Maharashtra Institute of Technology, Aurangabad

Affiliated to

Dr. Babasaheb Ambedkar Marathwada University Aurangabad

Course: Polymeric Materials-I

T. Y. B. Tech. (Plastic and Polymer Engineering) Semester-V
 Unit-III – Epoxies
• Structure-properties relationship, properties and application of
Epoxies
• References:
• Plastics Materials, J.A.Brydson, Seventh Edition, Butterworth-
Heinemann
• PLASTICS MATERIALS AND PROCESSES -A Concise
Encyclopedia, Charles A. Harper, Edward M. Petrie, Wiley-
Interscience
• PAINT AND SURFACE COATINGS Theory and Practice Second
edition, Editors: R LAMBOURNE and T A STRIVENS
Some Applications of Epoxy Resin
 Introduction
• The epoxide resins (also widely known as epoxy
resins and, occasionally, as ethoxyline resins) are
characterised by the possession of more than one 1,2-
epoxy group (I) per molecule.
• This group may lie within the body of the molecule
but is usually terminal.
• The three-membered epoxy ring is highly strained and is reactive to
many substances, particularly by with proton donors, so that
reactions of the following schematic form can occur:

• Such reactions allow chain extension and for cross-linking to occur

without the elimination of small molecules such as water, i.e. they
react by a rearrangement polymerisation type of reaction.

• In consequence these materials exhibit a lower curing shrinkage

than many other types of thermosetting plastics.

• There is, quite clearly, scope or a very wide range of epoxy resins.
The nonepoxy part of the molecule may be aliphatic, cycloaliphatic
or highly aromatic hydrocarbon or it may be non-hydrocarbon and
possibly polar. It may contain unsaturation.
• Epoxy resins are characterized by the epoxide group
(oxirane rings), which make these resins cross-
linkable.
• The most widely used resins are diglycidyl ethers of
bisphenol A (DGEBA). These are made by reacting
epichlorohydrin with bisphenol A in the presence of
an alkaline catalyst.
• By controlling the operating conditions and varying
the ratio of the epichlorohydrin to bisphenol A,
products of different molecular weights can be
made.
• For liquid resins, n (see Fig. E.1) is normally less than
1; for solid resins, n is 2 or greater. Solids with very
high melting points have n values as high as 20.
• The resins in this group range from low-viscosity liquids to
solid resins melting up to 175°C. Generally the higher the
melting point, the less curing agent is needed.
• The cured properties of all these resins are similar, but the
toughness increases as the melting point increases.
• Although most of the DGEBA epoxies are light amber,
transparent, colorless epoxies are available for optical
embedments.
• The electronic industry demands epoxy resins with
minimum ionic contamination, particularly sodium and
chlorine. Most manufacturers supply DGEBA epoxy with
less than 100 ppm ionic contaminants and some with less
than 1 ppm chlorine and sodium.
• Chlorinated or brominated bisphenol A is used to produce flame-resistant epoxies. These are
nowadays used in many applications like

(i) Structural laminates

(ii) Electrical laminates
(iii)Potting and encapsulation compounds
(iv)Adhesive and coatings

• As the halogen content increases, the viscosity generally increases.

• Epoxies have also been synthesized that contain high weight percents of fluorine.

• They can be used with silicone amines to yield products with very low moisture pickup, 0.25% at
20°C.

• These materials are extremely stable on high temperature exposure and during outdoor weathering.

• Epoxy resins based on biphenyl F have some important advantages over the bis A epoxies.

• Compared with bis A epoxies, bis F epoxies have a lower room-temperature viscosity; a
crystallization time twice as long; better resistance to sulfuric acid, acetone, and methanol; but at
twice the price.

• The cured epoxy bis F is generally tougher than bis A epoxy cured with the same curing agent, but it
will have a lower glass transition temperature, (Tg).
• Another class of epoxy resins is the novolacs,
particularly the epoxy cresols and the epoxy phenol
novolacs.

• These are produced by reacting a novolac resin,

usually formed by the reaction of o-cresol or phenol
and formaldehyde with epichlorohydrin.

• These highly functional materials are particularly

recommended for transfer molding powders,
electrical laminates, and parts in which superior
thermal properties, high resistance to solvents and
chemicals, and high reactivity with hardeners are
needed.
• The novolacs cure more rapidly than DGEBA resins and have higher
exotherms.

• The cured novolacs have higher heat deflection temperatures than DGEBA
resins.

• They have excellent resistance to solvents and chemicals. Novolacs also

have excellent electrical properties, which are retained at high service
temperatures.

• Another group of epoxy resins, the cycloaliphatics, is particularly

important when superior arc track and weathering resistance are
necessary requirements.

• A distinguishing feature of cycloaliphatic resins is the location of the epoxy

group(s) on a ring structure rather than on an aliphatic chain.

