Molecular weight distribution and moments for condensation polymerization with variant reaction rate constant depending on chain lengths

1988 ◽  
Vol 21 (3) ◽  
pp. 732-735 ◽  
Author(s):  
O Ok Park
Keyword(s):  
Molecular Weight ◽  
Molecular Weight Distribution ◽  
Rate Constant ◽  
Weight Distribution ◽  
Reaction Rate ◽  
Reaction Rate Constant ◽  
Condensation Polymerization ◽  
Chain Lengths

scholarly journals Kinetics and Thermodynamics Study of Ultrasound-Assisted Depolymerization of k-Carrageenan in Acidic Solution

2020 ◽  
Vol 15 (1) ◽  
pp. 280-289
Author(s):  
Ratnawati Ratnawati ◽  
Nita Indriyani
Keyword(s):  
Molecular Weight ◽  
Rate Constant ◽  
Reaction Rate ◽  
Acidic Solution ◽  
Biomedical Application ◽  
Bond Cleavage ◽  
Reaction Rate Constant ◽  
Order Kinetic ◽  
Kinetics And Thermodynamics ◽  
Ultrasound Assisted

K-carrageenan is a natural polymer with high molecular weight ranging from 100 to 1000 kDa. The oligocarrageenan with low molecular weight is widely used in biomedical application. The aim of this work was to depolymerize k-carrageenan in an acidic solution with the assistance of ultrasound irradiation. The ultrasonication was conducted at various pH (3 and 6), temperatures (30-60 °C), and depolymerization time (0-24 minutes). The results show that the depolymerization reaction follows pseudo-first-order kinetic model with reaction rate constant of 1.856×10-7 to 2.138×10-6 s-1. The reaction rate constant increases at higher temperature and lower pH. The Q10-temperature coefficients of the depolymerization are 1.25 and 1.51 for pH 6 and 3, respectively. The enthalpy of activation (ΔH‡) and the Gibbs energy of activation (ΔG‡) are positive, while the entropy of activation (ΔS‡) is negative, indicating that the activation step of the ultrasound-assisted depolymerization of k-carrageenan is endothermic, non-spontaneous, and the molecules at the transition state is more ordered than at the ground state. The ΔH‡ and the ΔS‡ are not affected by temperature, while the ΔG‡ is a weak function of temperature. The ΔH‡ and ΔS‡ become smaller at higher pH, while the ΔG‡ increases with the increase of pH. The kinetics and thermodynamics analysis show that the ultrasound-assisted depolymerization of k-carrageenan in acidic solution is possibly through three mechanisms, i.e. bond cleavage due to cavitational effect of microbubbles, hydroxyl radical and hydrogen peroxide, as well as proton. Copyright © 2020 BCREC Group. All rights reserved 

Application of the Monte Carlo simulation method to the Investigation of the effect of chain-length-dependent bimolecular termination on ATRP

e-Polymers ◽  
2009 ◽  
Vol 9 (1) ◽  
Author(s):  
Mohammad Najafi ◽  
Vahid Haddadi-Asl ◽  
Mehdi Salami-Kalajahi ◽  
Hossein Roughani Mamaghani
Keyword(s):  
Molecular Weight ◽  
Monte Carlo Simulation ◽  
Monte Carlo ◽  
Reaction Time ◽  
Chain Length ◽  
Molecular Weight Distribution ◽  
Rate Constant ◽  
Weight Distribution ◽  
Polymer Chains ◽  
Termination Rate

AbstractAn optimized and high-performance Monte Carlo simulation is developed to take thorough account of the influence of chain-length-dependent termination rate constant on polymer microstructure in ATRP. According to the simulation results, bimolecular termination rate constant sharply drops throughout the polymerization when chain length dependency is applied to the program. The dependence of on reaction time, as a common feature of ATRP, is almost linear. Moreover, the polymerization proceeds to higher conversion when the chain-length-dependent termination rate constant is applied to the simulation model. In addition, the plot of against reaction time is completely linear; also, the initiator is entirely decomposed at the early stages of the polymerization as the plot of CIagainst time shows. The concentration of the catalyst in lower oxidation state decreases first and then plateaus at higher conversion. Furthermore, the amount of Mtn Y/L used in the polymerization is lower when the chain-length-dependent termination rate constant is employed in the simulation. Finally, the peak of molecular weight distribution of polymer chains shifts toward higher molecular weight during the reaction. Besides, the molecular weight distribution broadens at higher conversion. However, the molecular weight distribution of polymer chains produced under conditions of applying chain-lengthdependent termination rate constant is narrower.

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