320 ALKYD RESINS

15.6. MODIFIED ALKYDS

Oxidizing alkyds can be modified by reaction with vinyl monomers. The most widely used
monomers are styrene, vinyltoluene, and methyl methacrylate, but essentially any vinyl
monomer can be reacted in the presence of an alkyd to give a modified alkyd. Methyl
methacrylate imparts better heat and weather resistance than styrene but at higher cost.
In making styrenated alkyds, an oxidizing alkyd is prepared in the usual way; then
styrene and a free radical initiator such as benzoyl peroxide are added. The resulting
free radical chain process leads to a variety of reactions, including formation of low
MW homopolymer of styrene, grafting of polystyrene onto the alkyd, and dimerization
of alkyd molecules. The reaction is generally carried out at about 1308C, which favors
decomposition of benzoyl peroxide to form phenyl free radicals; phenyl radicals have a
greater tendency to abstract hydrogen, which favors grafting. After the reaction is com-
plete, the resin is diluted with solvent. The ratio of alkyd to styrene can be varied over
a wide range; commonly 50% alkyd and 50% styrene is used. The ratio of aromatic
rings to aliphatic chains is greatly increased, and as a result, the Tg of styrenated alkyds
is higher and the tack-free time is shorter. Styrenated alkyds give a dry film in 1 hour
or less versus 4 to 6 hours for the counterpart non-styrenated alkyd. However, the
average functionality for oxidative cross-linking is reduced, not just by dilution with
styrene, but also because the free radical reactions involved in the styrenation consume
some activated methylene groups. As a result, the time required to develop solvent resist-
ance is longer than for the counterpart alkyd. The fast drying and low cost make styrenated
alkyds very attractive for some applications, but in other cases, the longer time required for
cross-linking is more critical, in which case styrenated alkyds are not appropriate.
Styrenated alkyd vehicles are often used for air dry primers. One must be careful to
apply the top coat almost immediately, or not until after the film has had ample time to
cross-link. During the intermediate time interval, application of the top coat is likely to
cause nonuniform swelling of the primer, leading to what is called lifting of the primer.
The result of lifting is the development of wrinkled areas in the surface of the dried
film. End users who are accustomed to using alkyd primers, which do not give a hard
film until a significant degree of cross-linking has occurred, are particularly likely to
encounter problems of lifting if they switch to styrenated alkyd primers.
Acrylate-functional alkyds are reported to dry more rapidly than the corresponding
unmodified resin. For example, the carboxylic acid groups on an alkyd prepared from
PE, TMP, soy oil, and IPA with an acid number of 8.6 is reacted with glycidyl methacry-
late (GMA). Using zirconium and cobalt driers, films through dried in 9 hours, in contrast
to .11 to ,20 hours for the unmodified resin [30].

15.7. URALKYDS AND OTHER AUTOXIDIZABLE URETHANES

Diisocyanates are used to make a variety of resins that share similar characteristics with
alkyds, as discussed in this section. For a description of the isocyanates, see Section 12.3.

15.7.1. Uralkyds
About 39,000 metric tons of uralkyds were used in the United States in 1997 [31].
Uralkyds are also called oil-modified urethanes. The largest use for uralkyds is as the
 15.7. URALKYDS AND OTHER AUTOXIDIZABLE URETHANES 321

vehicle for urethane varnishes for use by contractors and the do-it-yourself market. The
abrasion and hydrolytic resistance of such coatings are greatly superior to that obtained
with conventional varnishes or alkyd resins. Many varnishes sold to consumers today
are based on uralkyds; they are not really varnishes in the original sense of the word.
They are used as transparent coatings for furniture, woodwork, gymnasium floors, and
hardwood floors; applications in which good abrasion, mar, scuff, chemical, and saponi-
fication resistance are important. They are also widely used in maintenance paints.
To prepare uralkyds, one transesterifies a drying oil with a polyol such as glycerol or PE
to make a monoglyceride, which is then reacted with somewhat less diisocyanate than
the equivalent amount of NCO based on the free OH content. To assure that no NCO
groups remain unreacted, methyl alcohol (or other low MW alcohol) is commonly
added at the end of the process. For lower cost, one can use a combination of phthalic
anhydride and diisocyanate. Color retention is superior with aliphatic diisocyanates, but
Tg is higher and cost is lower with aromatic diisocyanates. An extensive review paper
is available [32].
A comparison of the properties of uralkyds, alkyds, and 2K urethane coating has been
published [33]. Four uralkyds prepared from linseed oil and safflower oil, each with TDI or
MDI, were compared with linseed and safflower alkyds. All of the alkyds and uralkyds had
an oil length of 60%. They were compared with two 2K polyester MDI resin systems.
Primers and pigmented top coats were formulated with each resin. The cohesive strengths
of the uralkyd paint films were greater than those of the alkyd films and approached those
of the 2K coatings. Of the uralkyds, the highest cohesive strength was with films made
using the linseed oil TDI resin. Scratch resistance and tensile strength tests showed the
same ranking of the films made from the eight resins. Salt spray resistance and humidity
resistance of the uralkyd coatings were superior to those of the alkyd coatings but inferior
to the 2K urethane coatings. Particularly notable, the chemical and solvent resistance of
the uralkyd films were markedly better than the alkyd films, although somewhat inferior
to the 2K films. Studies of the permeability rate of water into uralkyd and alkyd films indi-
cated that alkyd films are more permeable than uralkyd films [34].
By far the most widely used diisocyanate is TDI. A uralkyd with improved color reten-
tion compared to that of a uralkyd made with TDI can be made by reacting the polyol made
by transesterification of linseed oil with PE, then reacting with H12MDI [35].
Another advantage of uralkyds over alkyds is ease of manufacture. The time for the
reaction of the isocyanate groups is substantially shorter and the reaction temperature is
on the order of 708C, compared to 220 to 2458C for the esterification of alkyds. This
results not only in lower production costs and higher equipment utilization but also in
less dimerization of the unsaturated chains, hence reduced viscosity at the same molar
ratios.
Traditionally VOC of uralkyd varnishes has been over 500 g L21. As of 2005, EPA
VOC regulations for varnishes require less than 450 g L21, California south coast as
well as northeastern states regulations require less than 350 g L21, and the California regu-
lations will be further reduced to 275 g L21 in 2006. It is reported that uralkyds with a
VOC of 345 g L21 can be made by reducing the MW. Meeting the 275 g L21 regulation
will require greater changes. With careful balancing of driers and accelerators, the dry
time and performance of higher VOC uralkyds can be approached. One approach is to
use the exempt solvent 4-chlorobenzotrifluoride (PCBTF) to replace part of the mineral
spirits solvent (Section 18.9.1). The higher-solids varnishes have the advantage that two
coats are sufficient instead of the usual three; however, great care must be taken to
322 ALKYD RESINS

