Photo courtesy of Betz Dearborn, Div. of Hercules Inc.

Formulating VOC-Compliant
Coatings with Exempt Solvents
A Case Study on Tertiary-Butyl Acetate (TBAc™)

By D.B. Pourreau, G.B. Kelly, L.J. Junker, R.T. Wojcik, S.L. Goldstein
and M.J. Morgan / Lyondell Chemical Co., Newtown Square, PA

M
anufacturers of coatings, ink and adhesives proposing to tighten the criteria for exempting VOCs
have come under increasing pressure to from regulation.6 Therefore, it is unlikely that many new
eliminate HAPs and VOCs from formula- practical coating solvents will be added to the list of
tions. Some of the latest regulations to VOC-exempt compounds.
affect coatings manufacturers include the Architectural However, the EPA has recently proposed7 to add Lyon-
and Industrial-Maintenance (AIM) rule,1 Automotive dell Chemical’s tertiary-butyl acetate (TBAc) to the list of
refinish rule,2 Wood Furniture CTG and NESHAP,3 and VOC-exempt materials based on its negligible photo-
National Ambient Air Quality Standard (NAAQS).4 chemical reactivity. This would make TBAc one of only a
Since many common solvents are both HAPs and handful of HAP- and VOC-compliance tools available to
VOCs, these rules have forced many producers to switch coatings formulators. TBAc is an effective viscosity reduc-
to low-solvent technologies such as high-solids, water- er with an intermediate flash point and evaporation. It
borne, powder and low-energy-curable systems. These has been formulated in a variety of low-VOC coatings,
technologies have their own inherent limitations that ink, adhesives and cleaners, including the following.
can make them more costly and less convenient to use • Nitrocellulose wood coatings
than the traditional lower-solids formulations. • Urethane automotive refinish coatings
An alternative approach to these technologies is to • Air-drying and baking alkyd enamels for metal
use non-HAP, VOC-exempt solvents such as acetone and • Aerosol coatings
p-chlorobenzotrifluoride (PCBTF). Unfortunately, both • Flexible packaging ink
have performance features that make them less-than- • Pressure-sensitive adhesives
ideal solvents for coatings. In addition, the EPA is • Industrial degreasers
reviewing its VOC policy5 and, at least in the interim, is • Paint strippers
 Figure 1 / Maximum Incremental Reactivities of Common
Coating Solvents and Additives

14

Ultimately, the EPA’s VOC policy will probably evolve 12

to a weighted reactivity scale similar to what is being Average

MIR, g ozone/g VOC

proposed by the California Air Resources Board (CARB) 10
for aerosol coating products.8 Another possibility is that 8
VOCs would be classified in reactivity “bins,” again using
some reactivity scale. Regardless of the outcome of this 6
policy reevaluation, TBAc and other low-reactivity sol-
4
vents will likely continue to be less regulated than the
more reactive solvents used today. 2

0
Formulating Coatings

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for Future Compliance

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Assuming the EPA will move to a reactivity-based VOC
A

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policy, reformulating today with low-reactivity solvents
and additives could mean fewer compliance issues in
the future. This could impact not only the type of sol-
vents used, but also the choice between waterborne and
THE
high-solids technologies. For example, waterborne coat-
ings are generally considered more environmentally
friendly than solventborne coatings because of their
Environmental
Protection Agency
lower VOC content. That’s because the current VOC pol-
icy regulates VOCs on a mass (lb/gal) basis and ignores
reactivity differences between VOCs. However, the fol- Last year, the U.S. Environmental Protection Agency
lowing three factors may become important in the future
(EPA) announced its intent to review its VOC policy in
and should be considered in assessing the environmen-
tal impact of coatings. light of new scientific understanding of photochemical
• The photochemical reactivity of the contained VOCs reactivity. It also promulgated new rules limiting the
• The solids content of the coating VOC content of architectural and industrial-maintenance
• The durability of the coating
(AIM), automotive refinish, and wood coatings, and pro-
Many of the coalescents, additives and amine neu-
tralizers used in waterborne coatings are VOCs, and posed reducing the Nonattainment Air Quality Standard
some are quite photochemically reactive (see Figure 1). (NAAQS) to 8 parts per billion (ppb). Although the new
For example, glycol ethers are commonly used to coa- VOC rules have had an immediate impact on producers
lesce acrylic latexes and urethane dispersions. They
and users of the affected coatings, the reduction in the
have maximum incremental reactivities (MIRs)9 in the
3–4.5 g ozone/g VOC range. Glycols, used in architectur- NAAQS and the VOC policy review could have an even
al paint as freeze-thaw stabilizers, have MIRs in the greater impact.
3–6 g ozone/g VOC range. Alkylamines are also com- For example, under the new NAAQS standard, the num-
monly used to neutralize water-dispersible resins and
ber of nonattainment areas in the United States would
have MIRs above 10 g ozone/g.
On the other hand, the aliphatic hydrocarbons, esters, jump from 245 to 546 in 2002, subjecting many manu-
alcohols and ketones commonly used to formulate facturers to stricter VOC emission limits. On the other
medium- and high-solids coatings have relatively low hand, a reactivity-based VOC-policy could bring regulato-
reactivities. Aromatic solvents, mostly xylene and
ry relief in the form of a greater selection of compliant
toluene, are the only solvents used in solventborne
coatings that, on average, have higher reactivities than technologies and more formulation latitude. Although
those used in waterborne coatings. By replacing high this relief is unlikely to come in time to help achieve
reactivity solvents with low reactivity ones, it is possible compliance with the NAAQS deadline, producers and
to formulate solventborne coatings with a lower ozone
users of coatings can take steps to prepare for it today. 
impact than that of their waterborne counterparts. It is
Formulating with Exempt Solvents

