UNIT-III

Polymers, Elastomers and Polyurethanes-I

 Contents
• Introduction
• Characteristics of Polymers
• Classification of Polymers
• Polymerization Reactions
• Polymerization Reactors
• Polyethylene
• Polypropylene
• Polyvinyl Chloride (PVC)
• Polystyrene
• Epoxy Resin
• Polycarbonates
 Introduction
• Polymers have penetrated into all fields of application and in volume of around 205
million tonnes per annum including standard polymers, engineering resins,
elastomers, fibers and textiles, dispersions. Polyolefins (LDPE, LLDPE, HDPE and
polypropylene) are by far the largest group of thermoplastic polymers [CMAI 2003].

• Polypropylene resins along with polyester resins (PET), are one of the fastest-growing
categories of commodity thermoplastic resins in the world. The United States and China
now represent more than 15% and 22%, respectively, of world polypropylene
consumption.

• Polymers have penetrated into all fields of application and in volume of around 205
million tonnes per annum including standard polymers, engineering resins, elastomers,
fibers and textiles, dispersions. Amongst the plastics, thermoplastic market represents
approximately 10 percent of global chemical industry. World polymer demand in 2010
was 280 million tones.
Introduction
 Plastic Consumption, according
World Total Polymer Demand to Industry and Polymer
• Polyolefins are by far the largest group of thermoplastic polymers.
As per CMAI 2003, polyolefins (LDPE, LLDPE, HDPE and
polypropylene) represent the largest segment of the global
thermoplastics business at approximately 88 million tonnes (about
62 percent of the total market in 2002).
• Major success factors for polyolefins are: easy accessible,
reasonable raw materials (oil & natural gas based), low production
cost by modern energy saving and non polluting processes,
resources saving products, environmentally harmless products,
energetically exploitable products after usage, broad product
portfolio, and tailor made products.
Various Types of Polymer and their Application
• Polyvinyl Chloride (PVC) is the second largest commodity
thermoplastic in the world, after the polyethylenes.
• According to global production and consumption of polyvinyl
chloride (PVC) in 2010 was approx. 34 million metric tons.
• Global consumption of polyethylene in 2009 was approximately 64
million metric tons. Global capacity utilization was 80% in 2009,
down from 82% in 2008.
• Average global utilization of polyethylene rates are expected remain
under 80% during the next five years, gradually increasing to the
high-80% by 2019.
• World polyethylene per capita consumption is targeted to grow from
9.0 kg - 11.0 kg from 2001-06.
• High density PE (HDPE) accounted for around 45% of global
polyethylene consumption in 2009, followed by linear low density
PE (LLDPE) and low density PE (LDPE).
Uses of polymers
• Global demand for polymers is estimate to increase at 5% per
annum to reach 227 MMT by 2015.
• Polymer demand in India is expected to grow at 13-14% p.a. and
will account for 9% of global polymer demand by 2015. The total
polymer demand in India by 2015 is estimated to be around 22 MMT.
• India’s share in The Global Polymer Demand by 2015
Demand of Thermoplastics in world
Classification of polymer
 Classification According To Physical Properties
• Polymers can also be classified according to physical properties
as: i. Thermoplastic ii. Thermosetting
iii. Elastomers iv. Fibers
Thermoplastic :
• The polymers in this category are composed of monomers
which are linear or have moderate branching.
• They can be melted repeatedly and casted into various shapes and
structures.
• They are soluble in solvents, but do not have appreciable
thermal resistance properties.
• Vinyls, cellulose derivatives, polythene and polypropylene fall
into the category of thermoplastic polymers.
Thermosetting :
 There are some polymers which, when heated, decompose, and hence,
cannot be reshaped. Such polymers have a complex 3-D network
(cross-linked or branched) and are called Thermosetting Polymers.
 They are generally insoluble in solvents and have good heat resistance
quality.
 Thermosetting polymers include phenol-formaldehyde, urea-
aldehyde, silicones and allyls.
Elastomers :
• These are resistant solids which have considerable flexibility. They are
composed of polymers with glass transition temperature below room
temperature.
• One major difference between elastomers and plastics is that the
elastomer is in a liquid state, while plastics are in the glassy state.
• Examples of elastomers are Butadiene, Butadiene co – polymers
and their derivatives,polycondensationproducts , silicones and
thiokols.
Fibers :

