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Suspension polymerization is a heterogeneous
radical polymerization
In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks ( repeat units). Free radicals can be formed by a number of different mechani ...
process that uses mechanical agitation to mix a
monomer
In chemistry, a monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization.
Classification
Mo ...
or mixture of monomers in a
liquid phase
A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, ...
, 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 for ...
, forming spheres of polymer. The monomer droplets (size of the order 10-1000 μm) are suspended in the liquid phase. The individual monomer droplets can be considered as undergoing bulk polymerization. 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
The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water.
Viscosity quantifies the inte ...
, high
thermal conductivity
The thermal conductivity of a material is a measure of its ability to conduct heat. It is commonly denoted by k, \lambda, or \kappa.
Heat transfer occurs at a lower rate in materials of low thermal conductivity than in materials of high thermal ...
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 can be achieved without monomer boil-off. During this process, there is often a possibility of these monomer droplets to stick to each other and cause creaming in the solution. To prevent this, the mixture is carefully stirred or a protective
colloid
A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend ...
is often added. One of the most common suspending agents is
polyvinyl alcohol
Poly(vinyl 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) ...
(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 rea ...
, and the initiator used in this is monomer-soluble.
This process is used in the production of many commercial resins, including
polyvinyl chloride (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 is a ...
,
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, as well as
poly(styrene-acrylonitrile) and
poly(methyl methacrylate)
Poly(methyl methacrylate) (PMMA) belongs to a group of materials called engineering plastics. It is a transparent thermoplastic. PMMA is also known as acrylic, acrylic glass, as well as by the trade names and brands Crylux, Plexiglas, Acrylite, ...
.
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 Concentration, diluting agent. Certain fluids are too Viscosity, viscous to be pumped easily or too density, dense to flow from one particular point to the other. This can be prob ...
, 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:
:
d is the average particle size, k includes parameters related to the reaction vessel design, D
v is the reaction vessel diameter, D
s is the diameter of the stirrer, R is the volume ratio of the monomer to the liquid matrix, N is the stirring speed, ν
m and ν
l are the viscosity of the monomer phase and liquid matrix respectively, ε is the interfacial tension of the two phases, and C
s is the concentration of stabilizer. The most common way to control the particle size is to change the stirring speed.
See also
*
Radical polymerization
In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks ( repeat units). Free radicals can be formed by a number of different mechani ...
*
Polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
*
Polymerization
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer, monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are ...
*
Step-growth polymerization
*
Emulsion polymerization Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer ...
*
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 cla ...
References
{{reflist
Polymerization reactions
fr:Procédé de polymérisation#Polymérisation en suspension