Figure 2 / VOC Content and Ozone Impact of increase the actual amount of VOCs emitted. Coating
Representative Industrial-Maintenance Coatings, durability is the most difficult performance characteris-
Assuming Comparable Durability
tic to quantify, but gloss or hardness retention data from
accelerated UV or chemical resistance testing could be
4.5
4.5 appropriate measures, depending on the application.
VOC Content, lbs/gal
4.0 Table 1 shows how these concepts may be used to cal-
lbs ozone/lbs solids
3.5 3.4
culate the actual ozone impact of different coatings. For
the purpose of illustration, the durability of these coat-
3.0
ings was assumed to be equal but may need to be quan-
Pounds

2.5 tified for a more accurate comparison.

2.2
2.0 1.8
In this example, the 2K waterborne urethane had the
1.7
1.5 1.5
1.4 1.4
lowest ozone impact of the five systems considered,
1.0
despite having a slightly higher VOC content than the
1.0 0.8 acrylic latex. The high-solids system had the same ozone
0.5 impact as the acrylic latex, despite having a VOC content
0.0 three times higher (4.5 lbs/gal vs. 1.5 lbs/gal). This demon-
strates that a high-solids solventborne system can gener-
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ate less ozone than a lower VOC waterborne coating.

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The urethane dispersion selected here had the high-

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2K

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2K

2K

est ozone impact despite a VOC content of 1.8 lbs/gal,

mainly because triethylamine (MIR ~10 g ozone/g) was
also possible to formulate waterborne coatings with used to neutralize the resin. This does not mean that
lower ozone impacts by selecting less reactive coales- urethane dispersions cannot be formulated to have low
cents and additives. ozone impact. In fact, the 2K-urethane dispersion for-
The solids content of the coating may also be consid- mulated with TBAc had one of the lowest ozone impacts
ered. When comparing coatings, the most appropriate (1.0 lb. ozone/lb. solids) despite containing a glycol
measure of VOC content is pounds VOC per pound of ether coalescent and a relatively high VOC content (3.4
solids applied, not pounds per gallon of paint. Water- lbs/gal).
borne coatings typically have solids content in the

T
30–50% range, whereas high-solids coatings have solids his discrepancy between the actual ozone impact
content in the 55–100% range. At best, it takes the same of a coating and its VOC content is illustrated in
amount of waterborne coating to get the same film build Figure 2. It underscores the limitation of using
as a high-solids coating. However, in most cases, it takes pounds VOC per gallon of paint for regulatory purposes
30–50% more waterborne coating. This affects the actual and the need to refine coatings regulations.
amount of VOCs emitted during the coating operation.
Finally, the durability of the coating should be consid- Environmental Considerations
ered. The durability of many waterborne coatings, Despite these limitations, the current policy does
although significantly improved, still lags behind that of encourage the use of negligibly reactive exempt sol-
solventborne versions. This means that waterborne vents. Unfortunately, most of these are either halo-
coatings need to be applied more frequently, which can genated or extremely volatile. Halogenated solvents are

Table 1 / Relative Ozone Impact of Representative Industrial-Maintenance Coatings

Typical 2K Waterborne 2K Urethane Acrylic 2K Urethane
Formulation Urethane Dispersion with TBAc Latex High-Solids Urethane Dispersion
Constants
Weight % solids 42 54 40 57 36
MIR of VOCs 2.0 1.5 3.8 1.6 4.0
lbs/gal 10.0 9.2 10.0 9.2 9.2
lbs ozone/gal 3.4 5.1 5.6 7.4 7.2
VOC content, lbs/gal 1.7 3.4 1.5 4.5 1.8
lbs ozone/lbs solids 0.8 1.0 1.4 1.4 2.2
Formulating with Exempt Solvents

