Synthesis of Polymer Part 2

Department of Chemical Engineering, MNIT, Jaipur
1 B. Tech Project

CHAPTER 1
Introduction

1.1 Polymerization-
The process in which reacting monomer molecules react together in a chemical reaction to
form three-dimensional networks or linear polymer chains, is called polymerization. It occurs
via a variety of reaction mechanisms that differ from each other due to different functional
groups present in the reacting compound & due to their inherent steric effects explained by
Valance shell electron pair repulsion(VSEPR) theory.
There are various types of polymerization process viz. Emulsion Polymerization, Bulk
Polymerization, Suspension Polymerization, Cationic Polymerization, Solution
Polymerization, Precipitation Polymerization, Step- Growth Polymerization, Coordination
Polymerization, Anionic Polymerization, Living Polymerization etc.

1.2 Types of Polymerization-

1.2.1 Bulk Polymerization-
In bulk polymerization a soluble initiator is added to pure monomer which is in liquid state.
Altough bulk polymerization has certain advantages over other methods,as the system is
simple, require no thermal insulation, high product purity, direct preparation of large castings
& very molecular weights are obatained; there are certain disadvantage to this process. For
example, heat and mass transfer becomes difficult as the viscosity of reaction mass increases.
The problem of heat transfer increases because of the highly exothermic nature of its
mechanism- free radical addition polymerization. The polymerization is obtained with a
broad molecular weight distribution due to high viscosity and lack of good heat transfer,
which reduces the product quality.


2 B. Tech Project
1.2.2 Suspension Polymerization-
This polymerization is also known as pearl polymerization/ bead polymerization/ granular
polymerization. It uses mechanical agitation to mix monomer or mixture of monomers in a
liquid phase such as water, due to which monomer droplets polymerize while they are
dispersed by continous agitation. The major application of this process is in production of
PVC, a widely used plastic, as well as Sodium polyacrylate, a superabsorbent polymer used
in disposable diapers.

1.2.3 Solution Polymerization-
This method is used majorly in industrial level of polymerization. A monomer is dissolved in
a non reactive solvent that also has catalyst. The heat released by the reaction is absorbed by
the solvent and so the reaction rate is reduced. Major application of this process is in the
production of sodium polyacrylate, a superabsorbent polymer used in disposable nappies. The
benefitspf such type of polymerization, as compared to bulk polymerization is that is reduces
the viscosity and does not allow auto-acceleration at high monomer concentrations.

1.2.4 Emulsion Polymerization-
Its a type of radical polymerization that usually starts with an emulsion in water, surfactant
and monomer. The most common type of emusion is oil-water emulsion, which has droplets
of monomer(the oil) in continous phase of water. There are water soluble polymers such as
certain polyvinyl alcohols or hydroxyethyl cellulose which are used as emulsifiers/stabilizers.
The name emulsion polymerization is a misnomer that arises from a historical misconception.
Instead of occurring in emulsion droplets, polymerization occurs in the latex particles that
form spontaneously in the beginning of the process. These latex particles are generally 100
nm in size and have many individual polymer chains. The particle are stopped from
coagulating with each other because each particle is surrounded by surfactant, as the charge
present on the surfactant repels other particles electro-statically. When water soluble
polymers are used as stabilizers, the repulsion among the particles arises due to formation of
hairy layer of water soluble polymers as pushing away particles together would involve
compressing these chains.


3 B. Tech Project
Emulsion polymerization is used in manufacture of many polymers. Most of those are used as
solid materials and they must be isolated from the aqueous dispersion after polymerization,
while in others the dispersion itself is the end product. The dispersion formed is called latex
or an emulsion. These emulsions are used in adhesives, paints, paper coating and textile
coatings. They are finding increasing acceptance and are preferred over solvent-based
products due their eco-friendly nature as they dont contain VOCs (Volatile Organic
Compunds).

A general recepie for polymerization on laboratory level would require following proportions
of ingredient (Parts by weight):
100 of monomer,
180 of water,
2-5 of fatty acid soap,
0.2-1.5 of initiator.

Now cationic soaps may be used instead of fatty acid soaps (e.g.dodecylamine
hydrochloride). Various initiator may replace the usual persulphateinitiator(e.g. hydrogen
peroxide and ferrous ion/ water soluble organic hydroperoxide).
The mechanisms and kinetics of an emulsion polymerization process is divided into 3
intervals-

Interval I: Free radicals are produced in the aqueous phase by initiator decomposition. They
are captured by micelles swollen with monomer. The polemerization begins in these micelles.
This interval corresponds to particle nucleation and stops when all the micelles have
disappeared.

Interval II: While the particles grow in size, monomer diffuse rapidly from monomer droplets
towards the particles which are saturated with monomer as long as monomer droplets exist.
This interval ends when monomer have disappeared.
Interval III: In this final period, the monomer concentration starts depleting.


4 B. Tech Project
1.2.4.1 Advantages of Emulsion Polymerization-
-Due to high molecular weight polymers can be produced at fast rate. While in bulk and
solution polymerization, there is a trade off between molecular weight and rate of
polymerization.
-As the polymer molecules are contined within the particles, viscosity remains close to that of
water and is not dependent on molecular weight.
-The water has continous phase which is a good conductor of heat and so helps in removing
heat from the system, allowing many methods to increase their polymerization rate.
-The final product obtained can be used in its original form or can be altered/ processed
before its application.

1.2.4.2 Disadvantage of Emulsion Polymerization-
-For dry polymers, removal of water is very energy-intensive process.
-surfactants and other polymerization ingredients remain in the polymer and are difficult to
remove.
-This process is usually designed to operate at high conversion rate of monomer to polymer,
which results in significant chain transfer to polymer.
-This process cannot be used for condensation, ionic or Ziegler-Nutta polymerization,
although some exceptions are there.

1.2.4.3 Applications of Emulsion Polymerization-
Polymers produced can be categorized into three applications-
1.2.4.3.1 Synthetic Rubber
-Some grades of styrene-butdiene (SBR)
-Some grades of polybutadiene


5 B. Tech Project
-Polychloroprene (Neoprene)
-Nitrile rubber
-Acrylic rubber
Fluoroelastomer (FKM)

1.2.4.3.2 Dispersions
-Polyvinyl acetate
-Polyvinyl acetate copolymers
-Latex acrylic paint
-Styrene-butadiene
-VAE(vinyl acetate-ethylene copolymers)
-Some grades of polybutyl-acrylate

1.2.4.3.3 Plastics
-Some grades of PVC
-Some grades of polystyrene
-Some grades of PMMA
-Acrylonitrile-butadiene-styrene terpolymer (ABS)
-Polyvinylidene fluoride
-PTFE


6 B. Tech Project
1.3 Poly(butyl-acrylate)-
Poly(butylacrylate0 is a sponge in nature and thermoplastic. It is the synthetic polymer of
butylacrylate.

1.3.1 Synthesis-
Poly(butylacrylate) is produced by emulsion polymerization, solution polymerization.
Generally radical initiation is used but anionic polymerization of butyl-acrylate can also be
used.
1.3.2 Applications-
Poly(butyl-acrylate) has major applications in various industries. Most important applications
out of them are as follows-
Pressure sensitive adhesives-
These are the materials which can provide strong adhesion to solid surface for a short period
of time. The most common application is to use it as a thin layer over a substrate such as
PET, PP and PVC. These can also be used in many sophisticated applications. PSAs can be
separated into 2 groups- Solution PSA and emulsion PSA. Although it has outstanding
performance, application of PSA has gradually decreased because of the economic and
environmental reasons. In contrast, emulsion PSA, especially acrylate solution has been
widely researched due to its environmental safety, lo cost and optical clarity. In general, the
glass transition temperature(T
g
) of PSAs should be lower than room temperature.

Latex paint formation-
The basic phenomena of film and paint formation by latex is not new. Although a wide
variety of synthetic latexes are used for binders for paint and related coating materials.


7 B. Tech Project

CHAPTER 2
Literature Review

The following chapter comprises the literature on mechanisms, kinetics, optimisation and
control related to emulsion polymerization, on which our polymer production is based on.
2.1 Emulsion Polymerization-
Emulsion polymerization is a process that is used to produce waterborne resins with various
colloidal and physicochemical properties.These processes are frequently applied for the
production of rubbers, coatings and many other products. This heterogeneous free radical
polymerization process involves emulsification of the relatively hydrophobic monomer in the
water by an oil-in-water emulsifier, followed by the initiation reaction with either a water
insoluble initiator(e.g. ammonium persulphate) or an oil soluble initiator(e.g. 2-2-
azobisisobutyronitrile).
M.J.J. Mayer,(1994), worked on emulsion polymerization in various types of reactor and with
different recipies with high monomer contents. The effect of the monomer on polymerization
of styrene was analysed in a batch reactor, a continuously operated stirred tank reactor. The
experiment show that no. of particles at complete conversion and the polymerization rate in
interval 2 are well predicted by Smith-Stewart theory for styrene fractions upto 0.4 in the
recepie, the polymerization rate in interval 2 increses with the monomer content and reaction
volume.
The high viscosity and the psuedoplastic rheological behaviour of the latex, leading to
imperfect mixing and poor heat transfer to the reactor wall is reason behind this increased
rate of reaction. In a batch process,when a pulse of emulsifier is addedto the reaction mixture,
a second generation of particles is produced and heat transfer limitation is avoided. This is
caused by the lower viscosity of latex with bimodal particle size distribution as compared to
unimodal particle size distribution and the same polymer content. While experiments in the
CSTR show that both the particle number and the polymerization rate in the steady state is
predicted by the theory of DeGraff and Poehlin for conversion. When steady state conversion


8 B. Tech Project
is higher than 0.5, the polymerization rate appeared to be higher than that predicted by the
above theory. These high reaction rates are caused by a gel effect which occurs particularly in
the largest particles in the reaction mixture.

