Synthesis of Novel Hyper‐Branched Polymers From Trimethoxysilyl‐Terminated Polylactides and Their Utilization for Modification of Poly(l‐Lactide) Materials

Silyl-terminated oligomers of poly(l-lactide) (mSi-PLLA) and poly(d-lactide) (mSi-PDLA) were synthesized by hydrosilylation of allyl-terminated derivatives. They were readily hydrolyzed into hyper-branched polymers having particulate morphology. When a mSi-PDLA oligomer was blended with a PLLA sample (52.5 kDa) in 1–10 wt.-% by solution casting, small cross-linked particles with stereocomplex form were generated and distributed homogenously in the PLLA matrix, and by which the homo-chiral crystallization of PLLA was efficiently suppressed. When another mSi-PLLA oligomer was blended with PLLA, the cross-linked particles formed from mSi-PLLA were amorphous and distributed inhomogeneously. It was, therefore, indicated that the hydrolytic polycondensation of mSi-PDLA and mSi-PLLA was induced during the film casting, changing the inner structure and properties of the blend films with PLLA.