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  • 1
    Publication Date: 2020-12-11
    Description: Convexity is an important property in nonlinear optimization since it allows to apply efficient local methods for finding global solutions. We propose to apply symbolic methods to prove or disprove convexity of rational functions over a polyhedral domain. Our algorithms reduce convexity questions to real quantifier elimination problems. Our methods are implemented and publicly available in the open source computer algebra system REDUCE. Our long term goal is to integrate REDUCE as a workhorse'' for symbolic computations into a numerical solver.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 2
    Publication Date: 2016-06-30
    Description: Applications which need exclusive access to a shared resource in distributed systems require a fault-tolerant and scalable mechanism to coordinate this exclusive access. Examples of such applications include distributed file systems and master/slave data replication. We present Flease, an algorithm for decentralized and fault-tolerant lease coordination in distributed systems. Our algorithm allows the processes competing for a resource to coordinate exclusive access through leases among themselves without a central component. The resulting system easily scales with an increasing number of nodes and resources. We prove that Flease ensures exclusive access, i.e. guarantees that there is at most one valid lease at any time.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 3
    Publication Date: 2020-08-05
    Description: We propose an efficient column generation method to minimize the probability of delay propagations along aircraft rotations. In this way, delay resistant schedules can be constructed. Computational results for large-scale real-world problems demonstrate substantial punctuality improvements. The method can be generalized to crew and integrated scheduling problems.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 4
    Publication Date: 2022-01-07
    Description: In optimal control problems with nonlinear time-dependent 3D PDEs, full 4D discretizations are usually prohibitive due to the storage requirement. For this reason gradient and quasi-Newton methods working on the reduced functional are often employed. The computation of the reduced gradient requires one solve of the state equation forward in time, and one backward solve of the adjoint equation. The state enters into the adjoint equation, again requiring the storage of a full 4D data set. We propose a lossy compression algorithm using an inexact but cheap predictor for the state data, with additional entropy coding of prediction errors. As the data is used inside a discretized, iterative algorithm, lossy coding maintaining an error bound is sufficient.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 5
    Publication Date: 2020-03-11
    Description: Bovine fertility is the subject of extensive research in animal sciences, especially because fertility of dairy cows has declined during the last decades. The regulation of estrus is controlled by the complex interplay of various organs and hormones. Mathematical modeling of the bovine estrous cycle could help in understanding the dynamics of this complex biological system. In this paper we present a mathematical model of the bovine estrous cycle that includes the processes of follicle and corpus luteum development and the key hormones that interact to control these processes. Focus in this paper is on development of the model, but also some simulation results are presented, showing that a set of equations and parameters is obtained that describes the system consistent with empirical knowledge. Even though the majority of the mechanisms that are included are only known qualitatively as stimulatory or inhibitory effects, the model surprisingly well features quantitative observations made in reality. This model of the bovine estrous cycle could be used as a basis for more elaborate models with the ability to study effects of external manipulations and genetic differences.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 6
    Publication Date: 2022-03-14
    Description: Learning during search allows solvers for discrete optimization problems to remember parts of the search that they have already performed and avoid revisiting redundant parts. Learning approaches pioneered by the SAT and CP communities have been successfully incorporated into the SCIP constraint integer programming platform. In this paper we show that performing a heuristic constraint programming search during root node processing of a binary program can rapidly learn useful nogoods, bound changes, primal solutions, and branching statistics that improve the remaining IP search.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 7
    Publication Date: 2020-08-05
    Description: We propose a novel integer programming approach to transfer minimization for line planning problems in public transit. The idea is to incorporate penalties for transfers that are induced by “connection capacities” into the construction of the passenger paths. We show that such penalties can be dealt with by a combination of shortest and constrained shortest path algorithms such that the pricing problem for passenger paths can be solved efficiently. Connection capacity penalties (under)estimate the true transfer times. This error is, however, not a problem in practice. We show in a computational comparison with two standard models on a real-world scenario that our approach can be used to minimize passenger travel and transfer times for large-scale line planning problems with accurate results.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 8
    Publication Date: 2016-06-09
    Description: The aim of this paper is to devise an adaptive timestep control in the contact--stabilized Newmark method (CONTACX) for dynamical contact problems between two viscoelastic bodies in the framework of Signorini's condition. In order to construct a comparative scheme of higher order accuracy, we extend extrapolation techniques. This approach demands a subtle theoretical investigation of an asymptotic error expansion of the contact--stabilized Newmark scheme. On the basis of theoretical insight and numerical observations, we suggest an error estimator and a timestep selection which also cover the presence of contact. Finally, we give a numerical example.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 9
    Publication Date: 2020-08-05
