JAGRAT SEVAK - Project For Polymer

Polyester Polyol Project 2018-19
Project Report on
Synthesis and characterization of polyester polyol obtained

from Renewable resource
A Dissertation Thesis
Submitted for partial fulfilment of the requirement for

The award of the Degree of
Master in Industrial Chemistry of Sardar Patel University
Year: 2018-2019
Under the guidance of

Dr. MANDAR KARVE
(Department of Industrial Chemistry)

INSTITUTE OF SCIENCE AND TECHNOLOGY FOR ADVANCED STUDIES AND
RESEARCH (ISTAR), V.V. Nagar
Submitted by
Mr. JAGRAT SEVAK (17IC27)
Mr. DEVENDRA JADAV (17IC12)
Mr. NEEL PATEL (17IC45)
Mr. KASHYAP GOHIL (17IC37)
MR. JAIMIN PATEL (17IC28)
Mr. HIREN PATEL (17IC26)
ISTAR-V.V.N. 1
CERTIFICATE
It is to certify that, Mr. Jagrat D. Sevak (17IC27) has

successfully completed his work incorporated in this
dissertation entitled. “Synthesis and characterization of
polyester polyol obtained from Renewable resource”
Submitted towards partial fulfilment of the requirement for
the Degree of Master of Science in Industrial Chemistry -
ISTAR (PS04CICH21 – PRACTICAL – PROJECT) of the
Sardar Patel University, Vallabh-Vidhyanagar, Anand.
The result embodied in the dissertation is to the best of my
knowledge and have not been submitted to any
University/Institute for the award of any degree.
The work is carried out by his under my supervision and
guidance.
__
Dr. MANDAR KARVE Dr. JIGAR V. PATEL

Project Guide, Asso Prof. & HoD
Asst. Prof. IC Dept. Dep. of IC
ISTAR ISTAR
ISTAR-V.V.N. 2
CERTIFICATE
It is to certify that, Mr. Jaimin V. Patel (17IC28) has

the Degree of Master of Science in Industrial Chemistry –
Sardar Patel University , Vallabh-Vidhyanagar , Anand.
guidance.
__

ISTAR ISTAR
ISTAR-V.V.N. 3
CERTIFICATE
It is to certify that, Mr. Devendra Jadav (17IC12) has

the Degree of Master of Science in Industrial Chemistry -
SardarPatel University , Vallabh-Vidhyanagar , Anand.
guidance.
__

ISTAR ISTAR
CERTIFICATE
ISTAR-V.V.N. 4
It is to certify that, Mr. Neel Patel (17IC12) has successfully

completed his work incorporated in this dissertation entitled.
“Synthesis and characterization of polyester polyol obtained
from Renewable resource” Submitted towards partial
fulfilment of the requirement for the Degree of Master of
Science in Industrial Chemistry - ISTAR (PS04CICH21 –
PRACTICAL – PROJECT) of the
SardarPatel University, Vallabh-Vidhyanagar, Anand.
guidance.
__

ISTAR ISTAR
CERTIFICATE
ISTAR-V.V.N. 5
It is to certify that, Mr. Hiren Patel (17IC26) has successfully

completed his work incorporated in this dissertation entitled.
“Synthesis and characterization of polyester polyol obtained
from Renewable resource” Submitted towards partial
fulfilment of the requirement for the Degree of Master of
Science in Industrial Chemistry - ISTAR (PS04CICH21 –
PRACTICAL – PROJECT) of the
SardarPatel University, Vallabh-Vidhyanagar , Anand.
guidance.
__

ISTAR ISTAR
CERTIFICATE
ISTAR-V.V.N. 6
It is to certify that, Mr. Kashyap Gohil (17IC37) has

the Degree of Master of Science in Industrial Chemistry -ISTAR
(PS04CICH21 – PRACTICAL – PROJECT) of the
SardarPatel Universit , Vallabh-Vidhyanagar , Anand.
guidance.
__

ISTAR ISTAR
Preface
ISTAR-V.V.N. 7
“manufacture process of polyester polyol from phthalic acid and

castor oil is bio-based and this idea has been shaped by the
uncompromising demand of green chemistry this process
involved unit process and also unit operation .The idea is cost
effective, safe and environmentally benign. Manufacture of
Polyester polyol is multi-disciplinary effort involving chemical,
analytical and engineering input. This report gives rout for
manufacturing of bio based polyester polyol process and
analytical technique of it. Majorly the chemical process involves
evolution of environmentally hazards, which influences to work
on this kind of project.”
***
Acknowledgement
ISTAR-V.V.N. 8
We sincerely thank to ISTAR VALLABH VIDHYANAGAR.

