## 3 Results and Discussion  
NCPAE was synthesized as a result of acylation of ethanoloamine by 2-chloropropionyl chloride (Scheme 1). The synthesized NCPAE was used as an initiator for polymerization of N-isopropylacrylamide (NIPAM) via the ATRP mechanism (Figure 1, Stage I). Due to the presence of chlorine atoms in the molecule of NCPAE it can be used as an initiator of ATRP for such active monomers as NIPAM. On \begin{table}
\begin{tabular}{c c c c} \hline \hline
**Sample** & \(\mathbf{t_{0}}\) [\({}^{\circ}\)C] & \(\mathbf{t_{p}}\) [\({}^{\circ}\)C] & \(\mathbf{t_{r}}\) [\({}^{\circ}\)C] & \(\Delta\)H [J/g] \({}^{a}\) \\ \hline P1 & 42.8 & 43.0 & 42.8 \(\div\)44.6 & 14.4 \\ P2 & 42.8 & 42.9 & 42.8 \(\div\) 44.3 & 14.3 \\ P3 & 43.1 & 43.8 & 43.1 \(\div\) 45.1 & 2.98 \\ P4 & 40.7 & 41.1 & 40.7 \(\div\) 43.0 & 6.43 \\ P5 & 43.4 & 43.4 & 43.4 \(\div\) 44.7 & 8.06 \\ P6 & 40.7 & 40.6 & 40.7 \(\div\) 42.4 & 6.74 \\ \hline \hline \end{tabular} \({}^{a}\) determined as endothermic peak area calculated per 1 g of solution (concentration of all solutions 1.5% (_v/v_)).  
\end{table} 
Table 2: Results of Differential Scanning Calorymetry (DSC) measurements of aqueous solutions of homopolymers (1.5% _v/v_). The temperatures given below corresponds to: \(t_{0}\)—onset of the peak, \(t_{\text{P}}\)—minimum of the peak and \(t_{\text{r}}\)— range of temperatures within the transition occurs. The phase transition enthalpies \(\Delta\)H have been estimated as the areas of the endothermic peaks corresponding to the phase transitions. the other hand, application of NCPAE as an initiator enables synthesis of chlorine atom-terminated polymers on one side and hydroxyl groups on the opposite side of the molecule. Our earlier investigations proved that practically it is not possible to achieve a chain extension with styrene when PNIPAM is chlorine terminated (Table S1 in Supplementary Material). In such a macroinitiator (PNIPAM-Cl), the chemical bond formed between chlorine atoms and the growing polymer chain terminated with styrene is probably so strong that a transfer of chlorine atom on to the catalytic system is not possible. Therefore, we decided to design such an initiator, which enables modification of the PNIPAM chain with bromine. The hydroxyl group in the polymers, prepared using the method developed by us, provides such a possibility. However, before the modification of the polymers with bromine, the removal of terminal chlorine atoms was performed. This is because our earlier studies showed, that 2-8 (no more) of styrene mers can be attached to PNIPAM's chains terminated with chlorine under ATRP conditions. This process may contribute to the deterioration of the polydispersity of the synthesized polymers. Figure 1: The scheme of the procedure leading to the preparation of PNIPAM-block-PS copolymers using the bifunctional initiator 2-chloro-N-(2-hydroxyethyl)propanamideamide (NCPAE). After the dehalogenation process (Figure 1 Stage II), the next step was to functionalize the polymer chains using \(\alpha\)-bromoisobutyryl bromide. As a result, PNIPAM-Br macroinitiators were synthesized that could be used in the polymerization of styrene (Figure 1, Stage IV). The developed procedure allowed the successful synthesis of amphiphilic and thermosensitive block copolymers with PNIPAM, as the first block and PS as the second one. The synthesized (co)polymers were characterized using spectroscopic (\({}^{1}\)H NMR) and chromatographic (SEC) methods, thermal analyses (DSC) and dynamic light scattering method (DLS). The molar ratios applied in the polymerization of NIPAM and characteristic of the obtained homopolymers from SEC analyses are presented in Table 1.  
The polymerization of NIPAM was carried out using a procedure described in the literature [22] but with several modifications. First of all, we used an initiator which allows terminal functionalized polymers with hydroxyl groups to be obtained. It is worth pointing out that this is the first time such an initiator has been used in ATRP.