• These are solids which can form thread –

like structures and have high tensile
strength.
• Examples of fibers are Polyamides,
Polyesters, Polyurethanes, Protein
derivatives.
 Classification according to applications:
Adhesives:
• Some polymers can be used for bonding . They are usually of
the resin type and require some water resistance .
Some common adhesives are –
• Cellulose adhesives ; which consist of cellulose derivatives
dissolved in a solvent. Eg.Duco cement.
• Vinyls ; these are rubber base type water-emulsified latex
adhesives.
• Apart from these, some cheap natural products such as
starch, dextrins, proteins and natural rubber may also be
used for adhesive formulations.
Coatings and films :
• A large bulk of the polymers produced are used for
manufacturing coatings and films.
• Free films of polyethylene and cellulosic types, protective
and decorative coatings are the products of the polymer
industry.
• Coatings can be manufactured by solvent evaporation
followed by polymerization. Emulsion and casting or
extrusion of free films by mechanical methods can also
produce coatings and films.
Fibers:
• These are formed by extrusion or spinning of linear
monomer molecules into thin sections of diameter in the
range of 10 – 50 microns.
• Fibers have excellent tensile strength.
• Fibers are extensively used in the textile industry . Cotton, wool
etc. are the examples of some natural fibers.
 Classification According To Preparation Methods
• Preparation methods for polymers may be roughly divided
into two categories: (A). Condensation Polymerization
Methods. (B). Addition Polymerization Methods.
Condensation Polymerization Methods :
• These methods are usually employed for low molecular
weight functional group reactions, where the stoichiometric
proportions of the reactions are fixed for the desired final
products.
• During processing, solvent addition may or may not be
important.
• These reactants are usually mixed in a batch reactor with
controlled temperature and addition of catalysts.
• Vacuum processing or Azeotropic Distillation may be
employed to remove condensation products such as H2O to
obtain a higher degree of polymerization.
Addition Polymerization Methods :
• These methods are carried out with controlled thermal and
catalyst conditions. They may be further classified as:
Bulk Polymerization :
• This mode of polymerization may be employed to obtain the
purest form of polymer, and the greatest yield of polymer
per unit volume may be obtained using this method.
• This method involves only the monomer molecule, an
initiator and a chain transfer agent ( if necessary).
• In a large scale batch form, the process is to be run slowly or
in continuous mode with large heat transfer area. Casting of
objects of various shapes may be accomplished using the
Batch Bulk Polymerization. Using continuous bulk
polymerization processes, polystyrene and other thermoplastic
compounds may be moulded.
Solution Polymerization :
• An inert solvent is added to the reacting components in the reaction
vessel in this process.
• The solvent enhances the heat capacity, thereby reducing the
viscosity and facilitating heat transfer.
• Some of the solvent may be refluxed to remove heat from the
reaction vessel. But , much of the reactor space is taken up by the
solvent.
• As such , compared to Bulk Polymerization, Solution Polymerization
reduces both the reaction rate and the molecular weight of the
compounds. Additional batch and continuous processes are used to
separate the final polymer product and to recover and store the
solvent used.
Suspension Polymerization :
• Inorder to control the enormous amount of heat release in Bulk
Polymerization, Suspension Polymerization method was developed.
• The reaction mass is dispersed as minute droplets of size 0.01 – 1 mm in
diameter in a continuous aqueous phase. Each of these droplets act as tiny
bulk reactors.
• Heat transfer occurs from the droplets to the water having large heat
capacity and low viscosity.
• Cooling jackets are used to facilitate heat removal.
• Agitators are used along with suspending agents in the aqueous phase in
order to maintain a specific droplet size and dispersion.
• The Suspension Polymerization process cannot be run in a continuous
mode , since, such a system has stagnant corners where polymer
accumulation may occur. On a commercial scale, Suspension
Polymerization is carried out in jacketed, stainless steel or glass – lined
stirred tanks, which may have a capacity of 20,000 gal or 75.5 m3.
• Suspension Polymerization produces small, uniform polymer spheres. These
are used directly, or may be extruded and chopped to form larger, moulded
pellets.
Emulsion Polymerization :
• This is the most widely used method of polymerization. This process
overcomes the difficulty of heat control and low degree of
polymerization.
• The organic reaction mass is emulsified with soap in a continuous
aqueous phase.
• The dispersed particles are smaller in size than in Suspension
Polymerization ( ≤ 0.1 μm) .
• In addition, due to stabilizing action of soap, the emulsion obtained is
stable and agitation may not be necessary.
• In some methods, a water – soluble initiator may be used. The main
product of Emulsion Polymerization is latex, which forms the basis
of the popular latex paints. By coagulating the latex with ionic salts
and acids, solid rubber may also be obtained.
HomogeneousPolymerization:
• In case of homogeneous bulk polymerization, the feed is a gas
, liquid or solid monomer. Noinitiators or additives are used.
• For homogeneous Solution polymerization, the monomer is
completely dissolved in a solvent.
HeterogeneousPolymerization:
• In heterogeneous Emulsion polymerization, the monomer
molecules are emulsified in aqueous media in the form of
micelles.
• For heterogeneous Suspension polymerization, the monomer
is suspended in a n aqueous or other type of media as large
droplets.
• Addition polymerization process are
three types: Bulk polymerization;
Solution polymerization and
Suspension polymerization
• One or more monomers are polymerized
in the liquid or vapor phase along with
catalyst and initiators
In solution polymerization:
• The monomer and initiator are dissolved
into a non reactive solvent and the
monomer, initiator, solvent and catalyst
are heated and during polymerization the
solvent is removed.
• This method produces polymers of low
and medium molecular weights.
In emulsion polymerization:
• Water rather than organic solvent is used.
In suspension polymerization:
• The monomer is suspended in water by
agitation along with some stabilizers and
polymerization reaction proceeds in
suspension.
In Condensation polymerization:
• During reaction a small molecule like water is
eliminated e.g. in nylon 66 synthesis where
Hexamethylene diamine and adipic acid
condense, water is eliminated.
• Some of the important catalysts used in
polymerization reactions are the Ziegler-
Natta catalyst, metal oxide catalysts and
metallocene catalysts
• American Society For Testing And Materials (ASTM) has
classified polyethylene into the following four groups:

