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ROLL NO- 2K15/PS/501

 Since polymer molecules are contained within the particles.  The final product can be used as is and does not generally need to be altered or processed. there is a tradeoff between molecular weight and polymerization rate. enabling fast polymerization rates without loss of temperature control. the viscosity of the reaction medium remains close to that of water and is not dependent on molecular weight. in bulk and solution free radical polymerisation..e.EMULSION :- An emulsion is a mixture of two or more liquids that are normally immiscible (unmixable or unblendable). By contrast. Disadvantages of emulsion polymerization include:  Surfactants and other polymerization adjuvants remain in the polymer or are difficult to remove . The polymerization of monomers in the form of emulsions (i. EMULSION POLYMERISATION Emulsion polymerization is a complex process in which the radical addition polymerization proceeds in a heterogeneous system. colloidal dispersions). Emulsions are part of a more general class of two-phase systems of matter called colloids.  The continuous water phase is an excellent conductor of heat. KEY POINTS  High molecular weight polymers can be made at fast polymerization rates.

. • These polymeric dispersions are called latexes • Polymer particles are mostly spherical • Average diameter 80 to 300 nm (more than one order of magnitude smaller than suspension polymerization particles) • The solids content spans from 40 to 65 wt% • The dispersed system is thermodynamically unstable. water removal is an energy-intensive process  Emulsion polymerizations are usually designed to operate at high conversion of monomer to polymer. ionic or Ziegler-Natta polymerization. most often water. • Emulsion polymerization is a technique leading to colloidal polymer particles dispersed in a continuous medium.  Can not be used for condensation. For dry (isolated) polymers. This can result in significant chain transfer to polymer. although some exceptions are known. and kinetic stability is provided by emulsifiers (ionic and non-ionic) and by incorporation of hydrophilic groups into the polymer.

Main products and markets of EMULSION POLYMERISATION Main ingredients of emulsion polymerization 1) monomer 2) dispersion medium 3) emulsifier 4) initiator .

acrylonitrile. for monomer droplets and polymer particles. can be used Monomer The major monomers used in emulsion polymerization include butadiene. and vinyl chloride Dispersion medium The dispersion medium. buffers.Further auxiliaries. vinyl acetate.. acrylate ester and methacrylate ester monomers. acrylic acid and methacrylic acid. (ii)Micelle generating substances (iii) Stabilizing the monomer droplets in an emulsion form (iv) Serving to solubilize the monomer within emulsifier micelles (v) Stabilizing the growing latex particles (vi) stabilizing the particles of the final latex . acids. anti-aging agents. inert and environmentally friendly. It provides an excellent heat transfer and low viscosity. is generally water as well as liquids other than water. biocids. styrene. bases. Water is cheap. such as chain transfer agents. etc. It also acts as the medium of transfer of monomer from droplets to particles Emulsifier These materials perform many important functions in emulsion polymerizations (i) reducing the interfacial tension between the monomer phase and the water phase .

The free radicals can be commonly produced by two main ways: (i) thermal decomposition (ii) redox reactions. The most used type of these emulsifiers is that with a head group of ethylene oxide (EO) units are Polyoxyethylenated alkylphenols. sodium-. converting it to a growing radical . polyoxyethylenated straight-chain alcohols and polyoxyethylenated polyoxypropylene glycols Initiator The function of the initiator is to generate free radicals. in the second stage the primary radicals react with the monomer. potassium-. In the first stage the initiator is decomposed to free-radicals. which in turn lead to the propagation of the polymer molecules. For example. In addition. and ammonium-persulfate Kinetics and mechanism of emulsion polymerization The three stages of the free-radical polymerization are shown in the following steps Initiation: The reaction of initiation can be described as a twostage process.(vii) Acting to solubilize the polymer. the free-radical initiators can be either water or oil-soluble The most commonly used water-soluble initiators are persulfates (peroxodisulfates).

is equal to the rate of dissociation of an initiator. The rate of this dissociation. and so the dissociation of the initiator is the ratedetermining step in the initiation sequence . Rd.The most common method used in emulsion polymerizations is thermal initiation in which the initiator (I) dissociates homolytically to generate a pair of free-radicals where kd is the rate constant for the initiator dissociation. In the second stage. The rate of initiation. is given by:- where [I] is the concentration of the initiator and f is the initiator efficiency. Because the primary radical adds to monomer is much faster than the first stage. the free radicals generated from the initiator system attack the first monomer (M) molecule to initiate chain growth: where ki is the rate constant for the initiation. Ri.

There are two main mechanisms. In these mechanisms. recombination and disproportionation. This involves essentially the addition of a large number of monomer molecules (n) to the active centers (RM ) for the growth of polymer chain where kp is the rate constant for propagation The rate of polymerization. is known as the rate of monomer consumption. Rp. The corresponding rate of polymerization is then: The amount of monomer consumed in the initiation step can be neglected due to the number of monomer molecules reacting in the initiation step is far less than the number in the propagation step for a process producing high polymer. . the polymerization rate can be written: Termination: In last step of the polymerization.Propagation: The propagation step is only one which produces polymer. the growing polymer chain react with another growing chain or another free radical of some kind Recombination. Monomer is consumed by the propagation reactions as well as by the initiation reaction. the growing polymer chain is terminated. and a very close approximation of the polymerization rate can be given simply by the rate of propagation. for termination reactions. Then.

some substances such as polymer. impurities. or initiator can act as a chain transfer which two growing chains constitute the coupling with each other resulting in a single polymer molecule Disproportionation. solvent. additives. monomer. An example of these reactions is given The equation for the steady state conditions is: rearranging . in which one growing chain abstracts a hydrogen atom from another. This mechanism occurs more rarely than recombination. one saturated and one unsaturated. leaving it with an unsaturated end group. The overall rate constant for termination reaction is given as kt=ktc+ktd In the chain transfer reactions. It results in the formation of two polymer molecules.

apply to propagation eq we get .


Schematic representation for the mechanism of emulsion polymerization .


is a useful approach to solving this problem The process uses an initiator yielding initiator radicals that impart surface-active properties to the polymer particles. either directly or by desorption. involving no added surfactant. can lead to coagulation or flocculation of the destabilized latex Surfactant-free emulsion polymerization.Surfactant-Free Emulsion Polymerization The presence of surfactant is a disadvantage for certain applications of emulsion polymers such as  The presence of adsorbed surfactant gives rise to somewhat variable properties since the amount of adsorbed surfactant can vary with the polymerization and application conditions  Removal of the surfactant. Persulfate is a useful initiator for this purpose Applications Polymers produced by emulsion polymerization can be divided into three rough categories Synthetic rubber       Some grades of styrene butadiene (SBR) Some grades of polybutadiene polychloroprene Nitrile rubber Acrylic rubber Fluoroelastomer (FKM) .

ethylene copolymers) .Plastics        Some grades of PVC Some grades of polystyrene Some grades of PMMA Acrylonitrile-butadiene-styrene terpolymer (ABS) Polyvinylidene fluoride Polyvinyl fluoride PTFE Dispersions      polyvinyl acetate polyvinyl acetate copolymers latexacrylic paint Styrene-butadiene VAE (vinyl acetate .