For giving us an opportunity to that kind of research at such a
stage of our career.
We express our heartiest thanks and deepest gratitude to our
guide Dr. Mandar Karve under whose guidance this work has
been successfully carried out.
We also express our sincere thanks to HoD Dr. Jigar Patel
extending help when required throughout the work.
We wishfully acknowledge the invaluable support given by
Dr. Rohit Dave, Dr.Nirmal patel.
We also thankful for arranging laboratory facilities to Mr.
Minesh Patel, Mr. Pinakin Patel, Mr. Raju Rathod and Mr.
Navin Darbar.
We also thankful to Mrs. Parul Thakkar to providing us
laboratory equipments and glassware.
And most importantly, we are very grateful to Almighty and
our parents for their blessings, encouragement and motivation
for the fruitful completion of the task.
At last but not the least, we are thanking to all those who have
help us in what so ever manner in our project work.
INDEX
Table of contents:-
ISTAR-V.V.N. 9
Sr. No. Content Page No.

i. Preface..................................................................................03
ii. Acknowledgment ................................................................04
iii. Abstract...............................................................................07
1.Introduction and processes..........................................................

08
 Aim of work--------------------------------------------------------- 08
 Process introduction------------------------------------------------------ 08
 Importance of Polyester polyol--------------------------------------10
2.Materials and methods................................................................11
 Materials and Equipments--------------------------------------------------11
 Raw materials------------------------------------------------------------------12
3.Method........................................................................................14
 Experimental method---------------------------------------------------------15
 Analytical methods------------------------------------------------------------20
4.Result and discussion..............................................................23
 Characterization (FTIR and GPC)----------------------------------------26
5.Applications.............................................................................30
6.Conclusion..............................................................................31
7.Future aspects.......................................................................32
8. References.............................................................................32
------------------------
***
Abstract
ISTAR-V.V.N. 10
The main objective of this work was to synthesize linear saturated

polyester polyols by polyesterification reaction from renewable resource
castor oil with phthalic acid in the presence of catalyst. The process
conditions were optimized by temperature profile, inert atmosphere,
monomer composition, reaction time, catalyst, and reaction conditions to
produce polyester polyol had average molecular 3959.8 gm/mol.
It is one of the most important polymer compound used in polyurethane
elastomers, flexible foams, coatings, adhesives, rigid foams, synthetic
leather, and sealants.
For characterization of the product FTIR spectroscopy and GPC analysis
carried out. Amount of free fatty Acid group also determined by acid
value analysis during process.
Keywords:- Castor oil; Polyester polyol; renewable resources; polyesterification;

Polyurethanes; Polyester polyol; Biodegradability.
1.0 Introduction
ISTAR-V.V.N. 11
1.1. Aim of work
“Looking to ease availability of castor oil in India, it was utilized as

precursor in the preparation of biodegradable polyester polyol synthesis.”
1.2. Process introduction

“Polyester polyol is the result of polyesterification of the bifunctional
carboxylic acid and fatty acid/oil as renewable source”
Fatty acid/oil is renewable resources and environmentally sustainable.

Benefits with renewable resources:- This idea has been shaped by the
uncompromising demand of green chemistry. This process involved unit
process and also unit operation. The idea is cost effective, safe and
environmentally benign.
Renewable resources: - The resources that can be renewed naturally with
certain time period. Air, Water, Wind, Sun energy, Plants and Cultivated
product etc. are all renewable resources.
A large volume of plant oils is used as renewable resources to produce
various chemicals which are industrially important to make soaps, cosmetic
products, surfactants, lubricants, diluents, plasticizers, inks, agrochemicals,
composite materials, and food industry.
Vegetable oils are one of the most important renewable resources in the
chemical industry due to their biodegradability, availability, low-cost price,
environmental acceptance, renewability, and non-toxic nature. It is widely
used for the production of various polymers including polyols.
Renewable resources which can be used in the production of Polyester
polyol are:- Castor oil, Olive oil, Groundnut oil, Soybean oil, Coconut oil
etc.
We can use many others Non-Drying oils.
During polyester polyol synthesis all process parameters handle preciously.

Polyester polyols are based on oil and aromatic dicarboxylic acids are one
of the most important materials in polymer technologies. Polyester polyol
was prepared from renewable resource castor oil and Phthalic acid.
ISTAR-V.V.N. 12
Polyester polyols from renewable resources were successfully synthesized

with sufficient molecular weight and low acid value. Properties of the
castor oil based polyester polyols same as petroleum-based analogues.
Process consumed very less time. Problem appeared when reaction carried
out in the presence of oxygen; it leads to black-brown colour to Polyester
polyol due to oxidation on saturated single bond of castor oil, so nitrogen
mandatorily purged to reaction mass.
Structurally Polyester polyol contain Ester linkage and hydroxy group.
Brown- black colored product having high viscosity and low acid value.
Phthalate polyester polyol was prepared from bio-based resource castor oil
and Phthalic acid in presence of catalyst. 22
This Bio-based polyester polyols from renewable resources were
successfully synthesized with different molecular weight at low acid value.
Problem arise when reaction carried out in the presence of oxygen; it leads
to black color to polyester polyol, so inert atmosphere is obligatory.22
1.3 Importance of Polyester polyols
ISTAR-V.V.N. 13
2Polyester polyols
3 1,2
4based on aliphatic and
aromatic
5dicarboxylic acids are
valuable materials in
polymer
6technologies.
7 3–5
8Among them are low-
molecular-
9weight oligomeric
derivatives of phthalic and
10 terephthalic acids that
are widely used in high-
ISTAR-V.V.N. 14
11 strength and rigidity

polyesters and polyurethane
12 foams.
13 4,6
14 The use of aromatic
acids offers many
15 advantages to polymer
properties including good
16 mechanical
characteristics, high thermal
stability,
17 resistance to major
chemical solvents, and low
flam-
18 mability.
ISTAR-V.V.N. 15
19 Polyester polyols
20 1,2
21 based on aliphatic and
aromatic
22 dicarboxylic acids are
valuable materials in
polymer
23 technologies.
24 3–5
25 Among them are low-
molecular-
26 weight oligomeric
derivatives of phthalic and
27 terephthalic acids that
are widely used in high-
ISTAR-V.V.N. 16
28 strength and rigidity