Type-I Low density: 910-925 kg/m3

Type-II Medium density: 926-940 kg/m3
Type-III High density: 941-959 kg/m3
Type-IV High density to Ultra density: 961 kg/m3 and above
Polyethylene (PE)
 Polyethylene (PE)
Polymer Chemistry:
• The manufacture of polyethylene follows addition
polymerization kinetics involving catalysis of
purified ethylene.
• Its molecular formula is -(CH2-CH2)n- with a
molecular weight of 1,500 to 100,000.
• Its melting point is 85 – 110oC.
• its density is 0.91 -0.93 , when produced by high pressure
process and 0.96, when produced by low pressure
process.
Technology: There are three processes by which
polyethylene is manufactured –
a High Pressure Process :
• This process was developed in the UK by ICI. It uses
peroxide catalyst at 100-300 oC and produces low density
randomly oriented polymer which have a low melting
point.
• The process is run at pressure of 1000 – 2500 atms. This
process yields Low Density Polyethylene (LDPE).
b .Intermediate Pressure Process :
• This process was developed in the USA by Phillips
Petroleum Co. for preparing high density polymer with
increased crystallinity, tensile strength and softening point.
• The process uses MoO3 and Cr2O3 on alumina as
catalyst and is operated at 30 – 100 atms.
c .Low Pressure Process :
• This process was originally developed in Germany
for preparing high density polyethylene (HDPE).
• The catalyst used in this process consists of aluminium
triethylactivated with heavy metal derivatives such as
TiCl4.
Description of Low Pressure Ziegler Process to produce polyethylene

