This paper reported the oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins under mild conditions without any additives. The results showed that the cobalt(II)(5,10,15,20-tetrakis(pentafluorophenyl))p...This paper reported the oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins under mild conditions without any additives. The results showed that the cobalt(II)(5,10,15,20-tetrakis(pentafluorophenyl))porphyrin was the best catalyst among the fluorinated metalloporphyrins. The conversion of ethylbenzene reached 38.6%, the selectivity to acetophenone reached 94.0%, and the turnover number is 2719 under the optimal conditions.展开更多
This minireview describes the strategies for synthesis of fluorinated surfactants potentially non- bioaccumulable. Various strategies have been focused on （Ⅰ） reducing the length of the perfluorocarbon chain, （Ⅱ...This minireview describes the strategies for synthesis of fluorinated surfactants potentially non- bioaccumulable. Various strategies have been focused on （Ⅰ） reducing the length of the perfluorocarbon chain, （Ⅱ） introducing hereto atoms into the fluorocarbon chain, （Ⅲ） introducing branch （herein and after branch means the fluoro-carbon chain section is not straight）. In most cases, the surface tensions versus the surfactant concentrations have been assessed. These above strategies led to various highly fluorinated （perfluorinated or not perfluorinated） surfactants whose chemical changes enabled to obtain novel alternatives to perfluorooctanoic acid （PFOA） and perfluorooctane sulphonate （PFOS）.展开更多
Ethyl-(2,2,2-trifluoroethyl)carbonate(ETFEC)is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4(LNMO).Our results show that the self-discharge behavior and the high temperature cycle...Ethyl-(2,2,2-trifluoroethyl)carbonate(ETFEC)is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4(LNMO).Our results show that the self-discharge behavior and the high temperature cycle performance can be significantly improved by the addition of 10%ETFEC into the normal carbonate electrolytes,e.g.,the capacity retention improved from 65.3%to 77.1%after 200 cycles at 60℃.The main reason can be ascribed to the high stability of ETFEC which prevents large oxidation of the electrolyte on the cathode surface.In addition,we also explore the feasibility of electrolytes using single fluoriated-solvents with and without additives.Our results show that the cycle performance of LNMO material can be greatly improved in 1 MLiPF6+pure ETFEC-solvent system with 2 wt%ethylene carbonate(EC)or ethylene sulfate(DTD).The capacity retention of the LNMO materials is 93%after 300 cycles,even better than that of carbonate-based electrolytes.It is shown that the additives are oxidized on the surface of LNMO particles and contribute to the formation of cathode/electrolyte interphase(CEI)films.This composite CEI film plays a crucial role in suppressing the serious decomposition of the electrolyte at high voltage.展开更多
A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late(PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization(ATRP).The ...A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late(PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization(ATRP).The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement,X-ray photoelectron spectroscopy(XPS),sum frequency generation(SFG) vibrational spectroscopy,surface tension and dynamic laser light scattering(DLS).It was found that with increasing PFMA block length,water and oil repellency de-creased,the ratio of F/C increased with increasing film depth,and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased.When the number of PFMA block units reached 10,PMMA segments were detected at the copolymer surface,which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface,which in turn affects surface structure formation during solution solidification.The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.展开更多
A new unsymmetrical and noncoplanar diamine containing trifluoromethyl and trimethyl groups, 1,4-bis（4- amino-2-trifluoromethylphenoxy）-2,3,5-trimethylbenzene （2）, was synthesized using 2,3,5-trimethylhydroquinone...A new unsymmetrical and noncoplanar diamine containing trifluoromethyl and trimethyl groups, 1,4-bis（4- amino-2-trifluoromethylphenoxy）-2,3,5-trimethylbenzene （2）, was synthesized using 2,3,5-trimethylhydroquinone and 2-chloro-5-nitrobenzotrifluoride as starting materials. A series of fluorinated poly（ether imide）s （PEIs） （4a-4d） were prepared from diamine 2 with four aromatic dianhydrides via a one-step high-temperature polycondensation procedure. The obtained PEIs were readily soluble in most organic solvents and could be solution-cast into flexible and strong films. The resulting thin films exhibited light color and good optical transparency with a cutoff wave- length of 356--376 nm. They also displayed good thermal stability with glass transition temperatures （Tg） above 281℃, 10% weight loss temperatures in the range of 482--486 ~C, and the weight residue more than 55% at 800℃ in nitrogen. Moreover, they revealed low dielectric constants （2.77-2.93 at 1 MHz） and low moisture absorp- tions （0.41%-0.57%）.展开更多
