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Side Groups (side + groups)

Distribution by Scientific Domains

Polymers and Materials Science	79%
Chemistry	16%
2 Other Domains	5%

Distribution within Polymers and Materials Science

Polymer Science & Technology General	75%
General & Introductory Materials Science	20%

Selected Abstracts

Ionic Iridium(III) Complexes with Bulky Side Groups for Use in Light Emitting Cells: Reduction of Concentration Quenching

ADVANCED FUNCTIONAL MATERIALS, Issue 13 2009
Carsten Rothe
Abstract Here, the photophysics and performance of single-layer light emitting cells (LECs) based on a series of ionic cyclometalated Ir(III) complexes of formulae and where ppy, bpy, and phen are 2-phenylpyridine, substituted bipyridine and substituted phenanthroline ligands, respectively, are reported. Substitution at the N,N ligand has little effect on the emitting metal-ligand to ligand charge-transfer (MLLCT) states and functionalization at this site of the complex leads to only modest changes in emission color. For the more bulky complexes the increase in intermolecular separation leads to reduced exciton migration, which in turn, by suppressing concentration quenching, significantly increases the lifetime of the excited state. On the other hand, the larger intermolecular separation induced by bulky ligands reduces the charge carrier mobility of the materials, which means that higher bias fields are needed to drive the diodes. A brightness of ca. 1000,cd,m,2 at 3,V is obtained for complex 5, which demonstrates a beneficial effect of bulky substituents. [source]

Photo-Induced Orientation of a Film of Ladderlike Polysiloxane Bearing Dual Photoreactive Side Groups,

ADVANCED MATERIALS, Issue 16 2003
H.W. Gu
A newly designed ladder-like polysiloxane (LPS) containing dual photoreactive side groups has been synthesized for the purpose of generating high-quality photo-alignment layers with controllable pretilt angle (,,1,7°, see Figure and cover). Integrated spectroscopic methods of UV dichroism, surface-enhanced Raman scattering (SERS), and FT-IR are used together for the first time to elucidate the photo-alignment mechanism and the real cause of the high pretilt angle. [source]

Photoinduced Microphase Separation in Block Copolymers: Exploring Shape Incompatibility of Mesogenic Side Groups

MACROMOLECULAR RAPID COMMUNICATIONS, Issue 11 2010
Yi Zhao
Abstract Photoinduced microphase separation in block copolymers (BCP) was achieved for the first time, using a rationally designed diblock copolymer composed of two side-chain liquid crystalline polymers (SCLCP). The miscibility of the two blocks was promoted by the miscibility between the two types of mesognic side groups, while upon UV exposure inducing the trans,cis isomerization of azobenzene mesogens on one SCLCP, the shape incompatibility of bent cis isomers with an ordered liquid crystalline phase drove the separation of the two blocks resulting in a microphase separated morphology. This result shows the perspective of using light to process and organize BCP morphology and related nanostructures in a lithography-free manner. [source]

Synthesis, Characterization, and Electrochemical Properties of Dinuclear Complexes Assembled from Asymmetric CoIII Bis(dioximates) and Boronic Acids

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2005
Renata Dreos
Abstract Bis(methylphenylglyoximate)cobalt(III) complexes exist both as cis and trans isomers due to the asymmetry of the equatorial ligand, and, when the axial ligands are different, the trans isomer is chiral. The reaction of racemic trans -[CH3Co(mpgH)2py] (1) with either 3- or 4-pyridylboronic acid affords dimeric units arranged on a crystallographic symmetry center such that the pyridyl nitrogen of one moiety coordinates to the Co atom of the symmetry-related unit. In principle, three structurally different dimeric species (two homodimers and one heterodimer) can be obtained. Time-resolved 1H NMR spectra of a 1:1 mixture of racemic 1 and either 3- or 4-pyridylboronic acid in CDCl3/CD3OD show that the reaction does not converge toward a unique species in solution. Nevertheless, X-ray structures show that the heterochiral dimers are the only products that crystallize from the reaction mixture. The nature of the dioximate side groups does not affect the geometry of the dimeric arrangements assembled by 4-pyridylboronic acid ("molecular box"). On the contrary, the geometry of the species assembled by 3-pyridylboronic acid varies from the "molecular parallelogram" obtained from the bis(dimethylglyoximates) to the highly squeezed "molecular box" obtained from bis(methylphenylglyoximates). Cyclic voltammetry studies show that the metal centers in the dimeric species do not interact with each other and undergo a simultaneous redox process. However, depending on the geometry of the systems, the redox process involves a single four-electron reduction for 3 and 5 or two consecutive two-electron reduction steps for 4 and 6. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Synthesis and Structure,Property Relations of a Series of Photochromic Molecular Glasses for Controlled and Efficient Formation of Surface Relief Nanostructures