• At the very onset, through the process of desulphurization

and removal of light ends, high purity ethylene is
prepared.
• The ethylene is further treated to remove traces of oxygen and
its compounds which can possibly deactivate the catalyst.
• The ethylene is first pumped into a reactor where it is
mixed with catalyst diluents stream.
• The optimum temperature and pressure maintained should be
70oC and 7 atms gage.
• The effluent stream then follows across a series of flash
drums inorder to remove the solvent from the catalyst.
• The residual catalyst at this point is removed by adding water.
• The flashed solvent is thereafter recycled to the catalyst
make –up unit after appropriate drying and redistillation.
• The slurry which results is then centrifuged to remove the
water, and the water is treated to remove the catalyst
before recycle.
• The final products of polyethylene solids are then dried,
extruded and given the required final forms.
Manufacture of Polythene
 Spherilene gas - phase technology-
Polyethylene
Application:
• New generation Spherilene gas-phase technology with
simplified process flow scheme, to produce linear-low-
density polyethylene (LLDPE), medium density polyethylene
(MDPE) and high-density polyethylene (HDPE) of narrow,
unimodal molecular weight distribution as well as bimodal
molecular weight distribution, using only a single Ziegler-
Natta titanium-based catalyst family, with full online swing
capability without shutdowns.
Description:
• Catalyst components are mixed and fed directly to a pre-
contact vessel (1), where the catalyst is activated under
controlled conditions.
• The activated catalyst system flows continuously into the first
gas phase reactor (GPR) (3). A cooler on the circulation gas
loop (2) removes the reaction heat.
• Product containing still active catalyst is continuously
discharged from the first GPR via a proprietary device to a
second GPR (5) with similar configuration.
• Resultant discharged gas is recovered, and no gas from the
first GPR enters the second GPR, due to a proprietary “lock-
hopper” system (4).
• The second GPR is independently supplied with
necessary monomer, comonomer and hydrogen to
maintain reaction conditions truly independent from
the first GPR.
• This gives Spherilene process the ability to produce truly
bimodal HDPE grades and the added freedom to obtain
“inverse” comonomer distribution in the final product by
selectively feeding comonomer only where necessary.
• Pressure and temperature in the GPRs are also independently
controlled; while no additional feed of catalytic components
to the second GPR is required.
• The polymer, in spherical form with particle size ranging
from approximately 0.5 mm to 3 mm, is then discharged in
a receiver recovering the resultant gas (6) and to a
proprietary unit for monomer stripping and neutralization
of any remaining catalyst activity (7).
• Residual hydrocarbons in the polymer are stripped out
and recycled back to reaction.
• The polymer is dried by a closed-loop nitrogen system (8)
and with no volatile substances, is sent to liquid and/or solid
additives incorporation step before extrusion (9).
Pre-contact vessel (1);Cooler (2); First gas phase reactor (GPR) (3); Lock-hopper” system
(4); Second gas phase reactor (GPR) (5); Receiver (6); Monomer stripping and
neutralization (7); Closed-loop nitrogen system for drying (8); Extrusion system(9)
Products:
• Product density range is very wide, from approximately 0.915 g/cc (LLDPE) to
> 960 g/cc (HDPE), including full access to the MDPE range (0.930 to 0.940
g/cc).
• Melt index (MI) capability ranges from 0.01 to > 100 g/10 min. Because of the
dual GPR set-up, Spherilene technology enables production of premium
bimodal grades (MI, density) in gas phase with “inverse” comonomer
distribution
• Commercially proven grades include bimodal HDPE for pressure pipe markets
with PE100 certification and bimodal HDPE grades for high-strength film
markets. Traditional HDPE grades for injection molding and extrusion
applications,
Commercial plants:
• Licensed from 1992, nine plants using Spherilene process and technology have
been licensed, with a total capacity of 1.8 million tpy. Single-line capacities in
operation range from 100,000 to 300,000 tpy, with current process design
available for plants up to 400,000 tpy in single-line capacity.
 Gas-phase UNIPOL PE process-Polyethylene
Application:
• To produce linear low-density polyethylene (LLDPE) to high
density polyethylene (HDPE) using the low-pressure, gas-
phase UNIPOL PE process.
Description:
• A wide range of polyethylenes is made in a gas-phase, fluidized-
bed reactor using proprietary solid and slurry catalysts. The
product is in a dry, free-flowing granular form substantially free
of fines as it leaves the reactor and is converted to pellet form
for sale.
• Melt index and molecular weight distribution are controlled by
selecting the proper catalyst type and adjusting operating
conditions.
• Polymer density is controlled by adjusting comonomer content
of the product. High productivity of conventional and
metallocene catalysts eliminates the need for catalyst removal.
• The simple and direct nature of this process results in low
investment and operating costs, low levels of environmental
pollution, minimal potential fire and explosion hazards, and
easy operation and maintenance.
• Gaseous ethylene, comonomer and catalyst are fed to a
reactor (1) containing a fluidized bed of growing polymer
particles and operating near 25 kg / cm2 and approximately
100 °C.
• A conventional, single-stage, centrifugal compressor (2)
circulates reaction gas, which fluidizes the reaction bed,
provides raw material for the polymerization reaction, and
removes the heat of reaction from the bed. Circulating gas is
cooled in a conventional heat exchanger (3)
• The granular product flows intermittently into product discharge
tanks (4) where unreacted gas is separated from the product and
returned to the reactor.
• Hydrocarbons remaining with the product are removed by purging with
nitrogen. The granular product is subsequently pelletized in a low-
energy system (5) with the appropriate additives for each application.
Products:
• Polymer density is easily controlled from 0.915 to 0.970 g/cm.
Depending on catalyst type, molecular weight distribution is either
narrow or broad.
• Melt index may be varied from less than 0.1 to greater than 200.
Grades suitable for film, blow-molding, pipe, roto-molding and
extrusion applications are produced.
Commercial plants:
• Ninety-six reaction lines are in operation, under construction or in the
design phase worldwide with single-line capacities ranging from
40,000 tpy to more than 450,000 tpy.
 25 kg / cm2 and
approximately 100 °C.