    Description: Railway scheduling is based on the principle of the construction of a conflict-free timetable. This leads to a strict definition of capacity: in contrast with road transportation, it can be said in advance whether a given railway infrastructure can accommodate - at least in theory - a certain set of train requests. Consequently, auctions for railway capacity are modeled as auctions of discrete goods -- the train slots. We present estimates for the efficiency gain that may be generated by slot auctioning in comparison with list price allocation. We introduce a new class of allocation and auction problems, the feasible assignment problem, that is a proper generalization of the well-known combinatorial auction problem. The feasible assignment class was designed to cover the needs for an auction mechanism for railway slot auctions, but is of interest in its own right. As a practical instance to state and solve the railway slot allocation problem, we present an integer programming formulation, briefly the ACP, which turns out to be an instance of the feasible assignment problem and whose dual problem yields prices that can be applied to define a useful activity rule for the linearized version of the Ausubel Milgrom Proxy auction. We perform a simulation aiming to measure the impact on efficiency and convergence rate.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 10
    Publication Date: 2022-01-07
    Description: This paper presents concepts and implementation of the finite element toolbox Kaskade 7, a flexible C++ code for solving elliptic and parabolic PDE systems. Issues such as problem formulation, assembly and adaptivity are discussed at the example of optimal control problems. Trajectory compression for parabolic optimization problems is considered as a case study.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 11
    Publication Date: 2020-08-05
    Description: In this paper a bottom-up approach of automatic simplification of a railway network is presented. Starting from a very detailed, microscopic level, as it is used in railway simulation, the network is transformed by an algorithm to a less detailed level (macroscopic network), that is sufficient for long-term planning and optimization. In addition running and headway times are rounded to a pre-chosen time discretization by a special cumulative method, which we will present and analyse in this paper. After the transformation we fill the network with given train requests to compute an optimal slot allocation. Then the optimized schedule is re-transformed into the microscopic level and can be simulated without any conflicts occuring between the slots. The algorithm is used to transform the network of the very dense Simplon corridor between Swiss and Italy. With our aggregation it is possible for the first time to generate a profit maximal and conflict free timetable for the corridor across a day by a simultaneously optimization run.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 12
    Publication Date: 2020-12-11
    Description: In solving large polynomial algebraic systems that are too big for standard Gröbner basis techniques one way to make progress is to introduce case distinctions. This divide and conquer technique can be beneficial if the algorithms and computer programs know how to take advantage of inequalities. A further hurdle is the form of the resulting general solutions which often have unnecessarily many branches. In this paper we discuss a procedure to merge solutions by dropping inequalities which are associated with them and, if necessary, by re-parametrizing solutions. In the appendix the usefulness of the procedure is demonstrated in the classification of quadratic Hamiltonians with a Lie-Poisson bracket $e(3)$. This application required the solution of algebraic systems with over 200 unknowns, 450 equations and between 5000 and 9000 terms.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 13
    Publication Date: 2020-12-11
    Description: In the paper arguments are given why the concept of static evaluation (SE) has the potential to be a useful extension to Monte Carlo tree search. A new concept of modeling SE through a dynamical system is introduced and strengths and weaknesses are discussed. The general suitability of this approach is demonstrated. A Remark: Among users of the Internet Go server KGS the abbreviation SE is used for 'Score Estimator'. Although different from 'Static Evaluation' a score estimator is easily obtained from static evaluation by adding up probabilities of chains to be alive at the end of the game or points to be owned by White or Black
    Keywords: ddc:510
    Language: English
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  • 14
    Publication Date: 2020-12-11
    Description: Linear Poisson brackets on e(3) typical of rigid body dynamics are considered. All quadratic Hamiltonians of Kowalevski type having additional first integral of fourth degree are found. Quantum analogs of these Hamiltonians are listed.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 15
    Publication Date: 2020-12-11
    Description: A classification problem is proposed for supersymmetric %scaling\/-\/in\-va\-ri\-ant evolutionary PDE that satisfy the assumptions of nonlinearity, nondegeneracy, and homogeneity. Four classes of nonlinear coupled boson\/-\/fermion systems are discovered under the weighting assumption $|f|=|b|=|D_t|=\oh$. The syntax of the \Reduce\ package \SsTools, which was used for intermediate computations, and the applicability of its procedures to the calculus of super\/-\/PDE are described.
    Keywords: ddc:510
    Language: English
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  • 16
    Publication Date: 2020-12-11
    Description: We consider the problem of constructing Gardner's deformations for the $N{=}2$ supersymmetric $a{=}4$--\/Korteweg\/--\/de Vries equation; such deformations yield recurrence relations between the super\/-\/Hamiltonians of the hierarchy. We prove the non\/-\/existence %P.~Mathieu's Open problem on constructing for of supersymmetry\/-\/invariant %Gardner's deformations that %solutions, retract to Gardner's formulas for the KdV equation %whenever it is assumed that, under the %respective component reduction. % in the $N{=}2$ super\/-\/field. the solutions . At the same time, we propose a two\/-\/step scheme for the recursive production of the integrals of motion for the $N{=}2$,\ $a{=}4$--\/SKdV. First, we find a new Gardner's deformation of the Kaup\/--\/Boussinesq equation, which is contained in the bosonic limit of the super\/-\/%$N{=}2$,\ $a{=}4$--\/SKdV hierarchy. This yields the recurrence relation between the Hamiltonians of the limit, whence we determine the bosonic super\/- /Hamiltonians of the full $N{=}2$, $a{=}4$--\/SKdV hierarchy.
    Keywords: ddc:510
    Language: English
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  • 17
    Publication Date: 2020-08-05
    Description: We provide an introduction into the mathematics of and with paths. Not on the shortest, but hopefully on an entertaining path!
