Coordination‐Insertion Copolymerization of Norbornene and p‐Substituted Styrenes Using Anilinonaphthoquinone‐Ligated Nickel Complexes

Abstract

Coordination‐insertion copolymerization of norbornene (N) and p‐substituted styrene (XS) (X = MeO, Me F, Cl, and Br) is carried out using anilinonaphthoquinone‐ligated nickel complexes [Ni(C10H5O2NAr)(Ph)(PPh3): 1a, Ar = C6H3‐2,6‐iPr; 1b, Ar = C6H2‐2,4,6‐Me; 1c, Ar = C6H5] with modified methylaluminoxane (MMAO) as a cocatalyst. The ligand of the nickel complex affects the catalytic activity. The effect of the p‐substituent on the activity is remarkable and the activity decreases in the following order, Br > Cl > F > Me > MeO. The molecular weight of the produced polymer also decreases with the same order. The activity increases with raising the temperature from 0 to 70 °C accompanied by the decrease in the molecular weight of the produced polymers. The incorporation of XS determined by 1H and 13C NMR decreases in the following order, MeO ≥ Me > F > Cl > Br. The glass transition temperatures of the N/XS copolymers determined by differential scanning calorimetry show a broad range from 120 to 365 °C according to the XS content.

Polymerization of Styrene Derivatives Using Anilinonaphthoquinone‐Ligated Nickel Complexes and Thermal/Rheological Properties of the Produced Polymers

“…As mentioned above, the nickel complexes [Ni(C 10 H 5 O 2 NAr)(Ph)(PPh 3 ): Ar = C 6 H 3 ‐2,6‐ i Pr (1a); Ar = C 6 H 2 ‐2,4,6‐Me (1b); Ar = C 6 H 5 (1c)] activated by MMAO in toluene exhibited high activities with high incorporation of StX for the copolymerization of norbornene with St and St derivatives. [ 28–30 ] We therefore conducted St polymerization with the same catalytic systems at various temperatures from 0 to 70 °C ( Table 1 ).…”

“…The signals attributed to the aromatic protons of the PStX units are observed in the range of 6.5–7.2 ppm. [ 28–30,32–36 ] Strong methyl peaks of PStOMe and PStMe are observed at 3.7 and 2.3 ppm, respectively. [ 29,32,35,36 ]…”

“…Recently we have reported copolymerization of norbornene with St and St derivatives (StX; X = OMe, Me, F, Cl, Br, or CH═CH 2 at 4‐position) using nickel complexes [Ni(C 10 H 5 O 2 NAr)(Ph)(PPh 3 ): 1a, Ar = C 6 H 3 ‐2,6‐ i Pr; 1b, Ar = C 6 H 2 ‐2,4,6‐Me; 1c, Ar = C 6 H 5 ], in the presence of modified MAO (MMAO). [ 28–30 ] The catalytic systems showed high activity with high incorporation of St and StX. Herein, we apply the catalytic systems for homopolymerization of StX (X = H, OMe, Me, or Cl) and studied the properties of the produced polymers.…”

Synthesis of norbornene/divinylbenzene copolymers catalyzed by anilinonaphthoquinone‐ligated nickel complexes and their applications for the synthesis of graft polymers

“…[14] The introduction of functional groups in NB-based copolymers or PNBs can improve various properties, such as their toughness, solubility, and surface properties. [15,16] ] The copolymerization of NB with a functionalized monomer is desirable, as it allows the controlled introduction of functional groups by a simple process. [17] The insertion of a vinyl functionality into polyolefin copolymers is attractive, since the C C bonds in the resulting copolymer provide reaction sites for vulcanization, graft polymerization, and the synthesis of functionalized polyolefins.…”

“…The introduction of functional groups in NB‐based copolymers or PNBs can improve various properties, such as their toughness, solubility, and surface properties. [ 15,16 ] The copolymerization of NB with a functionalized monomer is desirable, as it allows the controlled introduction of functional groups by a simple process. [ 17 ]…”