共轭聚合物发光和光伏材料研究进展

聚合物光电功能材料与器件因其广阔的应用前景,1990年以年来吸引了世界各国学术界的广泛关注和兴趣.聚合物光电子器件主要包括聚合物电致发光二极管、聚合物场效应晶体管和聚合物太阳能电池等,其使用的关键材料是共轭聚合物光电子材料,包括共轭聚合物发光材料、场效应晶体管材料和光伏材料等.本文主要对共轭聚合物电致发光材料和光伏材料的研究进展进行综述,介绍了这些聚合物材料的种类、结构和性质以及在聚合物电致发光器件和聚合物太阳能电池中的应用.并讨论了当前共轭聚合物光电子材料中的关键科学问题和今后的发展方向.     

聚合物太阳能光伏技术研究进展

聚合物太阳电池因其结构简单、成本低、重量轻和可制成柔性器件等突出优点,近年来受到广泛关注,成为发展绿色可再生能源的重要方向。聚合物太阳电池中的给体和受体光伏材料是决定器件性能的关键,本文综述了共轭聚合物给体和富勒烯受体光伏材料的最新研究进展,并在共轭聚合物给体材料中对聚噻吩衍生物以及窄带隙D-A共聚物进行了重点介绍。同时讨论了薄膜优化和器件稳定性,最后从提高电池效率的几个方面展望了聚合物太阳电池的发展方向。     

聚合物材料结晶度（上）

本文介绍了结晶度概念及IUPAC高分子专业委员会最近有关结晶度各述语的一些规定,几种常用的结晶度测定方法,如X射线衍射、量热法、密度测量、红外光谱法等,对X射线衍射方法作了重点叙述.     

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。     

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。     

含胍基抗菌聚合物的合成及应用

开发能与细菌非特异性结合的新型抗菌剂是解决细菌感染难题的方法之一。本文首先介绍了一种具有持久广谱高效抗菌性、无真核细胞毒性和细菌很难产生耐药性的含胍基抗菌聚合物;接着详细介绍了含胍基抗菌聚合物与细菌非特异性静电结合的抗菌机理;然后重点评述了主链含胍基抗菌聚合物、侧链含胍基抗菌聚合物以及表面接枝含胍基抗菌聚合物的设计理念、合成方法和抗菌性能;最后对新型含胍基抗菌聚合物的可控合成策略及应用前景进行了展望。     

光折变聚合物材料研究进展

综述近年来光折变聚合物的材料的研究现状，着重介绍光折变聚合物材料的化学结构，组成及光折变性能。简单分析当前研究工作所面临的问题。     

二次锂电池聚合物正极材料研究进展

近几十年,二次锂电池作为重要的储能装置得到迅猛发展,而开发高性能的锂电池电极材料一直是电化学能源领域的研究热点之一。与传统无机正极材料相比,聚合物正极材料具有比容量高、柔软性好、廉价易得、环境友好、加工方便、可设计性强等诸多优点。本文综述了导电聚合物、共轭羰基聚合物以及含硫聚合物正极材料的结构特点、电极反应机理、电化学性能和近五年来的重大研究进展,总结了这三类聚合物电极材料的优缺点,并重点介绍了含硫聚合物电极材料中存在的问题及改进手段,最后提出了综合这三类聚合物优点的含硫共轭导电聚合物将会是该领域的研究方向。     

仿生聚合物的制备及其分子识别作用

本文评述了仿生聚合物的制备及其对分子的识别作用和在分离和生物医用材料方面的应用。     

高聚物的热传导性质

对聚合物固体、熔体和溶液的传导性质分别进行了论述,介绍了各控制因素对它们热传导的影响,阐述了研究聚合物热传导性质今后的发展方向。     

基于吡咯并吡咯二酮和苯并噻二唑聚合物的合成及其近红外电致变色性能

给-受体型窄带隙聚合物是一类新型可见-近红外电致变色材料,虽然可调性强、颜色丰富,但是其电致变色性能如对比度、稳定性等需要进一步提高。 通过调节聚合物中构筑单元吡咯并吡咯二酮(DPP)、苯并噻二唑(BTZ)和噻吩(T)的比例(n(DPP):n(BTZ):n(T)分别为1:0:1、1.5:0.5:1、2:1:1和3:2:1),合成了4种新型窄带隙电致变色聚合物,研究聚合物结构和电致变色性能的关系。 研究发现,这类聚合物在近红外光谱区具有较高的对比度(ΔT:50%60%)和变色效率(CE:300600 cm²/C),尤其是在1550 nm处,聚合物P3的ΔT高达63%、P4的CE高达471 cm²/C。 相比之下,含有BTZ基团的聚合物的吸收更长、对比度更高且更稳定。 这为设计给-受体型高性能电致变色聚合物提供了新的思路。     