2.2 Emulsion Polymerization Mechanisms and Kinetics-
Chern C.S., (2006) studied on emulsion polymerisation mechanisms and kinetics. Emulsion
polymerization involves the propagation reaction of free radicals with monomer molecules in
very large number of polymer particles dispersed in the continous aqueous phase. The
nucleation and growth of latex particles control the colloidal and physical properties of latex
products. It includes nucleation and growth of particle nuclei, after that consumption of
residual monomer in a heterogeneous system. The propagation of free radicals with monomer
occurs in the latex particles and the emulsified monomer droplets serve to supply the growing
particles of monomer.
In non-uniform latex, polymerization is a potential candidate for offering different application
properties. The interfacial tension between polymer pairs and the particle-water interfacial
tension had an important role in the development of particles morphology. Furthermore, this
predicted theory must match with observed experimentally for the interfacial free energy.
Such a thermodynamic analysis only gives the ultimate morphology.

2.3 Modelling of Batch Emulsion Polymerization-
Silvia Curteanu, (2003), worked on modelling and simulation of free radical polymerisation
of styrene which was done under semi-batch reactor conditions. The approach was concerned
with the elaboration of a radical polymerisation model of styrene which is based on a kinetic
diagram that comprises thermal and chemical initiation, propagation and termination by
recombination and chain transfer mechanisms. The formalism which describes the modal in
terms of moments is explained. The model was then used to predict change in monomer
conversion and MW after intermediate addition of monomer and initiator. The obtained
results were dependent on conditions of reaction mass, quantity and moment of substance
addition. So, simulations were done at different times with respect to gel effect w.r.t. different
temperatures and initiators. Increasing the concentration of initiator before the gel effect


9 B. Tech Project
causes an earlier appereance of phenomena and finally leads to decrease in moleculer weight.
The ratio M
w
/M
n
gives polydispersity index smaller for the intermediate addition of initiator.
No significant occur during or after the gel effect. If with the initiator, unreacted monomer
also enter reactor, a decrease in conversion is observed.
MichealWulkow, (1990), experimented on weight distribution for free radical polymerization
systems. The modelling of this mechanism gives large system of ordinary differential
equations which cannot be solved easily. To solve these a new approach was made called
discrete galerkin method. This method is characterised by galerkin approximation based on
the orthogonal polynomials of discrete variable which represents the polymer degree. It uses
enough computations of complete kinetic schemes with time or moment dependent reaction
coefficients by reducing the complexity.
Victor M., (2005), worked on kinetics and modelling of microemulsion copolymerization. A
model for micro emulsion copolymerization was developed and compared with experimental
conversion vs. time data for the vinyl acetate/butyl acrylate system. The main features pf the
model comprise miceller, homogeneous nucleation and thermodynamic equilibrium to
calculate monomer partitioning between phases. Simulation was used with reported values
for kinetic parameters except for propagation rate constant in the water phase and radical
capture by particles and micelles coefficients which are estimated. The results of simulation
showed assent with experimental data.

2.4 Free Radical Polymerization Reactions-
YaacovAlmong, (1982), worked on radical polymerization of styrene and methyl
methacrylate in dispersed systems. Also, the effect of carbon black was studied. Styrene and
methyl methacrylate were polymerized to yield particles in the range of 10m diameter. In
case of styrene, there is interface by emulsion polymerization. This was minimized by using
lauryl peroxide (LP) as initiator and a low concentration of polyvinyl alcohol (PVA) or
submicellar concentration of sodium dodecyl sulphate (SDS) as emulsifier .Bridging of
submicron molecules on large dispersion particles happened when high molecular weight
PVA was used as steric stabilizer. Although when low molecular weight PVA was used , no
bridging happened amd submicron particles were washed away to yield smooth dispersion
particles.


10 B. Tech Project

Gupta S.K.,(2005), worked on free radical polymerization of n-butylacrylate under non-
isothermal conditions and with intermediate addition of initiator. Experiments and modelling
showed that experimental data on monomer conversion (X
m
) and the weight average
molecular weight (M
w
) were generated under various isothermal and non-isothermal
conditions for the polymerization of n-butyl acrylate. The non-isothermal results can be used
to provide better test of kinetic models than isothermal datas alone.

2.5 Optimisation of Emulsion Polymerization-
Polymerization reactions are affected by operating conditions such as temperature, pressure,
concentration etc.
G. Francois, (2003), discussed on run to run optimisation of batch emulsion polymerization.
The run to run optimization scheme is used in context tp simulation for the minimisation pf
the batch time of an emulsion polymerisation process with terminal constraints on conversion
and number average molecular weight. There were two possible extensions, the gains are
recomputed a few times to speed up the convergence and information regarding the effect
that uncertainity has on the value of the optimal. Uncertainity related update directions can be
found out using input parameters.


11 B. Tech Project

CHAPTER 3
Experimental Works

3.1 Ingredients-
3.1.1 Monomers-
Monomers are the units that undergo radical polymerization. They are liquid or gaseous at
reaction conditions and are poorly soluble in water. Solid monomers are difficult to disperse
in water. If monomer solubility is too high, particle formation may not occur and the reaction
kinetics reduces to that of solution polymerization.

3.1.1.1 n-Butyl acrylate monomer is used as main ingredient in batch emulsion
polymerization.

3.1.1.1.1 Structure-

Figure 3.0: Structure of n-butyl acrylate


12 B. Tech Project

3.1.1.1.2 Properties-
Form Liquid
Odour Ester like, strong
Colour Colourless
Melting temperature -64
o
C
Boiling temperature 148
o
C
Vapour pressure 4.3 mbar
Vapour density 4.4
Solubility in water 1.4 g/l
Table 3.0: Properties of n-butyl acrylate

3.1.1.1.3Applications-
- Butyl acrylate forms polymer and copolymers. Copolymers of it can also be prepared from
acrylic acid and its salts, amides and esters, methylacrylates, acrylonitrile, vinyl chloride,
styrene, butadiene and drying oils etc.
- Butyl acrylate is a very useful feedstock for chemical synthesis, because it easily undergoes
various addition reactions with many organic and inorganic compounds.

3.1.2 Initiators-
Redox and thermal generation of free radicals have been used in emulsion polymerization. In
general, persulphate ions are used in both type of initation modes. The persulphate ion readily
breaks up into sulphate ions above 50
o
C, giving a thermal source of initiation.

3.1.2.1 Potassium Persulphate is used as initiator in poly(butyl-acrylate) synthesis.


13 B. Tech Project


Figure: 3.1 Structure of Potassium persulphate


Molecular formula K
2
S
2
O
8

Molecular weight 270.322 g/mol
Appearance White crystal powder
Density 2.478 g/cm
3
Melting point 100
o
C
Solubility in water 1.75 g/100ml (0
o
C), 5.29g/100ml (20
o
C)
Minimum assay 98.1%
Chloride Not more than 0.05%
Table 3.1: Properties of Potassium per sulphate
3.1.2.1.3 Applications-
Potassium per sulphate is used for bleaching and textile designing, as an oxidizing agent and
antiseptic, also in purification of ammonium sulphate and in manufacture of soap and
pharmaceuticals.
It is food additive and used in hair dye substances such as whitening agent with hydrogen
peroxide. It also plays an important role as initiator in emulsion polymerization.


14 B. Tech Project
3.1.3 Surfactants-
The surfactants is used to enable a fast rate of polymerization and minimize coagulation or
fouling in the reactor and other process equipment, prevent high viscosity during
polymerization leading to poor heat transfer and to maintain properties in the final product
such as gloss, water absorption, tensile strength. Anionic, non-anionic, cationic surfactants
have been used, although anionic surfactants are most prevalent. Surfactants who have low
CMC (critical micelle concentration) are favoured, the polymerization rate shows increase
when MC level is higher than CMC and minimisation of surfactant is preferred for economic
reasons and the adverse effect of surfactant on properties of polymer. Mixtures of surfactant
are also used.

3.1.3.1 Sodium oleate (C
18
H
33
NaO
2
)
It is used as surfactant in the poly(butyl-acrylate) synthesis. It occurs as a whit to yellow
powder or as light brown-yellow coarse powder or lumps. As a fatty acid, sodium oleate is
not generally found but occurs as a component of more complex lipids. In its isolated form,
the substance exudes a tallow like scent and is white crystalline solid at room temperature.


Figure3.2 : Structure of Sodium Oleate

Molecular formula C
18
H
33
NaO
2

Phase Solid (STP)


15 B. Tech Project
Appearance Whit to yellow powder
Melting point 233.4
o
C
Density 1.1 g/cm
3

Minimum assay 99.1%
Maximum limit of impurities
Assay of fatty acid
Free alkali
Heavy metal
Chloride

>83%
<0.4%
<0.005%
<0.18%

Table3.2: Properties of sodium oleate

In the production of soap,
In the production of insoluble metallic stearates,
In the production of industrial lubricants,
In oil based cosmetics.

3.1.4 Other ingredients-
Other ingredients used in emulsion polymerization include chain transfer agents, buffering
agents and inert salts. These are usually added after polymerization.


16 B. Tech Project
3.1.4.1 Ion exchanged double distilled water is used as a solvent in the production of poly
(butyl-acrylate) by batch emulsion polymerization process.


