Poly(pyridinium ethyl methacrylate)was synthesized.The blends of polymeric solid anion conductor,P(PyEMAClO+4)/P(MEO_(16)—AM),were prepared. The temperature—dependence of both the conductivity and anionic mobility i...Poly(pyridinium ethyl methacrylate)was synthesized.The blends of polymeric solid anion conductor,P(PyEMAClO+4)/P(MEO_(16)—AM),were prepared. The temperature—dependence of both the conductivity and anionic mobility in the blends obey Arrhenius relationship,the transport of perchlorate anion being of thermal activation mechanism.Perchlorate anion is a free anion in the blends.展开更多
Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dos...Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dose and monomer concentration on grafting degree was determined. The grafted samples were verified by FTIR-ATR spectroscopy and swelling;thermal properties were analyzed by DSC and TGA. The stimuli-responsive behavior was studied by swelling and/or DSC. Thermo- and pH-sensitive films of (PP-g-DEAEMA)-g-NVCL presented a pH critical at 3.2 and LCST around 63.5℃.展开更多
Since tertiary amines (Cα-H) can be oxidized by peroxides and transition metal cations in high oxidation states into Ca2+ radicals to initiate vinylic polymerizations of methacrylates, Cu2+ and 2-(N,N-dimethylam...Since tertiary amines (Cα-H) can be oxidized by peroxides and transition metal cations in high oxidation states into Ca2+ radicals to initiate vinylic polymerizations of methacrylates, Cu2+ and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) form a polymerizable redox initiating pair, in which DMAEMA serves as an intrinsically reducing inimer. CuSOa-catalyzed aqueous self-initiated radical polymerizations of DMAEMA were successfully performed at ambient temperature via a continuous Cu2+-tertiary amine redox initiation based on catalyst regeneration in the presence of O2. The polymerization kinetics was monitored by gas chromatography and the structure of PDMAEMA was characterized by gel- permeation chromatography, nuclear magnetic resonance spectroscopy, laser light scattering and online intrinsic-viscosity analysis. Both the monomer conversion and the molecular weight of PDMAEMA increase with the reaction while the molecular weight distribution maintains rather broad, as the Cu2+-DMAEMA redox-initiation leads to linear PDMAEMA chains with terminal methacryloxyl moieties, and the Cu2+-PDMAEMA redox-initiation results in branched chains. The branched topology forms and develops only for the high-MW components of the PDMAEMA. Our results provide a facile strategy to prepare branched polymers from such commercially available intrinsically reducing inimers using a negligible concentration of regenerative air-stable catalysts.展开更多
'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85...'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09~1.22). The conversion can reach up to~100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.展开更多
Polypropylene microporous membranes are typical hydrophobic separation membranes, but the high hydrophobicity and lack of functionality easily cause bacterial adhesion, thus inducing membrane pollution. Poly(AMS-co-D...Polypropylene microporous membranes are typical hydrophobic separation membranes, but the high hydrophobicity and lack of functionality easily cause bacterial adhesion, thus inducing membrane pollution. Poly(AMS-co-DMAEMA) (PAD) was designed and synthesized by copolymerization of a-methyl styrene (AMS) and functional monomer 2-(dimethylamino)ethyl methacrylate (DMAEMA), and then grafted onto PP chains by melt blending. Microporous membranes of blended PP containing different contents of PAD are made by casting and stretching, and the polycation microporous membrane is then obtained via quaternization. The permeability and porosity of the microporous membrane achieve the best when the grafting efficiency reaches 42.16%, and the hydrophilicity of the microporous membrane is improved. The results show that the modified membranes fabricated in this method have good antibacterial properties.展开更多
文摘Poly(pyridinium ethyl methacrylate)was synthesized.The blends of polymeric solid anion conductor,P(PyEMAClO+4)/P(MEO_(16)—AM),were prepared. The temperature—dependence of both the conductivity and anionic mobility in the blends obey Arrhenius relationship,the transport of perchlorate anion being of thermal activation mechanism.Perchlorate anion is a free anion in the blends.
文摘Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dose and monomer concentration on grafting degree was determined. The grafted samples were verified by FTIR-ATR spectroscopy and swelling;thermal properties were analyzed by DSC and TGA. The stimuli-responsive behavior was studied by swelling and/or DSC. Thermo- and pH-sensitive films of (PP-g-DEAEMA)-g-NVCL presented a pH critical at 3.2 and LCST around 63.5℃.
基金financially supported by the National Natural Science Foundation of China(No.20674033)Natural Science Foundation of Jiangsu Province(No.BK2008142)Scientific Research Foundation for the Returned Overseas Chinese Scholars(State Education Ministry)
文摘Since tertiary amines (Cα-H) can be oxidized by peroxides and transition metal cations in high oxidation states into Ca2+ radicals to initiate vinylic polymerizations of methacrylates, Cu2+ and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) form a polymerizable redox initiating pair, in which DMAEMA serves as an intrinsically reducing inimer. CuSOa-catalyzed aqueous self-initiated radical polymerizations of DMAEMA were successfully performed at ambient temperature via a continuous Cu2+-tertiary amine redox initiation based on catalyst regeneration in the presence of O2. The polymerization kinetics was monitored by gas chromatography and the structure of PDMAEMA was characterized by gel- permeation chromatography, nuclear magnetic resonance spectroscopy, laser light scattering and online intrinsic-viscosity analysis. Both the monomer conversion and the molecular weight of PDMAEMA increase with the reaction while the molecular weight distribution maintains rather broad, as the Cu2+-DMAEMA redox-initiation leads to linear PDMAEMA chains with terminal methacryloxyl moieties, and the Cu2+-PDMAEMA redox-initiation results in branched chains. The branched topology forms and develops only for the high-MW components of the PDMAEMA. Our results provide a facile strategy to prepare branched polymers from such commercially available intrinsically reducing inimers using a negligible concentration of regenerative air-stable catalysts.
文摘'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09~1.22). The conversion can reach up to~100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.
基金supported by the National Natural Science Foundation of China(Nos. 21778055 and 21573250)
文摘Polypropylene microporous membranes are typical hydrophobic separation membranes, but the high hydrophobicity and lack of functionality easily cause bacterial adhesion, thus inducing membrane pollution. Poly(AMS-co-DMAEMA) (PAD) was designed and synthesized by copolymerization of a-methyl styrene (AMS) and functional monomer 2-(dimethylamino)ethyl methacrylate (DMAEMA), and then grafted onto PP chains by melt blending. Microporous membranes of blended PP containing different contents of PAD are made by casting and stretching, and the polycation microporous membrane is then obtained via quaternization. The permeability and porosity of the microporous membrane achieve the best when the grafting efficiency reaches 42.16%, and the hydrophilicity of the microporous membrane is improved. The results show that the modified membranes fabricated in this method have good antibacterial properties.