Synthesis of ethylene–norbornene–1-octene terpolymers with high 1-octene contents, molar masses, and tunable T_g values, in high yields using half-titanocene catalysts

Abstract

Terpolymerizations of ethylene (E) and norbornene (N) with 1-octene (O) using different aryloxo- or ketimide-modified half-titanocene catalysts, Cp’TiCl2(O-2,6-iPr2C6H3) [Cp’ = indenyl (1), C5Me5 (Cp*, 2), tBuC5H4 (3)] and Cp’TiCl2(N=CtBu2) [Cp’...

Progress in the catalyst for ethylene/α‐olefin copolymerization at high temperature

“…10 in Table 2). Boggioni et al [ 93 ] used ketimide‐modified CpTiCl 2 (N=C t Bu 2 ) (Figure 11C) to catalyze the terpolymerization of ethylene, norbornene, and 1‐octene at 60°C. The maximum activity of the catalyst was 9.77 × 10 7 g polymer/(mol h), and the 1‐octene insertion amount was 5.6 mol%.…”

“…Since then, Nomura et al [88][89][90][91][92]94] have done a lot of in-depth research on such catalysts from the crystal structure and catalytic mechanism to the ligand structure of the catalyst and the effect of the comonomer on the polymerization effect. Studies have found that such catalysts were suitable for not only the polymerization of ethylene but also the copolymerization of ethylene with monomers such as α-olefins, [88][89][90] substituted α-olefins, [91,92] cyclic olefins, [93] and silane olefins. [94] Kim et al [95] found that phenyl-substituted aryloxy semi-titanocenes Cp*Ti(O-2-PhC 6 H 4 )Cl 2 (Figure 11B) had higher activity than [Me 2 Si (C 5 Me 4 )(N t Bu)]TiCl 2 for ethylene/1-octene copolymerization at 140 C and also had better insertion ability of comonomers (see No.…”

Propylene/Cyclic Olefin Copolymers with Cyclopentene, Cyclohexene, Cyclooctene, Tricyclo[6.2.1.0(2,7)]undeca-4-ene, and Tetracyclododecene: The Synthesis and Effect of Cyclic Structure on Thermal Properties

“…In contrast to the ethylene (E)/cyclic olefin copolymers, reports for the synthesis of propylene (P) or α-olefin copolymers still have been limited to NBE [poly­(P- co -NBE)­s, − poly­(α-olefin- co -NBE)­s], − or the terpolymers (with styrene and 1-hexene). − We previously reported the synthesis of α-olefin copolymers with NBE and TCD (α-olefin = 1-hexene, 1-octene, and 1-dodecene) and demonstrated linear relationships between T g values and the NBE or CD contents; as described above, the T g values in poly­(α-olefin- co -TCD)­s were higher than those in poly­(α-olefin- co -NBE)­s with the same cyclic olefin contents . However, there were no reports for the synthesis of other amorphous propylene cyclic copolymers including the effect of the cyclic structure on the thermal property ( T g ) as well as a comparison with the ethylene copolymers.…”

Catalytic performance of tridentate versus bidentate Co(ii) complexes supported by Schiff base ligands in vinyl addition polymerization of norbornene

“…1–4 Both early and late transition metal complexes have been reported as active catalysts for the vinyl addition polymerization of NB. 1,5–11 Recently, promising catalytic activities have also been reported for late transition metal catalysts, such as Pd- and Ni-based catalysts. 12–15…”

“…[1][2][3][4] Both early and late transition metal complexes have been reported as active catalysts for the vinyl addition polymerization of NB. 1,[5][6][7][8][9][10][11] Recently, promising catalytic activities have also been reported for late transition metal catalysts, such as Pd-and Ni-based catalysts. [12][13][14][15] The choice of ancillary ligand signicantly affects the catalytic performance of the metal-based initiators in a polymerization reaction.…”