Ni(II) and Pd(II) complexes bearing benzocyclohexane–ketoarylimine for copolymerization of norbornene with 5‐norbornene‐2‐carboxylic ester

Abstract

A serial of late transition metal complexes, which bearing Benzocyclohexane-ketoarylimine ligand and named as Mt(benzocyclohexane-ketoarylimino) 2 {Mt(bchkai) 2 : Mt¼Ni or Pd; bchkai¼C 10 H 8 (O)CN(Ar)CH 3 ; Ar¼naphthyl or fluoryl}, have been synthesized and characterized. The molecular structures of the ligands and nickel complex have been confirmed by Xray single-crystal analyses. The nickel complexes exhibited very high activity up to 2.7 Â 10 5 g polymer /mol Ni Áh and palladium complexes showed high activity up to 2.3 Â 10 5 g polymer / mol Pd Áh for norbornene (NB) homo-polymerization with tris (pentafluorophenyl)borane as cocatalyst. The four complexes were effective for copolymerization of NB and 5-norbornene-2carboxylic acid methyl ester (NB-COOCH 3 ) in relatively high activities (0.1-2.4 Â 10 5 g polymer /mol Mt Áh) and produced the addition-type copolymers with relatively high molecular weights (0.5 Â 10 5 -1.2 Â 10 5 g/mol) as well as narrow molecular weight distributions (PDI < 2 for all polymers). Influences of the metals and comonomer feed content on the polymerization activity as well as on the incorporation rates (20.9-42.6%) were investigated. The achieved NB/NB-COOCH 3 copolymers were confirmed to be noncrystalline, exhibited good thermal stability (T d > 400 C) and showed good solubility in common organic solvents. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: [4695][4696][4697][4698][4699][4700][4701][4702][4703][4704] 2012

Switchable Polymerization of Norbornene Derivatives by a Ferrocene‐Palladium(II) Heteroscorpionate Complex

“…Vinyl polynorbornenes are important materials for optical applications due to their excellent thermal stability, high glass transition temperatures, small birefringence, and dielectric loss However, polynorbornenes are brittle, even at high molecular weights, display poor adhesion to common substrates, poor solubility in common organic solvents, and cannot be melt processed due to decomposition . Modifying the norbornene monomers with functional groups increases the solubility of the resulting polymers and improves their processability .…”

“…The substitution of norbornenes, typically at the 5‐position, can be achieved via a Diels–Alder reaction, in some cases, directly from dicyclopentadiene and a dienophile . Polymers obtained from the substituted monomers show improved adhesive and mechanical properties while retaining similar optical properties as the unsubstituted polynorbornenes , , …”

Vinylic copolymerization of norbornene and higher 1-alkene with three-dimensional geometry binickel catalyst

“…On the basis of our published polymerization procedure [38], in this work, the copolymerization of NB with 1-hexene or 1-decene was examined with the catalyst system threedimensional geometry binickel complex/B(C 6 F 5 ) 3 . The copolymerization procedure was shown in Scheme 1.…”

“…The (T d )s of poly (NB-co-1-hexene)s were lower than that of poly (NB-co-1-decene)s. The films of poly(NB-co-1-hexene)s and poly(NB-co-1-decene)s with high content of NB comonomer were mechanical brittleness, which lead to the difficulty for measuring the glass transition temperature (T g ) by DMA. Meanwhile, the (T g )s of poly(NB-co-1-alkene)s with the conventional planar catalyst systems were measured by DSC [38]. Therefore, for better comparison, the (T g )s of poly(NB-co-1-alkene)s with the three-dimensional geometry binickel catalyst were also measured by DSC.…”

Norbornene/n-Butyl methacrylate copolymerization over α-Diimine nickel and palladium catalysts supported on multiwalled carbon nanotubes

“…Therefore, it is very necessary to develop new heterogeneous catalytic systems for the preparation of polynorbornene. At present, much of the work is focused on the researching and development of homogeneous catalysts, the research of heterogeneous catalysts are still rare. Actually, the advantages of heterogeneous catalysts cannot be neglected, such as, mild reaction, highly activation and the controlling of the polymer morphology and properties.…”