Part 4: Plasticizers
MNL17-EB/Jun. 1995
Plasticizers
by Peter Tan 1 and Leonard G. Krauskopf 2
PAINTANDCOATINGFORMULATIONSoften incorporate high boil-
ing fluids as plasticizers where rigid or brittle resins fail to
meet toughness and flexibility requirements. The primary
function of the plasticizer is to impart flexibility to the resin,
thus minimizing film cracking. Depending on resin and other
ingredients used in the system, plasticizer choice may affect
compatibility, toughness, flammability, smoke generation,
heat and light stability, and other aging or permanence-re-
lated performances. Plasticizers are primarily employed in
heavy gage coatings and/or when improved toughness is re-
quired for industrial, automotive, and appliance applica-
tions.
Plasticizers function by reducing the glass transition tem-
perature of the resin to a point below its application tempera-
ture. The chemical mechanism of plasticization involves a
strong polar association of polymer-plasticizer molecules,
but not a chemical reaction between them. Plasticizers fun-
damentally reduce Van Der Waals forces between polymer-
polymer molecules in the amorphous regions and do not
penetrate crystallites [1-3]. The plasticized morphological
phase is then of a different nature than that of the neat
polymer and has unique mechanical properties.
The absence of a chemical bond between the plasticizer
and the polymer impairs permanence; plasticizer molecules
are free to leave the polymeric coating by means of extraction
and volatility. Plasticizer loss, however, is minimal in most
applications except for very low molecular weight plasticizers
and/or exposure to very severe thermal conditions. Thus,
plasticized coatings products have high durability and long
service life in most applications. Plasticizers are liquids of
molecular weight greater than that of solvents--to limit vola-
t i l i t y - b u t are not solids, such as alloying polymers, etc. It
should be noted that cross-linked resinous coatings signifi-
cantly reduce plasticizer loss due to diffusibility and volatil-
ity. Several thousand high boiling fluids are potential plasti-
cizers for coatings applications. The choice of plasticizer is
dependent on compatibility with the resin in use, cost, and
other desired attributes.
Plasticizers may be classified by both chemical structure
and performance characteristics, as shown in Table 1 [4].
Typical plasticizers are liquid esters of molecular weight be-
tween about 200 to 800, with specific gravities between 0.75
tManager, Marketing Technical Services, Exxon Chemical Asia
PTE LTD, Intermediates Technology Center, Block 14 (Maxwell) No.
02-03, Science Park Drive, Singapore 0511.
2Research associate, Exxon Chemical Company, Intermediates
Technology, P.O. Box 241, Baton Rouge, LA 70821.
Copyright9 1995 by ASTM International
17
and 1.35 at 20/20~ viscosities between 50 to 450 cSt, vapor
pressure of less than 3.0 m m of mercury at 200~ and flash
points greater than 120~ (248~ They are generally stable
and innocuous and should not be considered a significant
threat to humans or the environment [5-6].
Plasticizer extenders are commonly used in extruded or
molded flexible plastic shapes. Extenders are low-cost or-
ganic oils that may be subdivided as groups of aliphatic,
aromatic, or chlorinated hydrocarbons. They are seldom
used in coatings due to their relatively high volatility and
limited compatibility in polar resins.
This chapter lists the basic properties of plasticizers and
methods for their determination. Methods for the isolation,
identification, and quantitative determinations of these plas-
ticizers are also included.
PHYSICAL A N D CHEMICAL P R O P E R T I E S
Acidity
Plasticizer acidity may be due to improper processing, deg-
radation during storage, contamination, presence of by-prod-
ucts, or residual catalyst. ASTM Test Method for Acidity in
Volatile Solvents and Chemical Intermediates Used in Paint,
Varnish, Lacquer, and Related Products (D 1613) may be
used for determination of acidity. Either ethyl or isopropyl
alcohol may be used as diluent for the plasticizer, which is
titrated with aqueous sodium hydroxide or potassium hy-
droxide to the phenolphthalein end point. Results may be
expressed in weight percent, as weight equivalents of acetic
acid, acid number (milligrams potassium hydroxide con-
sumed per gram of sample), or if the plasticizer is an ester, as
weight percent of the parent acid of the ester (see section
entitled "Ester Value").
