Propene-cycloolefin polymerization

Highly active metallocenes and other single site catalysts have opened up the possibility of polymerizing cycloolefins such as norbornene (N) or of copolymerizing them with ethene (E) or propene (P). The polymers obtained show exciting structures and properties. E-N copolymers are industrially produced materials, with variable and high glass transitions depending on the wide range of their microstructures. By realizing the possibility in great variety of stereoregularity of propene and norbornene units and the difference in comonomer distribution, P-N copolymers were expected to have fine tuned microstructures and properties. Moreover, P-N copolymers should be characterized by higher Tg-values than E-N copolymers with the same norbornene content and molar mass. A review of the state of the art of P-N copolymerization by ansa-metallocenes of C2 symmetry, namely rac-Et(Ind)2ZrCl2 (I-I) and rac-Me2Si(Ind)2ZrCl2 (I-II), and rac-Me2Si(2-Me-Ind)2ZrCl2 (I-III), and of catalysts of Cssymmetry, namely (tBuNSiMe2Flu)TiMe2 (IV-I) and derivatives, is given here. Special emphasis is given to microstructural studies of P-N copolymers, including stereo- and regioregularity of propene units as well as of comonomer distribution, stereoregularity of norbornene units, and the structure of chain end-groups. This information allows us to find a rationale for the catalytic activities and the copolymer properties

Synthesis of ethylene–norbornene–1-octene terpolymers with high 1-octene contents, molar masses, and tunable Tg values, in high yields using half-titanocene catalysts

Synthesis of unique poly(E-ter–N-ter–O)s using half-titanocene catalysts: 1-octene does not behave as a chain termination/transfer agent unlike ansa-metallocenes

Моделирование лондонского текста в повести Е. И. Замятина "Островитяне"

Статья посвящена анализу лондонского текста русской культуры первой половины ХХ в. на материале повести Е. И. Замятина "Островитяне". Впервые образ города рассматривается сквозь призму модернистской поэтики. Лондон как центр научного, рационалистического метода познания становится воплощением идеологии модернизма. Это дает возможность говорить о многоуровневой структуре восприятия города в рамках русской ментальности. В статье показывается, как образ столицы западной цивилизации усваивается русским сознанием и включается в общерусский литературный и культурный контекст

Осуществление налогового планирования на различных этапах деятельности предприятия

Проанализированы основные условия реализации налогового планирования на разных стадиях жизненного цикла хозяйствующего субъекта. Показана возможность влияния налогов на принятие предпринимательских и управленческих решений внутри предприятия

Phase error estimation for synthetic aperture imagery.

The estimation of phase errors in synthetic aperture imagery is important for high quality images. Many methods of autofocus, or the estimation of phase errors from the measured data, are developed using certain assumptions about the imaged scene. This thesis develops improved methods of phase estimation which make full use of the information in the recorded signal. This results in both a more accurate estimate of the image phase error and improved imagery compared to using standard techniques. The standard phase estimation kernel used in echo-correlation techniques is shear-average. This technique averages the phase-difference between each ping over all range-bins, weighted by the signal strength. It is shown in this thesis that this is not the optimal method of weighting each phase estimate. In images where the signal to clutter ratio (SCR) is not proportional to the signal amplitude, shear-average does not meet the predicted error bound. This condition may be met by many image types, including those with shadows, distributed targets and varying surface structure. By measuring the average coherence between echos at each range-bin, it is possible to accurately estimate the variance of each phase estimate, and weight accordingly. A weighted phase-difference estimation (WPDE) using this coherence weighting meets the performance bound for all images tested. Thus an improved performance over shear-average is shown for many image types. The WPDE phase estimation method can be used within the framework of many echo-correlation techniques, such as phase-gradient autofocus (PGA), phase curvature estimation, redundant phase-centre or displaced phase-centre algorithms. In addition, a direct centre-shifting method is developed which reduces bias compared to the centre-shifting method used in PGA. For stripmap images, a weighted phase curvature estimator shows better performance than amplitude weighted shear-average for images with high SCR. A different method of phase estimation, known as sharpness maximisation, perturbs an estimate of the phase error to maximise the sharpness of the reconstructed image. Several improvements are made to the technique of sharpness maximisation. These include the reduction of over-sharpening using regularisation and an improvement in accuracy of the phase estimate using range-weighting based on the coherence measure. A cascaded parametric optimisation method is developed which converges significantly faster than standard optimisation methods for stripmap images. A number of novel insights into the method of sharpness maximisation are presented. A derivation of the phase that gives maximum intensity squared sharpness is extended from a noncoherent imaging system to a coherent spotlight system. A bound on the performance of sharpness-maximisation is presented. A method is developed which allows the direct calculation of the result of a sharpness maximisation for a single ping of a spotlight synthetic aperture image. The phase correction that maximises sharpness can be directly calculated from the signal in a manner similar to a high-order echo-correlation. This calculation can be made for all pings in a recursive manner. No optimisation is required, resulting in a significantly faster phase estimation. The techniques of sharpness maximisation and echo-correlation can be shown to be closely related. This is confirmed by direct comparisons of the results. However, the classical intensity-squared sharpness measure gives poorer results than WPDE and different sharpness measures tested for a distributed target. The standard methods of shear average and maximisation of the intensity-squared sharpness measure, both perform well below the theoretical performance bound. Two of the techniques developed, WPDE and direct entropy minimisation perform at the bound, showing improved performance over standard techniques. The contributions of this thesis add considerably to the body of knowledge on the technique of sharpness maximisation. This allows an improvement in the accuracy of some phase estimation methods, as well as an increase in the understanding of how these techniques work on coherent imagery in general

