SYNTHESIS AND CHARACTERIZATION OF NOVEL BIPOLAR PPV-BASED COPOLYMER CONTAINING TRIAZOLE AND CARBAZOLE UNITS*

Two new blue light-emitting PPV-based conjugated copolymers containing both an electron-withdrawing unit(triazole-TAZ) and electron-rich moieties (carbazole-CAR and bicarbazole-BCAR were prepared by Wittig condensationpolymerization between the triazole diphosphonium salt and the corresponding dialdehyde monomers. Their structures andproperties were characterized by FT-IR, TGA, DSC, UV-Vis, PL spectroscopy and electrochemical measurements. Theresulting copolymers are soluble in common organic solvents and thermally stable with a T_g of 147℃ for TAZ-CAR-PPVand of 157℃ for TAZ-BCAR-PPV. The maximum photoluminescence wavelengths of TAZ-CAR-PPV and TAZ-BCAR-PPV film appear at 460 nm and 480 nm, respectively. Cyclic voltammetry measurement demonstrates that TAZ-BCAR-PPVhas good electrochemical reversibility, while TAZ-CAR-PPV exhibits the irreversible redox process. The triazole unit wasfound to be an effective π-conjugation interrupter and can play the rigid spacer role in determining the emission colour ofthe resulting copolymer.     

Novel Bipolar Conjugated Polymer Containing Both Triphenylamine and Oxadizole Units

A novel bipolar conjugated polymer containing triphenylamine and 1,3,4-oxadiazole units was synthesized by Suzuki reaction.Its structure and properties were characterized by NMR,IR,UV-Vis,PL spectroscopy and electrochemical measurement. The photoluminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.     

共轭聚合物材料及电致发光器件

共轭聚合物是一种极有应用前景的有机半导体材料,本文综述其研究进展,包括典型共轭聚合物材料PPV、PT、PF等及PPP的工作原理,发展前景和存在的问题。     

导电高分子材料的应用和进展

论述了复合型及结构型导电高分子材料的导电机理、应用和研究进展。     

Orthogonal surface-grafted polymer gradients: A versatile combinatorial platform

Orthogonal polymer brush gradients are assemblies of surface-anchored macromolecules, in which two material properties of the grafted chains (e.g., grafting density, molecular weight) vary independently in orthogonal directions. Here, we describe the formation and applications of two such orthogonal assemblies, involving: (1) molecular weight and grafting density (MW/σ) gradients of a given polymer and (2) molecular weight gradients (MW1/MW2), of two different polymers. Each point on orthogonal gradient substrate represents a unique combination of the two surface properties being varied, thus facilitating systematic investigation of a phenomenon that depends on the two said properties. We illustrate this point by employing orthogonal structures to study systematically: (1) formation of polymer brush-nanoparticle composite assemblies, (2) protein adsorption and cell adhesion, and (3) chain conformations in tethered diblock copolymers exposed to selective solvents. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3384–3394, 2005     

含氟硅聚合物的合成及应用

含氟硅聚合物作为一种新型材料,有机结合了含氟聚合物和含硅聚合物的优点,成为材料领域研究开发的热点之一。本文综述了含氟硅聚合物合成的研究进展,介绍了其应用情况。     

聚甲基丙烯酸三乙基锡酯的溶度参数和溶液性质研究

本文研究了聚甲基丙烯酸三乙基锡酯(PTETM)在二十五种溶剂中的溶解性能。测定了PTETM试样在不同溶剂中的特性粘数,估算了PTETM的三维溶度参数为:δ=18.8(J/cm~3)~(1/2);δ_d=16.8(J/cm~3)~(1/2);δ_p=6.28(J/cm~3)~(1/2);δ_h=5.73(J/cm~3)~(1/2)。并就聚合物中锡原子上的取代基对其溶解性能的影响进行了讨论。作者还订定了PTETM在四氢呋喃溶液中,25℃时的MHS方程为[η]=2.55×10~(-3)M_w~(0.691);在甲苯溶液中,30℃时的MHS方程为[η]=2.79×10~(-3)M_w~(0.662)。利用Burchard-Stockmayer-Fixman关系,由四氢呋喃体系(25℃)和甲苯体系(30℃)所求得的Flory特征比C_∞=9.4。     

Polymers as drugs—Advances in therapeutic applications of polymer binding agents

Polymer drugs are those in which a polymer agent has a direct therapeutic effect on the body. A major investigated area of polymer drugs is their use as binding agents, or sequestrants, which can neutralize or remove undesired components from the body. By taking advantage of the unique properties of crosslinked, insoluble polymers, new polymer drugs continue to be developed for oral use, acting in the gastrointestinal tract and excreted in the feces. Soluble polymer binders may be administered by a variety of routes and act at diverse sites of therapeutic action. This article reviews the properties of polymer drugs, particularly sequestrants, with an emphasis on recent advances in polymer properties which may enhance the utility of this class of drugs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3146–3157     