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 18
    Publication Date: 2020-08-05
    Description: Wir stellen in dieser Arbeit ein mathematisches Optimierungsmodell zur Bestimmung eines optimalen Linienplans vor, das sowohl die Fahrzeiten und die Anzahl der Umstiege berücksichtigt als auch die Kosten des Liniennetzes. Dieses Modell deckt wichtige praktische Anforderungen ab, die in einem gemeinsamen Projekt mit den Verkehrsbetrieben in Potsdam (ViP) formuliert wurden. In diesem Projekt wurde der Linienplan 2010 für Potsdam entwickelt. Unsere Berechnungen zeigen, dass die mathematische Optimierung in nichts einer "Handplanung" des Liniennetzes nachsteht. Im Gegenteil, mit Hilfe des Optimierungsprogramms ist es möglich, durch Veränderung der Parameter mehrere verschiedene Szenarien zu berechnen, miteinander zu vergleichen und Aussagen über minimale Kosten und Fahrzeiten zu machen.
    Keywords: ddc:510
    Language: German
    Type: reportzib , doc-type:preprint
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  • 19
    Publication Date: 2020-12-11
    Description: The paper gathers evidence showing different dimensions of the game of Go: the continuous and discrete nature of the game and different types of relations between state variables happening on ultra local, local, regional, and global scales. Based on these observations a new continuous local model for describing a board position is introduced. This includes the identification of the basic variables describing a board position and the formulation and solution of a dynamical system for their computation. To be usable as a static evaluation function for a game playing program at least group-wide (regional)aspects will have to be incorporated.
    Keywords: ddc:510
    Language: English
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  • 20
    Publication Date: 2020-08-05
    Description: The track allocation problem, also known as train routing problem or train timetabling problem, is to find a conflict-free set of train routes of maximum value in a railway network. Although it can be modeled as a standard path packing problem, instances of sizes relevant for real-world railway applications could not be solved up to now. We propose a rapid branching column generation approach that integrates the solution of the LP relaxation of a path coupling formulation of the problem with a special rounding heuristic. The approach is based on and exploits special properties of the bundle method for the approximate solution of convex piecewise linear functions. Computational results for difficult instances of the benchmark library TTPLIB are reported.
    Keywords: ddc:510
    Language: English
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  • 21
    Publication Date: 2020-08-05
    Description: This paper presents a case study on a railway timetable optimization for the very dense Simplon corridor, a major railway connection in the Alps between Switzerland and Italy. Starting from a detailed microscopic network as it is used in railway simulation, the data is transformed by an automatic procedure to a less detailed macroscopic network, that is sufficient for the purpose of capacity planning and amenable to state-of-the-art integer programming optimization methods. In this way, the macroscopic railway network is saturated with trains. Finally, the corresponding timetable is re-transformed to the microscopic level in such a way that it can be operated without any conflicts among the slots. Using this integer programming based micro-macro aggregation-disaggregation approach, it becomes for the first time possible to generate a profit maximal and conflict free timetable for the complete Simplon corridor over an entire day by a simultaneous optimization of all trains requests. This also allows to to undertake a sensitivity analysis of various problem parameters.
    Keywords: ddc:510
    Language: English
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  • 22
    Publication Date: 2016-06-09
    Description: The thesis presents the analysis of a reduced model for modulation of internal gravity waves by deep convective clouds. The starting point for the derivation are conservation laws for mass, momentum and energy coupled with a bulk micro-physics model describing the evolution of mixing ratios of water vapor, cloud water and rain water. A reduced model for the identified scales of the regime is derived, using multi-scale asymptotics. The closure of the model employs conditional averaging over the horizontal scale of the convective clouds. The resulting reduced model is an extension of the anelastic equations, linearized around a constant background state, which are well-known from meteorology. The closure of the model is achieved purely by analytical means and involves no additional physically motivated assumptions. The essential new parameter arising from the coupling to a micro-physics model is the area fraction of saturated regions on the horizontal scale of the convective clouds. It turns out that this parameter is constant on the employed short timescale. Hence the clouds constitute a constant background, modulating the characteristics of propagation of internal waves. The model is then investigated by analytical as well as numerical means. Important results are, among others, that in the model moisture (i) inhibits propagation of internal waves by reducing the modulus of the group velocity, (ii) reduces the angle between the propagation direction of a wave-packet and the horizontal, (iii) causes critical layers and (iv) introduces a maximum horizontal wavelength beyond which waves are no longer propagating but become evanescent. The investigated examples of orographically generated gravity waves also feature a significant reduction of vertical momentum flux by moisture. The model is extended by assuming systematically small under-saturation, that is saturation at leading order. The closure is similar to the original case but requires additional assumptions. The saturated area fraction in the obtained model is no longer constant but now depends nonlinearly on vertical displacement and thus on vertical velocity.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 23
    Publication Date: 2022-03-14
    Description: We propose a hybrid approach for solving the resource-constrained project scheduling problem which is an extremely hard to solve combinatorial optimization problem of practical relevance. Jobs have to be scheduled on (renewable) resources subject to precedence constraints such that the resource capacities are never exceeded and the latest completion time of all jobs is minimized. The problem has challenged researchers from different communities, such as integer programming (IP), constraint programming (CP), and satisfiability testing (SAT). Still, there are instances with 60 jobs which have not been solved for many years. The currently best known approach, lazyFD, is a hybrid between CP and SAT techniques. In this paper we propose an even stronger hybridization by integrating all the three areas, IP, CP, and SAT, into a single branch-and-bound scheme. We show that lower bounds from the linear relaxation of the IP formulation and conflict analysis are key ingredients for pruning the search tree. First computational experiments show very promising results. For five instances of the well-known PSPLIB we report an improvement of lower bounds. Our implementation is generic, thus it can be potentially applied to similar problems as well.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 24
