Abstract
Statistical copolymers of norbornene (NBE) with cyclopentene (CP) were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs’ catalyst, in the presence or absence of triphenylphosphine, PPh3. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined.
Highlights
Ring Opening Metathesis Polymerization (ROMP), a relatively new tool in the field of polymer chemistry, has emerged as a powerful and broadly-applicable method for synthesizing macromolecular materials
We report the synthesis of statistical copolymers of norbornene, NBE, and cyclopentene, CP, via ROMP catalyzed by Grubbs’ catalyst
Different copolymers are symbolized by the various feed molar ratios of the monomers; for example, sample 20/80 indicates the copolymer for the synthesis where 20% NBE and 80% CP were employed as the molar feed composition
Summary
Ring Opening Metathesis Polymerization (ROMP), a relatively new tool in the field of polymer chemistry, has emerged as a powerful and broadly-applicable method for synthesizing macromolecular materials. Catalyst development for “living” ROMP has focused on ruthenium-based initiators, which are more selective for olefins, and are more tolerant to functionalities in the reaction system, expanding the range of monomers which can be employed [29]. It was found that the ratio of the initiation over the propagation rate constants, ki/kp, is equal to 10.2 when the polymerization takes place in the presence of excess PPh3 (5 fold molar excess over the catalyst), whereas ki/kp equals 0.73 in the absence of excess PPh3. We report the synthesis of statistical copolymers of norbornene, NBE, and cyclopentene, CP, via ROMP catalyzed by Grubbs’ catalyst This copolymerization reaction has been studied in the past employing various catalytic species [34,35,36,37,38,39,40]. The kinetics of thermal decomposition of the copolymers was investigated and compared with the respective homopolymers
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