Figure 3 / Ozone Creation Potential of Common Coating reactive solvents available to date, including currently
Solvents exempt solvents (see Figure 3).
Because of its limited atmospheric lifetime and low
molecular weight, TBAc also does not contribute signifi-
25
22.9 cantly to global warming, ozone depletion, acid rain for-
mation or fine particulate (PM2.5) formation. It is also
20 biodegradable, does not bioaccumulate and has low tox-
16.7 icity.11 Like reactivity, these factors may become more
Kg Ozone/Gal

15 important in future regulations, and will affect the mar-

ketability of solvents and the formulations that contain
9.8
10.4 them.
10
8.2 Using TBAc instead of common coating solvents is
environmentally sound, especially when considered on a
4.9 5.0
5 3.8
4.3 comprehensive basis. Also, because it is a pound-for-
2.8
2.2 2.3 2.3 pound replacement for these solvents in most applica-
0
0.5 0.6 0.7
tions, substitution for TBAc should not increase overall
emissions. In other words, the risk that increased TBAc
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emissions could outweigh the benefits of these substi-

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tutions is essentially nil.

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Over the past three years, since we petitioned the EPA

to add TBAc to the list of VOC-exempt compounds, it
seldom used in the coatings industry because of their has been tested in a number of coating, ink, adhesive
corrosiveness, poor solvency, toxicity, cost and odor. and cleaner formulations. The following paragraphs
There are only two nonhalogenated exempt solvents, compare TBAc’s key properties to other coating solvents
acetone and methyl acetate. They are so volatile and and illustrate how it can be a useful tool for formulating
flammable that they have found only limited use, compliant two-component urethane coatings, nitrocel-
despite their VOC-exempt status. lulose lacquers, and alkyds.
TBAc is one of the few nonhalogenated solvents with
negligible photochemical reactivity. Based on MIR and Key Solvent Properties
other reactivity data, TBAc produces 40–57% less ozone Viscosity Reduction. TBAc has solvency properties similar
than ethane on a per gram basis, whereas ethane pro- to other esters. It is an efficient viscosity reducer for a range
duces 40–57% less ozone than TBAc on a per-mole of commercial resins, including nitrocellulose, alkyds,
basis.10 This makes it one of the least photochemically epoxies, polyesters, acrylics, polyamides, urethanes and

Table 2 / Brookfield Viscosities of Commercial Coating Resins in Common Coating Solvents

Resin Supplier Type % TBAc MAK n-BuAc
Solids cps cps cps
Joncryl 587 SC Johnson Acrylic 50 4,560 826 1,230
Acryloid B-66 Rohm & Haas Acrylic 40 1,450 374 472
Epon 828 Shell Epoxy 80 197 89 187
12-035 Reichhold Alkyd 50 2,240 334 1,020
11-045 Reichhold Alkyd 50 108 49 69
12-102 Reichhold Alkyd 50 885 167 433
57-5776 McWhorter Polyester 73 885 531 531
57-5789 McWhorter Polyester 75 718 698 796
50-5071 McWhorter Alkyd 50 79 49 59
RS 1⁄2 second Hercules Nitrocellulose 12 49 39 39
Cymel 303 Cytec Amino 90 659 403 403
Versamid 115 Henkel Polyamide 75 3,380 4,670 1,710
Luxate HB9000 Lyondell Isocyanate 90 1,970 1,200 1,470
Luxate HT2000 Lyondell Isocyanate 90 619 403 413
Formulating with Exempt Solvents

amino resins. Table 2 lists representative resin viscosity Figure 4 / Evaporation Rate of Common Commercial
data in TBAc and other common coating solvents. Resins in Common Coating Solvents
TBAc is miscible in all proportions with common Relative Evaporation Rate (nBAc=100)
organic solvents but is virtually insoluble in water (~0.3 600
wt % at 20°C). Its solubility properties are similar to those
500
of other esters, such as n-Butyl acetate and PM Acetate.
Evaporation Rate. After solvency, evaporation rate is 400
probably the most important property for a coating sol-
vent. Unlike methyl acetate or acetone, TBAc evaporates 300
in the same range as toluene and MEK, making it an
especially good substitute for these two HAP-listed VOCs 200
(see Figure 4). Unlike the faster-evaporating solvents,
TBAc has good blush resistance in humid conditions. 100
Flash Point. Flammability is another important sol-
vent property, especially as it affects worker safety. Very 0

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VOC Policy Retrospective

he first step in the EPA’s today and want to know what, if have negligible impact on ozone