• Cycloaliphatics can be produced by the peracetic epoxidation of cycle

olefins and by the condensation of an acid such as tetrahydrophthalic
anhydride with epichlorohydrin, followed by dehydrohalogenation.
• Cycloaliphatic epoxy resins have
– superior arc-track resistance,
– good electrical properties under adverse conditions,
– good weathering properties,
– high heat deflection temperatures
– good color retention.

• Brominated epoxies have all the other characteristics

of the resins in the epoxy family, and in addition they
are relatively flame resistant because of the bromine
constituents in the molecular structure.
Typical reactions of the epoxide group
Typical grades of bisphenol epoxide
resins and properties
 Monomers and chemical commonly
used for preparing epoxy prepolymer
1.Bisphenol
–Bisphenol A
–Bisphenol F (higher crystallinity, better
heat resistance,but also more expensive)
2.Epichlorohydrin
3.Catalyst (such as NaOH)
PREPARATION OF RESINS FROM BIS-PHENOL A

• The first, and still the most important, commercial

epoxide resins are reaction products of bis-phenol A and
epichlorhydrin.
• Other types of epoxide resins were introduced in the late
1950s and early 1960s, prepared by epoxidising
unsaturated structures.
• The bis-phenol A is prepared by reaction of the acetone
and phenol as shown above.
• Phenol and acetone are available and the bis-phenol A
is easy to manufacture.

• Bisphenol A is comparatively inexpensive. This is one of

the reasons why it has been the preferred dihydric
phenol employed in epoxide resins manufacture.

• Since most epoxide resins are of low molecular weight

and because colour is not particularly critical the
degree of purity of the bis-phenol A does not have to
be so great as when used in the polycarbonate resins.

• Bis-phenol A with a melting point of 153°C is

considered adequate for the most applications whilst
less pure materials may often be employed
• Epichlorohydrin, the more expensive compound is derived from
propylene by the sequence of reactions shown below. The material
is available commercially at 98% purity and is a colourless mobile
liquid.
• Many of the commercial liquid resins consist essentially of the
low molecular weight diglycidyl ether of bis-phenol A together
with small quantities of higher molecular weight polymers.
• The formation of the diglycidyl ether is believed to occur in
the manner shown in the below mentioned figure, the
hydrochloric acid released reacting with the caustic soda to
form sodium chloride.
 Typical laboratory scale preparation
• 1 mole (228g) of bis-phenol A is dissolved in 4 moles (370g) of
epichlorohydrin and the mixture heated to 105-110°C under an
atmosphere of nitrogen.

• The solution is continuously stirred for 16 hours while 80g (2

moles) of sodium hydroxide in the form of 30% aqueous solution is
added dropwise.

• A rate of addition is maintained such that reaction mixture remains

at a pH which is insufficient to colour phenolpthalein.

• The resulting organic layer is separated, dried with sodium sulphate

and may then be fractionally distilled under vacuum.
Overall Reaction………..
Polymerization mechanism
BPA anion react with epichlorohydrin
The reaction is continued
Formation of epoxy prepolymer
• It appears, at first glance, that diglycidyl ether would be
prepared by a molar ratio of 2: 1 epichlorohydrin-bis-
phenol A, probability considerations indicate that some
higher molecular weight species will be produced.

• Experimentally it is in fact found that when a 2:1 ratio is

employed, the yield of the diglycidyl ether is less than 10%.

• Therefore in practice two to three times the stoichiometric

quantity of epichlorhydrin may be employed.

• The diglycidyl ether has a molecular weight of 340. Many of

the well-known commercial liquid glycidyl ether resins have
average molecular weights in the range 340-400 and it is
therefore obvious that these materials are composed
largely of the diglycidyl ether.
• Higher molecular weight products may be obtained
by reducing the amount of excess epichlorohydrin
and reacting the more strongly alkaline conditions
which favour reaction of the epoxide groups with bis-
phenol A.
• If the diglycidyl ether is considered as a diepoxide
and represented as

• this will react with further hydroxyl groups

• It will be observed that in these cases hydroxyl groups
will be formed along the chain of the molecule.
• The general formulae for glycidyl ether resins may thus
be represented by the structure shown.
• When n = 0, the product is the diglycidyl ether, and the
molecular weight is 340.

• When n = 10 molecular weight is about 3000. Since

commercial resins seldom have average molecular
weights exceeding 4000 it will be realised that in the
uncured stage the epoxy resins are polymers with a low
degree of polymerisation.
• Care should be taken to remove residual caustic soda and
other contaminates when preparing the higher molecular
weight resins and in order to avoid the difficulty of washing
highly viscous materials these resins may be prepared by a
two-stage process.

• This involves first the preparation of lower molecular

weight polymers with a degree of polymerisation of about
three.

