This method is evaluated on a simulation of the semibatch emulsion polymerization of styrenebutadiene. Experimental data available in the literature are employed to assess the proposed model. The effect of initiator concentration and monomer feeding time feed flow rate on the kinetics, fraction of gel, molecular weight distributions, and level of branches were studied. For situations where the mass trans fer rate of the small radicals from the particles into the water phase is much less than the propagation rate of the radicals, i. The most important advantage of the semi batch process in the emulsion polymerization is its operational flexibility in relation to the batch and continuous processes. Lx gy a macromonomers is performed to obtain nps with a low polydispersity index and a controlled size. Our results reveal that sufficient emulsification is essential for the control of the polymerisation process. Emulsion polymerization ferdowsi university of mashhad. There are three types of emulsion polymerization processes.
Two important features of semibatch emulsion polymerization reactions. The semibatch emulsion polymerization for a two monomer copolymerization is considered as a case study. The mathematical framework is based on the population. Eindhoven university of technology master dynamic modeling of. One of the most widely used methods of manufacturing vinyl polymers, emulsion polymerization involves formation of a stable emulsion often referred to as a latex of monomer in water using a soap or detergent as the emulsifying agent. A comprehensive mathematical model is developed for emulsion polymerisation of butyl acrylate to polybutyl acrylate in a semi batch reactor. The emulsion copolymer product is particularly useful in latex paints where it improves the gloss and scrub resistance of the paint. A bimodal polymer composition prepared by the process of carrying out an aqueous semi continuous emulsion polymerization is also provided. The effects of monomer concentration on the kinetics of emulsion polymeriza. Optimisation of emulsion copolymerization of styrene and mma. The polymerization is usually carried out using water as the dispersion medium.
A mathematical model for the computation of kinetics, branching frequency, sol molecular weight distribution, and gel fraction for the seeded semicontinuous emulsion polymerization of nba is presented. Nanoparticle formation by monomerstarved semibatch. Emulsion polymerization in which all the ingredients are placed in a reactor prior to reaction. Temperature control of an emulsion polymerization process. A modelbased framework for optimal operation of copolymerization processes was used in gproms environment and enables us to. It has been reported in the literature that semi batch emulsion polymerization processes gener ate a larger number of polymer particles com pared with. Robust dynamic optimization of a semibatch emulsion. The importance of robust control for polymerization processes is increasing due to the high industrial demands. The liquid phase polymerization takes place in a semibatch reactor, where two operating conditions are compared. On the other hand, semi batch operations are rarely used to carry out suspension polymerizations. Influence of semibatch operations on morphological. Us4946891a semicontinuous emulsion polymerization process.
Elaasser emulsion polymers institute and department of chemical engineering, lehigh university, bethlehem, pa, usa emulsion polymerization is a technologically and commercially important reaction used to produce synthetic polymers and latexes. Although the monomerstarved semi batch process is widely used, reports on the mass transfer and mixing aspects of this process are relatively scarce in the literature. Emulsion polymerization can be carried out using batch, semibatch or. The most important advantage of the semibatch process in the emulsion polymerization is its operational flexibility in relation to the batch and continuous processes.
Effect of 2eha as a soft monomer on the adhesion properties. As reactant monomer converts into polymer chains, the density of the reacting mixture often changes notably. Tromsdorff effect or autoacceleration mit opencourseware. A mathematical model for the computation of kinetics, branching frequency, sol molecular weight distribution, and gel fraction for the seeded semicontinuous emulsion polymerization of n. Semibatch emulsion polymerization of styrene under the monomer. This model can be used to design, optimize and control emulsion copolymerization in well. This paper presents an emulsionpolymerization model that is designed for an industrial, semibatch reactor. Instead of designing complicated control solutions, two relativly simple control structures that provide signi cant performance improvements are combined to manipulate the monomer feed directly so that. Relative importance of the effects of seed and feed stage. Pdf semibatch emulsion polymerization of methyl methacrylate mma with neat monomer feed in the presence of sodium lauryl sulphate as.
Effect of monomer feed rate on the properties of copolymer. Batch emulsion polymerization pure eindhoven university. Emulsion polymerization and emulsion polymers wiley. This in turn lowers the effective termination rate k.
