Brush Copolymers from 2-Oxazoline and Acrylic Monomers via an Inimer Approach

Abstract

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An ε-caprolactone-derived 2-oxazoline inimer for the synthesis of graft copolymers

“…Although, multiple distillations are not necessarily required, we have decided to obtain 2-npentanol-2-oxazoline at its highest purity as any impurities could lead to further unwanted side reactions in the third step. Compared to the thioether-linked oxazoline, as previously demonstrated by our group, 20 it is a less toxic and easily scalable procedure owing to the cheaper and non-toxic nature of the starting material, namely caprolactone.…”

“…Alkyl halides are known initiators of CROP, 32 and it was also reported by our group that a similar inimer structure can self-initiate even at 80°C, which is significantly lower than the standard CROP temperature of 140°C. 20 This could be associated with the electrophilicity of the tertiary alkyl halide also present in the inimer structure in this research, which could cause the initiation of the oxazoline and lead to unwanted hyperbranched structures. Therefore, a lower reaction temperature of 60°C was chosen for the polymerisation of the backbone by CROP.…”

“…The thioether linker containing inimer structure we previously reported showed narrow dispersity for block copolymers of EtOx and the inimer, but statistical copolymers of the two led to undesirable polymerisation reactions leading to poorly defined polymers. 20 In that report, it was concluded that the susceptibility of EtOx to the tertiary alkyl bromide of the inimer led to the polymerisation of the monomers, both by the initiator and the tertiary alkyl bromide of the inimer. However, upon copolymerisation of the inimer presented in this research (In) with EtOx at a ratio of 25 : 25 (P5), welldefined polymers were synthesized even at higher molecular weights (Fig.…”

“…8,[14][15][16][17][18] However, the combination of 2-oxazolines and acrylates as a graft copolymer has seldom been reported, with even fewer reports on the 2-oxazoline backbone and acrylate brush combination. [19][20][21][22][23] Graft copolymers can be synthesized from three synthetic routes: grafting to, grafting through, and grafting from. While each method is associated with its own advantages and disadvantages, [24][25][26] the grafting from approach, the chosen synthetic route in this research, can give superior control over the grafting density.…”

Amphiphilic Molecular Brushes with Regular Polydimethylsiloxane Backbone and Poly-2-isopropyl-2-oxazoline Side Chains. 2. Self-Organization in Aqueous Solutions on Heating

“…These polymers include some representatives of poly-2-alkyl-2-oxazolines (PAlOx), the use of which in medical applications is due to their biodegradability, biocompatibility, and low toxicity. At present, PAlOx are used in chromatography, bioseparation, heterogeneous catalysis, as well as in the preparation of complexes and conjugates [ 5 , 8 , 34 , 35 ]. One of the interesting representatives of PAlOx is poly-2-isopropyl-2-oxazoline (PiPrOx), which is a structural analog of both poly- N -isopropylacryamide and polypeptides [ 36 , 37 , 38 ].…”