12/17/2020 Monomers and Oligomers: Characteristics, functions, and applications

Improving Performance with Monomers and

Oligomers
Posted on June 30, 2017 by Ron Lewarchik

Properly chosen monomers and oligomers provide improved performance in a wide variety of
coatings applications, such as:

adhesion
chemical resistance
substrate wetting
improved weathering

A monomer can be defined as a molecule that can combine with other molecules to form an oligomer
or polymer. An oligomer can be described as a molecular complex comprised of a few monomer
units. This article will focus on functional monomers and oligomer types that may be used in radiation
cure compositions as well as solventless, high solids and waterborne coatings.

As the molecular weight increases in a solution polymer within a monomer type, viscosity increases,
solubility decreases and in general compatibility with other resins decrease. Accordingly, with these
basic relationships in mind, oligomers can be used to decrease volatile organic compound (VOC)

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12/17/2020 Monomers and Oligomers: Characteristics, functions, and applications

content and application viscosity. Some of the common monomers and oligomers used in light cure
systems include those in Figure 2.

Figure 2 – UV Cure Oligomer Types/Characteristics

Table 1. Acrylate oligomer types, their

performance effects and use in inks and
coatings1

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12/17/2020 Monomers and Oligomers: Characteristics, functions, and applications

Oligomer Type Performance Effects Use in Inks and Coatings

Increase reactivity, hardness, Oligomer of choice for

Epoxy Acrylate chemical resistance; decrease coatings; used to lower cost in
cost inks

Increase flexibility, toughness,

weathering; multi-functionals Increase flexibility or
Aliphatic urethane acrylate increase reactivity, hardness, hardness; for touch,
chemical resistance; decrease weatherable screen inks
yellowing

Increase flexibility, toughness;

multifunctionals increase
Increase flexibility or
Aromatic urethane acrylate reactivity, hardness, chemical
hardness; not weatherable
resistance; decrease cost (vs.
aliphatic)

For pigment wetting, adhesion;

Increase wetting; decrease oligomer of choice for litho
Polyester acrylate
viscosity inks due to water balance and
printability

Acrylic acrylate Increase adhesion, weathering Increase adhesion

In addition to monomers and oligomers employed in radiation cure formulations, there is a myriad
number of applications where these molecules are employed. For example, oligomers can be
nonfunctional, mono functional or multifunctional and be used to enhance performance or
environmental properties. Some common oligomer types used in applications in addition to light cure
systems include epoxy ester, urethane, epoxy, acrylic, polyester and polycaprolactone. As figure III
illustrates, many of these oligomers are functionalized with one or more functional groups to promote
crosslinking, flexibility or adhesion.

Table 2. Examples of Oligomers Employed in Various Coating Applications

Oligomer Type Functional Groups Potential Applications in Coatings

Silane – SH, – Si-OH, -OH Solvent free, multiple cures possible

Acrylic – OH 2K Urethanes, aminoplast cure

Brominated Epoxy Oxirane Flame retardant, cure with polyamines

Flexible topcoats, cure with –NCO,

Polyester urethane – OH
aminoplasts

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Polycaprolactone – OH Cure with –NCO, aminoplasts

In addition to the oligomer types described in Table 2, there are a host of other oligomers that are
used primarily to reduce viscosity and VOC in coatings or to enhance flexibility, adhesion, weathering
and substrate wetting.

As a class, the oligomers that are utilized to reduce viscosity in a formulation are commonly called
reactive diluents. A reactive diluent performs two functions:

to reduce viscosity similar to that of a solvent

to react with the resin and cross-linker in the coating and thus become part of the cured coating
film

The table below provides a number of examples of the types of functionalities that are available in
oligomers that are classified as reactive diluents and the compositions they are used in.

Table 3. Examples of Functionalities in Oligomeric Reactive Diluents

Functionality Coating Application

Acrylate Radiation cure

Vinyl Radiation cure

Isocyanate Urethanes

Oxirane Epoxy based coatings

Mercaptan Epoxy based coatings

Silane Multiple resin types

Hydroxyl Aminoplast or isocyanate

Acetoacetate Crosslink with amino or isocyanate functionality

Resources
1. Radtech, Printers’ Guide: UV/EB Chemistry and Technology
2. UL Prospector, UV-LED Cureable Coatings by Ronald Lewarchik, February 5, 2016
3. Organic Coatings, Science and Technology, Third Addition, wicks et.al., Wiley Interscience,
2007
4. UL Prospector raw material search engine

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Filed Under: Paint & Coatings

Tagged With: Material Deep Dive

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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