T VOC policy review was a

Reactivity Workshop, held
in March of 1998 in Research Tri-
any, regulatory relief will be
available in the interim. Studying
the evolution of the EPA’s VOC-
formation and therefore could be
exempted from VOC regulations
and emission controls. The rule
angle Park, NC. One outcome of policy provides some insights also stated that for VOCs with
this meeting was the creation of into these questions. reactivities close to ethane, other
a Reactivity Research Work In 1977, the EPA published its environmental benefits could be
Group whose function is to make first policy regulating VOCs in an considered for the purpose of
recommendations about what attempt to control the formation granting VOC exemptions. The
additional reactivity research is of toxic ozone in polluted urban rule did not specify how photo-
needed. However, the EPA’s goal environments. VOCs were known chemical reactivity would be
is much broader: Laying the foun- to react with nitrogen oxides measured or define the petition
dation for a new reactivity-based (NOx) in the presence of sunlight process in detail.
policy, which may consider not to give ozone. However, it was In 1990, the Clean Air Act
only the ozone-forming potential already clear that all VOCs did (CAA) amendments were passed,
of VOCs but also their impact on not contribute equally to the providing a definition of VOC and
fine particulates, global warm- ozone problem. Some VOCs a list of exempt compounds.
ing, acid rain, stratospheric reacted rapidly to generate ozone These exempt compounds were
ozone depletion, and human while others were relatively inert. said to have “negligible photo-
health. Many wonder where this Consequently, the first rule stat- chemical reactivity” because
will take us, how much it will ed that VOCs that were less pho- they reacted with atmospheric
cost and how long it will take. tochemically reactive than hydroxyl radicals much more
Others find it difficult to comply ethane would be considered to slowly than ethane. These radi-
Figure 5 / Flash Points of Common Coating Solvents an intermediate flash point, similar to that of many sol-
vents used in coatings today (see Figure 5).
90
Density. The density, in pounds per gallon, of a sol-
80 vent can also have an impact on VOC content and the
70 cost of a formulation. For most coatings, VOC content is
60 calculated by subtracting the pounds of exempt solvent
Flash Point (°F)

50 from the numerator and the gallons of exempt solvent

40 from the denominator. Theoretically, high-density sol-
vents such as PCBTF (11.2 lbs/gal) should reduce the
30
VOC content more than low-density solvents like ace-
20
tone (6.6 lbs/gal) or TBAc (7.2 lbs/gal), provided they
10 require the same amount of solvent to reduce viscosity.
0 However, more PCBTF is usually required to achieve the
-10 same viscosity reduction per gallon of paint. Also, the
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formulated cost of the solvent increases with increasing

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density since solvents are bought by the pound but coat-

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ings are sold by the gallon.

cals abstract hydrogens from ozone than high-solids systems better solvents. The only solvents
VOCs to form water and organic formulated with low-reactivity likely to meet the new ethane
radicals. The organic radicals solvents. standard are halogenated sol-
then undergo further decomposi- • The use of ethane as the vents, which are typically not
tion and reactions with NOx to boundary severely limits the used in coatings.
yield ozone. number of useful solvents that Most parties recognize that
The current VOC policy consid- are VOC exempt. If the EPA there are better ways to reduce
ers only two classes of VOCs — changes the cutoff from maxi- ozone formation than by continu-
exempt and nonexempt — with mum incremental reactivities ally reducing VOC content limits.
ethane as the boundary between (MIRs) expressed on a weight The EPA and scientific communi-
the two classes. This policy has basis to a stricter mole-based ty agree that all VOCs do not
the following two limitations. standard, as it has recently pro- contribute equally to ozone for-
• VOCs spanning a wide range of posed, this limitation will mation. Most of the current dis-
reactivities are regulated the become even more severe. cussion centers around which
same way. Hence, there is no The end result is that paint models best describe the extent
incentive to use less reactive sol- companies have little incentive to which VOCs’ reactivity differs.
vents unless they are less reac- to reformulate to less reactive There are several methods used
tive than ethane. In reality, for- VOCs. Since the new ethane cut- to estimate the ozone impact of
mulations with the same amount off virtually eliminates all oxy- VOCs, each with different impli-
of VOC can have vastly different genates and hydrocarbons from cations for a reactivity-based
ozone impacts. In fact, some contention as exempt solvents, VOC policy. 
low-VOC waterborne formula- solvent suppliers also are more
tions actually produce more limited in their ability to develop
 Formulating with Exempt Solvents

