Abstract
Linear, soluble polymers were produced from unsaturated
bio-based compounds using a carbocationic polymerization
process. The unsaturated bio-based compounds that were first
converted to vinyl ether monomers and subsequently polymerized were plant oil triglycerides, cardanol, and eugenol. As a
result of the much higher reactivity of the vinyl ether group
compared to the unsaturation derived from the bio-based
compounds and the ability to tailor the cationic polymerization
process, polymerization was exclusively limited to vinyl ether
groups. By preserving the unsaturation derived from the bio-based compounds, the polymers could be crosslinked into insoluble coatings by autoxidation. In addition, the unsaturation
can be converted to other functional groups, such as epoxy,
which enable other crosslinking mechanisms. This document
describes some of the polymers and coatings that have been
produced with the technology.
Introduction
Prior to the ample supply of petrochemicals, coatings were
largely derived from renewable resources such as plant oils, fats,
plant proteins, polysaccharides, terpenes, and minerals.1 As a re-
sult of the low cost and tremendous diversity of petrochemicals,
development of new coating components based on renewable/
bio-based resources was largely abandoned. Due to concerns
with the finite supply of fossil resources, geo-political events, the
environment, and human health, the use of bio-based materials
in the coatings industry is making a resurgence.
In general, technology innovation within the coatings industry has been largely driven by regulations aimed at protecting
both the environment and human health. These regulations
have historically been focused on the reduction of the VOC content of coatings. However, due to growing consumer demand
for environmentally friendly products, the chemical and materials industries have been placing more emphasis on the complete
environmental impact of products. The total environmental impact of a product or material is typically assessed by conducting
a life cycle analysis.
Of the coating resin technologies utilized today, alkyd resins utilize a significant fraction of bio-based materials. Alkyd
resins were developed in the mid-1920s primarily as a means
to reduce the drying time of coatings based on drying oils such
as linseed, tung, walnut, perilla, and poppy seed oil.2 Plant oil
triglycerides are highly flexible molecules and, as a result, a significant degree of crosslinking is required for a drying oil-based
coating to become dry-to-touch. With the availability of petrochemicals, aromatic monomers, such as phthalic anhydride
and isophthalic acid, were used to produce polyesters modified with fatty acid ester chains derived from a plant oil. The
higher glass transition temperature (Tg) of these polyesters,
referred to as alkyds, enabled films to become dry-to-touch
Novel Bio-based Poly(vinyl
ether)s for Coating Applications
Bret J. Chisholm,1,2, 3*Harjoyti Kalita,1,2 Deep Kalita, 3 Samim Alam, 3 Andrey Chernykh,1 Ihor Tarnavchyk,1, 3
James Bahr,1 Satyabrata Samanta,1 Anurad Jayasooriya,1 Shashi Fernando,1 Sermadurai Selvakumar, 4 Dona
Suranga Wickramaratne,1and Mukund Sibi4
1Center for Nanoscale Science and Engineering
2Materials and Nanotechnology Program
3Department of Coatings and Polymeric Materials
4Department of Chemistry and Biochemistry
North Dakota State University
Fargo, ND 58102
*To whom correspondence should be addressed: Bret.Chisholm@ndsu.edu
