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Recent advances in “living”/controlled radical polymerization of phosphorus-containing monomers and their potential applications

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Science China Chemistry 2015年第11期58卷 1633-1640页

作者： Tianchi Xu Lifen Zhang Zhenping Cheng Xiulin Zhu Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and Engineering College of Chemistry Chemical Engineering and Materials ScienceSoochow University

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.

关键词： living radical polymerization nitroxide-mediated polymerization （NMP） atom transfer radical polymerization （ATRP） reversible addition-fragmentation chain transfer （RAFT） phosphorus-containing monomer

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Synthesis of multifunctional ABC stars with a reduction-labile arm by consecutive ROP, RAFT and ATRP processes

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Science China Chemistry 2015年第11期58卷 1724-1733页

作者： Huanhuan Liu Dandan Tang Rupei Tang Youliang Zhao Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application College of Chemistry Chemical Engineering and Materials Science Soochow University School of Life Science Anhui University

This study aims at versatile synthesis of 3-arm ABC-type （A=poly（c-caprolactone）, PCL; B=poly（N-isopropylacrylamide）, PNIPAM; C=poly（tert-butyl acrylate）, PtBA, or poly（acrylic acid）, PAA） miktoarm star copolymers with a reducible disulfide linkage. Using 2-（（2-（（2-hydroxymethyo-2-（（2-bromo-2-methyl）propionyloxy）methyl）propionyloxy）ethyl）disulfanyl）ethyl 4- cyano-4-（phenylcarbonothioylthio）pentanoate （HBCP） as a heterotrifunctional initiator, consecutive ring-opening polymerization （ROP） of g-caprolactone （CL）, reversible addition-fragmentation chain transfer （RAFT） polymerization of N-isopropy- lacrylamide （NIPAM） and atom transfer radical polymerization （ATRP） of tert-butyl acrylate （tBA） afforded ABC1 star, and followed by a subsequent hydrolysis to give ABC2 star. IH nuclear magnetic resonance （IH NMR） and gel permeation chromatography （GPC） analyses revealed the desired stars and their precursors had well-controlled molecular weight and relatively low polydispersity （PDI≤1. 12）. As confirmed by GPC analysis, the disulfide linkage in ABCI star could be efficiently cleaved upon reductive stimulus, during which the topology was converted from star terpolymer to mixtures of homopolymer （B） and diblock copolymer （AC1）. In addition to acting as nanocarriers for stimuli-triggered drug delivery systems, ABC stars with terminal bromide, dithiobenzoate and hydroxyl functionalities are expected to form other reduction-cleavable multicomponent copolymers such as （BC-graft-A）m and dendritic graft copolymers via postpolymerization modification. Our research affords a straightforward ＂core-first＂ method to construct multifunctional star terpolymers with stimuli-responsive arms and reduction-labile linkage.

关键词： miktoarm star core-first method RAFT polymerization ROP ATRP

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Synthesis and Properties of Monocleavable Stimuli-sensitive ABCD-Type Miktoarm Star Quaterpolymers

Synthesis and Properties of Monocleavable Stimuli-sensitive ...

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第一届聚合物分子工程国际学术会议

作者： Youliang Zhao Huanhuan Liu Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationState and Local Joint Engineering Laboratory for Novel Functional Polymeric MaterialsCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

Synthesis and properties of complex topological polymers have been an enduring topic in current polymer science.1,2 The latest advance in living/controlled polymerization techniques and highly efficient linking reactions enables precise synthesis of various types of functional *** them,multicomponent miktoarm star copolymer(MMS)with at

关键词： Synthesis and Properties of Monocleavable Stimuli-sensitive ABCD-Type Miktoarm Star Quaterpolymers MMS

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SYNTHESIS AND PROPERTIES OF COMBLIKE-LINEAR BLOCK COpolymers WITH ALTERNATING GRAFTS

SYNTHESIS AND PROPERTIES OF COMBLIKE-LINEAR BLOCK COPOLYMERS...

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第七届高分子化学国际学术研讨会

作者： Youliang Zhao Min Tong Dandan Tang Xiao Jiang Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials College of Chemistry Chemical Engineering and Materials Science Soochow University

Well-defined architecture plays a crucial role in polymer materials,in which precise microstructure can endow materials with novel physicochemical properties,and the function integration can allow multipurpose *** various topological polymers,graft polymers and their derivatives have attracted much attention due to their special architecture and versatile functions. To further reveal

关键词： SYNTHESIS AND PROPERTIES OF COMBLIKE-LINEAR BLOCK COpolymers WITH ALTERNATING GRAFTS

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MULTICOMPARTMENT MORPHOLOGIES SELF-ASSEMBLED FROM FLUORINATED ABC TRIBLOCK TERpolymers:EFFECTS OF FLEXIBLE AND RIGID HYDROPHOBIC MOIETIES

MULTICOMPARTMENT MORPHOLOGIES SELF-ASSEMBLED FROM FLUORINATE...