Figure3.3: Structure of Water

Molecular weight 18.015 g/mol
Phase Liquid (at STP)
Melting point 0
o
C
Boiling point 100
o
C
Density 1 g/cm
3

Vapour pressure 17.5 mmHg (20
o
C)
Viscosity 8.9*10
-4
Pa S (25
o
C)
Refractive index 1.33

Table3.3: Properties of Water solvent


17 B. Tech Project
In chemical and biological laboratories, also in industries, cheaper alternatives such as
deionised water is preferred over distilled water. Although if these alternatives are not pure
enough then distilled water is to be used. When very high purity is required, double distilled
water is used.

3.1.4.2 Toluene (C
7
H
9
)-
Toluene is used as a solubiliser in synthesis of poly(butyl-acrylate) by emulsion
polymerization processes, which are used in making solution of polymer for testing of
viscosity, electrical conductivity and pH.


Fig 3.4: Structure of Toluene


18 B. Tech Project
Appearance Clear, colourless liquid
Physical state Liquid
Molecular weight 92.4
Chemical formula C
7
H
8

Odour Sweet, pungent
Specific gravity 0.867 at 20
o
C

Table 3.4: Properties of toluene Solubilizer

3.1.4.3 Methanol (CH
3
OH)-
Methanol is used as a terminator in synthesis of poly(butyl-acrylate) by emulsion
polymerization.


Fig3.5: Structure of Methanol


19 B. Tech Project
Molecular weight CH
4
Molar mass 32.05 gmol
-1

Appearance Colourless liquid
Density 0.7916 g/cm
3

Melting point -97
o
C
Boiling point 64.7
o
C
Solubility in water Miscible
Acidity 15.4 (pK
a
)
Viscosity 0.59 mPa.s (20
o
C)
Dipole moment 1.69 D (gas)
Minimum assay 99.1 %
Refractive index 1.328

Table Properties of methanol

3.1.4.3.3 Application-
-The largest use of methanol is in production of other chemicals.
-About 40% of it, is converted into formaldehyde and from there into products as diverse as
plastics, plywood, paints, explosives and permanent press textiles.
-It is used as a solvent and as antifreeze in piplines and windshield washer fluid.


20 B. Tech Project
3.2 Emulsion Polymerization Reactor-
A jacketed batch reactor provided with a high-speed mixer is used for emulsion polymerization.
Proper arrangements are provided for the control of reaction temperature and RPM of the mixer.
Proper arrangements are provided for administration the initiator under inert atmosphere.


21 B. Tech Project

Figure 3.6 A schematic representation of batch emulsion polymerization process.
(B= batch reactor, N= N
2
gas cylinder, R= gas regulator, C= gas supply controller, TW=
three way valve, v= initiator vessel, V=vacuum pump, MT=motor, T=thermometer, PM=
pump, W= water tank, M= monomer, I= initiator, P= polymer)


22 B. Tech Project
The experimental setup consists of the following parts:
1. A jacketed stainless-steel reactor with a volume of three litres, the pressure in which
can be varied from vacuum up to 60 bar, and a cover of nine standardized openings
used for temperature sensor, insert, the inlet of the monomer and solvent, the sampler
outlet etc. Its manufacturer is K C Engineers, Ambala Cantt.
2. A 8 spoke stirrer with gas-tight bearing, which can run at high speeds.
3. A 15 Litre water tank with built in heater for storing water and maintaining the
reactors temperature. It is manufactured by K C Engineers, Amabala Cantt.
4 A controller employed to control vacuum pump, water pump, heater and motor and
for reading the temperatures.
5 A 0.5 hp motor for the stirrer. Its rpm is 1500. The manufacturer is Eltek Equipments,
Bombay.
6 A 0.25 hp vacuum pump for creating inert atmosphere in the reactor. The rpm is 440.
The capacity is 50 L/min. The manufacturer is Promivac Engineers, New Delhi.
7 A water pump. Its rating is 0.25 hp. The maximum head is 2.5 meters. Maximum
capacity is 90 Litres per hour. The operating pressure is 0.25kg/cm
2
. The
manufacturer is Promivac Engineers, New Delhi.
8 A vacuum pressure gauge attached to the reactor. Its range is 0 to 760 mm Hg.
9 A nitrogen cylinder having a volume of 16 Litres. The supplier is Dinesh Gases,
Jaipur.
10 A rotameter for controlling the flow rate of Nitrogen. Its range is 0.51 LPM to 5.1
LPM. The manufacturer is Eureka.
11 A feed inlet to the reactor having a capacity of 20 ml.
12 An initiator inlet having a capacity of 500 ml. Through it we can feed the initiator to
the reactor in an inert atmosphere.
13 9 Temperature sensors.
14 Control Values for controlling water supply, nitrogen supply, vacuum etc.


23 B. Tech Project
3.3 Preparation of Poly (butyl-acrylate) by Emulsion Polymerization-
Following steps are used in poly (butyl-acrylate) synthesis-
1. Fill the hot water tank, select its temperature 50C and set it on the TIC (temperature
indicator controller) fixed at the front panel. Start the heater and wait until desired
temperature is reached.
2. Inhibitor is removed by heating n-butyl acrylate at a temperature of 45C.
3. Prepare the aqueous solution of emulsifier by thoroughly mixing with water,
4. Charge the aqueous solution of emulsifier and monomer into the reactor through the feed
inlet fixed at the top head of the reactor.
5. Prepare the initiator solution in about 20 ml of water and store it in the vessel provided at
top rear of set-up under an atmosphere of N
2
.
6. Evacuate the reactor up to 50 mmHg with the help of vacuum pump provided at the base of
setup then stop the vacuum pump and flash point with pure N
2
for some time.
7. Start the agitation at the rate of 700-750 rpm and simultaneously bubble the N
2
at 3 LPM
into the reaction mixture.(Ensure the absence of O
2
in the reactor)
8. Raise the temperature of reaction mixture to a constant reaction temperature by circulating
hot water through the jacket of the reactor. Wait until the desired reaction temperature is
reached and remains constant.
9. During the reaction, the stirring rate is to be maintained constant and N
2
supply has be
maintained all through.
10. After exactly ones hour 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.
11. After the reaction is initiated, collected 20 ml of reaction mixture at regular intervals of
time. Weigh the sample accurately and add 20 ml of methanol as terminator. The polymer
formed will precipitate in each sample.
12. Dry the polymer in the oven at 70-80C.


24 B. Tech Project
3.4 Recipe for Emulsion Polymerization of Poly (butyl-acrylate) in experimental runs-
Typical recipe consist of following ingredients-

Contents Quantity
Ion-exchanged double distilled water 180 gm
n-Butyl acrylate 100 gm
Sodium oleate 2-5 gm
Potassium per sulphate 0.2-1.5gm
N
2
gas 3 LPM
Methanol 50 ml
Temperature of Reaction 60
o
C
Stirring Speed N 325 rpm
Mixing time 1 hour

Table 3.6: Typical Recipe for Emulsion Polymerization


25 B. Tech Project
3.5 Experimental Data
3.5.1 Feed Data
Components Volume (ml) Mass (gm)
Double distilled water 500 481.83
n-Butyl acrylate 300 269.4
Sodium oleate 5
Potassium per sulphate 2
Total volume Total mass
800 758.73
Temperature of reaction 45
o
C
Stirring speed N 325 rpm
Mixing time 1 hour

Table 3.7: Ingredients for Experimental run 1 (I=2.5 gm)

Sodium oleate 5
Potassium per sulphate 4.5
850 760.73
o
C
Mixing time 1 hour



26 B. Tech Project
Sodium oleate 5
Potassium per sulphate 6.5
850 762.73
o
C
Mixing time 1 hour



27 B. Tech Project
3.5.2 Output Data

S. No. Time (min) Sample volume
(ml)
Wet sample
(gm)
Dry Sample
(gm)
1 0 20 87.50 0.00
2 10 20 97.95 0.45
3 20 20 88.48 0.98
4 30 20 88.97 1.47
5 40 20 90.68 3.18
6 50 20 91.39 3.89
7 60 20 92.25 4.75
8 70 20 92.71 5.21
9 80 20 93.23 5.73
10 90 20 93.53 6.03
11 100 20 93.94 6.44
12 110 20 94.01 6.51
13 120 20 94.10 6.60
14 130 20 94.28 6.78
15 140 20 94.34 6.84
16 150 20 94.48 6.98
17 160 20 94.59 7.09
18 170 20 94.63 7.13
19 180 20 94.64 7.14
20 190 20 94.69 7.19
21 200 20 94.70 7.20

Table 3.10 Average weight of samples for Experimental run 1 (I=2.5 gm)


28 B. Tech Project

(ml)
Wet sample
(gm)
Dry Sample
(gm)
1 0 20 87.5 0
2 10 20 89.37 1.15
3 20 20 91.26 2.13
4 30 20 92.08 4.18
5 40 20 94.49 5.98
6 50 20 94.39 6.89
7 60 20 95.46 7.96
8 70 20 95.92 8.42
9 80 20 96.03 8.63
10 90 20 96.41 8.91
11 100 20 96.56 9.06
12 110 20 96.58 9.08
13 120 20 96.65 9.15
14 130 20 96.67 9.17
15 140 20 96.65 9.15
16 150 20 96.69 9.19
17 160 20 96.71 9.21
18 170 20 96.73 9.23
19 180 20 96.74 9.24
20 190 20 96.74 9.24
21 200 20 96.74 9.24



