Effect of monomer feed rate on the properties of copolymer. Study of different types of monomer emulsion feedings to semibatch emulsion polymerization reactors article in journal of applied polymer science 8210. Experimental data available in the literature are employed to assess the proposed model. Reactor design and scaleup in emulsion polymerization m.
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. The model also comprises of diffusioncontrolled kinetics and covers the whole course of the polymerization reaction. Pentanol as cosurfactant polystyrene nanolatexes preparation. A bimodal polymer composition prepared by the process of carrying out an aqueous semicontinuous emulsion polymerization is also provided. Emulsion polymerization and emulsion polymers wiley. On the other hand, semibatch operations are rarely used to carry out suspension polymerizations. The most important industrial manufacturing technique is the semibatch process. There are three types of emulsion polymerization processes. Lovell manchester materials science centre, umist, manchester, uk and mohamed s. Operation of semibatch emulsion polymerisation reactors. Emulsion polymerization in various reactor types 4973 the water phase. 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. Eindhoven university of technology master dynamic modeling of.
Effect of 2eha as a soft monomer on the adhesion properties. An investigation of emulsion polymerisation of butyl acrylate in batch and semibatch reactors has been carried out. Modeling of seeded semibatch emulsion polymerization of nba. Semibatch emulsion polymerization of styrene under the monomer. Most of the water used in the batch is charged initially. 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. Pdf semibatch emulsion polymerization of methyl methacrylate. Biosynthetic emulsion polymer latexes for adhesive. Tromsdorff effect or autoacceleration autoacceleration usually occurs in radical chain polymerizations and normally in bulk polymerization. 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.
Seeded semibatch emulsion polymerization ofnbutyl acrylate. The polymerization is usually carried out using water as the dispersion medium. Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. Different composition polymethyl methacrylatecobutyl methacrylate copolymers through seeded semi batch emulsion polymerization. Tromsdorff effect or autoacceleration mit opencourseware. Influence of semibatch operations on morphological. Optimisation of emulsion copolymerization of styrene and mma in semibatch reactor wan hanisah b. Semibatch emulsion polymerization of methyl methacrylate with a. Emulsion polymerization is a heterogeneous, multiphase, free radical polymerization process. Pdf seeded semibatch emulsion polymerization ofnbutyl. The stabilizer system, buffer, and other miscellaneous components are added and dissolved in the water.
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. 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. Optimisation of emulsion copolymerization of styrene and. Abstract unseeded semibatch emulsion polymerization of butyl acrylate ba using sodium lauryl sulfate as emulsifier and potassium persulfate. Optimisation of emulsion copolymerization of styrene and mma. To understand the effect of each snp modification procedure, a series of controlled experiments was conducted. 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.
Optimal control of a hightemperature semibatch solution. 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. This in turn lowers the effective termination rate k. 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. Emulsion polymerization can be carried out using batch, semibatch or. Improved control through a semibatch process in raft. An extended dynamic model for semi batch ab initia emulsion polymerization is developed and validated for the emulsion polymerization of styrene. Semibatch emulsion polymerization of methyl methacrylate mma with neat monomer feed in the presence of sodium lauryl sulphate as emulsifier and potassium persulphate as.
Semibatch emulsion polymerization of methyl methacrylate with. 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. 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. A modelbased framework for optimal operation of copolymerization processes was used in gproms environment and enables us to. Emulsion polymerization in which all the ingredients are placed in a reactor prior to reaction. Our results reveal that sufficient emulsification is essential for the control of the polymerisation 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. Control of particle size distribution in emulsion polymerization using midcourse correction under structural plantmodel mismatch. 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. Modelling, simulation and control of an industrial, semi. Emulsion polymerization an overview sciencedirect topics.
A bimodal polymer composition prepared by the process of carrying out an aqueous semi continuous emulsion polymerization is also provided. This paper describes the research on chemical engineering aspects of emulsion polymerization in semi batchwise operated stirred tanks. The semibatch emulsion polymerization for a two monomer copolymerization is considered as a case study. This method is evaluated on a simulation of the semibatch emulsion polymerization of styrenebutadiene. The total amount of pre emulsion was continuously to the glass reactor with the speed 1. The emulsion copolymer product is particularly useful in latex paints where it improves the gloss and scrub resistance of the paint. The total amount of preemulsion was continuously to the glass reactor with the speed 1. Seeded semibatch emulsion polymerization of nbutyl 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. The modified snps were then incorporated in a semibatch emulsion polymerization to produce stable snpbased latexes.
