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Synteza amfifilowych kopolimerów szczepionych metodą kontrolowanej (ko)polimeryzacji rodnikowej hydrofilowego makromonomeru poli(tlenku etylenu)

Neugebauer D.

Wiadomości Chemiczne

2008

[Z] 62, 1-2

49-66

A combination of hydrophilic and hydrophobic characters in one macromolecule of a polymer provides amphiphilic behavior [1, 2]. Such unique properties, which have found significant interest, are exhibited by graft copolymers containing poly(ethylene oxide) (PEO) as side chains attached to the backbone (Scheme 1) [20]. They have greatly expanded a class of materials important for science and biomedicine. This review article describes the PEO graft copolymers prepared by a variety of synthetic procedures used for the atom transfer radical (co)polymerization (ATRP) (Scheme 2) [15-17], i.e. directly by the grafting through, which is also named as the macromonomer method or by the grafting from technique, which requires the use of a multifunctional macroinitiator. Densely homografted copolymers also called molecular brushes [21-25] were obtained by homopolymerization of PEO macromonomer (Scheme 3). The density of PEO grafts was decreased in the copolymerization of PEO macromonomer with a low molecular weight comonomer resulting in loosely grafted copolymers contai-ning uniform PEO side chains (Scheme 4) [46-48]. Consequently, the copolymerization of two macromonomers yielded heterografted brushes (Scheme 5) [21, 23, 26, 45, 53-57]. In this case, the composition of copolymers was designed by the selection of proper comonomers with comparable (rM1 = rM2/rM1 ~ rM2) or different (rM1 > rM2, rM1 < rM2) reactivity ratios, which can form alternating/ random copolymers or spontaneous gradient of PEO chains along backbone, respectively. Using monofunctional macroinitiators with comb or linear composition for polymerization of PEO macromonomer resulted in comb-comb [31] or semi-comb diblock copolymers [21, 23, 27-30]. The reverse structures were also obtained, when the PEO graft copolymers were applied as the monofunctional macroinitiators [31, 32]. The use of polymeric multifunctional macroinitiators (graft or linear) in the polymerization of monomer or macromonomer led to the heterografted copolymers (Scheme 4) [32, 50, 51] or more complexed double grafted copolymers (Scheme 3) [25]. The applications of the PEO graft copolymers in numerous fields are also presented to show their versatile potential [25, 26, 46, 53, 55, 56, 68-76].