29 foams.
30 4,6
31 The use of aromatic
acids offers many
32 advantages to polymer
33 mechanical
characteristics, high thermal
stability,
34 resistance to major
chemical solvents, and low
flam-
35 mability.
ISTAR-V.V.N. 17
Polyester polyols prepared from dicarboxylic acid and fatty acid are
valuable materials in polymer technologies. Among them are low-
molecular weight oligomeric derivatives of phthalic acids that are widely
used in high strength and rigidity polyesters and polyurethane foams. The
use of aromatic acids offers many advantages to polymer properties
including good mechanical characteristics, high thermal stability,
resistance to major chemical solvents, and low flammability.[6]
Polyurethanes are used in a wide range of industrial applications due to
their chemical versatility, high performance and low cost. They find use
in building and construction, consumer products, furniture and fixtures,
transportation and in industrial applications.[7]
Looking for alternatives to reduce carbon footprint bio based Polyester
polyol derived; the main demand for bio based polyurethane is derived
from application segments such as automotive, footwear and apparel.
Uses in applications such as electronics, carpets, and furniture among
others are also gaining momentum.[6]
Polyurethanes are usually synthesized by isocyanate reactions with
polyester polyols which has superior characteristics due to its better
crystalline structure in the urethane segment, compared to the majority of
polyether polyols which are amorphous. Due to the superior secondary
forces between the polyester chains it is superior thermal, fire resistance
and superior solvent resistance compared to polyether polyol based
polyurethanes.14
2.0 Materials and methods
ISTAR-V.V.N. 18
2.1 Materials
2.1.1 Raw materials:-

Sr. Chemicals Grade Company
1. Castor Oil LR Commercial
2. Phthalic Acid LR Chiti chem co.
3. Xylene LR Suhas Enter.
4. p-toluenesulfonic Acid LR Chiti chem co.
5. Acetone LR Chiti chem co.
6. KOH LR Atul chemicals.
7. Succinic Acid LR Sigma
8. TPP LR Atul chemicals
2.1.2 Equipments:-
Sr. Equipments
1. Three neck RBF
2. Water condenser
3. Mechanical stirrer
4. Dean stark condenser
5. Nitrogen perjure
6. Nitrogen balloon
7. Thermometer
8. Heating mantle
9. Beaker set
10. Viscometer
11. Conical flask
12. Measuring cylinder
13. Calibrator
2.2 Raw materials:-
ISTAR-V.V.N. 19
2.2.1 Castor oil:-

Extracted from the beans of the plant “Ricinus communis” .Castor is one
of the oldest cultivated crops. It seems viscous, pale yellow non-volatile
and non-drying. Viscosity, density, thermal conductivity, and pour point
for it is higher than lubricant oil.
Castor oil is known to consist of up to 90% ricinoleic, 4% linoleic, 3%
oleic, 1% stearic, and less than 1% linolenic fatty acids.
Due to the high content of ricinoleic acid (RA), it is used in a variety of
applications in the chemical industry. Castor oil is valuable due to the
high content of ricinoleic acid (RA), which is used in a variety of
applications in the chemical industry. The presence of the hydroxyl group
in RA and RA derivatives provides a functional group location for
performing a variety of chemical reactions including halogenation,
dehydration, alkoxylation, esterification, and sulfation. As a result, this
unique functionality allows the castor oil to be used in industrial
applications such as paints, coatings, inks, lubricants such- Fuel and
biodiesel, Polymer materials, Soaps-waxes and greases, Lubricants,
hydraulic, brake fluid and Fertilizers.[8]
Boiling point of castor oil - 308 °C
The ricinoleic acid triglyceride (castor oil) has the structural formula
as :-
Figure 1
2.2.2 Phthalic acid C6H4(CO2H)2 :-
ISTAR-V.V.N. 20
It is an isomer of isophthalic acid and terephthalic acid. Although

phthalic acid is of modest commercial importance, the closely related
derivative phthalic anhydride is a commodity chemical produced on a
large scale. It is colourless, crystalline organic compound. Presence of
oxygen atoms leads to electron withdrawing properties.[9]
Easy availability and low price of phthalic acid influence to use of it.
2.2.3 Xylene:-
xylene or dimethylbenzene is any one of three isomers of
dimethylbenzene, or a combination thereof. With the formula
(CH3)2C6H4, each of the three compounds has a central benzene ring with
two methyl groups attached at substituent. They are all colorless,
flammable liquids, some of which are of great industrial value. It act as
good solvent for castor oil to produce polyester polyol.[9]
2.2.4 p-toluene sulphonic acid (CH3C6H4SO3H):-
It is a white solid that is soluble in water, alcohols, and

