ABA triblock copolymers containing polyisoprene segments,such as polyisoprene b polystyrene b polyisoprene (PIP b PSt b PIP)and polyisoprene b poly(methyl methacrylate) b polyisoprene(PIP b PMMA b PIP),were prepared w...ABA triblock copolymers containing polyisoprene segments,such as polyisoprene b polystyrene b polyisoprene (PIP b PSt b PIP)and polyisoprene b poly(methyl methacrylate) b polyisoprene(PIP b PMMA b PIP),were prepared with macro iniferter technique.The macro iniferters (PSt CCDCM and PMMA CCDCM)bearing α and ω N,N diethyldithiocarbamyl (DC)groups were synthesized by bulk polymerization of St and MMA with diethyl 2,3 dicyano 2,3 di( p N,N diethyldithiocarbamylmethyl) phenylsuccinate (DDDCS) as a thermal iniferter.The block copolymerization of IP with PSt CCDCM or PMMA CCDCM was carried out under UV light irradiation.The block copolymers were characterized by 1H NMR,GPC and DSC analyses,and the polymerization proceeded as a living polymerization process.展开更多
A new monomer-iniferter,allyl 2- N,N- diethyldithiocarbamylacetate (ADCA),was synthesized from allyl alcohol with chloroacetyl chloride then the chlorine groups were subsequently reacted with sodium diethyldithiocarba...A new monomer-iniferter,allyl 2- N,N- diethyldithiocarbamylacetate (ADCA),was synthesized from allyl alcohol with chloroacetyl chloride then the chlorine groups were subsequently reacted with sodium diethyldithiocarbamate. The ADCA was used for preparation of well\|defined functionalized polystyrene via radical polymerization of styrene (St) in bulk under UV light irradiation at ambient temperature. The bulk polymerization of St with ADCA proceeded a “living" process, i.e., both the yield and molecular weight of the resultant PSt increased with the increasing of reaction time, and the average number of end group Et 2NCSS is about 1. The well\|defined polymer was characterized by 1 H\|NMR and FT IR spectroscopies to be an α-allyloxycarbonylmethylene-ω-diethyldithiocarbamyl-polystyrene.Under UV light irradiation,the C-S bond of -ω-end groups of PSt can cleavage reversibly to initiate MMA polymerization forming a well\|defined PSt-b-PMMA copolymer.展开更多
Living" radical polymerization of methyl methacrylate was investigated using a new initiating system, i.e. DCDPS/FeCl 3/PPh 3, in which diethyl 2,3 dicyano 2,3 diphenyl succinate(DCDPS) is a hexa substituted etha...Living" radical polymerization of methyl methacrylate was investigated using a new initiating system, i.e. DCDPS/FeCl 3/PPh 3, in which diethyl 2,3 dicyano 2,3 diphenyl succinate(DCDPS) is a hexa substituted ethane thermal iniferter. The polymerization mechanism belongs to a reverse ATRP process. The polymerization was closely controlled in bulk at 75 ℃, polymethyl methacrylate(PMMA) with a high molecular weight and quite narrow polydispersity ( M w/ M n=1 20—1 29) was obtained. End group analysis by 1H NMR spectroscopy shows that the resulting PMMA is ω functionalized by a chlorine atom, which is also confirmed by the chain extension reaction in the presence of CuCl/bipy catalyst via a conventional ATRP process. [WT5HZ]展开更多
Living radical polymerization of methyl methacrylate was investigated using a new initiation system, i. e. DCDPS/Fe(DC)3, in which diethyl 2,3-dicyano-2,3-diphenyl-succinate(DCDPS) is a hexa-substituted ethane thermal...Living radical polymerization of methyl methacrylate was investigated using a new initiation system, i. e. DCDPS/Fe(DC)3, in which diethyl 2,3-dicyano-2,3-diphenyl-succinate(DCDPS) is a hexa-substituted ethane thermal iniferter and ferric tri(diethyldithiocarbamate)(Fe(DC)3) is a ligand-free catalyst. The polymerization was successfully controlled in bulk at 95 ℃, PMMA with high molecular weight and quite narrow polydispersities(Mw/Mn=1.20～1.29) were obtained. End group analysis by 1H NMR spectroscopy shows that the resulting PMMA is ω-functionalized by a DC group.展开更多
文摘ABA triblock copolymers containing polyisoprene segments,such as polyisoprene b polystyrene b polyisoprene (PIP b PSt b PIP)and polyisoprene b poly(methyl methacrylate) b polyisoprene(PIP b PMMA b PIP),were prepared with macro iniferter technique.The macro iniferters (PSt CCDCM and PMMA CCDCM)bearing α and ω N,N diethyldithiocarbamyl (DC)groups were synthesized by bulk polymerization of St and MMA with diethyl 2,3 dicyano 2,3 di( p N,N diethyldithiocarbamylmethyl) phenylsuccinate (DDDCS) as a thermal iniferter.The block copolymerization of IP with PSt CCDCM or PMMA CCDCM was carried out under UV light irradiation.The block copolymers were characterized by 1H NMR,GPC and DSC analyses,and the polymerization proceeded as a living polymerization process.
文摘A new monomer-iniferter,allyl 2- N,N- diethyldithiocarbamylacetate (ADCA),was synthesized from allyl alcohol with chloroacetyl chloride then the chlorine groups were subsequently reacted with sodium diethyldithiocarbamate. The ADCA was used for preparation of well\|defined functionalized polystyrene via radical polymerization of styrene (St) in bulk under UV light irradiation at ambient temperature. The bulk polymerization of St with ADCA proceeded a “living" process, i.e., both the yield and molecular weight of the resultant PSt increased with the increasing of reaction time, and the average number of end group Et 2NCSS is about 1. The well\|defined polymer was characterized by 1 H\|NMR and FT IR spectroscopies to be an α-allyloxycarbonylmethylene-ω-diethyldithiocarbamyl-polystyrene.Under UV light irradiation,the C-S bond of -ω-end groups of PSt can cleavage reversibly to initiate MMA polymerization forming a well\|defined PSt-b-PMMA copolymer.
文摘Living" radical polymerization of methyl methacrylate was investigated using a new initiating system, i.e. DCDPS/FeCl 3/PPh 3, in which diethyl 2,3 dicyano 2,3 diphenyl succinate(DCDPS) is a hexa substituted ethane thermal iniferter. The polymerization mechanism belongs to a reverse ATRP process. The polymerization was closely controlled in bulk at 75 ℃, polymethyl methacrylate(PMMA) with a high molecular weight and quite narrow polydispersity ( M w/ M n=1 20—1 29) was obtained. End group analysis by 1H NMR spectroscopy shows that the resulting PMMA is ω functionalized by a chlorine atom, which is also confirmed by the chain extension reaction in the presence of CuCl/bipy catalyst via a conventional ATRP process. [WT5HZ]
文摘Living radical polymerization of methyl methacrylate was investigated using a new initiation system, i. e. DCDPS/Fe(DC)3, in which diethyl 2,3-dicyano-2,3-diphenyl-succinate(DCDPS) is a hexa-substituted ethane thermal iniferter and ferric tri(diethyldithiocarbamate)(Fe(DC)3) is a ligand-free catalyst. The polymerization was successfully controlled in bulk at 95 ℃, PMMA with high molecular weight and quite narrow polydispersities(Mw/Mn=1.20～1.29) were obtained. End group analysis by 1H NMR spectroscopy shows that the resulting PMMA is ω-functionalized by a DC group.
