TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES

363 P. Casal St., Quiapo, Manila

Different Polymer
Reactor

Marvin Brian J. Paras

Engr. Lina dela Cruz

January 3, 2018
 Polymerization involves highly complex reaction networks producing highly complex
molecular structures. Conditions such as the locus of polymerization will have a profound effect
on NACL, degree of branching, CCD, CSD, and other measures of molecular structure directly
affecting the end-use properties. Because of this, it is often said that polymers are “products of
process”. By thin is meant that the type of process (batch, semi-batch, or continuous
polymerization), as well as the processing conditions (recipe, temperature, etc.), will to a large
degree define the structure of the resulting polymer and, hence, its end-use properties.

There are three types of reactors that can be used or considered in the process of
polymerization — batch (or semi-batch) reactor, plug flow reactor (PFR) and the continuous
stirred tank reactor (CSTR).

 BATCH/SEMI-BATCH REACTOR
The most common polymerization reactor on a numerical basis is the batch kettle. Batch
kettles may range in size from a 5-gal pilot plant kettle to a 30000-gal production kettle.
They generally constructed of stainless steel or in cases where fouling of the walls with
polymer is severe, may be glass-lined. They may be heavily instrumented or operated
without controls. Removal of the heat of polymerization is accomplished by circulating
coolant through a jacket or by refluxing monomer and solvent. Batch reactors have the
advantage of flexibility to accommodate multiple products, but suffer from the disadvantage
of the batch-to-batch variability.
o Batch Reactors
Kinetically, the significance of the batch polymerizer lies in the fact that
all reactants are added at the beginning of the polymerization, and nothing is
removed until the end. Thus, the rate of polymerization changes constantly with
time as the monomer and initiator concentrations decrease. In a step-growth
polymerization, where the growth time of an individual chain is approximately
kettle time, the effects of changing conditions are not critical because all chains
will see the same (changing) environment. In a free radical polymerization, where
the time of formation of a single chain is a small fraction of the kettle time, a
batch reactor results in inhomogeneity because polymer chains are formed under
different conditions. this is especially significant in batch copolymerization,
where polymer chains formed early in the reaction may contain a high percentage
of the more reactive monomer, whereas those formed later will contain a high
percentage of the remaining (less reactive) monomer.
o Semi-batch Reactors
Semi-batch copolymerization is the most often done in an attempt to
maintain a reasonably constant copolymer composition when the comonomers are
widely varying reactivities. Semibatching of initiator is often done to maintain
temperature control in a heat transfer-limited kettle, and semibatch addition of an
initiator or chain transfer agent may be used to maintaina desired MWD.
 Quantitative strategies for semibatching may be developed through empirical
experimentation at the batch or pilot scale, or, if accurate mathematical models
are available, classical trajectory optimization techniques may be used.

 PLUG FLOW REACTORS

In a plug flow reactor, each element of the reaction mixture can be viewed as an
individual batch reactor. The batch time is the residence time in the tubular reactor, which is
easily calculated as the total volume of the tube divided by the volumetric flow rate. Because
no material enters or leaves the fluid element during the reaction time, all of the kinetic
relationships derived thus far for the batch reactor are directly applicable to the plug flow
reactor, the plug flow reactor, then, becomes the reactor of choice if it is desired to exploit
the kinetic advantages of the batch reactor while enjoying the operational advantages of
continuous processing.

 CONTINUOUS STIRRED TANK REACTORS

The use of continuous stirred tank polymerization (in a single CSTR or train multiple
CSTRs in series) may be warranted for high-volume products. The nature of the reactor
system results in low processing costs, high throughput, and, in most cases, a highly uniform
product. The fact that the polymerization rate is constant will contribute to product
homogeneity, but may be overshadowed by inhomogeneity induced by the broad residence
time distribution, particularly for emulsion free radical polymerizations. Large residence time
CSTR systems are not particularly flexible and are, therefore, best suited to extended
production runs of a small number of products. In low residence time CSTR (as in olefin
polymerization_, grade changes be made rapidly and low-volume products can be made
effectively.