The Polymerisations Industry

Atanu K Metya
atanu.metya@iitp.ac.in
Introduction
• Polymers are long chain molecules or materials made of many
repeating units (monomers) with high molecular weight about 103 –
107
Polymerization

• Polymers have unique properties, depending on the type of monomers

being bonded and how they are bonded. Some polymers bend and
stretch, like rubber and polyester. Others are hard and tough, like
epoxies and glass.
• Natural polymeric materials, such as wood and horn, have been used
since prehistoric times. Rubber tree latex and cellulose have been used
as raw material to make manufactured polymeric rubber and plastics.
 Introduction
• The first fully synthetic polymers were the phenol-formaldehyde
resins, which were developed in the beginning of the twentieth
century.
• The synthetic polymers industry has seen a spectacular growth and the
production of plastics (or thermoplastics), the largest class of polymers
by far (approximately 85% of synthetic polymers).
• Plastic industry is making significant contribution to the economic
development and growth in the country such as: Automotive,
Construction, Electronics, Healthcare, and Textiles etc. India is
currently net importer of PolyEthylene (PE), however with the
commissioning of IOCL plant at Panipat, the imports are expected to
go down significantly.
http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
Introduction
• India observes significant regional diversity in consumption of plastics
with Western India accounting for 47%, Northern India for 23% and
Southern India for 21%.

http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 India offers strong opportunity for manufacturing of petrochemicals in future with its plan
to increase the share of manufacturing in GDP from 16% to 25% by 2022. Plastics are the
major product that account for bulk of the Indian petrochemical industry
http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 Polymers
• Polymeric materials are broadly categorized as commodity, engineering
and specialty plastics.
• Commodity plastics comprise of Polyethylene (PE), Polypropylene (PP),
Polyvinyl Chloride (PVC) and Polystyrene.
• Engineering and specialty plastics are plastics that exhibit superior
mechanical and thermal properties and are used for specific purpose.
These include styrene derivatives, polycarbonate, poly methyl
methacrylate, polycarbonates, poly oxy methylene (POM) plastics etc.
• Major plastic materials like PE and PP are derived from Ethylene and
Propylene respectively, while other plastics such as PVC, PS & ABS and
PC are produced from benzene, butadiene and other feedstock.
• There are three broad types of PE, viz: Low-density Polyethylene
(LDPE), High-density Polyethylene (HDPE) and Linear Low-density
Polyethylene (LLDPE).
http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 Demand growth of plastics ('000 TPA), CAGR, FY08-13
• Polyethylene (PE) is the most largely used
plastic and demand has grown at 8% CAGR in
last 5 years to reach ~3.6 MnTPA in FY13.
• Polypropylene (PP) is the second largest with
consumption growing from 1.8 MnTPA in FY08
to 2.1 MnTPA in FY13 at a growth rate of 2%
p.a.
• Polyvinyl Chloride (PVC) demand has grown at
10% p.a. from 1.2 MnTPA to 2.1 MnTPA in
FY13.
• Poly-Styrene (PS) has observed a slower growth
rate of 3% p.a. to reach ~250,000 TPA in FY13,
• Other (PC/ ABS etc.) have grown at 7% p.a.
from 94,000 TPA to 141,000 TPA in FY13
http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 Demand-supply scenario of plastics, Fy13
• The major import source countries are Saudi
Arabia, Qatar, UAE, Korea, USA, Singapore,
Thailand, Germany, Spain and Malaysia.
• India is deficit in PE, PVC and engineering plastics.
In FY13, ~2.3 Mn TPA of PE was produced while
domestics consumption was ~3.4 Mn TPA.
• In case of PVC, the FY13 domestic demand stood
at 2.1 Mn TPA and the domestic production was 1.2
Mn TPA.
• Polyamides consumption was 54,000 TPA, while
domestic production was 13,000 TPA. Other major
engineering plastics were imported.

http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 Plastics applications in Agriculture

Potential benefits from Plasticulture applications are water saving, water use
efficiency and fertilizer use efficiency.
http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 Plastics applications in Food Processing
• Currently, in India, processed food
spends as a % of per capita GDP is Food processing segments (% share)
very low compared to other
developed nations.
• It has the potential to grow at ~8%
p.a. over the next 5 years & is
expected to be a $100 billion
industry by 2018.
• Currently, Gujarat, Maharashtra &
Andhra Pradesh are the major
food processing clusters in India.