    Publication Date: 2023-11-03
    Description: In contrast to the well known meshbased methods like the finite element method, meshfree methods do not rely on a mesh. However besides their great applicability, meshfree methods are rather time consuming. Thus, it seems favorable to combine both methods, by using meshfree methods only in a small part of the domain, where a mesh is disadvantageous, and a meshbased method for the rest of the domain. We motivate, that this coupling between the two simulation techniques can be considered as saddle point problem and show the stability of this coupling. Thereby a novel transfer operator is introduced, which interacts in the transition zone, where both methods coexist.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    European food research and technology 209 (1999), S. 389-392 
    ISSN: 1438-2385
    Keywords: Key words Gelation ; Polymerization ; Whey proteins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  The influence of protein concentration on the properties of gels obtained by a two-stage heating process was determined. In the first stage, whey protein dispersion (3–10%) was heated at pH 8.0, and in the second stage it was diluted to 3% protein, adjusted to pH 7.0 and heated again. Increased protein concentration in the first stage of polymerization resulted in the gels obtained in the second stage having a lower phase angle, increased storage modulus and increased hardness. Increased protein concentration also resulted in gels with an increased optical density, which suggests thathigher protein concentration leads to more and larger aggregates. Gels obtained from dispersions preheated at a higher protein concentration had higher permeability coefficient (B gel) values. The increase in B gel suggests that the higher protein concentration increased the size of the aggregates, which in a second stage of heating formed a gel matrix with a larger pore size.
    Type of Medium: Electronic Resource
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  • 26
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 102 (1999), S. 285-292 
    ISSN: 1432-2234
    Keywords: Key words: Ethylene insertion ; ab initio MO calculations ; Sm complexes ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract. Ethylene insertion into the Sm–C bond of H2SiCp2SmCH3, a model reaction of an olefin polymerization propagation step, has been studied by ab initio molecular orbital methods. The small electronegativity of the Sm atom makes the Sm–C bond ionic, the methyl group being negatively charged by −0.75. The reaction passes through a loose ethylene complex with a binding energy of 15 kcal/mol and then a tight four-centered transition state with an agostic interaction between the Sm atom and one of the methyl CH bonds. A small activation energy of 14 kcal/mol is required to pass through this transition state, indicating that this is an easy reaction. Compared with the reactions with group 4 cationic silylene-bridged metallocenes the activation energy is higher and the reaction is less exothermic. The origin of these differences is discussed. The results of molecular mechanics calculations on regio- and stereoselectivities in the insertion reaction of propylene are also reported.
    Type of Medium: Electronic Resource
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  • 27
    ISSN: 1611-4663
    Keywords: Coriolus versicolor ; Na2SO3-HCHO-AQ pulping effluent ; Polymerization ; Lignosulfonate ; Laccase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A strain of the fungusCoriolus versicolor was inoculated periodically into potato dextrose agar (PDA) slants containing the effluent to enhance the natural ability to grow in the effluent. The acclimated strain grown in the 50% effluent-containing PDA slant and the original strain were employed to treat the effluent. The acclimated strain could grow in a higher concentration of the effluent than the original unacclimated one. Both the original and acclimated strains improved the dispersing ability of the effluent, especially the acclimated strain because of its higher laccase secretion. The dispersing ability of the SFP effluent was improved to a level comparable to a commercial lignosulfonate product because it was strongly polymerized by the fungus. During the fungal treatment, more than 50% of the sugars were removed from the effluent, thereby increasing the purity of the SFP lignin product.
    Type of Medium: Electronic Resource
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  • 28
    ISSN: 1435-1536
    Keywords: Key words Reaction kinetics in microgravity ; Colloidal silica spheres ; Polymerization ; Transmitted-light intensity ; Dynamic light scattering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Polymerization reactions of colloidal silica spheres via the hydrolysis and dehydration processes of tetraethyl orthosilicate with ammonia and a tiny amount of water in ethyl alcohol have been studied in microgravity by the parabolic flights of a MU-300 rear-jet aircraft. Induction periods and polymerization rates are determined by fast-scanning transmitted-light-intensity measurements and the fast-scanning dynamic light-scattering method. Direct observation of the reaction mixtures is also made with a charge-coupled device video camera. Reproducible and reliable data are obtained in microgravity compared with those in gravity. Increases in the induction times and decreases in the polymerization rates are observed in microgravity compared with those in gravity. One of the main reasons for these observations is the fact that the translational Brownian movement of the reactants and/or product spheres is free from downward translational movement in microgravity. Very weak convection of the reaction suspensions in microgravity is another important factor.
    Type of Medium: Electronic Resource
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  • 29
    ISSN: 1435-1536
    Keywords: Key words Allyldimethyldodecylammonium bromide ; Liquid crystals ; Polymerization ; Polymerizable surfactant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Allyldimethyldodecylammonium bromide was polymerized by γ-ray irradiation in both hexagonal and cubic mesophases, and the conversion–time curves were obtained. The maximum conversion was about 35%, and the polymer remained in the liquid-crystalline structure formed by the nonpolymerized monomers. The influence of polymerization on the distribution of water in the different types related to the hydrophilic surfaces of microstructures was studied using Fourier transform infrared spectroscopy. The incomplete polymerization was explained by steric constraints in the liquid-crystalline structures.