29 B. Tech Project

(ml)
Wet sample
(gm)
Dry Sample
(gm)
1 0 20 87.50 0.00
2 10 20 88.97 1.47
3 20 20 93.43 5.93
4 30 20 95.63 8.13
5 40 20 97.15 9.65
6 50 20 97.48 9.98
7 60 20 98.28 10.78
8 70 20 98.73 11.23
9 80 20 99.26 11.76
10 90 20 99.34 11.84
11 100 20 99.69 12.19
12 110 20 99.70 12.20
13 120 20 99.73 12.23
14 130 20 99.95 12.45
15 140 20 100.06 12.56
16 150 20 100.11 12.61
17 160 20 100.12 12.62
18 170 20 100.13 12.63
19 180 20 100.13 12.63
20 190 20 100.13 12.63
21 200 20 100.12 12.62



30 B. Tech Project

3.6 Experimental Calculations-
3.6.1 Experimental Calculations method-
Initial weight fraction of monomer in the mixture
W
fo
= (weight of monomer taken)/Total weight of mixture
W
fo
= W
M
/W
T

Average density of the feed mixture= Total weight of mixture taken(gm)/total volume
taken(ml)
avg =
W
T
/V
T

Weight of polymer= weight of sample before drying-weight of sample after drying
W
p
= W
sample1
+W
sample2

At a particular time t degree of conversion X
X=weight of polymer in the sample/(weight of sample*weight of monomer fraction)
X= W
p
/W
samp
* W
fo

For each time t degree of conversion is calculated and is fitted to a 4
th
degree polynomial
passing through origin (0,0).
X= a
1
t+a
2
t
2
+a
3
t
3
+a
4
t
4
dX/dt = a
1
+2a
2
t+3a
3
t
2
+4a
4
t
3
Rate of polymerization: R
p
(gm/min.lit) = (dX/dt)*(Weight of monomer in feed in gm)/ Total
volume of feed mixture (lit)


31 B. Tech Project
3.6.1.1 Calculation of Conversion-
Following results were obtained by calculation of conversion with respect to time-
S. No.
Time conversion (i=2.5) conversion (i=4.5) conversion (i=6.5)
1
0 0 0 0
2
10 0.0144 0.0363 0.0468
3
20 0.0312 0.0659 0.1798
4
30 0.0465 0.1282 0.2408
5
40 0.098 0.1787 0.2814
6
50 0.12 0.2062 0.29
7
60 0.145 0.2355 0.3107
8
70 0.1583 0.2479 0.3222
9
80 0.1731 0.2538 0.3356
10
90 0.1816 0.2611 0.3376
11
100 0.1919 0.265 0.3464
12
110 0.1951 0.2656 0.3466
13
120 0.1978 0.2674 0.3474
14
130 0.2025 0.2679 0.3529
15
140 0.2042 0.2674 0.3556
16
150 0.2081 0.2685 0.3568
17
160 0.2111 0.269 0.3571
18
170 0.2122 0.2695 0.3573
19
180 0.2125 0.2698 0.3573
20
190 0.2139 0.2698 0.3573
21
200 0.2142 0.2698 0.3571

Table Conversion calculation


32 B. Tech Project
3.6.1.2 Calculation of Rate of polymerization (R
p
)-
Following results were obtained for the calculation of rate of polymerization with respect to
time-
Time R
p
(i=2.5) R
p
(i=4.5) R
p
(i=6.5)
0 0 - 0
10 0.0005 0.0019 0.0018
20 0.0014 0.0021 0.0052
30 0.0021 0.003 0.0063
40 0.0018 0.0046 0.0079
50 0.0029 0.0057 0.0083
60 0.0033 0.0058 0.0089
70 0.0034 0.0063 0.0097
80 0.0034 0.0071 0.0103
90 0.0036 0.0082 0.0117
100 0.0045 0.0086 0.0125
110 0.0047 0.0091 0.0139
120 0.0049 0.0089 0.0146
130 0.0052 0.0093 0.0147
140 0.0054 0.0103 0.0151
150 0.0053 0.0108 0.0153
160 0.0057 0.011 0.0159
170 0.0057 0.0113 0.0165
180 0.0059 0.0116 0.017
190 0.006 0.0116 0.0171
200 0.0061 0.0117 0.0172

Table Rate of polymerization calculation


33 B. Tech Project
3.6.1.3 Calculation of Kinetic chain length-
Time
Kinetic chain
length(V) (i=2.5gm)
Kinetic chain
length(V) (i=4.5)
Kinetic chain
length(V) (i=6.5)
0 119.97 78.23 23.43
10 154.78 80.05 25.26
20 167.46 81.23 25.6
30 174.65 87.49 27.12
40 176.31 91.27 28.75
50 182.68 93.24 30.02
60 197.77 98.99 30.55
70 198.05 102.15 31.63
80 198.21 117.54 32.41
90 205.25 119.57 34.15
100 210.96 132.95 34.94
110 217.76 139.61 35.39
120 218.47 141.24 36.59
130 223.1 146.78 37.15
140 237.35 153.63 37.13
150 242.94 155.47 38.36
160 242.99 158.95 39.22
170 249.32 158.99 41.22
180 255.35 161.32 40.7
190 255.16 163.75 41.92
200 262.78 163.87 42.27

Table Kinetic chain length calculation


34 B. Tech Project
3.6.1.4 Calculation of Number average molecular weight of samples (theoretical)-
Time M
n
(theo.) (i=2.5) M
n
(theo.) (i=4.5) M
n
(theo.) (i=6.5)
0 15412.157 10093.9 3212.567
10 19846.164 10325.77 3445.458
20 21461.207 10476.1 3489.162
30 22378.153 11273.63 3682.456
40 22589.012 11755.2 3889.541
50 23401.012 12006.18 4052.125
60 25323.012 12738.73 4119.856
70 25358.97 13141.31 4256.892
80 25379.654 15101.99 4356.625
90 26276.16 15360.62 4578.25
100 27003.524 17065.23 4678.931
110 27871.028 17913.71 4735.562
120 27960.19 18121.38 4889.127
130 28549.98 18827.17 4959.664
140 30366.524 19699.86 4957.653
150 31077.326 19934.28 5114.634
160 31083.696 20377.63 5224.662
170 31890.048 20382.73 5578.418
180 32659.454 20679.57 5712.682
190 32635.248 20989.15 6067.955
200 33605.946 21004.44 6312.465

Table Theoretical number average molecular weight calculation


35 B. Tech Project
3.7 Testing and Characterization
3.7.1 Viscosity
The viscosity of a polymer solution is a resistance force the flow of liquid. The solution of
viscosity is empirically related to molecular weight for linear polymers. Therefore, viscosity
measurements constitute a valuable tool for molecular weight characterization of polymers.
Measurement of solution viscosity () are usually made by comparing the efflux time t
required for a specific volume of polymer solution to flow through a capillary tube with the
corresponding efflux time t
o
for the solvent (of viscosity
o
)

Figure 3.7: Ostwald viscometer

Ostwald viscometer
Relative viscosity
rel
= /
o
=t/t
o

Where =viscosity of polymer solution
o
=viscosity of solvent
t=efflux time required for solvent
t
o
=efflux time for solvent


36 B. Tech Project
3.7.2 pH
A pH meter is used to measure the pH (acidity or basicity) of a liquid. A typical pH meter
consists of a special measuring probe (a glass electrode) connected to an electronic meter that
measures and displays the pH reading. The pH probe measures pH as the activity of hydrogen
ions surrounding a thin-walled glass bulb at its tip. The probe produces a small voltage (about
0.06 volt per pH unit) that is measured and displayed as pH units by the meter.
Calibration with at least two, but preferably three, buffer solution standards is usually
performed every time a pH meter is used. One of the buffers has a pH of 7.01 (almost neutral
pH) and the second buffer solution is selected to match the pH range in which the
measurements are to be taken: usually ph 10.01 for basic solutions and ph 4.01 for acidic
solutions at 25
O
C.

3.7.3 Electrical Conductivity
Electrical conductivity or specific conductance is a measure of a materials ability to conduct
an electric current. When an electric potential difference is placed across a conductor, its
movable charges flow, giving rise to an electric current. The conductivity is defined as the
ratio of current density J to the electric field strength E: J= E. Conductivity of polymer
solution is measured by conductivity meter. Conductivity meter is firstly calibrated with 0.1
N KCL solutions.
Conductivity is the reciprocal of electrical resistivity, , and has the SI units of Siemens per
meter (S.m
-1
) and CGS units of inverse second (s
-1
): =1/.

3.7.3.1 Electrical Conductivity Meter
An electrical conductivity meter (EC meter) measures the electrical conductivity in a
solution. Commonly used in hydroponics, aquaculture and freshwater systems to monitor the
amounts of nutrients, salts or impurities in the water.
The common laboratory conductivity meters employ a potentiometric method and four
electrodes. Often, the electrodes are cylindrical and arranged concentrically. The electrodes
are usually made of platinum metal. An alternating current is applied to the outer pair of the
electrodes. The potential between the inner pair is measured. Conductivity could in principle
be determined using the distance between the electrodes and their surface area using the
Ohms law but generally, for accuracy, a calibration is employed using electrolytes of well-
known conductivity.