http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 Plastics applications in Food Processing
• Flexible packaging consists of either Plastics in flexible packaging (% share)
monolayer or multilayer films of
plastics.
• Multilayered laminated sheets of
plastics mainly include PE, PP, PET,
and PVC.
• Polyethylene and polypropylene
account for ~ 62% of polymer usage
in the flexible packaging industry.
• The Indian packaging industry is
expected grow at 15% p.a. with
flexible packaging growing at 17%
p.a. and rigid growing at 14% p.a.

http://ficci.in/spdocument/20396/Knowledge-Paper-ps.pdf
 What is BPA, and what are the concerns about BPA?
• BPA stands for bisphenol A.

• BPA is an industrial chemical that has been

used to make certain plastics and resins since
the 1960s.
• BPA is found in polycarbonate plastics and
epoxy resins.
• Some research has shown that BPA can seep
into food or beverages from containers that are
made with BPA.
• Exposure to BPA is a concern because of
possible health effects of BPA on the brain and
prostate gland of infants and children.
https://www.mayoclinic.org/healthy-lifestyle/nutrition-and-healthy-eating/expert-answers/bpa/faq-20058331
How to know what plastics can be recycled
PET or PETE is the most common plastic for single-use bottled beverages, because it's
inexpensive, lightweight, and easy to recycle. It poses low risk of leaching breakdown products.
Found in: Soft drinks, water, ketchup, and beer bottles; mouthwash bottles; peanut butter
containers; salad dressing and vegetable oil containers

HDPE is a versatile plastic with many uses, especially when it comes to packaging. It carries
low risk of leaching and is readily recyclable into many types of goods.
Found in: Milk jugs; juice bottles; bleach, detergent, and other household cleaner bottles;
shampoo bottles; some trash and shopping bags; motor oil bottles; butter and yogurt tubs

PVC is commonly used for piping and siding. PVC is also cheap and can release highly
dangerous dioxins during manufacturing. Remember to never burn PVC, because it releases
toxins.
Found in: Shampoo and cooking oil bottles, blister packaging, wire jacketing, siding, windows,
piping

https://www.goodhousekeeping.com/home/g804/recycling-symbols-plastics-460321/
 How to know what plastics can be recycled
LDPE is a flexible plastic with many applications. Historically, it hasn't been accepted through most
American recycling programs, but more and more communities are starting to accept it.
Found: Squeezable bottles; bread, frozen food, dry cleaning, and shopping bags; tote bags; furniture

PP has a high melting point, so it's often chosen for containers that will hold hot liquid. It's gradually
becoming more accepted by recyclers.
Found in: Some yogurt containers, syrup and medicine bottles, caps, straws

PS can be made into rigid or foam products. Styrene monomer can leach into foods and is a
possible human carcinogen, while styrene oxide is classified as a probable carcinogen.
Found in: Disposable plates and cups, meat trays, egg cartons, carry-out containers, aspirin bottles

A wide variety of plastic resins that don't fit into the previous categories are lumped into this one.
Polycarbonate is the hard plastic. PLA (polylactic acid), which is made from plants and is carbon
neutral, also falls into this category.
Found in: Three- and five-gallon water bottles, bullet-proof materials, sunglasses, DVDs, iPod and
computer cases, signs and displays, certain food containers, nylon
https://www.goodhousekeeping.com/home/g804/recycling-symbols-plastics-460321/
Classification of polymers

• Physical and chemical structure

• Mode of polymerization

• Physical properties

• Applications
Physical and Chemical Structure of polymers
• Functionality
• Unifunctional (U-): CH3COOH

• Bifunctional (-B-): CH2=CH2

• Trifunctional: (-T-): trimethylol phenol.

• Physical structure and Functionality

• Linear polymers

• Cross-linked polymers

• Branched-chain polymers
• Polymeric chemical reactions
ØPolycondensation reaction: monomers reacts by repeatedly splitting off
small molecules like H2O, NH3, CH2O, NaCl, etc. Example: esterification
reaction- Benzoic acid reacts with ethanol gives Ethyl benzoate, expelling
one molecule of H2O. The polymer formed after the reaction is called the
condensation polymer.

