基于聚3-己基噻吩的嵌段共聚物研究进展

随着全球对新能源、新材料研究领域的战略提升,聚3-己基噻吩(P3HT)作为导电共轭聚合物的相关研究已成为近年来的一个热点,并取得了突飞猛进的进展。P3HT均聚物受其激发子寿命短的影响,其光电转换效率有限,而嵌段共聚物可以实现微相分离,进而可以实现提高有机光伏材料的光电转换效率的目的。总结了近年研究者们合成的嵌段共聚物及其合成方法。     

高等规聚3-己基噻吩的合成与研究

基于GRIM法合成了高等规的聚3-己基噻吩(rr-P3HT),研究了反应中催化剂和格氏试剂用量、反应温度和时间对产物产率的影响。采用GPC、1H-NMR和TGA法对其结构进行表征,结果显示该聚合物具有高度的规整性和良好的热稳定性。通过紫外吸收光谱、荧光发射光谱表征了聚合物的光物理性能,其最大紫外吸收峰和相应的发射峰分别位于455nm和573nm。     

聚3-己基噻吩/碳纳米管薄膜的制备及电导性能研究

利用化学氧化法原位聚合制备了聚3-己基噻吩(P3HT)/多壁碳纳米管(MWNT)纳米复合薄膜。透射电子显微镜表明,MWNT在复合薄膜中的分散均匀性得到了提高;通过UV-Vis光谱证实了MWNT和P3HT之间存在着强烈的相互作用;四探针法测试表明,P3HT/MWNT纳米复合物具有半导体电导特征,最高电导率可达0.15 S/cm。     

聚（3-己基噻吩）-聚苯乙烯嵌段共聚物的一锅法制备

采用具有聚苯乙烯高分子链为配位基团的聚合催化剂,催化2,5-二溴-3-己基噻吩单体进行Kumada缩聚反应,利用一锅法制备了聚（3-己基噻吩）-聚苯乙烯嵌段共聚物。结果表明：采用一锅法,在室温、常压条件下进行一步聚合直接生成嵌段共聚物,反应过程简单,聚（3-己基噻吩）与聚苯乙烯嵌段对接率接近100%;与聚（3-己基噻吩）相比,聚（3-己基噻吩）-聚苯乙烯嵌段共聚物的结晶性能更好。     

3-己基噻吩与3-乙羧基噻吩电化学共聚与性能研究

研究了 3 己基噻吩单体及 3 己基噻吩与 3 乙羧基噻吩电化学共聚合成的合成原理、合成条件及方法。对 3 己基噻吩与 3 乙羧基噻吩电化学共聚物的电导率、导电稳定性、溶解度、相对分子质量及红外光谱特性进行了测试和分析。结果表明 ,共聚物较单体分子量增大 ,性能得到明显改善 ,特别是导电稳定性和机械性能改善较大     

“聚(3-己基噻吩)性质表征”应用于聚合物现代仪器分析实验教学的探讨

聚(3-己基噻吩)(P3HT)是一种重要的导电聚合物,其化学结构、光物理性质、相对分子质量、结晶性、热稳定性及表面形貌等测试表征涉及的仪器非常广泛。文章分析了以“聚(3-己基噻吩)性质表征”作为聚合物现代仪器分析实验课程基本实验的可行性及优势。认为该综合实验贯穿于聚合物现代仪器分析的实验教学,可使实验分为四个方面相关的内容,“波谱分析法”、“凝胶渗透色谱法”“热分析法”“电子显微镜”等有机结合,不仅能帮助学生掌握各种相关仪器的使用原理及分析方法,又能使他们直观清晰地了解各种方法的关联性及独立性,并且在教学过程中结合了科研实际需求,将理论知识与实践紧密结合起来。     

4-（5-甲醛基-2-噻吩基）-7-（己-噻吩基）[2，1，3]苯并噻二唑的合成

采用两种不同的途径合成了4-（5-甲醛基-2-噻吩基）-7-（2-噻吩基）[2，1，3]苯并噻二唑。研究结果表明，DMF／POCl3体系较n—BuLi／DMF体系产率更高。改变两种合成途径的反应条件，或用单醛化产物进一步醛化，均未发现二醛取代产物的生成。     

2-乙基己基膦酸单(2-乙基己基)酯萃取钯(Ⅱ)的热力学研究

本文研究了2-乙基已基磷酸单（2-乙基已基）酯（P507）萃取钯（Ⅱ）的热力学过程．通过考察P507浓度对Pd（Ⅱ）分配比的影响，调出了萃取反应的表观平衡常数k、焓变△H、自由能变△G和熵变△S．     