Polymer density is easily controlled from

0.915 to 0.970 g/cm

fluidized bed reactor(1); Compressor(2); Heat exchanger (3); discharge tank(4);

pelletization section (5)
POLYVINYL CHLORIDE (PVC)
POLYVINYL CHLORIDE
• Polyvinyl chloride is second largest (after polyethylene) and
most versatile of all thermoplastics.
• Despite various environmental issues raised time to time PVC
has enjoyed on stant growth in demand because of its unique
properties which include stiffness, ease of processing and cost
effectiveness.
• PVC has been facing innumerable challenges to its usage and
growth. With use of suitable additives like stabilizer and
plasticisers can be made rigid or flexible for a variety of end
uses.
• It contains about 56.8% chlorine and balance being
hydrocarbon. A major portion of the chlorine produced in
the world is used in the manufacture of PVC.
• Global production and consumption of Polyvinyl Chloride
PVC in 2010 was approx. 34 million metric tons.
• Global capacity utilization was 72percent in 2010
Process technology for PVC
• The basic monomer for manufacture of PVC is vinyl chloride
which is made from either acetylene or ethylene. However,
ethylene is the chief source of vinyl chloride throughout
world.
• Various sources of ethylene are naphtha gas cracking,
acetylene route and alcohol route.
• Using a free radical initiator, PVC can be made with any of
four general methods of polymerization – suspension,
emulsion, bulk and solution polymerizes vinyl chloride
monomer. However, bulk of PVC is made by suspension
polymerization.
• Most resins produced by the suspension polymerization are
in the range of 125 - 165 microns in diameter while those
produced by bulk polymerization process are in the range of
1 micron diameter.
Suspension polymerization of
PVC manufacture involves
dispersion of vinyl chloride
monomer in water along with a
suspending agent polyvinyl
chloride.
Polymerization is initiated by
activators at temperature around
40-70oC heat produced is
continuously removed using heat
transfer medium.
After the polymerization is
completed the suspension is
transferred to degassing unit where
unreacted monomer is removed,
purified, condensed and recycled.
Polymer is from suspension is
separated by centrifuging and dried
by hot air.
VCM = VINYL CHLORIDE MONOMER
Introduction, History, Production Process,
Properties and Uses.
Polypropylene is a100% synthetic fiber which is
transformed from 85% propylene. The
monomer of polypropylene is propylene.
Polypropylene is a by-product of petroleum.
Phillips Petroleum chemists J. Paul Hogan and
Robert L. Banks first polymerized propylene in
1951.
Propylene was first
polymerized to a crystalline
isotactic polymer by Giulio
Natta as well as by the German
chemist Karl Rehn in March 1954.
This pioneering discovery led to
large-scale commercial production of isotactic
polypropylene by the Italian firm Montecatini from
1957 onwards.
Syndiotactic polypropylene was also first
synthesized by Natta and his coworkers.
Polypropylene is the second most important
plastic with revenues expected to exceed
US$145 billion by 2019. The sales of this
material are forecast to grow at a rate of 5.8%
per year until 2021.
Structure Property Relationship
CH2-CH
n
CH3

 PP is a linear polymer with little or no branching.

Methyl group in the chain leads to increase in melting point
and chain stiffening.
The tertiary carbon atom provides a site for oxidation so that
the polymer is less stable than PE in the presence of oxygen.
Methyl group leads to products of different tacticity.
Commercial polymers are usually about 90-95% isotactic.
Tacticity
H H H
Isotactic H
H H
C H C C C
H C H C C H
H
CH3 CH3 CH3

H H H H
C H CH3 H
Syndiotactic C C C
H C H C H C H
CH3 H
CH3

H H H
H H
Atactic H
C C CH 3
C C H
H C C C CH 3 C
H H
CH 3 CH 3
H H
It is said that PP has an
intermediate level of
crystallinity between low
density polyethylene
(LDPE) and high density
polyethylene (HDPE); On
the other hand PP has higher working
temperatures and tensile strength than
polyethylene
 Properties of isotactic PP
Compare to Polyethylene
 It has lower density (0.90 gm / cc).
 It has a higher softening point and hence a higher
maximum service temperature.
 Articles can withstand boiling water and can be
subjected to steam sterilizing operations.
 It has a higher brittle point.
 It is more susceptible to oxidation.

Atactic PP
 Atactic PP is an amorphous some what rubbery in nature.
 Commercial polymer is usually 90-95% isotactic and
rest is blocks of atactic and syndiotactic structures.
 Properties of Polypropylene
Name Value Unit
Specific gravity 0.90 --
Tensile Strength 35.5 MPa
Tensile modulus 1380 MPa
Flexural modulus 1690 MPa
Elongation at break 35-350 %
Impact Strength (Izod ) 37 J/m
Hardness R100 ---
HDT (under 1.82 MPa load.) 55 °C
Glass transition temperature 5 °C
Melting point 164 °C
Dielectric Strength 24-28 KV/mm
General Properties

Chemical properties

No solvent affects PP at room temperature. Polypropylene will

dissolve in Decaline at 130°C.

Aromatic and chlorinated solvents often swell polymer at

elevated temperature.

Strong oxidizing acids slowly attacks the resin (fuming

HNO3).
 Electrical properties
PP is an excellent insulator due to its non-polarity.
It is used in many molded products, as well as in winding
coils and transformers.