ØAddition reaction: occurs among molecules containing double or triple

bonds or with oxo-ring compounds.
• Step Reactions
• Chain Reactions
• Ionic Reactions
Polycondensation reactions
• Representative groups: aldehyde, amide, amine, anhydride, epoxy
etc.

• Complexity of reaction: reaction between terephthalic acid ethylene

glycol
 (AB)2 + (AB)2 → (AB)4
Addition reaction
...
(AB)r + (AB)s → (AB)r + s
• Step addition reaction: ethylene oxide and trace of methanol
Scheme 11.3 Reactions in step growth polymerization of a bifunctional monomer.

Chain growth Polymerization − Radical and Coordination Pathways

• polymerization
in growth Chain addition reaction:
(also called polymerization
addition polymerization) reaction
reaction occurs byoccurs byaddition
successive
successive
mer molecules addition
to the reactive of monomer
end (e.g., molecules
a radical end) to polymer
of a growing the reactive endvinyl
chain. The of amonome
growingstyrene,
s ethene, propene, polymer andchain. The vinyl
vinyl chloride monomers
are the such examples:
most important as ethene, propene,
styrene, and vinyl chloride are the most important examples:
n CH2 = CHX → −(−CH2 − CHX)n − (11.
X = H, CH3, C5H6, or Cl, respectively.
ch X = H, CH3 , C5 H6 , or Cl, respectively. Scanned by CamScanner
initiator or a catalyst is usually required to start the chain growth reaction.
ain growth polymerization can be classified (in order of commercial importance) as radical, coordinatio
Variation of Chain Addition Reactions

Let R and S be two different monomers

• Homopolymerization

• Copolymerization
• Random type
• Alternating type

• Block polymerization

• Graft polymerization
need an initiator to produce the first radical and thus start the chain of addition reactions. Th
nitiationChain
reactionaddition reaction
is the thermal kinetics
decomposition of molecules containing weak bonds, for exa
–O–O–) or azo compounds (–N=N–). The formed radicals then react with the monomers.
Radical
a chain will growPolymerization: Mostofradical
by repeated additions monomerpolymerizations
molecules with need an initiator
simultaneous creation
to produce the first radical. For example, peroxides (–O–O–) or azo
compounds (–N=N–).

Initiation: R-R → 2 R• ki ≈ 10−4 –10−6 /s (300–350 K

R• + M → RM1 •
Propagation: RM1 • + M → RM2 • kp ≈ 102 –104 m3 /kmol/s (300
RM2 • + M → RM3 •
Etc.
RMn-1 • + M → RMn •
Termination RMm • + RMn • → RMm = + RMn disproportionation
disproportion
RMm • + RMn • → RMm -Mn R recombination
recombination
Chain transfer: RMn • + S → RMn + S• to solvent
to solvent
RMn • + M → RMn + M• to monomer
to monomer
 Ionic addition reactions
• The preparation of polyisobutylene with boron trifluoride catalyst

Stereospecific Polymerization
• Example: Vinyl H-substituted polymer
Classification of polymers

• Physical and chemical structure

• Mode of polymerization

• Physical properties

• Applications
Mode of polymerization
• Condensation polymerization methods:
• Use for low molecular weight functional group reactions
• Stoichiometric proportions of reactants chosen for desired final properties
• Can be occurred with or without solvent addition
• Temperature regulation important to avoid premature gelation.

• Removal of condensation product required for higher degree of polymerization

• Vacuum processing, distillation used for separation.

• For tri-dimensional polymers,

• Two-stage processing.
• First stage: production of soluble and fusile polymer with low cross- linking;
reaction terminated by removal of catalyst, lowering of temperature, or non-
removal of condensation product.
• Second stage: heat curing to the final thermosetting product.
Addition polymerization methods
• Reaction route may be either through:
§ Homogenous polymerization
§ Heterogeneous polymerization