Color
The majority of plasticizers are colorless. As a class, esters
are very stable chemical reagents. However, exposure to ab-
normal conditions such as high thermal or ultra-violet en-
ergy, moisture, or chemically active surfaces may induce de-
velopment of color bodies and/or chemical decomposition of
the plasticizers. Higher molecular weight phthalates, poly-
meric plasticizers, and chlorinated paraffins may range in
color from light to bright yellow. ASTM Test Method for
Color of Clear Liquids (Platinum-Cobalt Scale) (D 1209) is
the standard color measurement method for plasticizers.
115
www.astm.org
116 PAINT AND COATING TESTING MANUAL
TABLE 1--Plasticizer family/performance grid.
General Strong Low
Family Purpose Solvating Volatility
Phthalates X ,/ ,/
Trimellitates . . . . . . X ,/
Aliphatic dibasic . . . . . . . . .
esters
Phosphates ... ,/ ...
Epoxides . . . . . . ,/
Polyesters . . . . . . ~/
Extenders X . . . . . .
NOTE: X = Primary performance function.
Source: Society of Plastics Engineers, Regional Technical Conference (SPE, RETEC) Vinyl I; 1992; reprinted with permission.
APHA is a scale that is likewise used for liquids of low color.
The standards are based on platinum solutions without co-
balt and are described in ASTM Standard Method of Testing
Urethane F o a m Polyol Raw Materials (D 2849).
ASTM Test Method for Color of Transparent Liquids
(D 1544) employs the Gardner Color Scale for amber a n d
dark-colored plasticizers which cannot be read on the plati-
num-cobalt (Pt-Co) or APHA scales. Gardner standards are
colored disks held in a "Hellige" gage. Gardner values of ' T '
and "2" are approximately equivalent to 250 and 400, respec-
tively, on the APHA scale. The Gardner scale goes up to "18"
for use with increasingly darker amber and brownish color
liquids.
The platinum-cobalt scale is also known as the Hazen scale,
but readers should be aware of potential confusion with The
American Public Health Association (APHA); APHA adopted
a version of this scale in which a Hazen color of one is the
same as APHA 100. To avoid confusion, it is r e c o m m e n d e d
that only the Pt-Co scale be used when referring to Procedure
D 1209.
The APHA color scale in ASTM D 2849 reflects a slightly
greenish hue for APHA versus the Pt-Co scale, which is
slightly yellowish. The scale readings are similar in the 25 to
50 range, but in the vicinity of 100 Pt-Co, the APHA scale (Pt
only) reads 10 to 20 units lighter (lower). Both the Pt-Co and
APHA scales cover a range from "3" up to "500," but are
r e c o m m e n d e d for use for liquids having colors -<250 units.
An instrumental method (Hunter Colorimeter) that is five
to seven times more precise m a y also be used for color mea-
surement, replacing the subjective comparisons of the above
methods using Nessler tubes; while c o m m o n l y used in com-
mercial practice, the Hunter Colorimeter is not yet defined as
an ASTM method.
Copper Corrosion
ASTM Test Method for Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test
(D 130), and ASTM Test Method for Copper Corrosion of
Industrial Aromatic Hydrocarbons (D 849), which is nor-
mally applied to hydrocarbon solvents, m a y be used to evalu-
ate the copper corrosive tendencies if suspected to be sourced
in plasticizer. The appearance of a copper strip, which has
been immersed in the test fluid, under standard conditions, is
c o m p a r e d with twelve special standard strips classified as
follow:
1. Slight tarnish (la,b) light orange, dark orange.
2. Moderate tarnish (2a,b,c,d,e) claret red, brassy, or gold.
Low Low Flame
Temperature Diffusibility Resistant Stabilizer
~/ ~/ ...
,/ ...
X . . . . . .
,/ ... X
,/ . . . . . . X
..- X -..
~/ . . . . . .
3. Dark tarnish (3a,b) magenta, multicolored.
4. Corrosion (4a,b,c) transparent black, jet black.
The historical application of copper corrosion testing to
plasticizers was an attempt to measure effects contributed by
residual sulfur c o m p o u n d s due to sulfur-based catalysts,
which m a y hydrolyze to acidic pH in the presence of mois-
ture. Current commercial grade plasticizers do not typically
contribute to copper corrosion. Commercial grade alkyl sul-
fonate esters of phenol [7] are plasticizers in which the sulfur
is organically "combined" and not readily susceptible to hy-
drolyses.
Distillation Range
Most plasticizers have high boiling points or boiling
ranges. This property can be used as a measure of its degree
of permanence or resistance to loss through volatilization.
