CATIONIC COPOLYMERIZATION OF ISOBUTYLENE WITH ISOPRENE: KINETICS OF THE PROCESS AND DETERMINATION OF KINETIC CONSTANTS

2015 ◽  
Vol 88 (4) ◽  
pp. 574-583 ◽  
Author(s):  
N. V. Ulitin ◽  
K. A. Tereshchenco ◽  
D. A. Shiyan ◽  
G. E. Zaikov
Keyword(s):  
Experimental Data ◽  
Molecular Weight ◽  
Cationic Polymerization ◽  
Methyl Chloride ◽  
Theoretical Description ◽  
Kinetic Constants ◽  
Molecular Weight Characteristics ◽  
Cationic Copolymerization ◽  
Kinetics Of

ABSTRACT A theoretical description has been developed of the kinetics of isobutylene with isoprene (IIR) cationic polymerization in the environment of methyl chloride on aluminum trichloride as the catalyst. Based on experimental data on the kinetics of copolymerization (isobutylene conversion curve) and the molecular weight characteristics of the copolymer of IIR, kinetic constants for the process were found. Adequacy of the developed theoretical description of the kinetics of the IIR copolymerization process was confirmed by comparing the experimental molecular-weight characteristics calculated by this description, independent characteristics, and IIR unsaturation.

Calculation and Analysis of the Molecular Weight Characteristics of the Polymer in the Synthesis of Butyl Rubber

2022 ◽  
Vol 1049 ◽  
pp. 224-231
Author(s):  
Irina Antonova ◽  
Regina Dmitricheva ◽  
Veronika Bronskaya ◽  
Guzel Aminova ◽  
Iliya Lapin ◽  
...  
Keyword(s):  
Mathematical Model ◽  
Molecular Weight ◽  
Catalytic System ◽  
Chain Transfer ◽  
Methyl Chloride ◽  
Chain Termination ◽  
Butyl Rubber ◽  
Chain Growth ◽  
Molecular Weight Characteristics ◽  
Cationic Copolymerization

The article compiled a mathematical model of the cationic copolymerization of isobutylene and isoprene using a catalyst AlCl3 in a CH3Cl solution, including the reactions of initiation, chain growth, chain transfer to the monomer, and chain termination. The molecular weight characteristics of butyl rubber synthesized in methyl chloride using a catalytic system based on aluminum trichloride have been investigated. Relationships are obtained for calculating the moments of the molecular weight characteristics of butyl rubber. The effect of the concentration of the initiator on the conversion versus time was investigated.

scholarly journals Cationic Copolymerization of Isobutylene with 4-Vinylbenzenecyclobutylene: Characteristics and Mechanisms

Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 201 ◽  
Author(s):  
Zhifei Chen ◽  
Shuxin Li ◽  
Yuwei Shang ◽  
Shan Huang ◽  
Kangda Wu ◽  
...  
Keyword(s):  
Mechanical Properties ◽  
Molecular Weight ◽  
Cationic Polymerization ◽  
Transfer Reaction ◽  
Chain Transfer ◽  
Solid Phase ◽  
Random Copolymer ◽  
Glass Transition Temperatures ◽  
Cationic Copolymerization ◽  
Chain Transfer Reaction

A random copolymer of isobutylene (IB) and 4-vinylbenzenecyclobutylene (4-VBCB) was synthesized by cationic polymerization at −80 °C using 2-chloro-2,4,4-trimethylpentane (TMPCl) as initiator. The laws of copolymerization were investigated by changing the feed quantities of 4-VBCB. The molecular weight of the copolymer decreased, and its molecular weight distribution (MWD) increased with increasing 4-VBCB content. We proposed a possible copolymerization mechanism behind the increase in the chain transfer reaction to 4-VBCB with increasing of feed quantities of 4-VBCB. The thermal properties of the copolymers were studied by solid-phase heating and crosslinking. After crosslinking, the decomposition and glass transition temperatures (Tg) of the copolymer increased, the network structure that formed did not break when reheated, and the mechanical properties remarkably improved.

