Ring opening metathesis copolymerization of norbornene with norbornadiene from solutions with different mole fractions of the comonomers catalyzed by Ru‐amine complexes

Abstract

Copolymers from norbornene (NBE) with norbornadiene (NBD) were synthesized via ring opening metathesis copolymerization varying the mole fractions of the comonomers (0.8 : 0.2; 0.6 : 0.4; 0.4 : 0.6; 0.2 : 0.8) for a total monomer quantity of 5000 equivalents/[Ru]. The batch reactions were performed with [RuCl2(PPh3)2(amine)] complex types as precatalysts, where amine is perhydroazepine (1) or piperidine (2), in CHCl3 (2 mL) in the presence of ethyl diazoacetate (5 μL) for different intervals of times (5, 30, 60, and 120 min) at 40°C. The copolymers were characterized by 13C NMR. Quantitative yields of isolated materials were obtained from solutions with NBD : NBE 0.8 : 0.2 mole fraction in the presence of 1, decreasing to 70% for NBD : NBE 0.2 : 0.8 solutions. Concerning 2, the yields were 70% at most. Polymeric materials obtained with 1 were less soluble in CHCl3 than those synthesized with 2. The dependence of the reaction yields and occurrence of crosslinking on the starting NBE : NBD proportion related to reactivity of the complexes 1 and 2 were discussed. A few differences in the amines such as ancillary ligands were sufficient to change the reactivity of the {RuCl2(PPh3)} moiety complex to provide copolymers with different compositions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Ethyl Linoleate Derivatives from Olefin Metathesis as a Function of the Starting Complex and Reactivity Conditions

“…In addition, studies with LN introduce this compound as an active pre-catalyst in this type of metathesis, considering that our research group has already reported the mathatetical activity of LN for ROMP reactions [13,14].The steric hindrance and electronic proprieties of LN allowed reactivity in the presence of SnCl2, promoting the olefin metathesis of EL.…”

“…The yields or selectivity are achieved by tuning the choice of the catalyst with the reaction conditions [12]. In this way, the application of catalytic precursors, such as the Lima-Neto Ru-compounds synthesized for ROMP reactions [13][14][15][16], can be modulated for other purposes inside of the metathesis type.…”

“…A possible interaction can occur with the phosphine phenyl rings, increasing the electronic π-acceptor nature of the phosphine, then increasing the oxidation potential of the Ru(II) species. The metathesis reaction occurs when phosphines are displaced from the metal coordination sphere to permit the coordination of olefin [13,14]. Thus the presence of SnCl2 interaction provides a more effective phosphine displacement to the occurrence of the metathesis reaction.…”

Self‐Metathesis of 10‐Undecen‐1‐Ol with Ru‐Amine‐Based Complex for Preparing the Soft Segment and Chain Extender of Novel Castor Oil‐Based Polyurethanes

“…In this paper, a diol from self‐metathesis of 10‐undecen‐1‐ol was synthesized to act as chain extender and soft segment in polyurethane synthesis. The self‐metathesis reactions were conducted with [RuCl 2 (PPh 3 ) 2 (perhydroazepine)] complex as an alternative to Grubbs’ catalyst . Commercially available Grubbs‐type catalysts are the most used initiators for olefin metathesis reactions in both academia and industry.…”

Desenvolvimento de sulfóxido complexos de Ru(II) para aplicação em polimerização via metátese de olefinas cíclicas por abertura do anel

“…Como já discutido na literatura, [68][69][70] NBD pode ser ligado por uma das duplas ligações (mono-coordenado) ou pelas duas duplas ligações (duplo-coordenado) num modo quelante, como ilustrado na Figura 24. Em sistemas onde o catalisador é gerado in situ, a quelação compete na reação do metal com a espécie carbeno e interfere na formação da espécie metal- carbeno.…”