- Discotic liquid crystals of transition metal complexes 58: Novel phthalocyanine-based mesogenic monomers and polymers exhibiting spontaneous homeotropic alignment and helical tetragonal columnar structure
-
Two synthetizations of a novel series of phthalocyanine-based discotic liquid crystals substituted by a polymerizable group, acryloyl group or a norbornene group: 2-(12-acryloyloxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexakis (3,4-dialkoxyphenoxy)phthalocyaninato copper(II) [abbreviated as (n,12)PcCu(OCH3)(Acryloyl) (7: e (n = 10), f (n = 12), g (n = 14))] and 2-(12-norborn-2-ene carbonyloxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexakis(3,4-dialkoxyphenoxy)-phthalocyaninato copper(II): [abbreviated as (n, 12)PcCu(OCH3)(Norb) (9e, f, g)]. Their liquid crystalline properties and homeotropic alignment were investigated using a polarizing microscope, a differential scanning calorimetry (DSC), and a temperature-variable X-ray diffractometer. As a result, each of the derivatives gave a Coltet mesophase in the higher temperature region, displaying perfect homeotropic alignment between the two glass plates. In order to obtain the thin film while keeping their homeotropic alignment at room temperature, attempts to polymerize the monomers, 7 and 9, in the Coltet phase showed homeotropic alignment. The polymerization of the acryloyl-substituted monomers (7) was not successful in any of the methods, whereas the polymerization of norbornene-substituted monomers (9) was quite successful by ring-opening metathesis polymerization with a Grubbs catalyst to obtain the novel polymers, poly-(n, 12)PcCu(OCH3)(Norb) (10e, f, g). Each of the polymers (10) were found to show a perfect homeotropic alignment from room temperature to ca. 200°C of the decomposition temperature. Moreover, it was also revealed from temperature-variable small-angle X-ray diffraction studies that each of the polymers 10 showed a helical Coltet (helical tetragonal columnar) structure. The helical Coltet phase structure may be able for use in organic electroluminescent devices and solar cells in the future.
- Suzuki-Ichihara, Ayumi,Sugibayashi-Kajita, Makiko,Ariyoshi, Masahiro,Yasutake, Mikio,Ohta, Kazuchika
-
p. 800 - 817
(2021/05/27)
-
- Recyclable iron(ii) caffeine-derived ionic salt catalyst in the Diels-Alder reaction of cyclopentadiene and α,β-unsaturated: N -acyl-oxazolidinones in dimethyl carbonate
-
Iron(ii) triflate was used in combination with caffeine-derived salts as recyclable catalysts for the Diels-Alder reaction run in dimethyl carbonate (DMC) as a green solvent. The catalyst was prepared as an ionic salt from a xanthinium salt and Fe(OTf)2. Various substrates including α,β-unsaturated carbonyl and N-acyloxazolidinone derivatives were reacted with cyclopentadiene using this recyclable catalyst. The use of a low catalyst loading (1 mol%) afforded high yields (up to 99%) of the corresponding cycloadducts. The recycling and the efficiency of the catalyst were demonstrated for several runs.
- Meng, Di,Li, Dazhi,Ollevier, Thierry
-
p. 21956 - 21963
(2019/07/30)
-
- Synthesis of Bicyclic Isocyanates and Bioisosteric 1,3-Disubstituted Ureas as Soluble Epoxide Hydrolase Inhibitors
-
(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.
- Burmistrov,D’yachenko,Rasskazova,Butov
-
p. 1166 - 1176
(2019/10/19)
-
- Visible Light-Mediated Decarboxylative Alkylation of Pharmaceutically Relevant Heterocycles
-
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.
- Sun, Alexandra C.,McClain, Edward J.,Beatty, Joel W.,Stephenson, Corey R. J.
-
supporting information
p. 3487 - 3490
(2018/06/26)
-
- Dye functionalized-ROMP based terpolymers for the use as a light up-converting material: Via triplet-triplet annihilation
-
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.
