826-62-0Relevant articles and documents
STEREOREGULAR FLUOROPOLYMERS: 6. THE RING-OPENING POLYMERIZATION OF N-PENTAFLUOROPHENYLBICYCLOHEPT-5-ENE-2,3-DICARBOXIMIDE
Blackmore, P. M.,Feast, W. J.
, p. 331 - 348 (1988)
Exo-N-pentafluorophenylbicyclohept-5-ene-2,3-dicarboximide (I) readily undergoes metathesis ring-opening polymerization when exposed to conventional metathesis catalysts such as WCl6/Me4Sn and MoCl5/Me4Sn; by contrast, its endo isomer (II) is not homopolymerized but can be copolymerized with (I).The microstructures of the resulting polymers are established and discussed.
Synthesis and ionic transport of sulfonated ring-opened polynorbornene based copolymers
Santiago, Arlette A.,Vargas, Joel,Cruz-Gomez, Javier,Tlenkopatchev, Mikhail A.,Gavino, Ruben,Lopez-Gonzalez, Mar,Riande, Evaristo
, p. 4208 - 4220,13 (2011)
The N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide (1a) and N-phenyl-exo-endo-norbornene- 5,6-dicarboximide (1b)monomers were synthesized and copolymerized via ring opening metathesis polymerization (ROMP) using bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride (I) and tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2- ylidene][benzylidene] rutheniumdichloride (II). Experiments, at distinct monomer molar ratios, were carried out using catalyst I in order to determine the copolymerization reactivity constants by applying theMayo-Lewis and Fineman- Ross methods. Moreover, both catalysts were used to produce random and block high molecular weight copolymers of 1a with 1b and 1a with norbornene (NB) which were further hydrogenated using a Wilkinson's catalyst. Then, the saturated copolymers underwent a nucleophilic aromatic substitution by reacting with sodium 4-hydroxybenzenesulfonate dihydrate to generate new polynorbornene ionomers bearing fluorinated pendant benzenesulfonate groups. A thorough study on the electrochemical characteristics involving electromotive forces of concentration cells and proton conductivity of cation-exchange membranes based on a block copolymer of norbornene dicarboximides containing structural units with phenyl and fluorinated pendant benzenesulfonate moieties is reported. The study of electromotive forces (emf) of concentration cells with the sulfonated membrane of copolymer 8 separating electrolyte solutions of different concentration indicate that the membranes exhibit high permselectivity to protons and sodium ions at moderately low concentrations. In principle, these results suggest that the membranes can be considered candidates for ionic separation applications.
Lewis acid catalyst system for Diels–Alder reaction
Kalepu, Rishir,Mishra, Satyendra
, (2020/03/06)
Abstract: Ca(OTf)2/Bu4NPF6 catalytic system has been illustrated for the synthesis of Diels–Alder adduct for the first time. This procedure tolerates substrate diversity and delivers high yield. Use of environmentally benign catalyst, high yields and substrate diversity are the highlight of the existing method. Graphic Abstract: Ca(OTf)2, along with n-Bu4NPF6 as the co-catalyst, is shown to be an effective Lewis acidic catalyst system for the Diels–Alder reaction. Apart from being sustainable and efficient, this procedure is robust and products are obtained in near-quantitative yields.[Figure not available: see fulltext.].
Synthetic method of aliphatic pentacyclic dianhydride
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Page/Page column 6-11, (2020/03/12)
The invention discloses a synthetic method of aliphatic pentacyclic dianhydride, and particularly relates to a synthetic method of pentacyclic [8.2. 1.14, 702, 903, 8] tetradecane-5, 6, 11, 12-tetracarboxylic dianhydride. The invention belongs to the field of preparation methods of fine chemicals. Maleic anhydride and cyclopentadiene are used as initial raw materials, an intermediate product norbornene dianhydride is synthesized through a 1, 4-addition reaction at a low temperature, then a solvent and a photocatalyst are added, the reaction process is monitored through HPLC under the illumination condition of a single-wavelength light source, and after the reaction is finished, a white solid is obtained through aftertreatment. The method disclosed by the invention is simple to operate, high in synthesis yield and few in byproducts.
ROMP polymer supported manganese porphyrins: Influence of C[dbnd]C bonds along polymer chains on catalytic behavior in oxidation of low concentration Fe2+
Li, Fanfan,Wang, Xuan,Zhang, Yanwu,Zhao, Huanhuan
, (2020/02/22)
One unsaturated polymer support was prepared through ring opening metathesis polymerization (ROMP) of norbornene-2,3-dip-toluene sulfonate initiated by Grubbs 2nd initiator and manganese porphyrins were immobilized on polymer through transesterification reaction. To investigate the effect of C[dbnd]C bonds along polymer chains on the catalytic behavior, the obtained polymer supported catalyst (P-PPIXMnCl) was applied in oxidation of low concentration Fe2+ to mimic catalytic behavior of Ceruloplasmin. In the presence of P-PPIXMnCl, the conversion of Fe2+ reaches to 91.92% and 96.46% at 10 °C and 37.5 °C (body temperature), respectively. Compared to manganese porphyrins, P-PPIXMnCl can dramatically increase oxidation rate of Fe2+ and the catalytic kinetic shows that the oxidation reaction changes from second-order to third-order. Upon hydrogenation of ROMP polymer, the oxidation reaction still conforms to the second-order kinetics. Density functional theory (DFT) calculation shows that the C[dbnd]C bonds along polymer chains play an important role in the coordination with Fe2+ in the catalytic microenvironment. The real time morphology of supported catalysts in aqueous environment characterized by Cryo-TEM indicates that hydrogenation can shrink the morphology of polymer-water skeleton. The catalyst could be recycled six times without any significant loss in activity. The liner heterogeneous catalyst is expected to be used as drugs for treating excessive iron accumulation in the human body.