Flammability
PP burns slowly and can be identified by an odour of crude
oil.
Flame–retardant grades are available for specific electrical
applications.
 Additives for Isotactic PP
Fillers
About 3% of PP compounds are filled with talc.
Talc filler improves stiffness and heat deformation resistance.
Talc filled PP compounds are used in heater housings, car mounting
components and several domestic appliances.
 Talc filled PP sheet is used as an alternative to carton board.
Rubbers
 Particularly butyl rubber is used to reduce the brittleness of PP.
 Rubbers are used because of their
• Reasonable price.
• Good weathering properties.
• Negligible toxicity easy processability and re-
processability.
Pigments
 The selection of pigments for PP follows the same considerations as
for PE because of the higher processing temperature and lesser
resistance to oxidation, selection does require more care.
Carbon black

 To improve the resistance to UV light, carbon

black is used as a light screener.
 Hindered amine UV stabilizers (HALS) are used to
improve the UV resistance of PP material.

Antioxidants

 Antioxidants are necessary for prevention from adversity

of oxidation.
 For optimum processing stability a single
antioxidant of the phenol alkane type, for e.g.,
1,1,3 –tris (4 hydroxy - 2 methyl, 5 – t – butyl phenyl)
butane, tends to give the best results.
Poly (propene) is produced from propene.
Propene is produced in large quantities from
gas oil, naphtha, ethane and propane.
Ziegler-Natta catalysts are used in the
polymerization process. These are produced by
interaction of titanium (IV) chloride and an
aluminium alkyl, such as triethyl aluminium.
There are two methods to make the polymer for the
production of Polypropylene:

› Gas Phase Process

› Liquid Phase Process

 Gas Phase Process:

› Union Carbide process:

PP A fluidized-bed process with one or two
reactors for the production of random
homopolymers, random copolymers and
impact copolymers propylene.
Catalyst: Proprietary catalyst (titanium catalyst
supported on MgCl2 and triethyl aluminium
(TEAL) as co-cayalyst
 I Reactor Operating
conditions: 65-70 oC and
33-35 kg/cm2 pressure
II Reactor Operating
conditions: 22 kg/cm2
pressure.

Polypropylene (Homopolymer, random copolymer and impact copolymer

Gas Phase Process:

› Novolen®:
A gas-phase stirred-bed process with two
reactors in series for the production of PP.
Gas Phase Process:

› A mixture of propene and hydrogen is passed

over a bed containing the Ziegler-Natta
catalyst at temperatures of 320-360 K and a
pressure of 8-35 atm.
› The polymer is separated from the gaseous
propene and hydrogen using cyclones and
the unreacted gas is recycled.
› Both processes can be operated continuously
and use 'stereo specific' Ziegler-Natta catalysts
to effect the polymerization. The catalyst
remains in the product and needs to be
destroyed using water or alcohols, before the
polymer is converted into pellets.
› Gas phase processes has virtually eliminated
gaseous and aqueous effluents by the use of high
activity catalysts, resulting in low residues in the
final polymer.
Novolen Process
Liquid Phase Process:

› Spheripol®:
A slurry process for the production of PP
homopolymer plus random copolymers.
Liquid Phase Process:
› In liquid-phase processes catalyst and polymer particles
are suspended in an inert solvent, typically a light or
heavy hydrocarbon.
› Super-critical slurry polymerization processes use
supercritical propane as diluent.
Liquid Phase Process:

› Slurry processes run in loop reactors with the solvent

circulating, stirred tank reactors with a high boiling
solvent or a “liquid pool“ in which polymerization takes
place in a boiling light solvent.
› A variety of catalysts can be used in these
processes.
Liquid Phase Process:
› Processes in solution require, as their last step,
the stripping of the solvent. Supercritical
polymerization in the slurry loop provides
advantages (e.g. higher productivity, improved
product properties) over subcritical
polymerization.
Liquid Phase Process:
› Advanced processes combine a loop reactor
with one or two gas-phase reactors, placed in
series, where the second stage of the
reaction takes place in the gas-phase
reactors. For bimodal polymers, lower
molecular weights are formed in the loop
reactor, while high molecular weights are
formed in the gas-phase reactor.
Spheripol Process
Polystyrene
Polystyrene, high impact
Application:
• To produce a wide range of general purpose and high impact
polystyrenes (PS) via the bulk continuous process using the
BP Chemicals/ABB Lummus Global technology.
Description:
• The production of HIPS begins with the granulating and
dissolving of rubber and other additives in styrene monomer
(1) and then transferring the rubber solution to a storage tank
(2).
• For general purpose product, controlled amounts of
ingredients are fed directly to the feed preheater (3).
• The feed mixture is preheated (3) and continuously fed to the
prepolymerizer (4) where the rubber morphology is
established.
• Following pre polymerization, the polymer mixture is pumped
to the polymerization reactor (5) of proprietary design. At the
exit of the reactor, the polymerization is essentially complete.
• The mixture is then preheated (6) in preparation for
devolatization.
• The devolatilizer (7) is held under a very high vacuum to
remove unreacted monomer and solvent from the polymer
melt. The monomer is distilled in the styrene recovery unit (8)
and recycled back to the prepolymizer.
• The polymer melt is then pumped through a die head (9) to form
strands, a waterbath (10) to cool the strands, a pelletizer (11) to
form pellets and is screened to remove large pellets and fines.
• The resultant product is air-conveyed to bulk storage and
packaging facilities.
Commercial plants:
• Plants in France, Germany, and Sweden are in operation
with a total capacity of approximately 450,000 mtpy of
GPPS and HIPS. Another 300,000 mtpy GPPS and HIPS
unit will start up in China in 2005.
styrene monomer (1); a storage tank (2); feed preheater (3).; prepolymerizer (4);
polymerization reactor (5); preheated (6); devolatilizer (7); styrene recovery unit (8) ;
die head (9); water bath(10); Pelletizer(11)
Epoxy Resins
• Found by C. Castan in 1930s on his search for
dental use and successfully introduced by Ciba by
end 1940s in the electro industry as insulating
material, as coating and laminating material, as
well as adhesive.
EpoxyResin

