Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

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PART 1: Chemistry of Epoxies

(including information on Novolac Epoxies and Epoxy Adducts)

PART 2: Underwater Epoxies

PART 3: Polyurethane Coatings

Your Host and Tour Guide:

Paul Oman, MS, MBA - Progressive Epoxy Polymers, Inc.

Member: NACE (National Assoc. of Corrosion Engineers), SSPC (Soc. of Protective Coatings)

"Professionals helping Professionals"

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

Return to Epoxy Index Page

tests of penetrating epoxies - CLICK HERE

Nonyl Phenol as an additive in epoxies - CLICK HERE

Underwater epoxies - Tech Article - CLICK HERE

Knowledge is Power - We like informed consumers!

Learn the basics of epoxy at our educational EPOXY 101 page - Click Here.

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Part 1: Epoxies

Epoxies consist of two components that react with each other forming a hard, inert material. Part A consists of
an epoxy resin and Part B is the epoxy curing agent, sometimes called hardener. Let's begin with taking a closer
look at the epoxy resin.

Epoxy resin begins with the reaction of two compounds, bisphenol A - Bis A -(or bisphenol F -Bis F- and/or
'Novolac' -(visit our novolac web page) used for superior temperature and chemical resistance) and
epichlorohydrin. Bisphenol A is the chemical product of combining one acetone unit with two phenol groups.
Phenol is a man-made chemical, although it is also found naturally in animal waste and decomposing organic
material. It was originally produced from coal tar and was named carbolic acid. Structurally it contains a
benzene ring with an attached hydroxyl (a carbon ring with an attached OH). Acetone is a organic ketone (.i.e.
it contains a carbonyl C=O group attached to two organic methyl groups) primarily used as a solvent or
chemical intermediate or raw material for many other products.

Nearly 70% of all epichlorohydrin is used in the production of epoxy resin. This colorless liquid with its
irritating chloroform like odor finds it way into the production process of various synthetic materials. Leading
producers are Dow Chemical (Texas) and Shell Chemical (Texas and Louisiana).

The reaction between bisphenol A and epichlorohydrin removes unreacted phenol and acetone and attaches two
glycidyl groups to the ends of the bisphenol A, creating a 'diglycidyl ether of bisphenol A (called DGEBA)',
which is standard epoxy resin. The glycidyl group on both ends of the bisphenol A are also referred to as an

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

oxirane or ‘epoxy group'. The size of the resulting molecule (and hence its molecular weight) depends upon the
ratio of epichlorohydrin to bisphenol A.

The ‘amine' curing agent has a molecular structure which typically consists of four hydrogen ‘arms and legs'.
These hydrogens react with the oxirane (epoxy group) ring unit on the ends of the epoxy resin. The result is a
new carbon-hydrogen bond, this time using the hydrogen from the curing agent and freeing the epoxy group's
hydrogen to unit with the group's oxygen to form an OH (hydroxyl) pendant. This hydroxyl group contributes
to the epoxy's outstanding adhesion to may substrates. The aromatic ring unit, which the hydroxyls attach to,
helps provide the epoxies positive thermal and corrosion properties.

Because there are at least four hydrogens on the curing agent they can react with four epoxy resin groups,
which causes giant interlocking structures (in a process known as ‘crosslinking').

Epoxy curing agents

The curing agent selection plays the major role in determining many of the properties of the final cured epoxy.
These properties include pot life, dry time, penetration and wetting ability. Curing agents come in many
different chemical flavors, generally based upon amines or amides. Some of the more common amines and
amides often listed in Material Data Safety Sheets (MSDS) include:

A) Aliphatic (carbon atoms forming open chains) and cycloaliphatic (ring structured aliphatics) amines and
polyamines. Amines are basically ammonia with one or more hydrogen atoms replaced by organic groups;

B) Amides and polyamides. Amides are basically ammonia with a hydrogen atom replaced by a carbon/oxygen
and organic group.

Amine based curing agents are considered to more durable and chemical resistant than amide based curing
agents but most have a tendency to ‘blush' in moist conditions. Blushing produces a waxy surface layer on
actively curing epoxy, the result a reaction with the curing agent and moisture in the air. Other potentially toxic
chemicals within the curing agent can also be released in the same manner, thus amines are often viewed in
light of these potential shortcomings. Amides, on the other hand, are more surface tolerant and less troubled by
moisture. More on Blushing.

Fortunately for epoxy end-users involved with underwater applications, there is a small subgroup of non-
benzene ring structured amines that maintain all the benefits of amines while removing the toxic leachability
and moisture attracting properties of typical amines. These special polyamines form the basis for today's cutting
edge underwater epoxies.

C) Cycloaliphatic curing agents. These curatives generally provide better water/moisture resistance,
weatherability, low blush and water spotting, and better chemical resistance. Cycloaliphatics there own web
page - CLICK HERE.