other polar organic solvents. The CH3C6H4SO2– group is known as
the tosyl group and is often abbreviated as Ts or Tos. Most often, TsOH
refers to the monohydrate, TsOH.H2O. It used as catalyst in our project.[9]
Many dicarboxylic acids will react with castor oil to
yield an elastomeric products, polyesters and polyester Figure 2
polyols. Castor oil is obtained pure in large quantities
from natural sources; it is safe and biocompatible.
2.3 Methods
2.3.1 Esterification:-
ISTAR-V.V.N. 21
When a carboxylic acid is treated with an alcohol and an acid catalyst, an

ester is formed (along with water). An ester is when a carbon is
connected with two oxygen atom, but one of the oxygen isn't connected
to anything else (so it is double-bonded to the carbon), while the other
oxygen is connected to another carbon. This reaction is called the
esterification.
Mechanism:-
Figure 3
2.3.2 Condensation Reaction:-

A condensation reaction is a class of an organic addition reaction that
proceed in a step-wise fashion to produce the addition product, usually in
equilibrium, and a water molecule (hence named condensation). The
reaction may otherwise involve the functional groups of the molecule and
formation of ammonia, ethanol, or acetic acid. [1]
2.3.3 Experimental method:-
Parameters
ISTAR-V.V.N. 22
1. Temperature-1200C– 1800C
2. Pressure- 760 mmHg
3. Continues stirring - 100 rpm approximate
4. Inert atmosphere
Esterification of Castor oil with Phthalic acid:-
 Para toluene sulphonic acid is used as the catalyst.
 Xylene used as solvent.
Making polyester polyol was not an easy task with short time period. High
precautions are required during entire process. Temperature possessed
crucial role to produce Polyester polyol.12
Maintaining optimum Temperature has been very difficult task and inert
atmosphere by nitrogen perjuring was the most difficult as well highly
sensible, precautionary part in the set up due to equipments sensitivity and
the Polyester polyol has highly oxidative property.12 After oxidation it
became black coloured and in our case became decomposed as well as.
Consistently adding nitrogen through perjured was done by dissolving

nitrogen through dilute sulphuric acid, because of its hygroscopic nature it
absorb unwanted water residue. It also indicated the flow rate of nitrogen
through bubbling in sulphuric acid. To maintained consistent pressured
nitrogen flow rate through its balloon achieved by using external forces on
it but after pressure within balloons seems disappeared.[11]
We best tried to keep, two nitrogen bubbles per second after the removing
air from RBF by nitrogen.16
The Dean–Stark apparatus - Dean–Stark receiver, distilling trap, or Dean–
Stark Head is a piece of laboratory glassware used to collect water from
a RBF. It is used in combination with a reflux condenser and a RBF for
continuous removal of the water that is produced during a chemical reaction
between ricinolics acid of castor oil and phthalic acid performed at reflux
temperature.[10]
RBF was firstly fed by solvent xylene (30 ml) than 93.30 gm of Castor oil
was added, just after phthalic acid added to RBF. The trace amount of p-
toluene sulfonic acid (1.5 gm) as catalyst has been added. Mechanical
ISTAR-V.V.N. 23
stirred approx 50 rpm is incorporated by motor to centre of RBF, which

played important role while production, it prevented suspension and
accumulations of solid particulate and mixed up reactant as well as.
Afterward the entire remained assembly settle.
The reaction mass was heated initial with low temperature almost 60 0C to
800C for first 20 minutes than gradually temperature had been arises to the
1400C to 150 0C, it took hardly 45 minutes, during that the first
homogenous mixture was seems within 30 minutes, contemporaries first
acid value had taken.[11] Afterwards Acid value was taken in every 15
minutes time interval. After 45 minutes, seen first water evaluated in trace
amount in Dean stark.
The maximum temperature was 1750C taken during all the batches. After
the completion of esterification water was produced 3.0 ml, 3.3ml, 3.3ml
and 3.5ml for batch-1, batch-2 , batch-3 and batch-6 respectively. Dean
stark had been feel with xylene up to desire level, which make azeotrope
with byproduct water. That water was separated out due to azeotrope
formation between xylene and water in the reaction mass and water
accumulated at the down end of dean stark due to its high density than
xylene.
So after just opening the valve of the bean stark water has been collected in
separate bottle and calibrated its amount in ml.[10]
Esterification of Castor oil with Phthalic acid
ISTAR-V.V.N. 24
Figure 4 - Assembly arrangement for esterification
Batch 1- complete assembly settled as per available sources, and followed

up all the procedure but this batch was failed. It was oxidized and the
reaction mass was oxidized due to lack of nitrogen gas availability. Outrun
temperature also decomposed the whole product, product of this batch was
become totally back and highly viscous.

up all the procedure but this batch was succeeded and got 3.3 ml of water
as side product but in coloured perspective failed, due to oxidization of the
product. Even that time we must carefully controlled temperature. But this
time also we didn’t have nitrogen atmosphere.

