Effect of conformational parameters on physical properties of polymers containing pendant phenoxyphthalonitrile substituents

Heteroaromatic polymers are considered to be high performance organic materials due to their unique and highly attractive properties, including outstanding thermal and mechanical resistance, that arise from their aromatic structure and strong interactions between macromolecular chains. Modification or designing new molecular architectures with tailored physico-chemical characteristics allows expanding the applications of these materials in various advanced technologies. Herein, a series of polymers containing bulky phenoxyphthalonitrile pendant units was synthesized and their physical properties were studied and correlated with their conformational parameters, as well as free and van der Waals volumes. For comparison, the related polymers without lateral moieties were also investigated to highlight the effect of bulky substituent on the polymer rigidity. Thus, it is shown that conformational rigidity determines the packing of macromolecules in solid state, and, therefore, the free volume, glass transition, and decomposition temperatures. The values found experimentally for T _g correlate well with those obtained using the conformational rigidity parameters. The dependence of T _g of these polymers on Kuhn segment is described by linear equations, with very good factors of convergence. The correlations established by Monte Carlo method allow obtaining the T _g values for related polymers where the experimental measurement of this parameter is difficult.     

Design of novel podand-like compounds with two short diphenylphosphine oxide pendant arms

Crystal and molecular structure of 1,3,5-benzenetris(methylenediphenylphosphine oxide) cyclohexylammonium chloride dibenzene solvate monohydrate has been determined. The overall arrangement of two diphenylphosphine oxide substituents atoms is imposed by intermolecular strong hydrogen bonds, O_(water) H···O_(oxide) and N H···O_{(oxide, water)}. Cyclohexylamine exists in almost ideal chair conformation and nitrogen atom is equatorial to the ring. The structure is build up from strong and weak intermolecular hydrogen bonds to form the three-dimensional infinite hydrogen bond network. Crystal and molecular structure of 1,4-bis[(diphenylphosphineoxide)methyl] - 2,5 - bis (ethoxymethyl) benzene has been determined. The phenyl rings are inclined at 80.91(7)° within the substituent, and they are involved in weak C_(phenyl) H···O_(oxide) hydrogen bonds. The arrangement of diphenylphosphine oxide substituents is imposed practically only by steric effects. Two intramolecular weak hydrogen bonds exist between diphenylphosphine oxide and ethoxymethyl substituents, which can provide additional stabilization to molecule, but it has no noticeable influence on overall molecule geometry. Molecules are assembled via weak intermolecular C H···O_(oxide) hydrogen bonds to the one-dimensional hydrogen-bonded chain along y axis. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:233–240, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20008     

Correlation between physical properties and conformational rigidity of some aromatic polyimides having pendant phenolic groups

Soluble polyimides based on an aromatic diamine containing pendant phenolic group and four different dianhydrides have been synthesized by two-step polycondensation reaction in solution. The polyimides were easily soluble in polar organic solvents and even in less polar solvents and showed high thermal stability, with initial decomposition temperature being above 420 °C. Monte Carlo method was used to calculate conformational rigidity parameters of these polyimides. Some physical properties such as solubility, glass transition temperature and initial decomposition temperature were investigated and compared with those of related polyimides which did not contain any pendant groups based on the same dianhydrides and a diamine without pendant phenolic group. All data were discussed in relation to the rigidity of the chain.

     

Synthesis and characterization of highly soluble fluorescent main chain copolyimides containing perylene units

A series of high molecular weight copolyimides containing various amount of perylene units in the main chain have been synthesized. The polymers were characterized by FT-IR, NMR, UV/Vis, fluorescence spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis measurements. They are highly soluble in conventional solvents such as CHCl₃, THF, cyclohexanone etc. and form optically transparent films by solution casting or spin coating. The incorporation of various amount of perylene units in the main chain allows the control of the fluorescence intensity in solution and in solid thin films. The copolyimide containing 0.28 mol% perylene units exhibits the highest solid-state fluorescence. The observed fluorescence intensities of the copolyimides in solid state film decreased with the increasing amount of perylene units in the main chain when the mole ratio of perylene units greater than 0.28 mol% indicating the aggregation of chromophores. The copolyimides are thermally stable up to 400 °C and exhibit glass transition temperatures in the range of 340-360 °C. The number average molecule weight ranges from 1.72×10⁴ to 1.25×10⁵ and the molecule weight distribution mediated between 1.9 and 2.4.     