ADVANCED FUNCTIONAL MATERIALS, Issue 16 2009
Roland Walker
Abstract This paper reports on the synthesis and properties of a new series of photochromic molecular glasses and their structure,property relations with respect to a controlled and efficient formation of surface relief nanostructures. The aim of the paper is to establish a correlation between molecular structure, optical susceptibility, and the achievable surface relief heights. The molecular glasses consist of a triphenylamine core and three azobenzene side groups attached via an ester linkage. Structural variations are performed with respect to the substitution at the azobenzene moiety in order to promote a formation of a stable amorphous phase and to tune absorption properties and molecular dynamics. Surface relief gratings (SRGs) and complex surface patterns can easily be inscribed via holographic techniques. The modulation heights are determined with an equation adapted from the theory for thin gratings, and the values are confirmed with AFM measurements. Temperature-dependent holographic measurements allow for monitoring of SRG build-up and decay and the stability at elevated temperatures, as well as determination of the glass transition temperature. SRG modulation heights of above 600,nm are achieved. These are the highest values reported for molecular glasses to date. The surface patterns of the molecular glasses are stable enough to be copied in a replica molding process. It is demonstrated that the replica can be used to transfer the surface pattern onto a common thermoplastic polymer. [source]

Multifunctional Deep-Blue Emitter Comprising an Anthracene Core and Terminal Triphenylphosphine Oxide Groups

ADVANCED FUNCTIONAL MATERIALS, Issue 4 2009
Chen-Han Chien
Abstract A highly efficient blue-light emitter, 2- tert -butyl-9,10-bis[4,-(diphenyl-phosphoryl)phenyl]anthracene (POAn) is synthesized, and comprises electron-deficient triphenylphosphine oxide side groups appended to the 9- and 10-positions of a 2- tert -butylanthracene core. This sophisticated anthracene compound possesses a non-coplanar configuration that results in a decreased tendency to crystallize and weaker intermolecular interactions in the solid state, leading to its pronounced morphological stability and high quantum efficiency. In addition to serving as an electron-transporting blue-light-emitting material, POAn also facilitates electron injection from the Al cathode to itself. Consequently, simple double-layer devices incorporating POAn as the emitting, electron-transporting, and -injecting material produce bright deep-blue lights having Commission Internationale de L'Eclairage coordinates of (0.15,0.07). The peak electroluminescence performance was 4.3% (2.9 cd A,1). For a device lacking an electron-transport layer or alkali fluoride, this device displays the best performance of any such the deep-blue organic light-emitting diodes reported to date. [source]

Effects of Annealing on the Nanomorphology and Performance of Poly(alkylthiophene):Fullerene Bulk-Heterojunction Solar Cells,

ADVANCED FUNCTIONAL MATERIALS, Issue 7 2007
H. Nguyen
Abstract The evolution of nanomorphology within thin solid-state films of poly(3-alkylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester (P3AT:PCBM) blends during the film formation and subsequent thermal annealing is reported. In detail, the influence of the P3AT's alkyl side chain length on the polymer/fullerene phase separation is discussed. Butyl, hexyl, octyl, decyl, and dodecyl side groups are investigated. All of the P3ATs used were regioregular. To elucidate the nanomorphology, atomic force microscopy (AFM), X-ray diffraction, and optical spectroscopy are applied. Furthermore, photovoltaic devices of each of the different P3ATs have been constructed, characterized, and correlated with the nanostructure of the blends. It is proposed that the thermal-annealing step, commonly applied to these P3AT:PCBM blend films, controls two main issues at the same time: a),the crystallization of P3AT and b),the phase separation and diffusion of PCBM. The results show that PCBM diffusion is the main limiting process for reaching high device performances. [source]