Upgrading Sustainable Polyurethane Foam Based on Greener Polyols: Succinic-Based Polyol and Mannich-Based Polyol

It is well known that the traditional synthetic polymers, such as Polyurethane foams, require raw materials that are not fully sustainable and are based on oil-feedstocks. For this reason, renewable resources such as biomass, polysaccharides and proteins are still recognized as one of the most promising approaches for substituting oil-based raw materials (mainly polyols). However, polyurethanes from renewable sources exhibit poor physical and functional performances. For this reason, the best technological solution is the production of polyurethane materials obtained through a partial replacement of the oil-based polyurethane precursors. This approach enables a good balance between the need to improve the sustainability of the polymer and the need to achieve suitable performances, to fulfill the technological requirements for specific applications. In this paper, a succinic-based polyol sample (obtained from biomass source) was synthesized, characterized and blended with cardanol-based polyol (Mannich-based polyol) to produce sustainable rigid polyurethane foams in which the oil-based polyol is totally replaced. A suitable amount of catalysts and surfactant, water as blowing reagent and poly-methylene diphenyl di-isocyanate as isocyanate source were used for the polyurethane synthesis. The resulting foams were characterized by means of infrared spectroscopy (FTIR) to control the cross-linking reactions, scanning electron microscopy (SEM) to evaluate the morphological structure and thermal gravimetric analysis (TGA) and thermal conductivity to evaluate thermal degradation behavior and thermal insulation properties

Greener Nanocomposite Polyurethane Foam Based on Sustainable Polyol and Natural Fillers: Investigation of Chemico-Physical and Mechanical Properties

Nowadays, the chemical industry is looking for sustainable chemicals to synthesize nanocomposite bio-based polyurethane foams, PUs, with the aim to replace the conventional petrochemical precursors. Some possibilities to increase the environmental sustainability in the synthesis of nanocomposite PUs include the use of chemicals and additives derived from renewable sources (such as vegetable oils or biomass wastes), which comprise increasingly wider base raw materials. Generally, sustainable PUs exhibit chemico-physical, mechanical and functional properties, which are not comparable with those of PUs produced from petrochemical precursors. In order to enhance the performances, as well as the bio-based aspect, the addition in the polyurethane formulation of renewable or natural fillers can be considered. Among these, walnut shells and cellulose are very popular wood-based waste, and due to their chemical composition, carbohydrate, protein and/or fatty acid, can be used as reactive fillers in the synthesis of Pus. Diatomite, as a natural inorganic nanoporous filler, can also be evaluated to improve mechanical and thermal insulation properties of rigid PUs. In this respect, sustainable nanocomposite rigid PU foams are synthesized by using a cardanol-based Mannich polyol, MDI (Methylene diphenyl isocyanate) as an isocyanate source, catalysts and surfactant to regulate the polymerization and blowing reactions, H2O as a sustainable blowing agent and a suitable amount (5 wt%) of ultramilled walnut shell, cellulose and diatomite as filler. The effect of these fillers on the chemico-physical, morphological, mechanical and functional performances on PU foams has been analyze