Studies in the Vulcanization of Rubber. III—Kinetics of Vulcanization of Rubber with Sulfur and Selenium

1930 ◽  
Vol 3 (4) ◽  
pp. 650-659
Author(s):  
John T. Blake
Keyword(s):  
Molecular Weight ◽  
Order Reaction ◽  
Order Equation ◽  
Second Order Reaction ◽  
Experimental Conditions ◽  
Mathematical Basis ◽  
First Order ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization

Abstract A procedure for the determination of combined selenium in rubber has been evolved. The rate of combination of selenium and rubber has been ascertained under certain conditions and shown to follow a first-order equation. A minimum value for the molecular weight of rubber has been estimated. The formation of hard rubber under chosen experimental conditions has been put on a mathematical basis and has been shown to follow a second-order reaction. The soft- and hard-rubber reactions have been shown qualitatively to be successive reactions and the function of accelerators has been discussed. The theory explains the anomalous results obtained by previous investigators.

Reactive Diffusion upon Planar Dissolving Copper in Solder Melts

2011 ◽  
Vol 309-310 ◽  
pp. 127-134 ◽  
Author(s):  
Jaromír Drápala ◽  
Pavel Jopek ◽  
Daniel Petlák ◽  
Petr Harcuba ◽  
Petr Kubíček
Keyword(s):  
Interphase Boundary ◽  
Time Course ◽  
Solid Phase ◽  
Accurate Determination ◽  
Theoretical Description ◽  
Reactive Diffusion ◽  
Boundary Movement ◽  
Original Metal ◽  
Kinetics Of

Problems of reactive diffusion at a solid phase - melt contact were studied theoretically. The main intention was to calculate the time course of the solid phase dissolving in the case of planar dissolving. In our work we give heed especially to the dominating process, which is the solid metal A dissolving in solder melt B. During the dissolving, melt B saturates with metal A, and the process is influenced by convections which are characteristic for a given experimental configuration. A theoretical description of the kinetics of solid phase dissolving in the melt will be presented for the case of planar dissolving. The aim is to derive a relation for the interphase boundary movement (t) depending on time and a time course of growth of the element A concentration in the melt B. There are difficulties in accurate determination of the interphase boundary movement after heating of specimens for certain time intervals. It should be performed experimentally, since intermetallic phases are formed in original metal A both via diffusion and upon cooling and some phases segregate upon cooling of the solidifying melt. The main intention was to study experimentally the copper dissolving in melts of various solder alloys and the related reactive diffusion. We used pure Sn and Sn-Cu, Sn-Ag-Cu, Sn-Sb, Sn-Zn alloys as solder materials. Experiments aimed at the study of a Cu plate dissolving in the solder melt were carried out at various selected temperatures and times. The problems of reactive diffusion were studied both theoretically and experimentally and the problems that have to be solved preferably were emphasized. Concentration profiles of elements and thickness of layers of phases can be determined with SEM and X-ray microanalyses (WDX, EDX) of specimens after their diffusion heating.

Realization of Detailed Kinetic Models for the Growth of II-VI Compounds: Adopting DFT Calculations and Experimental Evidences

1999 ◽  
Vol 584 ◽  
Author(s):  
Carlo Cavallotti ◽  
Valeria Bertani ◽  
Maurizio Masi ◽  
Sergio Carrà
Keyword(s):  
Experimental Data ◽  
Kinetic Theory ◽  
Gas Phase ◽  
Quantum Chemical ◽  
Kinetic Scheme ◽  
Kinetic Constants ◽  
Surface Processes ◽  
Gas Phase Reactions ◽  
Elementary Reactions ◽  
Kinetics Of

AbstractThe kinetics of deposition of CdTe, ZnS and ZnSe films was studied. An overall microkinetically reversible kinetic scheme consisting of elementary reactions, comprehensive of gas phase and surface processes was developed. Kinetic constants of gas phase reactions were either found in the literature or determined through quantum chemistry methods. Kinetic constants of surface reactions were first guessed combining kinetic theory with quantum chemical calculations and then their values were refined to reproduce experimental data. The kinetics schemes so developed were tested through the simulation of deposition reactors. Measured growth rates and gas phase compositions were thus compared with those calculated. The major finding of this studies is that the growth of CdTe, ZnS and ZnSe can be represented adopting a surface kinetic scheme constituted essentially by the same fundamental steps.