Modulation of the Lifetime of Water Bound to Lanthanide Metal Ions in Complexes with Ligands Derived from 1,4,7,10-Tetraazacyclododecane Tetraacetate (DOTA)

HELVETICA CHIMICA ACTA, Issue 5 2005
Shanrong Zhang
A series of di- and tetraamide derivatives of DOTA were synthesized, and their lanthanide(III) complexes were examined by multinuclear 1H-, 13C-, and 17O-NMR spectroscopy, and compared with literature data of similar, known complexes (Table). All ligands formed structures similar to the parent [LnIII(DOTA)], complexes, with four N-atoms and four O-atoms from DOTA and one O-atom from the inner-sphere water molecules. Interestingly, the lifetimes ,M of the inner-sphere, metal-bound water molecules vary widely, ranging from nano- to milliseconds, depending on the identity of the pendent amide side chains. In general, positively charged [LnIII(DOTA-tetraamide)]3+ complexes display the longest residence times (high ,M values), while complexes with additional charged functional groups on the extended amides display much smaller ,M values, even when the side groups are not directly coordinated to the central Ln3+ ions. The design of novel [LnIII(DOTA-tetraamide)]3+ complexes with a wide, tunable range of ,M values is of prime importance for the application of fast-responding, paramagnetic chemical-exchange-saturation-transfer (PARACEST) imaging agents used for the study of physiological and metabolic processes. [source]

Photo-Induced Orientation of a Film of Ladderlike Polysiloxane Bearing Dual Photoreactive Side Groups,

A Covalently Interconnected Phosphazene,Silicate Hybrid Network: Synthesis, Characterization, and Hydrogel Diffusion-Related Application,

ADVANCED MATERIALS, Issue 6 2003
Y. Chang
Sol,gel precursors of poly[bis(methoxyethoxyethoxy)phosphazene] have been synthesized by incorporating triethoxysilane in the polymer side groups. Studies of the water-swelling (see Figure, dry left, water-swollen, right) behavior and dye-release of the hybrid network indicate that the polyphosphazene,silicate network has potential as a biomaterial and for use in both passive and responsive membranes. [source]

Influence of azobenzene units on imidization kinetic of novel poly(ester amic acid)s and polymers properties before and after cyclodehydration

JOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010
Ewa Schab-Balcerzak
Abstract In this article, the imidization reaction kinetic of novel poly(ester amic acid)s with azobenzene units as side groups was studied by dynamic experiments by means of differential scanning calorimetry. Polymers differ in the number of chromophore moieties in their repeating unit and position in which azobenzene group is attached to the polymer chain. The kinetic parameters of poly(ester amic acid)s conversion to poly(ester imide)s was compared with data calculated for parent polymer, that is, without azobenzene groups. For the first time to our knowledge, the imidization kinetic of polymers with side azobenzene groups was studied. Kinetic parameters, such as the activation energy and frequency factor were estimated with the by Ozawa model [(E(O) and A(O)), respectively] and Kissinger model [(E(K) and A(K), respectively]. The values of activation energy determined with both models were in the range 167.1,198.3 kJ/mol. The lowest activation energy of imidization reaction exhibited polymer in which azobenzene units were placed between amide linkages. Polymers were characterized by FTIR, 1H-NMR, X-ray, and UV,vis methods. The glass transition temperature of resultant poly(ester imide)s was in the range of 217,237°C. The presence of chromophore units slightly decreased Tg and significantly improved their solubility and optical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]

