Effects of catalyst loading amount on the synthesis of poly（3-hexylthiophene） via externally initiated Kumada catalyst-transfer polycondensation  

作　　者：Jin WANG Tomoya HIGASHIHARA 

机构地区：[1]Advanced Materials Division, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 398 Ruoshui Road, Suzhou 215123, China [2]Department of Polymer Science and Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa City, Yamaqata 992-8510, Japan [3]Japan Science and Technology Agency (JST), 4-1-8, Honcho, Kawaguchi, Saitama, 332-0012, Japan

出　　处：《Frontiers of Materials Science》2014年第4期383-390,共8页材料学前沿（英文版）

摘　　要：A series of model polymerization are carried out via the one-pot externally initiated Kumada catalyst-transfer polycondensation （KCTP） of 2-bromo-5-chloromagne- slum thiophene monomers, and the excess amount of initiators or catalysts are found no need to be isolated during the polycondensation process. Especially, the impacts of the nickel catalyst loading variation on regioregularity （rr）, yield, molecular weight （Mn）, polydispersity （PDI） and initiation efficiency of poly（3-hexylthiophene） （P3HT） are systematically investigated. The IH NMR, size-exclusion chromatography （SEC）, and MALDI-TOF mass spectroscopy results indicated that an excess amount of catalyst does not influence yield, rr, Mn, and PDI of P3HT, nor the initiation efficiency. However, the PDI of the product is broad, and the Mn and rr values decreased in the absence of 1,3-bis （diphenylphosphino）propane （dppp）. It can be concluded that the in-situ KCTP polymerization of P3HT is a practical and effective process. These results are especially valuable for the synthesis of all-conjugated block copolymers where macroinitiators are used.A series of model polymerization are carried out via the one-pot externally initiated Kumada catalyst-transfer polycondensation （KCTP） of 2-bromo-5-chloromagne- slum thiophene monomers, and the excess amount of initiators or catalysts are found no need to be isolated during the polycondensation process. Especially, the impacts of the nickel catalyst loading variation on regioregularity （rr）, yield, molecular weight （Mn）, polydispersity （PDI） and initiation efficiency of poly（3-hexylthiophene） （P3HT） are systematically investigated. The IH NMR, size-exclusion chromatography （SEC）, and MALDI-TOF mass spectroscopy results indicated that an excess amount of catalyst does not influence yield, rr, Mn, and PDI of P3HT, nor the initiation efficiency. However, the PDI of the product is broad, and the Mn and rr values decreased in the absence of 1,3-bis （diphenylphosphino）propane （dppp）. It can be concluded that the in-situ KCTP polymerization of P3HT is a practical and effective process. These results are especially valuable for the synthesis of all-conjugated block copolymers where macroinitiators are used.

关 键 词：Kumada catalyst-transfer polycondensation （KCTP） poly（3-hexylthio-phene） （P3HT） regioregularity （rr） 

分 类 号：O643.36[理学—物理化学] TQ326.6[理学—化学]