Living Coordination Polymerization of Alkoxyallenes by π-Allylnickel Catalyst. 2.1Effect of Anionic Ligands on Polymerization Behavior and Polymer Structure

1998 ◽  
Vol 31 (9) ◽  
pp. 2779-2783 ◽  
Author(s):  
Koji Takagi ◽  
Ikuyoshi Tomita ◽  
Yoshiyuki Nakamura ◽  
Takeshi Endo
Keyword(s):  
Polymer Structure ◽  
Coordination Polymerization ◽  
Anionic Ligands ◽  
Polymerization Behavior

scholarly journals Fully Bio-Based Elastomer Nanocomposites Comprising Polyfarnesene Reinforced with Plasma-Modified Cellulose Nanocrystals

Polymers ◽  
2021 ◽  
Vol 13 (16) ◽  
pp. 2810
Author(s):  
Ilse Magaña ◽  
Dimitrios Georgouvelas ◽  
Rishab Handa ◽  
María Guadalupe Neira Neira Velázquez ◽  
Héctor Ricardo López López González ◽  
...  
Keyword(s):  
Cellulose Nanocrystals ◽  
Plasma Reactor ◽  
Plasma Generator ◽  
Model Systems ◽  
Characteristic Relaxation Time ◽  
Coordination Polymerization ◽  
Polymerization Behavior ◽  
Characteristic Features ◽  
Tunable Mechanical Properties ◽  
Surface Modified

This article proposes a process to prepare fully bio-based elastomer nanocomposites based on polyfarnesene and cellulose nanocrystals (CNC). To improve the compatibility of cellulose with the hydrophobic matrix of polyfarnesene, the surface of CNC was modified via plasma-induced polymerization, at different powers of the plasma generator, using a trans-β-farnesene monomer in the plasma reactor. The characteristic features of plasma surface-modified CNC have been corroborated by spectroscopic (XPS) and microscopic (AFM) analyses. Moreover, the cellulose nanocrystals modified at 150 W have been selected to reinforce polyfarnesene-based nanocomposites, synthesized via an in-situ coordination polymerization using a neodymium-based catalytic system. The effect of the different loading content of nanocrystals on the polymerization behavior, as well as on the rheological aspects, was evaluated. The increase in the storage modulus with the incorporation of superficially modified nanocrystals was demonstrated by rheological measurements and these materials exhibited better properties than those containing pristine cellulose nanocrystals. Moreover, we elucidate that the viscoelastic moduli of the elastomer nanocomposites are aligned with power–law model systems with characteristic relaxation time scales similar to commercial nanocomposites, also implying tunable mechanical properties. In this foreground, our findings have important implications in the development of fully bio-based nanocomposites in close competition with the commercial stock, thereby producing alternatives in favor of sustainable materials.

scholarly journals Ethylene Polymerization via Zirconocene Catalysts and Organoboron Activators: an Experimental and Kinetic Modeling Study

2020 ◽  
Author(s):  
Luis Valencia ◽  
Francisco Enríquez-Medrano ◽  
Ricardo López-González ◽  
Priscila Quiñonez-Angulo ◽  
Enrique Saldívar-Guerra ◽  
...  
Keyword(s):  
Active Sites ◽  
Optimization Procedure ◽  
Kinetic Mechanism ◽  
Least Square ◽  
Coordination Polymerization ◽  
Solvent Phase ◽  
Vapor Equilibrium ◽  
Kinetic Rate Constants ◽  
Rate Of Polymerization ◽  
Polymerization Behavior

