Homogenous catalytic homopolymerization and copolymerization of 1-hexene (H) with methyl methacrylate (MMA) were carried out in presence of two different types of mononuclear (MNC1 and MNC2) and dinuclear Ni-based catalysts (BNC1 and BNC2). Modified methylaluminoxane was used as cocatalyst due to good reactivity in MMA/H copolymerization. Among the structures, BNC1 showed the highest catalyst activity (6.9 × 104 g P. mol−1Ni. h−1). Although Mw of the copolymer made by BNC1 was higher than its mononuclear, molecular weight distribution was broader. The optimum molar ratios for mononuclear and dinuclear were obtained at [Al]/[Ni] = 1,000:1 and [Al]/[Ni] = 1,500:1, respectively. Surprisingly, introduction of MMA (up to [MMA]/[H] = 50:50 molar ratio) into the polymerization solution increased the activity of all catalysts. 1H NMR analysis study revealed that increasing of MMA in the feed composition raised incorporation of the comonomer into the obtained copolymers. The result was consistent on the calculated reactivity ratio of monomers, using Kelen–Tudos method. In addition, BNC1 (at [MMA]/[H] = 70:30 molar ratio) demonstrated more incorporation of MMA to the main copolymer chain (95.2% mol). On the other side, study on tacticity of the PMMA sample was investigated that showed a distribution of stereoregularity in the order of atactic > > syndiotatic > isotactic (53.2 > 26.7 > 20.1). In addition, for copolymers made by BNC1, an unusual pattern was observed as lower concentration of MMA in the feed (i.e., 30%) led to high isotactic blocks of MMA. The highest branching density of the polymer, however, was obtained by BNC1 (217/1000C) and the lowest by BNC2 (80/1000C). Higher extent of the polar comonomer (MMA) in the copolymer backbone led to increasing of Tg for the copolymer samples (from 74.4 to 98.9_C). The structural properties of the obtained copolymers were investigated using both Fourier transform infrared spectroscopy and Raman spectroscopies, as well.

Keywords