    Type of Medium: Electronic Resource
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  • 30
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 277 (1999), S. 203-209 
    ISSN: 1435-1536
    Keywords: Key words Microemulsions ; Vinylacetate ; Acrylic acid structure ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The composition ranges over which microemulsions are formed in systems containing vinyl acetate, acrylic acid, water with nonylphenol ethoxylated with 25 mol ethylene oxide monomaleate as surfactant were studied. Conductometric and refractometric investigations have shown the existence of some aqueous/organic, bicontinuous and organic/aqueous microemulsions. The types of precursor microemulsions influence the conversion of monomers. In the presence of a crosslinking agent, diethylene glycol bis maleate, hydrogels are formed whose water absorption depends on the composition of the initial microemulsions. The kinetics of water absorption suggests the modification of polymer network structures as a function of the crosslinked monomer content and the ratio of organic to aqueous phases.
    Type of Medium: Electronic Resource
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  • 31
    ISSN: 1572-8935
    Keywords: Anionic ; Polymerization ; Hydrogenation ; Head-to-head ; 2,3-Dimethyl-1,3-butadiene ; Polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Poly(2,3-Dimethyl-1,3-butadiene) (PDMB) with varying contents of 1,4-and 1,2-structures has been anionically synthesized using either n-butyllithium or sec-butyllithium as an initiator. The addition of tetrahydrofuran could enhance the rate of synthesis and effect the microstructure. The Tm was higher for PDMB with a lower content of 1,2-structure, and the Tg was lower. This PDMB was then hydrogenated with a nickelocene/n-butyllithium catalyst system leading to the formation of HPDMB. The trans 1,4-structure unit was more difficult to hydrogenate due to its steric hindrance. Repetitive hydrogenation was necessary in order to achieve a high degree of hydrogenation. The hydrogenated PDMB is an amorphous elastomeric material. The Tg’s were found to decrease with an increase in the degree of hydrogenation, concurrent with a gradual disappearance of the Tm’s. Since a HPDMS with a low content of 1,2-structure resembles a head-to-head polypropylene, our data suggest that the Tg of an atactic head-to-head polypropylene lie between −30 and −35 °C.
    Type of Medium: Electronic Resource
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  • 32
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 47 (1998), S. 470-474 
    ISSN: 1612-1112
    Keywords: Affinity chromatography ; Polymerization ; Imprinted polymer networks ; Colloid ; Silica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The article covers the methods that are currently available for the preparation of molecularly imprinted polymers. The disadvantages of the conventional grinding of bulk polymerized blocks of imprinted polymer are first identified. The newer methods are divided into four sections: suspension polymerization; modified surfaces; polymer colloids and finally miscellaneous techniques such as the use of linear polymers. Each alternative method is compared with the grinding method and the relative advantages and disadvantages identified.
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  • 33
    Publication Date: 2016-06-09
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
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  • 34
    Electronic Resource
    Electronic Resource
    Springer
    Sexual plant reproduction 10 (1997), S. 136-141 
    ISSN: 1432-2145
    Keywords: Key words Ginkgo biloba L. ; Tubulin ; Purification ; Polymerization ; Pollen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Tubulin was purified by a combination of acetone powder preparation, DEAE Sephadex A-50 chromatography, Sephacryl S-300 gel filtration, and Mono Q anion exchange chromatography from the pollen of ginkgo (Ginkgo biloba L.), a typical gymnosperm. The average yield of tubulin is 2 mg per 100 g of pollen grain. The purified tubulin is electrophoretically homogeneous. It seems to be composed of two subunits on SDS-PAGE and is resolved as two major spots on two-dimensional electrophoresis, preliminarily indicating that there are no obvious tubulin isotypes in ginkgo pollen. The apparent molecular weights of the two subunits are about 54 kDa and 52 kDa respectively, estimated from the SDS-PAGE. It was also demonstrated that tubulin from ginkgo pollen is immunochemically related to animal brain tubulin, and the purified tubulin was polymerized to microtubular aggregates in the presence of taxol and GTP in vitro.
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  • 35
    ISSN: 1432-1017
    Keywords: Key words Diacetylenic lipids ; Polymerization ; Microfluorescence ; Filmbalance ; AFM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Molecular films from polymeric materials play an important role in basic research as well as in technology. We have synthesized the double chain diacetylenic ammonium lipid N-bis-(10, 12-pentacosadiinoyl)-oxy-ethyl)-N-methyl-amine (ONCO). We have characterized monomolecular films at the air/water interface by means of microfluorescence filmbalance techniques and by atomic force microscopy (AFM). ONCO forms stable monomolecular films that exhibit a fluid-solid phase transition with a transition enthalpy of 90 kJ/mol at 10 °C and neutral pH. The coexistence pressure was found to decrease with decreasing protonation, which is in contrast to the commonly found Coulomb mechanism. A change in the chain packing due to a different nitrogen bond angle is discussed as a possible mechanism. This model is cor-roborated by the finding that crystals at high and at low pH differ in their polymerization properties as measured by microfluorescence.