• These are then reacted with bis-phenol A in the presence of

a suitable polymerisation catalyst such that the reaction
takes place without the evolution of by-products.
 Characteristics
The epoxide resins of the glycidyl ether type are usually
characterised by six parameters :

(1) Resins viscosity (of liquid resin)

(2) Epoxide equivalent.
(3) Hydroxyl equivalent.
(4) Average molecular weight (and molecular weight
distribution).
(5) Melting point (of solid resin).
(6) Heat distortion temperature (deflection temperature under
load) of cured resin.
• Resin viscosity
an important property to consider in handling the resins.
depends on the
molecular weight,
molecular weight distribution
chemical constitution of the resin
presence of any modifiers or diluents.
Diglycidyl ethers are highly viscous materials with viscosities of about 40-100
poise at room temperature it will be appreciated that the handling of such viscous
resins can present serious problems.
• Epoxide equivalent
It is a measure of the amount of epoxy groups.
This is the weight of resin (in grammes) containing 1 gram chemical equivalent epoxy.
For a pure diglycidyl ether with two epoxy groups per molecule the epoxide equivalent will
be half the molecular weight (i.e. epoxide equivalent = 170).
The epoxy equivalent is determined by reacting a known quantity of resin with hydrochloric
acid and measuring the unconsumed acid by back titration.
The reaction involved is
• Hydroxyl equivalent
The hydroxyl equivalent is the weight of resin
containing one equivalent weight of hydroxyl
groups. It may be determined by many
techniques but normally by reacting the resin
with acetyl chloride.
• Molecular weight and molecular weight
distribution
May be determined by conventional
techniques.
As the resins are of comparatively low
molecular weight it is possible to measure
this by ebullioscopic and by end-group
analysis techniques.
• Melting point of the solid resins
This can be done either by the ring and ball technique
(https://www.youtube.com/watch?v=-yBXl4z70mI) or by Durrans
mercury method.

Durrans Mercury Method

a known weight of resin is melted in a test tube of fixed
dimensions. The resin is then cooled and it solidifies.
A known weight of clean mercury is then poured on to the top
of the resin and the whole assembly heated, at a fixed rate,
until the resin melts and the mercury runs through the resin.
The temperature at which this occurs is taken as the melting
point.

• The ASTM heat distortion temperature (deflection temperature

under load) test may be used to characterise a resin. Resins must,
however, be compared using identical hardeners and curing
conditions.
Effect of varying the reactant ratios on the molecular
weight of the epoxide resins.

•Solid resins have been prepared having a very closely controlled molecular weight
distribution. These resins melt sharply to give low-viscosity liquids.

•It is possible to use larger amounts of filler with the resin with a consequent
reduction in cost and coefficient of expansion, so that such resins are useful in
casting operations.
• Epoxies are one of the most versatile and widely
used thermosetting resins, especially in the
electrical/electronic industries.
• This is primarily because of the wide variety of
formulations possible and the ease with which
these formulations can be made and utilized with
minimal equipment requirements.
• Formulations range from flexible to rigid in the
cured state and from thin liquids to thick pastes
and molding powders in the uncured state.
• Conversion from uncured to cured state is made
by use of hardeners, heat, or both.
 Application
• The largest application of epoxies is in
– embedding applications (potting, casting,
encapsulating, and impregnating),
– in molded parts, and in laminated constructions
• such as metal-clad laminates for printed circuits and
unclad laminates for various types of insulating and
terminal boards.
• Molded epoxy parts have excellent dimensional
stability.

Ref: Plastics Materials, J Brydson, 7th Edition

• Epoxy resins may be cooked into alkyd formulations, replacing part of the polyol. They also find a place unmodified as a third component
in alkyd/MF compositions to upgrade the resistance properties of the films.

• Epoxy resins react with PF resins to form insoluble coatings, and well-formulated high molecular weight epoxy/PF coatings meet the
highest standards of chemical resistance. These products are suitable for the linings of food cans and collapsible tubes, coatings for steel
and aluminium containers, and wire enamels.

• Curing probably involves the formation of polyether links between the hydroxyl groups of the epoxy, and methylol groups present in PF
resins of the resole type; the epoxy also reacts with phenolic hydroxyl groups on the PF. With some PF resins, compatibility problems on
cold blending may be solved by pre-condensation, involving refluxing the epoxy and PF resins together in solution, when some reactive
groups combine, leaving the remainder free to react in the curing process.

• Urea/formaldehyde resins or melamine/formaldehyde resins may be used to cure epoxy resins, giving stoved films of paler colour, but
with a reduced level of chemical resistance compared with phenol/formaldehyde resins. Again, the higher molecular weight epoxy resins
are preferred.

