Influence of Molecular Weight on the Performance of Organic Solar Cells Based on a Fluorene Derivative

The performance of organic photovoltaic (OPV) bulk‐heterojunction blends comprising a liquid‐crystalline fluorene derivative and a small‐molecular fullerene is found to increase asymptotically with the degree of polymerization of the former. Similar to various thermodynamic transition temperatures as well as the light absorbance of the fluorene moiety, the photocurrent extracted from OPV devices is found to strongly vary with increasing oligomer size up to a number average molecular weight, M_n ≈ 10 kg mol^?1, but is rendered less chain‐length dependent for higher M_n as the fluorene derivative gradually adopts polymeric behavior.     

Novel biodegradable amino acid containing anhydride oligomers for orthopedic applications

Novel synthetic biodegradable methacrylated anhydride oligomers (MAOs) based on methacrylated alaninyl maleamic acid (MAMA) and methacrylated aminocaproyl maleamic acid (MACMA) were synthesized and characterized. Injectable and in situ crosslinkable polymer networks were formulated by the copolymerization of MAOs with triethylene glycol dimethacrylate (TEGDMA). Furthermore, composites composed of MAOs, TEGDMA, and β‐tricalcium phosphate were prepared. The networks and composites were initiated by photopolymerization and redox polymerization, respectively. The initial compressive strength (CS) and diametral tensile strength (DTS) of these materials were determined and used to evaluate the effects of the MAO/TEGDMA ratios on the degradation behavior of the materials. The MAMA‐based composites had initial DTS values of 5.7–17.1 MPa and CS values of 30.7–114.2 MPa. The MACMA‐based composites had initial DTS values of 2.8–20.8 MPa and CS values of 19.1–119.5 MPa. During the course of degradation, the neat polymer resins lost 97 and 87% of their initial CS values after 6 months with 50/50 MAMA/TEGDMA and MACMA/TEGDMA ratios, respectively. The composite with a 25/75 MACMA/TEGDMA ratio showed a significant increase in CS after an initial decrease for 7 days and then lost 57% of its initial CS value after 3 months. The composite composed of 100% methacrylated anhydride oligomer (MAOs) showed complete degradation after 21 days. The degrees of conversion of the neat resins were 60–77%. Both the neat resins and the composites had low polymerization shrinkage ranging from 3.8 to 5.6%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1979–1984, 2005     

Structural symmetry breaking of silicon‐containing poly(amide‐imide) oligomers and its relation to electrical conductivity and Raman‐active vibrations

Optically active poly(amide‐imide) oligomers were synthesized by direct polycondensation between an aromatic diamine and a dicarboxylic acid both containing a diphenylsilylene unit. The reaction was carried out using triphenyl phosphite/pyridine in the presence of CaCl₂ and N‐methyl‐2‐pyrrolidone as solvent. Oligomers were obtained in good yields and showed high solubility in common aprotic polar solvents. The precursors, monomers and poly(amide‐imide) oligomers were characterized using elemental analysis and Fourier transform infrared and NMR (¹H, ¹³C, ²⁹Si) spectroscopy. Additionally, the main vibrations of the functional groups (C?O, C?C or N? H) in the oligomers with respect to temperature were characterized using Raman spectroscopy. The glass transition temperature was determined by studying the Raman spectra and corroborated using differential scanning calorimetry. The thermal stability was studied using thermogravimetric analysis. The molecular mass of the compounds was obtained from matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry and their optical properties were analyzed using UV‐visible diode array spectrophotometry. The electronic properties of the oligomers as well as the delocalization of charge carriers within their structures were analyzed using conductance‐voltage curves, which showed that these materials are excellent candidates for integrated optoelectronic applications. Copyright © 2011 Society of Chemical Industry     

Synthesis of thermoreactive polysiloxanes with cyclic fragments in the side chain

The synthesis of polysiloxanes with pendant unsaturated cyclic fragments have been successfully performed by hydrosilylation reactions of polymethylhydrosiloxane with 4‐vinyl‐1‐cyclohexene in the presence of platinum hydrochloric acid (0.1 M solution in THF), Karstedt's catalyst (Pt₂[(VinSiMe₂)₂O]₃) and platinum on the charcoal (5%). Reactions were carried out at various temperatures with different ratios of initial compounds. It was shown, that not all active ≡Si? H groups take part in the hydrosilylation reaction. Some kinetic parameters of reactions were studied. The synthesized oligomers were characterized by FTIR, ¹H, ¹³C, H,H‐COSY, and C,H‐correlation NMR spectroscopy. Calculations using the quantum‐chemical semi empirical AM1 method for modeling reactions between methyldimethoxysilane [Me(MeO)₂SiH] and 4‐vinyl‐1‐cyclohexene were performed to evaluate possible reaction paths. Synthesized oligomers were characterized by gel‐permeation chromatography, differential scanning calorimetric, thermogravimetric, and wide‐angle X‐ray analyses. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hydroxyalkylation of barbituric acid. III. Product analysis and reaction pathway

