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Solution & Bulk polymerization

Preprint · January 2019

DOI: 10.13140/RG.2.2.16472.96001/2

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 SOLUTION & BULK POLYMERIZATION
Written by student;
AbdAl-Rhman Magdy Abdullah Youssef
ID: 20160517
Date: January 2019
Department of chemical engineering, Higher Technological Institute-Tenth of Ramadan City, Egypt

Abstract
Bulk and solution polymerization are two very important methods for
manufacturing polymers. Solution polymerization occur in existence of inert solvent
and suitable catalyst, on the contrary of bulk polymerization which doesn’t need any
additives just monomer and a suitable initiator, which has two types batch and
continuous bulk polymerization. Both of bulk and solution polymerization used for
manufacturing many polymers such as polystyrene, polyethylene, and polymethyl
methacrylate for bulk polymerization and polyacrylonitrile, and polyesters such as
nylon for solution polymerization.

Solution Polymerization
I. Introduction
Monomer and initiator must be soluble in the liquid and the solvent must have the desired chain
transfer characteristics, boiling point (above the temperature necessary to carry out the
polymerization and low enough to allow for ready removal if the polymer is recovered by solvent
evaporation). The presence of the solvent assists in heat removal and control (as it also does for
suspension and emulsion polymerization systems). Polymer yield per reaction volume is lower than
for bulk reactions. Also, solvent recovery and removal (from the polymer) is necessary. Many free
radical and ionic polymerizations are carried out utilizing solution polymerization including water-
soluble polymers prepared in aqueous solution [namely poly (acrylic acid), polyacrylamide, and poly
(N-vinyl pyrrolidinone)]. Polystyrene, poly (methyl methacrylate), poly (vinyl chloride), and
polybutadiene are prepared from organic solution polymerizations, [1].
II. Solution polymerization system
In solution polymerization, the system consists of
1. Suitable inert solvent,
2. Monomer(s),
3. Catalyst,
4. Polymer
Some examples of solution polymerization are
1. Ethylene in isooctane polymerized at 150°C–180°C, 300–700 psi with chromia-silica-alumina
catalyst.
2. Aqueous solution of acrylonitrile at 80°C with persulfate catalyst resulting in polyacrylonitrile
precipitate.
3. Nylon rope trick—interfacial polycondensation of a solution of sebacoyl chloride in
tetrachloroethane plus aqueous solution of hexamethylene diamine yielding nylon 6/10 at the
boundary (interface) of both solutions, [2].
III. Mechanism of solution polymerization
a variety of ways. The batch may be mixed and held at a constant temperature while running
for a given time, or for a time dictated by tests made during the progress of the run. Alternatively,
termination is dictated by a predetermined decrease in pressures following monomer consumption.
A continuous reaction train, on the other hand, consists of a number of reactors, usually up to
about ten, with the earlier ones overflowing into the next and the later ones on level control, with
transfer from one to the next by pump. As the reaction progresses, solution polymerization
generally involves a pronounced increase in viscosity and evolution of heat. The viscosity increase
demands higher power and stronger design for pumps and agitators. The reactor design depends
largely on how the heat evolved is dissipated, [3].

Table (1): Topical solution polymerization processes, [3]

IV. Solution polymerization reactors
In solution polymerization service use jackets; internal or external coils; evaporative cooling
with or without compression of the vapor or simple reflux-cooling facilities, a pumped recirculation
loop through external heat exchanger; and combinations of these. A typical reactor has agitation,
cooling, and heating facilities; relief, temperature level, and pressure connections; and, frequently,
cleanout connections in addition to inlet and outlet fittings, [3].
V. Solution polymerization advantages and dis-advantages
• Advantages of solution polymerization:
1. Heating and stirring are much easier than in bulk polymerization due to the solvent medium.
2. The viscosity problem is minimized by the presence of solvent medium.
3. Heat removal is accomplished via solvent reflux.
4. Conversion of monomer(s) to polymer is high and typically about 80%–90%.
• Disadvantages of solution polymerization:
1. Large volume of solvent required—an added source of cost.
2. Separation and recovery of solvent is an extra step.
3. The solvent is an added source of contamination, [2].

