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1:1 Copolymerizations of glycolide (GL) and L-lactide (LA) is performed in bulk at 100°C and at 160°C with four cyclic tin catalysts. The resulting copolyesters are characterized by SEC measurements, 1H and 13C NMR spectroscopy and by MALDI TOF mass spectrometry. At 160°C and longer reaction time (22 h) nearly complete conversion of both monomers is achieved, and cyclic copolymers with nearly random sequences are formed. At shorter times (0.5-3.0 h, depending on catalyst) the conversion of LA is incomplete, and only cyclics having even numbers of lactyl units are obtained. At 100°C at 22 h again cycles mainly consisting of even numbered lactyl units are formed, but with even and odd numbers of glycolyl units. Copolymerization of lactide at 160°C with small amounts of GL show that formation of high Tm crystallites (Tm > 190°C) is hindered even when only > 2% of GL is added. For polyglycolide containing a smaller amount of lactide complete solubility in hexafluoroisopropanol is only observed around and above 20 mol% of lactide.
The catalytic potential of bismuth subsalicylate (BiSub), a commercial drug, for ring-opening polymerization (ROP) of L-lactide was explored by variation of co-catalyst and polymerization time. Various monofunctional phenols or carboxylic acids, aromatic ortho-hydroxy acids and diphenols were examined as potential co-catalysts. 2,2´-Dihydroxybiphenyl proved to be the most successful co-catalyst yielding weight average molecular weights (uncorrected Mw values up to 185 000) after optimization of reaction time and temperature. Prolonged heating (>1-2h) depending on catalyst concentration) caused thermal degradation. In polymerization experiments with various commercial Bi(III) salts a better alternative to BiSub was not found. By means of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry a couple of unusual and unexpected transesterification reactions were discovered. Finally, the effectiveness of several antioxidants and potential catalyst poisons was explored, and triphenylphosphine was found to be an effective catalyst poison.
Alcohol-initiated ROPs of L-lactide were performed in bulk at 160 °C for 72 h with variation of the catalyst or with variation of the initiator (aliphatic alcohols). Spontaneous crystallization was only observed when cyclic Sn(II) compounds were used as a catalyst. Regardless of initiator, high melting crystallites with melting temperatures (Tm) of 189–193 °C were obtained in almost all experiments with Sn(II) 2,2′-dioxybiphenyl (SnBiph) as catalyst, even when the time was shortened to 24 h. These HTm poly(lactide)s represent the thermodynamically most stable form of poly(L-lactide). Regardless of the reaction conditions, such high melting crystallites were never obtained when Sn(II) 2-ethylhexanoate (SnOct2) was used as catalyst. SAXS measurements evidenced that formation of HTm poly(L-lactide) involves growth of the crystallite thickness, but chemical modification of the crystallite surface (smoothing) seems to be of greater importance. A hypothesis, why the “surface smoothing” is more effective for crystallites of linear chains than for crystallites composed of cycles is discussed.
A set of strained aromatic macrocycles based on [n]cyclo2,7-(4,5,9,10-tetrahydro)pyrenylenes is presented with size dependent photophysical properties. The K-region of pyrene was functionalized with ethylene glycol groups to decorate the outer rim and thereby confine the space inside the macrocycle. This confined space is especially pronounced for n = 5, which leads to an internal binding of up to 8.0×104 M–1 between the ether-decorated [5]cyclo-2,7-pyrenylene and shape complementary crown ether–cation complexes.
Both, the ether-decorated [n]cyclo-pyrenylenes as well as one of their host–guest complexes have been structurally characterized by single crystal X-ray analysis. In combination with computational methods the structural and thermodynamic reasons for the exceptionally strong binding have been elucidated. The presented rim confinement strategy makes cycloparaphenylenes an attractive supramolecular host family with a favorable, size-independent read-out signature and binding capabilities extending beyond fullerene guests.
The catalytic potential of tin(II)acetate, tin(IV)acetate, dibutyltin-bis-acetate and dioctyl tin-bis-acetate was compared based on polymerizations of L-lactide conducted in bulk at 160 or 130°C. With SnAc2 low-Lac/Cat ratios (15/1–50/1) were studied and linear chains having one acetate and one carboxyl end group almost free of cyclics were obtained. Higher monomer/catalyst ratios and lower temperatures favored formation of cycles that reached weight average molecular weights (Mw's) between 100,000 and 2,500,000. SnAc4 yielded mixtures of cycles and linear species under all reaction conditions. Dibutyltin- and dioctyl tin bis-acetate yielded cyclic polylactides under most reaction conditions with Mw's in the range of 20,000–80,000. Ring-opening polymerizations performed with ε-caprolactone showed similar trends, but the formation of COOH-terminated linear chains was significantly more favored compared to analogous experiments with lactide. The reactivity of the acetate catalysts decreased in the following order: SnAc2> SnAc4>Bu2SnAc2~Oct2SnAc2
The definition of the term “conversion” is discussed for a variety of polymer syntheses. It is demonstrated that in contrast to organic and inorganic chemistry several different definitions are needed in polymer science. The influence of increasing conversion on structure and topology of homo- and Copolymers is illustrated. Chain-growth polymerizations, such as radical polymerization or living anionic polymerizations of vinyl monomers, condensative chain polymerization, two and three-dimensional step-growth polymerizations, ring–ring or chain–chain equilibration and chemical modification of polymers are considered.
