Control of the conjugation length and solubility in electroluminescent polymers

A new type of cyclolinear polymer, poly(phenylene vinylene‐alt‐cyclotriphosphazene), was synthesized through Heck‐type coupling reactions to produce π‐conjugated macromolecules with excellent solubility and precise electronic control of the band‐gap energy. This synthesis method is capable of producing well‐defined alternating polymers. The method is highly adaptable and can be readily used for other chromophore systems. The resulting polymers were also capable of accommodating a wide variety of substituents on the cyclophosphazene rings with minimal effect on the electronic properties. The band gap and electron affinities of the polymer were varied through the manipulation of the π‐conjugated unit located between the insulating phosphazene rings. Each chromophore matched the intended conjugation length consistently throughout the macromolecules. The polymers were good film formers because of the chosen substituents on the phosphazene rings. The absorbance of the polymers indicated minimal spectral shift from the monomer absorbance. This suggested an effective insulation of each chromophore unit from its neighbors by the phosphazene rings. Solution photoluminescence efficiencies were found to be up to 44.1%. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 69–76, 2006     

Plasma surface functionalization of poly[bis(2,2,2-trifluoroethoxy)phosphazene] films and nanofibers

Polyphosphazenes are a class of hybrid organic-inorganic macromolecules with high thermo-oxidative stability and good solubility in many solvents. Fluoroalkoxy phosphazene polymers also have high surface hydrophobicity. A method is described to tune this surface property while maintaining the advantageous bulk materials characteristics. The polyphosphazene single-substituent polymer, poly[bis(2,2,2-trifluoroethoxy)phosphazene], with flat film, fiber mat, or bead mat morphology was surface functionalized using an atmospheric plasma treatment with oxygen, nitrogen, methane, or tetrafluoromethane/hydrogen gases. Surface chemistry changes were detected by static water contact angle (WCA) measurements as well as X-ray photon spectroscopy (XPS). It was found that changes in the WCA of as much as 150 degrees occurred, accompanied by shifts in the ratio of elements on the polymer surface as detected by XPS. Overall this plasma technique provides a convenient method for the generation of specific surface characteristics while maintaining the hydrophobicity of the bulk material.     

Fluorine containing phosphazene polymers

In this paper we highlighted the synthesis, characterization, and practical exploitation of different types of polyphosphazenes substituted with fluorinated groups. There are several ways in which fluorine atoms can be inserted into polyphosphazenes, all of which leading to different polymers showing a wide range of characteristics. In general it is true that the insertion of fluorine atoms into phosphazene macromolecules leads to an enhancement of the thermal stability, flame resistance, low-temperature elastomericity, and chemical inertness of the phosphazenes obtained. The contribution of Italian research groups to the preparation and exploitation of organic commercial macromolecules grafted onto fluorinated polyphosphazenes is also reviewed.     

Functionalization of Poly(Organophosphazenes). IX. Light-Induced Grafting Reactions of Maleates onto Aryloxy-Substituted Poly(Organophosphazenes)

Abstract

In this paper the light-induced grafting reaction of dimethyl maleate, diethyl maleate, dibutyl maleate and diethyl fumarate, onto aryloxysubstituted phosphazene polymers, to form polyphosphazene copolymers containing grafted succinate groups, is investigated by means of IR spectroscopy and the equilibrium swelling technique of polyphosphazene films. The importance of several different experimental factors that can influence the final succinate grafting yields is discussed, i.e. the type and concentration of the polyphosphazenes and of the unsaturated products, reaction time, the absence or presence of molecular oxygen or of the 1-vinyl-2-pyrrolidone monomer, and the concentration of the benzoin ethyl ether photoinitiator.

Furthermore, it is shown that the overall efficiency of the lightinduced grafting process is lower than that previously measured for the reaction initiated thermally using peroxide species, and that the photochemical grafting reaction always occurs with no degradation of the phosphazene macromolecules.

The possibility of exploiting these new phosphazene substrates in blend technology has been considered.     

Synthesis of polyarylaminophosphazenes

The synthesis of a series of Polybis(arylamino)phosphazenes is described. The polymers usually were prepared by treatment of polydichlorophosphazene in benzene–tetrahydrofuran with arylamines/triethylamine at reflux for 48–144 hr. The polymers, having viscosities of 0.3–1.4dl/g, are essentially free of active chlorine sites, as shown by elemental analysis and their longterm hydrolytic stability. Thermal analysis revealed glass transition temperatures between 53 and 105°C and decomposition temperatures between 243 and 266°C. Analysis by differential scanning calorimetry revealed no first-order endothermic transitions. For comparison with the arylamino polymers, polydiethylaminophenylaminophosphazene, polybis(benzylamino)phosphazene, and polybis(β-phenethylamino)phosphazene were prepared and are described.     