up all the procedure but this batch was gave 3.3 ml of water as byproduct
but this time also not got accurate coloured of product, the reason was
same as happened in batch 2.
Batch-4 and Batch-5:- was completely failed due to unidentified error but
it might be happened due to insufficient and inaccurate addition and
ISTAR-V.V.N. 25
temperature control during reaction, one accurate result was oxidization of

the batches. Acid value for batch -3 and batch-4 was determined but it was
too high and not accurate as needed.
Batch 6- This batch is taken as per all required conditions and did in the
presence of nitrogen atmosphere; nitrogen was perjured through 15% of
dilute H2SO4 solution. The addition of nitrogen initially fast in the RBF to
remove remain air. Mechanical stirred is provided accurately and addition
was taken preciously by measured substances with adequate weigh
balance. Initially the reaction carried out at lower temperature at which
water condensation taken placed in trace amount. The reaction of batch-6
was succeeded because produced water amount (3.50 ml) was almost near
to the theoretical calculation and the product was brown coloured; that is
not enough sufficient to desire colour of product but it was ok as per the
resources we had for Polyester polyol synthesis.
Figure 5
ISTAR-V.V.N. 26
2.3.4 Reaction:-
Phthalic acid
Castor oil p-TSA
N2
Figure 6 Phthalate polyester polyol
Polyester polyol was synthesised by Esterification reaction where

condensation of water taken placed as reaction proceed. On the basis of
theoretical calculation the amount of water should produce 3.60 ml.
The reaction taken placed on the hydroxyl group of ricinoleic acid (on
12th number of carbon) of the castor oil by phthalic acid. That reaction
initiated by para-toluene sulfonic acid, it has ability to withdraw
electrons from substrate and it has also ability to protonate substrate.
Function of p-toluene sulfonic acid is to liberate H + ion and prevents
reaction and breaking of the double bond between 9 th and 10th number of
carbon of castor oil, so it control the site of reaction.
2.3.5 Analytical Methods
ISTAR-V.V.N. 27
Following analysis method was carried out after preparation of

Polyester Polyol:-
 Acid value
 Viscosity determination
 Fourier transform infrared spectroscopy (FTIR)
 Gel permission chromatography (GPC)
Acid value:-
Acid number is defined as the number of milligrams of potassium
hydroxide (KOH) required for neutralizing the acid in 1 gram of sample
(mg of KOH/ g of Polyester polyol).
Acid value determines the amount of free acid group present in the
sample;[3]
To measure the acid value of any polyester, we have to prepare the
alcoholic KOH solution of known normality. It is made in water and for
confirmation we can standardize this solution with 0.1N succinic acid.
Now this solution fill in burette, and known amount of sample is taken in
conical flask. This sample is dissolve in 25 ml of acetone. By using
phenolphthalein indicator, titrate against alcoholic KOH solution. It give
the colorless to light pink color change.4
V ( KOH )∗Conc . of KOH soultion∗mol . weigh of KOH

AV = Weigh of sample taken
Figure 7
ISTAR-V.V.N. 28
Viscosity:-
• Molecular weight of Polyesters polyol can be determined by

different techniques such as Gel Permeation Chromatography
(GPC), Static Light Scattering (SLS) and intrinsic viscosity
measurement.
• Determination of molecular weight by intrinsic viscosity

measurement is a simple method for characterization of Polyesters
polyol.
• Different concentrations of Polyesters polyol were prepared and

measurement was done at room temperature.
• Product Solubility with acetone is more preferable.
• The flow time data was used to calculate the intrinsic viscosity by
extrapolating the reduced viscosity to zero concentration.
• The value of intrinsic viscosity was then recalculated into the

viscosity-average molecular weight using Mark-Houwink equation.
• The intrinsic viscosity, η as function of average molecular weight,

M is represented by Mark-Houwink- Sakurada equations.
η = KMα
ISTAR-V.V.N. 29
• Where; K and α are constants for a given polymer–solvent–

temperature system.
Figure 8 Viscosity determination
FTIR:-
• In this method the Polyester polyol is dissolved in a solvent which

can be easily vaporized, after the solvent preparation the NaCl film
is prepared.15
• Now this sample is spread over the NaCl film and rest it to become
dry then it again cover by another NaCl film and this sample is
subjected to the FT-IR instrument.18
ISTAR-V.V.N. 30
• By the analysis of result we can find the functional groups present

in the sample.
• The functional groups are determined by their wavenumbers, which

were found in graphical form.
atic and aromatic
dicarboxylic acids are

valuable materials in polymer
technologies.
3–5
Among them are low-
molecular-
weight oligomeric derivatives
of phthalic and
terephthalic acids that are
widely used in high-
strength and rigidity
ISTAR-V.V.N. 31
foams.
4,6
The use of aromatic acids
offers many
advantages to polymer
mechanical characteristics,
high thermal stability,
resistance to major chemical
solvents, and low flam-
m
GPC:-
• An easy way to measure molecular weight of sample.

