Department of Chemical Engineering

Project Report
On
Modelling and Synthesis of Polystyrene
Using Batch Emulsion Polymerization
Presented By: Supervisor:
Rohit Wadhwani (2019UCH1681) Dr. Sushant Upadhyaya

Lakshya Kanungo (2019UCH1653) Co-Supervisor:

Dr. Manish Vashishtha
Ankit Parsoya (2019UCH1588)
 CONTENTS

1 Introduction
2 Literature survey
3 Material Used
4 Experimental Method
5 Recipe used
6 Properties of polymer measured
7 Results
8 References
 What is Polymer?
 A polymer is a substance composed of very large molecules, called
macromolecules, which are multiples of simpler chemical units called
monomers.
 Polymers range from familiar synthetic plastics such as polystyrene to natural
biopolymers such as DNA and proteins that are fundamental to biological
structure and function.
 Product made from polymers are all around us:

• clothing made from synthetic fibers • polymer-based paints

• polyethylene cups • epoxy glue
• Fiberglass • polyurethane foam cushion
• nylon bearings • silicone heart valves
• plastic bags • Teflon-coated cookware
Mustafa et al., 2015
 CHARACTERIZATION OF POLYMER
BASIS TYPES Example(s) CITATION

Origin of Natural - occur naturally and are found in animals and Proteins, Geeta et al.,
polymers plants. 2016
Rubber
Semi-synthetic - derived from naturally occurring Cellulose
polymers. nitrate
Synthetic - man made polymers. Plastic
Structure of the Linear - contains long and straight chain. PVC Mustafa et al.,
monomer chain Branched chain - when linear chains of polymers form Low density 2015
branches polyethene
Cross linked - they are composed of bifunctional and Bakelite,
trifunctional monomers.
Melamine
Mode of Addition polymers - polymers formed by the addition of Teflon, PVC Mustafa et al.,
polymerization monomers repeatedly without removal of by products. 2015
Condensation polymers - polymers formed by the Nylons ,
combination of two polymers.
Polyesters
BASIS TYPES EXAMPLE CITATION
(S)
Isotactic - all the pendant groups are located on the same side of Polypropyl- Omer et al.,
the hydrocarbon chain. ene 2013
Tacticity
Syndiotactic - in this the pendant groups have a regular , alternating Gutta-
pattern along the hydrocarbon chain. percha

Atactic - in this the pendant groups are randomly arranged along polystyrene
the hydrocarbon chain.
Homomer – consists of identical monomer units Polyethene Mustafa
et al., 2015
Based on Co-polymer or heteropolymer - it consists of different types of Nylon-6,6
monomers monomer units.
Thermal Thermoplastic – polymers that can be softened and melted by the PVC, PE Omer et al.,
response application of heat. 2013
Thermosetting – polymer that is obtained by irreversibly hardening Bakelite,
a soft solid or viscous liquid prepolymer(resin) .
silicones
 TYPES OF POLYMERIZATION
S.No Basis Free Radical Mechanism Ionic Polymerization Coordination Polymerization
1 Definition It is the process of forming It is the process of forming a In this the monomers with side
a polymer material via the polymer material using ionic groups are attached to the growing
addition of free radicals. chemical species as initial chain in a highly defined spatial
reactants. arrangement.

2 Types There are three main steps It can be divided further into Ligands that are commonly found
involved in this process: two groups as cationic and in this include polypyridines and
Initiation, Propagation, anionic polymerization. polycarboxylates.
Termination
3 Initiation It occurs through radicals It occurs via ionic species The significant feature of this
which contain an unpaired which has no unpaired mechanism is the ability to orient
electron electrons. each monomer and join it to the
growing polymer chain in a very
specific configuration.

4 Inhibitors Phenolic compounds Butyl lithium It act as corrosion inhibitors.

 POLYMERIZATION TECHNIQUES
Polymerization Advantages Disadvantages
Process
Bulk Products relatively pure due to minimum Exothermic nature of polymerization reactions.
contamination. Enhanced yield per reactor Product has broad molecular weight distribution.
volume Removals of tracers of unreacted monomer difficult.

Solution Heat transfer greatly enhanced resulting in Necessary to select an inert solvent to avoid
better process control. Resulting polymer possible transfer to solvent. Not particularly suitable
solution may be directly usable. for production of dry or relatively pure polymer.

