Copolymerization of 5,6-Dihydrodicyclopentadiene and Ethylene

Abstract

Supporting InformationGeneral Remarks. All manipulations were performed under an inert atmosphere using standard glove box and Schlenk techniques. 5,6-Dihydrodicyclopentadiene (HDCPD) was purchased from TCI. Toluene (anhydrous grade, Aldrich), norbornene and HDCPD were distilled over Na/K alloy. Ethylene was purchased from Conley gas (99.0%) and purified by contacting with molecular sieves and copper for several days under the pressure of 200 psig. The 1 H NMR (600 MHz) and 13 C NMR (150 MHz) spectra of the copolymers were recorded on a Bruker Avance 600 at 25 o C. Gel permeation chromatograms (GPC) were obtained at 30 o C in THF using Waters Model 150-C+ GPC and the data were analyzed using a polystyrene analyzing curve. Differential scanning calorimetry (DSC) was performed on a Thermal Analysis Q10. Glass transition Temperatures (T g ) were determined with DSC on a second heating at a heating rate of 15 o C/min. Ethylene/HDCPD copolymerization. In a glove box, 28 mL of toluene solution of HDCPD (5.37 g, 40 mmol) was added to a dried 60 mL glass reactor with a magnetic bar. The reactor was assembled and brought out from the glove box. The reactor was then heated to 70 o C with a mantle. After an activated

Preparation of novel cyclic olefin copolymer with high glass transition temperature

“…However, even alternating ethylene/DCPD copolymer ( 2 in Scheme ) does not exhibit high T g (DCPD mol % = 45%, T g = 125 °C) . Lee et al introduced 5,6‐dihydrodicyclopentadiene (HDCPD), which is obtained through regioselective hydrogenation of DPCD, to prepare the COC ( 3 in Scheme ) using o ‐phenylene‐bridged analogues of CGC . Whereas, the highest T g value attained in this study is only 114 °C with 44 mol % HDCPD content, which is lower than those of ethylene/NB and ethylene/DCPD copolymers at the same content of cyclic olefin.…”

Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization

“…Based on performance characteristics, the applications of COCs and COPs have now been extended to production of optical parts for digital cameras and laser beam printers, medical products, and electrical insulation [1,4]. As shown in Scheme 1, COCs are obtained through copolymerization of cycloolefin with ethylene or α-olefin [5][6][7][8][9][10][11][12][13][14], and commercialized under the trade names APEL ® by Mitsui and TOPAS ® by TOPAS advanced polymers (TAP: formerly Ticona and Hoechst) [15,16]. COPs are prepared via ring-opening metathesis polymerization (ROMP) of cycloolefin followed by hydrogenation [17][18][19][20][21][22][23][24], and commercialized under the trade names Zeonex ® and Zeonor ® by Zeon [25] and Arton ® by Japan Synthetic Rubber (JSR) [20,21].…”

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Abstract: Novel ester group functionalized cyclic olefin polymers (COPs) with high glass transition temperature, high transparency, good mechanical performance and excellent film forming ability have been achieved in this work via efficient ring-opening metathesis copolymerization of exo 4,4a,9,9a,10(1′, and comonomers (5-norbornene-2-yl methylacetate (NMA), 5-norbornene-2-yl methyl 2-ethylhexanoate (NME) or 5-norbornene-2-yl methyldodecanoate (NMD)) utilizing the Grubbs first generation catalyst, Ru(CHPh)(Cl)2(PCy3)2 (Cy = cyclohexyl, G1), followed by hydrogenation of double bonds in the main chain. The fully hydrogenated copolymers were characterized by nuclear magnetic resonance, FT-IR spectroscopy analysis, gel permeation chromatography, and thermo gravimetric analysis.

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Synthesis and structures of adamantyl-substituted constrained geometry cyclopentadienyl–phenoxytitanium complexes and their catalytic properties for olefin polymerization

“…On the basis of the above 1 H NMR results, it should be reasonable to suppose that the similar C s -symmetry catalyst 9 may produce racemo-ENBeENB sequence enriched PENB with more RR triads (4.9e5.4 ppm) in the polymer chain, while the less bulky catalyst 11, and especially the flexible nonbridged catalyst 12 may produce PENB with more meso-ENBeENB sequence and thus more RM and MM triads (5.5e5.8 ppm) in the polymer chain. 13 C NMR spectra of the PENB samples give little information on the microstructure of the polymer chain.…”

“…1 H and 13 C NMR spectra were measured on either a Bruker Avance-500 or a Varian Mercury-300 NMR spectrometer. 13 C NMR spectra of the copolymers were recorded on a Varian Unity-400 NMR spectrometer at 125 C with o-C 6 D 4 Cl 2 as the solvent. The intrinsic viscosity of the PENB samples was measured in decahydronaphthalene at 135 C with an Ubbelohde viscometer.…”