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Ring opening metathesis copolymerization of norbornene with norbornadiene from solutions with different mole fractions of the comonomers catalyzed by Ru‐amine complexes
Author(s) -
Silva Sá José L.,
Nascimento Eduardo S. P.,
Fonseca Larissa R.,
LimaNeto Benedito S.
Publication year - 2012
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.37741
Subject(s) - copolymer , norbornene , polymer chemistry , amine gas treating , norbornadiene , reactivity (psychology) , moiety , mole fraction , monomer , metathesis , piperidine , chemistry , catalysis , addition polymer , medicinal chemistry , organic chemistry , polymerization , polymer , medicine , alternative medicine , pathology
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 [RuCl 2 (PPh 3 ) 2 (amine)] complex types as precatalysts, where amine is perhydroazepine ( 1 ) or piperidine ( 2 ), in CHCl 3 (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 13 C 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 CHCl 3 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 {RuCl 2 (PPh 3 )} moiety complex to provide copolymers with different compositions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013