Suspension Heat removal and temperature control Possibility of polymer contamination by absorption
relatively easier. Resulting polymer of stabilizer on particle surface. Continuous
suspension or granules may be directly operation of system difficult.
usable.
Emulsion Good heat transfer easy to control reaction Difficult to get pure polymer due to contamination
temp. Low viscosity polymer produced from other components. Presence of water lowers
may be used directly as polymer latex. yield per reactor volume

Geeta et al.,2016
 POLYMER SYNTHESIS USING DIFFERENT
TECHNIQUES
POLYMER TECHNIQUE CONDITIONS REAGENTS USED MASS OF CITATION
USED POLYMER
(g/mol)
Polystyrene Batch emulsion 71° C, 60 min 1. Styrene 297,000 Ginsburger et al.,
polymerization 2. K₂S₂O₈ 2014
71° C, 120 min 224,000
3. Texapon
80° C, 90 min 4. Water 105,000
Polystyrene Free radical 80-90° C 1. Styrene 16,801 Aswin. S et al.,
polymerization 2. Benzoyl Peroxide 2022
Polystyrene Suspension 80-100° C 1. Styrene Dongbo Guan et
polymerization 2. Benzoyl peroxide al 2019
300-450 rpm
3. Polyvinyl alcohol
Polystyrene Emulsion 70-72° C 1. Styrene Amro K.F Dyab et al.,
polymerization 2. Potassium persulphate 2018
12 hr
3. Sodium dodecyl sulphate

Polystyrene Surfactant free 80° C 1. Styrene Yohanala et al., 2015

emulsion 2. Potassium Persulphate
400 rpm
polymerization
3. Distilled water
5-7 hrs

Polystyrene Dispersion 70° C 1. Syrene Jinhua et al., 2014

polymerization 2. Azobisisobutyronitrile
24 hr
3. Polyvinylpyrrolidone
80 rpm 4. 2-Methoxy ethanol
 DIFFERENT TYPES OF INITIATOR AND
SURFACTANT USED TO MAKE POLYSTYRENE
INITIATOR MONOMER SURFACTANT POLYMER CITATION
Potassium Styrene Texapon Polystyrene Ginsburger et al., 2014
persulphate
Benzoyl Styrene Polyvinyl alcohol Polystyrene Dongbo Guan et al., 2019
peroxide
Potassium Styrene Sodium dodecyl Polystyrene Amro K.F Dyab et al., 2018
persulphate sulphate

Azobisisobuty Styrene Polyvinylpyrrolido Polystyrene Jinhua et al.,2014

ronitrile ne
 MATHEMATICAL MODEL
POLYMER MODEL ASSUMPTIONS AND EQUATIONS REFERE
NCES
Polystyrene Emulsion 1. The semi-batch reactor was considered to be well mixed and
polymerization isothermal.
in semi batch 2. The coagulation between particles was neglected.
reactor 3. Pseudo-bulk kinetics was assumed.
4. All the particles were considered of the same size at a given time.
Polymethyl Batch 1. Steady state. Watanabe
methacrylate emulsion et al.,
2. The density of the mixture is a function of the conversion, the
(PMMA) polymerization 2021
amount of solvent introduced in the feed and the temperature.
POLYMER MODEL ASSUMPTIONS AND EQUATIONS REFERENCES
Polymethyl Continuous 1. The temperature dependence of the rate constants is Benyahiya et al.,
methacrylate solution assumed to follow the Arrhenius law. 2018
(PMMA) polymerizati 2. This reactor is assumed to be a jacketed, well-mixed
on tank.

Polystyrene Free Radical Curteanu et al.,

Polymerizati 2016
on under
semi batch
Reactor
 LITERATURE GAP

On the basis of above literature survey, the following gaps are identified:
1. It has been noticed in the literature survey that various authors has studied the effect
of monomer concentration on percentage conversion however the effect of initiator
concentration and reactor temperature on percentage conversion and other physical
properties like density, viscosity, melt flow index and impact strength is not observed
in the literature.
2. It has been also observed that the effect of surfactant concentration on percentage
conversion and other physical as well as mechanical properties not explored much in
the literature .
3. Further more, agitation speed may be one of the parameter to understand and control
the physical properties of synthesized polymer in terms of molecular weight
distribution. However, this parameter has not gained attention in the literature.
 OBJECTIVE OF PROJECT

On the basis of above mentioned literature gap, the objective of the work is as
follows:
1. Study and comparison of the effect of initiator and surfactant concentration on
percentage conversion and other physical properties like density, viscosity, melt
flow index and impact strength with experiment and mathematical model.
2. Study and comparison of the effect of agitation speed on percentage conversion
and other physical properties as it is a important factor on molecular weight
distribution.
3. Study and comparison of the effect of temperature on percentage conversion and
other physical properties.
 MATERIALS
SODIUM OELATE
STYRENE
(C₁₈H₃₃NaO₂)

