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Well-defined ABA- and BAB-type block copolymers of PDMAEMA and PCL

机译:定义明确的aBma-和BaB-型pDmaEma和pCL嵌段共聚物

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摘要

Triblock copolymers of ABA- and BAB-type consisting of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA, A) and poly(epsilon-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 epsilon-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.
机译:已成功制备了由聚甲基丙烯酸2-(二甲基氨基)乙酯(PDMAEMA,A)和聚ε-己内酯(PCL,B)组成的ABA型和BAB型三嵌段共聚物。 PDMAEMA-b-PCL-b-PDMAEMA(ABA)和PCL-b-PDMAEMA-b-PCL(BAB)通过epsilon-CL的开环聚合,DMAEMA的原子转移自由基聚合和端基的组合合成通过酰化或叠氮化物-炔的“点击”化学反应进行转化。通过尺寸排阻色谱法分析所有样品,发现由于PDMAEMA的热响应性,难以评估含PDMAEMA的聚合物,从而影响了SEC操作温度范围内的聚合物溶解度。从差示扫描量热法测量结果表明,可以通过改变嵌段的顺序来改变结晶度。当以PDMAEMA作为外嵌段(ABA)时,PCL的固有结晶度被破坏,而当以PCL作为外嵌段(BAB)时,结晶度与PCL均聚物的接近度相同。

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