Industrial Polymer

CHAPTER 3

Polymerization
reactions and techniques

Demis Zelelew (PhD)

January, @2024
Hossana; Ethiopia

05/11/2024
Chapter 3 Polymerization
techniques
 Bulk polymerization
 Solution polymerization
 Suspension polymerization
 Emulsion polymerization

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 Points for discussion

 Why liquid-phase polymerization reactions are commonly used? Why gas-

phase and solid-phase polymerization are not common?
 Discuss homogeneous and heterogeneous reactions

🖝Liquid-phase reactions
Polymerization reaction may take place in any of the three states of matter-solid,
liquid and gas.
o The solid state reactions are usually slow, they are not considered practical for this
reason. ???
o The gas-phase reactions do take place but normally they require maintenance
of
high temperatures, a condition in which almost all high-molecular
weight
polymers become unstable. ????
 Hence, almost all commercial process of polymerization are liquid-phase
Liquid-phase polymerization reactions.
1. Homogenous type
o Bulk Polymerization/Mass Polymerization
o Solution Polymerization

2. Heterogeneous type
o Emulsion Polymerization
o Suspension Polymerization/Pearl/Bead Polymerization

 Note that
o The homogenous or heterogeneous terms refers only to initial conditions of the
system and are not to the subsequent conditions.
o For example, polymerization of vinyl chloride (to PVC) by mass polymerization
method is considered a homogenous type of reaction, because initially the system
is homogenous. But the polymer being incompatible to the monomer phase, the
system subsequently becomes heterogeneous.
 Hence the concept of homogeneity or heterogeneity is based on only
the initial
conditions of the system 3
(I) Bulk/mass polymerization (monomer and initiators as main
components). ??????
 In this type of polymerization the monomer is taken in liquid form. The initiators
and chain transfer agents (used to control the MW) are dissolved in monomer
itself. Now the system becomes homogenous. ?????
 The reaction mass is heated or exposed
to a radiation source for the purpose of
initiating the polymerization reaction and
is kept under agitation for proper heat
and mass transfers. ???
 Heat removal is critical to avoid formation of
explosive compound.??????

 As the polymerization proceeds the viscosity of the medium increases and mixing
becomes difficult leading to products with very broad molecular weight
distribution or a wide range of molecular masses are produced
 The phenomenon in which the MW of a substance increase tremendously is
as “Autoaccleration” ?????
known 4
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 It is used for most step-growth polymers and many types of chain-growth polymers
such as polyurethanes, polycaprolactam (Nylon 6), polycarbonates and polyester
(PET).
 •In the case of chain-growth reactions, which are generally exothermic, the
heat
evolved may cause the reaction to become too vigorous and difficult to control
efficient cooling
unless
Advantages
o High molecular weight and molecular weight distribution.
o No solvent contamination as it is carried out in the absence of any solvent .
o Longer polymerization time for high MW polymers (10-16 hrs.)
o Product can be used directly and no isolation is required due to its resistance
towards solvents.
o Simple and cheap, It uses few ingredients, Good flow characteristics.
o High rate and degree of polymerization (High MW polymers are produced)..
o It gives high yield per reactor volume and high purity of 6
product
Limitations/disadvantages

o Difficult to control heat (needs efficient cooling), and the reaction has to be

run slowly
o High viscosity. ???

o Very low molecular weights are obtained. ???

o Difficulty in removing heat and the last traces of unreacted monomer. ???

o Stirring becomes difficult after 30-40% conversion as the viscosity increases

rapidly. ????
 As a result the polymerization is obtained with a broad molecular
weight distribution (due to the high viscosity and lack of good heat
transfer.
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2. Solution polymerization
 This is also known as method of industrial polymerization, and it is carried out in
the presence of inert solvent and initiator/catalyst (20% monomer + 80% solvent
typical)
 It is a polymerization process in which the monomers and the polymerization
initiators are dissolved in a non-monomeric liquid solvent at the beginning of the
polymerization reaction. The liquid is usually also a solvent for the resulting
polymer or copolymer and also act as heat sink.
 It is also used to solve the problems associated with the bulk polymerization
because
the solvent is employed to lower the viscosity of the reaction, thus help in the
heat
transfer from the reaction and reduce autoacceleration. ????

