-04-18 | 2021-10-05 | Zhejiang Hyproof Technology Co., Ltd. | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor |
| GB2575951B (en) * | 2017-04-18 | 2022-07-13 | Zhejiang Hyproof Tech Co Ltd | Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same |
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Application publication date: 20130508 |