This paper describes the research on chemical engineering aspects of emulsion polymerization in semibatchwise operated stirred tanks. An overview of polymerization processes is given in asua 2007. Most of the water used in the batch is charged initially. Modelling, validation and effect of operating conditions. A bimodal polymer composition prepared by the process of carrying out an aqueous semicontinuous emulsion polymerization is also provided. Machado, in reference module in materials science and materials engineering, 2017. Reaction kinetics in semibatch emulsion polymerization of methyl methacrylate, were monitored by automatic continuous online monitoring of. Optimal control of a hightemperature semibatch solution. Emulsion polymerization in various reactor types 4973 the water phase. Pressure sensitive adhesives psas were produced using latexes synthesized via a starved seeded semibatch emulsion polymerization process with butyl acrylate ba, methyl methacrylate mma and. To understand the effect of each snp modification procedure, a series of controlled experiments was conducted. Semibatch emulsion polymerization of butyl acrylate. This approach leads to multivariate statistical process control plots which are very powerful in detecting subtle changes in process variable trajectories throughout the batch. Scheme for timeoptimal operation of semibatch emulsion.
The semi batch emulsion polymerization for a two monomer co polymerization is considered as a case study. The process is complex as nucleation, growth and stabilization of polymer particles are controlled by free radical polymerization mechanisms in combination with other colloidal phenomena. The total amount of pre emulsion was continuously to the glass reactor with the speed 1. Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. Reactor design and scaleup in emulsion polymerization m. Emulsion polymerization an overview sciencedirect topics.
The total amount of preemulsion was continuously to the glass reactor with the speed 1. Emulsion polymerization is an industrially important process for the production of polymers used as synthetic rubber, adhesives, paints, inks, coatings, etc. The most common type of emulsion polymerization is an oilinwater emulsion, in which droplets of monomer the oil are emulsified with surfactants in a continuous phase of water. Modeling of seeded semibatch emulsion polymerization of nba. Abstract unseeded semibatch emulsion polymerization of butyl acrylate ba using sodium lauryl sulfate as emulsifier and potassium persulfate. This was achieved by using no emulsifier in the initial reactor charge. Publishers pdf, also known as version of record includes final page. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. Although the monomerstarved semibatch process is widely used, reports on the mass transfer and mixing aspects of this process are relatively scarce in the literature. The seeded semibatch emulsion polymerization of nbutyl acrylate was investigated using potassium persulfate as initiator at 75 c. This makes emulsion polymerization less detrimental to the environment than other.
An extended dynamic model for semi batch ab initia emulsion polymerization is developed and validated for the emulsion polymerization of styrene. Heat balances about the latex reactor and cooling jacket with proportionalintegral control are included. Unseeded semibatch emulsion polymerization of butyl acrylate ba using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator was carried out at the conditions where secondary nucleation was probable. Pentanol as cosurfactant polystyrene nanolatexes preparation. In this example you will look at how this effect impacts the total production of polymer in a process. Stirring in both types is very efficient, which allows batch and semibatch reactors to assume a uniform composition and temperature throughout.
The key process technique involved in the semibatch process, however, is the delayed monomer addition which permits easy control over the polymerization rate, polymer ization temperature, the copolymer composition, particle size and polymer molecular weight. Unseeded semibatch emulsion polymerization of butyl acrylate. Improved control through a semibatch process in raft. Optimisation of emulsion co polymerization of styrene and mma in semi batch reactor wan hanisah b. Semicontinuous emulsion polymerization process download pdf. Emulsion polymerization and emulsion polymers polymer. Proportionalintegralderivative pid control works well for incremental batch emulsion polymerization but. Good chemical engineering is important to guarantee product quality and to minimise the energy consumption as well as the production of waste material.
Temperature control of an emulsion polymerization batch is crucial for final product quality such as crosslinking when using diene monomers such as 1,3 butadiene. The key process technique involved in the semibatch process, however, is the delayed monomer addition which permits easy control over the polymerization rate, polymerization temperature, the copolymer composition, particle size and polymer molecular weight. On the other hand, semibatch operations are rarely used to carry out suspension polymerizations. Optimisation of emulsion copolymerization of styrene and. Different composition polymethyl methacrylatecobutyl methacrylate copolymers through seeded semi batch emulsion polymerization. Introduction the objective of this work is to investigate the effects of seed stage and feed stage agitation in a semibatch emulsion copolymerization of nbutyl methacrylate and nmethylol acrylamide. As an alternative to microemulsion polymerization, the monomer starved semibatch emulsion polymerization can be used to produce the nanolatex 3.
Pdf semibatch emulsion polymerization of methyl methacrylate. Emulsion polymerization and emulsion polymers edited by peter a. Among these processes the most versatile is the semi batch, although it is not so used as the other types. This paper presents an emulsion polymerization model that is designed for an industrial, semi batch reactor. The model consists of a reaction model and a calorimetry model, and as such enables us to predict the reactor temperature and the batchoutput parameters, i. An aqueous semi continuous emulsion polymerization process for producing bimodal polymer particles in volumes large than a single batch size is provided. The model consists of a reaction model and a calorimetry model, and as such enables us to predict the reactor temperature and the batch output parameters, i. An extended dynamic model for semibatch ab initia emulsion polymerization is developed and validated for the emulsion polymerization of styrene. Agitation effects in emulsion copolymerization of nbutyl.