Selective Ring‐Opening Polymerization of Non‐Strained γ‐Butyrolactone Catalyzed by A Cyclic Trimeric Phosphazene Base

A new superbase, the cyclic trimeric phosphazene base (CTPB), was prepared with high yield and purity. In the presence of alcohol, the CTPB serves as a highly efficient organocatalyst for ring‐opening polymerization of the “non‐polymerizable” γ‐butyrolactone to offer well‐defined poly(γ‐butyrolactone) with high conversions (up to 98 %) at −60 °C. The produced polymers have high molecular weights (up to 22.9 kg mol⁻¹) and low polydispersity distributions (1.27–1.50). NMR analysis of initiation process and the structural analysis of resulting polymers by MALDI‐TOF suggest a mechanism involving an activating initiator which leads only to linear polymers with BnO/H chain ends.     

9-Anthryldiazomethane in the Synthesis of Anthracene- Containing Polymers

Methods of the preparation of anthracene-containing monomers and polymers have been developed. They are based on the ability of 9-anthryldiazomethane to react with carboxylic groups of macromolecules and unsaturated carboxylic acids, to co-polymerize with diazoalkanes, and to generate 9-anthrylcarbene. These methods are used to obtain: (1) polymers with a low content (< 0.1 mole %) and different arrangement of anthracene groups in macromolecules (i. e., polymers with luminescent marks used to investigate macromolecules by luminescent methods) and (2) polymers with a high content (up to 100%) of anthracene-containing units, (which imparts to polymers specific photophysical and photochemical properties).     

在线红外光谱法研究丙烯腈聚合物高温热解的气态产物

本文介绍了用傅里叶变换红外光谱法在线连续测定了三种丙烯腈聚合物在氮气气氛中高温(300—960℃)热解试验的研究结果。据光谱峰的变化规律和有关分析数据,发现大分子中的氮主要是以NH_3,和HCN的形式逸放出,提出了在热裂解丙烯腈聚合物过程中形成无定形碳素组元,且相互交联而成共轭碳的网状结构。文中还就三种试样热解情况作了对比研究。结果表明,在热解过程中大分子进行缩合,所生成的主要挥发性产物组成有HCN、NH_3、CH_4、C_2H_6和腈类等,而共聚物还伴随着生成CO和CO_2。     

Polyphosphazene Based Star‐Branched and Dendritic Molecular Brushes

A new synthetic procedure is described for the preparation of poly(organo)phosphazenes with star‐branched and star dendritic molecular brush type structures, thus describing the first time it has been possible to prepare controlled, highly branched architectures for this type of polymer. Furthermore, as a result of the extremely high‐arm density generated by the phosphazene repeat unit, the second‐generation structures represent quite unique architectures for any type of polymer. Using two relativity straight forward iterative syntheses it is possible to prepare globular highly branched polymers with up to 30 000 functional end groups, while keeping relatively narrow polydispersities (1.2–1.6). Phosphine mediated polymerization of chlorophosphoranimine is first used to prepare three‐arm star polymers. Subsequent substitution with diphenylphosphine moieties gives poly(organo)phosphazenes to function as multifunctional macroinitiators for the growth of a second generation of polyphosphazene arms. Macrosubstitution with Jeffamine oligomers gives a series of large, water soluble branched macromolecules with high‐arm density and hydrodynamic diameters between 10 and 70 nm.

     

Preparation of Porous Polymers Based on the Building Blocks of Cyclophosphazene and Cage-like Silsesquioxane and Their Use as Basic Catalysts for Knoevenagel Reactions

Phosphazene-containing porous materials are of a great interest due to their unique properties, caused by the synergetic presence of nitrogen and phosphorus atoms, and have found applications as adsorbents, basic catalysts, etc. On the other hand, cage-like silsesquioxanes are ideal building blocks for the preparation of covalently-linked porous materials. Here two new phosphazene-functionalized organosilsesquioxane cage-based porous polymers were synthesized successively by a Friedel-Crafts reaction of hexapyrrolylcyclotriphosphazene with octavinylsilsesquioxane in the presence of AlCl₃ and CF₃SO₃H as catalysts. The nature of acid catalysts barely influenced the character of pores due to the interaction of catalysts with basic nitrogen atoms of phosphazene units. The obtained polymers exhibited high efficiency as metal-free catalysts for the Knoevenagel reaction. This work opens new perspectives in the use of porous polymers based on cage-like organosiloxane compounds as basic catalysts for various reactions.     