• GPC that separate molecules in a polymers by size and provide
molecular weight distribution of material.
• Dissolve in appropriate solvent.
• Inject than with flow of mobile phase.
• Stationary phase contain porous particles which lead to separation
by molecular weight.
ISTAR-V.V.N. 32
Figure 9 GPC instrument block diagram
3.0 Result and discussion
 Effect of temperature:-
Table 1
No Time Temperature (°C) Acid value
1. 140 15.18
2. 160 6.24
6 hour
3. 180 6.38
4. 200 Product decomposed
By changing in this temperature there is improvement in the acid value of

the polyester polyol up to 1700C temperature. But still they were not
satisfactory. In between 155 to 165°C temperature we got the optimum
temperature at which the reaction can carry out with getting good and
maximum product.
ISTAR-V.V.N. 33
 Effect of reaction time:-
Table 2
No Time (hr.) Temperature Acid value
1. 4 160°C 14.38
2. 5 10.61
3. 6 8.87
In esterification process for polymer manufacturing is long reaction time

process but it is also important to carry it out at proper condition to obtain
the maximum yield and quality
Batch of 4 and 6 hour give optimum result at 160 0C but with changes in
time we got not satisfied result, but still 6 hr. Of reaction gave suffice
result
ISTAR-V.V.N. 34
Viscosity:-
• Viscosity and molecular weight have a direct relation, generally
viscosity of the product is increases as product molecular weight
increases.
• It was determined by Mark-Houwink- Sakurada equations.
η = KMα
K and a has values are 6.8×10-5 and 0.71 respectively.
Table 3
Sr. No. Conc. (C) Time (sec.) η = t/t0 ηsp = (η – 1) ηred = ηsp/C
1. Solvent 8.80 0 - -
2. 0.2 % 8.88 1.018 0.018 0.031
3. 0.4 % 8.94 1.028 0.028 0.033
4. 0.6 % 9.00 1.032 0.032 0.036
5. 0.8 % 9.04 1.058 0.058 0.037
6. 1.0 % 9.08 1.079 0.079 0.045
ISTAR-V.V.N. 35
Figure 10- Graph for reduced η v/s concentration
ISTAR-V.V.N. 36
Graphical representation of intrinsic viscosity of η red v/s concentration is

used to determined η value on y-axis by interception line.
η = KMα
η= intrinsic viscosity
0.028 = 6.8× [M]0.71
411.764 = [M]0.71
[M] = [411.764]1/0.71
M = 4802.03 gm/mol.
Molecular weight of polyester polyol was 4802.03 gm/mol achieved by

using Ostwald’s viscometer.13
Determined molecular weight for polyester polyol was not exactly
matched with molecular weight determined by GP but it seem near to
result of GPC value.21
Acid value and molecular weight have also direct relation.

If the acid value decreased which shows the acid gets react with alcohol
and forming a high molecular weight product.
Characterization of Polyester polyol:-
The characterization for the product para nitro benzyl bromide was confirmed by
two different analytical techniques:
1. FTIR
2. GPC
ISTAR-V.V.N. 37
•
• The IR spectra of saturated polyester resin can be seen in last figure,
where the different function group show their peak in the graph.
There is some variation in location of peak due to absorption by
other function group.
• Ester group(C=O) shows the strong peak at range of 1730-1750

cm-1, where it is detect at 1738.371cm -1. Which is perfectly matches
and shows the presence of the ester group in compound.
• C-O group form the peak in range of 1000-1200cm-1, in between

two peaks- detected at the 1075.76cm-1 and 1097.70cm-1.
• C-H/C-C-H (sp3) shows the strong peak at range of 2850-2960cm-1,

where it was detected at 2924.61cm-1.
• Saturated ester R-COO –R’ group has streaching wavenumber is

around 1735cm-1 , we got peak near it at 1738.31
• Presence of Aromatic is confirmed by 1561.20cm-1 because C=C

Ar. has peak range 1500-1600cm-1 in between.
• Ester Aromatic R-COO –Ar is confiremed by 1706.48 (Strong).
• -OH group for polyol in polyester polyol did not detected because
sample was prepared by using NaCl plate instead of KBr, which
make the test somehow unreliable.
ISTAR-V.V.N. 38
GPC:-
Molecular weight:-
ISTAR-V.V.N. 39
• A characteristic GPC chromatogram showing most typical MW

values.
• The highest value of MW is 52395.6 and least one is 485.4
• Average MW value is 3959.8 polyester polyol shown by GPC
analysis.
General properties:-
 Boiling point:----------------------------------------------More than 3000C
 Colour: ----------------------------------------------------------Dark brown
 Physical phase: -----------------------------------------Viscose thick liquid
 Density of taken castor oil:-----------------------------------0.958 gm/cm3
 Bulk density of Polyester polyol:-----------------------------0.975 gm/ml
4.0 Applications of polyester polyol
• The most important segments of polyester polyol applications are

