CHE417

Polymer Process Engineering

 Recommended Textbooks
1. Organic Polymers: Advances in Research and Applications. By Tomos Fisher.
Nova Science Publisher
2. Basics of Polymers: Fabrication and Processing Technology. By:
Muralisrinivasan Natamai Subramanian. Published by Momentum Press, 2015
3. Introduction to Polymer Chemistry, 3rd Edition. By: Charles E. Carraher Jr.
Published by CRC Press, Tailor and Francis, 2014
Introduction to the manufacture organic polymeric
materials
• Organic polymers are linear, branched, or cross linked, and they give rise
to different types of synthetic materials, such as amorphous or semicrystalline
thermoplastics, elastomers, and high-strength fibers, which are essential to
many modern technologies.
• Organic polymers are macromolecules in which the primary backbone of
the molecular chain is composed, at least partially, of carbon atoms.
• Organic polymers can be further classified according to their presence in the
environment as either natural (occurring mostly without anthropomorphic
activity) or synthetic (created primarily due to anthropomorphic activity).
• Hence, organic polymer materials are largely classified into natural
biodegradable and synthetic nontoxic.
• Elastomers are the rubbers with viscoelasticity (viscosity and elasticity).
• Elastomers (E) are polymers that exhibit extreme elastic extensibility
when subjected to relatively low mechanical stress.
• Some elastomers can be stretched by a factor of 10 and yet completely
recover to their original shape. Although their properties are quite
different from thermosets, they have a similar molecular structure that is
different from the thermoplastics.
• Some examples of natural polymers are as follows:
Natural Polymers
• (a) Polysaccharides: starch, cellulose, glycogen, pectin, seaweed gums (e.g.,
agar), vegetable gums (e.g., arabic)
• (b) Polypeptides (proteins): silk, collagen, casein, albumin, globulin, keratin,
insulin, DNA, RNA, and many others
• (c) Hydrocarbons: rubber and gutta percha or polyisoprene (some silicones;
these are in organic)
• Some examples of synthetic polymers are as follows:
Synthetic
• (a)Thermoplastics
• Thermoplastics are polymers that exist in a solid state at one temperature, and
soften to become pliable at very specific elevated temperatures.
• Cooling these materials back to below their respective transition temperatures
allows them to once again solidify due to the reformation of intermolecular
forces between associating chains; chemical (covalent) bonds are not formed
or broken via this process.
• Examples of thermoplastics include nylon, polyvinyl chloride, polyethylene
(linear), polystyrene, polypropylene, fluorocarbon resins, polyurethane,
acrylate resins, poly(glycolic acid), poly(lactic acid), and copolymers of
various descriptions including poly(lactic-co-glycolic acid).
(b) Thermosets
•Thermosets are polymers that form chemical (mostly covalent) bonds with
associating chains when heated.
•These bonds are maintained below certain temperatures, while heating the
cured material beyond a certain point results in the decomposition of bonds
within the thermoset material.
•The physical properties of thermosetting materials become fixed once they are
cured, in contrast to the more reversible intermolecular forces present in
thermoplastics.
•Examples of thermosets include polyethylene (cross-linked) (PE), phenolics,
alkyds, polyesters (CO-O bonds), and polyurethanes (O–CO–N bonds along
the backbone).
Semisynthetic Polymers
•These polymers largely consist of naturally occurring polymers that have been
post-functionalized in some way, either by cleavage, addition, cross-linking, or
other means.
•Some examples of semisynthetic polymers are rayon, methylcellulose,
cellulose acetate, and modified starches (e.g., starch acetate).
Manufacture/processing organic polymeric materials
• Organic polymers can be synthesized by various polymerization procedures.
The synthesis by bulk polymerization involves a homogeneous system where
the reagents, mixed in the reaction medium, polymerize via radicalar
reactions.
• The synthesis must be made in inert atmosphere, since the presence of
oxygen can delay the polymerization process. The polymerization reaction is
induced by heating or UV radiation, depending on the employed monomer in
the synthesis.
• Several monomers can be used, in accordance to the desired application and
interaction with the analyte.
 Bulk Polymerization
• Bulk polymerization of a liquid monomer is relatively simple in the absence
of oxygen where small bottles or test tubes are used as the reaction vessel.
• The monomer can be heated in the presence of an initiator giving a clear
plastic shaped like the container, but a little smaller because of shrinkage.