3-正构烷氧基噻吩的合成工艺

以CuBr为催化剂,NMP为溶剂,在110°C条件下,先用3-溴噻吩与过量的甲醇钠发生取代反应合成3-甲氧基噻吩,收率为82.3%。再以无水NaHSO4为催化剂,用正戊醇与3-甲氧基噻吩反应,合成了3-戊氧基噻吩。通过正交反应研究了反应物摩尔比、反应时间、反应温度以及催化剂用量对合成3-戊氧基噻吩收率的影响,得出了最佳反应条件为:n(3-甲氧基噻吩)∶n(戊醇)=1∶1.1;反应时间3.5 h;反应温度115°C;催化剂用量:0.25%。然后根据合成3-戊氧基噻吩的最佳工艺条件并加以适当修改,合成了3-乙氧基噻吩、3-丙氧基噻吩、3-丁氧基噻吩、3-戊氧基噻吩、3-己氧基噻吩、3-辛氧基噻吩,收率分别为78.5%、73.5%、71.5%、69.7%、67.2%、64.3%。这些化合物结构都通过IR,1H NMR和MS进行了表征,并对其进行了初步香味评价。结果表明它们都具有基本肉香味的特征。     

Structure and conductivity of multi-walled carbon nanotube/poly(3-hexylthiophene) composite films

This work reports a structure-property investigation of a conjugated polymer nanocomposite with enhanced conductivity. Regioregular poly(3-hexylthiophene) (rrP3HT) was used to prepare composites with thin, short, multi-walled carbon nanotube (MWNT) addition over a wide range of concentrations. Scanning and transmission electron microscopies demonstrated an excellent dispersion and good wetting properties within the carbon nanotube composites. Coated MWNTs showed superstructures of P3HT self-organized on nanotube surfaces. Changes in the long range order and on the self-ordered mesophase of the bulk material were investigated by infrared and Raman spectroscopies, differential scanning calorimetry and X-ray diffraction. Interplay between charge transport through the semiconducting polymer and carbon nanotube network increased the composite's conductivity after percolation to values close to 10⁻² S cm⁻¹.     

Electrochemical behavior of poly(3-hexylthiophene). Controlling factors of electric current in electrochemical oxidation of poly(3-hexylthiophene)s in a solution

Electrochemical response of regio-random and regio-controlled poly(3-hexylthiophene), P3HexTh, was investigated by cyclic voltammetry. P3HexTh underwent electrochemical oxidation at about 0.4 V vs. Ag⁺/Ag in a THF solution, and the peak anode electric current, i_pa, was proportional to the sweeping rate v; i_pa=const×v^1/2. These data indicated that diffusion of the P3HexTh molecule in the solution was important to determine i_pa. Application of a Matsuda's equation with assumptions gave a diffusion coefficient, D, of about 1×10⁻⁷ cm² s⁻¹ at molecular weight of about 5000, and the D value steeply decreased with increase in the molecular weight.     

Effect of surface-modified zinc oxide nanowires on solution crystallization kinetics of poly(3-hexylthiophene)

Interfacial interactions between donor and acceptor molecules are determinative to the device performance of hybrid photovoltaics. However, the dynamic process of such interactions remains largely obscure. In this work, we report the kinetic behavior of solution crystallization of poly(3-hexylthiophene) (P3HT) in anisole in the presence of ZnO nanowires by means of ultraviolet-visible absorption spectroscopy. ZnO nanowires are surface-modified by covalently attaching aliphatic and aromatic ligands to enhance the miscibility and interfacial interactions between P3HT and ZnO nanowires. Upon cooling the hot solution to room temperature, a significant time-dependent chromism occurs spontaneously. Analysis of the kinetics of isothermal solution crystallization across a range of crystallization temperature displays that the growth rate of the crystals scales with polymer concentration as R ∝ C^1.6 for both the control P3HT and P3HT with ZnO nanowires. The Lauritzen–Hoffman theory of secondary nucleation is utilized to analyze the kinetic behavior of crystallization, and the fold surface free energies of the crystals of P3HT in anisole are calculated to be 6.6–10.3 × 10⁻² J m⁻². It is found that the addition of surface-modified ZnO nanowires decreases the fold surface free energy by 21.5% and 43.8%, respectively, for aliphatic and aromatic ligands.     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Synthesis and characterization of poly(dimethyl siloxane) containing poly(vinyl pyrrolidinone) block copolymers

ABA‐type block copolymers containing segments of poly(dimethyl siloxane) and poly(vinyl pyrrolidinone) were synthesized. Dihydroxyl‐terminated poly(dimethyl siloxane) was reacted with isophorone diisocyanate and then with t‐butyl hydroperoxide to obtain macroinitiators having siloxane units. The peroxidic diradical macroinitiators were used to polymerize vinyl pyrrolidinone monomer to synthesize ABA‐type block copolymers. By use of physicochemical methods, the structure was confirmed, and its characterization was accomplished. Mechanical and thermal characterizations of copolymers were made by stress–strain tests and differential scanning calorimetric measurements. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1915–1922, 1999     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001     

导电聚合物PEDOT/PSS-MPEG的制备及性能

引言导电高分子既有导体材料的光电学特性,又有良好的力学性能和可加工性[1],这使得导电高分子材料具有广泛的应用前景。聚噻吩类有机导电材料[2]就是这类材料中的一种。聚噻吩的室温电导率     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry