A Tailor‐Made Metallocene for the Copolymerization of Ethene with Bulky Cycloalkenes

Abstract

Sly1 en01 etlici (4.5 nirnol) was dissolved in henzene (8 mL) in a quartz tuhe. The irted (300 nm: light source: Rayonet R P R 3000) and a solution of [I iiig. 1.5 mmol. 152 ILL) in henzene ( 2 mL) was slo\rly added to the rc:iction mixtiirc hy ii syringe (within cii. 2 h). As soon as the aldehyde was fully con'iiiined (TLCJ llie irsxli~ition was slopped and the solvent ecaporated i n v~icuo. The dinstcrconicric tiitlo was detemiincd hy GLC' m d ' H N M R iinnlyses. Escccs s l y 1 e n d ethcr and the desired oxetanc were obtained by coluinn chromatography (ilasli c1iroinatogr;ipliy: eluent. cyc1ohexane;ethyl acetate as ii gradient 200:l + 95, 5 ) . boi-oset;ine\ m -2d.riic~3d and ru(.-2f;ru~3f ii complcte separation of diii-\tcrcoi~umci-\ uiis posiblc. In the other eximples only ;in enrichment of the major diwtercoiwmera could he ~h i e v e d .

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

“…[9,31]. In contrast to many reports of the ethylene/NBE copolymerization , there have been reports for the copolymerization using metallocene catalysts (Scheme 3) [3,[32][33][34][35] and others [36], however, these catalysts generally exhibited low catalytic activities and/or less efficient TCD incorporation [35]. and others [36], however, these catalysts generally exhibited low catalytic activities and/or less efficient TCD incorporation [35].…”

“…160 °C, corresponding to ethylene/TCD copolymer containing moderate TCD Scheme 3. Reported metallocene catalysts for copolymerization of ethylene with tetracyclododecene (TCD) [3,[32][33][34][35].…”

“…[31]. There have been reports on the copolymerizations using metallocene catalysts [3,[32][33][34][35] and others [36], however, these catalysts have generally exhibited low catalytic activities and/or less efficient TCD incorporation. For examples, activities (TCD content) by [Et(Ind)2]ZrCl2 [32], [Ph2C(Ind)(Cp)]ZrCl2 [33], [Ph2C(Cp)(Flu)]ZrCl2 [33], [Me2C(3-MeC5H3)(Flu)]ZrCl2 [3], [Me2C(3-t BuC5H3)(Flu)]ZrCl2 [3] were 25 kg-polymer/mol-Zr•h (35 mol %), 31 (85 mol % at 90 °C), 24 (68), 1.3 (40), 0.4 (44), and respectively.…”

“…There have been reports on the copolymerizations using metallocene catalysts [3,[32][33][34][35] and others [36], however, these catalysts have generally exhibited low catalytic activities and/or less efficient TCD incorporation. For examples, activities (TCD content) by [Et(Ind)2]ZrCl2 [32], [Ph2C(Ind)(Cp)]ZrCl2 [33], [Ph2C(Cp)(Flu)]ZrCl2 [33], [Me2C(3-MeC5H3)(Flu)]ZrCl2 [3], [Me2C(3-t BuC5H3)(Flu)]ZrCl2 [3] were 25 kg-polymer/mol-Zr•h (35 mol %), 31 (85 mol % at 90 °C), 24 (68), 1.3 (40), 0.4 (44), and respectively. Design of molecular catalysts for synthesis of new polymers with specified functions is one of the most attractive targets in the field of catalysis, polymer chemistry, and organometallic chemistry [37][38][39][40][41][42][43][44][45][46][47][48].…”

Synthesis of hydrocarbon polymers containing bulky dibenzobicyclic moiety by ROMP and their characteristic optical properties

“…[1][2][3][4] Copolymerization of bulky cyclic olefins with a simple olefin is a promising method to give the corresponding polymer material, so-called cyclic olefin copolymer (COC), with a great advantage of low-cost starting olefinic monomers. [1][2][3] Conversely, ring-opening metathesis polymerization (ROMP) [5][6][7] can be another sophisticated manner by applying olefinic ring monomers bearing bulky substituents. 8 ROMP has actually been utilized in industrial chemistry for a long time to provide a huge variety of engineering plastics with high thermal stability and good optical properties.…”