Two-Component Urethane Coatings especially for the California market. Their use is limited,
Two-component (2K) urethane coatings are high-perfor- however, by their physical properties and cost.
mance systems that are finding increased use in auto- Acetone, for example, evaporates very rapidly and can
motive and industrial-maintenance applications cause “dry-spray edge” and blushing, a haze caused by
because of their durability, chemical resistance, and moisture condensation in the coating due to excessive
ease of application. Unlike one-component melamine evaporative cooling. Its flammability also makes it diffi-
coatings that must be baked for crosslinking to occur, 2K cult to use in pigment grinding applications. PCBTF, on
urethane systems cure under ambient conditions when the other hand, is relatively expensive and is not as effi-
the acrylic (or polyester) polyol and isocyanate parts are cient at reducing viscosity as many of the solvents it
mixed just before application. This is particularly useful replaces.
for coating large parts that cannot be baked or thermal- TBAc is an active solvent for acrylic polyols and
ly sensitive substrates such as plastics and wood. aliphatic isocyanates, the two main components of ther-
mosetting urethane coatings. It is a
slightly less effective viscosity
Photo courtesy of ABB Flexible Automation, Paint Automation Group

reducer for these polyols than n-

BuAc, but still yields low viscosity
solutions. These slight viscosity
differences in the pure solvents are
undetectable in fully formulated
systems. For example, TBAc was
used to reformulate the automo-
tive refinish clearcoat formulations
in Tables 4 and 5.
In both formulations, n-BuAc was
replaced with TBAc with no effect
on any of the formulation or coat-
ing properties. With TBAc being
VOC-exempt, the VOC content of
these formulations would decrease
from 4.4 to 3.3 lbs/gal for the low-
solids formulation and from 4.0 to
2.9 lbs/gal for the high-solids for-
mulation. These clearcoats could
High-solids acrylic polyols are typically supplied as be applied over conventional 6.6 lb. VOC/gal basecoats
80%-solids solutions in solvents such as MAK or n-BuAc. and still easily meet the 5.0 lb. VOC/gal limit for 2-stage
The isocyanate part, typically HDI or IPDI trimers, may topcoats based on the standard calculation:
also be supplied with up to 25% solvent. After mixing the
two components, additional solvent must be added to Topcoat VOC content (lbs/gal) = (6.6 lbs VOC/gal) + [2 x (3.3 lbs VOC/gal)]
achieve sprayable viscosity. Typical solids contents at 3
spray viscosity are in the 55–65% range. = 4.40 lbs/gal topcoat
Recently, the EPA published a federal rule2 restricting
the VOC content of coating formulations supplied to the
automotive refinish industry. The new VOC content lim- Table 3 / VOC Content Standards for Automotive Refinish
its are listed in Table 3. The compliance date was Janu- Coatings
ary 11, 1999. Coating Category g/L lbs/gal
These new VOC content limits are difficult to achieve Pretreatment wash primer 780 6.5
without exempt solvents. Waterborne coatings still do Primer/Primer surfacer 580 4.8
not have the dry times and ease of use required by the Primer sealer 550 4.6
refinish market. High-solids resins are more difficult to Single/2-stage topcoats 600 5.0
spray and have shorter pot lives than their lower-solids Topcoats of 3 or more stages 630 5.2
counterparts. Acetone and PCBTF are currently being Multicolored topcoats 680 5.7
used to lower the VOC content of some refinish systems, Specialty coatings 840 7.0
Formulating with Exempt Solvents

Table 4 / Formulation Constants

Conventional TBAc-Based High-Solids TBAc-Based
G-Cure 105 P70 100.0 100.0 50.0 50.0
SCX 920 0.0 0.0 50.0 50.0
T-12 (1% in toluene) 1.9 1.9 0.3 0.3
FC 430 (10% in toluene) 0.3 0.3 0.3 0.3
Luxate HT2090 or XHT2090T 28.3 28.3 33.9 25.4
Luxate XIT1070T 0.0 0.0 0.0 15.6
MAK 25.0 25.0 24.0 24.0
n-Butyl acetate 25.0 0.0 24.0 0.0
TBAc 0.0 25.0 0.0 24.0
Total lbs 205.5 205.5 206.5 213.6
% solids 46 46 51 51
Lbs VOC/gal 4.40 3.28 3.96 2.86
Viscosity, sec #2 Zahn 21.2 21.1 20.9 20.8
Dry Time, hours 3.2 3.5 7 4

Table 5 / Coating Properties

Conventional TBAc-Based High-Solids TBAc-Based
20° gloss 88 88 90 90
60° gloss 95 95 95 95
DOI 90 90 90 90
Reverse Impact, lbs 160 160 160 160
Direct Impact, lbs 160 160 160 160
Cross hatch adhesion, % 100 100 100 100
10% acid resistance (30 min) Pass Pass Pass Pass
100 MEK double rubs Pass Pass Pass Pass
Gloss retention, 2,500hr QUVB 25.42 25.16 ——- ——-

Nitrocellulose Lacquers environmental impacts. For example, switching to

Nitrocellulose lacquers are still used extensively in the waterborne coatings requires that waste products be
wood coating industry as clearcoats because of their segregated and can create additional issues in areas
unmatched clarity, depth and ease of use. They are also such as product application and performance. Even con-
commonly used as fast-drying primers in the automotive trolling emissions can have a negative environmental
refinish industry. Because of their high solvent content, impact — incineration of VOC emissions generates NOx,
these coatings have also come under increasing regula- another precursor to tropospheric ozone. In NOx-limited
tory pressure. areas, incinerating VOCs could actually make the ozone
problem worse than emitting them.