Highly efficient red-electrophosphorescent devices based on polyfluorene copolymers containing charge-transporting pendant units

We have systematically examined the photoluminescence (PL) and electroluminescence (EL) behavior of blends comprising two efficient red phosphors doped, respectively, into the blue-emitting polyfluorene derivatives PF-TPA-OXD and PF-OXD. The host polymers, which contain both hole- and electron-transporting or merely electron-transporting side chains, are capable of facilitating charge injection and transport. After determining the HOMO and LUMO energy levels of these materials, we were able to match the dopant with its most suitable host to achieve the direct formation and confinement of an exciton at the dopant. This configuration also leads to a reduction in the electrical excitation of the host polymer, which in turn decreases the degree of exciton loss arising from nonradiative decay of the host triplet. Using this approach, we were able to realize the production of high-performance red-electrophosphorescent devices. For Os(fppz)-doped devices, we obtain a balanced charge recombination in conjunction with higher current and luminance when using PF-TPA-OXD as the host matrix; this device reached a maximum external quantum efficiency of 8.37% with a peak brightness of 16 720 cd/m2. The absence of charge-transporting pendant units, i.e., the device fabricated from poly[9,9-dioctylfluorene-2,7-diyl] (POF), led, however, to relatively poor electroluminescence characteristics (5.81% and 2144 cd/m2).     

Fluorenyl cardo copolyimides containing poly(ethylene oxide) segments: Synthesis,characterization, and evaluation of properties

A set of new block copolyimides containing fluorenyl cardo moieties (FR) in the polyimide blocks and poly(ethylene oxide) (PEO) sequences has been prepared using the two‐step method of polyimide synthesis. The combination of both moieties led to novel copolyimides with good solubility in a variety of solvents, which could easily be processed into films. Copolyimides with PEO content from 30 to 56 wt % were amorphous, showed good mechanical properties, and absorbed less water than other PEO‐containing polyimides previously reported. Copolyimides with higher PEO content (60 and 65%) showed crystallinity and yielded soft films. All of the copolymers showed two glass transition temperatures, the first one around ?25 °C attributed to the PEO segments, and the second one at much higher temperature, which corresponded to the polyimide domains. The thermal degradation occurred in two steps, the first one being associated with the degradation of the PEO segments and the second one with the generalized aromatic polyimide decomposition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8170–8178, 2008     

Synthesis and conformational preferences of unnatural tetrapeptides containing l-valine units

The stereoselective synthesis of non-proteinogenic tetrapeptides 7, 16 and 17 containing two l-valine units and two modified α-amino acids (proline and aspartic acid) has been accomplished starting from the l-valine derived chiral synthon 1. Investigations of the conformational preference and structure of these unnatural peptides were carried out using ¹H NMR and IR spectroscopic techniques and a conformational analysis based on quenched molecular dynamics (QMD).     

Thermal behavior of copolyimides containing bisbenzoylamine groups

In an effort to improve the processibility of full aromatic polyimides, copolybisbenzoylamine imides were synthesized. As this study is a continuation of our work on flexibilization of the polyimide main chain, the bisbenzoylamine group was introduced stepwise into the polyimide main chain. Mixtures of pyromellitic anhydride, the rigid component, and a bisbenzoylamine-3,3′, 4,4′-tetracarboxylic acid dianhydride, the flexible component, were polymerized with aromatic diamines in a two-step procedure. The thermal stability of the four series of resulting copolyimides shows parallel changes that depend on the dianhydride ratio. The functional dependence of glass transition temperature (T_g) on copolymer composition differs for hydrogen or alkyl group substitution on the nitrogen in the bisbenzoylamine group. The solubility of the copolyimides in dimethylformamide changes from 0 to 33 wt %; there is a nonlinear dependence between solubility and the dianhydride ratio.     