A 1, 2, 3, 4 - cyclopentane tetracarboxylic dianhydride of the preparation method (by machine translation)
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Paragraph 0005; 0020-0021; 0025-0026; 0030-0031; 0035-0036, (2019/05/04)
The invention discloses a 1, 2, 3, 4 - cyclopentane tetracarboxylic dianhydride of the preparation method, the invention belongs to the field of fine chemicals preparation method. The main technical proposal is to maleic anhydride and the cyclopentadiene as the starting material, the low temperature by 1, 4 - addition reaction intermediate of synthesis of 5 - norbornene - 2, 3 - dicarboxylic acid anhydride; through the ozone oxidation, hydrolysis, hydrogen peroxide oxidation reaction to obtain the cyclopentane tetracarboxylic acid; finally to acetic anhydride as the dehydrating agent, the dehydration ring-closure of the synthesized target product 1, 2, 3, 4 - cyclopentane tetracarboxylic dianhydride. The proposal to the traditional process, mild reaction conditions, the product has high purity, high yield, pollution-free and the like, and is suitable for large-scale industrial production. (by machine translation)
A Crystalline Ready-to-Use Form of Cyclopentadiene
Krupp, Felix,He, Shiliang,Frey, Wolfgang,Richert, Clemens
supporting information, p. 1707 - 1710 (2018/07/03)
Cyclopentadiene (Cpd) is widely used as a starting material in organic and inorganic chemistry. In neat form, Cpd dimerizes, making it necessary to distill it prior to use to obtain fully reactive material. We have screened three different tetraphenyladamantane octaethers for their ability to act as encapsulating organic crystal (EnOC) hosts for Cpd. To this end, we also synthesized 1,3,5,7-tetrakis(3,5-dimethoxyphenyl)adamantane, a new octaether, dubbed iso -TDA. Only one of the octaethers was found to produce inclusion complexes with Cpd in the crystalline state. The encapsulated diene was stable for one month and showed full reactivity in a series of different synthetic transformations.
Cyclopentadienyl binuclear chair-shaped cobalt-nitrogen complex as well as preparation method and application thereof
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Paragraph 0038; 0039; 0040, (2017/07/21)
The invention discloses a cyclopentadienyl binuclear chair-shaped cobalt-nitrogen complex as well as a preparation method and an application thereof. The complex utilizes bicyclo[2.2.1]-2-heptene-5,6-dicarboxylic acid as a main ligand, utilizes 1,10-phenanthroline as an auxiliary ligand and has a special cyclopentadienyl binuclear chair-shaped structure. The preparation method of the complex comprises steps as follows: the complex is synthesized from bicyclo[2.2.1]-2-heptene-5,6-dicarboxylic acid, cobalt salt and 1,10-phenanthroline as raw materials through one step, and [Co2[C7H8(COO)2]2(C12H8N2)2].5H2O crystals are obtained through self-volatilized crystallization. The preparation method is simple to operate, reaction conditions are mild, yield is high, product crystal phase is uniform, purity is high, and besides, the cobalt-nitrogen complex is stable in structure, shows better catalytic activity when applied to an esterification reaction as a catalyst, and is particularly suitable for catalyzing a reaction for synthesizing polyester from dibasic acid and dihydric alcohol.
An analysis of the structural, thermal and optical characteristics as well as the electrical resistivity of tert-butyldiphenylsilyl substituted poly(norbornene-dicarboximide)s
Spring, Andrew M.,Maeda, Daisuke,Ozawa, Masaaki,Odoi, Keisuke,Qiu, Feng,Yamamoto, Kazuhiro,Yokoyama, Shiyoshi
, p. 189 - 198 (2015/03/03)
A sequence of well controlled tert -butyldiphenylsilyl substituted poly(norbornene-dicarboximide)s with ascending molecular weights have been prepared using the Grubbs 1st generation catalyst in anhydrous chloroform. The kinetics of the polymerization was examined using nuclear magnetic resonance spectroscopy and gel permeation chromatography. By decreasing the Grubbs catalyst concentration, the polymer molecular weights increased linearly. The glass transition temperatures and thermal decomposition temperatures initially increased with polymer molecular weight, then reached a plateau. Regardless of molecular weight the polydispersities remained narrow. The polymers exhibited a predominantly trans microstructure and matrix-assisted laser desorption/ionization mass spectrometry was utilized to determine polymer end groups and to calculate the absolute molecular weights. The residual ruthenium content of the polymers was quantified using inductively coupled plasma mass spectrometry and the influence on the resistivity, refractive indices and thin film optical transmittance was evaluated.
Functional norbornanyl ester derivatives, polymers and process for preparing same
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Paragraph 0225, (2013/12/04)
This invention relates to the new functional norbornanyl ester derivative and/or polymer compositions which are easily obtainable by reacting the Diels-Alder adduct of appropriate dienes and dienophiles with carboxylic acids. In particular, this invention relates to a new process for making cyclic chemical raw materials suitable for production coating, ink, adhesive, plasticizer, thermoplastic or thermosetting plastic and functional polymers.