- Hollauf,Zach,Borisov,Müller,Beichel,Tscherner,K?stler,Hartmann,Knall,Trimmel
-
p. 7535 - 7545
(2017/08/16)
-
- Biorenewable ROMP-based thermosetting copolymers from functionalized castor oil derivative with various cross-linking agents
-
A new norbornenyl-functionalized castor oil alcohol (NCA) was synthesized and ring-opening metathesis copolymerized separately with two norbornene-based cross-linking agents: dicyclopentadiene (DCPD) and a bifunctional norbornene crosslinker (CL). Isothermal differential scanning calorimetry (DSC) was used to examine the cure behavior of NCA/DCPD and NCA/CL resins, through which a reasonable cure schedule was determined. The glass transition temperature (Tg) and storage modulus (E′), characterized by dynamic mechanical analysis (DMA), increased significantly in both copolymer systems with the addition of cross-linking agents. Cross-link density of the two systems was evaluated using a modified empirical equation from the kinetic theory of rubber elasticity. Differences in tensile stress-strain behavior and thermal stability between polymerized NCA/DCPD and NCA/CL were correlated to the structural rigidity and cross-linking density resulting from the cross-linking agents.
- Ding, Rui,Xia, Ying,Mauldin, Timothy C.,Kessler, Michael R.
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p. 5718 - 5726
(2014/12/11)
-
- Photo-initiated thiol-ene "click" hydrogels from RAFT-synthesized poly(N-isopropylacrylamide)
-
Despite the efficiency and robustness of the widely used copper-catalyzed 1,3-dipolar cycloaddition reaction, the use of copper as a catalyst is often not attractive, particularly for materials intended for biological systems. The use of photo-initiated thiol-ene as an alternative "click" reaction to synthesize "model networks" is investigated here. Poly(N- isopropylacrylamide) precursors were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and were designed to have trithiocarbonate moieties as end groups. This structure design provides opportunity for subsequent end-group modifications in preparation for thiol-ene "click." Two reaction routes have been proposed and studied to yield thiol and ene moieties. The advantages and disadvantages of each reaction path were investigated to propose a simple but efficient route to prepare copper-free "click" hydrogels.
- Ooi, Huey Wen,Jack, Kevin S.,Whittaker, Andrew K.,Peng, Hui
-
p. 4626 - 4636
(2013/10/21)
-
- Characterization of large molecular weight ester-functionalized norbornene and hydroxylated norbornane carboxylic acid polymers prepared by ring-opening metathesis polymerization
-
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.
- Stidham, Sarah E.,Weinberg, Benjamin H.,Grinstaff, Mark W.
-
p. 5185 - 5190
(2013/01/15)
-
- Rheokinetics of ring-opening metathesis polymerization of bio-based castor oil thermoset
-
Ring-opening metathesis polymerization (ROMP) of norbornenyl-functionalized castor oil has been evaluated using small-amplitude oscillatory shear flow experiments as a function of angular frequency, temperature, and curing time. At the onset temperature of the curing process, an abrupt increase in dynamic shear moduli, G and G″, and complex shear viscosity, ν*, was observed during the dynamic temperature ramps (2 °C/min heating rate) of the sample over a wide range of angular frequencies. A dramatic increase in zero-shear viscosity, ν0, was also observed at the gelation temperature, Tgel. The value of Tgel obtained from the abrupt increase in ν0 was found to be in good agreement with the value evaluated from the crossover point of G and G″. The real time curing kinetics was investigated under isothermal conditions over a wide range of angular frequencies at different constant curing temperatures (40, 45, 50, and 55 °C). The isothermal gelation kinetics was found to be strongly curing temperature dependent; i.e., the higher the curing temperature, the faster the gelation process. Both G and G″ showed a power law relationship with angular frequency at the gel point, with critical power law exponents at the gel point in good agreement with the value predicted using percolation theory. Furthermore, ν0 and the equilibrium storage modulus, G eq, were found to be well described by power law scaling functions with the relative distance from the gel point. The molecular dynamics and thermal stability of the fully cured sample were also investigated by dynamic mechanical analysis and thermogravimetry, respectively.
