Synthesis of two dihydropyrroloindoledione‐based copolymers for organic electronics

Two novel dihydropyrroloindoledione (DPID)‐based copolymers have been synthesized in a two directional approach and characterized (gel permeation chromatography (GPC), ultraviolet‐visible (UV–vis), cyclic voltammetry, and computational models). These planar, broad absorption copolymers show promise for use in organic electronics, with deep energy levels and low bandgaps. The two‐directional Knoevenagel condensation used demonstrates the versatility of DPID as a useful yet underexploited conjugated unit. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of polythiophene block copolymer and fullerene derivative capable of “three‐point” complementary hydrogen bonding interactions and their application in bulk‐heterojunction solar cells

We report the synthesis and characterization of a polythiophene block copolymer (P4) selectively functionalized with diaminopyrimidine moieties and a thymine tethered fullerene derivative (F1). Self‐assembly between P4 and F1 through “three‐point” complementary hydrogen bonding is studied by ¹H NMR spectroscopy and differential scanning calorimetry. A large Stern‐Volmer constant (K_SV) of 1.2 × 10⁵ M^?1 is observed from fluorescence quenching experiments, revealing strong complexation between these two components. Solar cells employing P4 and F1 at different weight ratios as active layers are fabricated and tested; corresponding thin film morphologies are studied in detail by optical imaging and atomic force microscopy. Correlations between polymer complex structures, film morphologies, and device performance are discussed. Thermal stability of benchmark poly(3‐hexylthiophene) bulk heterojunction solar cells is found to be improved by the addition of a few weight percent of P4/F1 complexes as compatibilizers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3339–3350     

On the redox reactions of radicals with AlIII(phthalocyaninate) pendants covalently bonded to poly(ethyleneamide). Mechanistic alterations when radicals are formed inside pockets of micelle‐like polymer aggregates

The mechanisms of the redox reactions between a polymer containing Al(III) sulfonated phthalocyanine pendants, (Al^III(^?NHS(O₂)trspc)^2?)₂, and radicals have been investigated in this work. Pulse radiolysis and photochemical methods were used for these studies. Oxidizing radicals, OH^?, HCO₃^?, (CH₃)₂COHCH₂^?, and N₃^?, as well as reducing radicals, e_aq^?, CO₂^??, and (CH₃)₂C^?OH, respectively accept or donate one electron forming pendent phthalocyanine radicals, Al^III(^?NHS(O₂)trspc ^?)^{? or 3?}. The kinetics of the redox processes is consistent with a mechanism where the pendants react with radicals formed inside aggregates of five to six polymer strands. Electron donating radicals, that is, CO₂^?? and (CH₃)₂C^?OH, produce one‐electron reduced phthalocyanine pendants that, even though they were stable under anaerobic conditions, donated charge to a Pt catalyst. While the polymer was regenerated in the Pt catalyzed processes, 2‐propanol and CO₂ were respectively reduced to propane and CO. The reaction of SO₃^?? radicals with the polymer stood in contrast with the reactions of the radicals mentioned above. A first step of the mechanism, the coordination of the SO₃^?? radical to the Al(III), was subsequently followed by the formation of a SO₃^?? ‐ phthalocyanine ligand adduct. The decay of the SO₃^?? ‐ phthalocyanine ligand adduct in a ～10² ms time domain regenerates the polymer, and it was attributed to the dimerization/disproportionation of SO₃^?? radicals escaping from the aggregates of polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymer electrolyte membranes based on polystyrenes with phosphonic acid via long alkyl side chains

