POLYMERIZATION CHEMISTRY OF EPOXY RESIN

The term “epoxy” has been widely adapted for many uses beyond fiber reinforced polymer
composites. Today, epoxy adhesives are sold in local hardware stores, and epoxy resin is used as
the binder in countertops or coatings for floors. The different uses of epoxy continue to expand,
and variants of epoxies are constantly being developed to fit the industries and products they are
used in. Some applications of epoxy include: (1) general purpose adhesives, (2) binder in cement
and mortars, (3) rigid foams, (4) non-skid coatings, (5) solidifying sandy surfaces in oil drilling,
(6) industrial coatings, (7) potting and encapsulating media, (8) fiber-reinforced plastics.

Epoxy resins are a highly versatile family of synthetics used as binders for coatings, adhesives,
sealants and matrices for composite materials, or fiber-reinforced plastics. Those products are in
turn used in many applications, such as wind turbines, construction and civil engineering, autos,
aerospace, flooring, piping, packaging, electronics, sport and leisure, and household appliances.
They can be mixed with a variety of curing agents, opening a world of possibilities to enhance
durability, reliability, and safety.

Epoxy is classified as a thermosetting polymer resin. This type of resin is a wide class of
prepolymers and polymers that contain at least one epoxy group, usually referred to as oxirane or
glycidyl group. Depending on the end use, the chemistry of the polymer resin may be adjusted to
optimize the molecular weight or viscosity required. The chain length and purity grade of the cured
epoxy resin is dependent on the type of reaction that occurred to produce said resin, resulting to
either a low-molecular liquid with honey-like viscosity or a high-molecular solid substance.

Low molecular epoxy resins with a molecular weight of 380 will be fluid at room temperature,
while resins with a molecular weight of 1000 and beyond will be solid. This number is also
indicative to calculate the amount of hardener to use when curing the resin. Low molecular epoxies
can be handled without solvents and are used for castings, thick coatings, gap-filling glues, etc.
High molecular epoxy resins can be dissolved in organic solvents to become manageable and are
mostly used for paints and lacquers. In their solid form they are often employed as powder
coatings.
Epoxies may form through either the reaction between a hardener and an epoxy resin or by reacting
the resin with itself. A commonly known formulation of glycidyl epoxy resin is through the
reaction between Bisphenol-A and epichlorohydrin. Another commonly used epoxy is the novolac
based epoxy resin.

The performance of epoxy resins are optimized only through curing. These resins are cured in the
presence of a curing agent, usually known as a hardener. The curing of epoxy resins often require
a high ratio resin to hardener, usually a 1:1 ratio or a ratio of 2:1. Most epoxy resins are industrial
products derived from petroleum and are products of a reactive process that involve epoxide units.
The resin may be fortified through the addition of thermoplastic polymers. There are two general
types of epoxies: the glycidyl epoxy, and the non-glycidyl. Glycidyl epoxies can further be
classified into glycidyl-amine, glycidyl ester, and glycidyl ether, whereas non-glycidyl epoxies are
either aliphatic or cyclo-aliphatic resins.

Epoxy resins are also measured by its epoxide number, which based on its epoxide content. The
number represents the amount of epoxide found in 1 kilogram of resin or the equivalent weight,
which is the weight of the resin containing 1 mole equivalent of epoxide.

References
Epoxy Europe. (n.d.). Chemistry basics. Retrieved from Epoxy Europe.