Synthesis of polyamines with pendant cyanoimidazole units and their electrochemical properties

The 2-(1-methyl-4,5-dicyanoimidazolyl) group was attached to poly(diallylamine) and polyethylenimine, affording polymers containing an electron-withdrawing pendant group. The key to their preparation is high reactivity of 1-methyl-2-fluoro-4,5-dicyanoimidazole (1) toward nucleophilic aromatic substitution (NAS) reactions with aliphatic amines. Cyclic voltammograms of these polymers show reduction waves at −2.6 to −2.7 V vs. Ag/Ag⁺ but no reoxidation waves, unlike those of monomeric and oligomeric model compounds, which are quasi-reversible. The cyclic voltammetry studies of oligomeric model compounds with different alkyl spacers show that the degree of quasi-reversibility decreases as dicyanoimidazoles are crowded together in a molecule, suggesting that a certain degree of chemical reaction occurs between reduced dicyanoimidazole groups. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2619–2629, 1998     

Influence of sequential lithium insertions on the physical properties of spinel manganese oxide

We present first principles studies based on density functional theory (DFT) to investigate the lithium intercalation process in spinel manganese oxide compound. The lattice volume change, energetics, and insertion voltage were systematically examined upon sequential lithium insertions into the lattice. The charge transfer mechanism upon lithium intercalation was studied by analyzing the calculated spectra of density of states. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Influence of physical properties and operating parameters on hydrodynamics in Centrifugal Partition Chromatography

Besides the selection of a suitable biphasic solvent system the separation efficiency in Centrifugal Partition Chromatography (CPC) is mainly influenced by the hydrodynamics in the chambers. The flow pattern, the stationary phase retention and the interfacial area for mass transfer strongly depend on physical properties of the solvent system and operating parameters. In order to measure these parameters we visualized the hydrodynamics in a FCPC-chamber for five different solvent systems with an optical measurement system and calculated the stationary phase retention, interfacial area and the distribution of mobile phase thickness in the chamber. Although inclined chambers were used we found that the Coriolis force always deflected the mobile phase towards the chamber wall reducing the interfacial area. This effect increased for systems with low density difference. We also have shown that the stability of phase systems (stationary phase retention) and its tendency to disperse increased for smaller values of the ratio of interfacial tension and density difference. But also the viscosity ratio and the flow pattern itself had a significant effect on retention and dispersion of the mobile phase. As a result operating parameters should be chosen carefully with respect to physical properties for a CPC system. In order to reduce the effect of the Coriolis force CPC devices with greater rotor radius are desirable.     

Synthesis and physical properties of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units

Six series of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units have been synthesized and characterized. Their mesomorphic properties were characterized by polarizing optical microscopy and differential scanning calorimetry. All these compounds are thermotropic liquid crystalline materials. All three-ring compounds (series A, B and C) and most four-ring compounds (series D, E and F) exhibit only a nematic phase, while some four-ring compounds with long terminal alkyl chains show nematic, smectic A and even smectic B phases. In addition, four compounds containing a 1,3-dioxane unit were prepared, and their mesomorphic properties compared with their 1,3,2-dioxaborinane analogues. The dielectric anisotropies of selected target compounds were determined; some showed a negative anisotropy. The relationships between the properties and chemical structures of these new compounds are discussed.     

Synthesis and physical properties of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units

Six series of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units have been synthesized and characterized. Their mesomorphic properties were characterized by polarizing optical microscopy and differential scanning calorimetry. All these compounds are thermotropic liquid crystalline materials. All three-ring compounds (series A, B and C) and most four-ring compounds (series D, E and F) exhibit only a nematic phase, while some four-ring compounds with long terminal alkyl chains show nematic, smectic A and even smectic B phases. In addition, four compounds containing a 1,3-dioxane unit were prepared, and their mesomorphic properties compared with their 1,3,2-dioxaborinane analogues. The dielectric anisotropies of selected target compounds were determined; some showed a negative anisotropy. The relationships between the properties and chemical structures of these new compounds are discussed.     

Synthesis and photophysical properties of conjugated polymers with pendant 9,10-anthraquinone units

We have synthesized and investigated the photophysical properties of a series of electron-donor conjugated copolymers with pendant electron-acceptor units. The copolymers consist of diethynyl-1,4-phenylene, fluorene, or phenylene rings alternating with a phenylene unit bearing a pendant 9,10-anthraquinone moiety. The pendant donor-acceptor polymers were designed to have different optical pi-pi* band gaps, while the oxidation potential of the polymer backbone remains approximately constant in the series. The reduction potential of the donor-acceptor polymers is associated with the pendant acceptor units. This leads to the special situation that the electrochemical gap between oxidation and reduction potentials is constant, while the optical band gap decreases, going from PPP, via PPF, to PPE. This design is used to study the effect of the optical gap on the photoinduced electron-transfer reaction that occurs between the main chain electron donor and the pendant acceptor, while the same polymer architecture and energy of the charge separated state are maintained. Fluorescence and photoinduced absorption spectroscopy are used to study the electron transfer following photoexcitation in relation to solvent polarity and in thin solid films. For the fluorene-phenylene alternating copolymer, intramolecular photoinduced electron transfer occurs in the Marcus optimal region.     