无机聚合物正极材料聚三硫代磷氮烯的制备与表征

合成了无机化合物聚三硫代磷氮烯[NPS3]n,借助红外光谱与元素分析测试确定了聚合物的重复单元结构;并通过比表面积分析、粒度测试和扫描电子显微镜观察了无机聚合物材料的微观形貌;热重分析测试表明材料在300℃以下能够稳定使用;循环伏安实验发现,作为锂二次电池正极材料使用,聚三硫代磷氮烯的电化学还原反应在2.25 V(versus Li/Li+)发生,其可逆的电化学氧化反应在2.51 V(versus Li/Li+)进行;充放电测试显示这种无机材料具有745.2 mAh.g-1的首次放电容量,与理论值(759.0 mAh.g-1)十分接近,经过60次充放电循环后放电容量保持在708.8 mAh.g-1,容量保持率95.1%,循环性能优秀.     

Condis-crystal structure of flexible-chain polymers in polymer blends

When heated above the melting point, a thermodynamic equilibrium mesophase of conformationally disordered crystal type (so-called condis state) has been found in some flexible-chain polymers (not containing mesogenic groups) dispersed in a matrix of another polymer. Typical organic and inorganic polymers such as polyethylene (PE) and poly[bis (2, 2, 2-trifluoroethoxy) phosphazene] (PPh) were taken as main components of the polymer blends under investigation. The most interesting situation is realized if two mesophase polymers are used in the same binary blend.     

聚离子亚基化合物结构影响外源基因转染效率

合成了带正电荷密度不同的聚离子亚基化合物,探讨了聚合物结构对外源基因转染真核细胞的影响规律。从实验结果看,聚离子亚基化合物结构影响外源基因转染效率,但其影响程度与靶细胞的种类相关,对ＨｅＬａ细胞,ＮＩＨ３Ｔ３细胞,聚离子亚基化合物的正电荷密度加大,其促基因转移功能加强;而对ＰＡ３１７包装细胞,结果相反。     

STUDY ON THE GASEOUS PRODUCTS OF HIGH TEMPERATURE PYROLYSIS OF ACRYLONITRILE POLYMERS BY ON-LINE FTIR METHOD

The gaseous products of high temperature pyrolysis (300℃ to 960℃) of aerylonitrile polymers were measured continuously under nitrogen atmosphere by on-line Fourier Transform Infrared Spectroscopic method (FTIR). From the variations of characteristic peaks it was found that the nitrogen of macromolecules evolved were mainly in the form of hydrogen cyanide and ammonia. During the pyrolysis amorphous carbonaceous element was formed, and crosslinked to form network structure. Three kinds of samples were used for comparison. The experimental results show that the gaseous products of volatile small molecules were HCN, NH_3, CH_4, C_2H_6 and cyanide. CO and CO_2 were also formed when copolymers of PAN were thermally pyrolyzed.     

聚乙烯亚胺表面改性硅藻土及其对苯酚吸附特性的研究

使用紫外吸收光度法研究了硅藻土对聚乙烯亚胺(PEI)的等温吸附;采用浸渍法,用PEI对硅藻土进行了表面改性;使用4-氨基安替比林光度法研究了经PEI表面改性的硅藻土对苯酚的捕集行为.研究结果表明,凭借强烈的静电相互作用,表面带负电荷的硅藻土粉体对阳离子性大分子PEI具有很强的吸附能力,等温吸附满足Freundlich吸附方程;经PEI表面改性后,硅藻土粉体表面的电性发生了根本性改变,且等电点由pH=2.0移至pH=10.5;在中性溶液中,改性粉体通过氢键作用与静电相互作用的协同,对水溶液中的苯酚会产生很强的捕集作用,饱和吸附量可达92 mg/g;在酸性溶液中改性粉体通过氢键相互作用,对水溶液中的苯酚产生一定的吸附作用,但由于PEI分子链高度的质子化,氮原子对苯酚的氢键相互作用很弱,吸附量很低.     