Micellar behavior of well-defined polystyrene-based block copolymers with triethoxysilyl reactive groups and their hydrolysis,condensation

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2010
Cé Guinto Gamys
Abstract Block copolymers of acryloxy propyl triethoxysilane and styrene were prepared through nitroxide-mediated polymerization using alkoxyamine initiators based on N - tert -butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide. The copolymers were characterized by 1H NMR, size exclusion chromatography and differential scanning calorimetry. Their micellar behavior in dioxane/methanol solutions was examined through static light scattering and transmission electron microscopy (TEM). TEM indicated the successful formation of spherical micelles which were subsequently frozen by the sol,gel process. Hydrolysis,condensation of the reactive ethoxysilyl side groups was followed by FTIR, 1H NMR, and 29Si NMR. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 784,793, 2010 [source]

Synthesis and hierarchical superstructures of side-chain liquid crystal polyacetylenes containing galactopyranoside end-groups

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2009
Ming-Shou Ho
Abstract Three kinds of chiral saccharide-containing liquid crystalline (LC) acetylenic monomers were prepared by click reaction between 2-azidoethyl-2,3,4,6-tetraacetyl-,- D -galactopyranoside and 1-biphenylacetylene 4-alkynyloxybenzoate. The obtained monomers were polymerized by WCl6 -Ph4Sn to form three side-chain LC polyacetylenes containing 1-[2-(2,3,4,6-tetraacetyl-,- D -galactopyranos-1-yl)-ethyl]-1H -[1,2,3]-triazol-4,-biphenyl 4-alkynyloxybenzoate side groups. All monomers and polymers show a chiral smectic A phase. Self-assembled hiearchical superstructures of the chiral saccharide-containing LCs and LCPs in solution state were studied by field-emission scanning electron microscopy. Because of the LC behavior, the LC molecules exhibit a high segregation strength for phase separation in dilute solution (THF/H2O = 1:9 v/v). The self-assembled morphology of LC monomers was dependent upon the alkynyloxy chain length. Increasing the alkynyloxy chain length caused the self-assembled morphology to change from a platelet-like texture (LC-6) to helical twists morphology (LC-11 and LC-12). Furthermore, the helical twist morphological structure can be aligned on the polyimide rubbed glass substrate to form two-dimensional ordered helical patterns. In contrast to LC monomers, the LCP-11 self-assembled into much more complicate morphologies, including nanospheres and helical nanofibers. These nanofibers are evolved from the helical cables ornamented with entwining nanofibers upon natural evaporation of the solution in a mixture with a THF/methanol ratio of 3:7. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6596,6611, 2009 [source]

Liquid crystalline conjugated polymers and their applications in organic electronics

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2009
Sheng-Hsiung Yang
Abstract This article describes the syntheses and electro-optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p -phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p -phenylenevinylene)s, the Suzuki- or Yamamoto-coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main-chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side-chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field-effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo-fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713,2733, 2009 [source]

Cationic, water-soluble, fluorene-containing poly(arylene ethynylene)s: Effects of water solubility on aggregation, photoluminescence efficiency, and amplified fluorescence quenching in aqueous solutions