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  • 36
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 399-404 
    ISSN: 0009-2940
    Keywords: Disilylamides ; Group 4 Complexes ; Polymerization ; Metallacycles ; Titanium ; Zirconium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of metallacyclodisiladiazanes has been prepared. Lithiated (SiMe2NHtBu)2 (1) reacts with TiCl4 · 2 THF to give (SiMe2NtBu)2TiCl (4). Methylation or fluorination of 4 leads to (SiMe2NtBu)2TiMe2 (8) and (SiMe2MtBu)2TiF2 (9), respectively. The reaction of ZrCl4 · 2 THF with lithiated 1 or [SiMe2NH(4-FC6J4)]2 (2) yields (SiMe2NtBu)2ZrCl2 (5) and [SiMe2N(4-FC6H4)]ZrCl2 · THF (7), respectively. The lithiated ligand [SiMe2NH(2,6-iPr2C6H3)]2 (3) reacts with noncoordinated ZrCl4 to give [SiMe2N(2,6-iPr2C6H3)]2ZrCl2 (6). X-ray structural analysis of 9 showed it to be a fluorine-bridged dimer in the solid state. Compounds 4, 6, 8 and 9 were found to be catalysts for the polymerization of ethylene.
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  • 37
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 291-294 
    ISSN: 0009-2940
    Keywords: Halogenoacetates ; Silver salts ; Solid-state reactions ; Polymerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of silver chloroacetate was determined by single-crystal X-ray structure analysis. This represents the first salt of a monohalogenoacetic acid with a monovalent metal whose structure was determined with high precision. The salt undergoes a thermally induced solid-state polymerization to polyglycolide under elimination of silver chloride. A probable mechanism for a structure-determined reaction in the solid state is discussed.
    Additional Material: 4 Ill.
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  • 38
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 81-85 
    ISSN: 0947-3440
    Keywords: Halogenocarboxylates ; Solid-state reactions ; Polyesters ; Thermal analysis ; Polymerization ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heating of the sodium salts of chlorocarboxylic acids leads to exothermic elimination of sodium chloride and oligomerization of the organic backbone of the molecule. Thermochemical data of sodium 2-chloropropionate (1), sodium 3-chloropropionate (2) and sodium 2-chlorobutyrate (3) were derived. The reaction products were characterized by IR and NMR spectroscopy, and the degree of polymerization was determined by gel permeation chromatography (GPC).
    Additional Material: 3 Ill.
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1123-1129 
    ISSN: 0009-2940
    Keywords: Halogenoacetates ; Solid-state reactions ; Polyglycolide ; Thermal analysis ; Polymerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nine salts of halogenoacetic acids MOOC-CH2—X were prepared and characterized by their thermochemical reactivity. It was found that in seven cases elimination of MX led to polymerization of the organic part of the molecule. The resulting polyester, polyglycolide, could be isolated easily by washing the reaction product with water. It has a distinct porous morphology. The reaction takes place at moderate temperatures (100—200°C).
    Additional Material: 6 Ill.
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  • 40
    Publication Date: 2020-08-05
    Description: The present dissertation deals with the structure of polyhedral subdivisions of point configurations. Of particular interest are the global properties of the set of all subdivisions of a given point configuration. An important open problem in this context is the following: can one always transform any triangulation of a given point configuration to any other triangulation of the same configuration by means of bistellar operations? In other words, is the set of all triangulations of a given point configuration always bistellarly connected? The results presented in this thesis contribute progress from two directions. \begin{itemize} \item The set of all subdivisions that are induced by a polytope projection is in general not bistellarly connected in a generalized sense. This result is obtained by constructing a counterexample to the so-called Generalized Baues Conjecture.'' \item The set of all triangulations of a cyclic polytope forms a bounded poset. The covering relations are given by increasing bistellar operations. Thus we get an affirmative answer to the above question in the case of cyclic polytopes. \end{itemize} In the introduction, the mathematical environment of the structures under consideration is illuminated. The "Generalized Baues Conjecture" has connections to various mathematical concepts, such as combinatorial models for loop spaces, discriminants of polynomials in several variables, etc. The triangulation posets of cyclic polytopes are natural generalizations of the well-studied Tamari lattices in order theory. Moreover, there is a connection to the higher Bruhat orders, which have similar structural properties. As a by-product, the investigations yield the shellability of all triangulations of cyclic polytopes without new vertices. This is in particular interesting because most triangulations of cyclic polytopes are non-regular.