37 B. Tech Project
3.7.4 Poly (butyl-acrylate) testing-
3.7.4.1 Viscosity of different concentrations of poly (butyl)-acrylate-
( t
o
= 5.16seconds)
S.No Weight of
polymer
(gm)
Conc. In 50ml
benzene(gm/lit)
Effluix time
t for
polymer
solution
rel
=
/
o
=t/t
o

in cp
1
0
8 8.57 1.38 1.389
2
0.65
18 8.76 1.42 1.423
3
3.80
36 8.93 1.43 1.451
4
4.21
48 9.17 1.48 1.488
5
5.58
64 9.43 1.53 1.530
6
6.46
76 9.68 1.57 1.571
7
5.89
82 9.84 1.61 1.597
Table 3.13 Viscosity of various concentration of polymer solution in experiment 1
( t
o
= 6.30seconds)
S.No Weight of
polymer (gm)
Conc. In 50ml
benzene(gm/lit)
Effluix time t
for polymer
solution
rel
=
/
o
=t/t
o

in cp
1
0.00
0 7.55 1.42 1.426
2
0.76
54 7.76 1.46 1.466
3
3.99
80 7.93 1.50 1.498
4
4.96
100 8.16 1.53 1.541
5
5.53
114 8.42 1.58 1.590
6
6.06
124 8.67 1.64 1.637
7
7.89
130 8.83 1.68 1.667


38 B. Tech Project

(t
o
= 7.13seconds)
S.No Weight of
polymer
(gm)
Conc. In 50ml
benzene(gm/lit)
Effluix time t
for polymer
solution
rel
=
/
o
=t/t
o

in cp
1
0.00
0 7.59 1.41 1.409
2
0.81
59 7.78 1.47 1.468
3
4.03
83 7.96 1.52 1.517
4
4.87
102 8.18 1.55 1.549
5
5.57
115 8.50 1.60 1.597
6
6.18
123 8.65 1.67 1.671
7
7.98
135 8.87 1.71 1.714

3.7.4.2 Conductivity and pH of different concentration of poly(butyl)-acrylate-

S. No. Conductivity (mhos) pH
1 2.700 7.56
2 2.701 7.61
3 2.701 7.66
4 2.701 7.71
5 2.701 7.76
6 2.701 7.81
Table 3.15 Conductivity and pH of various concentration of polymer solution in
experiment 1


39 B. Tech Project

1 2.97 7.30
2 3.13 7.12
3 4.03 7.22
4 4.00 7.00
5 5.32 7.12
6 5.36 7.42
Table3.16 Conductivity and pH of various concentration of polymer solution in
experiment 2

1 3.03 7.27
2 3.19 7.14
3 4.09 7.11
4 4.13 7.11
5 5.39 7.13
6 5.45 7.14
Table 3.17 Conductivity and pH of various concentration of polymer solution in
experiment 3


40 B. Tech Project
3.7.5 Melt Flow Index (MFI)-
MFI is a measure of ease of flow as a thermoplastic polymer is melted. It is defined as the
mass of polymer (gm), flowing in ten minutes through a capillary of a specific diameter and
length by a pressure applied via prescribed alternative gravimetric weights for alternative
prescribed temperatures.
It is an indirect measurement of molecular weight, with high melt flow rate corresponding to
the ability of materials flow under pressure. It is inversely proportional to the viscosity of the
melt at the conditions of the test, though it should be borne in mind that the viscosity for any
such material depends on the applied pressure. Ratios between 2 values for one material at
different gravimetric weights are used as a measure of the broadness of molecular weight
distribution.
Procedure-
Following steps are considered while calculating MFI-
1. A small amount of the polymer sample (4 gms) is taken in the specially designed MFI
apparatus which is nothing but a miniature model of extruder. The apparatus has 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 around 6 min at 230C.
5. After the preheating, a specified weight is introduced onto the piston of weight 1.2kg.
6. The weight exerts a shear force on the molten polymer and it immediately starts flowing
through the die.
7. A sample of the melt is taken after period of 35sec and is weighed accurately.
8. MFI is expressed as grams of polymer/10 minutes of flow time. MFI= 5.447 gm/10min


41 B. Tech Project

3.7.6 Melting Point-
The sample is heated and analyzed through microscope. The temperature changes gradually
and the point at which we can see the change in the shape of sample put in the slide under
microscope, the temperature reading will be our melting point. The temperature in
microscope is 140.22
o
C.

3.7.7 Density-
Test Method- ASTM D 792 at CIPET Jaipur
Density of poly (butyl-acrylate) as per test result comes out to be 850.95 kg/m
3
.

3.7.8 Molecular Weight Distribution-
Molecular weight distribution of the polymer nBA was found out using Gel Permeation
Chromatography technique. In this technique, molecular weights of different samples
collected at different time are calculated and using that an average molecular weight is
calculated.
Gel permeation chromatography (GPC) is a type of size exclusion chromatography (SEC)
that separates analysts on the basis of size. The technique is often used for the analysis of
polymers. As a technique, SEC was first developed in 1955 by Lathe and Ruthven. It is often
necessary to separate polymers, both to analyze them as well as to purify the desired product.
When characterizing polymers, it is important to consider the polydispersity index (PDI) as
well the molecular weight. Polymers can be characterized by a variety of definitions for
molecular weight including the number average molecular weight (M
n
), the weight average
molecular weight (Mw) (see molar mass distribution), the size average molecular weight
(M
z
), or the viscosity molecular weight (M
v
). GPC allows for the determination of PDI as
well as M
v
and based on other data, the M
n
, M
w
, and M
z
can be determined.


42 B. Tech Project
The number average molecular weight and weight average molecular weight of samples were
measured by gel permeation chromatograph (HPLC- high performance liquid
chromatography) using tetrahydrofuran (THF) as the medium. Sample solutions of nBA were
prepared by THF to give different concentrations of nBA. The solution was filtered using
0.10-micron filter and 100 microliters of solution was then injected into THF stream
(5ml/min) of a GPC system operating at 45
o
C. Polymers were separated on as series of 5
columns of microstyragel 10
5
, 10
4
, 10
3
, 10
2
, 10 . The instrument was calibrated against 16
polystyrene standards in the range of 1.05*10^6 to 520. Following molecular weight
distribution curves were obtained.
3.7.8.1 Procedure-
A GPC/SEC instrument consists of a pump to push the solvent through the instrument, an
injection port to introduce the test sample onto the column, a column to hold the stationary
phase, one or more detectors to detect the components as they leave the column, and software
to control the different parts of the instrument and calculate and display the results.The
polymer sample is first dissolved in a solvent. This is an important step, because although
polymer molecules can be described as long chains of monomers linked together, they dont
exist like that in solution. Once they have been dissolved, the molecules coil up on
themselves to form a coil conformation, which resembles a ball of string. So although they
are chains, when we analyze them by GPC/SEC they behave like tiny spheres, with the size
of the sphere dependent on the molecular weight; higher molecular weight polymers coil up
to form larger spheres.These coiled up polymer molecules are then introduced into the mobile
phase and flow into the GPC/SEC column. The dissolved polymer molecules move past the
beads as the mobile phase carries them down the column. As the polymer coils move past
each bead, several things can happen. If the polymer coils are much larger than the biggest
pores in the beads, they cannot enter the pores and so are carried straight past by the mobile
phase. If the polymer coils are a little smaller than the biggest pores they can enter the larger,
but not the smaller pores as they pass by, occupying some, but not all of the available
stationary phase. If the polymer coils are smaller than the smallest pores in the beads, then
they can enter any of the pores and so can potentially occupy all of the stationary phase. As
the molecules enter the column, this partitioning occurs repeatedly, with diffusion acting to
bring the molecules into and back out of any pores they pass as they travel down the column.
As a result, small polymer coils that can enter many pores in the beads take a long time to
pass through the column and therefore exit the column slowly. Conversely, large polymer


43 B. Tech Project
coils that cannot enter the pores take less time to leave the column, and polymer coils of
intermediate size exit the column somewhere between these examples. Thus, the way in
which the samples elute from the column depends very much on the size of the pores in the
beads. Imagine you are walking with a child through the toy section of a department store.
You want to get straight to the car park, but your small companion wanders off to sample all
the delights on offer, so you will reach the exit straight away while junior takes his time to
get there, pausing to investigate all the toys on display. It is the same with GPC/SEC the
larger bodies get to the exit first. The separating mechanism is shown in Figure 1. This
diagram shows how different sized sample molecules can be excluded completely, partially,
or not at all from entering the pores in the particles, depending on the size of the pores and of
the sample molecules.
As the components exit the column they are detected in various ways, and the elution
behaviour of the sample is displayed in a graph, or chromatogram. The chromatogram shows
how much material exited the column at any one time, with the higher molecular weight,
larger polymer coils eluting first, followed by successively lower molecular weight (and
therefore smaller) chains emerging later. The primary separation is according to elution
volume. This is converted to time for ease of measurement, on the assumption that you have a
constant flow rate. The time it takes for a group of molecules of the same size (a fraction) to
emerge from the column is called the retention time, because the molecules have been
retained on the column. The data at produced the chromatogram is then compared to a
calibration that shows the elution behaviour of a series of polymers for which the molecular
weight is known. This allows the molecular weight distribution of the sample to be
calculated, providing important information for polymer chemists because they can use the
distribution to predict how the polymer will perform.
One important thing to bear in mind about GPC/SEC the separation is based on size, not
chemistry. These techniques give information regarding the size of polymer molecules in
solution that are converted into molecular weights through the use of a calibration. They
dont tell us anything about the chemistry of the sample, or even if the sample has
components of different chemistries. GPC/SEC is purely a physical partitioning of the sample
on the basis of size.