- Madbouly, Samy A.,Xia, Ying,Kessler, Michael R.
-
p. 7729 - 7739,11
(2020/09/15)
-
- Rapid photoassisted access to N,O,S-polyheterocycles with benzoazocine and hydroquinoline cores: Intramolecular cycloadditions of photogenerated azaxylylenes
-
Ring the changes: A new photoassisted approach to give conformationally constrained N,O,S-polyheterocyclic scaffolds of unprecedented topologies was achieved by intramolecular [4+4] and [4+2] cycloadditions of photogenerated o-azaxylylenes (23 examples; see scheme). The precursors can be readily assembled by simple and high-yielding reactions, thus making this a powerful synthetic method amenable to high-throughput diversity-oriented synthesis.
- Mukhina, Olga A.,Bhuvan Kumar,Arisco, Teresa M.,Valiulin, Roman A.,Metzel, Greg A.,Kutateladze, Andrei G.
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supporting information; experimental part
p. 9423 - 9428
(2011/11/06)
-
- Polymerizable compound, lactone-containing compound, method for manufacturing lactone-containing compound and polymer compound obtained by polymerizing the polymerizable compound
-
A polymerizable compound having a lactone structure represented by formula (1) is provided: wherein A represents a polymerizable site; R2 represents a single bond or an alkylene group; R3 represents a hydrocarbon group in which hydrogen atoms are substituted with a fluorine atom; R4 represents a halogen atom, a cyano group, a hydroxyl group, an amide group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenol group, an acyl group, an alkoxycarbonyl group, or a group represented by R-C(=O)- or R-C(=O)O-, wherein R represents an alkyl group or a cycloalkyl group; X represents an alkylene group, an oxygen atom or a sulfur atom; Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or urea bond; n represents an integer of from 0 to 5; and m represents an integer of from 0 to 7.
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Page/Page column 21; 22
(2010/07/03)
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- Variable-color poly(3,4-propylenedioxythiophene) electrochromics from precursor polymers
-
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.
- Invernale, Michael A.,Bokria, Jayesh G.,Ombaba, Matthew,Lee, Ki-Ryong,Mamangun, Donna M.D.,Sotzing, Gregory A.
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scheme or table
p. 378 - 382
(2011/02/24)
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- Shape memory behavior of side-chain liquid crystalline polymer networks triggered by dual transition temperatures
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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.
- Ahn, Suk-Kyun,Deshmukh, Prashant,Kasi, Rajeswari M.
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experimental part
p. 7330 - 7340
(2011/10/30)
-
- Metal-free intramolecular cyclopropanation of alkenes through iodonium ylide methodology
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Intramolecular cyclopropanation of alkenes occurs thermally with iodonium ylides in the absence of conventional metal catalysts such as Rh(II) and Cu(II). In rigid molecular systems conversions are near quantitative. A mechanism is proposed involving formal 2+2 cycloaddition followed by reductive elimination of PhI to yield the cyclopropane. Intramolecular cyclopropanation of alkenes occurs thermally with iodonium ylides in the absence of conventional metal catalysts such as Rh(II) and Cu(II). In rigid molecular systems conversions are near quantitative. A mechanism is proposed involving formal 2+2 cycloaddition followed by reductive elimination of PhI to yield the cyclopropane.
