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Photo-induced Living Cationic Copolymerization of Isobutyl Vinyl Ether and Vinyl Ether with Carbazolyl Groups

Chinese Journal of polymer Science 2014年第11期32卷 1564-1574页

作者： Ming Li 张丽芬 Mei-xia Tao 程振平 Xiu-lin Zhu Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationDepartment of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

In this work, a fluorescent monomer 2-（9-carbazolyl） ethyl vinyl ether（CEVE） was synthesized in our lab, and its photo-induced living cationic copolymerization behavior with isobutyl vinyl ether（IBVE） was investigated in detail using diphenyliodonium chloride（DPICl）/2,2-dimethoxy-2-phenylacetophenone（DMPA） and zinc bromide（Zn Br2） initiating system in dichloromethane solution at 5 °C, -5 °C, and -15 °C, respectively. The living nature of this copolymerization system was confirmed by adding fresh comonomer method after the copolymerization almost finished. In addition, the obtained fluorescent copolymer poly（IBVE-co-CEVE） has a low glass transition temperature（Tg）, below -10 °C.

关键词： Photopolymerization Kinetics（polym.） Copolymerization Cationic polymerization Living cationic polymerization.

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Special Odd-Even Effect of Degree of Oligomerization on Properties of Cyclic Oligoesters

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Chinese Journal of polymer Science 2015年第8期33卷 1069-1069,1070-1073页

作者： Jun Wu Tao-guang Qu Ling-feng Gao Xiao-ming Yang Xiao-hong Li 屠迎锋 Xiu-lin Zhu Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

We demonstrate here seven pure cyclic samples, which belongs to two series of oligoesters, cyclic oligo（trimethylene terephthalate）s （COTTs） and cyclic oligo（butylene terephthalate）s （COBTs）, showing odd-even effect of degree of oligomerization （repeating units number） on properties. The pentamer of COTT and trimer of COBT show much lower melting temperature, and the trimer of COTT and trimer of COBT show significant lower refractive index, which can be ascribed to the low packing density of cyclic oligoesters with odd number of degree of oligomerization. Our results reveal the discrete property change as a function of cyclic size of oligomers, which can be used to design materials with special properties.

关键词： Cyclic polymer Oligomer Odd-even effect Refractive index.

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Synthesis of ultrathin semicircle-shaped copper nanowires in ethanol solution for low haze flexible transparent conductors

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Nano Research 2018年第7期11卷 3899-3910页

作者： Ye Zhan~ Jiangna Guo Dan Xu Yi Sun Feng Yan 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 Suzhou 215123 China

Copper nanowires （CuNWs） are becoming an indispensable item for next- generation transparent optical devices due to their excellent conductivity and transparency. In this work, ultrathin semicircle-shaped copper nanowires （SCuNWs） with a diameter of - 15 nm and a length of - 30 μm （aspect ratio of -2,000） were synthesized in ethanol solution. The mechanism and factors that affect the morphology and dispersity of the SCuNWs were investigated. The prepared SCuNWs were coated on polyethylene terephthalate （PET） or polyd- imethylsiloxane （PDMS） substrate to fabricate flexible transparent conductors （FTCs）. The fabricated FTCs exhibited excellent optoelectrical performance and low haze. In addition, the fabricated FTCs showed high mechanical stability during stretching and bending, indicating their great potential in flexible optical devices.

关键词： copper nanowires semicircle-shaped ultrathin low haze flexible transparent conductors

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Synthesis of Sulfur/Selenium-containing Polyester with Recyclability and Controllable Hydrophilicity and Glass Transition Temperature

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Chinese Journal of polymer Science 2023年第12期41卷 1836-1845,I0004,I0005页

作者： Wen-Jing Li Xiang-Qiang Pan Jian Zhu Zheng-Biao Zhang Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhou 215123China

We present a ring-opening polymerization of bridged cyclic lactone utilizing alcohol as the initiator and organic base as the *** γ-butyrolactone monomers(PhSGBL and PhSeGBL)were synthesized efficiently from commercially available 3-cyclohexene-1-carboxylic *** to the ring strain of the bridged structure,ring-opening polymerization of this type of γ-butyrolactone derivative was successfully carried out under mild conditions,e.g.,using ethylene glycol as the initiator and a commercial catalyst[1,5,7-triazabicyclo[4.4.0 dec-5-ene(TBD)]]as the catalyst at 30℃.The obtained polymer could be degraded to its monomer for recycling in the presence of ZnCl_(2) as a *** and PhSeGBL could also be copolymerized with ε-caprolactone to tune the glass transition ***,the hydrophilicity of the obtained sulfur-containing polymers could be adjusted by selectively oxidizing the thioether side group to sulfone/sulfoxide,which offered a way to tune the hydrophilicity of *** the other hand,the obtained selenium-containing compound could be degraded in the presence of m-CPBA(3-chloroperbenzoic acid),which offered potential application in sustained drug release.

