Mechanical properties and chemical stability of pivalolactone-based poly(ether ester)s

The processing, mechanical and chemical properties of poly(ether ester)s, prepared from pivalolactone (PVL), 1,4-butanediol (4G) and dimethyl terephthalate (DMT), were studied. The poly(ether ester)s could easily be processed by injection moulding, owing to their favourable rheological and thermal properties. The tensile response of a poly(ether ester) with a butylene terephthalate (4GT) content of 72 mol%, which exhibited the phenomena of necking and strain-hardening, was related to the morphology of these copolymers. The influence of the short 4G-PVL segments was reflected in a high Young's modulus and yield stress, and resulted in a tough behaviour for the poly(ether ester), with an ultimate elongation of 500%. The poly(ether ester)s were stable towards treatment at room temperature with water or weakly acidic or alkaline solutions. Conditioning at 90°C in water for 264 h resulted in a water uptake of 1 wt%, whereas the rate of hydrolysis was 0.0003 (expressed in An rel h-1) for the poly(ether ester) with a 4GT content of 72 mol%. Although a decay in the mechanical properties for the PVL-based poly(ether ester) after exposure to water at 90°C was observed, these materials were assumed to have a higher hydrolytical stability than other poly(ether ester)

Investigations on vinylene carbonate, 2. Copolymerization with N-vinyl-2-pyrrolidone and ethyl vinyl ether

Functional monomers and polymers have received considerable attention in recent years, especially in the biomedical field. In this respect, poly(viny1ene carbonate) is very interesting, because the reactive carbonate groups offer the possibility of coupling with bioactive compounds containing amino groups, e. g. proteins or enzymes. Copolymerization of vinylene carbonate with other vinyl monomers will affect the amount of carbonate groups as well as other properties of the copolymers. In a previous paper we described the preparation and properties of poly(viny1ene carbonate) I), and this paper reports the copolymerization of vinylene carbonate with N-vinyl-2-pyrrolidone and with ethyl vinyl ether

Pivalolactone, 1 interchange reactions with polypivalolactone

Ester interchange, alcoholysis, and acidolysis of polypivalolactone (PPVL) were studied by melting PPVL with bisphenol diacetates, 1, 4-butanediol, or aromatic diacids. Interchange of PPVL with the diacetates and the diol occured readily, in particular in the presence of a titanium catalyst. Melting PPVL with 10 mol-% of bisphenol-Adiacetate in the presence of 0,5 wt.% tetrabutylorthotitanate resulted in an incorporation of 33% of the diacetate in the polymer chains, whereas the logarithmic viscosity number decreased by 81%. The ester interchange was suggested to proceed by an initial cleavage of ester bonds in the polymer chain of PPVL, resulting in the formation of shorter chains, followed by a reaction between the newly formed ester end-groups and initially present hydroxyl chain ends. The acidolysis of PPVL with the diacids proved to be less effective; in the case of the acidolysis of PPVL with 10 mol-% isophthalic acid, less than 1% of the diacid was incorporated in the polymer chains and a decrease in the logarithmic viscosity number of only 22% was found. Both the high stability of the ester bond in PPVL towards acids in general and the heterogeneity of these systems were supposed to cause the behaviour of PPVL with respect to acidolysis. The results concerning the interchange reactions with PPVL were compared with studies on other polyesters

Implementatie van TalentenKracht bij het universiteitsmuseum en de kinderuniversiteit

Een museumbezoek draagt iets bij aan het leerniveau van leerlingen, maar een op zichzelf staand museumbezoek heeft geen meerwaarde voor het ontwikkelen van kennis bij leerlingen. In dit artikel wordt gepoogd antwoord te krijgen op de vraag hoe de programma’s van het universiteitsmuseum en de kinderuniversiteit uitgebreid kunnen worden, met integratie van TalentenKrachtprincipes, zodat het wetenschappelijk denkproces van de leerlingen in het gehele arrangement gestimuleerd wordt. Om antwoord te kunnen krijgen op deze vraag is een beschrijvend onderzoek gedaan waarin realistische settings zijn gebruikt die bestaan uit museumbezoeken en klassikale lessen waarbij de interactie tussen de begeleiders en leerlingen zijn gemeten. De resultaten van het onderzoek laten zien dat begeleiders die kennis van TalentenKracht hebben een hoger redenatieniveau bij leerlingen uitlokken. De begeleiders die kennis van TalentenKracht hebben stellen veel open vragen aan leerlingen om wetenschappelijk redeneren bij leerlingen uit te lokken. De resultaten van een statistische analyse laten significante verschillen zien tussen de begeleiding van een begeleider die intensieve kennis van TalentenKracht heeft en begeleiders die geen kennis van TalentenKracht hebben. De begeleider die intensieve kennis van TalentenKracht heeft lokt complexere redenaties bij leerlingen ui