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2006
Yan-Qin Huang
Abstract Three novel fluorene-containing poly(arylene ethynylene)s with amino-functionalized side groups were synthesized through the Sonogashira reaction. They were poly{9,9-bis[6,-(N,N -diethylamino)hexyl]-2,7-fluorenylene ethynylene}- alt - co -{2,5-bis[3,-(N,N -diethylamino)-1,-oxapropyl]-1,4-phenylene} (P1), poly{9,9-bis[6,-(N,N -diethylamino)hexyl]-2,7-fluorenylene ethynylene} (P2), and poly({9,9-bis[6,-(N,N -diethylamino)hexyl]-2,7-fluorenylene ethynylene}- alt - co -(1,4-phenylene)) (P3). Through the postquaternization treatment of P1,P3 with methyl iodide, we obtained their cationic water-soluble conjugated polyelectrolytes (WSCPs): P1,,P3,. The water solubility was gradually improved from P3, to P1, with increasing contents of hydrophilic side chains. After examining the ultraviolet,visible absorption and photoluminescence (PL) spectra, fluorescence lifetimes, and dynamic light scattering data, we propose that with the reduction of the water solubility from P1, to P3,, they exhibited a gradually increased degree of aggregation in H2O. The PL quantum yields of P1,,P3, in H2O displayed a decreasing tendency consistent with the increased degree of aggregation, suggesting that the pronounced degree of aggregation was an important reason for the low PL quantum yields of WSCPs in H2O. Two structurally analogous water-soluble trimers of P2, and P3,, model compounds 2,7-bis(9,,9,-bis{6,-[(N,N -diethyl)- N -methylammonium] hexyl}-2,-fluorenylethynyl)-9,9-bis{6,-[(N,N -diethyl)- N -methylammonium]hexyl}fluorene hexaiodide and 1,4-bis(9,,9,-bis{6,-[(N,N -diethyl)- N -methylammonium]hexyl}-2,-fluorenylethynyl)benzene tetraiodide, were synthesized. The amplified fluorescence quenching of these WSCPs by Fe(CN)64, in H2O was studied by comparison with a corresponding analogous trimer. The effects of aggregation on the fluorescence quenching may be two-edged in these cases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5778,5794, 2006 [source]

Living cationic polymerization of azobenzene-containing vinyl ether and its photoresponsive behavior

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2005
Tomohide Yoshida
Abstract The living cationic polymerization of 4-[2-(vinyloxy)ethoxy]azobenzene (AzoVE) was achieved with various Lewis acids in the presence of an ester as an added base. When Et1.5AlCl1.5 was used as a catalyst, the living polymerization system was controllable by UV irradiation as a result of cis and trans isomerization of the azobenzene side groups. Furthermore, an initiating system consisting of SnCl4 and EtAlCl2 realized fast living polymerization of AzoVE. The polymerization rate of this system was 3 orders of magnitude faster than that obtained with Et1.5AlCl1.5. Poly(4-[2-(vinyloxy)ethoxy]azobenzene) was soluble in a diethyl ether/hexane mixture at 25 °C but became insoluble upon irradiation with UV light. This phase-transition behavior was sensitive and reversible upon irradiation with UV or visible light and reflected the change in polarity occurring with cis and trans isomerization of the azobenzene side groups in the polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5138,5146, 2005 [source]

Synthesis and optical properties of soluble polyethers containing oligophenyl in the main chain and p -styrylbenzene side groups

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2002
Ioakim K. Spiliopoulos
Abstract New polyethers containing alternating conjugated segments of p -terphenyl or p -quinquephenyl with p -styrylbenzene side groups and aliphatic spacers were synthesized with pyrylium salts. They had moderate molecular weights, were amorphous, and dissolved in tetrahydrofuran, chloroform, and other common organic solvents. The glass-transition temperatures were 68,82 and 110,153 °C for the polymers that carried p -terphenyl and p -quinquephenyl moieties, respectively. The absorption spectra showed a peak around 325 nm, and the band gaps were 3.27,3.34 eV, which were calculated from the onset absorption in solution. The photoluminescence maxima were at 393,398 nm in solution and 422,449 nm in thin films, indicating that the polymers were violet-blue-emitting materials. The photoluminescence quantum yields in solution were up to 0.25. The polymers displayed both in concentrated solutions and in the solid state intramolecular or intermolecular interactions. The polarity of the solvent influenced the shape of the photoluminescence curve. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 682,693, 2002; DOI 10.1002/pola.10151 [source]

Synthesis and properties of amorphous blue-light-emitting polymers with high glass-transition temperatures