Cycloaliphatic chemistry explained by "The Chemist" - the hands-down expert on epoxies - in a

2/18/03 post on the Wooden Boat Forum --

"The cycloaliphatic structure refers to a six-member carbon-atom ring in the backbone of the curing
agent instead of carbon-carbon linkages between amines in some other curing agents such as West
or Sys. 3. The cycloaliphatic curing agents have the amine groups connected to the rings. Both use
Diglycidyl ether of Bisphenol-A as the major component of the epoxide curing agent, and both

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

contain benzyl alcohol, a volatile plasticizer which acts as a molecular lubricant and facilitates curing
[although systems with cycloaliphatic curing agents contain much more, typically 20-30%, as they
simply do not cure more than about half-way at room temperature without it.]

While the cycloaliphatic ring is resistant somewhat to Uv degradation, more that the carbon-carbon
linkages between amines in some other types of curing agents, both contain the aromatic ring
structure of diglycidyl ether of Bisphenol-A, which breaks down fairly readily on UV exposure, and
both contain amines; these give both molecular breakdown and yellowing all by themselves.

None of these structures should be considered UV-stable, even though the cycloaliphatic structures
are better than the aliphatic amine-structures in that regard."

Amines vs. amides in coal tar epoxies - CLICK HERE

How Epoxies Work

The well known adhesion of epoxies is due to the strong polar bonds it forms with the surfaces it comes in
contact with. On dry surfaces the bond between the surface and the epoxy displaces the air, which is a fluid. The
same is true underwater. As on dry surfaces, the polar bond attraction is strong enough to displace the fluid, in
this case the water, and produce an strong bond even underwater. Thus, painting underwater is, in theory, no
different that painting above the water. The crosslinking reaction of epoxies should be independent of the
surrounding environment. Still, as mentioned above, many or most curing agents will react with water
molecules rather than the epoxy base, resulting in a waxy layer, also mentioned above, known as amine blush.
This makes them unsuitable for underwater application.

At least one modern hydrophobic, underwater epoxy goes one step farther to ensure a strong underwater polar
bond with the introduction of a proprietary ‘bond enhancer'. This is important because many marine structures
are subjected to active cathodic protection systems. Such systems place an electrical charge on the structure's
surface that will literally and actively repel the epoxy's existing polar bonding surfaces. The enhancer provides
additional polar bond surfaces that are also firmly anchored into the crosslinking epoxy structure.

A more technical third-party article:

By: A. SEN. Consultant, Protective & Functional Coatings Bombay, INDIA.

Epoxy resins must be crosslinked in order to develop the coating's required characteristics. This crosslinking
process is achieved by chemically reacting the resin with a suitable curing agent or hardener. The reactive
groups of molecules in the epoxy resin formulations are the terminal epoxide groups and the hydroxyl groups.
For protective coatings, the principle crosslinking reaction is between the epoxide group and the curing agent.
Amine curing agents are the most common type used in epoxy formulations.

Primary amines are organic materials containing a nitrogen atom linked to two hydrogen atoms (-NH2). In
epoxy formulations, the active hydrogen of the amine is what reacts with the epoxide group of the resin. The
structure of the amine-containing organic compound and the number and type of amine groups in the
compound is what determine the rate of crosslinking and the coating's properties.

There are different types of polyamine curing agents: aliphatic, cycloaliphatic, aromatic, polyamine adduct, etc.

The aliphatic amines like EDA, DTA, & TETA contain short, linear chemical chain between amine groups.

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

Coatings produced with them tend to have highly crosslinked layers with good resistance to heat and chemicals,
including solvents. However, they are rather brittle and possess poor flexibility & impact resistance. Because of
their reaction with moisture, they are not suitable for use under damp conditions.

Modified cycloaliphatic amines from IPDA are probably the most used curing agents for epoxy resins today.
Because of their low viscosities, they can be used in low VOC coatings. They produce coatings with a fast cure
rate, short pot life and are also suitable for low temperature cure. They provide very good resistance to
chemicals, solvents & water, which makes them suitable for use in portable water tanks.

In the aromatic amines, the amine group is separated by rigid benzene rings rather than flexible chains of
molecules as in the aliphatic amines. Coatings produced with them have good physical properties like impact
resistance as well as high resistance to heat and chemicals. But being aromatic in nature, they produce dark
coatings. They are used to produce chemical & solvent resistant coatings. And particularly when they are
formulated with epoxy novolac & phenolic epoxy resins, they produce coatings that can resist high
temperatures. Aromatic amines are generally modified for use as curing agents, which although reduces their
heat resistance are still good for chemical resistance. They have good resistance to water and hence work well in
damp conditions & low temperatures.

