## 3 Results and Discussion
#### 3.2.1 Copolymerization of Ethylene with 1-Hexene  
Data obtained on the homopolymerization of ethylene and copolymerization of ethylene (C\({}_{2}\)) with 1-hexene (C\({}_{6}\)), using TMC of different compositions are presented in Table 2 and Figure 1. To maintain a close concentration of 1-hexene in the reaction medium, the copolymerization experiments were carried out under conditions where the conversion of 1-hexene at the end of the experiment did not exceed 20%. So, the polymerization time was limited to the production of no more than 20 g of the copolymer. To estimate the copolymerization ability of various TMCs, copolymerization constants (\(r_{1}\)) were calculated from the dependence of the content of the comonomer (1-hexene) in the polymer on the molar ratio of monomers in the reaction medium (heptane) using Equation (1):  
\[(\alpha\text{-olefin}/\text{C}_{2}\text{H}_{4})\ (\text{polymer})=1/r_{1}\ ([\alpha\text{-olefin}]/[\text{C}_{2}\text{H}_{4}]\ (\text{heptane}) \tag{1}\]  
According to Table 2, all the tested TMCs have close levels of the average activity in the homopolymerization of ethylene (1.4-3.0 kg PE/(g cat \(\times\) h)). The maximum activity was observed for TMC-3, which contains TiCl\({}_{4}\) as the active component. The TMC-2 catalyst has a lower activity (1.4 kg/(g cat \(\times\) h)). The decreased activity of this catalyst may be caused by the presence of dibutyl ether in it. The TMC-1 and TMC-1-2 catalysts, which contain only the isolated monomeric compounds of Ti(II) and Ti(III), have close activity and similar forms of kinetic curves, which are characterized by high initial activity and a minor decrease during polymerization (Figure 1A). In the case of TMC-2 and TMC-3 catalysts containing titanium chlorides in different oxidation states (TiCl\({}_{3}\) and TiCl\({}_{4}\)) as the active component, the activity changes slightly with the polymerization time (Figure 1B,C). \begin{table}
\begin{tabular}{c c c c c c c c c c c c c} \hline \multirow{2}{*}{**Catalyst**} & **Exp.** & **[C\({}_{2}\)/IC\({}_{2}\)]** & \(\tau_{p}\)\({}^{1}\), **kg/ & **T\({}_{\rm r}\)** & **X\({}_{\rm r}\)** & **MI(S)** & **M\({}_{\rm n}\)** & **M\({}_{\rm w}\)** & **M\({}_{\rm w}\)** /** & **CH\({}_{\rm s}\)** / & **Bu/** & **mol.\%** \\  & **No.** & **(mol)** & **min** & **(g\({}_{\rm sat}\times\) h)** & **’C** & **’\%** & **’0 min** & **kg/mol** & **kg/mol** & **M\({}_{\rm n}\)** & **1000 C** & **1000 C** & **1-hexene** & \\ \hline TMC-1 & 1 & 0 & 60 & 2.42 & 139.5 & 63 & 0.26 & 53 & 270 & 5.1 & - & 0 & 0 & \\ (1.5 wt.\% Ti) & 2 & 1.1 & 14 & 9.4 & 127.5 & 31 & 3.4 & 24 & 115 & 4.8 & 14.0 & 12.8 & 2.6 & 49 \\  & 3 & 2.3 & 12 & 12.2 & 127.3 & 35 & 7.1 & 22 & 100 & 4.5 & 21.6 & 20.3 & 4.1 & \\ \hline TMC-1-2 & 4 & 0 & 60 & 2.2 & - & - & 0.2 & 55 & 285 & 5.2 & - & 0 & 0 \\ (1.5 wt.\% Ti) & 5 & 0.94 & 13 & 11.2 & 127.9 & 42 & 0.8 & 46 & 190 & 4.1 & 7.4 & 6.8 & 1.4 & 68 \\  & 6 & 2.3 & 18 & 9.6 & 128.0 & 30 & 5.5 & 22 & 115 & 5.2 & 18.0 & 16.7 & 3.34 & \\ \hline TMC-2 & 7 & 0 & 60 & 1.4 & 139.8 & 66 & 0.13 & 66 & 300 & 4.5 & - & 0 & 0 & \\ (1.5 wt.\% Ti) & 9 & 0.94 & 15 & 6.0 & 128.5 & 41 & 0.67 & 54 & 230 & 4.3 & 7.3 & 6.8 & 1.4 & 99 \\  & 10 & 4.5 & 19 & 5.6 & 126.8 & 26 & 1.82 & 23 & 97 & 4.2 & 22.6 & 21.4 & 4.3 & \\ \hline  & 11 & 0 & 60 & 3.0 & 139.7 & 63 & 0.12 & 73 & 290 & 4.0 & - & 0 & 0 & \\ TMC-3 & 12 & 0.94 & 17 & 8.4 & 128.1 & 47 & 1.1 & 39 & 170 & 4.4 & 7.1 & 6.4 & 1.3 & \\ (1.2 wt.\% Ti) & 13 & 2.3 & 22 & 6.6 & 127.6 & 36 & 1.7 & 40 & 150 & 3.8 & 11.9 & 11.2 & 2.2 & \\  & 14 & 5.2 & 19 & 8.6 & 126.1 & 36 & 1.8 & 38 & 141 & 3.7 & 20.0 & 19.2 & 3.8 & \\ \hline  & & & & & & & & & & & & & \\ \end{tabular} 1  
* \(\tau_{p}\)—the polymerization time. \({}^{2}\) The average polymerization rate R\({}_{\rm p}\) during polymerization time \(\tau_{p}\), which was calculated using the polymer yield (kg PE/g cat) and polymerization time values.  
\end{table}