- Moriarty, Robert M.,Tyagi, Sachin,Kinch, Mark
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scheme or table
p. 5801 - 5810
(2010/09/18)
-
- The thermo responsive behavior of glycol functionalized ring opening metathesis polymers
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Herein a further step towards self-assembly of poly-mers exhibiting a lower critical solution temperature (LCST) effect is presented. Ring opening metathesis polymerization has been chosen as polymerization method because of its high functional group tolerance, the reliability and the capability to synthesize different polymer architectures such as self-assem- bling block copolymers, which currently gain much attention in nanotechnology, electronics, and biomedical applications. In a first step, the polymerization behavior of oligofethylene glycol) monoalkyl ether [HO-(CH2CH2-O) n-R, n = 2, 3 and 5-9, R = Et or Me] substituted norbornene derivatives with [(H2lMeS) (py)Cl2Ru(3-phenyl-indenylid-1- ene)] (H2lMeS = N, N-bis(mesi-tyl) 4,5-dihydroimidazol-2-yl, py = pyridine) was assessed. While monomers bearing short oligo(ethylene glycol)mono-alkyl ether groups (n = 2 or 3) allowed for controlled polymer- ization, the monomers featuring long oligofethylene glycol) monoalkyl ether groups could not be polymerized in a controlled manner. Only polymers prepared from endo,exo-bicyclo [2.2.1]hept-5-ene-2,3-dicarboxylic acid, bis[2-[2-(2-ethoxyethoxy)ethoxy]ethyl] ester (2) showed satisfactory water solubility and a LCST of about 25 °C. This temperature is largely independent from the molecular weight and the macromolecular architecture of the polymers as it was revealed from determination of the LCST of a series of statistic and block copolymers incorporating less-polar comonomers. The molecular weight affects the complete transition value (δT), which is rising with increasing degree of polymerization. δT values smaller than 1 °C can be obtained with statistic copolymers of 2 with less polar monomers like endo, exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid dimethyl ester.
- Bauer, Thomas,Slugovc, Christian
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experimental part
p. 2098 - 2108
(2011/03/22)
-
- Castor oil-based thermosets with varied crosslink densities prepared by ring-opening metathesis polymerization (ROMP)
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Two castor oil-based monomers, (1) norbornenyl-functionalized castor oil (NCO), which has ~0.8 norbornene rings per fatty acid chain and (2) norbornenyl-functionalized castor oil alcohol (NCA), which has ~1.8 norbornene rings per fatty acid chain, have been prepared. Ring-opening metathesis polymerization (ROMP) of different ratios of NCO/NCA using the 2nd generation Grubbs catalyst results in rubbery to rigid biorenewable-based plastics with crosslink densities ranging from 318 to 6028mol/m3. Increased crosslink densities result in shorter gelation times, better incorporation of the monomers into the polymer network, and much less soluble materials in the bulk materials. The increased crosslink densities obtained by adding NCA enhance the thermal properties, including the glass transition temperature (Tg) and room temperature storage modulus, which increase from -17.1°C to 65.4°C and from 2.4MPa to 831.9MPa, respectively. The TGA results, where T10 increased from 285°C to 385°C, illustrate that improved thermal stabilities can be obtained for thermosets with higher crosslink densities. Young's modulus (11-407MPa), tensile strength (1.6-18MPa) and toughness (0.14-1.6MPa) are also improved dramatically with higher crosslink densities.
- Xia, Ying,Larock, Richard C.
-
experimental part
p. 2508 - 2514
(2011/11/12)
-
- POTASSIUM CHANNEL MODULATORS
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Disclosed herein are KCNQ potassium channels modulators of formula (I) wherein ring G1, X, R1, and R2 are as defined in the specification. Compositions comprising such compounds; and methods for treating conditions and disorders using such compounds and compositions are also described
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Page/Page column 54
(2010/12/26)
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- Method for Coating the Internal Surface of a Reaction Vessel
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The present invention involves the application of ROMP polymers to the internal surfaces of a device for the purpose of carrying out a solid-phase radiochemical process within the device. An additional embodiment of the invention is an automated synthesis system comprising a number of devices of the invention in order that a series of processes can be carried out in direct sequence. In a preferred embodiment, the present invention is a microfabricated device.