A comparison of tributyltin chloride, dibutyltin dichloride,and butyltin trichloride as catalysts of ring-opening polymerizations(ROPs) of l-lactides at 160°C in bulk reveals increasing reactivity in the above order, but only the least reactive catalysts, Bu3SnCl, yield a uniform reaction product, namely cyclic poly(L-lactide)s with weight average molecular weights (Mw ́s) in the range of 40,000–80,000. A comparison of dimethyltin , dibutyltin , and diphenyltin dichlorides resulted in the following order of reactivity: Me2SnCl2<Bu2SnCl2<<Ph2SnCl2. In this series also, the most reactive catalyst yields cyclic polylactides, but the extent of cyclization varies with the molecular weight. The formation of cyclic polylactides is explained by ROP combined with simultaneous polycondensation involving end-to-end cyclization (ROPPOC method). ROP of meso-lactide at 80 or 60°C yields even-numbered linear chains as main products, a result supporting the ROPPOC mechanism.
Spirocyclic phenoxides of germanium, zirconium, and tin were prepared from 2,20-dihydroxybiphenyl and 2,20-dihydroxy-1,10-binaphthyl. Ring-expansion polymerizations of L-lactide are mainly studied at 160 or 180 °C. The reactivity of the catalysts increases in the order: Zr < Ge < Sn. Regardless of catalyst, the weight-average molecular weights (Mw) never exceed 50,000 g mol−1. The resulting poly(L-lactide)s are optically pure and have a cyclic architecture. Decreasing temperature and time favor Formation of even-numbered cycles, and at 102 ° cyclics, almost free of odd-numbered rings are obtained. Analogous polymerizations of meso-lactide give similar results >120 °C, but different results at 100 or 80 °C. Surprisingly, bell-shaped narrow molecular weight distributions are obtained <140 °C, resembling the pattern of living polymerizations found for alcohol-initiated polymerizations. An unusual transesterification mechanism yielding narrow distributions of odd-numbered cycles is discovered too.
MALDI time-of-flight mass spectrometry (MALDI-TOF MS) has become a widely used tool for the classification of biological samples. The complex chemical composition of pollen grains leads to highly specific, fingerprint-like mass spectra, with respect to the pollen species. Beyond the species-specific composition, the variances in pollen chemistry can be hierarchically structured, including the level of different populations, of environmental conditions or different genotypes. We demonstrate here the sensitivity of MALDI-TOF MS regarding the adaption of the chemical composition of three Poaceae (grass) pollen for different populations of parent plants by analyzing the mass spectra with partial least squares discriminant analysis (PLS-DA) and principal component analysis (PCA). Thereby, variances in species, population and specific growth conditions of the plants were observed simultaneously. In particular, the chemical pattern revealed by the MALDI spectra enabled discrimination of the different populations of one species. Specifically, the role of environmental changes and their effect on the pollen chemistry of three different grass species is discussed. Analysis of the Group formation within the respective populations showed a varying influence of plant genotype on the classification, depending on the species, and permits conclusions regarding the respective rigidity or plasticity towards environmental changes.
At first, formation of cycles in commercial poly(Llactide)s is discussed and compared with benzyl alcoholinitiated polymerizations performed in this work. This comparison was extended to polymerizations initiated with 4-cyanophenol and pentafluorothiophenol which yielded cyclic polylactides via end-biting. The initiator/catalyst ratio and the acidity of the initiator were found to be decisive for the extent of cyclization. Further polymerizations of L-lactide were performed with various diphenols as initiators/co-catalysts. With most diphenols, cyclic polylactides were the main reaction products. Yet, only catechols yielded even-numbered cycles as main reaction products, a result which proves that their combination with SnOct2 catalyzed a ring-expansion polymerization (REP). The influence of temperature, time, co-catalyst, and catalyst concentrations was studied. Four different transesterification reactions yielding cycles were identified. For the cyclic poly(L-lactide)s weight average molecular weights (Mw’s) up to 120,000 were obtained, but 1H NMR end group analyses indicated that the extent of cyclization was slightly below 100%.
The influence of various parameters like structure of Initiator and catalyst and temperature on the formation of cyclic poly(Llactide)s has been investigated. Depending on the chosen conditions, the course of the polymerization can be varied from a process yielding exclusively linear polylactides to mainly cyclic polylactides. Three different reaction pathways for cyclization reactions have been identified.