Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as in...Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.展开更多
A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3)], was developed and used for the atom transfer radical polymerization (ATRP) of styre...A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3)], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)(3) as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)(2) as catalyst under UV light irradiation via a conventional ATRP process.展开更多
Atom transfer radical polymerizations （ATRPs） of styrene （St） in bulk initiated by six iniferter reagents were carried out, respectively, in the present of copper （1） bromide （CuBr） and N, N,N＇,N＂,N＂-pentam...Atom transfer radical polymerizations （ATRPs） of styrene （St） in bulk initiated by six iniferter reagents were carried out, respectively, in the present of copper （1） bromide （CuBr） and N, N,N＇,N＂,N＂-pentamethyldiethylenetriamine （PMDETA） at 115℃. All the kinetic plots were first-order with respect to the monomer concentrations. At the same time, the corresponding molecular weights of the polymers increased linearly with the respective monomer conversions. Furthermore, the molecular weight distributions remained relatively narrow （Mw/Mn〈1.50） in all cases. Solution ATRP of St in dimethyl- formamide （DMF） initiated by benzyl N, N-diethyldithiocarba- mate （BDC） also showed the characteristics of living radical polymerization. The results of 1H NMR analysis and chain extension experiment confirmed that the well-defined polystyrene （PS） bearing photo-liable group has been obtained via ATRP of St using photoiniferter reagents as the initiators.展开更多
The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by ir...The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.展开更多
The efficient Cu(0) wire-catalyzed single-electron transfer-living radical polymerization (SET-LRP) in organic solvents and mixtures of the organic solvents with water has been thoroughly investigated. 01igo(ethylene ...The efficient Cu(0) wire-catalyzed single-electron transfer-living radical polymerization (SET-LRP) in organic solvents and mixtures of the organic solvents with water has been thoroughly investigated. 01igo(ethylene oxide) methyl ether acrylate was used as an exemplar oligomer monomer to determine the optimum polymerization conditions for rapid, controlled, and quantitative production of well-defined polymers. The effects of Cu(0)-wire length (12.5 or 4.5 cm), ligand type (tris(dimethylaminoethyl)amine, Me6-TREN, or tris(2-aminoethyl)amine, TREN), and solvent type (dipolar aprotic solvents, cyclic ethers, alcohol, or acetone) on the polymerization have been evaluated. Kinetic experiments were performed for all polymerizations to assess the "living" behavior of each system employed. Importantly, TREN could be used as a replacement for Me6-TREN in Cu(0) wire-catalyzed SET-LRP of oligomer monomer, which probably provides the most economical and efficient methodology since TREN is 80 times less expensive than Me6-TREN. The high chain-end fidelity of resulting polymer was experimentally verified by thiol-Michael addition reaction at the a-Br chain end and subsequent chain extension with methyl acrylate.展开更多
In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. α-Bromine-terminated polystyrenes(...In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br_2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br_2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93. 8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate (MMA) in the presence of copper (I ) halogen and 2, 2' -bipyridine (bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1. 2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by ~1H NMR spectra.展开更多
This tutorial review summarizes recent progress in the research field of controlled/"living" radical polymerization (CLRP) from Soochow University.The present paper gives a broad overview of the mechanism st...This tutorial review summarizes recent progress in the research field of controlled/"living" radical polymerization (CLRP) from Soochow University.The present paper gives a broad overview of the mechanism study and molecular design in CLRP.The mechanism study in CLRP aided by microwave,initiated by γ-radiation at low temperature,mediated by iron,in reversible addition-fragmentation chain transfer (RAFT) polymerization and the mechanism transfer between different CLRP processes are reviewed and summarized.The molecular design in CLRP,especially in RAFT polymerization for mechanism study,and in achieving tailor-made functional polymers is studied and discussed in the later part.展开更多
Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)...Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)polymerization of phosphorus-containing monomers. In addition, different properties of the polymers involved in the phosphonate group in various chemical environments are demonstrated, and their potential applications are briefly discussed.展开更多
文章通过两步反应简单高效地制备出目标多孔有机笼RCC3,将其作为配体和CuBr_(2)配位构建多孔有机笼配合物RCC3@Cu。采用X-射线衍射(X-ray diffraction,XRD)和电喷雾电离质谱(electrospray ionization mass spectrometry,ESI-MS)表征RCC3...文章通过两步反应简单高效地制备出目标多孔有机笼RCC3,将其作为配体和CuBr_(2)配位构建多孔有机笼配合物RCC3@Cu。采用X-射线衍射(X-ray diffraction,XRD)和电喷雾电离质谱(electrospray ionization mass spectrometry,ESI-MS)表征RCC3@Cu的结构与组成,结果表明,RCC3@Cu配位稳定,有望用于介导原子转移自由基聚合(atom transfer radical polymerization,ATRP)。采用RCC3配体介导甲基丙烯酸甲酯(MMA)的ATRP,2 h其转化率达到80%,聚合物分散性指数(polymer dispersity index,PDI)为1.15;最终转化率为98.5%,PDI为1.16。聚合动力学显示RCC3介导的ATRP为近似一级反应动力学,符合活性聚合特征。该文研究RCC3配体介导不同类型单体的聚合,验证了RCC3配体具有单体泛用性。研究结果表明,RCC3体可有效应用于ATRP催化,有进一步研究价值。展开更多
Dispersity(D)of polymers has a great effect on the properties of polymeric materials,and therefore how to control θ is very important but still a huge challenge in polymer synthesis,especially for reversible-deactiva...Dispersity(D)of polymers has a great effect on the properties of polymeric materials,and therefore how to control θ is very important but still a huge challenge in polymer synthesis,especially for reversible-deactivation radical polymerization(RDRP)strategy.Herein,we successfully developed a novel strategy to adjust D of polymers by visible light-controlled reversible complexation mediated living radical polymerizatio n(RCMP)and combi nation of single-electron transfer-degenerative chain tran sfer living radical polymerization(SET-DTLRP)at room temperature.In RCMP system,2-iodo-2-methylpropionitrile(CP-I)and ethyl 2-iodo-2-phenylacetate(EIPA)were used as alkyl iodide initiators,by using methyl methacrylate(MMA)as the model monomer and n-butylacrylate(BA)as the end-capping reagent to regulate D of polymers.Subsequently,we successfully prepared the block copolymer PMMA-b-PBA with adjustable D by reactivating the polymer end-chains via SET-DTLRP in the presence of copper wire,fully dem on strati ng that it is a promising strategy that can keep the"living"feature of polymers while regulating their molar mass dispersities easily.展开更多
基金The Project is supported by the National Natural Science Foundation of China (Grant No. 29634010-2), Shanghai Education Development Foundation Shuguang Program (Project SG97008) and Research Institute of Beijing Yanshan Petrochemical Corporation.
文摘Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.
文摘A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3)], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)(3) as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)(2) as catalyst under UV light irradiation via a conventional ATRP process.
基金Acknowledgments： The work was supported by the National Nature Science Foundation of China （No. 20574050）, the Science and Technology Development Planning of Jiangsu Province （No. BK2007702 and BK2007048）, and the Nature Science Key Basic Research of Jiangsu Province for Higher Education （No. 05KJA15008）.
文摘Atom transfer radical polymerizations （ATRPs） of styrene （St） in bulk initiated by six iniferter reagents were carried out, respectively, in the present of copper （1） bromide （CuBr） and N, N,N＇,N＂,N＂-pentamethyldiethylenetriamine （PMDETA） at 115℃. All the kinetic plots were first-order with respect to the monomer concentrations. At the same time, the corresponding molecular weights of the polymers increased linearly with the respective monomer conversions. Furthermore, the molecular weight distributions remained relatively narrow （Mw/Mn〈1.50） in all cases. Solution ATRP of St in dimethyl- formamide （DMF） initiated by benzyl N, N-diethyldithiocarba- mate （BDC） also showed the characteristics of living radical polymerization. The results of 1H NMR analysis and chain extension experiment confirmed that the well-defined polystyrene （PS） bearing photo-liable group has been obtained via ATRP of St using photoiniferter reagents as the initiators.
文摘The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.