those of polyurethane elastomers, flexible foams, coatings,
adhesives, rigid foams, synthetic leather, and sealants.8
• In pharmaceutical and agriculture industries for Microencapsulation
of drugs and ingredients. 12
• Polyurethanes are usually synthesized by isocyanate reactions with
polyester polyols which has superior characteristics.
• They find use in building and construction, consumer products,
furniture and fixtures, transportation and in industrial applications
with PU.15
• Properties including good mechanical characteristics, high thermal
stability, resistance to major chemical solvents, and low
flammability achieved by cross linking with polymers.
• In urethane resin application as support expansion.
ISTAR-V.V.N. 40
Conclusion
Castor oil based Phthalate polyester polyol was prepared by esterification
utilizing para toluene sulphonic acid as catalyst and Castor oil and
Phthalic acid as main raw material with. Temperature and inert
atmosphere play very crucial role. It’s important significant in
polyurethanes industries, adhesive industries, paint industries, coating,
and Urethane resin application as support expansion. Process has no
much long reaction time but unless oxidation is not taking place, it is one
of the drawback. At the end product has brown-black colored with high
viscosity achieved. FTIR data analysis comparison was confirmed
product’s function groups while analysis of GPC shows Molecular
Weight of the product, both analyses successfully studied.
ISTAR-V.V.N. 41
Future Aspects
 Green polyols and bio polyols are eco -friendly alcohol solutions
containing multiple hydroxyl groups.
 Green polyol is derived from recycled polyethylene terephthalate and
polyurethane while bio polyol is extracted from different vegetables oil
canola castor and corn polyether polyols and polyester polyols are the two
primary type of green polyol and bio polyol which are commonly used.
 These products are used in series of applications such as adhesive
sealants coatings and polyurethane foams (flexible & rigid). Different end
user consumers of these polyols include packaging construction
transportation furniture and carpets among others.21
 The demand for green and bio polyols market has been majorly growing
from cretins end user industries such as transportation and construction.
 Several growth factors such as availability of raw materials and
increasing price of crude oil leading to price rise in conventional polyol
have contributed to the growth of the market.
 Other factors such as the lower carbon footprint have also lead to a
higher sustainability for green polyols and bio polyols.
 Where soybean and corn are the commonly used ram material to
manufacturers bio polyol future market growth is expected to be from
emerging region such as assai pacific with growth of the end user
industries such as automotive and packaging which are also expected to
provide growth opportunities to the market.18
ISTAR-V.V.N. 42
References
1. Sperling, Leslie Howard. Introduction to physical polymer science. John Wiley &
Sons, (2005).
2. Vallombroso, Thomas. Organic chemistry: Pearls of wisdom. Jones & Bartlett
Learning, (2007).
3. Competence Center Titration; Metrohm International Headquarters; Determination
of the acid value, hydroxyl value, and isocyanates in raw materials for the fabrication
of plastics by automatic potentiometric titration.
4. Van Krevelen, Dirk Willem, and Klaas Te Nijenhuis. Properties of polymers: their
correlation with chemical structure; their numerical estimation and prediction from
additive group contributions. Elsevier,(2009).
5. www.wikipedia.org/wiki/Dicarboxylicacid
6. Kadkin, Oleg, et al. "Polyester polyols: synthesis and characterization of diethylene
glycol terephthalate oligomers." Journal of Polymer Science Part A: Polymer
Chemistry 41.8 ; (2003)
7. Engels, Hans‐Wilhelm, et al. "Polyurethanes: versatile materials and sustainable
problem solvers for today’s challenges." Angewandte Chemie International
Edition 52.36 (2013)
8. Vinay R. Patel1–3, Gerard G. Dumancas4–6, Lakshmi C. Kasi Viswanath5, Randall
Maples7 and Bryan John J. Subong8; “Castor Oil: Properties, Uses, and
ISTAR-V.V.N. 43
Optimization of Processing Parameters in Commercial Production” Academica
(August 9, 2016);
9. Vinay R Patel, Gerard G. Dumancas, Lakshmi C . Kasi Viswanath, Randall Maples
and Bryan John J. Subong. Castor oil: properties, Uses, and Optimization of
Processing parameters in Commercial Production. Published by Libertas Academica.
August 9 , 2016
10. University of Yalova, Department of Polymer Engineering, 77100, Yalova,
Turkey, Hürkimsa Chemical Industry, Çayirova, Kocaeli, Turkey “Synthesis and
Characterization of Bio-Based Polyester Polyol” ( November 19, 2016)
11. Konda Reddy Kunduru, Arijit Basu, Moran Haim Zada, Abraham J Domb,
Hebrew University of Jerusalem “Castor Oil-Based Biodegradable Polyesters”
Article in Biomacromolecules (August 2015)
12. Norzita Yacob, Norhashidah Talip, Maznah Mahmud, Nurul Aizam Idayu
Mat Sani, Nor Akma “Determination of Viscosity-average Molecular weight of
chitosan using intrinsic viscosity measurement” ; Malaysian Nuclear Agency (Nuclear
Malaysia) Bangi, 43000 KAJANG, MALAYSIA; (2009)
13. www.wikipedia.org/wiki/poise
14. Konda Reddy Kunduru, Arijit Basu, Moran Haim Zada , and Abram J.
Domb. Castor oil- Based Biodegradable Polyesters.ACS publications. August 24,
2015
15. Dr.J.N. Gurtu . Amit Gurtu, Important Facts in experimental chemistry.
Pragati prakashan publishers. Third Edition 2007Mithat celebi. Synthesis and
ISTAR-V.V.N. 44
characterization of Bio-based polyester polyol.Published yalova universities.
December 2016
16. Martin Alberto masuelli. "Mark-Houwink parameters for aqueous-Soluble
polymers and biopolymers at various temperature"Intrinsic
viscosity.macromolecular. January 2014
17. Ibrahim. Esterification reaction for novel synthesis castor based polyester.
Volume 3 issue 12 December 2014. Www.ijsr.net
18. Milan M vyas, Vishal S Makadia, Ankur P Shukla. Preparation of polyester
polyols by modifying the ricinoleic acid of castor oil. Volume 3 issue 05 May 2016
19. L.H .sperlling, J.A. Manson, Devia - Manjarres. Tough Plastic based on
castor oil elastomer- Reinforced Vinyl polymers .March. 3, 1981
20. Oleg Kadkin Kazan (Volga Region), Federal University. Karol Osajda, Piotr
Kaszynski, Thomas A. Barber Journal of Polymer Science Part A Polymer
Chemistry (J Polymer Sci Polymer Chem) April 2003
21. Van Krevelen, Dirk Willem, and Klaas Te Nijenhuis. Properties of polymers:
their correlation with chemical structure; their numerical estimation and prediction
from additive group contributions. Elsevier, 2009.
22. George magnus, Melvin Loeb, Robert J. Wood; Self-compatibilizing
phthalate-based polyester polyol. July 15,1985
23. Parker, Sybil P. Fluid mechanic source Book 1st edition 1988
ISTAR-V.V.N. 45
Declaration
I hereby declare that this project work entitled “Synthesis and
characterization of polyester polyol obtained from Renewable resource ,”
is a presentation of my original research-project work and has not
submitted to any other university or college for any award. Wherever
contributions of others are involved, every effort is made to indicate this
clearly, with due reference to the literature, and acknowledgement of
collaborative research and discussions.
ISTAR-V.V.N. 46
THANK YOU
ISTAR-V.V.N. 47

