@article{BehlBalkMansfeldetal.2021, author = {Behl, Marc and Balk, Maria and Mansfeld, Ulrich and Lendlein, Andreas}, title = {Phase morphology of multiblock copolymers differing in sequence of blocks}, series = {Macromolecular materials and engineering}, volume = {306}, journal = {Macromolecular materials and engineering}, number = {3}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1439-2054}, doi = {10.1002/mame.202000672}, pages = {9}, year = {2021}, abstract = {The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. It is hypothesized that a strictly alternating sequence should impact phase segregation. A library of well-defined MBC obtained by coupling oligo(epsilon-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification results in strictly alternating (MBCalt) or random (MBCran) MBC. The three different series has a weight average molecular weight (M-w) of 65 000, 165 000, and 168 000 g mol(-1) for MBCalt and 80 500, 100 000, and 147 600 g mol(-1) for MBCran. When the chain length of OCL building blocks is increased, the tendency for phase segregation is facilitated, which is attributed to the decrease in chain mobility within the MBC. Furthermore, it is found that the phase segregation disturbs the crystallization by causing heterogeneities in the semi-crystalline alignment, which is attributed to an increase of the disorder of the OCL semi-crystalline alignment.}, language = {en} } @article{BalkBehlLendlein2020, author = {Balk, Maria and Behl, Marc and Lendlein, Andreas}, title = {Actuators based on oligo[(epsilon-caprolactone)-co-glycolide] with accelerated hydrolytic degradation}, series = {MRS advances : a journal of the Materials Research Society (MRS)}, volume = {5}, journal = {MRS advances : a journal of the Materials Research Society (MRS)}, number = {12-13}, publisher = {Cambridge University Press}, address = {New York, NY}, issn = {2059-8521}, doi = {10.1557/adv.2019.447}, pages = {655 -- 666}, year = {2020}, abstract = {Polyester-based shape-memory polymer actuators are multifunctional materials providing reversible macroscopic shape shifts as well as hydrolytic degradability. Here, the function-function interdependencies (between shape shifts and degradation behaviour) will determine actuation performance and its life time. In this work, glycolide units were incorporated in poly(epsilon-caprolactone) based actuator materials in order to achieve an accelerated hydrolytic degradation and to explore the function-function relationship. Three different oligo[(epsilon-caprolactone)-co-glycolide] copolymers (OCGs) with similar molecular weights (10.5 +/- 0.5 kg center dot mol(-1)) including a glycolide content of 8, 16, and 26 mol\% (ratio 1:1:1 wt\%) terminated with methacrylated moieties were crosslinked. The obtained actuators provided a broad melting transition in the range from 27 to 44 degrees C. The hydrolytic degradation of programmed OCG actuators (200\% of elongation) resulted in a reduction of sample mass to 51 wt\% within 21 days at pH = 7.4 and 40 degrees C. Degradation results in a decrease of T-m associated to the actuating units and increasing T-m associated to the skeleton forming units. The actuation capability decreased almost linear as function of time. After 11 days of hydrolytic degradation the shape-memory functionality was lost. Accordingly, a fast degradation behaviour as required, e.g., for actuator materials intended as implant material can be realized.}, language = {en} }