    Description: Die vorliegende Dissertation beschäftigt sich mit strukturellen Fragen in der Theorie der polyedrischen Unterteilungen von Punktkonfigurationen. Hierbei sind vor allem globale Eigenschaften der Menge aller Unterteilungen einer gegebenen Punktkonfiguration von Interesse. Eine wichtige ungelöste Frage in diesem Zusammenhang ist die folgende: Ist es immer möglich, von einer beliebigen Triangulierung einer gegebenen Punktkonfiguration zu jeder anderen Triangulierung derselben Konfiguration zu gelangen, indem man sogenannte bistellare Operationen durchführt? Mit anderen Worten, ist die Menge aller Triangulierungen einer gegebenen Punktkonfiguration stets bistellar zusammenhängend? Die Ergebnisse der vorliegenden Doktorarbeit liefern auf zwei Seiten dieser nach wie vor offenen Frage Fortschritte: \begin{itemize} \item Die Menge aller durch eine Polytopprojektion induzierten Unterteilungen ist nicht immer --- in einem verallgemeinerten Sinne --- bistellar zusammenhängend. Dieses Resultat wird durch ein Gegenbeispiel zur sogenannten "Verallgemeinerten Baues Vermutung"' erzielt. \item Die Menge aller Triangulierungen eines zyklischen Polytops bildet eine beschränkte Halbordnung. Die Ueberdeckungsrelationen sind gerichtete bistellare Operationen. Für zyklische Polytope ist die obige Frage nach bistellarem Zusammenhang also positiv beantwortet. \end{itemize} In der Einleitung wird das mathematische Umfeld der betrachteten Strukturen näher beleuchtet: Die "Verallgemeinerte Baues Vermutung" steht in Verbindung mit verschiedensten mathematischen Konzepten, angefangen von kombinatorischen Modellen von Schleifenräumen bis hin zu Diskriminanten von Polynomen in mehreren Variablen. Die Triangulierungs-Halbordnungen von zyklischen Polytopen sind zugleich natürliche Verallgemeinerungen der gut studierten Tamari-Verbände in der Ordnungstheorie. Ausserdem existiert ein Zusammenhang mit den höheren Bruhat-Ordnungen, die ähnliche Struktureigenschaften aufweisen. Ein Nebenprodukt der Untersuchungen ist die Schälbarkeit aller Triangulierungen von zyklischen Polytopen ohne neue Ecken. Das ist um so interessanter, da die meisten Triangulierungen von zyklischen Polytopen nicht-regulär sind.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
    Format: application/postscript
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  • 41
    ISSN: 1572-8935
    Keywords: Microstructure modifier ; Isomers ; SBS ; Block copolymer ; Polymerization ; Kinetics ; Diethylether
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Diethylether (DEE) was used as a structure modifier during the synthesis of linear styrene-butadiene block copolymers of poly A-block-polyB-block-polyA type (SBS). The microstructures of synthesized polymers were analyzed, and the effect of DEE on polymerization kinetics was studied. Addition of DEE at 2 wt% concentration results in the highest styrene polymerization rate, while addition at 6 wt% concentration gives the highest butadiene polymerization rate. The vinyl content of the polybutadiene portion increases from 14 to 47% with an increase in the DEE concentration from 500 ppm to 10 wt% while thetrans- l,4 andcis-1,4 isomers decrease. For SBS polymer synthesized via a sequential method, the addition of DEE as a structure modifier minimizes the crossover deficiency which would otherwise result in a skewed molecular weight distribution with a higher polydispersity. For SBS polymers made via a coupling method, the coupling efficiency appears to be constant in a range of DEE concentration from 500 ppm to 1 wt% before declining with a further increase in DEE.
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  • 42
    Electronic Resource
    Electronic Resource
    Springer
    Journal of statistical physics 80 (1995), S. 389-404 
    ISSN: 1572-9613
    Keywords: Polymerization ; Markov process ; limit behavior ; stationary distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We consider a reversible Markov process as a chemical polymerization model and study the asymptotic behavior (in the thermodynamic limit asN→+∞) of a particular probability distribution on the set ofN-dimensional vectors, thekth component of which is the number ofk-mers. The study establishes the existence of three stages (subcritical, near-critical, and supercritical stages) of polymerization, depending on the value of the strength of the fragmentation reaction. The present paper concentrates on the analysis of the subcritical stage. In the subcritical stages we show that the size of the largest length of polymers of sizeN is of the order logN asN→+∞.
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  • 43
    ISSN: 0570-0833
    Keywords: alkenes ; catalysis ; metallocenes ; polymerizations ; Catalysis ; Metallocenes ; Polymerization ; Polyolefins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Current studies on novel, metallocenebased catalysts for the polymerization of α-olefins have far-reaching implications for the development of new materials as well as for the understanding of basic reaction mechanisms responsible for the growth of a polymer chain at a catalyst center and the control of its stereoregularity. In contrast to heterogeneous Ziegler-Natta catalysts, polymerization by a homogeneous, metallocene-based catalyst occurs principally at a single type of metal center with a defined coordination environment. This makes it possible to correlate metallocene structures with polymer properties such as molecular weight, stereochemical microstructure, crystallization behavior, and mechanical properties. Homogeneous catalyst systems now afford efficient control of regio- and stereoregularities, molecular weights and molecular weight distributions, and comonomer incorporation. By providing a means for the homo- and copolymerization of cyclic olefins, the cyclopolymerization of dienes, and access even to functionalized polyolefins, these catalysts greatly expand the range and versatility of technically feasible types of polyolefin materials.For corrigendum see DOI:10.1002/anie.199513681
    Additional Material: 10 Ill.
