CHAPTER 1

1.1 INTRODUCTION

The 1 st production of epoxy resins occurred simultaneously in Europe and in the United
States in the late 1930s and early 1940s.Credit is most often attributed to Pierre Castan of
Switzerland and S.O. Greenlee of the united states who investigated the reaction of Bisphenol a
with epichlorohydrin. The families of epoxy resins that they commercialized were first used as
casting compounds and coatings. The term 'epoxy resin' is applied to both the pre-polymers and
to the cured resins; the former contain reactive epoxy groups, hence their name. In the cured
resins all of the reactive groups may have reacted, so that although they no longer contain epoxy
groups the cured resins are still called epoxy resins. Epoxy resins are a class of thermoset
polymers used extensively in structural and specialty composite applications because they offer a
unique combination of properties that are unattainable with other thermo-set resins. Available in
a wide variety of physical forms from low viscosity liquid to high melting solids, they are
amenable to wide range of processes and applications. The epoxy resins have steadily grown in
their use in the plastics and related industries due to the variety of forms in which they may be
processed. Epoxy resins are now produced in most of the developed countries of the world. In
India only few companies are manufacturing epoxy resins and their production is not sufficient
to meet the growing demand. The demand is mainly met by imports from either country,
Germany, U.K. Netherland, Belgium etc. Asia pacific represents the fastest growing regional
market for epoxy resins. The worldwide market for epoxy resin is slated to reach 3.03 million
tons by the year 2017. Epoxy resin is used in a wide range of fields,such as paints, electricity,
adhesives, coatings etc. this is because epoxy resin has excellent bonding property, mechanical
strength, chemical resistance, electrical insulation, ease of handling and processability. In
addition epoxy resin is able to have various different properties as it is combined and cured
together with various curing agents.
1.2.LITERATURE REVIEW
 CHAPTER 3

3.1. SYNTHESIS OF EPOXY RESIN

Epoxy resins are complex network polyethers usually formed in a two stage process.
The first stage involves a base-catalyzed step-growth reaction of an excess epoxide, typically
epichlorohydrin with a dihydroxy compound such as bisphenol A. The molar ratio of
epichlorohydrin to bisphenol A can range from as high as 10:1 to as low as 1.2:1.This produces
resins ranging from liquid to semisolid to solid and varying molecular weights and softening
points. The products are oligomers or prepolymers, which are hardly used as such; they have
pendant hydroxyl groups and terminal epoxy groups.

The pre-polymer may be a viscous liquid, generally for commercial epoxies, or a hard and tough
solid depending on the value of n. Other hydroxyl-containing compounds such as resorcinol,
glycol, and glycerol can also be used but commercial epoxy resins are based on bisphenol A. In
the second stage, a cross-linked network structure is formed by curing the prepolymer with
active hydrogen-containing compounds. These curing agents include polyamines, polyacids and
acid anhydrides, polyamides, and formaldehyde resins.
3.2.EXPERIMENTAL PROCEDURE:
The experimental set up consists of 2 neck round bottom flask, dropping funnel, magnetic stirrer,
condenser and magnetic stirred heater.

Fig 3.1:
10 gm of Bisphenol-A and 32.57 gm of epichlorohydrin is taken into the flask at a ratio
of 4:1. 5N aqueous solution of NaOH is prepared and taken in the dropping funnel from which it
is added drop-wise to the reaction as the solution is brought to the boiling point. Magnetic stirrer
is provided for the purpose of stirring. Heating is done with the help of heater and the reaction is
carried out at a temperature of 90-1100c. The reaction is carried out for about 3-4 hours.
 Fig 3.2:
After the reaction has been completed the product is taken out and kept in a separating
funnel. Into this 30ml of distilled water is also added and kept undisturbed for about 12 hours.
The purpose of adding distilled water is to wash the product in order to remove impurity since it
contains water molecules resulting in poly-condensation, un-reacted molecules etc. Two
separating layer is observed, the bottom layer is the organic layer while the water layer remains
above this layer. The bottom layer is then separated by opening the stopper through which it is
taken into a beaker and the remaining water in the funnel is drained out. But the organic layer
still contains traces of water. This water must be removed before the required compound can be
properly characterized. Therefore, two methods of drying solutions are commonly used,
saturated aqueous sodium chloride and solid drying agents.
By adding saturated aq sodium chloride to the organic solution in the funnel and shaking
the organic layer with brine the bulk of water can often be removed. The salt water works to pull
the water from the organic layer to the water layer. This is because the concentrated salt solution
wants to become more dilute and because salts have stronger attraction to water than to organic
solvents. As a result two layers get separated. The lower organic layer is drained off from funnel
and the aqueous layer is then disposed off.