A new aromatic diamine containing trifluoromethyl and methyl groups, namely a,a-bis（4-amino-3-methylphetayl）-4-（trifluoromethyl）phenylmethane （1）, was synthesized from 2-methylaniline and 4-（trifluoromethyl）- ...A new aromatic diamine containing trifluoromethyl and methyl groups, namely a,a-bis（4-amino-3-methylphetayl）-4-（trifluoromethyl）phenylmethane （1）, was synthesized from 2-methylaniline and 4-（trifluoromethyl）- benzaldehyde. A series of fluorinated polyimides （PIs） were prepared from the diamine with four commercially available aromatic tetracarboxylic dianhydrides using a one-step high-temperature polycondensation procedure. These obtained PIs showed excellent solubility, with the dissolvability at a concentration of 10 wt% in most solvents, and they could afford flexible and strong films. Thin films of these PIs exhibited high optical transparency and light color, with the cutoff wavelength at 324-357 nm and transmittance higher than 74% at 450 nm. Moreover, these Pls possessed eminent thermal stability and good mechanical properties.展开更多
Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering ...Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter. Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail. Results show that the particle size of the latex has the minimum value knd the zeta potential of the latex is increased when the amount of DMDAAC is increased. In addition, the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%. However, the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%. The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%. Nevertheless, the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 2.5%.展开更多
New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carb...New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu<sup>3+</sup> ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.展开更多
Pyrazole carboxamide derivatives represent an important class of fungicides in agrochemicals. To find more novel structural pyrazole carboxamides, a novel series of 3-（trifluoromethyl）-lH-pyrazole-4-carboxamide comp...Pyrazole carboxamide derivatives represent an important class of fungicides in agrochemicals. To find more novel structural pyrazole carboxamides, a novel series of 3-（trifluoromethyl）-lH-pyrazole-4-carboxamide compounds were prepared from ethyl 4,4,4-trifluoroace- toacetate and triethyl orthoformate as starting materials. All the products were characterized by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance （NMR）, 13C NMR, 19F NMR and mass spectrography. The bioassay results showed these fluorine-containing pyrazole carboxamides have a weak fungicidal activity but some of them exhibit a good nematocidal activity against M. incognita.展开更多
文摘This paper reported the oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins under mild conditions without any additives. The results showed that the cobalt(II)(5,10,15,20-tetrakis(pentafluorophenyl))porphyrin was the best catalyst among the fluorinated metalloporphyrins. The conversion of ethylbenzene reached 38.6%, the selectivity to acetophenone reached 94.0%, and the turnover number is 2719 under the optimal conditions.
基金supported by the National Natural Science Foundation of China(No.21102167)the Science and Technology Commission of Shanghai Municipality(No.12DZ1930902)Shanghai Green Chemical Engineering Technology Research Center and the Knowledge Innovation Program of the Chinese Academy of Sciences
文摘This minireview describes the strategies for synthesis of fluorinated surfactants potentially non- bioaccumulable. Various strategies have been focused on （Ⅰ） reducing the length of the perfluorocarbon chain, （Ⅱ） introducing hereto atoms into the fluorocarbon chain, （Ⅲ） introducing branch （herein and after branch means the fluoro-carbon chain section is not straight）. In most cases, the surface tensions versus the surfactant concentrations have been assessed. These above strategies led to various highly fluorinated （perfluorinated or not perfluorinated） surfactants whose chemical changes enabled to obtain novel alternatives to perfluorooctanoic acid （PFOA） and perfluorooctane sulphonate （PFOS）.
基金financially supported by National Key Research and Development Program of China(Grant no.2018YFB010440)the National Natural Science Foundation of China(Grant nos.21761132030,21621091).
文摘Ethyl-(2,2,2-trifluoroethyl)carbonate(ETFEC)is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4(LNMO).Our results show that the self-discharge behavior and the high temperature cycle performance can be significantly improved by the addition of 10%ETFEC into the normal carbonate electrolytes,e.g.,the capacity retention improved from 65.3%to 77.1%after 200 cycles at 60℃.The main reason can be ascribed to the high stability of ETFEC which prevents large oxidation of the electrolyte on the cathode surface.In addition,we also explore the feasibility of electrolytes using single fluoriated-solvents with and without additives.Our results show that the cycle performance of LNMO material can be greatly improved in 1 MLiPF6+pure ETFEC-solvent system with 2 wt%ethylene carbonate(EC)or ethylene sulfate(DTD).The capacity retention of the LNMO materials is 93%after 300 cycles,even better than that of carbonate-based electrolytes.It is shown that the additives are oxidized on the surface of LNMO particles and contribute to the formation of cathode/electrolyte interphase(CEI)films.This composite CEI film plays a crucial role in suppressing the serious decomposition of the electrolyte at high voltage.