44 B. Tech Project

Fig 3.8 GPC Process

Fig 3.8 Chromatogram (log(MW) vs. %Wt fraction)


45 B. Tech Project
3.7.8.2 Differential and cumulative weight fraction analysis-
Following results were also obtained from the testing for a sample from the experimental
run1 (i=2.5gm) -
S. No. Log(MW) Wt. fraction % Cumulative wt. fr. %
1 3.8 1.20 1.20
2 3.84 1.01 2.21
3 3.9 3.46 5.67
4 3.95 4.95 10.62
5 4.01 8.15 18.77
6 4.06 11.53 30.3
7 4.11 21.85 52.14
8 4.17 15.43 67.58
9 4.21 11.99 79.57
10 4.29 7.81 87.38
11 4.36 5.23 92.61
12 4.39 4.00 96.61
13 4.42 2.03 98.64
14 4.46 1.15 99.79
15 4.5 0.18 99.97

Table Chromatogram readings


46 B. Tech Project
3.7.8.3 Number average molecular weight analysis-
Number average molecular weight were calculated for all the samples for different initiator
concentration-
Time M
n
(exp.) (i=2.5) M
n
(exp.) (i=4.5) M
n
(exp.) (i=6.5)
0 15451.025 10115.23 3212.567
10 18563.848 10523.54 3445.458
20 20468.216 10624.31 3489.162
30 21478.051 10874.95 3682.456
40 21879.642 11345.62 3889.541
50 22361.894 11945.85 4052.125
60 23479.125 12450.24 4119.856
70 25457.166 12758.62 4256.892
80 26941.023 14527.89 4356.625
90 26978.221 15124.95 4578.25
100 27078.962 16897.56 4678.931
110 28015.165 17964.57 4735.562
120 28452.982 18054.32 4889.127
130 28986.124 18529.13 4959.664
140 29145.466 19784.63 4957.653
150 32015.587 19852.77 5114.634
160 32841.265 19923.24 5224.662
170 32921.542 20842.36 5578.418
180 33110.254 21117.24 5712.682
190 33245.845 21245.23 6067.955
200 33548.205 21513.78 6312.465

Table Experimental reading for number average molecular weight


47 B. Tech Project
3.7.8.4 Polydispersity index analysis-
In following table, variation of Polydispersity index with weight fraction of nBA in THF
solvent is shown for I=2.5 gm.

S. No. Temperature
(K)
Wt. fraction
in THF
solvent
M
w
M
n
PDI=M
w
/M
n

1 343 10 12146 9874 1.23
2 343 20 18675 10639 1.76
3 343 40 23987 11767 2.03
4 343 60 28605 13698 2.08
5 343 80 34003 16118 2.1

Table Variation of Polydispersity index with weight fraction of nBA in THF solvent


48 B. Tech Project

CHAPTER 4
Mathematical Modelling

The model is developed to formulate the temperature controlling in the batch emulsion
polymerisation and emulsion of butyl acrylate at the steady state. Conversion of energy
accounts for the heat generated by the propagation reaction and heat removal through the wall
of the reactor and by convective fluid flow. The density of mixture is the function of the
conversion , amount of solvent introduced in the feed and the temperature.

4.1 ASSUMPTIONS
Emulsion polymerisation occurs in batch reactor at steady state.
The density of the mixture is a function of the conversion amount of the solvent
introduced in the feed and the temperature.
Heat capacities of the monomer, solvent and the polymer are assumed to be constant,
independent of temperature.
On a unit mass basis monomer and polymer are assumed to have same heat capacity.
Homogeneous nucleation is assumed.
Free radical mechanism is considered for the polymerization of n-butyl acrylate,
which has 3 major steps namely-
1. Initiation
2. Propagation
3. Termination

Following classical model is considered as the reference model-


49 B. Tech Project
k
d

k
i

Classical Model

Initiation
I +
Where I is the Initiator
is the radical formed
K
d
is the initiator decomposition rate constant
Here,
[]
[]
Where R
d
is the rate of decomposition of initiator

+M R
Where is the monomer
[]
[][]
Where R
i
is the Rate of initiation
As the free radicals have high reactivity and as soon as they are formed by decomposition of
initiator, they attack the monomer and start the initiation process. Therefore it can be assumed
the rate of formation of free radicals is equal to the rate of decomposition of the same.
Therefore,
R
i
=R
d
=2k
d
[I]
In actual practice, some radicals of the initiator disproportionate are not effective as they are
either lost as side products by way of processes such as recombination or are not
disprortionated at all.

[]
[]
Where f is the fraction of free radicals produced effective in initiating the chain growth (0.5).


50 B. Tech Project
k
p

k
p
k
p
k
tc
k
td

Propagation
R + RM
RM + M RMM
RMM +nM PM
n+2

Where k
p
is the propagation rate constant

[]
[][]
Where R
p
is the Rate of propagation.

Termination
Coupling
RM
n1
+ RM
n2
RM
n1
MMM
n2
R
Where k
tc
is the termination rate constant by combination

Disproportionation
RM
n1
+ RM
n2
RM
n3
+ RM
n4
Where RM
n3
has the saturated chain end and represents the inactive polymer chain to which
an electron has been transferred.
RM
n4
represents the inactive chain with an unsaturated chain end.
Here k
td
is the rate constant for disproportionation step

[]
[]

At steady state i.e. when the number of chain growths initiated equals the number of chain
growth arrested. The rate of initiation is equal to the rate of termination i.e.
R
i
= R
t

2k
d
f[I] = 2k
t
[]
2

[]
[]


51 B. Tech Project
[]
[]

But []
[]

Therefore
[]
[]

[]
[]
[]

Where k
t
=k
tc
+k
td
Also,
[]
[]
[]

But
[]
[]

[]
[]
[]

Using, k
t
= k
tc
+ k
td

[]
[]


52 B. Tech Project
k
tri
k
b
k
bb
Following model is proposed to be compared with reference model and experimental
measurements-

Developed Model
Other than the reactions taking place in the classical mechanism we can also consider the
following reactions to take place.

Initiation
The initiator may react with the monomer radical to terminate the monomer chain and form
polymer.
R + RMR
Where k
tri
is termination rate constant by transfer to initiator
Combination reaction of Initiator
2 I
Where k
b
is the combination reaction rate constant
Therefore, the rate of initiation is give by

[]
[]
[]
[]

Propagation
The occurrence of intramolecular radical transfer, also termed backbiting, thus changing the
structure of the radical
R
n
R
n

Where k
bb
is the backbiting rate constant


53 B. Tech Project
k
p1
k
td
k
tc

k
tri
k
trm

Reinitiation
R
n
+ M RM
n

Where k
p1
is the reinitiation rate constant
Assuming quasi steady state for both radicals RM
n
and R,
[]
[][]

[]
[]
[]
[]
[]

Termination
In termination reaction polymer chain radicals are destroyed. This occurs only when a
polymer radical reacts with another polymer radical or with a primary radical. The former is
called mutual termination and the latter is called primary termination.
Mutual Termination
RM
n1
+ RM
n2
RM
n3
+ RM
n4

RM
n1
+ RM
n2
RM
n1
MMM
n2
R
Primary Termination
RM
n1
+ RM
n1
MR
Similar Reactions are found to occur quite commonly in radical polymerization with
monomers.
RM
n1
+ M + RM
n1
MR
Where k
tri
is termination rate constant by transfer to initiator
K
trm
is termination rate constant by transfer to monomer
Therefore,
[]
[]
[]
[][]
[][]
But []
[]


54 B. Tech Project
[]
[]
[]
[]
[]

Using, k
t
= k
tc
+ k
td

[]
[]
[]
[]

Estimation of Kinetic Chain Length-
The simplest estimation of the molecular weight from the kinetics is given by kinetic chain
length, defined as the ratio of the rate of propagation divided by rate of initiation. Kinetic
chain length V of a radical chain polymerization is given as the average number of monomer
molecules consumed per each radical-

[]
[]
[]
[]
[]
[]
[]

Where [M] and [I] are the monomer and initiator concentration, f is the initiator efficiency
and the k values are rate constants.
Estimation of Number Average Molecular Weight-
The number average degree of polymerization is given by
X
n
= V+1
The number average molecular weight of a polymer is given by

Where M
o
= molecular weight of monomer


55 B. Tech Project
Degree of Polymerization
As the kinetic chain length gives the average number of monomer molecules present in a
growing chain at the time of termination, the average degree of polymerization, D
p
, is
correlated as:
1. D
p
= 2V, when termination occurs by coupling
2. D
p
= V , when termination occurs by disproportionation
3. D
p
= V/N where N has a value of 0.5 for termination by coupling and 1 for coupling
by disproportionation.
In the current case it is taken as 0.8 due to termination by disproportionation, coupling
and termination by initiator and monomer.


56 B. Tech Project
Results & Discussion

The synthesis of poly (butyl-acrylate) was done in batch emulsion polymerization reactor and
its characterization was done in CIPET Jaipur. Rate of polymerization and degree of
conversion at particular time is calculated for different runs. When monomer and initiator
started to disappear, rate of monomer and rate of initiator consumption were calculated. For
characterization of the polymers, viscosity, conductivity, density, melting point, melt flow
index (MFI) and pH values of polymers were calculated for different runs. As emulsion
polymerization is exothermic reaction in nature, temperature of reactor fluctuates at the
starting of reaction because of heat of reaction. Temperature can be maintained by external
medium. Control valve are also used to control the flow rate of cold water. The simulation of
the kinetics of the reaction was modelled assuming homogenous free radical polymerization
using MatLab and the corresponding results were plotted graphically.


57 B. Tech Project

5.1 Degree of conversion profile for batch emulsion polymerization for poly(butyl
acrylate)-
Degree of conversion X increases with time. From fig 5.1, it is clear that at a particular time
t=120 the conversion in experiment is 0.43 and in experiment 2 is o.40. the difference is
because of the difference in concentration of monomer.

