COVENANT UNIVERSITY

COLLEGE OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMISTRY
COURSE TITLE: POLYMER TECHNOLOGY
COURSE CODE: CHM423
UNIT: 2
SESSION: 2019/2020
LECTURER: A. A. Akinsiku (PhD)
STUDIES OF MAJOR THERMOSETTING RESINS

INTRODUCTION

Resins are polymers made by repeatedly linking discrete molecules (monomers) together to
form chains or networks. The word plastic is a common name used for many synthetic
materials or semi-synthetic nature. Many plastic items are manufactured synthetically
relating to packaging, clothing, automobiles, electronics, aircraft, medical supplies etc.
Plastics are used in appliances and technology today. Plastic can be classified to
thermoplastics and thermosetting plastics (thermosets) based on their behaviour and
structures.

Thermosetting resins

Thermosetting resins are polymers which do not soften under heat and pressure and cannot
be remoulded or recycled. They are often incinerated to remove them from the environment.
Thermosets have cross-linked or network structures with covalent bonds between molecules.
Once solidified by the cross-linking process, they cannot be re-melted or reshaped. Since
thermosets cannot be-remelted, engineers use them in applications that require high
resistance to heat; they are also used as fillers.
Thermosetting resins are brittle materials whose load-bearing qualities can be improved by
reinforcing with fibres instead of wood and steel. Fibres are a better choice because of their
excellent chemical resistance, strength to weight ratio and weatherability properties.
Common examples of thermosetting resins include epoxy resins, phenolics, amino plastics,
silicones, unsaturated polyester resins, alkyd, vinyl esters, urethane, furfural and many more.

1. EPOXY RESINS

Epoxies are thermosetting polymer where the resin molecule contains one or more epoxide
groups which are very reactive to many substrates. There are two primary types of epoxies,
glycidyl epoxy and non-glycidyl. Glycidyl epoxy resins are glycidyl-amine, glycidyl ester or
glycidyl ether, while the non-glycidyl epoxy resins are either aliphatic or cyclo-aliphatic resins.
Epoxy resins are used extensively as reinforced composites, adhesives, high-performance
coatings and potting and encapsulating materials. Under the influence of heat or catalysts,
thermosetting resins change irreversibly. The material formed is insoluble, covalently cross-
linked and thermally stable networks.

1
One of the most common glycidyl epoxy resins is created using Bisphenol-A and is synthesised
in a reaction with epichlorohydrin. The other frequently used type of epoxy is known as
novolac based epoxy resin. Epoxy resin can be "toughened" with the addition of thermoplastic
polymers.

The epoxide resins (also widely known as epoxy resins and, occasionally, as ethoxylate 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 unit, 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 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.

Epoxy resins are cured with the addition of a curing agent, which is commonly called a
hardener. Perhaps the most common type of curing agent is amine-based. Unlike in polyester
or vinyl ester resins where the resin is catalysed with a small (1-3%) addition of a catalyst,
epoxy resins usually require the addition of the curing agent at a much higher ratio of resin
to hardener, often 1:1 or 2:1.

The properties of epoxy can be altered and tweaked to fit the desired need.

Epoxy resins are superior to polyester resins in many ways; they are stronger and stiffer, bond
more effectively to fibres, possess minimal cure shrinkage, and have much higher service
temperatures.

There is, quite clearly, an extensive range of epoxy resins, and the non-epoxy 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. Similar remarks also apply to
the chain extension/cross-linking agents, so that cross-linked products of great diversity may

2
be obtained. About half of epoxide resin production is used for surface coating applications,
with the rest divided approximately equally between electronic applications (particularly for
printed circuit boards and encapsulation), the building sector and miscellaneous uses. In
tonnage terms consumption of epoxide–fibre laminates are only about one-tenth that of
polyester laminates, but in terms of value, it is much greater.

The properties of the cross-linked resins depend very significantly on the curing system used
and on the type of resin. The most characteristic features of industrial materials are their
toughness, low shrinkage on cure, high adhesion to many substrates, excellent alkali
resistance and versatility in the formulation.