Johnson, T. (2018, June 22). Epoxy Resin. Retrieved November 5, 2018, from Thought Co. Web
site: https://www.thoughtco.com/what-is-epoxy-resin-820372
 The most popular epoxy monomers are those derived from the reaction of bis(4 - hydroxy
phenylene) - 2,2 propane (called bisphenol A) and 1 - chloroprene 2 - oxide (called
epichlorohydrin), in the presence of sodium hydroxide. The structure of the major product,
bisphenol A diglycidyl ether (DGEBA or BADGE) and its condensed forms (Table 1.1 a), is
dependent upon the stoichiometry of the reactants. Typical monomers ( “ resins ” ) are marketed
with n values lying in the range 0.03 – 10. At room temperature these monomers are crystalline
solids for n values close to zero, liquids for n values up to n = 0.5, and amorphous solids (glass
transition temperature, Tg ∼ 40 – 90 ° C) for higher n values.
Epoxy polymers can be produced by step or chain polymerizations or, eventually, by a
combination of both mechanisms. Step - growth polymerization proceeds via a step - by - step
succession of elementary reactions between reactive sites. Each independent step causes the
disappearance of two co - reacting sites and creates a new covalent bond between a pair of
functional groups. The number of reactive sites per monomer (functionality) and the molar ratio
between co - reactive sites are the main parameters that control the polymer structure. To obtain
linear polymers, the reactants must be bifunctional; monofunctional reactants interrupt the polymer
growth. A condition to obtain crosslinked polymers is that at least one of the monomers has a
functionality higher than 2. The molar mass of the product grows gradually and the polydispersity
tends to 2 for a linear polymer; for a crosslinked polymer the mass - average molar mass becomes
infi nite at a critical conversion (gelation). Chain - growth polymerization is characterized by the
presence of initiation, propagation, chain transfer and termination steps. In the case of epoxies, the
initiation step produces an ion (either an anion or a cation) that is called the active center of the
polymerization. The ion may be generated by a chemical reaction or by an adequate source of
irradiation. Once active centers are generated they produce primary chains by the consecutive
addition of monomers through the propagation step of the reaction. As active centers are always
present at the end of primary chains, the propagation reaction continues until it becomes
interrupted by a chain transfer step or a termination step. The main parameters controlling the
polymer structure are the functionality of monomers, the molar ratio between initiator and
monomers, the concentration of species that are involved in chain transfer steps, and temperature
(thermal cycle) that affects the relative rates of different steps.
Step Growth Polymerization Epoxy
Groups can react with amines, phenols, mercaptans, isocyanates or acids. Amines are the
most commonly used curing agents/hardeners for epoxides and the case of step - growth
polymerizations is mainly represented by epoxy - amine reactions. Epoxy groups react with
primary and secondary amino hydrogens (NH):
Chain Homopolymerization
Epoxy groups can react with both nucleophilic and electrophilic species. Thus both Lewis
acids and bases are able to initiate the chain polymerization of epoxy monomers [1] . Commonly
used initiators (often named “ catalytic ” curing agents in the literature) include tertiary amines,
imidazoles, or ammonium salts for anionic chain polymerization, and boron trifl uoride complexes,
complex aromatic salts of Lewis acids such as diaryl iodonium, triarylsulfonium, or arene
diazonium for cationic chain polymerization. Propagation proceeds through an alkoxide (anionic
polymerization) or an ozonium (cationic polymerization):

.
Manufacturing of Epoxy Resin

Most common epoxy resins are produced from a reaction between epichlorohydrin (ECH) and
bisphenol-A (BPA), though the latter may be replaced by other raw materials (such as aliphatic
glycols, phenol and o-cresol novolacs) to produce specialty resins. (Guichon Valves)

These resins are synthesized by the condensation reaction of bisphenol A (4,4 (propane-2,2-diyl)
diphenol) and epichlorohydrin in the presence of sodium hydroxide catalyst. In 1960, Lee and
Neville as well as Wallace, developed the well-known construction of a product called the
diglycidyl ether of bisphenol A (DGEBA). (Paluvai, 2014)
 The epoxy resins can be obtained in either liquid or solid states. The two processes are
similar. Firstly ECH and BPA are charged into a reactor. A solution of 20-40% caustic soda is
added to the reaction vessel as the solution is brought to the boiling point. (Guichon Valves)

Generally, the reaction occurs at 110oC for about 16h with an excess of epichlorohydrin,
and the resulting resin has terminal epoxy groups. Low molecular weight resins are produced by
increasing 10 to 20 mol epichlorohydrin per mol of bisphenol A. (Paluvai, 2014)

Most of the commercial DGEBA epoxies are low in molecular weight with high reactive
functional groups and high cross-linking density, which improves the glass transition temperature.
High molecular weight resins are generally semisolids, and they need to be melted for
compounding. These resins have more hydroxyl groups in their backbones, which provide greater
adhesion when cured with hardeners. (Paluvai, 2014)

After the evaporation of unreacted ECH, the two phases are separated by adding an inert
solvent such as methylisobutylketone (MIBK). The resin is then washed with water and the solvent
is removed by vacuum distillation. The producers will add the specific additives to create a formula
that lend special properties such as flexibility, viscosity, color, adhesiveness, and faster curing,
depending on a particular application. (Guichon Valves)
Works Cited
Guichon Valves. (n.d.). Epoxy resins – Manufacturing process of Epoxy resins. Retrieved 2018,
from Guichon Valves: http://guichon-valves.com/faqs/epoxy-resins-manufacturing-process-of-
epoxy-resins/

Paluvai, N. R. (2014). Modifications of Epoxy Resins and Their Composites: A Review.

Polymer-Plastics Technology and Engineering , 1723-1758.

Pascault , J.P. , Sautereau , H. , Verdu , J. , and Williams , R.J.J. ( 2002 ) Thermosetting

Polymers , Marcel Dekker , New York .

Mat eˇ jka , L. , Chabanne , P. , Tighzert , L. , and Pascault , J.P. ( 1994 ) J. Polym. Sci., Part A:
Polym. Chem. , 32 , 1447 .

Leukel , J. and Burchard , W. ( 1996 ) Macromol. Rapid Commun. , 17 , 359

 Adamson University
College of Engineering
Chemical Engineering Department

TECHNICAL ELECTIVES 2-
PAINTS AND COATINGS
MWF 4:00-5:00

SUBMITTED BY:

Name Course Student No.

Arciaga, Tristan Jedidiah A. BS ChE 201413528

Cruz, Juan Miguel M. BS ChE 2014

Granados, Paul Dillon A. BS ChE 2014

Perey, Patricia Jane L. BS ChE 2014

SUBMITTED TO:
Engr. Jerry G. Olay

November 07, 2018