O olymer_12012EC_Legesse 8
Solvent requirements
 Both the initiator and the monomer should be soluble in the solvent used
 The solvent have acceptable chain transfer characteristics and suitable melting and
boiling points for the conditions of the polymerization and subsequent solvent-
removal step.
 Solvent choice may be influenced by other factors such as flash point, cost and toxicity
 Reactors are usually stainless steel or glass lined. Why ??????
🖝Industrially important polymers produced by solution polymerization.
Example
• Polyacrylonitrile (PAN) is manufactured by radical polymerization
in
dimethylformamide (DMF), dimethyl sulfoxide (DMSO), organic carbonates,
sulfuric acid, nitric acid or water solutions of inorganic salts and converted to fibers
• Polyacrylic acid (PAA) and polyacrylamide are obtained by radical polymerization in
water solution and used as thickeners, adhesives or flocculants.
• Acrylate and methacrylate homo- and copolymers are made by radical polymerization in
toluene-acetone for coating applications.
Advantages of the solution polymerization
 The catalyst is not coated by the polymer thereby increasing the efficiency and
simplifying the removal of the catalyst from the product, control of
temperature, heat transfer, and reaction rates are also simplified

 Disadvantages

 Small yield per reactor volume. This is because the presence of solvent may reduce
monomer concentration which results in decreasing the rate of the reaction and the
degree of polymerization. ?????
 The requirements or additional cost for solvent recovery/recycling step or it is
difficult to remove the solvent. ??????
 If not selected carefully, solvent may cause chain transfer or chain transfer to
solvent may limit the growth (MW) of polymer obtained. ?????? (This limits the
usefulness of the technique).
 Toxicity and other environmental impacts of most of organic solvents.
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 Summary: homogenous system

Process Advantages Disadvantages

Bulk •Simple, few Autoacceleration will occur.
ingredients, cheap. Possible problems with heat transfer
•Make polymer and use it. during polymerization.
Solution • Solvent will •Potential toxicity, flammability and
absorb exothermic of environmental pollution of solvents
polymerization (or there is a •Polymer product contains solvent
better heat/thermal control); impurities/or difficult to remove the
solvent from the product/.
• Can avoid autoacceleration; •Yield is significantly lower than in bulk
• Polymer ends up in solution, polymerization
may be used directly. •Expensive due to additional solvent
• Reduce viscosity costs

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3. Suspension polymerization
 Suspension= a mixture in which particles are dispersed throughout the bulk of a fluid
 This is a polymerization process in which the monomer, or mixture of monomers, is
dispersed by mechanical agitation in a liquid phase, usually water, in which the
monomer droplets are polymerized while they are dispersed by continuous agitation.
Example: Practically all common thermplastic polymers such as PVC,
ployethene, polystyrene, polyvinyl acetate and polymethylmethayl acrylate can be
made using suspension polymerization. ??????

Organic polymer _12012EC_Legesse 12

 It is similar to bulk polymerization where the reaction mixture is suspended as
droplets in an inert medium. If the monomer is insoluble in water, bulk
polymerization can be carried out in suspended droplets, i.e., monomer is
mechanically dispersed.
 This method is used also to solve the problem of heat transfer. The water
phase
becomes the heat transfer medium. ????
Advantages
⚫ Low viscosity
⚫ Excellent temperature control
⚫ Easy

product

separation

and
appreciable amount of money 13
little contamination
Organic polymer_12012EC_Legesse 14
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 4. Emulsion Polymerization
🖝Emulsion = a fine dispersion of minute droplets of one liquid in another in which it
is not soluble or not miscible
 It is a type of radical polymerization that usually involves the following
main components of monomer(s) only slightly soluble or completely insoluble in
dispersing
water), medium (usually water), emulsifier, and water-soluble initiator. The
dispersion medium is water in which hydrophobic monomers is emulsified by surface-
active agents (surfactant such as soap).
 This is similar to suspension polymerization except that the initiator is soluble in
suspension media and insoluble in the monomer.????
 It has several advantages over other polymerization techniques that include
o it is more rapid than bulk or solution polymerization at the same temperature
o the conversion is essentially 100 percent,
o the average MW is usually (much) higher than at the same polymerization rate
in bulk or solution polymerization. Why????
o heat dissipation and viscosity control are much less problematic than in 1b5ulk
polymerization.
 Emulsion polymerization is one of the most important methods for