One common modification to aliphatic amines is to form a polyamine adduct by reacting the curing agent with a
small amount of epoxy resin. This gives high molecular weight polyamines that produce coatings with low
vapour pressure, with more practical mixing ratios and less formation of amine bloom than the simple aliphatic
amines. Adducting has little effect on other properties. Polyamine adducts can be prepared from either aliphatic
or aromatic polyamines.

Polyamides are formed by the reaction of aliphatic polyamines and dimer acids of either tall oil fatty acids or
from soya or castor oil. Here again adducting polyamides is common and produce coatings with good low
temperature curing and reduced tendency for amine bloom. Good colour and good chemical resistance can be
achieved using these adducted polyamides. They generally produce coatings with excellent adhesion, water
resistance & flexibility. Unmodified polyamides produce coating layers that are much more open in terms of
their chemical structure because of their large distances between amine groups in the chemical chain.
Consequently they are more flexible. This open structure of the curing agents results in coatings with low
resistance to chemicals, solvents and acids. However, their resistance to water & corrosion are enhanced
because of their surface wetting and adhesion properties.

When an aliphatic polyamine is reacted with a monofunctional fatty acid rather than a dimer acid, then an
amidoamide is formed. These curing agents are less volatile and have less irritation potential than polyamines,
and they have properties that although are similar but inferior to polyamides. For instance, polyamides are
better in water resistance and provide better adhesion than the amidoamides.

In addition to the above types of curing agents there are many other curing agents based on polyamines, and
there are also non-amine based curing agents. Finally, either aromatic or aliphatic isocyanates may also be used
as curing agents for epoxy resins. The isocyanates react through the hydroxyl groups of the epoxy resin and
provide very good low temperature curing, good flexibility, good impact & abrasion resistance as well as good
adhesion.

I trust this brief discussion helps. The "World of Epoxy Curing Agents" is so large and varied that it is
impossible to explain them in a forum of this nature. Over the years, both JPCL & PCE have carried several
articles and several viewpoints on the different classes of epoxy hardeners. Perhaps a search through them will
yield lot more. Reference may also be made to "Protective Coatings - Fundamentals of Chemistry &
Composition" by Clive H. Hare.

Another more technical third-party article: click here

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

Yet another (really good) third-party tech article: click here

Everyone's Guide to Instant Epoxy Knowledge - Click Here

Novolac Epoxies
Epoxies made with Bis F, a Bis F and novolac mixture, or Novolac resin exhibit greatly improved chemical and
heat resistance compared to the much more common Bis A epoxies. Probably 98% of all epoxies are 'regular'
Bis A epoxies. Assume Bis A epoxy unless specifically told otherwise. Novolac epoxies are more expensive than
regular epoxies. They exhibit higher 'heat distortion temperatures', higher 'T sub G temperatures' (both of
these are measures of when the epoxy begins to soften with heat). The values for these measurements vary slight
with the different resins, and by whether the vendor reports conservative values or optimistic numbers.
Generally Bis A epoxies will begin to soften in the 120-160 degree F range. Novolac epoxies initially raise this
value by about 25 degrees F. More important is what happens above this temperature. All epoxies will reharden
when the elevated temperatures fall below this transition temperature. However, Bis Novolac epoxies will
continue to cure when exposed to temperatures of about 150 degrees F for a few hours. After this 'additional
curing' they generally can withstand about 300 degrees F (dry environment) without problems. An exception to
this is our non-hazmat novolac epoxy (FC 2100 N). The non-hazmat curing agents used greatly reduce the
temperature resistance (but not the chemical resistance). For 'true' novolac temperature resistance use our
Nova Clear hazmat novolac epoxy.

Chemical Resistance: A good quality Bis A epoxy will handle 70% sulfuric acid. A novolac epoxy will handle 97
or 98% sulfuric acid.

The bad news: You get good chemical resistance or good heat resistance, generally not both.

A more technical third-party article: click here

We are the supplier of an inexpensive marine and industrial clear novolac epoxy as well as a pigmented
industrial novolac floor epoxy.

Epoxy Adducts -- example: NSP 120 epoxy, also our NO BLUSH 2 marine
epoxy.
Adduct epoxies are two part epoxies but the curing agent actually contains a bit of the epoxy resin. In affect, the
'mixture' has started to cure even before the two parts are mixed. They perform much like other epoxies, but
have improved overall physical properties. These include, but are not limited to better color stability and curing
at slightly cooler temperatures. Also time (cure time) to 'back in service' can be much faster than with 'regular'
epoxies.

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

Part 2: Specialty Epoxies -

Underwater Epoxy Evolution
In general terms, three generations of apply underwater epoxies have emerged over the years. Each has pushed
the technology window forward. The success of first generation epoxies seems to be in their ability to be applied
and cured underwater. The next generation moved these epoxies into true coating status, albeit with issues of
user friendliness and chemical safety issues still to be addressed. The new third generation epoxies have
addressed those issues successfully.

