Acrylic Resin Fundamentals

Posted on April 22, 2016 by Ron Lewarchik 5 comments

http://knowledge.ulprospector.com/4320/pc-acrylic-resin-fundamentals/
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

Table I Tg of Nonfunctional Homopolymers

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 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.

Table II Relationship of Tg to Physical Properties

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 50s
to the 70s, but their use has dramatically declined due to the high molecular 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, selfcrosslinking, improved adhesion or pigment wetting are provided in Table III.

Table III Functional Acrylic Monomers

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 selfcrosslinking. 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 selfcrosslinking. Other 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: http://knowledge.ulprospector.com/3069/pc-fundamentalswaterborne-resin-technology/ as well as additional information on viscosity versus reduction
characteristics of waterborne resins: http://knowledge.ulprospector.com/639/flow-levelingviscosity-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.
The views, opinions and technical analyses presented here are those of the author, and are not
necessarily those of UL, ULProspector.com or Knowledge.ULProspector.com. While the editors
of this site make every effort to verify the accuracy of its content, we assume no responsibility for
errors made by the author, editorial staff or any other contributor. All content is subject to
copyright and may not be reproduced without prior authorization from Prospector.
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.