Presence of lighter components can also be detected. The
measurement of vapor pressure is a costly and time-con-
suming procedure. Thus, commercial liquids of high molecu-
lar w e i g h t - - l o w vapor pressures--are typically characterized
by boiling ranges in which one determines initial, mid, and
final (or drypoint) boiling point temperatures. For fluids with
dry point > 140~ ASTM Test Method for Distillation of Pe-
troleum Products (D 86) is used. Fluids with dry point
< 140~ are measured using ASTM Test Method for Distilla-
tion Range of Volatile Organic Liquids (D 1078). For very
high boiling fluids or where decomposition m a y occur, distil-
lation m a y be done under v a c u u m regulated at 5 m m Hg. The
initial and final boiling points or the mid boiling point are
typically reported.
Gas chromatographic (GC) techniques are c o m m o n l y ap-
plied as a fundamental measure of plasticizer chemical purity
and isomer distribution. Direct relationships between GC
traces and boiling ranges have not yet been established for
plasticizers.
Both distillation range and GC analyses are means to relate
vaporization characteristics of plasticizers to practical needs.
The fundamental characteristic of vapor pressure m a y be
measured by ASTM Test Method for Vapor Pressure-Temper-
ature Relationship and Initial Decomposition Temperature
of Liquids by Isoteniscope (D 2879). The log of plasticizer
vapor pressure varies linearly with the reciprocal absolute
temperature (degrees Kelvin) according to the Clausius-
Clapeyron equation [8]
In - R ~22 - ~
1) (1)

where
P1 and P2 = vapor pressure, g.cm2.s -2,
T1 and T2 = respective temperatures, K,
AH = molar heat of vaporization, cal.g- 1, and
R = gas constant, 1.99 cal ~
Vapor pressure values are useful to estimate normal boiling
points at 760 m m mercury and solubility parameters [1].
Sears and Darby have reported that the vapor pressure of
binary plasticizer blends may be expected to fall between the
values of the neat plasticizers, but cannot be predicted from a
knowledge of the blend ratio and the neat vapor pressures.
Ester Value
Esters are the largest group of materials that are commer-
cially useful as plasticizers. This is a result of reasonable costs
and broad utility in a wide range of polymers having moder-
ate to high polarity characteristics. Ester value can be used to
estimate the purity or ester content of the plasticizer. ASTM
Test Method for Ester Value of Lacquer Solvents and Thin-
ners (D 1617) or ASTM Methods of Sampling and Testing
Plasticizers Used in Plastics (D 1045) may be used for this
determination. The methods involve saponification of the
ester in a known excess amount of KOH. The excess amount
of KOH is then determined by titration with standard sulfuric
acid. The amount o f / ( O H consumed in the saponification
process is a measure of the ester content of the plasticizer.
A gas chromatography method, ASTM Test Method for
Purity of Monomeric Plasticizers by Gas Chromatography
(D 3465), may also be used to determine the purity of mono-
merle plasticizers. The GC method does not provide "ester
values." It is useful to characterize major isomers present
versus known standards and to ascertain trace quantities of
nonparent organic compounds. GC instrumentation is costly
and requires comparison of output traces against a library of
known materials that have been characterized under a spe-
cific set of conditions using specific GC instruments and col-
umns.
Flash P o i n t
Most plasticizers are high flash materials. Either ASTM
Test Method for Flash and Fire Points by Cleveland Open Cup
(D 92) or ASTM Test Method for Flash Point by Pensky-
Martens Closed Tester (D 93) may be used. Preference should
be for the dosed cup method; this yields a more conservative
number and is consistent with Department of Transportation
(DOT) regulations in the United States. DOT has revised the
definitions and classifications of hazardous materials, effec-
tive 1 Oct. 1993, as follows:
Flash Point
Not Regulated >_93~ (200~
Combustible 61 to 92.5~ (142 to 199~
Flammable <_60.5~ (141~
The "flash point" is defined as the minimum temperature at
which a liquid gives off vapor within a test vessel in sufficient
concentration to form an ignitable mixture with air near the
surface of the liquid as determined by ASTM Test Method for
Flash Point by Tag Closed Tester (D 56) or ASTM Test Meth-
CHAPTER 17--PLASTICIZERS 117
ods for Flash Point of Liquids by Setaflash Closed Cup Appa-
ratus (D 3278).