• Also called "epoxy" or "polyepoxide".

• Second most widely used family of thermosets copolymer(after
polyesters)
• Large portion of uses are non-reinforced (adhesives, paints, etc.)
• Circuit boards are the largest reinforced application (low
conductivity, low volatiles)
• General Properties:
• High Mechanical Properties: large cohesive force
• Good Adhesive Performance: great number of polar group
• Excellent stability: without impurities(base and salt)
• Flexibility and diversity in Designing

Because of the stability and mechanical properties, epoxy resin

coating owns great chemical and physical resistance.
EpoxyStructure

Epoxy ring Epoxy ring

C C( )n C C
O O

Polymer portion

Number ofrepeat units

Demand and Applications for Epoxy
The Industry of Epoxy Resins

• China produces 30% or the worldwide market.

• $5 Billion industry in North America
• Hexion (Shell Development Company)
• Dow Chemical Company
• Huntsman Corporation’s Advanced Materials

• Some current applications are on “under-the-hood”

automotive components, floor coatings, underground
tanks/pipes/cables, electrical connectors, circuit boards,
adhesives, structural support additive in high stress areas
like wind turbines and aerospace frames
Marketability
Marketability
BisphenolA epoxyresin

 Epoxy resin is made by reaction of Bisphenol-A with excess of

epichlorohydrin in the presence of alkaline catalyst at elevated
temperatures.
 The reaction involves the formation of dichlorohydrin of
Bisphenol-A followed by hydrohalogenaation with NaOH.
 CuringEpoxies:
 The reactive epoxies are cured or cross-linked by polymerization into a 3D
infusible network through the use of curing agents like anhydrides,
aliphatic amines or polyamides.
The overall reaction for the synthesis of epoxy resin
What makes epoxy resins special ?

• The aromatic structure of the resin implements a strong hydrophobic

performance far over competitive resins like polyurethanes or acrylics,
which were developed at thesame time.
Corrosion resistance
Epoxy based formulations give corrosion resisting coatings or laminates
• Absolutely non porous
• Tough and resistant toimpact
• Flexible enough to withstand expansion without damage due to
temperature changes
• Excellent adhesions on various substrates
• Film thickness isadaptable
• Highly resistant to chemicals, solvents, moisture andelevated
temperatures
• Film-forming time is as short as possible
• Long pot life of room temperature curable systems
• Easy to apply
Other advantages of epoxy systems

• Excellent adhesion

• Low shrinkage on cure typically > 3%

• Excellent water, heat and chemical resistance

• Versatile (formulations can be tailor made to theneeds)

• No release of volatiles during curing (addition reaction)

Corrosion protection of crude oil tanks

• The compete absence of volatile components in combination

with liquid epoxy resins, reactive diluents and low viscose
hardeners makes it possible to formulate coatings – or
reinforced with glass fibres as laminates – with high corrosion
resistance performance to protect the inside of storage tanks
for crude oil and other chemicals.
• Several tank farms in the Middle East have been successfully
coated many years
ago and are still functional.
Corrosion protection of ship ballast tanks

• This
highly corrosive environment requires a rugged
epoxy coating, designed for immersion service in salt
water ballast tanks and fuel/sea water ballast tanks.
Engineering

• Protective coatings are therefore usually based on

primers containing a linseed oil or alkyd binder and anti-
corrosion pigments such as red lead, lead chromate, zinc
chromate, potassium zinc chromate, and zinc dust.
• The completed coating system will have a dry thickness
of 5 to 10 mils.
As for Epoxy ResinCoatings...