基金financially supported by the National Natural Science Foundation of China (Nos. 21774107, 21774029, and 21801217)the Natural Science Foundation of Jiangsu ProvinceGeneral Program (No. BK20171273)+2 种基金"Six Talent Peak" High-level Talent Project (JNHB-068)Qing Lan Project of Jiangsu Provincethe Initial Scientific Research Foundation of Yancheng Institute of Technology (No. KJC2014002)
文摘The efficient Cu(0) wire-catalyzed single-electron transfer-living radical polymerization (SET-LRP) in organic solvents and mixtures of the organic solvents with water has been thoroughly investigated. 01igo(ethylene oxide) methyl ether acrylate was used as an exemplar oligomer monomer to determine the optimum polymerization conditions for rapid, controlled, and quantitative production of well-defined polymers. The effects of Cu(0)-wire length (12.5 or 4.5 cm), ligand type (tris(dimethylaminoethyl)amine, Me6-TREN, or tris(2-aminoethyl)amine, TREN), and solvent type (dipolar aprotic solvents, cyclic ethers, alcohol, or acetone) on the polymerization have been evaluated. Kinetic experiments were performed for all polymerizations to assess the "living" behavior of each system employed. Importantly, TREN could be used as a replacement for Me6-TREN in Cu(0) wire-catalyzed SET-LRP of oligomer monomer, which probably provides the most economical and efficient methodology since TREN is 80 times less expensive than Me6-TREN. The high chain-end fidelity of resulting polymer was experimentally verified by thiol-Michael addition reaction at the a-Br chain end and subsequent chain extension with methyl acrylate.
基金the National Natural Science Foundation of China!(No. 29634010-2) Research Institute of BeijingYanshan Petrochemical Corpor
文摘In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br_2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br_2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93. 8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate (MMA) in the presence of copper (I ) halogen and 2, 2' -bipyridine (bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1. 2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by ~1H NMR spectra.
基金supported by the National Natural Science Foundation of China (20874069, 50803044, 20974071, 20904036)the Specialized Research Fund for the Doctoral Program of Higher Education (200802850005)the Qing Lan Project the Program of Innovative Research Team of Soochow University
文摘This tutorial review summarizes recent progress in the research field of controlled/"living" radical polymerization (CLRP) from Soochow University.The present paper gives a broad overview of the mechanism study and molecular design in CLRP.The mechanism study in CLRP aided by microwave,initiated by γ-radiation at low temperature,mediated by iron,in reversible addition-fragmentation chain transfer (RAFT) polymerization and the mechanism transfer between different CLRP processes are reviewed and summarized.The molecular design in CLRP,especially in RAFT polymerization for mechanism study,and in achieving tailor-made functional polymers is studied and discussed in the later part.
基金supported by the National Natural Science Foundation of China(21174096,21274100,21234005)the Specialized Research Fund for the Doctoral Program of Higher Education(20123201130001)+2 种基金the Project of Science and Technology Development Planning of Suzhou(ZXG201413,SYG201430)the Project of Science and Technology Development Planning of Jiangsu Province(BK20141192)the Project Fund of the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)polymerization of phosphorus-containing monomers. In addition, different properties of the polymers involved in the phosphonate group in various chemical environments are demonstrated, and their potential applications are briefly discussed.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22071168 and 21774082)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Dispersity(D)of polymers has a great effect on the properties of polymeric materials,and therefore how to control θ is very important but still a huge challenge in polymer synthesis,especially for reversible-deactivation radical polymerization(RDRP)strategy.Herein,we successfully developed a novel strategy to adjust D of polymers by visible light-controlled reversible complexation mediated living radical polymerizatio n(RCMP)and combi nation of single-electron transfer-degenerative chain tran sfer living radical polymerization(SET-DTLRP)at room temperature.In RCMP system,2-iodo-2-methylpropionitrile(CP-I)and ethyl 2-iodo-2-phenylacetate(EIPA)were used as alkyl iodide initiators,by using methyl methacrylate(MMA)as the model monomer and n-butylacrylate(BA)as the end-capping reagent to regulate D of polymers.Subsequently,we successfully prepared the block copolymer PMMA-b-PBA with adjustable D by reactivating the polymer end-chains via SET-DTLRP in the presence of copper wire,fully dem on strati ng that it is a promising strategy that can keep the"living"feature of polymers while regulating their molar mass dispersities easily.
