Advances in Chemical Engineering and Science

Advances in Chemical Engineering and Science

2017, 7, 408-419

引用网址

ISSN Online: 2160-0406 

ISSN Print: 2160-0392

DOI:  10.4236/aces.2017.74029   Oct. 17, 2017  408  Advances in Chemical Engineering and Science  

Modeling and Simulation of an Isothermal

Suspension Polymerization Reactor for PMMA

Production Using Python 

Aldo Okullo *, Noah Tibasiima, Joshua Barasa

Department of Chemistry, Kyambogo University, Kampala, Uganda 

        Abstract  

        This paper presents the modeling and simulation of a suspension polymeriz ation for methylmethacrylate in an isothermal reactor to produce poly methyl methacrylate using Python 3.5. The numeral solution to the stiff ordinary di ferential equations was performed by building a custom module which was used with the inbuilt NumPy and matplotlib modules that come with the Anaconda python distro. Python was used in order to obtain a realistic solution that considers the gel, glass and cage effects that affect the non-linear polymerization kinetics established in literature. The results showed that a maximum monomer conversion of about 92.8% at a minimum batch time of about 2.2 hours could be achieved at the specified conditions to obtain a polydisperse polymer with an index of 27. It is further concluded that Python can be employed to perform similar studies with equal success as any other programming language. 

        Keywords 

Suspension Polymerization, Modeling, Simulation, Python  

        Context

        1. Introduction 

        Poly (methyl methacrylate) (PMMA) is a transparent thermoplastic used in a wide range of fields including medicine, art, and aesthetics. It is also used as an alternative to glass due to its shatter -resistance property  [1]. There has been a widespread need to use PMMA based components in Uganda especially for construction and medicine purposes, however advancing the technology that addresses industrial polymerization process es is often hampered by a lack of fundamental research activities in academic and the few industrial labs available in How to cite this paper:  Okullo, A., Tibasiima, N. and Barasa, J. (2017) Modeling and Simulation of an Isothermal Suspension Polymerization Reactor for PMMA Production Using Python .  Advances in Chemical Engineering and Science ,

        This work is licensed under the Creative Commons Attribution International the country. 

Industrially, PMMA is obtained from the freeradical polymerization of methyl methacrylate [2] which may be produced via methanolysis of methylcrylamide sulphate [3] . The polymerization reaction is commonly initiated by the rmal radical forming agents often employing organic peroxy compounds and azo-compounds [4]. Suspension polymerization is used for the commercial  production of many important polymers other than PMMA such as polyvinyl chloride and polystyrene [5] with similar properties to those produced from bulk  polymerization. The limitations of increased viscosity, reaction temperature, and  volume contraction in the latter process are always avoided [6]. The process may be described as being operated batch -wise however, in essence it is often in a semi-batch mode since some material enters the reactor after the start of polymerization. 

        During the process, the monomer is stirred with about twice its volume of water and dispersants forming droplet -like distribution of the monomer phase in water. The mechanism of polymerization corresponds to that of bulk polymerization and as such, the droplets  become increasingly viscous during the course of polymerization. Distributors such as gelatin stabilize the suspension and prevent the droplets from adhering to one another during collisions. The system is heterogeneous therefore the polymer is collected  as granular beads on completion of polymerization and it is washed to remove adhering distributor and salts then dried [7]. 

        Various works have been published on the modeling of methyl methacrylate polymerization processes. A major feature of these studies is the observation in the increase of the mass reaction viscosity with monomer conversion resulting into a deviation from the “normal” kinetic. The severe reduction in the mobility of the macroradicals auto accelerates the reaction causing an increase in the gel effect and a decrease in the termination rate constant. If the polymerization is carried out at lower temperatures, the glass effect occurs when the transiti on state is reached at a certain conversion causing a decrease in the propagation rate constant. This results in the interruption of the reaction before the monomer is completely consumed. The increased viscosity at high monomer conversion leads to a decrease in the initiator efficiency due to the cage effect [8]. In most of the reviewed works, gel and glass effects are modeled according to Chiuet al. [9] and the cage effect is modeled according to Achilias Kiparissides [10]. Most of the models considered are reported to have worked well for MMA polymerization [11], however the general model developed by Seth and Gupta [12] and reworked by Ghosh et al . [13] using free volume theory is noted as being most superior [8]. Several simulation packages to assess the performance of the models under consideration have been used such as MATLAB [14],gPROMS [15], FORTRAN  [16], which are based on utilization of sequential quadratic programming, ordinary differential equations and fuzzy-neural modeling. 

        From the above, it can be seen that techniques applied in modeling polymerization processes are reasonably well developed and several commercial simulation packages are available. However a user of such techniques and packages should keep in mind that software cannot be a substitute for engineering judgement and its use without understanding is a dangerous abandonment of professional responsibility [17]. The aim of this paper is to model and simulate the polymerization of methyl methacrylate to PMMA in an isothermal suspension reactor. The reactor performance is studied by modeling and simulation using Python 3.5 instead of using experimental assessment. This is because the procedure requires low computational demand in performing the reactor studies and besides high -quality data is available for validation and comparison with literature values.  

        2. Model Formulation 

        The kinetics of MMA polymerization are described basing on the free radical polymerization mechanism scheme in Table 1   below. The scheme map comprises the initiation step, where the initiator (I ) decomposes to form reactive radicals (R), the addition of monomer molecules ( M ) to the reactive polymer chain formed from the reactive radicals and the termination step where deactivation of polymer radicals occur. The initiator used is Benzo Peroxide (BPO).  P and D represent the live and dead polymer with n and m monomeric units respectively; whereas the kinetic constants for the initiator decomposition, initiation, propagation and termination are respectively. 