Figure (1): Flow sheet for manufacturing low viscosity polyvinyl acetate by solution polymerization, [3].
Bulk polymerization
I. Introduction
Simplest of the techniques requiring only monomer and monomer-soluble initiator, and
perhaps a chain transfer agent for molecular weight control. Characterized on the positive side by
high polymer yield per volume of reaction, easy polymer recovery. Difficulty of removing unreacted
monomer and heat control are negative features. Examples of polymers produced by bulk
polymerization include poly (methyl methacrylate), polystyrene, and low-density (high-pressure)
polyethylene, [1].
II. Bulk polymerization systems
• Batch – bulk polymerization system
It requires simple equipment, also it may require solution and subsequent precipitation for
purification and/or fabrication; may require reduction to usable particle size heat control important;
broad molecular weight distribution, [1].
• Continuous – bulk polymerization system
It’s easy in heat control; narrower molecular weight distribution, also it may require reactant
recycling; may require solution and subsequent ppt. for purification and/or fabrication; requires
more complex equipment; may require reduction to usable particle size, [1].
III. Mechanism of bulk polymerization
• Batch – Bulk polymerization
Bulk polymerization is widely practiced in the manufacture of step-growth polymers. However,
since condensation reactions are not very exothermic and since the reactants are usually of low
activity, high temperatures are required for these polymerization processes. Even though medium
viscosities remain low throughout most of the course of polymerization, high viscosities are generally
experienced at later stages of the reaction. Such high viscosities cause not only problems with the
removal of volatile byproducts, but also a possible change in the kinetics of the reaction from a
chemical-controlled regime to a diffusion-controlled one. To obtain a product of an appropriate
molecular weight, therefore, proper cognizance must be given to this problem in the design of the
reactor.
Organic systems have low heat capacities and thermal conductivities. Free-radical reactions are
highly exothermic in nature. This coupled with the extremely viscous reaction media for these
systems prevents effective convective (mixing) heat transfer, leading, as a consequence, to very low
overall heat transfer coefficients. The problem of heat removal is accentuated at higher conversions
because the rates of polymerization and heat generation are usually enhanced at these stages of
reaction. This leads to the development of localized hot spots or runaway reactions, which if
uncontrolled may be ultimately disastrous. The occurrence of local hot spots could result in the
discoloration and even possible degradation of the polymer product, which usually has a broadened
molecular weight distribution due to chain transfer to polymer.
Because of the above heat transfer problems, bulk polymerization of vinyl monomers is
restricted to those with relatively low reactivities and enthalpies of polymerization. This is
exemplified by the homogeneous bulk polymerization of methyl methacrylate and styrene. Some
polyurethanes and polyesters are examples of step-reaction polymers that can be produced by
homogeneous bulk polymerizations. The products of these reactions might be a solid, as in the case
with acrylic polymers; a melt, as produced by some continuous polymerization of styrene; or a
solution of polymer in monomer, as with certain alkyd-type polyesters.
Sheets, rods, slabs, and other desired shapes of objects are produced from poly (methyl
methacrylate) in batch reactors by keeping at least one dimension of the reaction mass thin, thereby
facilitating heat transfer. Typically, the monomer containing a small amount of an initiator such as
benzoyl peroxide is poured between two glass plates separated by a flexible gasket of poly (vinyl
chloride) tubing and held together by spring clips to compensate for shrinkage. Depending upon the
thickness, the filled mold is heated from 45 to 90°C for about 12 to 24 h. After cooling, the molds are
stripped from the casting and the sheets are annealed at 140 to 150°C. The resulting sheet has good
optical properties, but the process suffers from a number of problems. These include possible
bubbles from dissolved gases, long curing times, and large shrinkage (about 21%). These problems
may be overcome by using prepolymerized syrup rather than the pure monomer. The syrup is
prepared by carefully heating methyl methacrylate monomer containing 0.02 to 0.1% benzoyl
peroxide or azo-bis isobutyronitrile in a well-agitated stainless-steel vessel to initiate polymerization.
A good syrup is obtained after a prepolymerization cycle of 5 to 10 min at a batch temperature of
90°C.
• Continuous – Bulk polymerization
Another way of circumventing the heat transfer problems is by continuous bulk polymerization.
An example is the polymerization of polystyrene, which is carried out in two stages. In the first stage,
styrene is polymerized at 80°C to 30 to 35% monomer conversion in a stirred reactor known as a
prepolymerized.
The resulting reaction mass — a viscous solution or syrup of polymer in monomer — subsequently
passes down a tower with increasing temperature. The increasing temperature helps to keep the
viscosity at manageable levels and also enhances conversion, which reaches at least 95% at the exit
of the tower (Figure 2).
By removal of the heat of polymerization at the top of the tower and proper temperature control
of the finished polymer at the bottom of the tower, an optimum molecular weight may be achieved
and channeling of the polymer may be minimized, [3].
IV. Advantages and dis – advantages of bulk polymerization
• Advantages of bulk polymerization:
1. Purity of the product can be controlled since there are few components (medical plastics).
2. It is simple and economical.
3. Excellent color and clarity can be achieved.
• Disadvantages of bulk polymerization:
1. Heat control and removal can be a source of problem— “Trommsdorf effect.”
2. Stirring ability can be reduced and made difficult by the increase in viscosity.
3. Complete conversion of monomer to polymer is difficult to achieve; typically, conversion rate is
less than 80%.
4. Traces of monomer in the polymer can be a source of contamination, [2].
 Figure (2): Vertical column reactor for the continuous bulk polymerization of styrene, [3].

References
1. [1] Charles E. Carraher, Jr, 2003, Polymer chemistry, 6Th edition, chapter 8, CRC Press
LLC, New York.
2. [2] Christopher c. ibehCRC, 2011, Thermo plastic materials Properties, Manufacturing
Methods, and Applications, from page 83 to page 86, Taylor & Francis Group LLC, New
York.
3. [3] Robert O. Ebewele, 2000, Polymer since and technology, chapter 10, CRC Press LLC,
New York

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