Knowledge Center

Acrylic Resin Fundamentals

Posted on April 22, 2016 by Ron Lewarchik

Coatings utilizing acrylic resins are the leading polymer technology in the coatings
industry. Historically alkyd finishes have held the leading position in coatings for decades.
Acrylics are utilized in architectural coatings, product finishes for original equipment
manufacture including automotive (OEM) and refinish, as well as special-purpose
coatings.

Acrylic resins are primarily based on acrylate and methacrylate monomers and provide
good weather resistance, resistance to hydrolysis, gloss and color retention in exterior
applications. Due to their versatility and performance, acrylic coatings account for over
25% of all coatings and global sales approaching $25 billion. Acrylic resins can be
thermoplastic or thermosett and are used in organic solvent born, waterborne, powder
and radiation-curable coatings

Three broad classes of liquid coatings

utilizing acrylic resins include
thermoplastic, thermoset and
waterborne. Many acrylic resins may also
include other vinyl monomers such as
styrene or vinyl acetate primarily to
reduce cost. Acrylic monomers have a
lower Tg than their analogous
methacrylate monomers (for example
compare the Tg for n-butyl acrylate
versus n-butyl methacrylate see Table I
and Table II). As Table II suggests, the
Table I – Tg of Nonfunctional Homopolymers glass transition temperature of the
monomers selected for synthesis of a
resin can be selected to enhance
multiple properties that may include weather resistance, moisture resistance, oxygen
permeability, flexibility reactivity, cure and hardness. In addition, acrylics can be
functionalized with a variety of monomers to provide improved adhesion to metal, or to
react for example with aminoplast or isocyanate crosslinkers.
 Thermoplastic acrylic polymers (TPA) in
general have excellent properties
including exterior durability. Such resins
were widely used in automotive OEM and
Refinish topcoats from the 50’s to the
70’s, but their use has dramatically
declined due to the high molecular
Table II Relationship of Tg to Physical Properties weight necessary to provide properties,
they require a high amount of organic
solvent to enable air atomized spray
application. Accordingly these paints apply at about 20% weight solids. Thermoplastic
resins typically use a high level of methyl methacrylate in their polymer backbone to
provide excellent hardness and exterior durability.

Figure I – Structure of poly MMA and poly MA

Thermosetting acrylic resins (TSA) are designed with functional monomers to either react
with themselves when exposed to heat or moisture, or with that of a cross-linker to form a
cross-linked film. Thermoset resins as a group are lower molecular weight and thus have
higher application solids. Once cross-linked, as a class they offer films with excellent
resistance to organic solvents, moisture and UV light and do not soften appreciably when
exposed to moderately high temperatures as thermoplastics do. An example of acrylic
monomers with functional groups that can be used to functionalize acrylic polymers to
provide properties such as crosslinking, self-crosslinking, improved adhesion or pigment
wetting are provided in Table III.

Being able to functionalize an acrylic resin with a wide range of reactive moieties provides
the ability to tailor the performance of the resin backbone to provide improved adhesion
over a variety of substrates, improved pigment wetting and/or the ability to provide
crosslinking or self-crosslinking. Other acrylic monomers are also available to impart
sulfonic acid, or phosphoric acid functionality to the acrylic resin.
 Being able to functionalize an acrylic
resin with a wide range of reactive
moieties provides the ability to tailor the
performance of the resin backbone to
provide improved adhesion over a
variety of substrates, improved pigment
wetting and/or the ability to provide
crosslinking or self-crosslinking. Other

Table III – Functional Acrylic Monomers

acrylic monomers are also available to
impart sulfonic acid, or phosphoric acid
functionality to the acrylic resin.

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Carbamate functional acrylics can also be made for example by reacting an isocyanate
functional acrylic with hydroxypropyl carbamate. Many of the acrylics in the category of
functionalized acrylic resins are used in automotive OEM and refinish clearcoats to
provide an excellent combination of mar resistance, chemical resistance and light
stability.

Acrylic polymers are also used extensively to make water reducible and emulsion resins.
Water reducible acrylic resins typically have acid numbers of 40 to 60. An example of a
water reducible TSA would have a resin composition comprised of MMA/STY/BA/HEMA/AA
in a weight ratio of 40/20/22/10/ 8 prepared by free radical polymerization in a water
reducible solvent such as a glycol ether solvent like 2-butoxy ethanol with butyl alcohol.
To begin the process of making paint, a suitable amine is used to neutralize the acrylic
acid in the resin backbone to provide an acid salt. The amine is used at less than the
theoretical level of neutralization using for example 2-(dimethyl amino) ethanol (DMEA)
or 2-Amino-2-methyl-1-propanol (AMP). The next step in the paint making process
involves the addition of water. Please refer to a previous Prospector article concerning
waterborne resins: https://www.ulprospector.com/knowledge/3069/pc-fundamentals-
waterborne-resin-technology/ as well as additional information on viscosity versus
reduction characteristics of waterborne resins:
https://www.ulprospector.com/knowledge/639/flow-leveling-viscosity-control-water-
born-coatings/.
Acrylic emulsion polymerization is carried out in water with monomers, a water soluble
initiator and surfactants. Many of the same monomers are used in emulsion
polymerization as that in solution polymerization, however the properties of the latex can
be greatly affected by changes in the: polymerization conditions, monomer structure and
solubility, monomer concentration, surfactant type and level, temperature, initiator type
and initiator concentration are all variables that can effect the emulsion particle size,
structure and molecular weight of the final polymer. A detailed examination of latex
polymerization is a significantly large subject and is thus out of scope for this article.
Acrylic polymers are also used in powder coatings along with acrylate functional acrylic
resins for radiation cure coatings. The fundamental influence of monomer Tg, molecular
weight and functional monomers remain the same for all the applications described
herein.

In summary it is the goal of this article to provide a heightened understanding of acrylic

resin technology and its ramifications on paint performance characteristics and
mechanical properties.

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Filed Under: Paint & Coatings

About Ron Lewarchik

Ronald J. Lewarchik, President and CEO of Chemical Dynamics,
LLC, brings 40 years of paint and coatings industry expertise to
his role as a contributing author with the Prospector Knowledge
Center. As a contributing writer, Ron pens articles on topics
 relevant to formulators in the coatings industry. He also serves as a consultant for
the Prospector materials search engine, advising on issues related to optimization
and organization materials within the database.

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