After 40 years of the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigate the synthesis of PE via three different zirconocene catalysts, with different alkyl substituents, activated via different organoboron compounds. The polymerization behavior, as well as the properties of the materials, are evaluated. The results demonstrate that the highest catalytic activity is shown by Bis(cyclopentadienyl)dimethylzirconium activated by trityl tetra(pentafluorophenyl)borate. Also finding that toluene is the optimum solvent for these systems and at these reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model is developed on the basis of thermodynamic and kinetic principles. The concentration of ethylene transferred to the solvent phase (toluene) in a liquid-vapor equilibrium (LVE) system is estimated based on the Duhem’s theorem. Arrhenius expressions for the kinetic rate constants of a proposed kinetic mechanism are estimated by a kinetic model, in which the rate of polymerization is fitted by a least-square optimization procedure and the molecular weight averages by the method of moments. The simulations of the coordination polymerization suggest the presence of two types of active sites, principally at low temperatures, and the reactivation of the deactivated sites via a boron-based activator. However, the effect of the temperature on the reactivation step is no clear; a deeper understanding via designed experiments is required.

scholarly journals Ethylene Polymerization via Zirconocene Catalysts and Organoboron Activators: An Experimental and Kinetic Modeling Study

Processes ◽  
2021 ◽  
Vol 9 (1) ◽  
pp. 162
Author(s):  
Luis Valencia ◽  
Francisco Enríquez-Medrano ◽  
Ricardo López-González ◽  
Priscila Quiñonez-Ángulo ◽  
Enrique Saldívar-Guerra ◽  
...  
Keyword(s):  
Active Sites ◽  
Optimization Procedure ◽  
Kinetic Mechanism ◽  
Least Square ◽  
Coordination Polymerization ◽  
Solvent Phase ◽  
Vapor Equilibrium ◽  
Kinetic Rate Constants ◽  
Rate Of Polymerization ◽  
Polymerization Behavior

Forty years after the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigated the synthesis of polyethylene (PE) via three different zirconocene catalysts, with different alkyl substituents, activated via different organoboron compounds. The polymerization behavior, as well as the properties of the materials, were evaluated. The results demonstrate that the highest catalytic activity is shown by bis(cyclopentadienyl)dimethylzirconium activated by trityl tetra(pentafluorophenyl)borate. Additionally, it was found that toluene is the optimum solvent for these systems and at these reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model was developed on the basis of thermodynamic and kinetic principles. The concentration of ethylene transferred to the solvent phase (toluene) in a liquid–vapor equilibrium (LVE) system was estimated based on Duhem’s theorem. Arrhenius expressions for the kinetic rate constants of a proposed kinetic mechanism were estimated by a kinetic model, in which the rate of polymerization was fitted by a least-square optimization procedure and the molecular weight averages by the method of moments. The simulations of the coordination polymerization suggest the presence of two types of active sites, principally at low temperatures, and the reactivation of the deactivated sites via a boron-based activator. However, the effect of the temperature on the reactivation step was not clear; a deeper understanding via designed experiments is required.

ULTRASONIC STUDIES OF THE POLYMER STRUCTURE OF THE CHALCOGENIDE GLASSES

1981 ◽  
Vol 42 (C4) ◽  
pp. C4-955-C4-958
Author(s):  
V. A. Ratobylskaja ◽  
L. A. Simonova
Keyword(s):  
Chalcogenide Glasses ◽  
Polymer Structure

Biodegradable Polyurethanes Cross-Linked by Multifunctional Compounds

2017 ◽  
Vol 14 (6) ◽  
pp. 778-784 ◽  
Author(s):  
Joanna Brzeska
Keyword(s):  
Polymer Structure ◽  
Cross Linking ◽  
Plant Oils ◽  
Lignocellulosic Materials ◽  
Soft Or ◽  
Native State ◽  
Synthetic Compounds ◽  
Multifunctional Compounds ◽  
Hard Segments ◽  
Synthetic Origin

