## 4 Conclusions  
In summary, we have presented a novel strategy for the synthesis of block amphiphilic and thermosensitive copolymers with the sequence PNIPAM-\(b\)-PS. The proposed synthetic route consists of four stages and is based on the application of 2-chloro-N-(2-hydroxyethyl)propanamide (NCPAE) as bifunctional initiator. First, NCPAE was used in the ATRP of N-isopropylacrylamide (NIPAM) and hydroxyl functionalized PNIPAMs with low polydispersities (\(1.1\leq\mathrm{PDI}\leq 1.3\)) and molecular masses in the range 2,000-12,000 Da were synthesized. Next, terminal chlorines were removed from the prepared PNIPAM molecules by a dehalogenation process, followed by polymer chain modification using \(\alpha\)-bromoisobutyryl bromide. The obtained modified polymers (PNIPAM-Br) were used as macroinitiators in ARGET ATRP of styrene. The developed procedure gave well-defined block copolymers, with two chemically different blocks phase separated in the molecules. We proved that the use of CuCl\({}_{2}\)/PMDETA as catalytic system at concentration as low as 9 ppm, under the conditions of ARGET ATRP, results in copolymers with relatively low polydispersities (PDI \(\approx 1.3\)). To achieve narrower MWDs of the prepared copolymers, further improvement of the proposed procedure is necessary. We think that the slowing down of NIPAM's polymerization and increasing of degree of PNIPAMs' functionalization with bromine should be crucial factors. Further experiments are in progress. Both the DSC and DLS techniques verified thermosensitive behavior of the synthesized PNIPAMs and PNIPAM-\(b\)-PS copolymers generated from them. The proposed procedure can be applied not only for the preparation of PNIPAM-\(b\)-PS copolymers, but can also be used for the synthesis of other block copolymers that are built of monomers with different activities in ATRP. Changing the terminal halogen atoms is necessary to achieve good control over the polymer chain extension. Due to their amphiphilic character, thermosensitive behavior and biocompatibility, the synthesized copolymers may find numerous interesting applications e.g., drug delivery systems, tissue engineering, regenerative medicine, construction of smart membranes. **Supplementary Materials:** The following are available online at [[http://www.mdpi.com/2073-4360/11/9/148/s1](http://www.mdpi.com/2073-4360/11/9/148/s1)]([http://www.mdpi.com/2073-4360/11/9/148/s1](http://www.mdpi.com/2073-4360/11/9/148/s1)). The number averaged hydrodynamic diameter distribution in aqueous solutions (1.5% _w/w_) of homopolymers (desorption of the samples in Table 1 in main document) at 25, 35 and 40 \({}^{\circ}\)C from DLS measurements. For P5 the changes in the size of particles at 35 \({}^{\circ}\)C have not be observed in comparison with the sizes which observed at 25 \({}^{\circ}\)C. The conditions under which the chain extensions of PNIPAM-Cl with styrene via ARGET ATRP were conducted; number-averaged molecular masses (\(M_{\mathrm{n}}\)) of copolymers and macroinitiation determined from SEC analyses; estimated number of styrene mers in copolymers' chains; Results of SEC analyses (with THF as eluent) for the prepared homopolymers before and after removal of terminal chlorine atoms as well as after esterification by using  
Figure 10: The DSC thermograms for the synthesized homopolymer, copolymer and \(T_{\mathrm{g}}\)s determined from the thermograms (cooling scan, cooling rate of 20 K/min). \(\alpha\)-bromoisobutyryl bromide; The 300 MHz \({}^{1}\)H NMR spectrum of diblock copolymer PNIPAM-b-PS (recorded for the sample denoted as PNPS3 in Table 3) in CDCl3; The photo of aqueous solution of the synthesized diblock copolymer PNIPAM-\(b\)-PS (a solution of sample PNPS3).