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Page/Page column 8; Sheet 1/11
(2010/11/28)
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- Asymmetric Diels-Alder reaction between acrylates and cyclopentadiene in the presence of chiral catalysts
-
Asymmetric Diels-Alder reaction between cyclopentadiene and alkyl and cycloalkyl acrylates in the presence of new chiral catalysts, BBr 3?MentOEt, AlCl2OMent, BBr2OMent, and BBr(OMent)2, was studied. Optically active bicyclo[2.2.1]hept-2-ene- 5-carboxylates were synthesized. The influence of the reaction conditions on the total and optical yields and on the stereoselectivity of the adducts synthesized was examined. Nauka/Interperiodica 2006.
- Mamedov
-
p. 1621 - 1625
(2008/02/07)
-
- Precursors to fluoroalkanol-containing olefin monomers and associated methods of synthesis and use
-
The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted α,β-unsaturated esters. The fluoroalkanol-substituted α,β-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.
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Page/Page column 13
(2008/06/13)
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- Precursors to fluoroalkanol-containing olefin monomers, and associated methods of synthesis and use
-
The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted αβ-unsaturated esters. The fluoroalkanol-substituted αβ-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.
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Page/Page column 13
(2008/06/13)
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- USE OF EPOXIDES AS FUNGICIDES
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The present invention relates to the use of one or more epoxides as mould preventive agents, the epoxide being an aliphatic epoxide ester or ether or glycidyl ester or ether, and to a method for preventing mould buildup.
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Page/Page column 22-24
(2008/06/13)
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- First examples of intramolecular addition of primary amidyl radicals to olefins
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The first examples of intramolecular addition of primary amidyl radicals to olefins are described. Amidyl radicals were generated from N-(phenylthio)amides in refluxing benzene using a catalytic amount of 2,2′- azobis(isobutyronitrile) (5 mol%) and tributyltin hydride (sim;2.2 equiv.). The resulting yields of cyclic products ranged from 63% to 85%.
- Gaudreault, Philippe,Drouin, Christian,Lessard, Jean
-
p. 543 - 545
(2007/10/03)
-
- Synthesis and hydrolysis behavior of side-chain functionalized norbornenes
-
The stabilities of various functionalized norbornenes that are monomers for the ring-opening metathesis polymerization (ROMP) in aqueous solution were evaluated toward hydrolysis under a range of temperatures (37, 60, and 80 °C) and pH values (3-9). All monomers contain hydrolyzable linkages to pendant functional groups, and conclusions were drawn relating to how the chemical diversity of these pendant functional groups, in accordance with the pH and temperature variations, affect hydrolysis of the aforementioned linkages. The hydrolysis was monitored by reverse phase HPLC analysis, and/or NMR spectroscopy. As expected, monomers containing ester linkages were fairly labile at higher pH values, while acetal-based linkers were cleaved at lower pH values. β-Amino ester groups experienced a significant increase in hydrolysis rate, while carboxylic acid-containing monomers did not follow any clear trend. Saccharide-containing monomers exhibited unique behaviors for various pH values and temperature ranges.
- Carlise, Joseph R.,Kriegel, Robert M.,Rees Jr., William S.,Weck, Marcus
-
p. 5550 - 5560
(2007/10/03)
-
- Preparation and utilization of catalyst-functionalized single-walled carbon nanotubes for ring-opening metathesis polymerization
-
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.
- Liu, Yuanqin,Adronov, Alex
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p. 4755 - 4760
(2007/10/03)
-
- Synthesis and corrosion-protective properties of acetylenic esters of bicyclo[2.2.1]hept-5-ene-2-carboxylic acid
-
A procedure was developed for preparing acetylenic esters of bicyclo[2.2.1]hept-5-ene-2-carboxylic acid. The structures of the compounds were confirmed by IR and 1H NMR spectroscopy. The Kovats indices of the compounds were determined, and their boiling points were estimated by gas-liquid chromatography. The protective properties of the esters against acid corrosion of steel were studied.