• The volume of the monomers is generally larger than the final polymers,
thus, the density of the polymer is greater than that of the original monomer.
• Poly(methyl methacrylate) (PMMA) is sold under the trade names Lucite and
Plexiglass as an atactic amorphous polymer.
• Bulk polymerization produces a monolithic rigid polymer matrix, needing to
be broken into large, nonuniform particles in which the binding sites are
distributed heterogeneously in the polymer matrix. Usually, the product
obtained is dried, macerated and, depending on the use, separated by particle
size.
• This polymerization technique is characterized by the following:
• 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 PMMA,
polystyrene and low-density (high pressure) polyethylene.
 Emulsion Polymerization
• Many water-soluble vinyl monomers may be polymerized by the emulsion
polymerization technique.
• This technique, which differs from suspension polymerization in the size of
the suspended particles and in the mechanism, is widely used for the
production of a number of commercial plastics and elastomers.
• While the particles in the suspension process range from 10 to 1000 nm, those
in the emulsion process range from 0.05 to 5 nm in diameter.
• The small beads produced in the suspension process may be separated by
filtering, but the latex produced in emulsion polymerization is a stable system
in which the charged particles cannot be recovered by ordinary separation
procedures.
• Since relatively stable macroradicals are produced in the emulsion process,
the termination rate decreases and a high molecular weight product is rapidly
produced.
• It is customary to use a water-soluble initiator such as potassium persulfate,
an anionic surfactant such as sodium sterate, and to stir the aqueous mixture
of monomer, initiator, and surfactant in the absence of oxygen at 40°C–70°C.
 Suspension Polymerization
• Suspension polymerization is used to make a number of thermoplastic
polymers.
• In suspension polymerization, all reactions are carried out in relatively large
droplets or in polymer particles stabilized by a small amount of water-soluble
gum.
• Water-insoluble monomers such as vinyl chloride may be polymerized as
suspended droplets (10–1000 nm in diameter) in a process called suspension
(pearl) polymerization.
• Organic peroxide initiators are used to generate radicals within the droplets.
• Coalescence of droplets is prevented by the use of small amounts of
water-soluble polymers, such as poly(vinyl alcohol) (PVA). The
suspension process is characterized by good heat control and ease of
removal of the discrete polymer particles.
• A solvent may be used to dissolve a monomer at a relatively high
concentration.
• The main advantages of suspension polymerization over emulsion
systems are that no surfactants, which are difficult to remove from the
product, are used, and no ionic end groups are present, which may be
unstable during processing at high temperatures.
 Solution Polymerization
• Monomers may also be polymerized in solution using good or poor solvents
for homogeneous and heterogeneous systems, respectively.
• In solution polymerizations solvents with low chain transfer constants are
used to minimize reduction in chain length.
• Solution polymerization uses solvent in the reactor to enhance heat transfer.
• At the beginning of the process, the initiator and the solvent are added into
the reactor. Initiator will initiate the polymerization process by
decomposition to form primary free radicals.
• These free radicals will then react with the monomer added in the reactor in
homogeneous solution until the end of the process.
• The decomposition of the initiator molecules depends on the initiator
efficiency, f.
• Not all the initiator molecules decompose to form primary radicals since
some of them might either have self-terminate or react with other reactants in
the system which make the initiator efficiency less than 100%.
• Poly(vinyl acetate (PVAc) may be produced by the polymerization of vinyl
acetate (see figure below). The viscosity of the solution continues to increase
until the reaction is complete.
• Dilute polymer solutions are used to prevent the onset of auto acceleration
because of the gel effect.
• PVAc is used in adhesives and coatings and is hydrolyzed producing water-
soluble PVA; The PVA may be reacted with butyraldehyde to produce
poly(vinyl butyral) used as the inner lining of safety glass.
• When a monomer such as acrylonitrile is polymerized in a poor solvent,
macroradicals precipitate as they are formed (see figure below). Since these
are “living polymers,” the polymerization continues as more acrylonitrile
diffuses into the precipitated particles.
• This heterogeneous solution polymerization has been called precipitation
polymerization.
• Polymer processing technology helps to convert polymer into long-life
applications for use in areas such as transportation, appliances, electronics,
and construction markets.
• Polymer processing operations are extrusion and injection molding, blow
molding, rotational moulding, thermoforming, calendering, vacuum forming,
and compression moulding.