117835-14-0Relevant articles and documents
Variable-color poly(3,4-propylenedioxythiophene) electrochromics from precursor polymers
Invernale, Michael A.,Bokria, Jayesh G.,Ombaba, Matthew,Lee, Ki-Ryong,Mamangun, Donna M.D.,Sotzing, Gregory A.
, p. 378 - 382 (2010)
We have developed two approaches to processable precursors to conjugated polymers: main-chain and side-chain. Upon oxidative conversion to the conjugated polymer, a main-chain precursor yielded a nearly perfect spectral match, an identical λmax, and an equivalent band gap to that of electrodeposited chromophore, resulting in a color match. This precursor method has the potential to incorporate any chromophore and achieve spectral and color matching with relative ease, as opposed to extensive synthetic monomer design. We describe the synthesis and characterization of a new side-chain and two new main-chain precursor polymers, each of which contains a derivative of 3,4-propylenedioxythiophene, ProDOT-Me2. The side-chain precursor tethers one ProDOT-Me2 molecule to a poly(norbornene) backbone; the main-chain systems are perfectly alternating copolymers of ProDOT-Me2, one with dimethylsilane and one with tetramethyldisiloxane. Electronic and optical properties for these converted precursors were described and compared to electrodeposited PProDOT-Me2.
Characterization of large molecular weight ester-functionalized norbornene and hydroxylated norbornane carboxylic acid polymers prepared by ring-opening metathesis polymerization
Stidham, Sarah E.,Weinberg, Benjamin H.,Grinstaff, Mark W.
, p. 5185 - 5190 (2012)
5-Norbornene-2-ethyl ester (mixture of endo and exo) is polymerized via ring-opening metathesis polymerization, yielding polymers with molecular weights ranging from 50,000 to 5,000,000 g/mol. The polymers are hydroxylated and saponified without alteration of the molecular weight. The polymers are analyzed by NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. Films are cast from the polymers at several molecular weights and their rheological properties are investigated. The results showed greater solid-like character with increasing molecular weight for all polymers analyzed. Cell viability studies showed that the films possessed minimal cytotoxicity.
Synthesis of Bicyclic Isocyanates and Bioisosteric 1,3-Disubstituted Ureas as Soluble Epoxide Hydrolase Inhibitors
Burmistrov,D’yachenko,Rasskazova,Butov
, p. 1166 - 1176 (2019)
(1S)-1-Isocyanato-4,7,7-trimethyl-2-oxabicyclo[2.2.1]heptan-3-one and 2-isocyanatobicyclo[2.2.1]-hept-5-ene were prepared by the Curtius rearragement reaction from the corresponding carboxylic acids. The synthesized isocyanates were used to synthesize, in high yields of 74–93%, bioisosteric 1,3-disubstituted ureas as potential human soluble epoxide hydrolase inhibitors.
Synthesis of novel, cubane-containing norbornene-based polymers
Priefer, Ronny,Nguyen, Sophie,Farrell, Patrick G.,Harpp, David N.
, p. 5435 - 5436 (2003)
The synthesis of novel, cubane-containing norbornene-based polymers was discussed. The synthesis was accomplished by tethering a cubane derivative to the polymer backbone via an ester linkage. The polymers were shown to behave thermally like simple cubane derivatives. The weight loss from the TGA curves corresponded to the loss of the carboxyl group as well as the cubane functionality.
Palladium-catalyzed double activation and arylation of 2° and 3° C(sp3)-H bonds of the norbornane system: Formation of a C-C bond at the bridgehead carbon and bridgehead quaternary stereocenter
Parella, Ramarao,Babu, Srinivasarao Arulananda
, p. 1395 - 1402 (2014)
Pd-catalyzed activation and direct arylation of both 2° and the bridgehead 3° (sp3) C-H bonds and an unprecedented C-C bond formation at the bridgehead carbon of the norbornane system are reported. The assembly of bridgehead-substituted norbornane frameworks having contiguous stereocenters was accomplished. X-ray crystal structure analysis of representative molecules unambiguously established the stereochemistry.
Shape memory behavior of side-chain liquid crystalline polymer networks triggered by dual transition temperatures
Ahn, Suk-Kyun,Deshmukh, Prashant,Kasi, Rajeswari M.
, p. 7330 - 7340 (2010)
We report synthesis and characterization of a new class of side-chain liquid crystalline random terpolymers (SCLCP), its cross-linked network (SCLCN), and the corresponding shape memory properties. The SCLCP comprising three monomers, 5-{15-(cholesteryloxycarbonyl)-pentadecyloxycarbonyl}-bicyclo[2.2.1] hept-2-ene (NBCh15), 5-(acryloyl butoxycarbonyl)-bicyclo[2.2.1]hept-2-ene (NBBA), and poly(ethylene glycol) functionalized norbornene (NBPEG), is synthesized by ring-opening metathesis polymerization (ROMP) using Grubbs catalyst second generation, resulting in a random terpolymer. Each monomer provides a specific function in the terpolymer: (1) NBCh15 affords liquid crystalline properties, (2) NBBA is a cross-linkable unit, and (3) NBPEG acts as an internal plasticizer. The mesomorphic structure of the terpolymer investigated by X-ray diffraction (XRD) exhibits highly interdigitated smectic A (SmA) mesophase comprising cholesteryl ester mesogens. The acrylate end group in the NBBA undergoes cross-linking by curing at 120 °C, resulting in the SCLCN. Optimal cross-linking conditions are determined by monitoring gel fraction produced from different curing times. Thermal transitions including glass transition temperature (Tg) and clearing temperature (T cl) before and after cross-linking are analyzed by differential scanning calorimetry (DSC). Linear viscoelastic properties of the SCLCN reveal three different relaxations associated with dynamic soft elasticity as well as Tg and Tcl. One-way shape memory cycles (1W-SMCs) of the SCLCN are programmed using (1) Tg, (2) Tcl, and (3) combined (Tg and Tcl) as a shape memory transition temperature (Ttrans). The Tg-based SMCs exhibits excellent shape fixing (>97%) and shape recovery ratio (>96%) with large strain (>150%). In the Tcl-based SMCs, the cooling induced elongation of strain is observed due to the development of interdigitated SmA mesophase. The shape fixing by interdigitated SmA is achieved during the Tcl-based SMCs unlike conventional shape fixing methods such as vitrification or crystallization. If both Tg and Tcl serve as T trans for SMCs, the permanent shape is restored by two stages of shape recovery around Tg and Tcl. The dual T trans (Tg and Tcl) inherent in this SCLCN allows for creating different types of SMCs and for the memorization of shape at two different temperature windows, thereby, programmed shapes by different mechanism would be recovered in a more precise manner.