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2001
V. Deimede
Abstract A series of soluble poly(arylene ether)s containing the phenylphosphine oxide moiety were synthesized by the polymerization of substituted oligophenylene diols with bis(fluorophenyl)phenylphosphine oxide. These amorphous polyethers had well-defined structures and showed blue photoluminescence combined with good thermal stability, especially when phenyl or ethoxy side groups were used. The glass-transition temperatures increased when the size of the oligophenylene segment increased from three to five rings or when the length of the alkoxy substituents decreased. Polymers with glass-transition temperatures up to 270 °C were obtained. The absorption and photoluminescent spectra shifted to longer wavelengths with an increase in the oligophenylene block. A redshift was also observed on photoluminescent spectra in the transition from solution to the solid state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3168,3179, 2001 [source]

Photoluminescent Color and Polarized Light Emission Tuning of Fluorene Derivatives Using a Photoreactive H-Bonded Liquid Crystalline Polymer

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 16 2010
Nobuhiro Kawatsuki
Abstract Three fluorene (FL) derivatives with pyridine end groups were synthesized to control the photoluminescence (PL) wavelength and polarized light emission using a photoreactive H-bonded polymer containing cinnamic acid side groups (P6CAM). The FL derivatives, which possessed pyridine end groups, formed H-bonds with cinnamic acid, and changed the PL behavior of the derivatives. The controllability ,max of the PL depended on the position of the N-atom at the pyridine end group and the degree of the photoreaction of the P6CAM. For F1, ,max of the PL was tuned from 470 to 518,nm. Employing P6CAM as the photoalignment layer to reorient the cinnamic acid side groups realized polarized PL up to PL||/PL,,=,3.9. Furthermore, photopatterning of the PL color and the direction of the polarized light emission using patterned P6CAM films were demonstrated. [source]

4-Alkylphenoxymethyl-Substituted Polystyrenes for Liquid Crystal Alignment Layers

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2009
Hyo Kang
Abstract We synthesized a phenoxymethyl-substituted polystyrene (PHP) and a series of 4-alkylphenoxymethyl-substituted polystyrenes, where the alkyl group is (CH2)nH (n,=,1, 2, 4, 6, and 8), using polymer analogous reactions, in order to study the effect of the phenoxymethyl and 4-alkylphenoxymethyl side groups on the liquid crystal (LC) alignment properties. The LC cell fabricated with the rubbed PHP film exhibited homogeneous planar and perpendicular LC alignment with respect to the rubbing direction. On the contrary, the LC cells made from the 4-alkylphenoxymethyl-substituted polystyrenes showed homeotropic LC alignment behaviors even at a very high rubbing density of 250, regardless of the length of the alkyl groups. Previously, n -alkylsulfonylmethyl-substituted polystyrenes with alkyl groups having more than 8 carbons (n,>,8) showed homeotropic LC alignment behavior. Therefore, the additional phenoxy group in the side chain was found to improve the homeotropic LC aligning ability of the polystyrene derivatives. [source]

Copolymerization of Ethylene with 2,7-Octadienyl Methyl Ether in the Presence of Metallocene and Nickel Diimine Catalysts

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 7 2009
Mércia Fernandes
Abstract In this work, copolymers of ethylene with 2,7-octadienyl methyl ether have been synthesized in the presence of three single-site catalysts. The obtained copolymers not only have a polar ether function but also a double bond in the side chains that is useful for secondary reactions. The polymers were characterized by GPC, EA, DSC, NMR, and FT-IR. The catalytic activity depends on the kind of catalysts, the concentration of the polar monomer, and the concentration of the protecting agent. Up to 7.3 wt.-% of MODE could be incorporated by the metallocene catalyst. These are in average 120 functional side groups in a polymer molecule with a molecular mass of 230,000. [source]

Hydroxylated Linear Polyurethanes Derived from Sugar Alditols

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2009
Romina Marín
Abstract A set of linear [m,n]-type polyurethanes was synthesized by reaction of HDI or MDI with conveniently protected sugar alditols L -threitol (LTh), L -arabinitol (LAr) and xylitol (Xy). of the resulting polyurethanes ranged between 10,000 and 60,000 with polydispersities around 2. They were thermally stable, showing no decomposition up to temperatures near 300,°C. They all were amorphous polymers with Tg highly dependent on the constitution of the diisocyanate, but scarcely dependent on the structure of the alditol. Hydrogenation of the LThBn-HDI polyurethane yielded partially debenzylated products with Tg values ranging between 20 and 30,°C. Fully benzylated polyurethanes showed high resistance to hydrolytic degradation, whereas polyurethane with free hydroxyl side groups degraded significantly in saline buffer at pH,=,10 and 37,°C. [source]