A series of polystyrenes with phosphonic acid ( 5 ) via long alkyl side chains (4, 6, and 8 methylene units) were prepared by the radical polymerization of the corresponding diethyl ω‐(4‐vinylphenoxy)alkylphosphonates, followed by the hydrolysis with trimethylsilyl bromide. The resulting phosphonated polystyrene membranes had a high oxidative stability against Fenton's reagent at room temperature. The membranes prepared from 5 exhibited a very low water uptake, similar to that of Nafion 117 over the wide range of 30 to 80% relative humidity (RH). The proton conductivities of these membranes are lower than that of Nafion 117 in the range of 30 to 90% RH, but comparable or higher than those of the reported phosphonated polymers with higher IEC values, such as the phosphonated poly(N‐phenylacrylamide) (PDPAA, IEC: 6.72 mequiv/g) and fluorinated polymers with pendant phosphonic acids (M47, IEC: 8.5 mequiv/g), at low RH conditions despite the much lower IEC values (3.0–3.8 mequiv/g) of these membranes. These results suggest that the flexible pendant side chains of 5 would contribute to the formation of hydrogen‐bonding networks by considering the very low water uptake of these polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Syntheses and structural characterization of New Tl + and K + complexes of 3,5-dinitrobenzoic acid (HDNB), [Tl(μ-DNB)] n and [K(μ-DNB)(μ-HDNB)] n

Two new Tl⁺ and K⁺ complexes of 3,5-dinitrobenzoic acid (HDNB), [Tl(μ-DNB)] _n and [K(μ-DNB)(μ-HDNB)] _n have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. Determination of the structure of the [K(μ-DNB)(μ-HDNB)] _n and [Tl(μ-DNB)] _n by X-ray crystallography shows that there are nine coordinate K atoms (KO₉) and eight coordinate Tl atoms (TlO₈). The [Tl(μ-DNB)] _n and [K(μ-DNB)(μ-HDNB)] _n complexes are 2D and 3D coordination polymers, respectively.     

Synthesis and characterization of phenol‐based biaryl proton conducting polymers

Biaryl hydroxy polymers with orthogonal disposition of proton transporting ? OH moieties have been synthesized via conventional free radical polymerization. The polymers are characterized for their thermal stability and proton conductivity, and the results are compared with the corresponding styrenic hydroxy polymers. The orthogonal disposition of ? OH moieties in biaryl polymers does result in lower E_a for proton transport. However, the lower E_a values in biaryl polymers did not translate into a net increase in proton conductivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

聚苯乙烯芪盐L—B膜的二阶非线性光学性质研究

首次合成了一种称之为聚苯乙烯芪盐的有机高分子材料.此材料可以在水面上形成稳定的单分子层膜,并且所形成的单分子层膜可以转移到固体衬底上去.对聚苯乙烯芪盐单分子层膜进行光学二次谐波产生测量,得到聚苯乙烯芪盐对应于每个发色团的二阶非线性极化率为1.2×10~(-28)esu.制备了该材料两种不同类型的多层膜,讨论了多层膜二次谐波产生信号不随层数增加而增加的可能原因.     

The electrical properties of semiconductor/metal,semiconductor/liquid,and semiconductor/conducting polymer contacts

Critical comparisons are drawn between the basic electrical properties of semiconductor/metal, semiconductor/liquid, and semiconductor/conducting polymer junctions. A theoretical model is developed to describe the basic current-voltage properties of semiconductor contacts, with emphasis on the contrasts between ideal and observed behavior. Using the concepts from this model, the characteristics of a variety of semiconductor contacts are evaluated. The discussion focuses on the following semiconductors: Si, GaAs, InP, and II-VI compounds based on the Cd-(chalcogenide) materials.     

HIPS的γ辐照效应的正电子寿命谱研究

测量了高强度聚苯乙烯（ＨＩＰＳ）的正电子寿命谱随γ辐照剂量的变化，观察到自由体积孔洞的平均半径随辐照剂量的增加而基本不变，且自由体积孔洞的浓度和半径分布宽度随辐照剂量的增加而减小．这一实验结果表明，γ辐照后高强度聚苯乙烯力学性能的改善与自由体积特性的变化相关联．     

含丙氧甲基冠醚侧基的线型聚甲基硅氧烷液膜离子传输性能

烯丙氧甲基１５－冠－５和１８－冠－６与甲基二氯硅烷进行硅氢加成，再与端羟基硅油反应，三甲基氯硅烷封端，得到两种冠醚含量适中、结构确定的含冠醚侧基的线型聚甲基硅氧烷．以两种聚合物冠醚为流动载体，采用大块液膜装置，研究了载体和阳离子的种类、成盐阴离子的种类、载体的浓度及盐的浓度对离子迁移的影响，并考察了膜的稳定性．