Chemical transformations of poly(arylene ether ketones) containing side functional groups

Conditions for chemical transformations of poly(arylene ether ketones) containing side carboxyl and phthalimidine functional groups have been investigated. The reason why the chemical modification of poly(arylene ether ketones) with side acid chloride groups leads in some cases to the formation of insoluble products is established. Ionogenic and comb-shaped poly(arylene ether ketones) with hydrophobic fragments in side branches are obtained through chemical transformations of previously synthesized polymers containing side carboxyl, hydroxyl (alcohol), and phthalimidine groups. The properties of poly(arylene ether ketones) can be varied in a wide range via chemical reactions of side reactive groups.     

Dielectric and optical properties of liquid crystalline side chain polymers. A MNDO-analysis

Semiempirical quantum mechanical MNDO-calculations were performed on side chain liquid crystalline polymers to predict their electronic properties and thus their anisotropic dielectric and optical properties. These predictions are compared with the corresponding experimental results. The conclusion is that the predictions are sufficiently accurate, which suggests to use such methods for screening potentially interesting polymer liquid crystals prior to synthesizing them.     

The glass transition and the glassy state in isotropic and liquid crystalline polymers

PVT-measurements on atactic polystyrene shows that the Ehrenfest equations, which describe a thermodynamic transformation of the second order, are not applicable for the glass transition. The introduction of one internal ordering parameter ζ in addition to the conventional variables T and P, is sufficient to describe the behaviour in case of atactic PS in the isotropic glassy state. The usually observed way dependences in the glassy state can be explained by the concept of ordering parameters. In recent years liquid crystalline side chain polymers were developed. The liquid crystalline phases of these polymers can be supercooled and frozen-in like isotropic liquids. As the nematic or smectic liquid crystalline structure freezes-in, and can be conserved by this process, glasses with anisotropic properties are obtained. These glasses show e.g. a high optical birefringence. The glass transition of the liquid crystalline polymers can only be described by the assumption of at least two parameters ζ_i. Therefore the Ehrenfest equations are not applicable for the glass transition of isotropic as well as anisotropic glasses.     

Optically detected magnetic resonance of thiol-capped CdTe nanocrystals

The optical properties of thiol-stabilized CdTe nanocrystals have been examined. The thiol groups -SR generate a CdS shell at the interface, leading to a CdTe/CdS core—shell structure. The present paper describes our efforts to identify the influence of the CdTe–SR interface on the optical properties of the nanocrystals, utilizing photoluminescence and optically detected magnetic resonance (ODMR) spectroscopy. The photoluminescence spectrum consists of an excitonic peak, overlapped by a broad band at lower energies. The ODMR spectrum, in the spectral regime of the broad band, showed two resonance signals. They are associated with a trapped hole at an anisotropic site of a cadmium vacancy at the Cd–SR interface and an electron in the conduction band.     

Effect of the Chiral Center Position of an Optically Active Terminal Group on the Induction of Optical Activity in Polysilanes

Summary Polysilanes with an optically active alkoxy group, i.e., (S)-(+)-2-butoxy, (R)-(-)-2-butoxy, (S)-(-)-2-methyl-1-butoxy, and (S)-(+)-3,7-dimethyl-1-octoxy, at the terminal positions, the chiral carbon centers of which were located at the α, β, and γ positions relative to the oxygen, respectively, were prepared, and the effect of the position of chiral center of the terminal optically active group on the induction of optical activity in polysilanes was investigated. The circular dichroism (CD) spectra of these polymers showed positive Cotton signals around 340 nm at temperatures below -20 °C, but the intensities were small, indicating that the optically active groups at the terminal positions have some ability, albeit small, to induce optical activity to the polysilanes. Further, the optically active (S)-(+)-2-butoxy and (R)-(-)-2-butoxy groups did not control the helical sense direction of the polymers, despite the different chiral stimuli from the 2-butoxy groups introduced to the terminal positions. To control the helical structure of polysilanes by the use of optically active terminal groups, appropriate optically active groups are required.     

Polymeric materials containing bile acids

Bile acids are biological compounds in the body that have interesting properties and have been used to make special chemical structures in molecular recognition. Various polymers have been synthesized from bile acids. The materials should preserve some of the properties of bile acids, such as biocompatibility, high stability of the steroid nucleus, reactivity of the side groups, optical activity and self-assembling capacity. The synthesis and applications proposed for such polymers are discussed.     