the polymerization of a large number of monomers, like styrene-

butadiene,, vinyl acetate, vinyl chloride, chloroprene, acrylamide, acrylates, and

methacrylates. (Give the chemical structures of the monomers and representation of

the polymers)

It is also used for the production of various copolymers, like acrylonitrile-

butadiene-styrene (ABS). (Give the chemical structures of the monomers and

representation of the polymers mentioned above)

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 The polymer particles have diameter smaller than
suspension polymerization product. ??????
 The most common type of emulsion polymerization is an oil-in-water
emulsion,
in which droplets of monomer (the oil) are emulsified (with surfactants) in
a
continuous phase of water.
 Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl
celluloses, can also be used to act as emulsifiers/stabilizers.

Organic polymer_12012EC_Legesse 17
Organic polymer_12012EC_Legesse 18
Mechanism of emulsion polymerization
• The surfactant molecules surround small
amounts of monomer molecules,
creating micelles (emulsifier molecules
dissolved in water forming colloidal
clusters).
• There are also large droplets of
monomer that are stabilized by small
amounts of surfactant.
• Initiator forms free radicals in the
water, where they may find a few
monomers to react with. In any case, the
radicals diffuse into the micelles, where
they find lots of monomer but no other
growing chains to cause termination (at
least, for a while).
• The growing chain is then protected
from termination until a second radical
diffuses into the micelle. This is why the
MW can be so high in emulsion
polymerization without slowing the rate of
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conversion.
 Schematic representation of emulsion
polymerization

 A small portion of the emulsifier molecule is dissolved in water to form

colloidal cluster also known as “micelles”, emulsifier molecules arrange their
portions towards the interioOrrgaanncidpotlhymeeh_ry12d0r1o2EpCh_iLleigcseesne ds towards
hydrocabon 20
 Advantages of emulsion
polymerization
• High MW polymers can be made at fast polymerization rates. By contrast, in bulk
and solution free radical polymerization, there is a tradeoff between molecular
weight and polymerization rate.
• The continuous water phase is an excellent conductor of heat and allows the heat
to
be removed from the system, allowing many reaction methods to increase their
rate.
• Since polymer molecules are contained within the particles, viscosity remains close
to
that of water and is not dependent on molecular weight.
• The final product can be used as it is and does not generally need to be altered
or processed. It is environmentally friendly
Disadvantages
o For dry (isolated) polymers, water removal is an energy-intensive process
o Emulsion polymerizations are usually designed to operate at high conversion of monomer
to rubbers,
as [Link],
This canandresult in significant
artificial [Link] transfer to polymer. 21
o It is very difficult to totally remove all the additives from the product. Therefore, emulsion
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Summary: two phase process
Process Advantages Disadvantages
Suspension o Simple, few ingredients, cheap. • Autoacceleration will
o Reaction medium is mostly still
water, which absorbs the hear of occur.
polymerization. • Low yield
o Produces beads that • Isolation of the polymer can
have technological uses be laborious if beads are not
(xerographic toner, catalyst carriers, wanted
ion exchange resins, substrates for • May need to purify polymer
combinatorial synthesis, etc.) from suspending agent.

Emulsion oMakes very high MW polymer •Isolation of the polymer can

quickly. Reaction medium is mostly be laborious if you didn't
water, which absorbs the hear of want tiny particles
polymerization. •May need to purify polymer
oCreates very tiny particles of from surfactant. Otherwise
polymer that have technological uses the product may be
(paint, coatings, drug delivery, etc.). contaminated

Reading assignment
 Discuss the differences between emulsion and suspension polymerizations. ??
05/11/2024