Recent results for synthesis of conjugated polymers, poly(arylene vinylene)s exemplified as poly(fluorene vinylene)s and poly(phenylene vinylene)s, by acyclic diene metathesis (ADMET) polymerization have been introduc...Recent results for synthesis of conjugated polymers, poly(arylene vinylene)s exemplified as poly(fluorene vinylene)s and poly(phenylene vinylene)s, by acyclic diene metathesis (ADMET) polymerization have been introduced. The methods using molybdenum and ruthenium catalysts afforded defect-free, high molecular weight polymers with all trans olefinic double bonds, and significant reduction of by-products (halogen, sulfur etc.) in addition of decrease of structurally defects have been attained. The methods also demonstrated precise synthesis of end-functionalized polymers that showed unique optical properties combined with the end groups. Catalytic one-pot syntheses of end-functionalized poly(9,9-dialkylfluorene-2,7-vinylene)s have been attained by both ruthenium (by chain-transfer) and molybdenum catalysts and the method should provide more green route for synthesis of conjugated materials with better device performance.展开更多
Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate （BTMC） with poly （vinyl pyrrolidone） （PVP） was successfully synthesized using immobilized porcine pancreas lipase （IPPL） or SnOct2 as catalyst. Hydrox...Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate （BTMC） with poly （vinyl pyrrolidone） （PVP） was successfully synthesized using immobilized porcine pancreas lipase （IPPL） or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a rnacroinitiator. The resulting copolymers were characterized by GPC, ^1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio （[B]/[P]） resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn. Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.展开更多
4-(3-(4-(Dimethylamino)phenyl)acryloyl)phenyl-2-bromo-2-methylpropanoate(APPBr)was used for the heterogeneous atom transfer radical polymerization(ATRP)of styrene(St)with copper(I)bromide/N,N,N',N",N"-pe...4-(3-(4-(Dimethylamino)phenyl)acryloyl)phenyl-2-bromo-2-methylpropanoate(APPBr)was used for the heterogeneous atom transfer radical polymerization(ATRP)of styrene(St)with copper(I)bromide/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)catalytic system.The functional end group was characterized via UV-Vis and ^(1)H NMR spectra.The polymerization showed a first-order kinetic characteristic and each of the obtained polymers had well-controlled molecular weight and relatively low polydispersity index(PDI).Furthermore,the obtained end-functionalized polystyrene(PS)in solution showed strong green-light emission which is further affected by mixing different metal cations.In particular,the fluorescent intensity of the polymer was decreased in the presence of Ag^(+),Cu^(2+)and Fe^(3+).展开更多
文摘Recent results for synthesis of conjugated polymers, poly(arylene vinylene)s exemplified as poly(fluorene vinylene)s and poly(phenylene vinylene)s, by acyclic diene metathesis (ADMET) polymerization have been introduced. The methods using molybdenum and ruthenium catalysts afforded defect-free, high molecular weight polymers with all trans olefinic double bonds, and significant reduction of by-products (halogen, sulfur etc.) in addition of decrease of structurally defects have been attained. The methods also demonstrated precise synthesis of end-functionalized polymers that showed unique optical properties combined with the end groups. Catalytic one-pot syntheses of end-functionalized poly(9,9-dialkylfluorene-2,7-vinylene)s have been attained by both ruthenium (by chain-transfer) and molybdenum catalysts and the method should provide more green route for synthesis of conjugated materials with better device performance.
基金the financial support of National Key Fundamental Research Program of China （Grant No. G1999064703） the National Natural Science Foundation of China （Grant No. 20104005）.
文摘Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate （BTMC） with poly （vinyl pyrrolidone） （PVP） was successfully synthesized using immobilized porcine pancreas lipase （IPPL） or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a rnacroinitiator. The resulting copolymers were characterized by GPC, ^1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio （[B]/[P]） resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn. Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.
基金This work is supported by the National Natural Science Foundation of China(Nos.21336005,21371128 and 21176164).
文摘4-(3-(4-(Dimethylamino)phenyl)acryloyl)phenyl-2-bromo-2-methylpropanoate(APPBr)was used for the heterogeneous atom transfer radical polymerization(ATRP)of styrene(St)with copper(I)bromide/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)catalytic system.The functional end group was characterized via UV-Vis and ^(1)H NMR spectra.The polymerization showed a first-order kinetic characteristic and each of the obtained polymers had well-controlled molecular weight and relatively low polydispersity index(PDI).Furthermore,the obtained end-functionalized polystyrene(PS)in solution showed strong green-light emission which is further affected by mixing different metal cations.In particular,the fluorescent intensity of the polymer was decreased in the presence of Ag^(+),Cu^(2+)and Fe^(3+).