§ Homogeneous polymerization:
ØBulk polymerization and
ØSolution polymerization

§ Heterogeneous polymerization:
ØEmulsion polymerization and
ØSuspension polymerization
Addition polymerization methods: Homogeneous polymerization
ØBulk polymerization
üCan be either gas phase or liquid phase.
üCommonly used for production of pure polymers.
üPolymerization mixture includes monomers, initiators, and chain transfer
agent (if required).
üCan be done either in batch or continuous operation.
üChallenges include large heat transfer surface requirement for effective
temperature control coupled with increase in liquid viscosity with increasing
polymer length.
üPolystyrene powder production: uses liquid polymer atomized in an inert gas
spray chamber.
Addition polymerization methods: Homogeneous polymerization

ØSolution polymerization
üReaction conducted in the presence of an inert solvent which takes up
significant portion of the vessel.
üSolvent reduces the reaction rate, causes chain termination, and regulates the
chain length (MW of the polymer).
üSolvent enhances heat capacity, reduces viscosity, increases heat transfer.
üAdditional batch and/or continuous processes required for separation of
polymer and recovery of solvent for reuse.
üIdeal solvent is one in which the monomer solubility is high, but the solubility
of protein with the required molecular weight (chain length) is insoluble,
thereby causing precipitation of the polymer and enabling continuous removal
of product. Should have a high specific heat capacity and low viscosity.
Addition polymerization methods: Heterogeneous polymerization

• Emulsion polymerization
üMonomer and water is emulsified with suitable reagents (surfactant or soap) to
produce spherical micelles in the range of 1-10 μm diameter.
üEasy for temperature control and for forming higher MW polymers.
üHeat produced during polymerization is absorbed with the aqueous phase.
üViscosity of the emulsion remains constant throughout.
üEmulsion obtained is stable; minimum agitation requirement.
üLatex used for latex paints are produced using this method.
üCoagulation of the emulsion (with salts / acids) can produce solid rubber like
polymer matrix.
Addition polymerization methods: Heterogeneous polymerization

• Suspension polymerization
üPhases suspended using high shear agitators.
üPolymers are formed in droplets, resulting in spherical polymer
beads which can be either used as such or extruded and chopped to
form larger, molded pellets.
üHeat transfer occurs between droplets in the size range of 0.01 – 1
mm diameter.
üDegree of polymerization not as high as emulsion polymerization
process.
Classification of polymers

• Physical and chemical structure

• Mode of polymerization

• Physical properties

• Applications
Classification according to Physical Properties
Polymers can also be classified according to physical properties as –
• Thermoplastic
• Thermosetting
• Elastomers
• Fibers

• Thermoplastics
§ Generally linear or slightly branched molecules, mostly solvent soluble.
§ Can be melted and shaped repeatedly.
§ Polyethylene, cellulose derivatives, vinyls, polylacticacid (PLA), etc.
Physical properties
• Thermosetting polymers
§ Cross-linked or heavily branched molecules, largely solvent insoluble.
§ Good heat resistance, but cannot be melted after initial forming.
§ Silicones, phenol-formaldehyde etc.
• Elastomers
§ Exhibits viscoelasticity, has weak intermolecular forces, low Young’s modulus,
and high failure strain.
§ displays rubber-like elasticity.
§ Generally, glass transition temperature is below room temperature.
§ butadiene and derivatives, chloroprene and nitrile rubbers, silicones, etc.
• Fibers
§ Forms threads with high tensile strength.
§ polyesters, cellulose derivatives, protein derivatives, etc.
Classification of polymers

• Physical and chemical structure

• Mode of polymerization

• Physical properties

• Applications
Classification according to Polymer Applications
• Adhesives
§ Used for bonding between solid surfaces.
§ Resins: where water repelling is required (for plywood laminate gluing).
§ Cellulose adhesives: consists of cellulose derivatives dissolved in solvents.
§ Vinyls: rubber based latex adhesive emulsified in water (polyvinyl acetate
emulsion in Fevicol).
§ Dispersion of starch, dextrins, proteins, etc. in a solvent (typically water) can
also act as simple adhesives.

• Solid shapes
§ Polymers may be molded, casted, laminated, or extruded into various shapes.
§ Popular in making most articles used in industry as well as household.
§ Finishing operations involve machining, grinding, polishing, etc.
Polymer Applications
• Coatings and Films
§ Generally formed by solvent evaporation followed by polymerization.
§ Emulsion casting or extrusion by mechanical means also used in production.
§ Used for protective or decorative purposes.
§ e.g. polyethylene & cellulose films.