• Epoxy coatings were developed for heavy duty service on

metal substrates and use less energy than heat-cured powder
coatings.
• Their low volatility and water clean up makes them useful
for factory cast iron, cast steel, cast aluminum
applications and reduces exposure and flammability
issues associated with solvent-borne coatings.
Industrial Flooring

Waterproofing
Industrial Applications

• Waterproofing – roofing, sealing,bonding

• Concrete repairs – weather, lightweight yet
strong
• Metal protection – corrosionresistant

Before

After repair
Industrial Applications
Industrial flooring
• rubber carpet: playgrounds, water parks, bathrooms chemical
resistant andhard-wearing
• non-slip flooring: stadiums, gyms, industry
 Health risks
Primary risk associated with epoxy use is often related to the
hardener component
• Amine hardeners –corrosive, toxic and/or carcinogenic or
mutagenic.
• Aromatic amines -health hazard (most are known or suspected
carcinogens) their use is now restricted to specific industrial
applications.
• safer aliphatic or cycloaliphatic amines are commonly employed.
• Liquid epoxy resins in their uncured state-irritant to the eyes and
skin, as well as
toxic to aquatic organisms.
• Solid epoxy resins are generally safer than liquid epoxy resins.
• Exposure to epoxy resins can, over time, induce an allergic
reaction.
POLYCARBONATE
History

• Dr. Hermann Schnell and

his team at “Bayer”
company discovered
polycarbonate in 1953,
forever changing how we
live our lives.
• PC was introduced in
United States Of America
in 1960 by “general
electric” company
• As the next 63 years have
shown, polycarbonate has
evolved, finding its way
into a multitude of
products that touch our
lives every day.
What is polycarbonate?

• Polycarbonates received their name because they are

polymers containing carbonate groups (-O-(C=O)-O-).
• Its most popular trade name is LEXAN.
• PC is a good material choice in industry not only due to
its characteristics, but also because its processing is
environmentally friendly, and it can be recycled.
• About 2.7 million tons of polycarbonate are produced
annually worldwide.
Structure of PC
• A polycarbonate molecule is
composed by a Bisphenol-A
part and a carbonate group.
• Bisphenol-A contains two
aromatic rings, which are
responsible for PC’s stiff
backbone.
• The Bisphenol-A group also
contributes to PC’s inability to
crystallize. This amorphous
structure gives the polymer its
particular transparency
 Polymer production
 The Phosgene Process:
The main polycarbonate material is produced by the reaction of
bisphenol A and phosgene (COCl2). The overall reaction can be written
as follows:

Here, disodium salt of BPA dissolved in water reacts with phosgene

dissolved in a chlorinated organic solvent such as CH2Cl2 (methylene
chloride). However, the phosgene process entails a number of drawbacks
including the toxicity of phosgene, the use of low-boiling-point solvent,
and the large quantity of waste water containing methylene chloride
which must be treated. The use of concentrated sodium hydroxide and
hydrogen chloride adds the problem of corrosion that should be
considered.
 Polymer production

• Polycarbonate is transformed from pellets into the desired

shape for its intended application by melting the
polycarbonate and forcing it under pressure into a mold or
die to give it the desired shape depending on the
application. This process is repeated thousands of times.
Processing

Polycarbonate

Extrusion Moulding
The molten PC is passed
The through
moltena die PC is passed The PC
The PCmelt
melt is pressedinto
is pressed intoa mold with
through a die that gives the a mold with the defined
that gives the material its finalitsshape.
material final shape. After shape of the shape
the defined final of
product.
the final product.
this, the melt is cooled The melt is then cooled
After this, the meltrapidly.
is cooled rapidly.
Long pipes and the melt
inside theis then cooledThis
mold. inside themold.
sheets are created by this process is ideal for specific
process parts such as automotive
and computer parts
Block flow Diagram
Manufacturing
 Non phosgene process:

Another approach,in which Diphenyl Carbonate (R-OCO-O-R)

and Bisphenol-A, can be reacted at temperatures between 180-
220ºC to yield PC and a phenol molecule. This process results
in more impurity, and is more expensive because higher
temperatures are necessary
Properties
• Excellent toughness
• Transparent
• Fair processing
• Good electrical insulating properties
• Light weight
• Good scratch resistance
• Excellent thermal properties
• Very durable
• The addition of glass fibers to polycarbonate significantly
increases the tensile strength, and heat deflection
temperature .The greater the amount of glass fiber added to
the polycarbonate, the greater the effect on each property
will be.
 Applications

bullet proof glass lenses face shield

bottles

Safety glasses
 Applications

Electronic components Construction headlamp lenses

Riot shields Data storage