Investigation of polyimides containing naphthalene units. III. Influence of monomers structure on polymers properties

A series of polymers from dinaphthalene dianhydrides and aromatic diamines has been synthesized using one-step high-temperature polycondensation. The influence of the monomers structure on the polymers properties has been investigated. © 1997 John Wiley & Sons, Inc.     

Structural aspects in polymers: interconnections between conformational parameters of the polymers with their physical properties

This article focuses on the influence of the geometric structure of the polymer chain on the physical properties of polymers. It is shown that for polyheteroarylenes the Kuhn segment calculated based on the geometric structure of the polymer chain has a good correlation with the physical properties of those polymers. For aliphatic polymers, a volume factor is suggested that equals the ratio of the Van der Waals volume of pendant substitute to the volume of the whole polymer chain. It is shown that the properties of aliphatic polymers that depend on free volume are well described by this value.     

Photoinduced hydrophosphinylation of alkenes with diphenylphosphine oxide

Photoinduced hydrophosphinylation of alkenes with diphenylphosphine oxide took place regioselectively affording the corresponding phosphine oxide in good yields. This hydrophosphinylation is of simple operation and widely tolerant to a variety of the functionalities.     

Synthesis of urea‐containing ABA triblock copolymers: Influence of pendant hydrogen bonding on morphology and thermomechanical properties

Reversible addition‐fragmentation chain transfer (RAFT) polymerization produced novel ABA triblock copolymers with associative urea sites within pendant groups in the external hard blocks. The ABA triblock copolymers served as models to study the influence of pendant hydrogen bonding on polymer physical properties and morphology. The triblock copolymers consisted of a soft central block of poly(di(ethylene glycol) methyl ether methacrylate) (polyDEGMEMA, 58 kg/mol) and hard copolymer external blocks of poly(2‐(3‐hexylureido)ethyl methacrylate‐co‐2‐(3‐phenylureido)ethyl methacrylate) (polyUrMA, 18‐116 kg/mol). Copolymerization of 2‐(3‐hexylureido)ethyl methacrylate (HUrMA) and 2‐(3‐phenylureido)ethyl methacrylate (PhUrMA) imparted tunable hard block T_g's from 69 to 134 °C. Tunable hard block T_g's afforded versatile thermomechanical properties for diverse applications. Dynamic mechanical analysis (DMA) of the triblock copolymers exhibited high modulus plateau regions (∼100 MPa) over a wide temperature range (−10 to 90 °C), which was indicative of microphase separation. Atomic force microscopy (AFM) confirmed surface microphase separation with various morphologies. Variable temperature FTIR (VT‐FTIR) revealed the presence of both monodentate and bidentate hydrogen bonding, and pendant hydrogen bonding remained as an ordered structure to higher than expected temperatures. This study presents a fundamental understanding of the influence of hydrogen bonding on polymer physical properties and reveals the response of pendant urea hydrogen bonding as a function of temperature as compared to main chain polyureas. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1844–1852     

A study on the effect of spirocyclic structures in the main chain on the physical properties of copolyimides

A series of copolyimides were prepared from two alicyclic dianhydrides having the common molecular formula C₁₀H₈O₆, rel‐[1S,5R,6R]‐3‐oxabicyclo[3.2.1]octane‐2,4‐dione‐6‐spiro‐3′‐(tetrahydrofuran‐2′,5′‐dione) (DAn) and c‐3‐carboxymethyl‐r‐1,c‐2,c‐4‐cyclopentanetricarboxylic acid 1,4:2,3‐dianhydride (TCAAH), with p‐phenylenediamine (PPD) by a conventional two‐step procedure. With increasing DAn fractions in the backbones, the copolyimides showed better film formability, enhanced solubility, increased glass transition temperatures and birefringences, and decreased average refractive indices. The unsymmetric spiroalicyclic structure of DAn might be responsible for these results. Films of copolyimides obtained by both thermal and chemical imidization were fully transparent and were colorless or pale yellow depending on the film thickness.