Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst, resulting from the reaction of diphenyltin sulfide with bis(3-dimethyl-aminopropyl)zinc, was found to be R(C6H5)2Sn(SZn)2R with R = (CH2)3N(CH3)2. Using this catalyst, an anionic coordination polymerization was observed with neither stereoselectivity nor living type or cationic features. At low catalyst concentration (0,03 mol-% Zn) a high-molecular-weight poly(propylene oxide) (PPOX) was obtained in 80-90% yield ([bar M ]w = 500000; 40% isotactic). Lowering of the catalyst concentration and increasing the polymerization temperature changed the kinetics and the stereochemistry of the polymerization leading to polymers of lower molecular weight and to a decrease in the isotactic PPOX fraction to 20%, probably due to an association of the catalytic species

Novel "green" catalysts for controlled ring-opening polymerization of lactide

Syntéza polylaktidu (PLA) polymerací za otevření kruhu cyklického monomeru (ROP) může být uskutečněna různými způsoby. Literatura uvádí více než 100 katalytických systémů, jejichž pomocí lze polylaktid a jiné biodegradabilní alifatické polyestery získat. Například organokovové katalyzátory na bázi Sn, Zn, Al atd. se po splnění své polymerační funkce stávají kontaminanty a pro humánní implantáty je použití takového materiálu diskutabilní. V současné době jsou v centru výzkumné pozornosti nové N-heterocyklické karbenové katalyzátory. Tyto „metal-free“ katalytické struktury jsou schopné reprodukovatelně řídit syntézu polymerů předem definované molekulové hmotnosti s definovanými koncovými skupinami a nízkou polydisperzitou, která je charakteristická pro živý průběh polymerace. Nabízí se možnost syntézy blokových kopolymerů a různorodých makromolekulárních architektur. Předložená diplomová práce se zabývá studiem polymerace cyklického monomeru D,L-laktidu katalyzované N-heterocyklickým karbenem. Polymerace byly vedeny v přítomnosti benzylalkoholu jako iniciátoru v roztoku THF. Byl sledován vliv složení reakčního systému monomer – iniciátor – katalyzátor. Dále byly připraveny polymery opticky čistého L-laktidu s makroiniciátory PEG s Mn = 1000 a 2000 g/mol. Střední číselná molekulová hmotnost (Mn) a polydisperzita (PDI) byly stanoveny pomocí GPC. Definovatelnost koncových skupin vybraných polymerů byla prokázána pomocí 1H NMR.The synthesis of polylactide (PLA) by ring-opening polymerization (ROP) of cyclic monomer can be realized by different routes. More than 100 catalysts for the synthesis of polylactide and other biodegradable aliphatic polyesters are published in the literature. For example organometallic catalysts based on Sn, Zn, Al etc. after finishing polymerization function became contaminants and using obtained polymer material in human body is controversial. At present, the research is focused on novel N-hererocyclic carbene catalysts. These metal-free catalysts are able to produce polymers with controlled molecular weight, narrow polydispersity, end-group fidelity with high reproducibility as well as to synthesize the block copolymers and complex macromolecular architectures, which is characteristic for living polymerization system. This diploma thesis is focused on study of polymerization of cyclic monomer D,L-lactide catalyzed by N-hererocyclic carbene. Polymerizations were carried out at the presence of benzylalcohol as initiator at THF. We were focused on the influence of composition of reaction system monomer – initiator – catalyst. Polymers of optically pure L-lactide with macroinitiators PEG with Mn of 1000 a 2000 g/mol were prepared as well. Number average molecular weight (Mn) and polydispersity index (PDI) was determined by GPC. 1H NMR was used to prove end-group fidelity.

Multimetallic lithium complexes derived from the acids Ph₂C(X)CO₂H (X = OH, NH₂) : synthesis, structure and ring opening polymerization of lactides and lactones