导电性聚西佛碱的研究：Ⅰ含硫聚西佛碱的合成,性能及表征

采用对氯苯甲醛和联苯二胺为原料,合成了4,4′-二氯代苄叉联苯胺,发现该化合物具有热致液晶性。利用所合成的二氯代化合物与硫化钠在醋酸锂催化下缩取得得到了含硫聚西佛碱探讨了高分子量含硫聚西佛碱的合成方法。测出该含硫聚西佛碱具有3.4×10~(-11)S/cm本征导电率。使用红外光谱、元素分析等方法表征了所合成的聚合物。     

Synthesis and fabrication of highly functionalized Jeffamine antimicrobial polymeric coating

A simple, robust, and eco‐friendly technique for the fabrication of functionalized Jeffamine polymer in an aqueous medium is developed. The polymer is prepared by post polymerization modification of Jeffamine ED‐2003 of molecular weight 2000. The structure of the modified polymer was studied in detail using FTIR and NMR (¹H and ¹³C NMR) spectroscopic methods. The thermal properties and degradation of the polymer were examined by DSC and TGA techniques. The polymer exhibited glass transition temperature (T_g) at 115°C. The functionalized polymeric compound showed good antimicrobial activity against gram‐negative bacterium Escherichia coli, a tubercular variant Mycobacterium smegmatis, and gram‐positive bacterium Staphylococcus aureus with a zone of inhibition of 6 to 12, 9, and 5 to 9 mm diameter, respectively. The compound also showed good activity against the fungus, Candida albicans, with a zone of inhibition of 6 to 11 mm diameter. The morphology of the polymer films and interaction of the microbes with functionalized Jeffamine polymer were investigated by using scanning electron microscopy (SEM).     

环糊精与聚合物的包合作用

本文着重介绍了环糊精及其衍生物与聚合物所形成的各种包合物,并扼要介绍了它们的研究和应用前景。     

Template-Free Self-Assembly of Two-Dimensional Polymers into Nano/Microstructured Materials

In the past few decades, enormous efforts have been made to synthesize covalent polymer nano/microstructured materials with specific morphologies, due to the relationship between their structures and functions. Up to now, the formation of most of these structures often requires either templates or preorganization in order to construct a specific structure before, and then the subsequent removal of previous templates to form a desired structure, on account of the lack of “self-error-correcting” properties of reversible interactions in polymers. The above processes are time-consuming and tedious. A template-free, self-assembled strategy as a “bottom-up” route to fabricate well-defined nano/microstructures remains a challenge. Herein, we introduce the recent progress in template-free, self-assembled nano/microstructures formed by covalent two-dimensional (2D) polymers, such as polymer capsules, polymer films, polymer tubes and polymer rings.     

两亲性笼型倍半硅氧烷（POSS）杂化高分子的自组装

笼型倍半硅氧烷（POSS）是一种由si-O-si键构成的高度对称笼型结构、端基具有极高的可设计性及高反应性新型有机一无机杂化材料,空间尺寸1～3nm;选取带有特定结构的光、电、磁等特性单元,利用活性聚合的方法可制得不同形状的POSS-Polymer杂化材料,通过溶剂、热、电、纳米印刷等方法“梳理”分子链结构,使之成为长程有序的纳米序列结构材料,获取具有预期结构和功能特性的高分子实体。本文从分子自组装的角度对两亲性笼型倍半硅氧烷（POSS）杂化高分子材料进行了介绍,分析了其在生物医药用高分子、智能高分子及低介电高分子材料等多个领域内的最新研究进展,并对今后的发展做了相关的预测与展望。     

树形聚醚的合成及其应用

树形聚合物高度支化,与线形结构的聚合物相比具有较低的粘度及良好的溶解性,而且其单分子尺寸通常在纳米尺度,在多方面具有广阔的应用前景。树形聚合物通常分为3种,即树枝状聚合物、超支化聚合物和树枝化聚合物。作为树形聚合物的主要一类,树形聚醚由于其良好的化学、物理稳定性,良好的水及有机溶剂的溶解性,以及生物相容性等诸多优点,其合成及应用研究得到了广泛重视。本文对不同种类树形聚醚的合成及其应用作一详尽的综述,包括树枝状聚醚、树枝化聚醚及超支化聚醚3种主要类型,同时报道了作者等在该领域的最新研究进展,并对该领域的研究进行了相应的展望。     