The physiological linkage between molar inclination and dental macrowear pattern

Objectives: Exact symmetry and perfect balance between opposite jaw halves, as well as between antagonistic teeth, is not frequently observed in natural masticatory systems. Research results show that asymmetry in our body, skull, and jaws is often related to genetic, epigenetic, environmental and individual ontogenetic factors. Our study aims to provide evidence for a significant link between masticatory asymmetry and occlusal contact between antagonist teeth by testing the hypothesis that tooth inclination is one of the mechanisms driving distribution of wear in masticatory phases in addition to dietary and cultural habits. Materials and Methods: The present work investigates the relationship between dental macrowear patterns and tooth inclinations on a sample of complete maxillary and mandibular 3D models of dental arches from 19 young and adult Yuendumu Aboriginal individuals. The analysis was carried out on first molars (M1) from all quadrants. Occlusal Fingerprint Analysis was used for the quantification of macrowear patterns, and 2D cross-sectional geometric analysis was carried out to investigate asymmetry in dental arches. Results: The asymmetry is highly variable on both arches, and it is associated with differences in the inclination of upper M1 crowns. Each molar has variable inclination (buccal/lingual) which influence tooth to tooth contact, producing greater or lesser variation in wear pattern. Interindividual variability of morphological variation of the occlusal relationship has to be considered in macrowear analysis. Discussion: Our results suggest that overall asymmetry in the masticatory apparatus in modern humans affects occlusal contact areas between antagonist teeth influencing macrowear and chewing efficiency during ontogeny

Terpolymerization of Substituted Cycloolefin with Ethylene and Norbornene by Transition Metal Catalyst

Ethylene-norbornene terpolymerization experiments using 5-alkyl-substituted norbornenes (5-pentyl-2-norbornene (C5N) and 5-octyl-2-norbornene (C8N)) or dicyclopentadiene (DCPD) were conducted with two ansa-metallocenes, [Zr{(η5-C9H6)2C2H4}Cl2] (1) and [Zr{(η5-2,5-Me2C5H2)2CHEt}Cl2] (2), activated by methylaluminoxane (MAO). The terpolymers obtained were investigated in detail by determining the microstructure and termonomer contents by 13C NMR, molar masses and thermal properties. Results were compared to those of ethylene (E)-norbornene (N) terpolymerizations with 1-octene. 2, with lower steric hindrance and a shorter bridge, gave the best activities, termonomer incorporation and molar masses. The size of the substituent in 5-alkyl substituted norbornene also plays a role. C8N gives the highest activities and molar masses, while DCPD terpolymers have the highest cycloolefin content. Terpolymers are random; their molar masses, much higher than those in 1-octene terpolymers, are in a range useful for industrial applications. Finally, Tg values up to 152 °C were obtained. For similar N content, poly(E-ter-N-ter-C8N)s and poly(E-ter-N-ter-DCPD)s have the lowest and the highest Tg values, respectively. Thus, the presence of an eight-carbon atom pendant chain in C8N increases the flexibility of the polymer chain more than a five-carbon atom pendant chain in C5N. The higher rigidity of C5N may lead to lower activities and to increasing probability of σ-bond metathesis and chain termination, as evidenced by chain-end group analysis

Microstructure of Copolymers of Norbornene Based on Assignments of 13C NMR Spectra: Evolution of a Methodology

An overview of the methodologies to elucidate the microstructure of copolymers of ethylene and cyclic olefins through 13C Nuclear magnetic resonance (NMR) analysis is given. 13C NMR spectra of these copolymers are quite complex because of the presence of stereogenic carbons in the monomer unit and of the fact that chemical shifts of these copolymers do not obey straightforward additive rules. We illustrate how it is possible to assign 13C NMR spectra of cyclic olefin-based copolymers by selecting the proper tools, which include synthesis of copolymers with different comonomer content and by catalysts with different symmetries, the use of one- or two-dimensional NMR techniques. The consideration of conformational characteristics of copolymer chain, as well as the exploitation of all the peak areas of the spectra by accounting for the stoichoimetric requirements of the copolymer chain and the best fitting of a set of linear equation was obtained. The examples presented include the assignments of the complex spectra of poly(ethylene-co-norbornene (E-co-N), poly(propylene-co-norbornene (P-co-N) copolymers, poly(ethylene-co-4-Me-cyclohexane)s, poly(ethylene-co-1-Me-cyclopentane)s, and poly(E-ter-N-ter-1,4-hexadiene) and the elucidation of their microstructures