Figure 5.1(a) Degree of conversion v/s time profile Exp 1

Figure 5.1(b) Degree of conversion v/s time profile Exp 2
y = 5E-10x
4
- 2E-07x
3
+ 1E-05x
2
+ 0.0023x - 0.0089
R = 0.9905
-0.05
0
0.05
0.1
0.15
0.2
0.25
0 50 100 150 200 250
X
(
C
o
n
v
e
r
s
i
o
n
)

Time (min)
conversion (i=2.5)
Poly. (conversion (i=2.5))
y = 6E-11x
4
+ 8E-08x
3
- 4E-05x
2
+ 0.0062x - 0.0155
R = 0.9894
-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0 50 100 150 200 250
X
(
C
o
n
v
e
r
s
i
o
n
)

Time (min)
conversion (i=4.5)


58 B. Tech Project

Figure 5.1(c) Degree of conversion v/s time profile Exp 3

Figure 5.1(d) Degree of conversion v/s time profile

y = -1E-09x
4
+ 7E-07x
3
- 0.0001x
2
+ 0.0115x - 0.0149
R = 0.9864
-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 50 100 150 200 250
X
(
C
o
n
v
e
r
s
i
o
n
)

Time (min)
conversion (i=6.5)
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 50 100 150 200 250
X
(
c
o
n
v
e
r
s
i
o
n
)

Time(min)
conversion (i=2.5)
conversion (i=4.5)
conversion (i=6.5)


59 B. Tech Project
5.3 Rate of Polymerization v/s Time profile for Emulsion Polymerization of Poly(butyl-
acrylate)-
The rate of polymerization R
p
increases with time. From fig 5.3 it is clear that at a particular
time t=120, the rate of polymerization in experiment 1 is 7.003 gm/lit.min and in
experiment 2 it is 9.24 gm/lit.min. Difference in the rate of polymerization is because of the
difference in the concentration of monomer.

Fig 5.3(a) Rate of polymerization v/s time profile for Exp 1

Fig 5.3(b) Rate of polymerization v/s time profile for Exp 2

0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0 50 100 150 200 250
R
p

(
R
a
t
e

o
f

p
o
l
y
m
e
r
i
z
a
t
i
o
n
)

g
m
/
l
i
t
.
m
i
n

Time (min)
Series1
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0 50 100 150 200 250
R
p
(
R
a
t
e

o
f

p
o
l
y
m
e
r
i
z
a
t
i
o
n
)

g
m
/
l
i
t
.
m
i
n

Time (min)
Rp


60 B. Tech Project

Fig 5.3(c) Rate of polymerization v/s time profile for Exp 3

Fig 5.3(d) Rate of polymerization v/s time profile
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0.02
0 50 100 150 200 250
R
p

(
R
a
t
e

o
f

p
o
l
y
m
e
r
i
z
a
t
i
o
n
)

g
m
/
l
i
t
.
m
i
n

Time(min)
Rp
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 50 100 150 200 250
R
p

(
R
a
t
e

o
f

p
o
l
y
m
e
r
i
z
a
t
i
o
n
)

g
m
/
l
i
t
.
m
i
n

Time (min)
conversion (i=2.5)
conversion (i=4.5)
conversion (i=6.5)


61 B. Tech Project
5.4 Weight of polymer vs. time profile for Emulsion Polymerization of poly(butyl-
acrylate)-
The weight of polymer W
p
increases with time. From figure 5.4 it is clear that at a particular
time t=120, the weight of polymer in experiment 1 is 5.89gm and in exp 2 it is 7.5gm. The
weight of polymer increases due to monomer conversion increase with time. This difference
in weight of polymer is due to difference in concentration of monomer.

Fig 5.4 (a) Weight of polymer v/s time profile for exp 1

Fig 5.4(b) Weight of polymer v/s time profile for exp 2

0
1
2
3
4
5
6
7
8
0 50 100 150 200 250
W
e
i
g
h
t

o
f

p
o
l
y
m
e
r

(
g
m
)

Time (min)
wt of polymer (P)
0
1
2
3
4
5
6
7
8
9
10
0 50 100 150 200 250
W
e
i
g
h
t

o
f

p
o
l
y
m
e
r

(
g
m
)

Time (min)
wt of polymer


62 B. Tech Project

Fig 5.4(c) Weight of polymer v/s time profile for exp 3

Fig 5.4(d) Weight of polymer v/s time profile for exp 3
0
2
4
6
8
10
12
14
0 50 100 150 200 250
W
e
i
g
h
t

o
f

p
o
l
y
m
e
r

(
g
m
)

Time (min)
wt of polymer
0
2
4
6
8
10
12
14
0 50 100 150 200 250
W
e
i
g
h
t

o
f

p
o
l
y
m
e
r

(
g
m
)

Time (min)
wt of polymer(i=2.5)


63 B. Tech Project

5.5 Kinetic chain length vs. time profile for emulsion polymerization of n-(butyl
acrylate)-
Kinetic chain length was calculated for every sample drawn at specific time intervals as the
ratio of rate of propagation to rate of initiation.

Fig Kinetic chain length v/s time profile

0
50
100
150
200
250
300
0 50 100 150 200 250
Kinetic chain length(V) (i=2.5)


64 B. Tech Project

5.6 Number average molecular weight v/s time profile for emulsion polymerization of
poly (butyl acrylate)-
Number average molecular weight was calculated from kinetic chain length calculation for
different initiator concentration and experimental data were obtained from gel permeation
chromatography.

Fig Number average molecular weight v/s time

0
5000
10000
15000
20000
25000
30000
35000
40000
0 50 100 150 200 250
N
o
.

a
v
g
.

M
w

(
g
m
)

Time (min)
Mn (exp.) (i=2.5)
Mn (exp.) (i=4.5)
Mn (exp.) (i=6.5)
Mn (theo.) (i=2.5)
Mn (theo.) (i=4.5)
Mn (theo.) (i=6.5)


65 B. Tech Project
5.5 Rate of initiator Disappearance v/s time profile for emulsion polymerization of
poly(butyl acrylate)-
Rate of initiator disappearance decreases with time linearly as shown in figure 5.5(a) and (b),
This may be because initially high concentration of initiator is available which break down to
free radicals and as polymerization starts. As the reaction f proceeds, the concentration of
initiators decreases linearly and hence the rate of disappearance of initiator also decreases.

Fig Rate of initiator disappearance v/s time

0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 2000 4000 6000 8000 10000 12000 14000
model 1(i=2.5)
model 2 (i=2.5)
model 1(i=4.5)
model 2(i=4.5)
model 1(i=6.5)
model 2(i=6.5)


66 B. Tech Project
5.6 Rate of monomer disappearance v/s time profile for emulsion polymerization of
poly(butyl acrylate)-
Figure 5.6 shows the relation of rate of disappearance of monomer with time. Rate decreases
continuously as in beginning high concentration of monomer is present which after initiator
reacts rapidly. As the reaction proceeds, the concentration of monomer decreases and hence
the rate of disappearance of initiator also decreases

Fig Rate of monomer disappearance v/s time

0
0.5
1
1.5
2
2.5
3
0 2000 4000 6000 8000 10000 12000 14000
exp (i=2.5)
exp(i=4.5)
exp(i=6.5)
model 1 (i=2.5)
model 2 (i=2.5)
model 1(i=4.5)
model 2(i=4.5)
model 1(i=6.5)
model 2(i=6.5)


67 B. Tech Project
5.7 rate of polymer formation v/s time profile for emulsion polymerization of poly
(butyl acrylate)-
Figure 5.7 shows the relation of rate of formation of polymer with time. Rate decreases
continuosly as in beginning high concentration of monomer is present which after initiation
reacts rapidly. As the reaction proceeds, the concentration of monomer and initiator decreases
and hence the rate of formation of polymer also decreases.

Fig Rate of polymer formation v/s time

0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0.02
0 2000 4000 6000 8000 10000 12000 14000
exp(i=2.5)
exp(i=4.5)
exp(i=6.5)
model 1(i=2.5)
model 2(i=2.5)
model 1(i=4.5)
model 2(i=4.5)
model 1(i=6.5)
model 2(i=6.5)


68 B. Tech Project
5.8 Comparison of Experimental results with classical model (1) and applied model (2)-
On the basis of monomer concentration obtained from experimental run (for i=2.5gm) results
obtained from classical model and proposed model and coefficient of correlation and MAPE
were calculated.
time(min) experimental R
2
1 R
2
2 %MAPE1 %MAPE
0 2.5631 2.5633 2.5633 7.8E-05 7.8E-05
10 2.387 2.4334 2.3983 0.019439 0.004734
20 2.223 2.3122 2.249 0.040126 0.011696
30 2.1 2.1999 2.114 0.047571 0.006667
40 1.9587 2.0952 1.9915 0.069689 0.016746
50 1.8519 1.9983 1.8805 0.079054 0.015444
60 1.8389 1.9078 1.7793 0.037468 0.032411
70 1.6561 1.8238 1.6868 0.101262 0.018538
80 1.5774 1.7453 1.6022 0.106441 0.015722
90 1.4789 1.6724 1.5244 0.13084 0.030766
100 1.4523 1.6042 1.4528 0.104593 0.000344
110 1.4165 1.5404 1.3867 0.087469 0.021038
120 1.3549 1.4808 1.3256 0.092922 0.021625
130 1.2487 1.4248 1.2691 0.141027 0.016337
140 1.215 1.3723 1.2166 0.129465 0.001317
150 1.1533 1.323 1.1679 0.147143 0.012659
160 1.0959 1.2766 1.136 0.164887 0.036591
170 1.0701 1.2329 1.0804 0.152135 0.009625
180 1.0178 1.1918 1.041 0.170957 0.022794
190 1.0089 1.153 1.0042 0.142829 0.004659
200 0.9353 1.1164 0.9698 0.193628 0.036887
Rsq 0.9958607 0.997151 0.102811 0.016032
MODEL1 MODEL2 MAPE1 MAPE2

Table Calculation of coefficient of correlation and MAPE
Since the value of coefficient of correlation for classical model (model 1) on comparison with
experimental values (R
2
1=0.9958) and for proposed model (model 2) on comparison with
experimental values (R
2
2=0.9971) were almost equal, so further MAPE was calculated which
is 10.28 for classical model (Model 1) as compared to proposed model (model 2) 1.60. So
this is clear that proposed model is better fit for the actual process than the classical model.