• Fibers
§ Linear molecules, formed by extrusion or spinning into small diameters (10-50
μm) or thin sections.
§ Have excellent tensile strength, creep, and resilience.
§ Extensively used in textile industry.
 Polymer Processing Technologies
• Mixing:
• occur under the action of gravitational forces in a tumble mixer or
in a ribbon mixer is known as cold mixers
• In hot mixers, the polymers are heated by contact with heated metal
components.
• Rolling and Kneading:
• Pelletizing
• Shredding and Grinding
• Storage and Transportation
Polymer Processing Technologies

• Pressureless Processing Techniques

• Casting
• Dipping
• Coating
• Foaming

• Polymer Processing under pressure

• Compression molding
• Rolling and Calendering
• Extrusion
• Blow Molding
• Injection Molding
Polymer Processing Technologies
Melt Processing
• Extruded into fibers, films, tubes, or other linear and complex shapes
• Molding: shaping plastic using a rigid frame or mold (i.e., hollow metal block into
which molten plastic is injected to from a certain fixed shape).
• Molding Techniques
• Injection molding
• Blow molding
• Rotational molding
• Compression molding
 Injection moulding
• Industrially used for the mass production of complex molding geometries.
• Injects the molten polymer into a closed cooled mold where it solidifies to
give the product.
• High pressure of molten polymer is maintained inside the mold until it is
cooled and set.

https://www.polyplastics.com/en/support/mold/outline/ani1.htm
Blow molding
• Blow molding takes place on a separate unit where the preform is
reheated from room temperature to the orientation temperature
followed by stretch blow molding.
• For making hollow parts (bottles, containers, suit cases, fuel tanks,
etc.) from thermoplastics.
• divided blow mold four types as:
• Extrusion blow molding
• Injection blow molding
• Stretch blow molding
• Reheat and blow molding.
• The process is discontinuous or batch wise in nature, involving a
sequence of operations
• The steps involved are as follows:
• Initially, from the extruded plastic, an hollow tube of plastic is made, termed
parison.
• The parison is closed and captured inside a mold.
• Air is blown into the parison, inflating it into the shape of the mold.
• Once the plastic is cold enough, the mold is opened and the part is ejected.

https://www.pinterest.com/pin/
441423200971723298/
 Rotational molding / rotomolding
• A versatile process for creating many kinds of mostly hollow plastic
ranging from liquid storage tanks to containers of various shapes.

Annual growth from 1994 to 2002 in

consumption of plastics manufactured by
rotational molding and other techniques.
https://www.sciencedirect.com/topics/engineering/rotational-moulding
Compression Molds
• Compression molding involves the placement of polymers on a heated metal
mold, and as heating softens the material, it is forced to conform to the shape of
the mold as the mold closes.
• There are two forms of compression molding: SMC (sheet molding compound)
and BMC (bulk molding compound).

http://mold-technology4all.blogspot.com/2011/08/plastic-processing-methode-types.html
 Rolling and Calendering
• The rolling mills consist of two rolls that are used exclusively for the
compounding of thermoplastics. PVC and rubber are processed using this
process.
• When the rolls are more than to in number, and the polymer is to be shaped
using these rolls is called a calendar
• Floor coverings and films made of plasticised PVC, cotton, many linens
and silks, and various man-made fabrics.

a) Winder and Edge Cutter; b)Cooling Rolls; c)Four-roll calendar; d)Extruder; e)Mixing Roll Mill.
Extrusion
• Melt extrusion processes are usually the most convenient, economical, and
environmentally favorable for film and sheet manufacturing

• Processes require close monitoring of the various parameters, such as

viscosity, variation of viscosity with shear rate and temperature, elasticity,
extensional flow, and slippage of the material over hot metal surfaces

• Single or twin screw extruders are most common in industry.

 Extrusion

• A die with a round opening produces pipe. Other continuous shapes, such as the
film, sheet, rods, tubing, and filaments, can be produced with appropriate dies.
Extruders are also used to apply insulation and jacketing to wire and cable and to
coat substrates such as paper, cloth, and foil.

https://www.sciencedirect.com/topics/engineering/extrusion-process