The first and still the most important class of commercial epoxy resins is the reaction product
of bis-phenol A (BPA) and epichlorohydrin in the presence of sodium hydroxide. It is called
the diglycidyl ether of bis-phenol A (DGEBA).

Diglycidyl ether of bis-phenol-A (DGEBA)

Another type of epoxy resin is a high molecular weight resin. It is prepared by reducing the
excess of epichlorohydrin and reacting under strongly alkaline conditions. The non-epoxy part
of the molecule may be an aliphatic, cyclo-aliphatic or aromatic hydrocarbon. It may also be
non-hydrocarbon and polar. Addition of curing agents results in an insoluble and intractable
thermoset. Properties of epoxy resin can be modified by introducing solvents, plasticisers,
accelerators, diluents, etc. Epoxy resins are cured with the addition of a curing agent, which
is commonly called a hardener. The most common type of curing agent is amine-based.
Examples of harders are anhydrides (acids), amines, polyamides, dicyandiamide, etc.

3
Example 2: The reaction of diepoxy and the diamine

When two parts are mixed, e.g. diepoxy and diamine, they react in a way that links all the
diepoxy and diamine molecules together in a crosslinked network like this:

Characteristics of epoxy resins

Epoxy resins have found a broad range of application, mainly because the proper selection of
resin, modifiers, and a cross-linking agent allows the properties of the cured epoxy resin to
be tailored to achieve specific performance characteristics. This versatility has been a
significant factor in the steady growth rate of epoxy resins over the years. Besides this
versatility feature, properly cured epoxy resins have other attributes:

1. Excellent chemical resistance, particularly to alkaline environments.

2. Outstanding adhesion to a variety of substrates.
3. Very high tensile, compressive, and flexural strengths.
4. Low shrinkage on cure.
5. Excellent electrical insulation properties and retention thereof on ageing or exposure to
difficult environments.
6. Remarkable resistance to corrosion.
7. A high degree of resistance to physical abuse.
8. Ability to cure over a wide range of temperatures.
9. Superior fatigue strength.

4
Applications

Epoxies are frequently used in aerospace and defence, chemical plant and high-performance
automotive applications. It is also used as the resin matrix to hold the fibre in place efficiently.
It is compatible with all conventional reinforcing fibres including fibreglass, carbon fibre,
aramid, and basalt. Further applications for epoxy resins are extensive and include:

• Adhesives.
• Paints and coatings.
• Application as composite materials in carbon fibre and fibreglass reinforcements.
• Industrial tooling and composites.
• Electrical systems and electronics.
• Consumer applications.
• Marine applications.
• Aerospace applications.
• Biology.
• Art.

2. PHENOLIC RESINS

Phenolic resins were the first polymeric resins produced commercially from simple low
molecular weight compounds. They are also widely known as phenol-formaldehyde resins, PF
resins and phenoplasts. Phenol formaldehyde (PF) resins are prepared by the
polycondensation between phenol and formaldehyde in the presence of either an acid or a
base catalyst. The initial phenol-formaldehyde reaction products may be of two types,
novolacs and resols. The reaction of phenol with less than equimolar proportions of
formaldehyde under acidic conditions gives novolac resins containing aromatic phenol units
linked predominantly by methylene bridges. Novolac resins are thermally stable and can be
cured by cross-linking with formaldehyde donors such as hexamethylenetetramine. Bakelite
is a trademarked phenolic plastic, revolutionized the market for moulded and laminated parts
for use in electrical equipment.
Preparation of phenolic prepolymers from aromatic phenol and formaldehyde;

(a) several possible structures can be formed as shown below;

5
(b) novolacs result during acid catalysis

(c) resol result from an excess of formaldehyde and alkaline catalysis.