Background: Cross-linking structure of polyurethanes determines no degradability of these materials. However, introducing the hydrolysable substrates (of natural or synthetic origin) into the cross-linked polyurethanes structure makes them biodegradable. Moreover compounds (such as polycaprolactone triol, glycerin, lysine triisocyanate, etc.) that are used for polyurethane cross-linking are degraded in non-toxic products. All these kinds of compounds can be introduced into soft or hard segments via urethane bonds. Objective: The review focuses on kind of multifunctional polyols and isocyanates, and low molecular crosslinkers used for cross-linked polyurethanes obtaining. These compounds are natural substrates (in the native state or after modification) or are synthetic compounds with degradable linkages. They belong to polyesters, plant oils, proteins, saccharides, and others (e.g. lignocellulosic materials), and they are synthesized chemically or via biosynthesis by algae, plants, microorganisms, and by animals. Conclusion: Incorporation of degradable groups (such as ester moieties) into the polymer structure, and using of substrates with the structure known and metabolized by microorganisms for soft or hard segments building, facilitate degradation of cross-linked polyurethanes.

Mechanism of the propagation step in the anionic polymerization of styrene

1980 ◽  
Vol 45 (4) ◽  
pp. 1047-1055 ◽  
Author(s):  
Miroslav Kašpar ◽  
Jiří Trekoval
Keyword(s):  
Experimental Data ◽  
Induction Period ◽  
Anionic Polymerization ◽  
Reactive Intermediate ◽  
Coordination Polymerization ◽  
Kinetic Dependence ◽  
Mathematical Solution ◽  
Slow Reaction

The paper is dealing with an investigation of the kinetic dependence of the propagation step in the anionic coordination polymerization of styrene in benzene at 303 K with "living" oligostyryllithium as initiator at the onset of the reaction. A short but distinct induction period was found, indicating a preceding slow reaction leading to the formation of a reactive intermediate, which behaves as the initiator of the reaction. Using results obtained in the first paper of this series, a new mechanism of propagation has been suggested, the mathematical solution of which is correlated with experimental data.

The mechanism of the anionic coordination polymerization of isoprene

1980 ◽  
Vol 45 (9) ◽  
pp. 2391-2399 ◽  
Author(s):  
Miroslav Kašpar ◽  
Jiří Trekoval
Keyword(s):  
Chromatographic Method ◽  
Initial Period ◽  
Reaction Scheme ◽  
Polymerization Kinetics ◽  
Coordination Polymerization ◽  
Initial Concentration ◽  
The Cross ◽  
Gas Chromatographic Method ◽  
Kinetics Of

The polymerization kinetics of isoprene (2-methyl-1,3-butadiene) in benzene with butyllithium as the initiator was investigated by the gas chromatographic method. After completion of the initial period of the reaction, its order with respect to the initial concentration of initiator is negative at the concentrations of the latter between 0.01 and 0.25 mol/l, and positive at higher concentrations. A reaction scheme has been suggested with respect to the "cross" association of butyllithium and of the "living" oligoisoprene.

Polymer structure and catalytic activity of ion exchangers

1981 ◽  
Vol 46 (7) ◽  
pp. 1577-1587 ◽  
Author(s):  
Karel Jeřábek
Keyword(s):  
Catalytic Activity ◽  
Ethyl Acetate ◽  
Active Sites ◽  
Crosslinking Agent ◽  
Reaction Medium ◽  
Polymer Structure ◽  
Local Concentration ◽  
Ion Exchangers ◽  
Styrene Divinylbenzene ◽  
Kinetics Of

Catalytic activity of ion exchangers prepared by partial sulphonation of styrene-divinylbenzene copolymers in reesterifications of ethyl acetate by methanol and propanol, hydrolysis of ethyl acetate and in synthesis of bisphenol A has been compared with data on polymer structure of these catalysts and with distribution of the crosslinking agent, divinylbenzene, calculated from literature data on kinetics of copolymerisation of styrene with divinylbenzene. It was found that the polymer structure of ion exchangers influences catalytic activity predominantly by changing the local concentration of acid active sites. The results obtained indicated that the effect of transport phenomena on the rate of catalytic reactions does not depend on the degree of swelling of the ion exchangers in reaction medium but it is mainly dependent on the relative affinity of reaction components to the acid groups or to the polymer skeleton.

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