基金Supported by the National Natural Science Foundation of China(Grant Nos. 50573069 and 20704038)Program for Changjiang Scholars and Innovative Research Team in University (Grant No.IRT 0654)
文摘A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late(PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization(ATRP).The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement,X-ray photoelectron spectroscopy(XPS),sum frequency generation(SFG) vibrational spectroscopy,surface tension and dynamic laser light scattering(DLS).It was found that with increasing PFMA block length,water and oil repellency de-creased,the ratio of F/C increased with increasing film depth,and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased.When the number of PFMA block units reached 10,PMMA segments were detected at the copolymer surface,which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface,which in turn affects surface structure formation during solution solidification.The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.
基金This work was supported by the National Natural Science Foundation of China （No. 51103016）, the Natural Science Foundation of Jiangsu Province （No. BK2011232 and BK2011241）, the Grant-in-aid for Youth Innovation Fundation of Changzhou University （No. ZMFll020017 and ZMFl102037）, and the Open- ing Project of State Key Laboratory for Modification of Chemical Fibers and Polymer Materials （No. LK1001）.
文摘A new unsymmetrical and noncoplanar diamine containing trifluoromethyl and trimethyl groups, 1,4-bis（4- amino-2-trifluoromethylphenoxy）-2,3,5-trimethylbenzene （2）, was synthesized using 2,3,5-trimethylhydroquinone and 2-chloro-5-nitrobenzotrifluoride as starting materials. A series of fluorinated poly（ether imide）s （PEIs） （4a-4d） were prepared from diamine 2 with four aromatic dianhydrides via a one-step high-temperature polycondensation procedure. The obtained PEIs were readily soluble in most organic solvents and could be solution-cast into flexible and strong films. The resulting thin films exhibited light color and good optical transparency with a cutoff wave- length of 356--376 nm. They also displayed good thermal stability with glass transition temperatures （Tg） above 281℃, 10% weight loss temperatures in the range of 482--486 ~C, and the weight residue more than 55% at 800℃ in nitrogen. Moreover, they revealed low dielectric constants （2.77-2.93 at 1 MHz） and low moisture absorp- tions （0.41%-0.57%）.
基金Acknowledgement This word was supported by the National Natural Science Foundation of China （No. 51103016）, Natural Science Foundation of Jiangsu Province （Nos. BK2011232 and BK2011241）, the Grant-in-aid for Youth Innovation Fundation of Changzhou University （Nos. ZMF 11020017 and ZMF 1102037）, and the Opening Project of State Key Laboratory for Modification of Chemical Fibers and Polymer Materials （No. LK1001）.
文摘A new aromatic diamine containing trifluoromethyl and methyl groups, namely a,a-bis（4-amino-3-methylphetayl）-4-（trifluoromethyl）phenylmethane （1）, was synthesized from 2-methylaniline and 4-（trifluoromethyl）- benzaldehyde. A series of fluorinated polyimides （PIs） were prepared from the diamine with four commercially available aromatic tetracarboxylic dianhydrides using a one-step high-temperature polycondensation procedure. These obtained PIs showed excellent solubility, with the dissolvability at a concentration of 10 wt% in most solvents, and they could afford flexible and strong films. Thin films of these PIs exhibited high optical transparency and light color, with the cutoff wavelength at 324-357 nm and transmittance higher than 74% at 450 nm. Moreover, these Pls possessed eminent thermal stability and good mechanical properties.
基金supported by the Science and Technology Department of Zhejiang Province under Grant No. 2010C31040the financial support of Zhejiang Provincial Natural Science Foundation of China(No. Y4100152)Zhejiang University of Technology Natural Science Foundation(No.20100202)
文摘Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter. Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail. Results show that the particle size of the latex has the minimum value knd the zeta potential of the latex is increased when the amount of DMDAAC is increased. In addition, the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%. However, the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%. The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%. Nevertheless, the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 2.5%.
文摘New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu<sup>3+</sup> ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.
文摘Pyrazole carboxamide derivatives represent an important class of fungicides in agrochemicals. To find more novel structural pyrazole carboxamides, a novel series of 3-（trifluoromethyl）-lH-pyrazole-4-carboxamide compounds were prepared from ethyl 4,4,4-trifluoroace- toacetate and triethyl orthoformate as starting materials. All the products were characterized by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance （NMR）, 13C NMR, 19F NMR and mass spectrography. The bioassay results showed these fluorine-containing pyrazole carboxamides have a weak fungicidal activity but some of them exhibit a good nematocidal activity against M. incognita.