- Mamedov
-
p. 1316 - 1320
(2007/10/03)
-
- Organometal-containing norbornene monomer, photoresist containing its polymer, manufacturing method thereof, and method of forming photoresist patterns
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The present invention relates to norbornene monomers with a novel functional group containing an organometal as shown in the following Formula (I) or (II), a photoresist containing its polymers, manufacturing method thereof, and a method of forming photoresist patterns. Unlike existing polymers for photoresist matrix, polymers made by norbornene monomers described in the present invention is a chemical amplification type induced by photosensitive acids and can result in difference in silicon content between the exposed area and unexposed area due to dissociation of side chain containing silicon. The difference in the silicon content results in different etch rate with respect to oxygen plasma which makes dry developing possible.
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-
-
- High silicon content monomers and polymers suitable for 193 nm bilayer resists
-
Polymerizable monomers having silicon containing groups that are transparent at 193 nm; and ethylenically unsaturated group are provided. Polymers from these monomers can be used in processes for forming sub-100 nm images with a chemically amplified, radiation sensitive bilayer resist. The bilayer resist is disposed on a substrate and comprises (i) a top imaging layer comprising a radiation sensitive acid generator and (ii) an organic underlayer. The bilayer resist can be used in the manufacturing of integrated circuits.
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-
-
- Synthesis of novel, cubane-containing norbornene-based polymers
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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.
- Priefer, Ronny,Nguyen, Sophie,Farrell, Patrick G.,Harpp, David N.
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p. 5435 - 5436
(2007/10/03)
-
- Tandem catalysis and self-assembly: A one-pot approach to functionalized polymers
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(equation presented) Side-chain functionalized polymers possessing terminal palladated SCS pincer complexes at each repeat unit were synthesized via ring-opening metathesis polymerization. These palladium centers function as both well-defined Heck catalysts and recognition units capable of quantitative self-assembly of pyridine-containing molecules. Exploitation of both the catalytic and self-assembly properties has led to the development of a controlled, one-pot tandem catalysis/self-assembly sequence for the synthesis of functionalized polymers.
- Pollino, Joel M.,Weck, Marcus
-
p. 753 - 756
(2007/10/03)
-
- Dipyridyl amide-functionalized polymers prepared by ring-opening- metathesis polymerization (ROMP) for the selective extraction of mercury and palladium
-
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.
- Sinner, Frank,Buchmeiser, Michael R.,Tessadri, Richard,Mupa, Mathew,Wurst, Klaus,Bonn, Günther K.
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p. 2790 - 2797
(2007/10/03)
-
- The synthesis of the novel adenosine agonists, exo- and endo-N6-(5,6-epoxynorborn-2-yl)adenosine
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Both racemic exo and endo isomers of N6-(5,6-epoxynorborn-2-yl)adenosine have been synthesised and shown to be potent agonists for the A1 adenosine receptor. Crucial to the preparation of these compounds is the synthesis of exo and endo norbornenylamines which are accessed through an optimised Curtius rearrangement.
- Scammells,Baker,Bellardinelli,Olsson,Russell,Wright
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p. 4735 - 4744
(2007/10/03)
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- Asymmetric induction of cyclopentadiene in the Diels-Alder reaction on acrylic derivatives of arabinose and ribose O-methylene acetals
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The acrylates of methyl β-D-arabinopyranoside and methyl β-D-ribofuranoside protected respectively as 3,4- and 2,3-O-methyleneacetals have been used as chiral templates in the asymmetric Diels-Alder reaction with cyclopentadiene. Sugar moieties are very stable towards Lewis acids and the arabinose derivative is very efficient for asymmetric induction.
- Nouguier,Gras,Giraud,Virgili
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p. 6245 - 6252
(2007/10/02)
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