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Two kinds of synthesized NiAl (NiAl-LDH) and MgAl (MgAl-LDH) layered double hydroxides were melt blended with commercial polylactide to prepare different polymer based nanocomposites. The MgAl-LDH based nanocomposites and NiAl-LDH based nanocomposites have a diferent but mixed intercalated / exfoliated structure. Based on the different structures, the crystallization behaviors of polymer based nanocomposites were investigated by differential scanning calorimetry (DSC) and temperature modulated differential scanning calorimetry (TMDSC) specificly where the heating and cooling rates were varied in a extrmely wied range. In a first step, the cooling rate where crystallization can be completely surpressed is estimated. In a second step, based on a specified temperature program the crystalline fraction (CF), the rigid amorphous fraction (RAF) and the mobile amorphous fraction (MAF) were calculated from the the enthalpy and specific heat capacity in dependence on the concentration of the nanofiller. The rigid amorphous fraction was considered as resulting from the the crystallites and the nanofiller. For the first time both fractions were calculated quantitatively without any additional assumption.
Different strategies for the synthesis of polylactides were presented with special focus on Ring-opening Polymerization (ROP) and simultaneous ROP and Polycondensation (ROPPOC) mechanism. The mechanism of the formation of cyclic Polyesters is discussed in detail and established theories about the formation of cycles in polycondensation reactions are critically reviewed.
In addition to molar mass distribution (MMD) synthetic polymers often exhibit an additional chemical heterogeneity distribution, expressed by different end groups and other structural variations (e.g. tacticity, copolymer composition etc.). Ionization in MALDI MS is always strongly affected by such chemical properties. For example, the abundance of cyclics in MALDI TOF mass spectra is frequently reported to greatly exceed that of linears. Thus, the MALDI ionization behavior of various neat end-capped linear poly(L-lactide)s and one cyclic poly(L-lactide) was investigated and compared with that of blends of both structures. Moreover, the influence of the cationizing salt was investigated too.
Neat compounds and various blends of cyclic and linear species were prepared and studied using two MALDI TOF mass spectrometers under identical conditions with regard to sample preparation and instrumental conditions, except for the laser power and the salt used for cationization. Polymer samples were additionally characterized by NMR and SEC.
The steady increase of the laser intensity caused an exponential increase of the peak intensities of both linear and cyclic polylactides.The response of linear polylactides (in the investigated molecular mass range), whether as neat polymer or in blends with other linear polylactides was almost similar. This clearly supports our assumption that ionization in MALDI is probably unaffected by the end group structure.The variation of the laser power shows only little effect on the intensity ratio of linear-to linear and cyclic-to-linear polylactides in blends. Whereas neat linear polylactides at all laser intensities have a significantly higher abundance than neat cyclics, in mixtures of both an overestimation of cyclic species in MALDI TOF mass spectra of polylactides was found. However, this is far less distinct than frequently reported for other polymers.Concluding, peak suppression of linear polymers in mixtures of both architectures can be excluded, which also means, that polylactides showing only peaks of cyclic compounds in their MALDI - TOF mass spectra do not contain a significant fraction of linear analogues.
Our study is the first systematic comparison of the MALDI ionization of neat and blended cyclic and linear polylactides.