Reaction of LiOR (R=t-Bu, Ph) with the acids 2,2/-Ph₂C(X)(CO₂H), X=OH (benzH), NH₂ (dpgH) was investigated. For benzH, one equivalent LiOt-Bu in THF afforded [Li(benz)]2⋅2THF (1⋅2THF), which adopts a 1D chain structure. If acetonitrile is used (mild conditions), another polymorph of 1 is isolated; LiOPh also led to 1. Robust work-up afforded [Li₇(benz)₇(MeCN)] 2MeCN THF (2⋅2MeCN⋅THF). Use of LiOt-Bu (2 equivalents) led to {Li₈(Ot-Bu)₂[(benz)](OCPh₂CO₂CPh₂CO2t-Bu)₂(THF)₄} (3), the core of which comprises two open cubes linked by benz ligands. For dpgH, two equivalents of LiOt-Bu in THF afforded [Li6(Ot-Bu)₂(dpg)₂(THF)₂] (4), which contains an Li₂Ov 6-step ladder. Similar reaction of LiOPh afforded [Li₈(PhO)₄(dpg)₄(MeCN)₄] (5). Complexes 1–5 were screened for their potential as catalysts for ring opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL), rac-lactide (rac-LA) and δ-valerolactone (δ-VL). For ROP of ϵ-CL, conversions > 70 % were achievable at 110 °C with good control. For rac-LA and δ-VL, temperatures of at least 110 °C over 12 h were necessary for activity (conversions > 60 %). Systems employing 2 were inactiv

The effect of oxidation state on the viscosity of melts in the system Na2O-FeO-Fe2O3-SiO2

The viscosities of two melts in the system Na2O-FeO-Fe2O3-SiO2 have been measured as a function of oxidation state. The experiments were conducted by concentric-cylinder viscometry, on melts equilibrated with gas mixtures in a vertical tube, gas-mixing furnace. Viscosity determinations were made during stepwise reduction and oxidation of the melts. 57Fe Mössbauer spectra were obtained on quenched melt samples recovered during the viscometry experiments. In addition, a series of loop fusion experiments were performed at calibrated ƒO2 values in order to relate viscosity determinations directly to ƒO2. The viscosities of acmite and NS4F40 (Na-rich and Si-poor relative to acmite) melts decrease with reduction of Fe in the melts, as nonlinear functions of , yielding a region of viscosity invariance at moderate to low values of (<0.4). The 57Fe Mössbauer spectra of quenched melts as a function of indicate the presence of one (network-modifying) ferrous species and two ferric species with ferric iron acting dominantly as a network-former in oxidized melts and dominantly as a network-modifier in reduced melts. The presence of two ferric iron species produces a minimum in the degree of polymerization of the melt at intermediate values of : the region of viscosity invariance corresponds to this minimum. If viscosity is positively correlated with polymerization for all values of then the viscosity of very reduced melts will increase with reduction, as the melt polymerizes. The effect of oxidation state on viscosity is large and illustrates that ferric iron should be considered as a separate component in calculation schemes for estimating the viscosity of natural magmas

Development of covalent triazine frameworks as heterogeneous catalytic supports

Covalent triazine frameworks (CTFs) are established as an emerging class of porous organic polymers with remarkable features such as large surface area and permanent porosity, high thermal and chemical stability, and convenient functionalization that promotes great potential in heterogeneous catalysis. In this article, we systematically present the structural design of CTFs as a versatile scaffold to develop heterogeneous catalysts for a variety of chemical reactions. We mainly focus on the functionalization of CTFs, including their use for incorporating and stabilization of nanoparticles and immobilization of molecular complexes onto the frameworks

Synthesis of neutral nickel catalysts for ethylene polymerization – the influence of ligand size on catalyst stability

A facile synthesis of nickel salicylaldimine complexes with labile dissociating ligands is described. In addition to producing highly active ethylene polymerization catalysts, important insights into the effect of ligand size on catalyst stability and information on the mechanism of polymerization are provided

An infrared investigation of the catalyst formation in the system Ni(acac)2, C3H4, (iBu)3AL for propadiene polymerization

The catalyst formation in the system Ni(acac)2, C3H4, (iBu)3Al was investigated by means of infrared spectroscopy. It was found that the Al(acac)3 and (iBu)2Al(acac) formed are both by-products of catalyst formation without a catalytic activity. Ni(acac)2 loses its acac groups forming the unstable (iBu)2Ni compound; without C3H4 being present, this compound disproportionates to Ni metal and isobutane and isobutene. In the presence of C3H4 an allyl-nickel complex is formed, which reacts with (iBu)3Al to give the actual catalyst, possibly a bimetallic allyl—nickel-aluminium complex. Catalysts such as Ni(acac)2, C3H4, (iBu)3Al and (πC3H5)2Ni with or without (iBu)3Al all selectively give 1, 2, 1, 2-polypropadiene. A Lewis base like pyridine not only decreases the polymerization rate but also changes the selectivity towards the formation of 1, 2, 2, 1-polymer