Equilibrium Molecular Weight Distribution of Cyclic and Linear Methylsiloxanes

1967 ◽  
Vol 40 (4) ◽  
pp. 1084-1093 ◽  
Author(s):  
Jack B. Carmichael ◽  
James Heffel

Abstract Data are reported for the equilibrium molecular size distributions of cyclic and linear methylsiloxanes in five polymers with number average molecular weights ranging from 459 to 1348. The distributions of linear species agree with the earlier work of Scott and agree reasonably well with the Flory theory of random reorganization. The amounts of cyclic molecules are sharply dependent on molecular weight. However, the equilibrium constants for cyclic formation for cyclic species with four to eight units are shown to be virtually identical with the equilibrium constants for cyclic formation in high molecular weight polymers reported in a previous publication. For octamethylcyclotetrasiloxane, Kav in moles of siloxane units per liter was found to be 0.72 in this study. For high polymers, Kav was previously reported to be 0.74.

2021 ◽  
Author(s):  
Johannes Steindl ◽  
Rafael Eduardo Hincapie ◽  
Ante Borovina ◽  
Christoph Puls ◽  
Johann Badstöber ◽  
...  

Abstract Various polyacrylamide polymers have been successfully applied in chemical EOR projects. These polymers are characterised by high molecular weights (MW) to achieve high viscosifying power. The molecular weight distribution (MWD) of the polymers has a major impact on polymer properties and performance. Measuring the molecular weight distribution is challenging using conventional methods. Field-Flow Fractionation (FFF) enables the determination of the distribution to select and quality check various polymers. Polymers with high molar masses (> 1 MDa) are used for EOR to obtain highly viscous aqueous solutions. The MWD of the polymers is crucial for the solution characteristics. Conventional analysis of polymers is performed using either viscometry – which is able to determine the average MW but does not give information on MWD, or size-exclusion chromatography – which is restricted to molecular weights of < 20 MDa. FFF is based on the analytes flowing at different speeds in a channel dependent on their size and mass. This effect leads to separation, which is then used to determine the MWD. FFF allows to determine the MW and MWD of various ultra-high molecular weight polyacrylamides (HPAAMs). The FFF measurements showed, that despite similar MWs are claimed, substantial differences in MWD are observed. This technology offered the quantification the MWD of HPAAMs up to a MW of 5 GDa. Furthermore, gyration radii of the HPAAM molecules were determined. Selecting polymers on viscosifying power only is not addressing issues related to different MW and MWDs such as selective polymer retention and degradation of the high molar mass part of the distribution. The results were used to improve the polymer selection for chemical EOR projects. Overall, this work presents a new technique for analysis of ultra-high molecular weight EOR polymers, which enables the possibility to determine the full range of polymer MWD. This available information enhances the EOR polymer selection process addressing selective polymer retention and mechanical degradation in addition to the viscosifying power of polymers.


Author(s):  
A. A. Khvostov ◽  
S. G. Tikhomirov ◽  
I. A. Khaustov ◽  
A. A. Zhuravlev ◽  
A. V. Karmanov

The paper deals with the problem of mathematical modeling of the process of thermochemical destruction using the theory of graphs. To synthesize a mathematical model, the Markov chain is used. For the formalization of the model a matrix-graph method of coding is used. It is proposed to consider the process of destruction as a random process, under which the state of the system changes, characterized by the proportion of macromolecules in each fraction of the molecular mass distribution. The intensities of transitions from state to state characterize the corresponding rates of destruction processes for each fraction of the molecular weight distribution (MWD). The processes of crosslinking and polymerization in this work have been neglected, and it is accepted that there is a probability of transition from any state with a lower order index (corresponding to fractions with higher molecular weights) to any state with a higher index (corresponding fractions with lower molecular weights). A computational formula is presented for estimating the number of arcs and model parameters from a given number of fractions of the molecular weight distribution of the polymer. An example of coding in a matrix form of a graph model of the process of degradation of polybutadiene in solution for the case of six fractions of the molecular weight distribution is shown. As the simulation environment, the interactive graphical simulation environment of MathWorks Simulink is used. To evaluate the parameters of the mathematical model, experimental studies of the degradation of polybutadiene in solution were carried out. The chromatography of the polybutadiene solution was used as the initial data for the estimation of the MWD polymer. The considered matrix-graph representation of the structure of the mathematical model of the polymer destruction process makes it possible to simplify the compilation of the model and its software implementation in the case of a large number of vertices of the graph describing the process of destruction


2021 ◽  
Author(s):  
Maciej Łojkowski ◽  
Adrian Chlanda ◽  
Emilia Choińska ◽  
Wojciech Swieszkowski

<p>The formation of complex structures in thin films is of interest in many fields. Segregation of polymer chains of different molecular weights is a well-known process. However, here, polystyrene with bimodal molecular weight distribution, but no additional chemical modification was used. It was proven that at certain conditions, the phase separation occurred between two fractions of bimodal polystyrene/methyl ethyl ketone solution. The films were prepared by spin-coating, and the segregation between polystyrene phases was investigated by force spectroscopy. Next, water vapour induced secondary phase separation was investigated. The introduction of moist airflow induced the self-assembly of the lower molecular weight into islands and the heavier fraction into a honeycomb. As a result, an easy, fast, and effective method of obtaining island/honeycomb morphologies was demonstrated. The possible mechanisms of the formation of such structures were discussed.</p>


RSC Advances ◽  
2015 ◽  
Vol 5 (101) ◽  
pp. 83295-83303 ◽  
Author(s):  
Min Zhang ◽  
Jingjing Zhang ◽  
Xufeng Ni ◽  
Zhiquan Shen

Polyhexyl isocyanantes catalyzed by N-heterocyclic carbene rare earth metal complexes show high molecular weight with narrow molecular weight distribution.


2021 ◽  
Author(s):  
Maciej Łojkowski ◽  
Adrian Chlanda ◽  
Emilia Choińska ◽  
Wojciech Swieszkowski

<p>Segregation of polymer chains of different molecular weights is a well-known process. A traditional experimental approach of studying phase segregation in thin films composed of polymer blends with identical chemical compositions but different molecular weights was focused on functionalisation of chemical group or modification of end-group. In this study, however, a different approach was proposed. Polystyrene with bimodal molecular weight distribution, but no additional chemical modification was used. The films were prepared by spin-coating and the segregation between polystyrene phases was investigated by force spectroscopy. The solubility of bimodal polystyrene was explored. At the right molecular weight distribution and soluted in Methyl Ethyl Ketone, the phase segregation occurred. Introduction of moist airflow induced the separation of the lower molecular weight into micropillars and the heavier fraction self-organized into a honeycomb. As a result, an easy, fast, and effective method of obtaining micropillar/honeycomb morphologies was demonstrated. The mechanism of formation of such structures was explained. </p>


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