Bulk Polymerization of Styrene using Multifunctional Initiators in a Batch Reactor: A Comprehensive Mathematical Model

2016 ◽  
Vol 14 (1) ◽  
pp. 315-329 ◽  
Author(s):  
E. Berkenwald ◽  
M. L. Laganá ◽  
P. Acuña ◽  
G. Morales ◽  
D. Estenoz
Keyword(s):  
Mathematical Model ◽  
Molecular Weight ◽  
Batch Reactor ◽  
Kinetic Mechanism ◽  
Bulk Polymerization ◽  
Diethyl Ketone ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
Global Reaction ◽  
The Mathematical Model

AbstractA detailed, comprehensive mathematical model for bulk polymerization of styrene using multifunctional initiators – both linear and cyclic – in a batch reactor was developed. The model is based on a kinetic mechanism that considers thermal initiation and chemical initiation by sequential decomposition of labile groups, propagation, transfer to monomer, termination by combination and re-initiation reactions due to undecomposed labile groups. The model predicts the evolution of global reaction variables (e.g, concentration of reagents, products, radical species and labile groups) as well as the evolution of the detailed complete polymer molecular weight distributions, with polymer species characterized by chain length and number of undecomposed labile groups. The mathematical model was adjusted and validated using experimental data for various peroxide-type multifunctional initiators: diethyl ketone triperoxide (DEKTP, cyclic trifunctional), pinacolone diperoxide (PDP, cyclic bifunctional) and 1,1-bis(tert-butylperoxy)cyclohexane (L331, linear bifunctional). The model very adequately predicts polymerization rates and complete molecular weight distributions. The model is used to theoretically evaluate the influence of initiator structure and functionality as well as reaction conditions.

Polymerization of styrene using 1,1,2,2-tetraphenyl-1,2- ethanediol as initiator in the presence of 2,2,6,6-tetramethyl- 1-piperidinyloxy

e-Polymers ◽  
2004 ◽  
Vol 4 (1) ◽  
Author(s):  
Gang Wang ◽  
Xiulin Zhu ◽  
Dijun Hu ◽  
Zhengping Cheng ◽  
Jian Zhu
Keyword(s):  
Molecular Weight ◽  
Monomer Concentration ◽  
Bulk Polymerization ◽  
Polymerization Rate ◽  
First Order ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
End Groups

Abstract The bulk polymerization of styrene using 1,1,2,2-tetraphenyl-1,2-ethanediol as initiator in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) was investigated. The results show that polymerization proceeded in a controlled/ ’living’ way, i.e., polymerization rate is first order with respect to monomer concentration. Molecular weights increase linearly with conversion and molecular weight distributions are relatively low (Mw/Mn = 1.10 - 1.35). Well-defined polystyrenes with α-hydrogen and TEMPO end groups were obtained.

The Use of Novel F-RAFT Agents in High Temperature and High Pressure Ethene Polymerization: Can Control be Achieved?

2007 ◽  
Vol 60 (10) ◽  
pp. 788 ◽  
Author(s):  
Markus Busch ◽  
Marion Roth ◽  
Martina H. Stenzel ◽  
Thomas P. Davis ◽  
Christopher Barner-Kowollik
Keyword(s):  
Molecular Weight ◽  
High Pressure ◽  
High Temperature ◽  
Degree Of Polymerization ◽  
Molecular Weight Distributions ◽  
High Pressure High Temperature ◽  
Reversible Addition ◽  
Weight Distributions ◽  
Raft Agent ◽  
Initial Results

Simulations are employed to establish the feasibility of achieving controlled/living ethene polymerizations. Such simulations indicate that reversible addition–fragmentation chain transfer (RAFT) agents carrying a fluorine Z group may be suitable to establish control in high-pressure high-temperature ethene polymerizations. Based on these simulations, specific fluorine (F-RAFT) agents have been designed and tested. The initial results are promising and indicate that it may indeed be possible to achieve molecular weight distributions with a polydispersity being significantly lower than that observed in the conventional free radical process. In our initial trials presented here (using the F-RAFT agent isopropylfluorodithioformate), a correlation between the degree of polymerization and conversion can indeed be observed. Both the lowered polydispersity and the linear correlation between molecular weight and conversion indicate that control may in principle be possible.

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