However, resoles are the most widely used phenolic resins for composites. They are
manufactured by reacting phenol with a higher than the equimolar amount of formaldehyde
under alkaline conditions. Besides, resoles are mostly hydroxymethyl functional phenols or
polynuclear phenols. Unlike novolac, they are low-viscosity materials and more comfortable
to process. Phenolic resins can also be prepared from other phenols such as cresols or
bisphenol. The general formula is:

Phenolics are of particular interest in structural applications owing to their inherent fire-
resistant properties. This high level of intrinsic flame resistance often means that no further
flame retarding is necessary to create composites having required performance levels.
However, their main disadvantages are low toughness and a curing reaction that involves the
generation of water. The water produced during curing can remain trapped within the
composite, and during a fire, steam can be generated, which can damage the structure of the
material. This evolution is complemented by that produced chemically during the first step of
thermal degradation, which may be because of phenol-phenol condensation, as shown
below:

6
The released water then helps in the oxidation of methylene groups to carbonyl linkages,
which then decompose further, releasing CO, CO2, and other volatile products to yield char
ultimately.

In the case of highly crosslinked material, water is not released until above 400°C, and
decomposition starts above 500°C. This was the case for all the phenolic resin samples. The
amount of char depends upon the structure of phenol, initial crosslinks and tendency to
crosslink during decomposition, and the primary decomposition products are methane,
acetone, carbon monoxide, propanol and propane.

Where phenolic resins require flame-retardant treatment, additive and reactive flame
retardants can be used. Tetrabromobisphenol A, various organic phosphorus compounds,
halogenated phenols and aldehydes (e.g. p-bromobenzaldehyde) are some of the reactive
flame retardants used for phenolics. Phosphorus can be introduced by direct reaction of the
phenolic resin with phosphorus oxychloride. Likewise, inorganic compounds such as boric acid
may be incorporated into the phenolic resin by chemical reaction. Chlorine compounds (e.g.
chloroparaffins) and various thermally stable aromatic bromine compounds may be utilised
as an additive flame retardant, and antimony trioxide is usually added as a synergist. Suitable
phosphorus compounds include halogenated phosphoric acid esters such as tris(2-
chloroethyl) phosphate, halogenated organic polyphosphates, calcium and ammonium
phosphates. Zinc and barium salts of boric acid and aluminium hydroxide also find a frequent
application. To suppress the afterglow of phenolic resins, compounds like aluminium chloride,
antimony trioxide and organic amides are used.

Novolac Resins

An acidic catalyst and a molar excess of phenol to formaldehyde are conditions used to make
novolac resins. The following simplified chemistry illustrates the full range of polymers
possible. The initial reaction is between methylene glycol and phenol.

7
The reaction creates a methylene bridge at either the ortho position or the para position of
the phenolic aromatic rings. Branching occurs because the reaction can occur at any of three
sites on each ring. As the reaction continues, the random orientations and branching quickly
result in an extremely complex mixture of polymers of different sizes and structures. The
reaction stops when the formaldehyde reactant is exhausted, often leaving up to 10% of un-
reacted phenol. Distillation of the molten resin during manufacturing removes the excess
phenol and water.

The final novolac resin is unable to react further without the addition of a cross-linking agent.
novolac resins come with and without a curing agent. The most common phenolic resin cross-
linking agent is hexamethylenetetramine, also known as hexa, hexamine, or HMTA. Due to
the bond angles and multiple reaction sites involved in the reaction chemistry, the resulting
polymer is not a long straight chain but rather a complex three-dimensional polymer network
of extreme molecular weight. This tightly cured bonding network of aromatic phenolics
accounts for the cured materials' hardness, and heat and solvent resistant properties.

Novolac resins made with catalysts tend to cure more rapidly than the standard randomly
linked resins. Novolac resins are amorphous (not crystalline). As they are most typically used,
they are solid at room temperature and will soften and flow between 150° and 220°F (65°C -
105°C). Novolac resins are soluble in many polar organic solvents (e.g., alcohols, acetone), but
not in water.

8
 Resol Resins

A basic (alkaline) catalyst and, usually but not necessarily, a molar excess of formaldehyde is
used to make resol resins. The following two stages describe a simplified view of the reaction:
First, phenol reacts with methylene glycol to form methylol phenol:

Methylol phenol can react with itself to form a longer chain methylol phenolic:

or form dibenzyl ether:

or react

with phenol to form a methylene bridge.

The most
important point in resol resin chemistry is that, when an excess of formaldehyde is used, a
sufficient number of methylol and dibenzyl ether groups remain reactive to complete the
polymerization and cure the resin without incorporation of a cure agent such as hexa.