Deformation and degradation of polymers in ultra-high-pressure liquid chromatography

Ultra-high-pressure liquid chromatography (UHPLC) using columns packed with sub-2 μm particles has great potential for separations of many types of complex samples, including polymers. However, the application of UHPLC for the analysis of polymers meets some fundamental obstacles. Small particles and narrow bore tubing in combination with high pressures generate significant shear and extensional forces in UHPLC systems, which may affect polymer chains. At high stress conditions flexible macromolecules may become extended and eventually the chemical bonds in the molecules can break. Deformation and degradation of macromolecules will affect the peak retention and the peak shape in the chromatogram, which may cause errors in the obtained results (e.g. the calculated molecular-weight distributions). In the present work we explored the limitations of UHPLC for the analysis of polymers. Degradation and deformation of macromolecules were studied by collecting and re-injecting polymer peaks and by off-line two-dimensional liquid chromatography. Polystyrene standards with molecular weight of 4 MDa and larger were found to degrade at UHPLC conditions. However, for most polymers degradation could be avoided by using low linear velocities. No degradation of 3-MDa PS (and smaller) was observed at linear velocities up to 7 mm/s. The column frits were implicated as the main sources of polymer degradation. The extent of degradation was found to depend on the type of the column and on the column history. At high flow rates degradation was observed without a column being installed. We demonstrated that polymer deformation preceded degradation. Stretched polymers eluted from the column in slalom chromatography mode (elution order opposite to that in SEC or HDC). Under certain conditions we observed co-elution of large and small PS molecules though a convolution of slalom chromatography and hydrodynamic chromatography.     

聚[(六氟异丙氧基)_(2-x)(三氟乙氧基)_x]磷腈合成和气体分离性能研究

合成制备了聚磷腈类高分子——聚[(六氟异丙氧基)2-x(三氟乙氧基)x]磷腈,并通过NMR、FTIR、XRD、GPC、DSC等测试手段对聚合物进行了结构表征和性能测试,通过压力法透气性能测定仪测定了聚合物膜对N2、O2、CH4、CO2、He、H2等气体的透过性能.结果表明,三氟乙氧基的竞争取代能力较六氟异丙氧基稍强;得到x值分别为1.64、1.72和1.81的3种聚合物;其玻璃化温度Tg为-20.21℃、-42.83℃和-43.41℃;重均分子量为5.06×105、1.49×105和2.69×105;两种取代基比例适中时显示出较高的气体透过性能,渗透系数PN2=20barrer,PCO2=124barrer,PHe=85barrer;CO2/CH4和He/CH4的选择系数达到11.5和4.8,在天然气的净化和回收He中显示了潜力;H2/N2的选择系数达到6,而PH2=43barrer,在合成NH3尾气中回收H2存在发展前景。     

The challenge of assembling molecules into materials

Linear organic chains and their architectural derivatives such as branched and crosslinked macromolecules have been the main focus of polymer science for many decades. A new direction which should be pursued in the field is the exploration of polymers as “nanostructures”. This exploration would study synthetic polymers as shape invariant objects with nanoscale dimensions which resemble the folded proteins of nature. Such synthetic macromolecules would have well defined shapes which may even include topographical features. Ideally, the definition of shape could include well defined dimensions as well, but molecular objects of common shape but varying dimensions could also exhibit interesting properties. One could for example envision polymers as flat plates (two-dimensional polymers), discs, ellipsoids, spheres with cavities, parallelepipeds, among many other possible shapes. Such objects must have fairly high molar masses, possibly in the range of hundreds to thousands of kilodaltons, and would therefore not be accessible as chemical compounds synthesized by conventional methods. At the same time, the prospects of learning “folding rules” for synthetic chemical sequences in a biomimetic approach to molecular nanostructures seems to be an extremely difficult goal at the present time. This is suggested given our contemporary difficulties in understanding the protein folding problem.     

New benzimidazole-2-yl-substituted polybenzimidazoles: Synthesis, properties, and hydrodynamic characteristics

The synthesis of novel benzimidazole-2-yl-substited polybenzimidazoles and initial compounds has been described. The polymers are studied by FTIR spectroscopy, TGA, and TMA. The hydrodynamic properties of macromolecules are investigated by translational diffusion and viscometry in 96% H₂SO₄; the molecular characteristics of the polymers are determined. Positive temperature dependences for intrinsic viscosities of the polymers are obtained. The polymers under study possess high hydrolytic stability with respect to sulfuric acid solutions up to 150°C and high thermal stability in the bulk. The TGA data correlate with the chemical structure of the polymers. The new polybenzimidazoles may be used as materials for the production of medium-temperature proton-conducting membranes.     

含咪唑功能基螯合树脂的研究进展

咪唑环是一种含有两个配位原子的功能基,能与重金属离子形成稳定配合物。将其接枝到有机或无机高分子上,制得的含咪唑功能基的螯合树脂,不仅对重金属离子表现出良好的吸附选择性能,且回收操作简单、回收利用率高。本文对该类螯合树脂的研究进展进行了综述。