Abstract
Triblock copolymers of ABA- and BAB-type consisting of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA, A) and poly(e-caprolactone) (PCL, B) have successfully been prepared. PDMAEMA-b-PCL-b-PDMAEMA (ABA) and PCL-b-PDMAEMA-b-PCL (BAB) were synthesised by a combination of ring-opening polymerisation of e-CL, atom transfer radical polymerisation of DMAEMA and end-group conversion, performed through either acylation or azide–alkyne “click” chemistry. All samples were analysed by size exclusion chromatography where it was found that the evaluation of PDMAEMA-containing polymers was difficult due to the thermoresponsivity of PDMAEMA, affecting the solubility of the polymer in the temperature range at which the SEC was operated. From differential scanning calorimetry measurements it was shown that the crystallinity could be altered by changing the order of the blocks; with PDMAEMA as the outer block (ABA), the inherent crystallinity of PCL was destroyed while with PCL as the outer block (BAB), the degree of crystallinity was in the same proximity as for a PCL homopolymer.
Highlights
Polymer architecture is of great interest as it enables tailoring of the properties for a nal application
All samples were analysed by size exclusion chromatography where it was found that the evaluation of PDMAEMAcontaining polymers was difficult due to the thermoresponsivity of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), affecting the solubility of the polymer in the temperature range at which the SEC was operated
From differential scanning calorimetry measurements it was shown that the crystallinity could be altered by changing the order of the blocks; with PDMAEMA as the outer block (ABA), the inherent crystallinity of PCL was destroyed while with PCL as the outer block (BAB), the degree of crystallinity was in the same proximity as for a PCL homopolymer
Summary
Polymer architecture is of great interest as it enables tailoring of the properties for a nal application. Atom Transfer Radical Polymerisation (ATRP)[1] is one technique available for the synthesis of well-de ned block copolymers of, for example, methacrylates,[2,3,4,5] acrylates[6,7,8] or styrenes.[9,10,11] ATRP yields polymers with low molar-mass dispersity (ĐM), controlled molecular weight and preserved end-group functionality.[12] when aiming for micellar applications, amphiphilic block copolymers, i.e., block copolymers composed of hydrophobic and hydrophilic segments are of particular interest. When an amphiphilic polymer is subjected to a solvent, solubilising only one of the segments, the chains of the insoluble block will self-assemble to form a micelle if the hydrophilic/hydrophobic balance is appropriate.[13,14] Micelles have gained signi cant attention since they can be used to
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