The self-condensing vinyl polymerization(SCVP) of a novel maleimide inimer(initiator-monomer) 1, N-(4-α-bromobutyryloxy phenyl) maleimide with the complex of CuBr/Bipy(2, 2′-bipyridine) as the catalyst was studied. ...The self-condensing vinyl polymerization(SCVP) of a novel maleimide inimer(initiator-monomer) 1, N-(4-α-bromobutyryloxy phenyl) maleimide with the complex of CuBr/Bipy(2, 2′-bipyridine) as the catalyst was studied. GPC was used to determine the molecular weight and the results show that the molecular weight increases exponentially with polymerization time during the first hour, and then the rate of increase molecular weight slows down. The molecular weight also increases with increasing dosage of the catalyst. The coincidence of the molecular weights determined by 1H NMR and GPC proves that the polymer obtained from the SCVP of inimer 1 has a linear structure, which is further verified by 13C NMR spectrum. A hyperbranched polymer was obtained by the copolymerization of inimer 1 and styrene.展开更多
A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living ra...A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.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
A photo-controlled approach is developed to regulate the interpenetrating polymer network(IPN)topology by varying the connecting structure between the first and second networks.The approach is based on multifunctional...A photo-controlled approach is developed to regulate the interpenetrating polymer network(IPN)topology by varying the connecting structure between the first and second networks.The approach is based on multifunctional inimer(Vinyl-o NB-Br)possessing three moieties,i.e.,an acrylate-based double bond for incorporation within a polymer network,a Br group for grafting polymerization to get connectIPN(c-IPN),and an o-nitrobenzyl spacer for photocleaving to convert the c-IPN to disconnected-IPN(d-IPN)with UV light irradiation.Such design allows for finely controlling the connection degree between two networks.A systematic study on the mechanical property of a series of samples with different connection degrees thus can be conducted.The results reveal that decreasing the connecting degree between two networks of IPN made a negligible contribution to materials'mechanical properties.展开更多
A class of constrained semi-infinite minimax problem is transformed into a simple constrained problem,by means of discretization decomposition and maximum entropy method,making use of surrogate constraint.The paper de...A class of constrained semi-infinite minimax problem is transformed into a simple constrained problem,by means of discretization decomposition and maximum entropy method,making use of surrogate constraint.The paper deals with the convergence of this asymptotic approach method.展开更多
文摘The self-condensing vinyl polymerization(SCVP) of a novel maleimide inimer(initiator-monomer) 1, N-(4-α-bromobutyryloxy phenyl) maleimide with the complex of CuBr/Bipy(2, 2′-bipyridine) as the catalyst was studied. GPC was used to determine the molecular weight and the results show that the molecular weight increases exponentially with polymerization time during the first hour, and then the rate of increase molecular weight slows down. The molecular weight also increases with increasing dosage of the catalyst. The coincidence of the molecular weights determined by 1H NMR and GPC proves that the polymer obtained from the SCVP of inimer 1 has a linear structure, which is further verified by 13C NMR spectrum. A hyperbranched polymer was obtained by the copolymerization of inimer 1 and styrene.
基金Supported by the National Natural Science Foundation of China(No. 2 980 40 0 6 ) and the Youth Foundation of Jiangsuprovince(No.BQ980 2 4)
文摘A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.
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.
基金financially supported by the National Natural Science Foundation of China(No.51973023)Sichuan Science and Technology Program(No.2021JDRC0014)the Colleges and Universities Twenty Foundational Projects of Jinan City(No.2021GXRC068)。
文摘A photo-controlled approach is developed to regulate the interpenetrating polymer network(IPN)topology by varying the connecting structure between the first and second networks.The approach is based on multifunctional inimer(Vinyl-o NB-Br)possessing three moieties,i.e.,an acrylate-based double bond for incorporation within a polymer network,a Br group for grafting polymerization to get connectIPN(c-IPN),and an o-nitrobenzyl spacer for photocleaving to convert the c-IPN to disconnected-IPN(d-IPN)with UV light irradiation.Such design allows for finely controlling the connection degree between two networks.A systematic study on the mechanical property of a series of samples with different connection degrees thus can be conducted.The results reveal that decreasing the connecting degree between two networks of IPN made a negligible contribution to materials'mechanical properties.
文摘A class of constrained semi-infinite minimax problem is transformed into a simple constrained problem,by means of discretization decomposition and maximum entropy method,making use of surrogate constraint.The paper deals with the convergence of this asymptotic approach method.