For this reason, the industry commonly refers to resol resins as "single-stage" or "one-step"
type products. Resol resin manufacture includes polymerizing to the desired extent, distilling
off excess water and quenching or tempering the polymerization reaction by rapid cooling.
Because resol resins continue the polymerization reaction at even ambient temperatures,
albeit, at much slower rates than during manufacturing, they demonstrate limited shelf lives
dependent on the resin character, storage conditions and application.
Resol resins are usually water-soluble to a certain degree.

9
Applications

Phenolics are not only strong, but they also have one of the highest elastic moduli of
conventional plastics and also have good fire resistance. They are excellent wood adhesives
for plywood and particleboard because they form chemical bonds with the phenol-like lignin
component of wood. They are used for a wide variety of applications, such as moulding
powders, laminating resins, adhesives, binders, surface coatings and impregnates. Phenolic
resins in adhesive and bonding applications include:

(1) Insulation materials.

(2) Fibrous and granulated wood.
(3) Foundry and shell moulding.
(4) Friction materials.
(5) Bonded and coated abrasives.

3. POLYESTER RESINS
Polyester resins are thermosets which may be classified into alkyds, unsaturated polyesters,
vinyl esters, allyl resins etc.

Unsaturated polyesters

Unsaturated polyester resins were the first type of matrix material to be used with glass fibres
to make polyester GRP (glass reinforced plastics) materials. The resins are cheap, easy to work
and cure at room temperature. They are still the most widely used matrix materials useful in
making trays, shower stalls, boats, swimming pool, water tanks etc.
These thermosets are the condensation products of unsaturated acids or anhydrides and diols
with/without diacids. The unsaturation present in this type of polyesters provides a site for
subsequent cross-linking:

When cross-linking is initiated with the help of a catalyst and accelerator styrene, the co-
reactive diluent facilitates cross-linking at the sites of unsaturation in the polyester chains.
For example, in thermoset products, where the resultant resin is blended with styrene for
cross-linking, and a small amount of peroxide as initiator. General-purpose unsaturated
polyester resins were prepared by using maleic anhydride, phthalic anhydride and propylene
glycol with the molar ratio of phthalic anhydride: maleic anhydride ranging from 1:2 to 2. For
example:

10
Characteristics
The main features of the unsaturated polyester resins include:

• Poor linear shrinkage.

• Excellent wettability of the fibres and charges.
• Minimisation of the effect of sagging in vertical stratification (thixotropic properties)
• Solid, after cross-linkage.
• Exceptional lightness
• Rigidity
• Good electrical insulation
• Dimensional stability against temperature changes
• A higher strength/weight ratio than steel
• Resistance to chemicals
• Excellent surface finish
• Resistance to wear and high temperatures
• Good mechanical resistance

Applications
Unsaturated polyester includes are used in:

• Composite materials
• Wood paints
• Flat laminated panels, corrugated panels, ribbed panels
• Gel coat for boats, automotive and bathroom fixtures

11
 • Colouring pastes, fillers, stucco, putties and chemical anchoring
• Self-extinguishing composite materials
• Quartz, marble and artificial cement

Bibliography

1. J. A. Brydson, Plastic materials 6th edition, Butterworths Heinemann, Oxford (1995).

2. A. A. Collyer, Ed. Rubber Toughened Engineering Plastics, Chapter 6, Chapman & Hall,
London (1994).
3. S. Alessi, A. Spinella, E. Caponetti, C. Dispenza, G. Spadaro. Radiation Physics and
Chemistry, 81(9),1328-1331 (2012).
4. Y.K. Su, in Comprehensive Semiconductor Science and Technology, 2011.
5. Polymers for aerospace structures, in Introduction to Aerospace Materials, 2012.
6. J.A. Brydson, in Plastics Materials (Seventh Edition), 1999.
7. D. J. Allen, H. Ishida, in Encyclopedia of Materials: Science and Technology, 2001.
8. A. R. Horrocks, B. K. Kandola, in Design and Manufacture of Textile Composites, 2005.
9. Z. B. Dholakiya. Use of non-traditional fillers to reduce the flammability of polyester
resin composites; Polimeri; 30 (1), 2009, 10-17.

12