Polyeter Polyol Project 2018-19

A
PROJECT REPORT
ON
“Bio based polyester polyol from castor oil”
A
DISSERTATION THESIS
Submitted for partial fulfillment 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. HIREN PATEL (17IC26)
Mr. NEEL PATEL (17I57)
Mr. KASHYAP GOHIL (17IC36)
Mr. KRUNAL PATEL (12IC28)

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CERTIFICATE
This is to certify that the project entitled "Bio
based polyester polyol from castor oil " towards
the partial fulfilment of the requirement for the
degree of Master of Science in Industrial
Chemistry of the Sardar Patel University,
Vallabh Vidhyanagar is the record of the work
carried out under supervision and guidance.
The results embodied in this dissertation to the
best of my knowledge have not been submitted to
any University/Institution for award of any degree.
__

_____________________
Dr. MANDAR KARVE
(Project Guide)
(Professor of Industrial Chemistry Department,
ISTAR)

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Acknowledgement

We sincerely thank INSTITUTE OF SCIENCE AND

TECHNOLOGY FOR ADVANCED STUDIES AND RESEARCH,
VALLABH VIDHYANAGAR. For giving us an opportunity to that
kind of research at such a stage of my 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 director Dr. Jigar patel for
permission and extending help when required throught out the work
at ISTAR.
We wishfully acknowledge the invaluable support given by Dr. Rohit
Dave, Dr.Nirmal kumar patel.
We also acknowledge the service of Mr. Minesh Patel and Mr.
Pinakin Patel (Lab Assistants), Mr. Raju Rathod and Navin bhai
(Non-technical staff of the department).
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 thank full to all those who have help
us in what so ever manner in our project throughout the year.

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INDEX
Table of contents
1. Certificates.............................................................................01
2. Abstract..................................................................................
3. Preface
4. Acknowledgment
5. Introduction
 Aim of work
 Basic processes definition
 Importance of PPPyol
 Chemicals and Equipment
6. Descriptions of raw materials
7. Synthesis rout
8. Method and Experiment
9. Analysis methods
10. Result and discussion
11. References
12. Future aspects
13. Declaration
Factors Affecting polyester polyol Production

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 Polyeter Polyol Project 2018-19

Abstract
Bio-based resource usage has been increased due to limited petroleum
resources, environmental concerns and ensuring sustainability.
The main objective of this work was to synthesize linear unsaturated
polyester polyols by polyesterification reaction from dicarboxylic acids
and diols. The process conditions were optimized by the temperature
profile and also inert atmosphere.
During the experimental production of each polyester polyol synthesis the
process, parameters were controlled. A special attention was paid to the
determination of the convention procedures such as determination of acid
as well as viscosity.
Polyester polyols are based on oil and aromatic dicarboxylic acids are one
of the most important materials in polymer technologies. Here phthalic
acid based polyester polyol was prepared from bio-based resource castor
oil and Phthalic acid. This Bio-based polyester polyols from renewable
resources were successfully synthesized with different molecular weight at
low acid value. In addition, the properties of the bio-based polyester
polyols were compared with petroleum-based analogues. The process can
carried out at optimum conditions and required very less time. Problem
arose when reaction carried out in the presence of oxygen; it leads to
black-brown colour to PPPyol so nitrogen mandatorily purged to reaction
mass. The most important segments of polyester polyol applications are
those of polyurethane elastomers, flexible foams, coatings, adhesives, rigid
foams, synthetic leather, and sealants. 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.

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

polyesterification; poly urethanes

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1.0 Introduction

1.1 Aim of the work:-

To synthesis the rout of the production of the bio-based
polyester poyol from castor oil at optimum temperature and
pressure.

1.2 Condensation Reaction:-

A condensation reaction is a class of an organic addition
reaction that proceeds 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.

1.3 Easterification:-
It is the process of forming esters from alcohol and carboxylic
acids. An ester is when a carbon is connected to two oxygen,
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. Here is the general formula for an
ester ('R' refers to a carbon chain).

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1.4 Polymerization process:-

Polymerization, any process in which relatively small molecules,
called monomers, combine chemically to produce a very large
chainlike or network molecule, called a polymer. The monomer,
molecules may be all alike, or they may represent two, three, or
more different compounds. Usually at least 100 monomer
molecules must be combined to make a product that has certain
unique physical properties—such as elasticity, high tensile
strength, or the ability to form fibres—that differentiate polymers
from substances composed of smaller and simpler molecules;
often, many thousands of monomer units are incorporated in a
single molecule of a polymer
1.5 Project description
Polyester polyols based on aliphatic and aromatic dicarboxylic acids are
one of the most important materials in polymer technologies. 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. Vegetable oils and their
derivatives have been widely used for the production of various polymers
including polyols. Vegetable oil derivatives, such as fatty acids, fatty acid
esters, and crude glycerol, can be obtained via hydrolysis or
transesterification of vegetable oils. Polyols properties comparable to
those of petroleum-based analogs have been prepared from vegetable oils
and their derivatives for various applications such as foams, coatings and
adhesives, etc.
Project has been worked on production of polyester polyols was carried
out by using dicarboxylic acids and polyol from renewable resources with
the presence of a catalyst.