scholarly journals Cationic polymerization of β-pinene in the presence of alkylaluminum chlorides as catalysts

2020 ◽  
pp. 98-107
Author(s):  
Maksim I. Hulnik ◽  
Olga V. Kuharenko ◽  
Sergei V. Kostjuk
Keyword(s):  
Molecular Weight ◽  
Nmr Spectroscopy ◽  
1H Nmr ◽  
Cationic Polymerization ◽  
1H Nmr Spectroscopy ◽  
Catalyst Concentration ◽  
Solvent Mixture ◽  
Electron Donors ◽  
Naturally Occurring ◽  
Molecular Weight Characteristics

Cationic polymerization of β-pinene, a naturally occurring monomer, was studied in the presence of different alkylaluminum chlorides ((iBu)3Al2Cl3, Et3Al2Cl3 и Мe2AlCl) in the solvent mixture dichloromethane/methylcyclohexane (DCM/MCH) at –78 °C. The effect of catalyst concentration [(iBu)3Al2Cl3] and various electron donors on the polymerization rat and molecular-weight characteristics of synthesized poly(β-pinenes) was investigated. Controlled cationic polymerization of β-pinene was carried out in the presence СumCl/Мe2AlCl initiating system. The polymers with controlled molecular weight up to 6400 g/mol and relatively low polydispersity (Mw/Mn < 1.42) were synthesized. Microstructure of synthesized poly(β-pinene) was investigated by 1H NMR spectroscopy.

Kinetics of the radical copolymerization of styrene and 2-methoxyethyl methacrylate

1983 ◽  
Vol 48 (9) ◽  
pp. 2656-2665 ◽  
Author(s):  
Jaroslav Stejskal ◽  
Dagmar Straková ◽  
Ondřej Procházka ◽  
Pavel Kratochvíl
Keyword(s):  
Experimental Data ◽  
Molecular Weight ◽  
Kinetic Data ◽  
Radical Copolymerization ◽  
Copolymer Composition ◽  
Monomer Mixture ◽  
Diffusion Controlled ◽  
Kinetics Of ◽  
Best Fit ◽  
Copolymerization Kinetics

Twenty low-conversion statistical copolymers of styrene and 2-methoxyethyl methacrylate with various composition were prepared. The dependence of the copolymer composition, molecular weight, initiation efficiency and other parameters on the composition of the monomer mixture is discussed. Kinetic data are correlated by means of various models of the copolymerization kinetics. The best fit with experimental data is provided by a diffusion-controlled termination model, especially its dyad variant suggested in this study.

scholarly journals Drying kinetics of fermented grape pomace: Determination of moisture effective diffusivity

2016 ◽  
Vol 20 (8) ◽  
pp. 763-768 ◽  
Author(s):  
Kricelle M. Deamici ◽  
Lucas C. de Oliveira ◽  
Gabriela S. da Rosa ◽  
Elizangela G. de Oliveira
Keyword(s):  
Experimental Data ◽  
Effective Diffusivity ◽  
Drying Kinetics ◽  
Grape Pomace ◽  
Desorption Isotherms ◽  
Drying Curves ◽  
Gab Model ◽  
Kinetics Of ◽  
Moisture Effective Diffusivity

ABSTRACT The aim of this study was to obtain the equilibrium moisture content of grape (variety ‘Tannat’) pomace through desorption isotherms, to evaluate the drying kinetics, determine the coefficient of effective diffusivity and physico-chemically characterize the grape pomace and the product obtained after drying. The desorption isotherms were determined at 50, 60 and 70 ºC and the experimental data were fitted using the GAB model (Gugghenheim, Anderson and de Boer). Drying was evaluated using a 22 factorial experimental design with three center points and effective diffusivity was obtained through the diffusion model of Fick’s second law. The grape pomace was characterized regarding the contents of moisture, protein, carbohydrates, lipids, ash and dietary crude fiber. The obtained isotherms showed sigmoid shape and the experimental data fitted well to the GAB model. The drying curves showed only a decreasing rate period. The effective diffusivity values were within the range for organic materials. Dry grape pomace showed high contents of protein and fiber and can be used in the development of new products, in order to increase the nutritional content and add value to this byproduct.

Sign in / Sign up

Export Citation Format

Share Document