Synthesis and Characterization of Supramolecular Polymeric Materials Containing Azopyridine Units

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 22 2006
Marta Millaruelo
Abstract Summary: The synthesis and characterization of a series of supramolecular polymeric complexes formed by H-bonding interactions between benzoic acid and azopyridine derivatives are described. A series of polymeric networks have been synthesized using a polymethacrylate bearing benzoic acid units as side groups, and several polymers with azopyridine as H-acceptor side groups. Furthermore, low-molecular-weight pyridine derivatives have been used to prepare an homologous side-chain polymer, and a network with azopyridine as a non-covalent crosslinker. Special attention was paid to the thermal and mesomorphic properties of these materials, which were studied by DSC, POM, and XRD. Micrograph of the mesomorphic melt of a sample taken at 130,°C on cooling from the isotropic state. [source]

New Poly(sodium carboxylate)s Based on Saccharides, 1.

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 18 2002
Characterization of Ionic Allyl Glycoside Polymers, Synthesis
Abstract New poly(sodium carboxylate)s, containing monosaccharide side groups with ether linkages to the main chain, are presented as substitutes for water-soluble homo- and copolymers of acrylic acid. Neutral and ionic allyl glycoside monomers, namely allyl- , - D -galactopyranoside and allyl- , - D -glucofuranosidurono-6,3-lactone, were synthesized by Fischer glycosidation. These monomers were copolymerized with maleic anhydride and itaconic acid in aqueous and nonaqueous solution. The corresponding copolymers with different structures, degrees of functionalization, and charge densities were characterized by 13C NMR spectroscopy, molecular-weight measurements, and intrinsic viscosity [,] determination. From these, the monomer reactivity ratios and Mark,Houwink relations were established (see Figure). Copolymerization curves of maleic acid copolymers 6 and 10. M1: mole fraction of allyl monomer 2, and 5, in the feed; m1: mole fraction of allyl monomer in the copolymer. The dashed line shows the course of an ideal alternating copolymerization (excepted: M1,=,0 mol-%, M1,=,100 mol-%). [source]

Photoinduced Microphase Separation in Block Copolymers: Exploring Shape Incompatibility of Mesogenic Side Groups

A Combination of Selective Light Reflection and Fluorescence Modulation in a Cholesteric Polymer Matrix

MACROMOLECULAR RAPID COMMUNICATIONS, Issue 3 2005
Dasha Medvedeva
Abstract Summary: The phase behavior and optical properties of a cholesteric ternary copolymer, containing nematogenic phenylbenzoate, cholesteric, and photochromic diarylethene side groups, and its mixture with 2 wt.-% fluorescent dopant were studied. The investigation of the kinetics of a photochemical opening-cycle process of the photochromic groups in the cholesteric mixture proved the energy transfer from the fluorescent dopant to the photochromic diarylethene groups. It was shown that the fluorescence intensity of the fluorescent dopant could be controlled by the portion of the "closed" form of the diarylethene groups. During the photocyclization of the photochromic groups a "degeneration" of the selective light reflection of the cholesteric matrix is observed. Fluorescence-resonance energy transfer makes possible the process of photosensitization of the back ring-opening photoreaction of the photochromic diarylethene groups in the cholesteric polymer matrix. [source]

Encapsulation of magnetic self-assembled systems in thermoreversible gels

MACROMOLECULAR SYMPOSIA, Issue 1 2003
Jean-Michel Guenet
Abstract We describe two different ways of encapsulating within the fibrils of thermoreversible polymer gels the filaments of a supermolecular polymer formed by self-assembly of a bicopper complex. Heterogeneous nucleation is brought about with gels made from isotactic poly(styrene) while compound formation occurs with gels made from poly(hexyl isocyanate). These ways depend upon the interaction between the wings of the supermolecular polymer and the side groups of the polymer. In all cases, the filaments retain their 1-D structure. Preliminary results from magnetic susceptibility measurements show a striking difference between the pure and the encapsulated supermolecular polymer. [source]