Novel optical material: Polyarylates with heterocyclic side chain groups

Several nonlinear optical polymers containing azometine side‐chain groups have been obtained by interfacial polycondensation. The structures of obtained monomers and polymers were confirmed by infrared, ¹H‐NMR, and ultraviolet spectroscopies. Mechanical, thermal, and optical properties of the obtained polymers were evaluated. The investigations show that some of the new polymers obtained in this study may find use in optical applications. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1017–1028, 1999     

Synthesis and characterization of side-chain liquid crystalline polyoxetanes containing 4-(alkanyloxy)phenyl 4-pentylbenzoate side groups

The synthesis and characterization of side-chain liquid-crystalline polyoxetanes containing 4-(alkanyloxy)phenyl 4-pentylbenzoate side groups is presented. Differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction measurements were used to characterize the mesomorphic properties of the polyoxetanes. Those polymers with three to five methylene units in the spacers exhibit the enantiotropic smectic A and a nematic phaser, whereas the polymers with longer spacers (n = 6 or 12) display polymorphism of smectic phases. The polyoxetane backbones are amorphous in nature. No side chain crystallization occurred for any of the polyoxetanes synthesized in this study.     

Chiral liquid crystal polymers

Summary Chiral glycidyl ethers containing biphenyl side groups have been synthesized starting from optically active isopropylidene glycidol. The anisotropic moiety can be bound to the oxirane ring either directly or through flexible spacers of varying length. Details relevant to the above reactions and to the reaction sequences adopted to get the corresponding glycidyl ethers are presented.     

Synthesis and characterization of optically active helical poly(α, β-unsaturated ketone) with bulky pendant of binaphthyl

The synthesis and chiroptical properties of a novel optically active helical polymers, poly[(S)-6-acryloyl-2,2′-bisalkoxy-1,1′-binaphthyl] (poly-3), were reported. All the monomers readily underwent anionic polymerization to yield the polymers displaying optical rotations and Cotton effects in the UV–vis absorption region of side groups distinct to monomers (3) and the corresponding model compounds such as (S)-6-propionyl-2,2′-bisalkoxy-1,1′-binaphthyl (4) and (S)-6-heptanoyl-2,2′-bisalkoxy-1,1′-binaphthyl (5), implying the formation of main-chain chirality, most probable helicity. Their helical conformations were quite stable as revealed by the almost unchanged chiroptical properties measured at different temperatures.     

Photoinduced orientation in ionic-bonding photo-cross-linkable polymers

Photosensitive polymer materials with photo-cross-linkable side chain group were prepared based on ionic self-assembly technology. The complex materials were constructed by the coupling of polyelectrolyte and cinnamate units with different spacer length (6 or 12 methylene units designated PCAM6 and PCAM12, respectively). Photochemical properties including photo-cross-linking and photoinduced alignment of such a complex materials with transparency in a visible region were investigated by irradiating with a polarized laser. Furthermore, a homogeneous and stable liquid crystals' alignment was achieved on the resultant anisotropic orientation film. This facile method to construct photosensitive polymers would be very attractive due to its practical applicability in versatile optical elements with birefringent characteristics.     

Synthesis and characterization of novel polyarylates bearing NLO moieties

A series of thermally stable second‐order nonlinear optical polyarylates containing azo side‐chain groups have been obtained by interfacial polycondensation. Theoretical calculations of the static hyperpolarizabilities, first‐ and second‐order hyperpolarizability, were carried out. The structures of the obtained monomers and polymers were confirmed by infrared, ¹H NMR and ultraviolet spectroscopies. Thermal and optical properties of the obtained polymers were evaluated. The investigations show that some of the new polymers obtained in this study may find use in optical applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2195–2201, 2006     

Synthesizing and characterization of comb-shaped carbazole containing copolymer via combination of ring opening polymerization and nitroxide-mediated polymerization

The macro-TEMPO agent (poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), PGTEMPO) was synthesized by anion ring-opening polymerization (ROP) of 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (GTEMPO) using potassium t-butoxide as the initiator. The comb-shaped copolymer, PGTEMPO-g-PVBK, was prepared via nitroxide-mediated free radical polymerization (NMP) using PGTEMPO as macro-TEMPO agent and 9-(4-vinylbenzyl)-9H-carbazole (VBK) as the monomer. The polymerizations showed characteristics of “living”/controlled behavior. The optical properties, thermal analysis and electrochemical properties of the comb-shaped copolymers were investigated. The fluorescence and ultraviolet intensity and cyclic voltammetries of the comb-shaped copolymers with different molecular weight showed a regular order.     