Polyetherols containing a thermally stable pyrimidine ring were obtained upon the reaction of hydroxymethyl derivatives of barbituric acid with an excess of ethylene or propylene oxide. The reaction was monitored by ¹H‐NMR and IR spectroscopy for the systems with variable starting molar ratios of reagents. We found that formaldehyde rearranged from N‐hydroxymethyl and oxymethylene bridges into the end of the polyetherol chain during the reaction. Simultaneously, the O‐hydroxymethyl groups underwent blocking by oxirane. The structures of the polyetherols was deduced on the basis of the course of the reaction and the analytical data. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Acid-catalyzed moisture-curing polyurea/polysiloxane ceramer coatings

The para-toluene sulfonic acid (p-TSA) was used to catalyze the moisture curing of an organic/inorganic hybrid coating system. The organic phase was based on the isocyanurate of 1,6-hexamethylene of diisocyanate (HDI). The inorganic phase was based on the prepolymerized oligomers of tetraethyl orthosilicate (TEOS). An alkoxysilane-functionalized HDI isocyanate was added into the coating formulation to aid in phase miscibility. The general coating and tensile properties were evaluated as a function of the acid catalyst concentration. In addition, the films were analyzed using differential scanning calorimetry (DSC) and dynamical mechanical thermal analysis (DMTA). The results indicated that the acid catalyst enhanced the adhesive properties of the hybrid coatings. The addition of the acid catalyst increased the changed crosslink density of films and decreased the crystallinity of the organic phase.     

Synthesis and properties of new derivatives of poly[9‐(2,3‐epoxypropyl)carbazole]

BACKGROUND: Carbazole derivatives are well known to exhibit interesting electro‐ and photo‐active properties due to their hole‐transporting ability, strong absorption in the ultraviolet spectral region and blue‐light emission. One of the most widely studied materials among carbazole‐containing oligomers is poly[9‐(2,3‐epoxypropyl)carbazole] (PEPK). The main field of application of this oligomer is electrophotographic microfilming. It is also used for the manufacture of multicolour slides and in the photothermoplastic recording of information. Unfortunately, due to its high ionization potential, which reaches 5.86 eV, the possibilities of application of this compound in optoelectronic devices are rather limited. RESULTS: PEPK‐based charge transporting oligomers, incorporating hydrazone moieties, are reported. The oligomers were prepared by chemical modification of PEPK. The materials obtained were examined using various techniques including differential scanning calorimetry and ultraviolet, infrared and NMR spectroscopy. Electron photoemission spectra of layers of the synthesized oligomers showed ionization potentials (I_p) in the range 5.4–5.5 eV. CONCLUSION: The synthesized oligomers possess a larger π‐conjugated system and show ionization potentials of ca 5.4 eV. Therefore, they are more suitable for use in optoelectronic devices with quicker photoresponse than unmodified PEPK. Copyright © 2008 Society of Chemical Industry     

A novel polymer chain growing mode and styrene copolymer prepared with low molecular weight copolymer of α‐methylstyrene and styrene as macroinitiator

A new polymer chain growth mode, having multiple potential chain propagation sites, initiated by oligomer of α‐methylstyrene (AMS) and styrene (St) (PAS) is presented in this article. The effects of PAS content, AMS fraction in PAS and reaction temperature on bulk polymerization of St have been investigated. It is demonstrated that the PAS performed as macroinitiator in the polymerization of St. The average molecular weights of products increase significantly with the evolution of the polymerization, which is different from conventional free radical polymerization. With 20 wt % macroinitiator, the molecular weights increase from 1.21 × 10⁵ to 3.00 × 10⁵ with the monomer conversion increasing from 15.3 to 83.0%. This unique feature is tentatively attributed to both the reversible polymerization–depolymerization of AMS segments at high temperature which could generate more than one propagation sites in a polymer chain and the combination termination of St free radical polymerization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41460.     

Synthesis,characterization, and thermal behaviors of tannin stearates prepared from quebracho and pine bark extracts

Reported is the preparation of various condensed tannin stearates and the associated chemical characterization and thermal properties of these products. Stearate esters of condensed tannins from both quebracho and pine bark extracts were prepared in generally high, isolated yields from reaction with stearic acid chloride. Tannin esterification was confirmed by both Fourier transform infrared and nuclear magnetic resonance (NMR), and the average degree of stearate substitution was calculated from ¹H‐NMR analysis. Product degree of substitution (DS) was observed to proportionately increase with higher stearic acid chloride ratio with maximum DS values of 4.0 and 5.1 achieved for quebracho and pine tannins, respectively. Thermal analysis revealed that tannin stearate products have increased thermal stability with a degradation onset at significantly higher temperature for those samples possessing relatively greater DS. Analysis using differential scanning calorimetry revealed isolated products to consist of multiple components which exhibit interesting melt behaviors, a likely result from their work up on isolation. However, multiple melt features of the individual components in products were lost on heating to give single, broad melt endotherms due to coalescence of sample components. Furthermore, tannin stearate samples with high DS show relatively greater endothermic melting at higher temperature than those samples with lower DS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

二氧化碳为原料合成水性聚氨酯材料

当今低碳经济发展的一项重要内容就是以二氧化碳为原料合成可生物降解的环保化合物,主要包括:①环碳酸酯,通过它与胺类固化剂反应合成非异氰酸酯聚氨酯(NIPU);②聚碳酸酯多元醇,通过它与—NCO、—COOH官能团反应合成聚氨酯材料(PU)。主要对NIPU的整个合成反应过程、机理、改性其水性化进行了讨论分析,概述了其特性、优势、研究前景、应用范围和发展现状。