Pivalolactone, 3. Reactive blending of polypivalolactone with polycarbonate

The occurrence of interchange reactions during heating of polypivalolactone (PPVL) with three polymers and their influence on the blend properties were studied. Physical blends of PPVL and bisphenol-A polycarbonate (PC) were found to be immiscible. By heating of PPVL/PC blends in the melt at 280°C, in diphenyl ether at 260°C and in a twin-screw extruder (TSE) at 280°C partial formation of copolymers was observed, provided that tetrabutyl orthotitanate (TnBT) was added. After heating of equimolar PPVL/PC blends in a TSE for 15 min, a PPVL-PC block copolymer could be isolated containing 25 mol-% pivalolactone (PVL) units. The results from thermal analyses indicated that PPVL/PC blends had become more miscible, due to the presence of copolymers formed by interchange reactions. After heating of equimolar mixtures of PPVL and a polyarylate (PAr) in a TSE for 15 min, PPVL-PAr copolymers with 5 mol-% PVL units could be isolated. Probably due to this low degree of interchange, no effect on the miscibility of the initially immiscible PPVL/PAr blends could be observed. PPVL/poly(butylene terephthalate) (PBT) blends, obtained after heating in a TSE, decomposed at a temperature between the melting temperatures of PPVL and PBT, indicating that interchange reactions may have occurred

Pivalolactone, 2. Copolyester synthesis via interchange reactions with polypivalolactone

The synthesis of copolyesters via interchange reactions of polypivalolactone (PPVL) with several compounds was studied. The synthetical procedures are two-stage melt processes: in the first stage ester bonds in the polymer chain are cleaved and new groups are incorporated in the polymer chain, while in the second step condensation of the end-groups formed occurs. For the synthesis of copolymers, three procedures were used, with tetrabutyl orthotitanate as a catalyst. PPVL was heated with equimolar mixtures of bisphenol-A diacetate (BPAac) and terephthalic acid (TA), but no copolymers were formed; instead, polycondensation of BPAac with TA occurred, leaving the PPVL unaffected. From PPVL and mixtures of BPAac and dimethyl terephthalate (DMT) polymers were obtained which contained a significant amount of copolymeric sequences. However, most of the polymeric chains consisted of PPVL and poly(bisphenol-A terephthalate) blocks. Random copolymers with thermal stability were obtained after heating PPVL with bisphenol-A polycarbonate and DMT. The latter process was studied in detail by IR, DSC, and solubility and selective degradation tests. Based on the results of these studies, the reactions occurring during the three procedures were discussed

Comparing Exploration Strategies for Q-learning in Random Stochastic Mazes

Balancing the ratio between exploration and exploitation is an important problem in reinforcement learning. This paper evaluates four different exploration strategies combined with Q-learning using random stochastic mazes to investigate their performances. We will compare: UCB-1, softmax, epsilon-greedy, and pursuit. For this purpose we adapted the UCB-1 and pursuit strategies to be used in the Q-learning algorithm. The mazes consist of a single optimal goal state and two suboptimal goal states that lie closer to the starting position of the agent, which makes efficient exploration an important part of the learning agent. Furthermore, we evaluate two different kinds of reward functions, a normalized one with rewards between 0 and 1, and an unnormalized reward function that penalizes the agent for each step with a negative reward. We have performed an extensive grid-search to find the best parameters for each method and used the best parameters on novel randomly generated maze problems of different sizes. The results show that softmax exploration outperforms the other strategies, although it is harder to tune its temperature parameter. The worst performing exploration strategy is epsilon-greedy