W
ood furniture manufacturers are subject to TBAc is an active solvent for nitrocellulose. Figure 6
both Control Technique Guidelines (CTG) that illustrates how it efficiently reduces the viscosity of both
limit VOC content and a National Emission RS and SS-type resins for spray application. Low-VOC
Standard for Hazardous Air Pollutants (NESHAP) that and low-HAP wood lacquer formulations were also
limits the HAP content of the products they use.3 These developed. Replacing xylene, MEK, and n-BuAc with
limits can have a significant economic impact on small TBAc and TBAc/PMAc blends reduced the VOC content
to medium-size manufacturers, who either have to from 4.0 lbs/lb. solids to 1.5 lbs/lb. solids and reduced
install emission control devices or switch to more VHAP (volatile hazardous air pollutant) content from 2.3
expensive technologies such as waterborne or UV-cur- lbs/lb. solids to 0.23 lbs/lb. solids.
able coatings. Dry times, gloss, and whiteness were slightly
Any switch involves conversion costs and a new set of improved over the high-VOC formulation. Propylene gly-
Formulating with Exempt Solvents

Table 6 / Solution Viscosities

Resin Type Chain-Stopped Medium-Oil Chain-Stopped
Alkyd Soya Alkyd Alkyd
Resin Name Beckosol Beckosol Beckosol
12-054 11-045 12-102
Solvent or Blend Solution Viscosity at 50% solids, cps Relative Evaporation Rate
TBAc 2,240 108 885 2.79
70:30 TBAc:MAK 511 89 295 1.05
n-BuAc 1,020 69 433 1.00
70:20:10 TBAc:PMAc:EEP 668 246 324 0.96
70:20:10 TBAc:MAK:Exxate 600 Gelled 108 344 0.95
70:20:10 TBAc:MAK:EEP 580 89 334 0.90
Xylene 6,400 89 1,690 0.70
70:30 TBAc:Exxate 600 1,170 98 492 0.64
85:15 TBAc:NMP 1,300 118 730 0.49
85:15 TBAc:Exxate 1000 2,530 98 718 0.40
MAK 344 49 167 0.33

col methyl ether acetate (PMAc), a non-HAP glycol ether coating formulators have developed high-solids, air-dry-
commercially available from Lyondell, reduced the vis- ing alkyds but drying rates and performance are typically
cosity of this nitrocellulose-based lacquer formulation inferior to their low-solids counterparts. The wood furni-
better than n-butyl acetate and gave equivalent dry ture, aerosol, general metal, light transportation, and
times and coating performance. machinery and equipment markets would benefit from
low-VOC, low-solids alkyd systems that performance as
Alkyd Coatings well as conventional formulations.
Alkyds are one of the leading coating technologies Table 6 lists solution viscosities for three alkyd resins
because of their low cost, ambient curing capability and from Reichhold Chemical in a range of solvents and
film properties.12 They are popular coatings in the archi- blends. Solvents and blends are listed in order of decreas-
tectural, industrial-maintenance and OEM market sec- ing evaporation rate. The 70:30 TBAc:MAK blend is a good
tors. However, they also have come under regulatory match for n-BuAc, giving similar solution viscosities for
pressure because of their relatively high VOC content. all three resins and a similar evaporation rate. The prop-
Alkyd resins are commonly supplied as 50–60% solids erties of xylene can be approximated with blends of TBAc
solutions in xylene or mineral spirits and further reduced and slower solvents such as MAK, PM Acetate, EEP, or
to 35–50% solids before application. Resin producers and Exxates. Low-VOC formulations with these base resins
have been developed and new TBAc-based resins are now
available from Reichhold. Figure 7 illustrates how using
TBAc significantly reduces the VOC content and ozone-
Figure 6 / Brookfield Viscosity of Nitrocellulose Solutions
in TBAc as a Function of Solids Content forming potential of these formulations.
First, xylene was replaced with a TBAc/MAK/DPM
1,000 acetate blend in a white enamel formulation based on
478 the commercial chain-stopped alkyd, Beckosol 12-102.
1/2 sec SS
This reduced the VOC content of the formulation from
Viscosity, cps