New second-order nonlinear optical polymers containing the same isolation groups: Optimized syntheses and nonlinear optical properties

Based on control experiments, a new series of second-order nonlinear optical polymers with fluorene moieties as isolation spacers were successfully prepared. In the polymers, the chromophore moieties were embedded into the polymer backbone with one position at the donor side, and another point in the π bridge. Different acceptors were used to construct the push-pull structure of chromophore moieties, including nitro groups, sulfonyl groups, 3-phenyl-5-isoxazolone, 1,3-diethylthiobarbituric acid and TCF groups. The tested NLO properties of the polymers demonstrated that the isolation groups with big size do not always benefit the resultant NLO effect. Also, for different acceptors, there should be different suitable isolation groups to balance the good and bad effects caused by the introduced isolation spacers.     

Study of optically active methacrylates containing 1,1′‐binaphthyl side‐groups polymerized by anionic,group transfer and free radical methods

Optically active and racemic poly(meth)acrylates with pendant 1,1′‐binaphthalene moiety of 2‐methacryloyloxy‐ and 2‐acryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene (MAMBN and AMBN) were synthesized by anionic, group transfer and free radical polymerization methods. Their polymerizability and chiroptical properties are somewhat different, depending on the three types of polymerization methods used. The yields for poly(MAMBN)s are lower than for poly(AMBN)s. The optical rotation of the optically active polymers is identical to that of the corresponding monomers. The values of specific rotation of optically active poly(AMBN)s are much larger than those of optically active poly(MAMBN)s. © 2002 Society of Chemical Industry     

Synthesis and characterization of novel optically active polyesters with high thermal stability

A new optically active diacid (DA) was prepared by nucleophilic substitution reaction of R‐(−)‐mandelic acid with terephthaloyl chloride in the presence of potassium hydroxide. This DA named terephthalic acid bis(carboxyphenylmethyl) ester was used as a monomer for the preparation of related optically active polyesters. Polycondensation of DA with different aromatic diols, including hydroquinone, 1,5‐dihydroxy naphthalene, 1,4‐dihydroxy anthraquinone, 1,8‐dihydroxy anthraquinone, 2,4‐dihydroxy benzophenone, and bisphenol A, in the presence of 4‐toluenesulfonyl chloride using high temperature solution method led to preparation of different polyesters. The prepared monomer and all the polymers were characterized by conventional methods. Thermal and physical properties of the polyesters, including thermal stability, thermal behavior, solution viscosity, and solubility behavior, in addition to optical activity were studied. The optically active polyesters showed high thermal stability, whereas the presence of bulky groups improved their solubility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photoresponsive optically active polymers—a review

Photoresponsive macromolecules are of interest both as novel organic materials for applications in photodevices and as models for photomodulated biological processes. The presence in polymer chains of photosensitive groups and of chiral groups capable of inducing optical activity into the polymer is very useful for the analysis of photomodulated structural variations and allows storage of the light effect in the form of chiral information. Polypeptides bearing photochromic groups in the side chains are very convenient as the chiroptical properties of the peptide chromophore can be correlated to the backbone conformation. Thus polymers of L-aspartic acid, L-glutamic acid and L-lysine with azobenzene or stilbene groups attached covalently to the side chains are discussed in terms of photoinduced conformational changes and chiroptical information storage in the spectral region of the peptide and of the photoresponsive chromophore. Optically active photochromic macromolecules with hydrocarbon backbone, such as copolymers of (—)-menthyl acrylate with vinyl or acryloyl derivatives of azobenzene, stilbene and indolinospirobenzopyran, also show in some cases photodependence of chiroptical properties with evidence of at least local conformational changes as a consequence of light irradiation which can be used for chiral information.     

Nanomorphology control in aqueous coatings

Using catalytic chain transfer polymerisation (CCTP) in emulsion polymerisation results in efficient molecular weight reduction. An additional benefit of polymers prepared with CCTP is that they have a chain terminal unsaturated group that can be used in a subsequent graft copolymerisation to yield comb-shaped polymer chains. By careful optimisation of the polymer parameters, film properties can be optimised to yield coatings with very interesting combinations of properties.     

E.s.r. study of formation of coke texture

The optical coke texture is a major factor in the high-temperature properties of metallurgical coke but the mechanism of formation of coke texture is not established yet. By studying the carbonization process during the formation of optically anisotropic coke with an e.s.r. spectrometer fitted with a high temperature cavity a relation between the concentration of the free-spins during carbonization and coke texture has been inferred for some organic compounds used as the model materials and for coals covering a range of coal rank.     

Helical polymers

A number of natural and synthetic helical polymers are briefly described. The relationship between polymer helicity and optical activity is discussed. The synthesis of optically active polymers based solely on macromolecular asymmetry is emphasized.