氟碳端基聚合物合成及其表面吸附性能

综述了近十年来氟端基聚合物的合成,表征及其在表面吸附行为的研究成果。通过含有氟烷基的引发剂或终止剂在活性阴离子聚合反应或自由基聚合反应中使聚合物接上氟端基。已经成功地利用活性阴离子聚合反应合成了氟端基聚苯乙烯,通过含氟自由基引发烯类单体（如丙烯酸,乙烯硅等）可在相应聚合物链上引入氟端基,另外,聚合物的化学改性方法也可将氟基团接在聚合物链端（如氟基聚氧乙烯,氟端基聚合物具有的表面活性,当水溶液中或聚     

An Overview of Important Microstructural Distributions for Polyolefin Analysis

Summary: Polyolefins with complex microstructures are becoming increasingly common in academic and industrial applications. Polyolefin analytical techniques are evolving to provide a more detailed picture of these microstructures, with the development and improvement of hyphenated-techniques and cross-fractionation methods. These modern analytical techniques provide a wealth of information on polyolefin microstructure and, despite being extremely useful, they can also be hard to interpret without the help of mathematical models that link polymerization kinetics to chain microstructure and polymer characterization results. In this paper we review some of the most important distributions for polyolefin microstructure and derive a few new expressions that help understand the results obtained with several polyolefin characterization techniques.     

一类新型的呈树状支化的合成高分子

树状支化高分子是一类近几年中新出现的高分子化合物.本文介绍了这类树状分子的发展与现状以及它们在结构、性能方面的特点;对这一领域内几位主要研究者,包括Dow化学公司Tomalia博士、South Florida大学Newkome教授、Cornell大学Frechet教授的工作做了简要的评述,同时对这类化合物在合成与应用方面的前景做了一些初步的讨论.     

Studies on Novel Polymer Materials Prepared through Intermacromolecular Complexation

The basic feature of polymers is their multi-order structure. Structure change at each level offers a possibility tomodify polymer properties and to develop new polymer materials. Therefore,novel polymer materials can be developed by tailoring their chain structure through chemical bonding among atoms, i.e., via the traditional molecular chemistry methods, e.g., polymerization of new monomer, controlling chain length (molecular weight and molecular weight distribution) and stereoregularity, copolymerization of different kinds of monomers, controlling sequence distribution,block of graft length of copolymer, etc., which have been the focus of polymer chemistry for several decades, as well as by tailoring specific supramolecular architecture using molecules as building block through intermolecular interactions, i.e., via supramolecular science methods, e.g., molecular self-assembly, intermacromolecular complexation, etc., which is a modern and fast-developing academic research field.This paper reports novel polymer materials prepared through intermacromolecular complexation,e.g., a new polymer solid electrolyte poly(metyl methacrylate-methacrylic acid)[P(MMA-MAA)]/poly(ethylene oxide) (PEO)/A2-LiClO4 developed by intermacromolecular complexation through hydrogen bonding, which has enhanced ambient ionic conductivity and fairly good mechanical and film-forming properties, a new polymer microcomposite poly(acrylonitrile-acrylamide-acrylic acid) [P(AN-AM-AA)]/poly(vinyl alcohol) (PVA) reinforced by the twin molecular chain microfibrils formed through intermacromolecular complexation of P(AN-AM-AA) with PVA through hydrogen bonding, which exhibits much better mechanical properties than its constituents and could be used to manufacture PVA based complexed fibers with higher modulus and better dyeability, a new polymer flooding agent poly(acrylamide-acrylic acid)[P(AM-AA)]/poly(acrylamide- dimethyldiallylammonium chloride) [P(AM-DMDAAC)] developed by intermacromolecular complexation of the oppositely charged polyions through Coulomb forces,which shows much higher viscosity and better resistance to temperature, shear rate and salt than its constituents, and has potential application in enhanced oil recovery.     

Carbenoid polycondensation with telechelic polyethers having dichloroacetic acid ester groups

Poly(ethylene oxide) [poly(EO)], with number-average molecular weights (M_ns) of 1000 and 2000, and poly(tetrahydrofuran) [poly(THF)] with M_ns of 1000 and 2000, possessing dichloroacetic acid ester end groups ( 1 , and 2 , respectively) were prepared from precursor diols by esterification with dichloroacetyl chloride in the presence of pyridine. 1 and 2 were subjected to the reaction with copper metal in DMSO to produce the corresponding segmented polyethers containing fumarate/maleate groups within the main chain ( 3 and 4 , respectively), through a polycondensation of carbalkoxy carbenoid intermedlates generated via α, α-dichloro elimination from the end groups of 1 and 2 . The radical polymerization of styrene in the presence of 3 and 4 produced network copolymers consisting of poly (EO) or poly(THF) and polystyrene segments. © 1994 John Wiley & Sons, Inc.