Molecular Weight 104.149 g/mol

Phase Liquid (at STP) Molecular Weight 304.443 g/mol
Melting Point -31° C Phase Solid (at STP)
Boiling Point 145.5° C Melting Point 233.5° C
Density 0.909 g/cm³ Boiling Point 360° C
Solubility Insoluble in water Density 1.1 g/cm³
Viscosity 6.95 x 10-4 Pa s (at 25° C) Solubility Soluble in water
Vapour Pressure 12.4 mm Hg
PubChem release 2021.05.07
PubChem release 2021.10.14
CID 23665730
CID 7501
 MATERIALS
POTASSIUM PER
ION EXCHANGED DOUBLE
SULPHATE
DISTILLED WATER
(K₂O₈S₂) Molecular Weight 18.0153 g/mol
Phase Liquid (at STP)
Molecular Weight 270.322 g/mol
Melting Point 0° C
Phase Solid (at STP)
Boiling Point 100° C
Melting Point 100° C
Viscosity 8.9 x 10-4 Pa s (at 25° C)
Boiling Point 170° C
Density 1 g/cm³
Density 2.477 g/cm³
Vapour pressure 17.5 mm Hg (at 25° C)
Solubility Soluble in water
Surface Tension 0.0728 N/m

PubChem release 2021.05.07

CID 24412
 EXPERIMENTAL METHOD
1) Fill the hot water tank up to 2/3 depth, select the reaction temperature 70° C and set it on the TIC fixed at the
front panel. Start the heater and wait till desired temperature is reached.
2) Prepare the aqueous solution of emulsifier by thoroughly mixing with water.
3) Charge the aqueous solution of emulsifier and monomer into the reactor through the feed inlet fixed at the top
head of the reactor. Prepare the initiator solution in about 40 ml of water and store it in the vessel provided at
the top rear of set-up under an atmosphere of N ₂.
4) Evacuate the reactor up to 50 mm Hg with the help of vacuum pump provided at the base of setup then stop the
vacuum pump and flash point with pure N₂ for some time.
5) Start the agitation at the rate of 700 to 750 rpm and simultaneously bubble the N ₂ (@3 LPM) into the reaction
mixture. Raise the temperature of reaction mixture to a constant reaction temperature by circulating hot water
through the jacket of the reactor. Wait till the desired reaction temperature is reached and remains constant.
6) After exactly one hour's mixing, add initiator to initiate the reaction from initiator vessel under N ₂ pressure.
Close the initiator feed valve after its delivery and also close the N ₂ supply to the initiator storage vessel.
7) After the reaction is initiated, collect 20 ml of reaction mixture at regular intervals of time. Weigh the sample
accurately, and add 50 ml of methanol containing small amount of hydroquinone as a terminator. The polymer
formed will precipitate in each sample. Dry the polymer in oven at 70 to 80° C.
 RECIPE USED

CONTENTS EXPERIMENT RUN

lon-exchanged double distilled water 360 ml
Styrene 200 ml
Sodium Oleate 2 gm
Potassium persulfate 2.5 gm
N₂ gas supply at rate of 3 LPM
Temperature of Reaction 70° C
Stirring speed N 700 rpm to 750 rpm
Time 4 hour
CIPET Jaipur
MELTING FLOW INDEX

Specifications
Type of test Single Weight
Test Temperature range °C 30 TO 400
°F 86 TO 752
Temperature accuracy ISO 1133-2 (Exceeds ISO
and stability 1133-1), ASTM D1238
Barrel material Nitrided Steel with
superior wear resistance
User interface 4-line LCD display
Electric supply V 115 or 230
Hz 50/60
Power consumption Maximum 1000 W
Basic machine weight kg 50
 PROCEDURE FOR DETERMINING MFI
1. A small amount of the polymer sample (around 4 to 5 gm) is taken in the specially designed
MFI apparatus. The apparatus consists of a small die inserted into the extruder, with the
diameter of the die generally being 2.09 mm and height 8 mm.
2. The material is packed properly inside the extruder barrel to avoid formation of air pockets.
3. A piston is introduced which acts as the medium that causes extrusion of the molten
polymer.
4. The sample is preheated for a specified amount of time: 6 min at 230° C for polystyrene.
5. After the preheating a specified weight is introduced onto the piston of weight 1.2 kg.
6. A sample of the melt is taken after period of 35 sec and is weighed accurately.
7. MFI is expressed as grams of polymer/10 minutes of flow time.