High performance weak donor-acceptor polymers in thin film transistors: effect of the acceptor on electronic properties, ambipolar conductivity, mobility, and thermal stability

We have studied the electronic, physical, and transistor properties of a family of donor-acceptor polymers consisting of diketopyrrolopyrrole (DPP) coupled with different accepting companion units in order to determine the effects of donor-acceptor interaction. Using the electronically neutral benzene (B), the weakly accepting benzothiadiazole (BT), and the strongly accepting benzobisthiadiazole (BBT), the accepting strength of the companion unit was systematically modulated. All polymers exhibited excellent transistor performance, with mobilities above 0.1 cm(2)V(-1)s(-1), even exceeding 1 cm(2)V(-1)s(-1) for one of the BBT-containing polymers. We find that the BBT is the strongest acceptor, enabling the BBT-containing polymers to be strongly ambipolar. The BBT moiety also strengthens interchain interactions, which provides higher thermal stability and performance for transistors with BBT-containing polymers as the active layer.     

Stereochemistry of the free‐radical polymerization of zinc methacrylates coordinated with a bidentate ligand

The polymerization of zinc methacrylates coordinated with a bidentate ligand ( 1 – 4 ) was carried out in chloroform at 60°C. The polymerization of these monomers gave chloroform‐insoluble polymers. Stereoregularity of the polymers was estimated from ¹H NMR spectra of poly(methyl methacrylate)s (PMMAs) derived from the original polymers. Monomers 1 and 2 gave slightly different polymers compared with conventional ones obtained by polymerization of methacrylic acid, while 3 afforded higher amounts of isotactic polymers than 1 and 2 . Conversely, 4 gave a polymer of high syndiotacticity. Furthermore, the relationship between triad tacticity and monomer concentration in the feed was studied. Consequently, it was demonstrated that the structure of bidentate ligands coordinated with zinc ion influences the stereoregularity of the resulting polymers.     

Synthesis and Characterization of Amphiphilic PEG Based Aliphatic and Aromatic Polymers and their Self-Assembling Behavior

Twelve amphiphilic polymers were synthesized using poly(ethylene glycols) (PEGs) of different molecular weights, viz. 1000, 2000 and 4000 as hydrophilic block and linkers namely azelaic acid, sebacic acid, dimethyl isophthalate acid and dimethyl terephthalate as hydrophobic block in the presence of catalyst Conc. H₂SO₄. Synthesized polymers were characterized by using ¹H-NMR, ¹³C-NMR and IR spectroscopy. Micellar sizes of the polymers were determined using Dynamic Light Scattering (DLS) which ranged from 51.6–174 nm for aliphatic polymers and 135.5–371 nm for aromatic polymers. Transmission Electron Microscope (TEM) results confirm the findings of DLS. Critical Micelle Concentrations (CMC) of the synthesized polymers were determined using electrical conductivity meter which ranged from 95 to 130 mg L^?1 for aliphatic polymers and 420–1500 mg L^?1 for aromatic polymers.     

类蜘蛛丝聚合物结构及分子运动的固体核磁共振研究

运用固体核磁共振(NMR)技术研究了聚丙氨酸多肽片段(Ala)5与高分子齐聚物聚苯乙烯(PS, 分子量2000)及聚异戊二烯(PI, 分子量2210)共聚而成的类蜘蛛丝蛋白聚合物——聚苯乙烯-co-聚丙氨酸聚合物(PS-co-PAL)和聚异戊二烯-co-聚丙氨酸聚合物(PI-co-PAL)的结构及分子运动. 聚合物13C CP/MAS NMR(交叉极化/魔角旋转核磁共振)谱及其旋转坐标系中自旋-晶格弛豫时间(T1ρ(13C))的结果表明, 此两种聚合物中多肽片段(Ala)5具有相同的化学位移, 即相似的化学环境和二级结构, 并具有相近的T1ρ(13C), 即类似的聚集态结构. 聚合物的宏观力学性质明显不同: 常温下, PS-co-PAL呈硬颗粒状, PI-co-PAL呈橡胶状且易拉伸. 结果说明聚合物力学性质与高分子链段的性质密切相关. PI-co-PAL聚合物的PI链段, 其骨架—CH2CH—的T1ρ为(5.3±0.4) ms, 而PS-co-PAL聚合物的PS链段, 其骨架—CH2CH—的T1ρ为(47.0±5.5) ms, 说明二聚合物中PI链段较PS链段更为柔软. 另外, 基于密度泛函理论(DFT)的化学位移计算证明, 聚合物PS-co-PAL和PI-co-PAL中多肽片段(Ala)5的二面角均为(-131°, 142°), 说明它们以β-折叠构象存在.     