1/2 sec RS
266 4.8 to 4.0 lbs/gal. More importantly, it reduced its ozone-
100
114 forming potential from 5.4 to 4.0 lbs ozone per pound of
solids applied.
72
A more significant reduction in both VOC content and
25
ozone impact was achieved when the resin itself was
18
supplied in 95/5 TBAc/xylene. The VOC content was
10 reduced to 1.7 lbs/gal and the ozone yield was 0.8 lbs
5 10 15 20 25
% Resin Solids ozone per pound of solids applied. These numbers are
 the greatest, ozone yield is high,

REACTIVITY:
the science behind
and the potential impact on
human population is highest.

the policy Recently, the accuracy of IR

scales in measuring photochemi-
cal reactivity has also come into
ecause hydrogen abstrac- ozone-forming potential of VOCs question. Most MIR critics point

B tion is a required first step

for most VOCs, the rate
constant for this step (kOH) was
than kOH because some organic
radicals, while slow to form,
decompose to yield more ozone
to the fact that MIR uses a sin-
gle-day atmospheric box model
instead of the more sophisticat-
originally considered to be a than more reactive VOCs. IRs ed multi-day, 3-D airshed models
crude but acceptable measure of also take into account the envi- available today. However, these
a VOC’s potential to form ozone. ronment in which the VOC sophisticated models require an
Since then, a few solvents have reacts. NOx, other VOCs, and the accurate inventory of the reac-
been added to the original list of amount of light present all affect tive organic gases present in the
VOC-exempt compounds includ- the amount of ozone formed atmosphere to correctly predict
ing acetone, p-chlorobenzotri- from the same VOC. Several IR the reactivity of individual VOCs.
fluoride (PCBTF), and per- scales have been developed to To date, regulatory agencies
chloroethylene (PERC). In the reflect the varying levels of pol- have been unable to maintain an
case of acetone, Incremental lution found in our cities. One of accurate inventory of the reac-
Reactivities (IRs) were used by those, the Base Scale, an aver- tive gases present in the atmos-
the EPA to demonstrate that ace- aged IR for 39 US cities with dif- phere. It is unlikely that industry
tone was less reactive than ferent NOx levels, was the basis can afford to quantify each VOC
ethane. IR is the amount of for the acetone exemption. Today, present in emissions, and bio-
excess ozone formed when a the MIR scale is most commonly genic VOC emissions are still not
VOC is added to a mixture of used to compare VOC reactivi- accurately tracked or modeled.
reactive organic gases in the ties. MIR is the most sensitive Because of these inventory limi-
presence of NOx and light. His- scale and represents a high Nox tations, it is still not clear that
torically, IRs have been expressed scenario, typical of a polluted airshed models can give a more
as grams ozone formed per gram urban environment. It describes realistic scale of VOC reactivities
of VOC added. an environment where VOC con- than the simpler box models.
IR is a better measure of the tribution to ozone formation is Until emissions inventories are

identical to the 2K waterborne urethane system Conclusion

described earlier. In addition, the ozone impact is lower The EPA is proposing to exempt TBAc from VOC-regula-
than either the commercial acrylic latex or urethane dis- tions because of its negligible potential to form ozone in
persions shown in Table 6. polluted urban environments. Although TBAc would
This example demonstrates that medium-solids alkyd become the latest VOC-exempt solvent, it also would be
systems, when properly formulated with exempt sol- one of the first practical solvents for coatings, ink, adhe-
vents, can not only rival the VOC content of water-based sives and cleaners to be added to the exempt list. In
and high-solids systems but can also have a lower ozone addition, its low reactivity, low toxicity and negligible
impact. environmental impact make it likely that TBAc will con-
Formulating with Exempt Solvents

tinue to enjoy a preferred regulatory status even after Figure 7 / VOC Content and Ozone-Forming Potential of a
the EPA completes its VOC policy revision. Commercial Alkyd Formulation.
Solventborne coatings, when properly formulated
with exempt solvents, can be as environmentally friend- 6.0
5.4
ly as their waterborne versions despite having higher lbs VOC/gal.
5.0 4.8
solvent contents. TBAc gives the formulator an addition- lbs Ozone/lb Solids
al tool for achieving VOC and HAP compliance without 4.0 4.0
4.0
compromising performance, switching to a different