Preparation and utilization of catalyst-functionalized single-walled carbon nanotubes for ring-opening metathesis polymerization
Liu, Yuanqin,Adronov, Alex
, p. 4755 - 4760 (2004)
Single-walled carbon nanotubes were oxidatively shortened and functionalized with ruthenium-based olefin metathesis catalysts. These catalyst-functionalized nanotubes were shown to be effective in the ring-opening metathesis polymerization of norbornene, resulting in rapid polymerization from the catalyst sites on the nanotube. It was found that high polymer molecular weights could be reached, and the molecular weight increased linearly with polymerization time. The resulting polynorbornene-functionalized nanotubes were found to exhibit solubility in organic solvents, whereas the starting materials and catalyst-functionalized nanotubes were completely insoluble. The polymerized materials were characterized by NMR, IR, DSC, AFM, and TEM.
Dye functionalized-ROMP based terpolymers for the use as a light up-converting material: Via triplet-triplet annihilation
Hollauf,Zach,Borisov,Müller,Beichel,Tscherner,K?stler,Hartmann,Knall,Trimmel
, p. 7535 - 7545 (2017)
In this paper we introduce and compare different terpolymers comprising covalently attached sensitizer and emitter chromophores for the use as a light up-converting material via triplet-triplet annihilation (TTA). Using the advantages of ring opening metathesis polymerisation it was possible to prepare five different polymer architectures in order to investigate the influence of polymer architecture and chromophore arrangement on the photon up-conversion behaviour. First, two new monomers containing the chromophores have been synthesized and characterized in regard to their photophysical characteristics suitable for triplet-triplet annihilation dye pair. For this purpose, a derivative of Pt(ii) meso-tetraphenyltetra(tert-butyl)benzoporphyrin as sensitizer and a perylenediester as emitter were attached to norbornene moieties via ester linkages. Polymerisations of these monomeric chromophores were performed in combination with dimethyl 5-norbornene-2,3-dicarboxylate as matrix monomer. Depending on the location of the dye molecules on the polymer chain, large differences in the TTA efficiency were observed. The best quantum yields have been achieved with a completely statistically distributed terpolymer showing an up-conversion quantum yield of up to 3% in solution.
Dipyridyl amide-functionalized polymers prepared by ring-opening- metathesis polymerization (ROMP) for the selective extraction of mercury and palladium
Sinner, Frank,Buchmeiser, Michael R.,Tessadri, Richard,Mupa, Mathew,Wurst, Klaus,Bonn, Günther K.
, p. 2790 - 2797 (1998)
Ring-opening-metathesis polymerization (ROMP) was used for the preparation of a dipyridylcarbamide-functionalized polymer suitable for solid-phase extraction of metal ions from aqueous solutions. Resins were prepared by the copolymerization of the functional monomer. N,N-di-2-pyridyl- endo-norborn-2-ene-5-carboxamide (I) with 1,4,4a,5,8,8a-hexahydro-l,4,5,8- exo-endo-dimethanonaphthalene (II), using the welldefined Schrock catalyst Mo(N-2,6-i-Pr2C6H3)CHCMe2Ph(OCMe(CF3)2)2 (III). The polymerization proceeds in a living manner, allowing the stoichiometric buildup of polymers. NMR investigations proved the expected backbone structure of the resulting polymers, where the binding site of the monomer remains unaffected in course of the polymerization. The new materials were investigated in terms of their complexation behavior versus a large Variety of mono-, di-, tri-, and tetravalent metal ions employing UV-vis spectroscopy as well as AAS and ICP- OES techniques. The polymer-bound dipyridylamide ligand showed excellent selectivity toward Hg2+ and Pd2+, allowing the selective extraction of both divalent metal ions over a broad range of concentrations from complex mixtures. Due to the stability of the resulting complexes, high loadings of the material with both metals were achieved. To elucidate the chemistry of complexation, X-ray structures of compound (I) as well as ESI-MS investigations of the complex of I with Pd2+ were performed. I crystallized in the monoclinic space group P21/c, and forms 1:1 complexes with Pd2+ under conditions identical to the SPE experiments.
Visible Light-Mediated Decarboxylative Alkylation of Pharmaceutically Relevant Heterocycles
Sun, Alexandra C.,McClain, Edward J.,Beatty, Joel W.,Stephenson, Corey R. J.
supporting information, p. 3487 - 3490 (2018/06/26)
A net redox-neutral method for the decarboxylative alkylation of heteroarenes using photoredox catalysis is reported. Additionally, this method features the use of simple, commercially available carboxylic acid derivatives as alkylating agents, enabling the facile alkylation of a variety of biologically relevant heterocyclic scaffolds under mild conditions.