Flash point values are reported for commercially sig-
nificant monomeric plasticizers in E. J. Wickson's Handbook
on PVC Formulating [7]. While not a very good analytical tool,
flash points will reflect presence of nonparent, low-flash-
point contaminants.
P o u r Point
Due to the high molecular weight and isomeric mixtures of
plasticizers, few have distinct freezing points. The pour point
can be useful information for handling plasticizers during
cold seasons. Method of measurement is described in ASTM
Test Methods for Pour Point of Petroleum Oils (D 97). Plasti-
cizer pour point temperatures may also be estimated from
viscosity/temperature plots as the temperature at which kine-
matic viscosity is 50 000 cSt. Most plasticizers have pour
points of less than - 30~ [7]; no known relationship exists
between pour point and plasticizer performance properties in
polymers under low-temperature conditions.
Refractive I n d e x
The refractive index of a plasticizer is measured using
ASTM Test Method for Refractive Index and Refractive Dis-
persion of Hydrocarbon Liquids (D 1218). Refractive index is
often thought of as a means of identifying the plasticizer. This
is an erroneous assumption. It may be used, however, to
differentiate between classes of plasticizers, as, for example,
between phthalates and adipates [10]. When used with other
physical measurements, refractive index may be used as a
supplemental test. Refractive index can also be used to check
for product contamination, but it is only useful to distinctify
commercial materials having very widely different refractive
indices.
R e s i d u a l Odor
Residual odor may be contributed by reaction by-products
from manufacturing or by residual raw ingredients which are
often more volatile and odorous than the plasticizer. When
ASTM Test Method for Odor of Volatile Solvents and Diluents
(D 1296) is used, tests at elevated temperatures (about 150~
can be considered to improve detection. Since odor is a
subjective characteristic, generalizations for plasticizers are
limited to terms such as "mild and characteristic."
Sampling
To obtain representative samples of plasticizers for evalu-
ation, ASTM Methods for Sampling and Testing Plasticizers
Used in Plastics (D 1045) may be followed. ASTM Recom-
mended Practice for Sampling of Industrial Chemicals
(E 300) can also be used.
Density a n d Specific Gravity
Density is an important characteristic for design engineer-
ing of plasticizer storage and building facilities. Specific grav-
ity is the density of the given reagent relative to that of water
118 PAINT AND COATING TESTING MANUAL
at the specified temperature; it is generally used in the charac-
terization of plasticizers or as a means to detect gross con-
tamination. Specific gravity at 20/20~ is measured with
ASTM Test Methods for Specific Gravity of Liquid Industrial
Chemicals (D 891) and is commonly employed in industry.
Commercial plasticizers typically fall within the range of 0.92
to 1.50 sp gr at 20/20~ ASTM Test Method for Density and
Relative Density of Liquids by Digital Density Meter (D 4052)
is the recommended procedure to measure specific gravity of
fluids that lie between 0.68 and 0.97; this method is applica-
ble to hydrocarbons that are commonly used as plasticizer
extenders.
Viscosity
Viscosity measures the fluid's resistance to flow; the thicker
the fluid, the higher its viscosity and the greater its resistance
to flow under gravity. In ASTM Test Method for Kinematic
Viscosity of Transparent and Opaque Liquids (and the Calcu-
lation of Dynamic Viscosity) (D 445), time is measured in
seconds for a fixed volume of the fluid to flow under gravity
through the capillary of a calibrated viscometer at constant
temperature. The kinematic viscosity of a plasticizer varies as
a log log function versus the log of absolute temperature
according to the following equation
log log ~ ---A - B log T (2)
where
= kinematic viscosity, centistokes,
T = temperature, degrees Kelvin, and
A and B = constants.
This reflects the tremendous influence of temperature on
viscosity and allows one to interpolate viscosity values at
specified temperatures. The kinematic viscosity (centistokes)
can be converted to its dynamic viscosity (centipoise) by
multiplying by the true density of the fluid at the specified
temperature: dynamic viscosity, cP = kinematic viscosity,
cSt, times density.
Water
Residual water from manufacturing processes and mois-
ture absorbed from the atmosphere can affect the quality and
clarity of coatings. Water content can be measured using
ASTM Test Method for Water in Volatile Solvents (Fischer
Reagent Titration Method) (D 1364). Plasticizers are hydro-
phobic liquids and typically have a limited capacity to take up
water and/or be dissolved into water. Higher-molecular-
weight phthalates are practically insoluble in water with solu-
bilities in the 0.1 to 1.2 mg/L (ppm) range with even less
solubility in salt water [6].