avoid too great a film thickness. Water-reducible urethane varnishes can be used (see the
next paragraph). Autoxidizable acrylic urethane hybrid dispersions permit preparation of
high quality products at a higher cost (Section 15.7.2). For the contractor market, 2K
waterborne urethanes have many advantages but are not suitable for the do-it yourself
market (Section 12.7.3) [36].
As with other types of coatings, VOC regulations stimulated development of water-
reducible uralkyds. An example is a maleated uralkyd prepared from a partial ester of
linseed oil fatty acid with PE, which is reacted with MDI and then with maleic anhydride
[37]. The resin is diluted in 2-butoxyethanol, neutralized with TEA, and diluted with
water. The resin is much more resistant to hydrolysis than is a corresponding alkyd.

15.7.2. Autoxidizable Polyurethane Dispersions

Water-reducible polyurethane dispersions (PUDs) (Section 12.7) can be made autoxidiz-
able by introducing appropriate fatty acids. For example, a PUD made by reacting a dii-
socyanate with a diol, a fatty acid monoglyceride, and dimethylolpropionic acid (DMPA)
is neutralized with an amine and then dispersed in water. Water acts as a chain extender for
terminal isocyanate groups [38]. Hydrolytic stability of the aqueous dispersions is excel-
lent, and the films also have the expected abrasion resistance. Drying speed, color, and cost
are dependent on the drying oil and diisocyanate used. For example, a PUD is made from a
dehydrated castor oil, pentaerythritol, phthalic alkyd reacted with DMPA, dimethylisopro-
pylamine, and isophorone diisocyanate (IPDI) [39]. A PUD for wood flooring coatings is
prepared from an unsaturated polyol prepared by transesterification of castor oil and soy
oil, DMPA, H12MDI, neutralized with TEA, dispersed in water, and chain-extended with
hydrazine hydrate and ethylenediamine [40]. The coatings are said to resist solvents,
abrasion, and heel marking.
Acrylic urethane hybrid dispersions have lower cost. For example, a drying oil fatty
acid amide of diethanolamine is reacted with DMPA, cyclohexanedimethanol, a mono-
methyl ether of polyethylene glycol, and TDI in N-methylpyrrolidone (NMP), methyl
methacrylate is added, the product is diluted with dipropylene glycol monomethyl
ether, neutralized with dimethylaminoethanol (DMAE), and then diluted with water
[41]. After dilution with water, the methacrylate monomer is polymerized; the resulting
PUD gives films that cross-link by autoxidation.

15.8. EPOXY ESTERS

BPA epoxy resins can be converted to what are commonly called epoxy esters by reacting
with fatty acids. Drying or semi-drying oil fatty acids are used so that the products cross-
link by autoxidation. The epoxy groups undergo a ring-opening reaction with carboxylic
acids to generate an ester and a hydroxyl group (Section 13.3.2). These hydroxyl groups,
as well as the hydroxyl groups originally present on the epoxy resin, can esterify with fatty
acids. They are generally made by starting with a low MW epoxy resin (i.e., the standard
liquid resin, n 0.13) and extending with BPA by the advancement process (Section
13.1.1) to the desired MW. Off-specification epoxy resin is often used to reduce cost.
The fatty acids are added to the molten, hot resin, and the esterification reaction is contin-
ued until the acid number is low, usually less than 7 mg of KOH per gram of resin. In the
esterification reaction with fatty acids, the average number of sites for reaction is the n