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第七届国际高分子化学学术研讨会

作者： Jinlin He Sen Li Mingzu Zhang Hairong Wang Peihong Ni College of Chemistry Chemical Engineering and Materials ScienceState and Local Joint Engineering Laboratory for Novel Functional Polymeric MaterialsSuzhou Key Laboratory of Macromolecular Design and Precision SynthesisJiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSoochow University

Multicompartment micelles self-assembled by a wide variety of synthetic macromolecules, which may be linear multiblock terpolymers,multiarmed or miktoarm star copolymers,and hyperbranched copolymers,have been found with various nanoscale or microscale morphologies,including spherical micelles,worm-like micelles,vesicles,fibers,tubules and films,cylindrical micelles,hamburger-like

关键词： PDMAEMA MULTICOMPARTMENT MORPHOLOGIES SELF-ASSEMBLED FROM FLUORINATED ABC TRIBLOCK TERpolymers:EFFECTS OF FLEXIBLE AND RIGID HYDROPHOBIC MOIETIES

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Synthesis of Low‐Dimensional Polyion Complex Nanomaterials via Polymerization‐Induced Electrostatic Self‐Assembly

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Angewandte Chemie 2017年第4期130卷

作者： Yi Ding Meng Cai Zhigang Cui Leilei Huang Lei Wang Xinhua Lu Yuanli Cai Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application State-Local Joint Engineering Laboratory for Novel Functional Polymer Materials College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 China

Nanostructured polyion complexes (PICs) are appealing in biomaterials applications. Yet, conventional assembly suffers from the weakness in scale‐up and reproducibility. Only a few low‐dimensional PICs are available to date. Herein we report an efficient and scalable strategy to prepare libraries of low‐dimensional PICs. It involves a visible‐light‐mediated RAFT polymerization of ionic monomer in the presence of a polyion of the opposite charge at 5–50 % w/w total solids concentration in water at 25 °C, namely, polymerization‐induced electrostatic self‐assembly (PIESA). A Vesicle, multi‐compartmental vesicle, and large‐area unilamellar nanofilm can be achieved in water. A long nanowire and porous nanofilm can be prepared in methanol/water. An unusual unimolecular polyion complex (uPIC)‐sphere‐branch/network‐film transition is reported. This green chemistry offers a general platform to prepare various low‐dimensional PICs with high reproducibility on a commercially viable scale under eco‐friendly conditions.

关键词： Blockcopolymere Nanopartikel Polyion-Komplexe Polymerisationsinduzierte Selbstorganisation RAFT-Polymerisation

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Sequence‐Controlled polymers with Furan‐Protected Maleimide as a Latent Monomer

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Angewandte Chemie 2017年第9期129卷

作者： Yuxuan Ji Liuqiao Zhang Xue Gu Wei Zhang Nianchen Zhou Zhengbiao Zhang Xiulin Zhu State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 China

Herein, a novel methodology for preparing sequence‐controlled polymers is illustrated by using a latent monomer, furan protected maleimide (FMI). At 110 °C, FMI is deprotected by retro Diels–Alder (rDA) reaction, and the released MI is immediately involved in the cross‐polymerization with styrene (St) to deliver heterosegments. At 40 °C the rDA reaction does not proceed, therefore homo‐poly(styrene) segments are produced. By implementing programmable temperature changes during polymerization of St and FMI, “living” polymers with tailored a sequence are created. A ternary copolymerization produces complex sequences as designed. Alkynyl‐functionalized FMI, used as a latent monomer, leads to the desirable placement of functional groups along the polymer chain. This latent‐monomer‐based strategy opens a new avenue for fabricating sequence‐controlled polymers.

关键词： Cycloadditionen Polymerisationen Radikale Reaktionskinetik Synthesemethoden

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INITIATOR-REGULATOR COMBO IN LIVING RADICAL POLYMERIZATION

INITIATOR-REGULATOR COMBO IN LIVING RADICAL POLYMERIZATION

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第七届高分子化学国际学术研讨会

作者： Jian Zhu Chunlai Ding Jiajia Li Na Li Xiulin Zhu Suzhou key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of Chemistry Chemical Engineering and Materials Science Soochow University

Living radical polymerization has been developed over 20 *** than ionic polymerization,radical polymerization using precursors(initiator)to generate radical under stimulus during the ***,in living radical polymerization,multi-components,such as initiator,mediator,monomers,*** be *** multi-components system ultimately caused the complicating polymerization reaction and resulted in the difficulty for structure controlling,especially the precisely

关键词： INITIATOR-REGULATOR COMBO IN LIVING RADICAL POLYMERIZATION

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PHOTO-CATALYST FREE LIGHT INDUCED LIVING RADICAL POLYMERIZATION MEDIATED BY XANTHATE AND ORGANOSELENIUM COMPOUNDS

PHOTO-CATALYST FREE LIGHT INDUCED LIVING RADICAL POLYMERIZAT...

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第七届高分子化学国际学术研讨会

作者： Chunlai Ding Xiangqiang Pan Zhengbiao Zhang Jian Zhu Xiulin Zhu Suzhou key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and Engineering College of Chemistry Chemical Engineering and Materials Science Soochow University

Photo-induced RDRP has attracted more and more attentions due to its charming advantages,such as environmentally benign natural resource,widely available,noninvasive,*** the current abstract,an interesting photo-induced RDRP system was *** such system,no photo-catalyst was added,which showed benefits on the following points:simple(only monomer and mediate agent),improved

关键词： MALDI PHOTO-CATALYST FREE LIGHT INDUCED LIVING RADICAL POLYMERIZATION MEDIATED BY XANTHATE AND ORGANOSELENIUM COMPOUNDS

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Visible light induced living radical polymerization of styrene in the presence of novel diselenide

Visible light induced living radical polymerization of styre...

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2016年两岸三地高分子液晶态与超分子有序结构学术研讨会（暨第十四届全国高分子液晶态与超分子有序结构学术论文报告会）

作者： Chunlai Ding Jiandong Zhang Xiangqiang Pan Zhengbiao Zhang Jian Zhu Xiulin Zhu Suzhou key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of Chemistry Chemical Engineering and Materials Science Soochow University

The objective of this work was to improve the controllability of diselenide based LRP by modifying DPDS structure to synthesis polymers with controlled molecular weight along and narrow molecular weight *** was well-known that the activity of free radical was affected by the structure of substitutions through so called electronic effect and steric ***,in here we designed and synthesized different diselenides with different electronic and

关键词： Visible light induced living radical polymerization of styrene in the presence of novel diselenide LRP

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