Synthesis, characterization and properties of polycarbonate containing carboxyl side groups

MACROMOLECULAR SYMPOSIA, Issue 1 2003
Ruifeng Zhang
Abstract Diphenolic Acid, DPA [bis(4-hydroxyphenyl)pentanoic acid] can be made from cellulose-rich waste. The t-butyl ester was converted to homo- and copolycar- bonates (with bis-phenol-A, BPA). Deblocking the ester yielded polycarbonates with pendent carboxyl groups that exhibit all the properties of polyelectrolytes and retain solubility in aqueous base without degradation for long periods. [source]

Mechanical and oxygen barrier properties of organoclay-polyethylene nanocomposite films

POLYMER ENGINEERING & SCIENCE, Issue 7 2007
Yang Zhong
An organically modified montmorillonite was compounded with ethylene vinyl acetate copolymer (EVA), low density polyethylene (LDPE), and high density polyethylene (HDPE) in a twin-screw extruder. The resulting organoclay-polyethylene nanocomposites were then blown into films. Tensile properties and oxygen permeability of these nanocomposite films were investigated to understand the effects of organoclay on different types of polyethylene. It was found that the clay enhancing effects are function of the matrix. The mechanical and oxygen barrier properties of clay/EVA systems increased with clay loading. Both the tensile modulus and oxygen barrier of EVA doubled at 5 wt% clay. Maleic anhydride grafted polyethylene (MAPE) usually is used as a compatibilizer for LDPE and HDPE-based nanocomposites. However, the MAPEs were found to weaken the oxygen barrier of the PEs, especially for HDPE. This is believed to be a result of less compactness caused by the large side groups and the increase in polarity of the MAPEs. Incorporating 5 wt% clay improves the oxygen barrier by 30% and the tensile modulus by 37% for the LDPE/MAPE system. Incorporation of clay does not enhance the properties of the HDPE-based systems, likely due to large domain structure and poor bonding. Halpin,Tsai equation and the tortuous path equation were used to model the tensile modulus and oxygen permeability of the clay/EVA nanocomposite films. POLYM. ENG. SCI., 47:1101,1107, 2007. © 2007 Society of Plastics Engineers [source]

Synthesis, characterization, in vitro degradation and cytotoxicity of polyphosphazenes containing N -ethoxypyrrolidone side groups

POLYMER INTERNATIONAL, Issue 2 2010
Yunmei Bi
Abstract A new biodegradable polyphosphazene (PYRMP) containing N -ethoxypyrrolidone and methoxyethoxyethoxy side groups was synthesized via a route of macromolecular substitution. The synthetic method of poly{bis[2-(2-oxo-1-pyrrolidinyl)ethoxy]phosphazene} (PYRP) was improved. The thermal properties of the polymers were investigated using differential scanning calorimetry. Degradation studies were carried out in vitro with varying pH conditions. The in vitro cytotoxicity of PYRMP and its hydrolysis products was evaluated using the methyl tetrazolium (MTT) cytotoxicity test in HepG2 cell culture. PYRMP and PYRP have low glass transition temperatures of ,68.8 and ,59.6 °C, respectively. The polymers show a higher degradation rate at pH = 5.0 than at both pH = 7.4 and 8.0. The degradation process of PYRMP in different buffer solutions is discussed. The MTT test reveals that PYRMP at concentrations below 800 µg mL,1 and its hydrolysis products are non-toxic to HepG2 cells. Moreover, the hydrolysis products diluted 10 times are able to promote cell proliferation. This study shows that polyphosphazene containing N -ethoxypyrrolidone subsituents provides interesting perspectives for various biomedical applications. Copyright © 2009 Society of Chemical Industry [source]