Suspension Polymerization
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polymer chemistry Polymer chemistry is a sub-discipline of chemistry that focuses on the structures, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are also applic ...
, suspension polymerization is a heterogeneous
radical polymerization In polymer chemistry, radical polymerization (RP) is a method of polymerization by which a polymer forms by the successive addition of a radical to building blocks ( repeat units). Radicals can be formed by a number of different mechanisms, usu ...
process that uses mechanical agitation to mix a
monomer A monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or two- or three-dimensional network in a process called polymerization. Classification Chemis ...
or mixture of monomers in a
liquid phase Liquid is a state of matter with a definite volume but no fixed shape. Liquids adapt to the shape of their container and are nearly incompressible, maintaining their volume even under pressure. The density of a liquid is usually close to that ...
, such as water, while the monomers
polymerize In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many form ...
, forming spheres of polymer. The monomer droplets (size of the order 10-1000 μm) are suspended in the
liquid phase Liquid is a state of matter with a definite volume but no fixed shape. Liquids adapt to the shape of their container and are nearly incompressible, maintaining their volume even under pressure. The density of a liquid is usually close to that ...
. The individual monomer droplets can be considered as undergoing
bulk polymerization Bulk polymerization or mass polymerization is carried out by adding a soluble radical initiator to pure monomer in liquid state. The initiator should dissolve in the monomer. The reaction is initiated by heating or exposing to radiation. As the re ...
. The liquid phase outside these droplets help in better conduction of heat and thus tempering the increase in temperature. While choosing a liquid phase for suspension polymerization, low
viscosity Viscosity is a measure of a fluid's rate-dependent drag (physics), resistance to a change in shape or to movement of its neighboring portions relative to one another. For liquids, it corresponds to the informal concept of ''thickness''; for e ...
, high
thermal conductivity The thermal conductivity of a material is a measure of its ability to heat conduction, conduct heat. It is commonly denoted by k, \lambda, or \kappa and is measured in W·m−1·K−1. Heat transfer occurs at a lower rate in materials of low ...
and low-temperature variation of viscosity are generally preferred. The primary advantage of suspension polymerization over other types of polymerization is that a higher
degree of polymerization The degree of polymerization, or DP, is the number of structural unit, monomeric units in a macromolecule or polymer or oligomer molecule. For a homopolymer, there is only one type of monomeric unit and the ''number-average'' degree of polymeriza ...
can be achieved without monomer boil-off. During this process, there is often a possibility of these monomer droplets sticking to each other and causing creaming in the solution. To prevent this, the mixture is carefully stirred or a
protective colloid A protective colloid is a lyophilic colloid that when present in small quantities keeps lyophobic colloids from precipitating under the coagulating action of electrolytes. Need for protective colloids When a small amount of hydrophilic colloi ...
is often added. One of the most common suspending agents is
polyvinyl alcohol Polyvinyl alcohol (PVOH, PVA, or PVAl) is a water- soluble synthetic polymer. It has the idealized formula H2CH(OH)sub>''n''. It is used in papermaking, textile warp sizing, as a thickener and emulsion stabilizer in polyvinyl acetate (PVAc) a ...
(PVA). Usually, the monomer conversion is completed unlike in
bulk polymerization Bulk polymerization or mass polymerization is carried out by adding a soluble radical initiator to pure monomer in liquid state. The initiator should dissolve in the monomer. The reaction is initiated by heating or exposing to radiation. As the re ...
, and the initiator used in this is monomer-soluble. This process is used in the production of many commercial resins, including
polyvinyl chloride Polyvinyl chloride (alternatively: poly(vinyl chloride), colloquial: vinyl or polyvinyl; abbreviated: PVC) is the world's third-most widely produced synthetic polymer of plastic (after polyethylene and polypropylene). About 40 million tons of ...
(PVC), a widely-used plastic, styrene resins including
polystyrene Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It i ...
,
expanded polystyrene Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It is a ...
, and
high-impact polystyrene Polystyrene (PS) is a synthetic polymer made from monomers of the Aromatic hydrocarbon, aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin pe ...
, as well as poly(styrene-acrylonitrile) and
poly(methyl methacrylate) Poly(methyl methacrylate) (PMMA) is a synthetic polymer derived from methyl methacrylate. It is a transparent thermoplastic, used as an engineering plastic. PMMA is also known as acrylic, acrylic glass, as well as by the trade names and bran ...
.


Particle properties

Suspension polymerization is divided into two main types, depending on the morphology of the particles that result. In bead polymerization, the polymer is soluble in its monomer and the result is a smooth, translucent bead. In powder polymerization, the polymer is not soluble in its monomer and the resultant bead will be porous and irregular. The morphology of the polymer can be changed by adding a monomer
diluent A diluent (also referred to as a filler, dilutant or thinner) is a diluting agent. Certain fluids are too viscous to be pumped easily or too dense to flow from one particular point to the other. This can be troublesome, because it might not be ...
, an inert liquid that is insoluble with the liquid matrix. The diluent changes the solubility of the polymer in the monomer and gives a measure of control over the porosity of the resulting polymer. The polymer beads that result can range in size from 100 nm to 5 mm. The size is controlled by the stirring speed, the volume fraction of monomer, the concentration and identity of the stabilizers used, and the viscosities of the different components. The following equation derived empirically summarizes some of these interactions: :\bar = k d is the average particle size, k includes parameters related to the reaction vessel design, Dv is the reaction vessel diameter, Ds is the diameter of the stirrer, R is the volume ratio of the monomer to the liquid matrix, N is the stirring speed, νm and νl are the viscosity of the monomer phase and liquid matrix respectively, ε is the interfacial tension of the two phases, and Cs is the concentration of stabilizer. The most common way to control the particle size is to change the stirring speed.


See also

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Dispersion polymerization In polymer science, dispersion polymerization is a heterogeneous polymerization process carried out in the presence of a polymeric stabilizer in the reaction medium. Dispersion polymerization is a type of precipitation polymerization, meaning th ...
*
Radical polymerization In polymer chemistry, radical polymerization (RP) is a method of polymerization by which a polymer forms by the successive addition of a radical to building blocks ( repeat units). Radicals can be formed by a number of different mechanisms, usu ...
*
Polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
*
Polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...
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Step-growth polymerization In polymer chemistry, step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Ma ...
*
Emulsion polymerization In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in ...
*
Superabsorbent polymer A superabsorbent polymer (SAP) (also called slush powder) is a water-absorbing hydrophilic homopolymers or copolymers that can absorb and retain extremely large amounts of a liquid relative to its own mass. Water-absorbing polymers, which are cl ...


References

{{reflist Polymerization reactions fr:Procédé de polymérisation#Polymérisation en suspension