Seeded semibatch emulsion polymerization of nbutyl acrylate. An aqueous semicontinuous emulsion polymerization process for producing bimodal polymer particles in volumes large than a single batch size is provided. Studies and practical applications of semibatch operations in heterogeneous systems are commonly found for emulsion polymerization systems in order to control copolymer composition, molecular. Emulsion polymerization in practice is a very simple process, consisting of a reaction system in which the monomers are stabilized via the use of surfactants and are dispersed in an aqueous phase. As an alternative to microemulsion polymerization, the monomer starved semi batch emulsion polymerization can be used to produce the nanolatex 3. Studies and practical applications of semi batch operations in heterogeneous systems are commonly found for emulsion polymerization systems in order to control copolymer composition, molecular. Among these processes the most versatile is the semibatch, although it is not so used as the other types.
The most important industrial manufacturing technique is the semibatch process. Pdf different composition polymethyl methacrylatecobutyl. The modified snps were then incorporated in a semibatch emulsion polymerization to produce stable snpbased latexes. Elaasser emulsion polymers institute and department of chemical engineering, lehigh university, bethlehem, pa, usa emulsion polymerization is a technologically and commercially important reaction used to produce synthetic polymers and latexes for a. Different composition polymethyl methacrylatecobutyl methacrylate copolymers through seeded semibatch emulsion polymerization. Optimization of emulsion polymerization of styrene and methyl methacrylate mma abstract this paper studies the optimization of emulsion copolymerization of styrene and methyl methacrylate mma. This paper describes the research on chemical engineering aspects of emulsion polymerization in semi batchwise operated stirred tanks. Optimisation of emulsion copolymerization of styrene and mma in semibatch reactor wan hanisah b. The stabilizer system, buffer, and other miscellaneous components are added and dissolved in the water. Philadelphia, pa 19146 abstractthis paper deals with the calculation and realtime implementation of optimal temperature and feed. Semibatch emulsion polymerization of methyl methacrylate with. Unseeded semibatch emulsion polymerization of butyl. Lovell manchester materials science centre, umist, manchester, uk and mohamed s. Semicontinuous microemulsion polymerization pdf free download.
Particle formation and growth in semibatch emulsion polymerisation. In industry latex products are usually produced in semi batch emulsion polymerisation processes. Modelling, simulation and control of an industrial, semi. Tromsdorff effect or autoacceleration autoacceleration usually occurs in radical chain polymerizations and normally in bulk polymerization. Study of different types of monomer emulsion feedings to semibatch emulsion polymerization reactors article in journal of applied polymer science 8210.
Toolbox for generation of nonlinear control models for semi. Semicontinuous ow microemulsion polymerization two approaches have been proposed to increase the polymer content using the excess surfactant remaining after the batch microemulsion polymerization. Semibatch emulsion polymerization of methyl methacrylate with a. Biosynthetic emulsion polymer latexes for adhesive. The model also comprises of diffusioncontrolled kinetics and covers the whole course of the polymerization reaction. Cunningham queens university the principles of designing and safely operating emulsion polymerization reactors will be presented in the context of how the selection of reactor type, mode of operation batch, semibatchsemicontinuous. Seeded semibatch emulsion polymerization ofnbutyl acrylate.
Control of particle size distribution in emulsion polymerization using midcourse correction under structural plantmodel mismatch. Study of different types of monomer emulsion feedings to. With the exception of miniemulsion polymerization, the term emulsion polymerization does not mean that polymerization occurs in the droplets of a monomer emulsion. Semibatch emulsion polymerization of methyl methacrylate mma with neat monomer feed in the presence of sodium lauryl sulphate as emulsifier and potassium persulphate as. An investigation of emulsion polymerisation of butyl acrylate in batch and semibatch reactors has been carried out. As a result emulsion polymerization was a challenge to model. Pdf seeded semibatch emulsion polymerization ofnbutyl. Emulsion polymerization is a heterogeneous, multiphase, free radical polymerization process. The objective of this work was to improve the operation of current processes and to allow for improvements in the development of novel emulsion polymerization processes. Semicontinuous emulsion polymerization springerlink. Semibatch emulsion polymerization of methyl methacrylate mma with neat monomer feed in the presence of sodium lauryl sulphate as emulsifier and potassium persulphate as initiator was investigated. We have studied the role of agitation in different aspects of semibatch emulsion copolymerization of a relatively waterinsoluble nbutyl. A semibatch reactor, however, allows partial filling of reactants with the flexibility of adding more as time progresses. Industrial emulsion polymerization is often performed as a semi.
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