Fig 3.
Final traces of water are removed by treating the organic solution with a drying agent. A drying
agent is an inorganic salt like sodium sulfate, calcium sulfate, magnesium sulfate etc. which
readily takes up water to become hydrated. Sodium sulfate has very high capacity of taking water
as it can absorb up to 10 water molecules to become sodium deca hydrate. It is less reactive, non
toxic and in granular form, is very easy to remove from liquids. Tetra-hydro furan solvent is also
added to soluble the organic layer and it is then filtered with the help of watt-man 41 filter paper
in order to remove sodium sulfate from the solution.
 Fig 3.5

The filtrate is then placed in the vacuum oven at 700c for 3-4 days to remove the tetra hydro-
furan solvent. The product obtained is a colourless gel liquid which is finally cured with hardener
poly-amido amine hardener.

3.3. Curing agents for epoxy resins:

curing is a term that refers to the toughening or hardening of a polymer material.In order
to convert epoxy resins to hard, infusible thermoset networks it is necessary to use crosslinking
agents. These cross linkers, hardeners or curing agents as they are widely known, promote
cross-linking or curing of epoxy resins. Curing can occur by either homo-polymerisation
initiated by a catalytic curing agent or a poly-addition or co-polymerisation reaction with a
multifunctional curing agent.
Curing agents are a significant part of epoxy resin product. Selecting the right curing agent is of
prime importance as it influences the viscosity, reactivity and working time of resins in general
and mechanical, chemical and optical properties specifically. Most commonly used curing agents
are amines which have several advantages over other curing agents. Amines are classified into
aliphatic, alicyclic and aromatic amines according to the type of hydrocarbons involved.
Aliphatic amine is curing agent, rapidly reacts with epoxy resin to cure at room temperature. On
the other hand aromatic amine has weaker basicity than aliphatic amines and slowly cures at
room temperature and requires thermal curing.

3.4. Film preparation:-

In making film for coating, the product is mixed with poly-amido amine hardener in different
proportions. Four proportions have been made mainly in weight ratios which are 1:1, 1:2, 2:1 and
1:4.
All of four mixtures are well mixed, keeping them in an ultra-sonicator at room temperature for
about 30 minutes. After mixing has done, these four mixtures are uniformly casted in four glass
slides and placed in a desicator connected with a vacuum pump. The vacuum is created by the
pump inside the desicator by pulling out the air and also removing the bubbles that could be
formed during curing process. The slides are then kept inside the desicator for 48 hours to be
cured well. After it has cured, the slides are put into the hot water where the temperature is
maintained at 700c. Finally the films are separated from the slides and it is then characterized
 CHAPTER

MATERIAL BALANCE

Bisphenol-A + Epichlorohydrin Epoxy Resin + Water

INPUT:-

Bisphenol-A:-10gm

Molecular weight -228

Therefore, moles of bisphenol –A = 10/228

=0.044 moles

No of hydroxyl groups present in Bisphenol -A = 2

No of hydroxyl groups present in 0.044 moles of Bisphenol -A= 2 0.044

= 0.088 moles

Epichlorohydrin:- 32.57 gm

Moleculer weight – 92.53

Moles of Epichlorohydrin = 4 0.088 moles

= 0.352 moles

Amount of epichlorohydrin = 0.352 92.53

= 32.57 gm

NaOH:- 3.52 gm

Moles of NaOH = Total moles of OH group = 0.088 mole

Distilled Water:- 17.6 gm

For 5N NaOH, Amount of water required = 3.52*5=17.6 gm

OUTPUT:-

Epoxy resin= 10.2 gm

 CHAPTER 4

EXPERIMENTAL RESULTS AND DISCUSSION

4.1.Characterization of uncured epoxy resin:

The generalized structure of bisphenol a type epoxy resins can be represented by the
structure formula. For solid resins the softening point and in general there are different species
present with different values of n, the number of structural units. A first approximation in
characterizing this resin is to determine the concentration of epoxy groups present since this is
needed to calculate the amount of hardener required. A similar consideration will apply to the
other types of epoxy resin that are commercially available. However, the composition of epoxy
resins is more complicated than that represented by the general structure and characterization
involves much more than only determination of the epoxy content. Thus, the most important
parameters that manufacturers of uncured epoxy resins provide as sales specifications include as
well as epoxy content, hydrolysable chlorine, specific gravity, color and for liquid resins t and a
solution viscosity are often specified. Some resin manufacturers give detailed instructions for
some analytical procedures; for instance Ciba Geigy (1988) give test methods for the
determination of epoxy content and readily hydrolysable and total chlorine contents. A detailed
treatment of the analysis of uncured resins is given by Urbanski (1977) with experimental details
of methods for the qualitative identification of epoxy resins and procedures for their quantitative
analysis. The characterization of uncured resins involves determination of their detailed
structure. One of the characterization techniques is FTIR Spectroscopy.
Fourier transform infrared spectroscopy (FTIR):- This is a technique used to obtain an
infrared spectrum of absorption or emission of a solid, liquid or gas which involves the
interaction of infrared radiation with matter. The working principle is mainly the vibration
energy which is measured in terms of percentage of transmittance. An FTIR spectrometer
simultaneously collects high-spectral-resolution data over a wide spectral range. The term
Fourier-transform infrared spectroscopy originates from the fact that a Fourier transform ( a
mathematical process) is required to convert the raw data into the actual spectrum. The IR
spectrum is visualized in a graph of infrared light absorbance or transmittance on the vertical
axis vs frequency or wavelength on horizontal axis. Typical units of frequency used in IR spectra
are reciprocal centimeters and units of IR wavelength are micrometers. Infrared spectroscopy
exploits the fact that molecules absorb frequencies that are characteristics of their structure.
These absorptions occur at resonance frequencies, i.e. the frequency of the absorbed radiation
matches the vibrational frequency.

120

100

80
Transmittance %

60

40

20

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Wavenumber (1/cm)

Discussion: From the graph as there is the epoxide group present in the sample, therefore the
product is epoxy resin.
Characterization techniques for cured resin as a film:
A)Thermo Gravimetric analysis (TGA):- Thermo gravimetric analysis (TGA) is one of the
members of the family of thermal analysis techniques used to characterize a wide variety of
materials. TGA provides complimentary and supplementary characterization information to the
most commonly used thermal technique, DSC. TGA measures the amount and rate (velocity) of
change in the mass of a sample as a function of temperature or time in a controlled atmosphere.
The measurements are used primarily to determine the thermal and/or oxidative stabilities of
materials as well as their compositional properties. The technique can analyze materials that
exhibit either mass loss or gain due to decomposition, oxidation or loss of volatiles (such as
moisture). It is especially useful for the study of polymeric materials, including thermoplastics,
thermosets, elastomers, composites, films, fibers, coatings and paints. TGA measurements
provide valuable information that can be used to select materials for certain end-use applications,
predict product performance and improve product quality. The technique is particularly useful
for the following types of measurements:
• Compositional analysis of multi-component materials or blends
• Thermal stabilities
• Oxidative stabilities
• Estimation of product lifetimes
• Effects of reactive atmospheres on materials
B)
.