Preparation and characterization of the soluble NLO polyarylates with enhanced electro-optic properties

Three novel nonlinear optical polyarylate polymers were prepared containing one main-chain polymer (mPAR-chr1) and two side-chain polymers (sPAR-chr1, sPAR-chr2) with different kinds of chromophores. The obtained polymers were characterized and evaluated by UV-Vis, ¹H NMR, DSC and TGA. All the polymers exhibited excellent thermal stability, film forming ability and good electro-optic (EO) activity. The relationship between EO coefficients (r ₃₃) and the chromophore concentration of the three polymers had been also characterized and discussed. There were no obvious differences found in EO activity between main-chain and side-chain polyarylates with the same chromophore (chr1). Due to the stronger electron-withdrawing tricyanopyrroline acceptor and the steric effect of the large dendritic groups of chromophore 2 (chr2), polymer sPAR-chr2 showed the largest EO cofficients (64 pm V^?1) in these new polymers.     

Control of polymer topology through transition-metal catalysis: synthesis of hyperbranched polymers by cobalt-mediated free radical polymerization

A novel approach was demonstrated for the synthesis of hyperbranched polymers by direct free radical polymerization of divinyl monomers controlled by a cobalt chain transfer catalyst (1). By controlling the competition between propagation and chain transfer with 1, the free radical polymerization of ethylene glycol dimethacrylate (3) afforded soluble hyperbranched polymers in one pot. The structure of the hyperbranched polymers was confirmed by (1)H and (13)C NMR. The molecular weight and intrinsic viscosity of the hyperbranched polymers were measured by matrix-assisted laser desorption ionization (MALDI) mass spectrometry and size exclusion chromatography (SEC) equipped with triple detectors. The intrinsic viscosities of the hyperbranched polymers are much lower than those of their linear analogues and do not show molecular weight dependence. The unique structure and properties of these hyperbranched polymers combined with the commercial availability of many divinyl monomers and the robustness of free radical polymerization make this new approach attractive for the preparation of new functional materials.     

Study of interpolymer complex formation of polyvinylpyrrolidone and poly(ethylene oxide) with phenolic polymers in nonaqueous media

A study was made of interpolymer complex formation between polyvinylpyrrolidone (PVP) and poly(ethylene oxide) (PEO) with phenolic polymers (PPF) in an acetone–methanol mixture by several methods; for example, viscosity, potentiometry, conductometry, turbidity, and precipitate (complex) weight. A distinct stepwise complex formation between PVP and phenolic polymers was observed by these methods. As in polycarboxylic acid, however, PEO formed a 1:1 complex with phenolic polymers. Some of these observations have been interpreted in terms of the structure of the polymers, preferential solvation of the component polymers, and the probable change in conformation of the complex molecules in mixed solvents.     

Synthesis and characterization of poly(4-vinylpyridine) substituted with a novel betaine salt derived from 4,5-dicyanoimidazole

A novel betaine internal salt ( 3 ) has been synthesized by the reaction of pyridine with 1-methyl-2-bromo-4,5-dicyanoimidazole ( 1 ). The reaction of pyridine with 1 serves as a model for the reaction of poly(4-vinylpyridine) with 1 . The reaction of poly(4-vinylpyridine) with 1 gives betaine salt substituted polymers which were characterized by IR, NMR, UV-visible spectroscopy, and viscometry. The substituted polymers were compared to the model compound ( 3 ) and to unsubstituted poly(4-vinylpyridine) in order to determine polymer structure and the degree of substitution. One of the substituted polymers shows polyelectrolyte behavior. Thermal characterization of the substituted polymers shows two exothermic transitions at 260 and 340°C attributed to chemical reactions of the pendant groups.     

Linear polymers of acrylic monomers containing an acetylenic moiety

1-Acryloxy-2-butyne and 1-methacryloxy-2-butyne were synthesized and polymerized by means of anionic initiators to soluble linear polymers containing acetylenic bonds in the pendant side chains. In contrast, insoluble, crosslinked polymers were formed when cationic and radical initiators were used. The unpolymerized acetylenic bonds in the resulting linear polymers were shown to be present by infrared spectroscopic methods and by the following post-reactions of these bonds: (1) the thermal- and radical-initiated crosslinking of the linear polymers through the acetylenic bonds; (2) the post-bromination of the acetylenic bonds; and (3) the reaction of decaborane with the acetylenic bonds. The anionic copolymerization of both monomers with a number of selected monomers was performed and the copolymer reactivity ratios for several of the comonomer pairs were determined. Dibromination of the linear polymers affords self-extinguishing polymers with apparently good hydrolytic stability. Decarbonation of the linear polymers yields soluble polymers which do not soften up to 300°C. The linear polymers and copolymers, as well as their partially brominated and partially decaboronated products, may be classified as “self-reactive” polymers which yield thermosetting polymers.