关键词： Ring-opening polymerization Polyester Closed-loop recycling Selective oxidation

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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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Characterization of single-handed,coiled,carbonaceous,tubular nanoribbons

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Chinese Chemical Letters 2014年第6期25卷 879-882页

作者： Dan Liu Yong-Min Guo Yi Li Bao-Zong Li Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

Left-handed, coiled, 4,4＇-biphenylene bridged polybissilsesquioxane, tubular nanoribbons were prepared according to the published literature. After carbonization and removal of silica using HF aqueous solution, left-handed, coiled, carbonaceous, tubular nanoribbons were obtained. The left- handed, coiled, carbonaceous, tubular nanoribbons were characterized using field-emission scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, Raman spectropho- tometer, diffuse reflectance circular dichroism （DRCD）, and N2 adsorptions. Micropores were formed due to the removal of silica. The nitrogen BET surface area is 1727 m2/g. A broad, positive DRCD signal, identified at 400-800 rim, indicates the carbonaceous, tubular nanoribbons exhibit optical activity. The helical pitch is proposed to play an important role in the position of the DRCD signal.

关键词： Nanoparticles Carbon/silica Sol-gel preparation Structural

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Preparation of single-handed helical phenolic resin nanoflbers using a supramolecular templating method

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Chinese Chemical Letters 2014年第10期25卷 1363-1366页

作者： Li-Qing Ma Hao Chen Yong-Min Guo Bao-Zong Li Yi Li Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

Single-handed helical phenolic resin nanofibers were synthesized through a supramolecular templating approach using the supramolecular self-assemblies of a pair of chiral low-molecular-weight amphiphiles as the templates and 2,4-dihydroxybenzoic acid and formaldehyde as the *** phenolic resin nanofibers were characterized using field-emission scanning electron microscopy,transmission electron microscopy and diffused reflection circular *** results indicated that the chirality of the supramolecular self-assemblies was successfully transferred to the phenolic resin *** left- and right-handed helical phenolic resin nanofibers exhibited opposite optical activity.

关键词： Supramolecular template Chirality Phenolic resins Nanofibers

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Preparation and characterization of helical carbon/silica nanofibers with lamellar mesopores on the surfaces

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Chinese Chemical Letters 2014年第2期25卷 253-256页

作者： Qing Wang Bao-Zong Li Yi Li Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

Helical 1,2-ethylene-silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like mesopores inside were prepared according to literature procedures. After carbonization, helical carbon/ silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like micropores inside were obtained. The morphologies and pore architectures of the carbon]silica nanofibers were characterized using transmission electron microscopy, field-emission scanning electron microscopy, powder X-ray diffraction and N2 sorptions. Although the mesopores inside shrank into micropores, the helical nanostructure remained. Moreover, several carbon/silica nanofibers with lamellar mesopores on the surfaces and concentric circular micropores inside were also obtained. After being calcined in air, helical silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like micropores inside were produced as well.

关键词： Nanoparticles Mesoporous Carbon/silica Sol-gel preparation Structural

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Controlling Morphology of Active Layer by Tuning Coplanarity of the Centrality in Acceptor-Donor-Acceptor Small Molecules for Photovoltaic application

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Chinese Journal of Chemistry 2013年第11期31卷 1439-1448页

作者： Pan Zhang Chao Li Yue Zhao Yaowen Li Yingfeng Tu 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 Suzhou Jiangsu 215123 China

A series of acceptor-donor-acceptor alternative small molecules were synthesized containing electron-donating central building moieties of phenothiazine, 2,7-carbazole and thieno[3,4-b]thiophene and electron-accepting moie- ties of tetrazine on both sides. The various conformations of the central blocks, with the coplanarity in an order of phenothiazine〈2,7-carbazole〈thieno[3,4-b]thiophene, have an obvious influence on the optical, electrochemical property and the crystallinity of small molecule. In addition, the blend films between small molecule and （6,6）-phenyl-C6rbutyric acid methyl ester offered significantly various morphologies, changing from uniform sur- face to interpenetrated networks. As a result, the bulk heterojunction photovoltaic devices based on the three small molecules provided varied performance, and the highest coplanar molecule based device exhibited the best photo- voltaic performance.

关键词： acceptor-donor-acceptor small molecules central blocks coplanarity morphology

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Influence from Thermal Elimination Temperature of Precursor polymer and Film-forming Methods on the Photophysics of the Poly（2,5-didodecyloxy-p-phenylenevinylene）

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Chinese Journal of Chemistry 2011年第10期29卷 2175-2181页

作者：王尚丽赵伟许晓前程丝范丽娟 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 Suzhou Jiangsu 215123 China

A series of poly（p-phenylenevinylene）s （PPVs） with good solubility were synthesized from thermal elimination of precursor poly（2,5-didodecyloxy-p-phenylenevinylene） at different temperature via Wessling method. The polymer photophysics were influenced by the thermal elimination condition, which was consistent with NMR and IR characterizations. The additional absorption peak at longer wavelength and the red-shifted emission maximum both in solution and in film, for PPVs obtained at high elimination temperature, indicated the existence of longer conjugated blocks in these systems. The emission maximum for drop-cast film （436 nm） for PPV obtained under 200 ℃ （PPV200） was 16 nm blue shifted to the spin-coated films （452 nm） or 29 nm to the solution （465 nm）. The SEM study showed drop-cast film had the morphology of isolated conjugated particles in the matrix while blurry linear structure was found for spin-coated film, which was consistent with the photophysics. The discussion about this difference was carried out based on the consideration of the flexibility of the polymer chains and different conjugated length of PPV in different states.

关键词： poly（p-phenylenevinylene） synthetic methods photophysics polymer precursor morphology

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