• Two-pack epoxy/isocyanate finishes require separate solutions of high molecular weight epoxy resin and polyisocyanate adduct as the
two components; the epoxy resin must be in alcohol-free solvent since the curing reaction is predominantly with in-chain hydroxyl groups
on the epoxy resin. One-pack finishes can be formulated with blocked isocyanates.

• Epoxy resins may also be used in two-pack compositions with polyamines or polyamides [134].The films obtained possess outstanding
chemical resistance, hardness, abrasion resistance, flexibility, and adhesion. Low molecular weight solid epoxy resins are used
most.Though primary or secondary amines such as triethylenetetramine may be used, in order to avoid the toxic hazards involved in
handling amines, amine adducts with low molecular weight solid epoxy resin will nowadays be used as hardeners.

• These adducts are prepared by the reaction of excess of an amine such as diethylene triamine with an epoxy resin to produce fully amine-
terminated adduct. Reactive polyamide resins formed from dimerized fatty acids with diamine are also used.

• Reactive coal tar pitches may be incorporated into an epoxy resin base for curing with amine, amine adduct, or with a polyamide resin.
The derived coatings have excellent chemical resistance and are not brittle; they hence find use as pipeline, tank and marine coatings.

• Epoxy resin modification with a silicone resin is possible to enhance water resistance; epoxy/silicone combinations are used in blends
with other polymers with the cure mechanisms mentioned above.
• Epoxy resins are commercially used in coating and
structural applications.
• Through the proper selection of resin, modifier and
curing agent, the cured epoxy resin system can be
tailored to specific performance characteristics.
• The choice depends on cost, processing and performance
requirements.
• Cured epoxy resins exhibit
– excellent adhesion to a variety of substrates;
– outstanding chemical and corrosion resistance;
– excellent electrical insulation;
– high tensile, flexural and compressive strength,
– thermal stability;
– a wide range of curing temperatures and low shrinkage upon
cure.
• Versatile epoxy resins are used in various industrial
applications:
– Anticorrosion & antifouling Coatings
– honeycomb structure
– for paint brush bristles and for concrete topping
compounds
– body solders and caulking compounds for the repair of
plastics and metal boats
– for automotive springs and casting compounds
– abrasive & water lubricated conditions for pump
applications
– electrochemical sensing
– conducting adhesives as a lead free alternative in
electronic packaging
– electro conductive resins filled with graphite for casting
application
• Electronic packaging
• potentiometric sensor for perchlorate ions
• for fabrication of stamping dies
• patterns tooling
• Caulking (Caulk or caulking is a material used to seal joints
or seams against leakage in various structures and piping.
The oldest form of caulk consisted of fibrous materials
driven into the wedge-shaped seams between boards on
wooden boats or ships)
• salient compounds in building and highway construction
applications
• for cryogenic use
• high voltage
• composite insulator
• in applications where high orders of chemical resistance are
required.
Other applications include
• potting and encapsulating compounds as impregnating resins for aerospace
applications
• filament wound structure and tooling fixtures
• adhesives for aircraft
• aerospace textile composites
• composite materials in space environment for development of a moon base
• in high performance vehicle

Epoxy based solutions are used as

• maintenance and product finishes,
• marine finishes
• structural steel coatings
• tank coatings
• aircraft finishes
• automotive primers and furniture finishes
• decorative floor applications;
• chemical resistant mortar
• floor topping compounds
• in printing ink, dental and surgical applications
• for cholesterol level lowering agents
• for voltammetric sensors
• for humidity sensors
• for manufacturing the jet-printed LCD color filter
• in fuel cells
• for optical ammonia sensor
• for marine primer steel coating applications
• light weight chemical resistant foams
 Major suppliers
• Akzo Nobel Chemical Inc.;
• Ciba Specialty Chemicals;
• Cytec Fiberite Inc.;
• Dow Plastics;
• Epic Resins;
• Magnolia
• Plastics Inc.;
• Resyn Corp.;
• Shell Chemicals;
• Thermoset Plastics, Inc.;
• Union Carbide Corp.;
• United Resin Corp
 CURING OF GLYCIDYL ETHER RESINS
• Epoxy resins must be cured with crosslinking agents
(hardeners) or catalysts to develop desirable
properties.
• The epoxy and hydroxyl groups are the reaction sites
through which cross-linking occurs.
• Careful selection
• of the proper curing agent is required to achieve a
balance of application properties and initial handling
characteristics.
• Major types of curing agents are aliphatic amines,
aromatic amines, catalytic curing agents, and acid
anhydrides.
 Extra Compulsory Reading on Curing
• Curing Agents for Epoxy Resin, Three Bond
Technical News, Issued December 20, 1990

• Epoxy Resin – Introduction

• Raju Thomas, Christophe Sinturel, Sabu
Thomas, and Elham Mostafa Sadek El Akiaby