Typical Properties
As shown in Table 1, commercial plasticizers fall into about
seven chemical family groups (eight if we were to add a
"miscellaneous" grouping). The major plasticizer types in use
are phthalates, trimellitates, and aliphatic dibasic esters such
as adipates. The families of esters are formed by reacting the
parent acid with monomeric alcohols ranging from C4H9OH
(butanol) to C13H27OH (tridecanol); the alcohol may also vary
in isomeric structure ranging from normal (unbranched) to
very specific and/or randomly branched structures. Two alco-
hols have found wide usage in synthesis of commercial plasti-
cizers--2-ethylhexanol and isononanol--a mixture of ran-
domly branched (primarily methyl branched) nonyl isomers.
Table 2 is a summary of typical properties of plasticizers
derived from these two alcohols with the major parent
acids--phthalic, trimellitic, and adipic [11].
METHODS OF IDENTIFICATION
A plasticizer may initially be characterized by its functional
groups. While absolute identification is complicated without
sophisticated chemical or instrumental methods, it is possi-
ble to identify the type of plasticizer by functional groups or
presence of elements associated only with the plasticizer by
the use of infrared analyses or wet chemistry. Most plasticiz-
ers are a member of one of the following families:
Plasticizer Type~Functional Group
Adipates
Chlorinated compounds
Epoxides (oxirane)
Phosphates
Phthalates
Polyesters
Trimellitates
Isolation of Plasticizers
Plasticizers may be separated from a lacquer or dried film
by solvent extraction if it is to be analyzed. The lacquer is first
dried to remove all solvents present. The dried solid is then
solvent extracted (in an appropriate apparatus) with hot ethyl
ether or another appropriate solvent that will extract the
plasticizers while leaving most of the resins behind. The ex-
tractant is concentrated, and a small amount of methyl or
ethyl alcohol is added. This will cause some of the dissolved
resin to precipitate out. Next, filter and concentrate the ex-
tractant. ASTM Test Method for Acetone Extraction of Phe-
nolic Molded or Laminated Products (D 494) may be applied.
Instrumental Methods
Modern instrumental analytical methods are able to
separate, identify, and quantify components in composite
mixtures. Rapidly falling costs of such instruments have en-
abled instrumental methods to be more widely available.
These include gas chromatography (GC), high-performance
liquid chromatography (HPLC), infrared spectroscopy
(FTIR), and other emerging analytical instruments like su-
percritical fluid chromatography (SFC), GC/FTIR, and
GC/MS (mass spectrometry).
Infrared Spectrophotometry
An infrared scan of the isolated plasticizer is by far the best
way to identify the functional groups in the molecule. Mix-
tures of plasticizers can present problems due to masking
effects. If one or more of the component plasticizers is known
and its IR scan available, subtracting it from the IR scan of
 CHAPTER 17--PLASTICIZERS 119

TABLE 2--Typical physical properties of plasticizer esters made with isononyl and 2-ethylhexyl alcohols.
Phthalate Trimellitate Adipate
DOP DINP TOTM TINTM DOA DINA
Alkyl 2EH INA 2EH INA 2EH INA
Molecular weight 390 424 546 596 370 404
Specific gravity at 20/20~ (68~ 0.986 0.973 0.992 0.979 0.927 0.924
Refractive Index n2D~ 1.484 1.486 1.482 1.484 1.445 1.449
Viscosity, cSt at 20~ 83 102 312 430 16 26
Pour point, ~ - 47 - 48 - 46 - 40 < - 60 - 59
Vapor pressure, mm Hg at 200~ 1.2 0.5 0.08 0.03 2.5 1.5
Mid boiling point, ~ at 5 turn Hg 230 245 300 331 215 233
Flash point, ~ 204 213 221 241 193 199
Color, Pt-Co <25 <25 < 100 < 100 <25 <25
Source: Edenbaum, J., Plastics Additives and Modifiers Handbook, Van Nostrand Reinhold, New York, 1992, p. 362. Reprinted with
permission.