ASTM D 1238
IMPACT STRENGTH TEST

 An impact test signifies the toughness of

material that is ability of material to absorb
energy during plastic deformation.
 Specifications for specimens with v-notch
(Charpy):
Length: 55 mm
Width: 10 mm; bar width at notch: 8 mm
Thickness: 10 mm
The v-notch is in the center of the specimen
and has an opening angle of 45
 PROCEDURE FOR DETERMINING
IMPACT STRENGTH TEST
• For conducting Charpy test, a proper striker is to be fitted firmly to the bottom of the hammer
with the help of the clamming piece.
• Bring the striking hammer to its top most striking position unless it is already there, and lock it at
that position.
• Firmly held the steel specimen in impact testing machine vice in such a way that it is simply
supported and the notch is opposite to the hammer.
• Release the pendulum to smash the specimen.
• The hammer will fall due to gravity and break the specimen through its momentum.
• At its topmost height after breaking the specimen, the indicator stops moving while the
pendulum falls back. Note the indicator reading at the topmost final position and note indicated
value.
• Remove the broken specimen by loosening the clamping screw.
ASTM E 23
DENSITY

PROCEDURE
1. Weigh the specimen in air.
2. If a wire is used, weigh the specimen in air
after hanging from the wire. In this case,
mass of specimen, a = (mass of specimen +
wire, in air) − (mass of wire in air).
3. Mount the immersion vessel on the support,
and completely immerse the suspended
specimen in water. Record this weight as b.
4. Density is calculated as follows:
Density = a / (a-b)

ASTM D 792
 ABSOLUTE VISCOSITY

Procedure for determining viscosity:

 Wash the viscometer thoroughly with water and methanol.
 A sufficient volume of distilled water is introduced by pipette in bulb C, so that the bend
portion of the tube and half or a little more than half of bulb c are filled up.
 Clamp the viscometer in vertical position.
 Using the pipette, suck the water up until it rises above the upper mark A and allows it
flow under its own weight .
 The time of flow of water from A to B is counted.
 Now remove the viscometer and dry it.
 Introduce in bulb C the same volume of liquid and measure the time of flow of liquid as
measured before.
Viscosity can be found out experimentally
using the formula:

Where t₁=time of flow of water

η₁= absolute viscosity of water
ρ₁=density of water
t₂=time of flow of liquid
η₂= absolute viscosity of liquid
ρ₂=density of liquid
 RESULTS
 It is observed that on increasing the reaction time
from 20 minutes to 40 minutes, the conversion of
monomer increased steeply from 0.3 to 0.49, 0.37
to 0.59, and 0.45 to 0.69 whereas from 40 to 160
minutes, the conversion increases gradually from
0.49 to 0.74, 0.59 to 0.95, and 0.69 to 0.99 at 2.5 g,
4.5 g , and 6.5 g of KPS as an initiator under
constant reaction temperature of 70° C and 35.7 %
(vol) of monomer concentration.
 The probable reason for this behaviour in
conversion is due the Le-chatlier principle.
 It is also found that the % conversion is higher at
6.5 g KPS concentration as compared to 2.5 g. The
Fig: Effect of time on conversion % increment in conversion is 33% after 160
[monomer concentration = 35.7 %, minute. At low initiator amount conversion did not
distilled water = 63 %, rpm = 700] reach one due to depletion of free radical particle
as termination of free radical starts..
  It is observed that on increasing the reaction
time from 20 minutes to 60 minutes, the
conversion of monomer increased steeply
from 0.41 to 0.72, 0.46 to 0.78, and 0.51 to
0.88 whereas from 60 to 160 minutes, the
conversion increases gradually from 0.72 to
0.98, 0.78 to 0.99, and 0.88 to 0.99 at 35 %,
40 %, and 45 % of styrene as monomer
under constant reaction temperature of 70° C
and 6.5 gm initiator.
 The probable reason for this behaviour in
conversion is due the Le-chatlier principle.
Fig: Effect of time on conversion  It is also found that the % conversion is
[initiator = 6.5 gm, surfactant = 2 gm, higher at 45 % initiator concentration as
distilled water = 360 ml, rpm = 700] compared to 35 %. The % increment in
conversion is 2% after 160 minute.
 REFERENCES

1. Modern Applied Science; Vol. 9, No. 7; 2015 ISSN 1913-1844 E-ISSN 1913-1852
Published by Canadian Center of Science and Education.
2. International Journal of Engineering & Technology Research, Volume-4, Issue-1,
January-February, 2016, www.iaster.com.
3. Polymer science and technology, Third Edition, Joel R. Fried.
4. Polymer science and technology by Robert O. Ebewele.
5. Novel polymerizable surfactants: synthesis and application in the emulsion
polymerization of styrene by Sofiane Mekki.
6. Modeling and Simulation of Free Radical Polymerization of Styrene under semi
batch reactor conditions by Silvia Curteanu.
THANK YOU