        In this work,the process model in [12] [13] with slight adjustments was followed. The assumptions used in this work are: 

1) The reactor operates isothermally at 70°C 

2) All reaction steps in the system are irreversible 

3)  Chain transfer to the monomer is negligible compared to other reactisteps 

4)  The dispersion generated in water isolates the monomer thus negligible evaporation rate 

5) Each droplet behaves as a batch reactor operating in bulk  

6) Termination is due to disproportionation only 

7) The volume of the liquid phase is unaffected by the small amount of initiator  

8) There is no polymer at the beginning of the process 

        Using the above assumptions, the initiator (I ), monomer ( M ) and radical species (R ) balances are; 

        3. Results and Discussion 

        A program to solve the above equations was developed using the object- oriented language Python 3.5 installed via the Anaconda distro. The NumPy module [22] and a customized module were used to solve for the stiff ODEs and results were ported to matplotlib whose output has a close resemblance to the well -known MATLAB format. In order to simulate the performance of the model, it was assumed that 2 tonnes of monomer were fed to the reactor and the initiator (1% wt. of monomer) was added in 1 minute at constant rate after which the addition rate was stopped. The temperature was fixed at 70°C. The reaction progressed for the 3 hours.

        4. Conclusion 

The simulation of suspension polymerization model has been performed in Python 3.5. The prediction results were in good agreement as those reported in literature. A maximum monomer conversion of about 92.8% at a minimum batch time of about 2.2 hours was achieved at the specified conditions. The results of this work have demonstrated that Python can be employed to perform modeling and simulation studies of polymerization based processes effectively with equal success as any other programming language.

        References 

[1] Arora, P., Jain, R., Mathur, K., Sharma, A. and Gupta, A. (2010) Synthesis of Poly-

methyl Methacrylate (PMMA) by Batch Emulsion Polymerization.  African Journal  of Pure and Applied Chemistry

[2] Billmeyer, F.W.  (1971) Textbook of Polymer Science.  John Wiley & Sons, New York.   

[3] Odian, G. (1970) Principles of Polymerization. McGraw-Hill, New York.   

[4] Allen, G. and Bevington, J.C.  (1989) Comprehensive Polymer Science.   PergamonPress, New York.   

[5] Caytano, T.R.A. and Machado, R.A.F. (2011) Soft-Sensor Based on Artificial Neuronal Network for the Prediction of Physico-chemical Variables in Suspension Polymerization Reactions. Chemical Engineering Transactions , 529-534.   

[6] Verros, G.D., Achilias, D.S. and Giannoukos, G.I. (2011) Development of a Comprehensive Mathematical Model for Free Radical Suspension Polymerization of Methyl Methacrylate. Polymer Engineering and Science

[7]  Klaus, A., Manfred, S. and Thomas, R. (2016) Polymethacrylates in Ullmann’s Polymers and Plastics: Products and Processes, Wiley-VCH 

[8] Silvia, C. and Victor, B. (1999) Free Radical Polymerization of Methyl Methacrylate Modeling and Simulation under Semibatch and Nonisothermal Reactor Conditions. 

[9]  Chiu, W.Y., Carratt, G.M. and Soong, S.D. (1983) A Computer Model for the Gel Effect in Free-Radical Polymerization.

[10]  Achilias, D.S. and Kiparissides, C. (1992) Development of a General Mathematical Advances in Chemical Engineering and Science Framework for Modelling Diffusion-Controlled Free-Radical Polymerization Reaction. 

[11] Garg, D.K., Serra, C.A., Hoarau, Y., Parida, D., Bouquey, M. and Muller, R. (2014) 

Analytical Solution of Free Radical Polymerization: Applications Implementing Gel Effect Using AK Model. 

[12]  Seth, V. and Gupta, S.K. ( 1995)  Free Radical Polymerizations Associated with the  Trommsdorff Effect under Semibatch Reactor Conditions: An Improved Model . 

[13]  Ghosh, P., Gupta, S.K. and Saraf, D.N.  (1998) An Experimental Study on Bulk and 

Solution Polymerization of Methyl Methacrylate with Responses to Step Changes in Temperature. 

[14] Rosa, J.N.D.  (2011) Modeling and Simulation of a Lab- Scale Polymerization Reactor. Dissertação de mestrado, ROSA, Jaquelino Nascimento da.  

[15] Ekpo, E.E.  (2006) Dynamic Optimisation and Control of Batch Polymerization Process. Ph.D. Thesis, University of Bradford, Bradford.   

[16] Fangbin, Z., Gupta, S.K. and Ray, A.K.  (2001) Modeling of the Sheet -Molding Process for Poly (Methyl Methacrylate).

[17] Moran, S.  (2015) An Applied Guide to Process Plant Design. Butter worth-Heinemann, 

Oxford. 

[18] Achilias, D.S.  and Kiparissides, C.  (1994) On the Validity of the Steady State A p-

proximations in High Conversion Diffusion Controlled Free -Radical Copolymerization Reactions. 

[19]  Penlidis, A.,  Ponnuswamy, S.R ., Kiparissides, C. and O'Driscoll, K.F. ( 1992) Polymer Reaction Engineering: Modeling Consideration for Control Studies . 

[20]  Dotson, N.A.,  Galvan, R. ,  Laurence,  R.L. and Tirrell, M. ( 1996)  Polymerization Process Modeling. VCH Publishers, New York. 

[21] Ray, W.H. ( 1972)  On the Mathematical Modeling of Polymerization Reactors .

[22]  Kiusalaas, J. (2010)  Numerical Methods in Engineering Using Python.  Cambridge  University Press, New York.