First Generation Underwater Epoxy Coatings

* Sticky, like ‘Bubble Gum' - similar to a thick putty

* Hard to mix and apply - knead the two parts together in hand-sized amounts and literally push on to the
surface

* Expensive on a ‘cost per square foot' - @ 1/4 thick and $50 gallon = $7.80 per square foot material cost

* Potentially difficult to ship and/or store - may require hazmat shipping (Corrosive Liquid - N.O.S.), may have
short shelf life

Second Generation Underwater Epoxy Coatings

* Good underwater adhesion - true bonding instead of ‘sticking'

* Poor storage stability (heating required) - products tended to crystalize over time

* Toxic - MDA and possible solvents (see footnote)

* Hazmat shipping required - keep away from foodstuffs

* Problem with cathodically protected surfaces - interference with the polar bonding

Third and Fourth Generation Underwater Epoxy Coatings

* Low cost - $2.50 per sq. ft. for 40 mils, $5.00 per sq. ft. for 80 mils ($100 per gallon)

* Stable storage - will not crystalize over time

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Chemistry of Epoxies / Epoxy Resin, Novolacs, and Polyurethanes

* Basically Non-toxic, 100% solids (0% VOC), no MDA

* Non-hazmat - unregulated shipping

* Good application on cathodically protected surfaces - additives to overcome polar bonding interference, easy
application results in productivity increase

NOTE: We at Progressive Epoxy Polymers, Inc. offer several underwater epoxies for water water, nuclear,
marine (boating and commercial). See links at bottom of page.

Part 3: Polyurethane Coatings

Rankings of Polyurethanes (from weakest to strongest)

one part (poly)urethanes: (sold at hardware stores, etc.)

moisture cured urethanes: (curing reaction takes place in presence of moisture - most not suitable for
exterior applications)

acrylic aliphatic (linear) isocynate polyurethanes: a two part epoxy (note not all these adjectives are
always used)

polyester aliphatic isocynate polyurethanes: the best of the polyurethanes. 'Awlgrip' by US Paint, and the
'LPU 100' Polyurethane, which we sell at both our marine and industrial sites, fall into this group. These paints
are often used for aircaft finishes and aircraft hanger floors. Our LPU 100 has its own web page - CLICK
HERE

Polyurethane Notes

Urethane resins are either aliphatic, aromatic or a combination of each. Aliphatic is straight chains (i.e. Linear)
of
carbons in the backbone - perfect example is polyethylene.

Aromatic molecules are composed of resonant benzene rings. The resonance is closely tied to
energy absorption in the visible spectrum - all dyestuffs exploit resonance in particular areas of the
visible spectrum - as the molecule shakes at a certain frequency it absorbs energy in that frequency
thus changing color, shine white light on a surface, extract blue from it and you are left with red to
be reflected off. Aromatics do not have to change much to become similar to a dyestuff structure
and mess up the reflected light thus appearing heavily discolored. Because of their chemical
stability they tend to be excellent for applications such as heat resistance or chemical resistance
but they do suffer from poor light stability.

Epoxies are part aliphatic, part aromatic. They therefore have the best and worst properties of each.

Polyurethane curing agents are often aromatic - toluene diisocyanate (TDI) for example. Notice how
exposed PU foams often discolor and crumble in strong sunlight? When the curing agent is purely
aliphatic (linear) it has much better UV resistance. Classic PU curing agent is HMDI or hexamethylene
diisocyanate which is a ring but a saturated, non-resonant structure which does not turn into a

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resonant ring upon exposure to UV. The "linear" term simply means a simple saturated line of
carbon atoms rather than the alternating unsaturated bonds characteristic of aromatic molecules.

Polyester polyurethanes improve upon the excellent properties of linear polyurethanes.

Third party FAQ on Polyurethanes - CLICK HERE

CONTACT INFO - ORDERING - HOW TO REACH US - PHONE/EMAIL/FAX INFO

We are also very involved with Epoxy/Coatings in the following

areas:

-- -Marine/Boat Repair/Building- -- -Pour On Bartop Epoxy- --

-Epoxy Floor Paints (massive info/options)- --
-Home/Commercial Epoxy Paints/Putties- -- -Pebble Deck
Recoat Epoxy- -- -Epoxy Education- -- -Underwater Epoxy
Painting/Repair- -- -EpoxyProducts Home Page- -- -EpoxyUSA
Home Page- -- -Ask Professor E.Poxy- --

Return to the Progresssive Epoxy Products Page

Return to the Marine (boating) Products Page

Return to Industrial Coatings Product Page

Return to Epoxy Index Page

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