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. As a result emulsion polymerization was a challenge to model. The most important advantage of the semibatch process in the emulsion polymerization is its operational flexibility in relation to the batch and continuous processes. Two important features of semibatch emulsion polymerization reactions. It has been reported in the literature that semi batch emulsion polymerization processes gener ate a larger number of polymer particles com pared with. Among these processes the most versatile is the semi batch, although it is not so used as the other types. 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. Relative importance of the effects of seed and feed stage. 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. The effects of monomer concentration on the kinetics of emulsion polymeriza. Stirring in both types is very efficient, which allows batch and semibatch reactors to assume a uniform composition and temperature throughout. This paper presents an emulsionpolymerization model that is designed for an industrial, semibatch reactor. Pdf semibatch emulsion polymerization of methyl methacrylate mma with neat monomer feed in the presence of sodium lauryl sulphate as.
Scheme for timeoptimal operation of semibatch emulsion. Among these processes the most versatile is the semibatch, although it is not so used as the other types. Temperature control of an emulsion polymerization process. Different composition polymethyl methacrylatecobutyl methacrylate copolymers through seeded semibatch emulsion polymerization. This was achieved by using no emulsifier in the initial reactor charge. Nanoparticle formation by monomerstarved semibatch. We have studied the role of agitation in different aspects of semibatch emulsion copolymerization of a relatively waterinsoluble nbutyl.
The importance of robust control for polymerization processes is increasing due to the high industrial demands. 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. This paper presents an emulsion polymerization model that is designed for an industrial, semi batch reactor. Agitation effects in emulsion copolymerization of nbutyl. This model can be used to design, optimize and control emulsion copolymerization in well. On the other hand, semi batch operations are rarely used to carry out suspension polymerizations. This paper describes the research on chemical engineering aspects of emulsion polymerization in semibatchwise operated stirred tanks. An extended dynamic model for semibatch ab initia emulsion polymerization is developed and validated for the emulsion polymerization of styrene. The liquid phase polymerization takes place in a semibatch reactor, where two operating conditions are compared. 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. With the exception of miniemulsion polymerization, the term emulsion polymerization does not mean that polymerization occurs in the droplets of a monomer emulsion. An aqueous semi continuous emulsion polymerization process for producing bimodal polymer particles in volumes large than a single batch size is provided. Publishers pdf, also known as version of record includes final page.
Emulsion polymerization and emulsion polymers edited by peter a. Optimisation of emulsion co polymerization of styrene and mma in semi batch reactor wan hanisah b. 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. In this example you will look at how this effect impacts the total production of polymer in a process. 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.
Unseeded semibatch emulsion polymerization of butyl acrylate. 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. In industry latex products are usually produced in semi batch emulsion polymerisation processes. Toolbox for generation of nonlinear control models for semi. A comprehensive mathematical model is developed for emulsion polymerisation of butyl acrylate to polybutyl acrylate in a semi batch reactor.
A semibatch reactor, however, allows partial filling of reactants with the flexibility of adding more as time progresses. Modelling, validation and effect of operating conditions. Industrial emulsion polymerization is often performed as a semi. Semibatch emulsion polymerization of butyl acrylate. 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. This makes emulsion polymerization less detrimental to the environment than other. Philadelphia, pa 19146 abstractthis paper deals with the calculation and realtime implementation of optimal temperature and feed. Us4946891a semicontinuous emulsion polymerization process. Semicontinuous microemulsion polymerization pdf free download. The mathematical framework is based on the population. Semicontinuous emulsion polymerization springerlink.
Emulsion polymerization is an industrially important process for the production of polymers used as synthetic rubber, adhesives, paints, inks, coatings, etc. As an alternative to microemulsion polymerization, the monomer starved semibatch emulsion polymerization can be used to produce the nanolatex 3. Study of different types of monomer emulsion feedings to. The semi batch emulsion polymerization for a two monomer co polymerization is considered as a case study. Lx gy a macromonomers is performed to obtain nps with a low polydispersity index and a controlled size. 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. An aqueous semicontinuous emulsion polymerization process for producing bimodal polymer particles in volumes large than a single batch size is provided. Pdf different composition polymethyl methacrylatecobutyl. Particle formation and growth in semibatch emulsion polymerisation. 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. 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. 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. Robust dynamic optimization of a semibatch emulsion.
Emulsion polymerization and emulsion polymers polymer. Studies and practical applications of semibatch operations in heterogeneous systems are commonly found for emulsion polymerization systems in order to control copolymer composition, molecular. Semicontinuous emulsion polymerization process download pdf. 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. Semicontinuous ow microemulsion polymerization two approaches have been proposed to increase the polymer content using the excess surfactant remaining after the batch microemulsion polymerization. As reactant monomer converts into polymer chains, the density of the reacting mixture often changes notably. 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. Emulsion polymerization ferdowsi university of mashhad. As an alternative to microemulsion polymerization, the monomer starved semi batch emulsion polymerization can be used to produce the nanolatex 3. An overview of polymerization processes is given in asua 2007. Proportionalintegralderivative pid control works well for incremental batch emulsion polymerization but. Batch emulsion polymerization pure eindhoven university. Heat balances about the latex reactor and cooling jacket with proportionalintegral control are included. 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.
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