Pounds
technology, negatively impacting the environment, or
3.0
significantly increasing costs.
2.0 1.7
Acknowledgements
The authors wish to thank Pat Peterson of Zeneca Resins,
1.0 0.8
Carol Fox of Hercules Inc., Roy and Carol Williams of Reich-
hold Chemical, and Henri Barnowski of Lyondell Chemical for 0
their technical contributions. Standard TBAc-Based With TBAc-
White Enamal Formulation Based Resin
Formulation

refined, MIR is still the best ating other environmental prob- should be encouraged.
available tool to rank VOCs for lems or significant economic What does this mean for the
the purpose of exemptions or a hardship. formulators and users of coat-
reactivity-based policy. ings? The bad news is that practi-
Regardless of their differences, Formulating for Today cal, VOC-exempt solvents will
both models give similar results and Tomorrow continue to be rare. The good
for most VOCs. For example, ter- Under the current policy, VOC news is that a handful are avail-
tiary butyl acetate (TBAc) is 3 exemptions are one way for the able today and that solvent-
times less reactive than ethane EPA to encourage the use of low- based coatings formulated with
using a box model and 2.5 times reactivity solvents. Unfortunate- low-reactivity solvents are likely
less reactive using a 3-D, multi- ly, most exempt solvents are not to be an acceptable compliance
day scenario. Compared to m- useful coating solvents and, option when the new VOC-policy
xylene, TBAc is 63 times less aside from TBAc, it appears is put in place.
reactive using a box model and unlikely that many more will be Consequently, reformulating
25 times less reactive using the exempted. Ultimately, the EPA’s today with non-HAP, low-reactivi-
3-D model. Although the magni- VOC policy will likely evolve to a ty solvents can pay both immedi-
tude of the difference depends weighted reactivity scale similar ate and lasting dividends to
on which model is used, the to that proposed by the Califor- those willing to invest. These div-
same basic conclusions can be nia Air Resources Board. Another idends can come in a variety of
drawn in either case: TBAc is less possibility is that VOCs will be forms, including the following.
reactive than ethane, and replac- classified in reactivity “bins,” • Lower compliance costs,
ing xylene with TBAc would sig- again using some reactivity • Lower reformulation costs,
nificantly reduce ozone forma- scale. Regardless of the outcome • Universally compliant formula-
tion of this policy reevaluation, using tions,
The challenge is formulating a low-reactivity solvents instead of • Improved corporate image and
policy that encourages substitu- more reactive solvents is more • Cleaner air. 
tions such as these without cre- environmentally sound and
Formulating with Exempt Solvents

For more information on solvents, contact Lyondell Chemical, 3 U.S. Environmental Protection Agency Home Page.
3801 West Chester Pike, Newtown Square, PA 19073; phone http://www.epa.gov/ttn/uatw/wood/riwood.html.
888/777.0232; visit www.lyondell.com; or Circle Number 83. 4 U.S. Environmental Protection Agency Home Page.

http://www.epa.gov/ttncaaa1/t1/meta/m25550.html.
For more information on Apollo Sprayers, write 1030 Joshua 5 Proceedings of the First Photochemical Reactivity

Way, Vista, CA 92083; call 760/727.8300 (Parts & Service) or Workshop, U.S. EPA, May 12-14, 1998.
800/578.7606 (Sales); fax 760/727.9325; e-mail 6 The EPA is proposing to use the reactivity of ethane

apollo@hvlp.com; or Circle Number 84. on a per-mole basis as the criterion for VOC-exemp-
tions. Previous EPA policy documents had stated that
For more information on BetzDearborn, write BetzDearborn, the exemption criterion should be the reactivity
Div. of Hercules Inc., 4636 Somerton Road, Trevose, PA ethane on a per gram basis.
19053-6783; phone 215/355.3300; visit 7 Proposed rule CFR 64-FR-52731.

www.betzdearborn.com; or Circle Number 85. 8 California Air Resources Board Home Page.

http://www.arb.ca.gov/consprod/regact/reactsub/react
For more information on ABB Flexible Automation, contact sub.htm.
Scott Baldwin, Director of Marketing, ABB Flexible Automa- 9 MIRs for many industrial chemicals and solvents can

tion, Paint Automation Group, 1250 Brown Road, Auburn be downloaded from Dr. William Carter’s website at
Hills, MI 48326; call 248/391.8492; e-mail scott.e.baldwin@ http://cert.ucr.edu/~carter/bycarter.htm
usfla.mail.abb.com; or Circle Number 86. 10 The full text of Dr. William Carter’s report on TBAc

reactivity can be downloaded from his website.9

References 11 A data sheet detailing the environmental properties of
1 U.S. Environmental Protection Agency Home Page. TBAc is available from Lyondell Chemical by calling
http://www.epa.gov/ttncaaa1/t1/meta/m17900.html. 888/777.0232
2 U.S. Environmental Protection Agency Home Page. 12 See, for example, Coatings, VI, A Multiple-Client Study,

http://www.epa.gov/ttnuatw1/183e/arc/arcpg.html. Skeist Incorporated, Whippany, NJ, October 1998.

Reprinted from Paint & Coatings Industry Magazine, November, '99 LCC-PC96-0002