(η³‐allyl)palladium(II) catalysts for the addition polymerization of norbornene derivatives with functional groups

Abstract

Cycloaliphatic polyolefins with functional groups were prepared by the Pd(II)‐catalyzed addition polymerization of norbornene derivatives. Homo‐ and copolymers containing repeating units based on bicyclo[2.2.1] hept‐5‐en‐2‐ylmethyl decanoate (endo/exo‐ratio = 80/20), bicyclo[2.2.1]hept‐5‐ene‐2‐carboxylic acid methyl ester (exo/endo = 80/20), bicyclo[2.2.1]hept‐5‐ene‐2‐methanol (endo/exo = 80/20), and bicyclo[2.2.1]hept‐5‐ene‐2‐carboxylic acid (100% endo) were prepared in 49–99% yields with {(η3‐allyl)Pd(BF4)} and {(η3‐allyl)Pd(SbF6)} as catalysts. The catalyst containing the hexafluoroantimonate ion was slightly more active than the tetrafluoroborate based Pd‐complex.

Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

“…[2][3][4][5][6][7][8][9][10][11][12][13] Heitz et al 2,3 investigated the addition-type copolymerizations of norbornene with norbornene carboxylic acid esters, and found that the solubility of the copolymers and the thermal properties, such as glasstransition and decomposition temperatures, were dependent on the content as well as structure of the substituents. Risse et al [4][5][6] came to the same conclusion by studying poly-(norbornene)s containing hydroxyl, carboxylic acid and ester. Goodall et al [7][8][9] and Grove et al 10 prepared alkyl-or alkoxysilyl-substituted poly(norbornene)s, which showed improved mechanical toughness and adhesion to common substrate materials.…”

Terpolymerization of Substituted Cycloolefin with Ethylene and Norbornene by Transition Metal Catalyst

“…This behavior may be partially related to the exo, endo isomer composition of C 5 N, C 8 N monomers. In general, the endo 5-alkyl norbornene isomers are known to be less reactive than the exo isomers [38][39][40] because of steric compression, as depicted in Figure 3, where the preferred cis-exo addition of norbornene to the Mt-P bond is shown. In the terpolymerization experiments with DCPD activities intermediate to those with the other termonomers are observed, Catalyst 2 is always more active than 1 under identical conditions (activities of Entries 15 vs. 7 in Table 1).…”

“…The resonances of all of these structural units, reported in Table 3, were attributed on the basis of a comparison with those reported in the literature [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43]. Scheme 1 describes the possible paths leading to terpolymer chain unsaturation with a last-inserted E, N, O or Nx (C5N or C8N) unit.…”

Structural analysis of thin films of novel polynorbornene derivatives by grazing incidence X-ray scattering and specular X-ray reflectivity along with ellipsometry

“…A representative cyclic olefin polymer is polynorbornene (Angiolini et al, 2003;Bhusari et al, 2001;Breunig & Risse, 1992;Byun et al, 2006;Grove et al, 1999;Heinz et al, 1998;Lipian et al, 2002;Mathew et al, 1996;Reinmuth et al, 1996;Shick et al, 1998). However, this polymer exhibits very low solubility in common organic solvents and poor processibility, as well as interfacial adhesion failure, making it unsuitable for use in applications such as flexible flat panel displays and microelectric and microfluidic devices.…”

“…However, this polymer exhibits very low solubility in common organic solvents and poor processibility, as well as interfacial adhesion failure, making it unsuitable for use in applications such as flexible flat panel displays and microelectric and microfluidic devices. Therefore, much research effort has been devoted to modifying this polymer via chemical functionalization and copolymerization so as to improve its solubility, processibility and interfacial adhesion properties (Breunig & Risse, 1992;Byun et al, 2006;Grove et al, 1999;Heinz et al, 1998;Reinmuth et al, 1996;Shin et al, 2004). As part of these efforts, a series of poly(norbornene carboxylic acid ester)s with high solubility were developed, and their mechanical, optical and electrical properties were investigated (Breunig & Risse, 1992;Mathew et al, 1996;Reinmuth et al, 1996;Heinz et al, 1998;Grove et al, 1999).…”