69 B. Tech Project

Conclusion

Butyl acrylate polymer was successfully prepared by the batch emulsion polymerisation and
characterized. The simulation of the process was carried Range kutta algorithm on
MATLAB. Corresponding graphs were plotted for concentration of initiator, monomer,
butyl acrylate with respect to time hence the complete analysis of batch polymerisation
process was done.
Butyl acrylate is characterised by estimation of properties of butyl acrylate solution like
viscosity, ph and conductivity. For particular time degree of conversion and rate of
polymerization is calculated which shows the Trommsdorff effect. The graphs are plotted
from results and discussed.
From the successful synthesis of butyl acrylate from emulsion polymerisation we got better
experimental yields as compared to other polymerisation techniques and thus it is suggested
that this technique can be extended for the preparation of other polymer as well.


70 B. Tech Project
References

1. Chern , C.S.[2006], Emulsion polymerization mechanism and kinetics, Process. In
Polymer Science. Volume 31, page 443-489.
2. Cowie , J.M.G. [2001], Polymer: chemistry & physics of modern materials, 2
nd

edition Nelson thrones, pages 132-154.
3. C.Welz, G.Frncois, B. Srinivasan, D. Bonvin and D. Hunkeler [2004], trajectory
following for the optimization of a batch polymerization reactor, Batch Pro PerPrints
symposium, page 153-159.
4. Flory, P. J. [1953] Principles of polymer chemistry, 1
st
edition, Cornell University
press, Ithaca, New York, Page 203- 217.
5. Gupta , S.K., Sangwai , J.S., Bhat, S.A., Saraf, D.N. [2005], bulk free radical
polymerization of butyl acrylate under non isothermal conditions and with
intermediate addition of initiator: experiments and modelling , polymer, vol.46, page.
6. G.Francois , B. Srinivasan and D.Bonvin [2002], Run to run optimization of batch
emulsion polymerisation , IFAC Worlds congress , pages 1258- 1263.
7. M. J. J. Mayer, J. Meuldijk and D. Thoenes. [1994], Emulsion polymerisation in the
various reactors types: recipes with high monomer content, Chemical Engineering
Science , Vol. 49. No. 24B, page 4971 4980.
8. Michael Wulkow and UweBudde [1991], Computation of molecular weight
distributions for free radical polymerization systems, Chemical Engineering Science,
Vol. 46 , No. 2, page. 497- 508.
9. Shi Yow Lin, Shuo Cheng Wu. Chorng Shyan Chern, Li Jen Chen [1997],
Critical micelle concentration of mixed surfactant SDS/ NP(EO)4 and its role in
emulsion polymerisation , colloids and surfactant A: physiochemical and engineering
aspects, vol . 122, page 161- 168.
10. Silvia Curteanu [2003], Modelling and simulation of free radical polymerization of
styrene under semi batch reactor conditions, Central European Journal of Chemistry,
Vol. 1, page , 69- 90.
11. Victor M. Ovandao Medinal , Eduardo Mendizabal 2 , Rene D. Peralta [2005] ,
Kinetics modelling of micro emulsion copolymer, Polymer Bulletin vol.54 , page 129
140.


71 B. Tech Project
12. YaacovAlmog& Moshe levy [1982], Free radical polymerization of styrene and butyl
acrylate in dispersed system and the effect of carbon black, Ind. Eng.Chem. Prod.
Res . Dev., Vol.21, No.2 , page. 164-170.
13. AswiniSood, aparnasingh [2013] lumped model for butyl acrylate emulsion
polymerisation, department of chemical engineering, HBTI Kanpur, 208002 india.
Accepted 27 Feb 2013.
14. OdianGeorge , [2004] Principles of polymerization 3
rd
edition ., John Wiley & Sons ,
New York , page , 335- 352.
15. Fried , Joel R ., Polymer Science and Technology, 2
nd
edition , Prentice Hall PTR,
1995 , New Jersey , Page, 23-72.
16. William L. Luyben [1996] , Process modelling , simulation , and control for chemical
engineering , second edition , McGraw- Hill Publishing , page , 23-27 and 46- 62.
17. Mohammad Anwar Hosen , MohdAzlanHussain , Farouq S . Mjalli . [2008],
optimum kinetics for polystyrene batch reactor by Neural Network approach
.Computers & chemical Engineering , Volume 21, supplement 1 , pages S463
S468.


72 B. Tech Project
APPENDIX A

Kinetics rate constant for free radical polymerization of Polybutyl acrylate:
Constants Value of Constants
F 0.58
K
d
0.001834 min
-1
K
p
49876.54 lit/mol-min
K
tr
M 1.40813 lit/mol-min
K
1
K
p

K
td
K
t

K
tc
0.0
K
t
1.414*109 lit/mol-min
K
tri
49876.54 lit/mol-min


73 B. Tech Project
APPENDIX B

Programming Algorithms on MatLab for Poly(butyl)-acrylate

For Classical model
function classicalmodel
% Initiator is potassium persulphate having molecular weight of 270.322
% Monomer is n butyl acrylate having molecular weight of 128.17
tspan=[0:60*10:200*60];
% time span is 200 minutes
x0=[(2.5/270.322)/.820 (269.4/128.17)/.820 0];
[t x]=ode15s(@poly_unstd,tspan,x0)
figure(1),plot(t,x(:,1))

function [dx] = poly_unstd(t,x)
dx=zeros(2,1);
R=0.008314;
T=343;
kd=8.5*10^-5;
% where kd is the rate constant of dissociation of initiator
% kd=(7.90*10^7)*exp(-78.62/(R*T))
kp=26.0671;
% where kp is the rate constant of propagation
% kp=(1.7*10^4)*exp(-17.4/(R*T));
kt=41728.43967;
% where kt is the rate constant of termination
%kt=(1.9*10^5)*exp(-4/(R*T))
f=0.5;
% where f is the fraction of free radicals produced effective in initiating
% the chain growth
dx(1)=(-2*f*kd*x(1));
% Gives concentration of Initiator
dx(2)=(-kp*((kd*f)^(0.5))*((kt)^(-0.5))*(x(1)^(0.5))*x(2));
% Gives concentration of Monomer
dx(3)=((kt*kd*f*x(1))/kt);
% Gives concentration of Polyner

end

end


74 B. Tech Project

For Developed model
function developedmodel
% Initiator is potassium persulphate having molecular weight of 270.322
% Monomer is n butyl acrylate having molecular weight of 128.17
tspan=[0:60*10:200*60];
% time span is 200 minutes
x0=[(6.5/270.322)/.820 (269.4/128.17)/.820 0];
[t x]=ode15s(@poly_unstd,tspan,x0);

function [dx] = poly_unstd(t,x)
dx=zeros(2,1);
R=0.008314;
T=343;
kd=(6.90*10^7)*exp(-78.62/(R*T));
% where kd is the rate constant of dissociation of initiator
% kd=7.3378*10^-5
kp=(1.7*10^4)*exp(-17.4/(R*T));
% where kp is the rate constant of propagation
% kp=38.0671
kt=(1.9*10^5)*exp(-4/(R*T));
% where kt is the rate constant of termination
% kt=4.6728*10^4
ktrm=(4*10^-5)*kp;
% where ktri is termination rate constant by transfer to monomer
ktri=(0.5)*kp;
% where ktri is termination rate constant by transfer to initiator
kp1=9.78*10^6;
% where kp1 is the reinitiation rate constant
kbb=3.14*1000;
% where kbb is the backbiting rate constant
f=0.5;
% where f is the fraction of free radicals produced effective in initiating
% the chain growth
keq=72.44;
% where keq is the equilibrium rate constant for the Initiator
kback=(kd/keq);
% where kb is the combination reaction rate constant
dx(1)=(-2*f*kd*x(1))+(0.5*x(1)*kback*f)-((ktri*((kd*f)/kt)^0.5)*(x(1)^1.5));
% Gives concentration of Initiator
dx(2)=(-kp*((kd*f)^(0.5))*((kt)^(-
0.5))*(x(1)^(0.5))*x(2))*(((kp1*x(2))+((2*f*kt*kd*dx(1))^0.5))/(kbb+(kp1*x(2))+((2*f*kt*kd*dx(1))^0.5)));
% Gives concentration of Monomer
dx(3)=((kt*kd*f*x(1))/kt)+((ktri*((kd*f)/kt)^0.5)*(x(1)^1.5))+(ktrm*x(2))*(((kd*f*x(1))/kt)^0.5);
% Gives concentration of Polymer
end

end


75 B. Tech Project
APPENDIX C

Poly(Butyl-acrylate) pictures

Synthesis of Polymer Part 2

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Synthesis of Polymer Part 2

Caricato da

Copyright:

Formati disponibili

Department of Chemical Engineering, MNIT, Jaipur

Potrebbero piacerti anche