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  • 44
    ISSN: 0570-0833
    Keywords: Stereospecific polymerization ; Polymerization ; Polycyclopentene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of cyclo-olefins, like that of olefins with an internal double bond, is sterically hindered. Within recent years it has become possible to prepare copolymers of these compounds with ethylene, with the aid of anionic coordination Ziegler catalysts. This copolymerization always results in cis-opening of the double bond. Despite the steric hindrance, cyclobutene and cyclopropene have also been homopolymerized, with opening of the double bond. - Rather surprisingly, the best catalysts for homopolymerization of cyclopentene are those which exhibit low activity in the polymerization of ethylene. Ring cleavage occurs with MoCl5/Al(C2H5)3 to give the cis-polypentenamer, whereas WCl6/Al(C2H5)3 gives the trans-polypentenamer. Both polypentenamers exhibit elastomeric properties. - Evidence from infrared spectra and oxidative degradation indicates that the monomer units in the trans-polypentenamer are linked head-to-tail. It is presumably the single bond adjacent to the double bond that is broken. Using X-ray methods at -50 °C, it was possible to determine the crystal structure of the crystalline trans-polypentenamer at about 400% elongation.
    Additional Material: 6 Ill.
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  • 45
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 32-41 
    ISSN: 0570-0833
    Keywords: Polymerization ; Polyethylene ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A two-component organometallic catalyst of composition CH3TiCl3·CH3AlCl2 effects high-speed polymerization of ethylene in the presence of chlorinated hydrocarbons at low temperatures. The catalyst does not undergo any alteration in the process. In contrast to the Ziegler catalysts, the titanium remains quadrivalent. Olefins of low-molecular-weight and with branched structures are produced. It proved possible to isolate the primary products of the polymerization at -50 to -100°C and to elucidate the mode of their formation from a knowledge of their structures. The findings are incompatible with either a cationic or anionic reaction mechanism. A novel type of mechanism is proposed, whereby the catalyst is supposed to have an ionic structure and molecular growth proceeds via π-complex formation of the olefin with the titanium cation. The formation of ethylene/olefin copolymers is also discussed.
    Additional Material: 1 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 295-308 
    ISSN: 0570-0833
    Keywords: Emulsion polymerization ; Polymerization ; Polymerization ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionizing radiation induces the polymerization of some vinyl monomers in aqueous emulsion with high radiation yields. With identical emulsion compositions, the kinetics of this reaction and the kinetics of emulsion polymerization induced by water-soluble initiators are very similar. The rate of reaction in emulsion polymerization is about one hundred times greater than in bulk polymerization. The initiation of emulsion polymerization by means of ionizing radiation permits uniform “illumination” of the reacting volume, as well as almost any desired variation in the frequency of initiation during the reaction. The sharp decrease in the overall rate of reaction when initiation is interrupted during emulsion polymerization of styrene induced by γ-rays contradicts the earlier concept of sharply separated reaction zones.
    Additional Material: 11 Ill.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 704-714 
    ISSN: 0570-0833
    Keywords: Titanium ; Alkenes ; Polymerization ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At low temperatures, ethylene and α-olefins (Δ1-olefins or 1-alkenes) are rapidly converted into oligomrs by the two-component organometallic catalyst CH3TiCl3·CH3AlCl2. To achieve smooth oligomerizations, aromatic or chlorinated hydrocarbons must be used as solvents. Although the activity of the titanium-carbon bond is enhanced by the aluminum component of the catalyst, the aluminum and its methyl group do not participate in the reaction proper; the latter proceeds exclusively at the titanium-carbon bond. The reaction will olefins can be used as an analytical method for the quantitative determination of the titanium-carbon bond in admixture with the organoaluminum component. It is thus possible to follow the reaction leading to formation of the catalyst from titanium tertrachloride, as well as the processes occurring at the titanium-carbon bond during the oligomerization of olefins. All the observations indicate that the catalyst possesses an ionic structure which is determined by the solvent. It is shown that the initial reaction step probably involves formation of a complex between the olefin and the alkyltitanium cation. The reaction scheme proposed is based on organometallic reactions which are characterized by carbanion and hydride transfers within the olefin-cation complex. This mechanism, which is unusual for Ziegler catalysts, is due to the predominance of hydride transfers.
    Additional Material: 2 Ill.
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  • 48
    ISSN: 0570-0833
    Keywords: Pyrrolidone ; Polyamides ; Fibers ; Lactams ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The industrial production of capryllactam (1-azacyclononan-2-one) and of laurolactam (1-azacyclotridecan-2-one) starts with cyclization of acetylene or butadeine to give cyclooctatetraene or cyclooctadiene, or cyclization of butadiene to give cyclododecatriene. Further steps are: oxidation of the cyclic hydrocarbon to the ketone, formation of the oxime, and rearrangement of the latter with sulfuric acid. Pyrrolidone can be prepared from acetylene and formaldehyde by way of butyrolactone. The behavior of the lactams during polycondensation is described and the properties of the resulting fibers are compared with those of the known polyamide fibers.
    Additional Material: 2 Ill.
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  • 49
    ISSN: 0570-0833
    Keywords: Lactams ; Polymerization ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Lactams can be prepared by cyclization of β-aimno acid esters. Recently they have become available also from olefins by addition of N-carbonysulfamyl chloride (isocyanatosulfonyl chloride) and from aldehydes by reaction with N-carbonylsulfamyl chloride and ketene. Condensative or anionic polymerization results in polyamides the chains of which contain many more amide groups than the chains of polyamides of the nylon-6 type. Hence the new polymers resemble silk moreclosely. Fibers and films can be prepared from solution.
    Additional Material: 7 Ill.
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