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Polyester Polyol Project 2018-19

Synthesis and characterization of polyester polyol obtained

Submitted for partial fulfilment of the requirement for

Under the guidance of

(Department of Industrial Chemistry)

It is to certify that, Mr. Jagrat D. Sevak (17IC27) has

Dr. MANDAR KARVE Dr. JIGAR V. PATEL

It is to certify that, Mr. Jaimin V. Patel (17IC28) has

Dr. MANDAR KARVE Dr. JIGAR V. PATEL

It is to certify that, Mr. Devendra Jadav (17IC12) has

Dr. MANDAR KARVE Dr. JIGAR V. PATEL

It is to certify that, Mr. Neel Patel (17IC12) has successfully

Dr. MANDAR KARVE Dr. JIGAR V. PATEL

It is to certify that, Mr. Hiren Patel (17IC26) has successfully

Dr. MANDAR KARVE Dr. JIGAR V. PATEL

It is to certify that, Mr. Kashyap Gohil (17IC37) has

Dr. MANDAR KARVE Dr. JIGAR V. PATEL

“manufacture process of polyester polyol from phthalic acid and

We sincerely thank to ISTAR VALLABH VIDHYANAGAR.

Sr. No. Content Page No.

1.Introduction and processes..........................................................

The main objective of this work was to synthesize linear saturated

Keywords:- Castor oil; Polyester polyol; renewable resources; polyesterification;

1.1. Aim of work

“Looking to ease availability of castor oil in India, it was utilized as

1.2. Process introduction

Fatty acid/oil is renewable resources and environmentally sustainable.

During polyester polyol synthesis all process parameters handle preciously.

Polyester polyols from renewable resources were successfully synthesized

1.3 Importance of Polyester polyols

11 strength and rigidity

28 strength and rigidity

2.0 Materials and methods

2.1.1 Raw materials:-

2.2 Raw materials:-

2.2.1 Castor oil:-

2.2.2 Phthalic acid C6H4(CO2H)2 :-

It is an isomer of isophthalic acid and terephthalic acid. Although

It is a white solid that is soluble in water, alcohols, and

When a carboxylic acid is treated with an alcohol and an acid catalyst, an

2.3.2 Condensation Reaction:-

2.3.3 Experimental method:-

 Para toluene sulphonic acid is used as the catalyst.

 Xylene used as solvent.

Consistently adding nitrogen through perjured was done by dissolving

stirred approx 50 rpm is incorporated by motor to centre of RBF, which

Esterification of Castor oil with Phthalic acid

Figure 4 - Assembly arrangement for esterification

Batch 1- complete assembly settled as per available sources, and followed

Batch 2- complete assembly settled as per available sources, and followed

Batch 3- complete assembly settled as per available sources, and followed

temperature control during reaction, one accurate result was oxidization of

Figure 6 Phthalate polyester polyol

Polyester polyol was synthesised by Esterification reaction where

Following analysis method was carried out after preparation of

V ( KOH )∗Conc . of KOH soultion∗mol . weigh of KOH

• Molecular weight of Polyesters polyol can be determined by

• Determination of molecular weight by intrinsic viscosity

• Different concentrations of Polyesters polyol were prepared and