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This polyester polyol can be produced by several chemical those contains

dicarboxylic acid group.

There is list of some dicarboxylic acid below:-

Malic acid Phthalic acid
o-phthalic acid

Tartaric acid Isophthalic acid

m-phthalic acid

Oxaloacetic Terephthalic acid

acid p-phthalic acid

Aspartic acid Diphenic acid

Biphenyl-2,2′-
dicarboxylic acid

α- Oxalic acid
hydroxyGluta
ric acid

Arabinaric Malonic acid

acid

Acetonedicar Succinic acid

boxylic acid

α- Glutaric acid
Ketoglutaric
acid

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Glutamic Adipic acid

acid

The above all di-acids can useful for polyester polyol, but due to
commercial easy availability and cheap price of phthalic acid our project is
carried out by this.
This process can carry out very fast and easily by phthalic anhydride due
to extra electron withdrawing Oxygen present so reactivity toward
alcoholic group presence in the castor oil is quick, but in this project it did
not used because it is banned by government of india.
The acid which is used in this process is phthalic acid whose react with
castor oil in the presence of para-toluenesulfonic acid as catalyst and
xylene incorporated as medium of solvent due to its easy solvasity for
castor oil.

Polyester polyols
1,2
based on aliphatic and
aromatic
dicarboxylic acids are
valuable materials in
polymer
technologies.
3–5
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Among them are low-

molecular-
weight oligomeric
derivatives of phthalic and
terephthalic acids that are
widely used in high-
strength and rigidity
polyesters and polyurethane
foams.
4,6
The use of aromatic acids
offers many
advantages to polymer
properties including good

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 Polyeter Polyol Project 2018-19

mechanical characteristics,
high thermal stability,
resistance to major chemical
solvents, and low flam-
mability.
1.6 Importance of PPPyols

2 Polyester polyols
3 1,2
4 based on aliphatic and
aromatic
5 dicarboxylic acids are
valuable materials in
polymer
6 technologies.
7 3–5

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8 Among them are low-

molecular-
9 weight oligomeric
derivatives of phthalic and
10 terephthalic acids that are
widely used in high-
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

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16 mechanical characteristics,
high thermal stability,
17 resistance to major
chemical solvents, and low
flam-
18 mability.
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

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25 Among them are low-

molecular-
26 weight oligomeric
derivatives of phthalic and
27 terephthalic acids that are
widely used in high-
28 strength and rigidity
polyesters and polyurethane
29 foams.
30 4,6
31 The use of aromatic acids
offers many
32 advantages to polymer
properties including good

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33 mechanical characteristics,
high thermal stability,
34 resistance to major
chemical solvents, and low
flam-
35 mability.
Polyester polyols based on aromatic dicarboxylic acids 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
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.
looking for alternatives to reduce carbon footprint bio based PPPyol
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.

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2.0 Raw materials and Equipment required during

project

2.1 Chemicals:-
Sr. Chemicals Grade Sr. Chemicals Grad
1. Castor Oil LR 6. Acetone LR
2. Phthalic Acid LR 7. KOH LR
3. Xylene LR 8. Succinic Acid LR
4. p-toluenesulfonic Acid LR 9. TPP LR
5. Sulphuric Acid LR 10. Water LR

2.2 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

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3.0 Descriptions of main raw materials

3.1 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.
Boiling point - 308 °C
The ricinoleic acid triglyceride has the structural formula as :-

3.2 Phthalic acid:-

3.3 Xylene:-
3.4 p-toluene sulphonic acid:-

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Many dicarboxylic acids will react with castor oil to yield an elastomeric
products, polyesters and polyester polyols.
Castor oil has been known for its medicinal value since ancient times. It
contains 90% ricinoleic acid, which enables direct chemical transformation into
polyesters without interference of other fatty acids. The presence of ricinoleic
acid (hydroxyl containing fatty acid) enables synthesis of various
polyester/anhydrides. In addition, castor oil contains a cis-double bond that can
be hydrogenated, oxidized, halogenated, and polymerized. Castor oil is
obtained pure in large quantities from natural sources; it is safe and
biocompatible.

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1. Synthesis method of castor oil polyester polyols, characterized by

comprising the steps of: (1) Castor oil and small molecular diols, in
Catalyst 130 ° C~180 ° C the reaction 2~3h, then the temperature was
lowered 1OO ° C~120 ° C,

Viscosity and molecular weight:-

Sr. No.Conc. (C) Time (sec.) η = t/t0 ηsp = (η – 1) ηred = ηsp/C

1. Solvent
2. 0.2 %
3. 0.4 %
4. 0.6 %
5. 0.8 %
6. 1.0 %

Acid value:-
Sr. No. Time interval (min) Burette reading Acid value
1. 0-30
2. 15
3. 15
4. 15
5. 15
6. 15
7. 15
8. 15
9. 15

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Malonic acid

Succinic acid

Glutaric acid

Adipic acid

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