NOTE:DOP di(2-ethylhexyl) phthalate
DINP di (isononyl) phthalate
TOTM tris(2-ethylhexyl) trirnellitate
TINTM tris(isononyl) trimellitate
DOA di(2-ethylhexyl) adipate
DINA di(isononyl) adipate

the mixture m a y aid in identification of the o t h e r c o m p o n e n t . Sulfur

Other c h r o m a t o g r a p h i c techniques could be used to s e p a r a t e
the c o m p o n e n t s before scanning.
Liquid Chromatography
C o l u m n c h r o m a t o g r a p h y involves d i s t r i b u t i o n of sub-
stances b e t w e e n liquid (mobile phase) a n d substrate (solid
phase). C o l u m n a n d thin layer c h r o m a t o g r a p h y can be used.
I n s t r u m e n t a l m e t h o d s using h i g h - p e r f o r m a n c e liquid chro-
m a t o g r a p h y (HPLC) with ultraviolet detection can be used
for separation, identification, a n d quantification of plasticiz-
ers w h i c h possess a suitable c h r o m o p h o r e .
Gas Chromatography
By c o m p a r i n g relative r e t e n t i o n t i m e s a n d p e a k s h a p e s
with k n o w n samples, a plasticizer o r mixture can often be
identified a n d quantified. W h e n coupled with IR (i.e.,
GC/FTIR), the IR s p e c t r u m of each c h r o m a t o g r a p h i c p e a k
can assist in the identification of functional groups a n d hence
plasticizer identity.
Qualitative Methods
F o r the detection of nitrogen, chlorine, sulphur, o r phos-
phorus, the s a m p l e needs to be fused with metallic sodium.
This p r e p a r a t i o n should be c a r r i e d out in a fume h o o d and
caution observed w h e n h a n d l i n g metallic sodium. A small
a m o u n t (about 3 m m 3) of metallic s o d i u m is p l a c e d in a d r y
6-in. (15.24-cm) test tube. The test t u b e should be held verti-
cally by c l a m p i n g it at the o p e n end. The test t u b e is t h e n
h e a t e d until a cloud of s o d i u m v a p o r begins to form. Remove
the flame immediately. Add two to three d r o p s of the plasti-
cizer s a m p l e directly to the s o d i u m vapor. W h e n the test tube
is cold, b r e a k off the end with the s o d i u m in a m o r t a r . Add
several milliliters of alcohol to d e s t r o y u n r e a c t e d sodium.
Add a b o u t 20 rnL of distilled o r deionized water, g r i n d u p the
sample, transfer to a beaker, b r i n g to boil, and filter. The
filtrate is t h e n used for the c h e m i c a l detection of the ele-
ments.
Add two to three d r o p s of 10% solution of lead acetate to
2 m L of a 10% solution of s o d i u m hydroxide. Add this mix-
ture to 5 m L of the filtrate, A b l a c k p r e c i p i t a t e of l e a d
sulphide indicates the presence of sulphur, Positive identifi-
cation suggests that the s a m p l e is either a s u l p h o n a m i d e o r
sulphate.
Nitrogen
Bring 2 mL of the filtrate to boil in a test tube. Add five
d r o p s of a 10% solution of N a O H a n d five d r o p s of 10%
ferrous sulphate solution. W h e n cold, add, dropwise, a 10%
solution of h y d r o c h l o r i c acid until the solution is acidic a n d
the precipitate of ferrous h y d r o x i d e has dissolved. Avoid us-
ing a n excessive a m o u n t of acid. A blue or green color o r blue
precipitate indicates p r e s e n c e of nitrogen. A positive test sug-
gests that the plasticizer could be an amide.
Chlorine
Acidify 5 m L of the filtrate with several d r o p s of dilute
sulfuric acid a n d b r i n g it to boil. Cool a n d acidify with nitric
acid. Add several d r o p s of a 10% silver nitrate solution. A
white precipitate indicates the presence of a c h l o r i n a t e d com-
pound.
Phosphorus
Boil 5 m L of the filtrate with 3 m L of c o n c e n t r a t e d nitric
acid for I rain. Cool and a d d twice the v o l u m e of 10% a m m o -
n i u m m o l y b d a t e solution. H e a t to a b o u t 60~ a n d set aside to
cool. A yellow precipitate indicates the presence of p h o s p h o -
rus. P h o s p h a t e plasticizers will result in a positive test.
Phthalates
Add a b o u t 0.05 g of resorcinol and 0.05 g of p h e n o l to sepa-
rate 6-in. (15.24-cm) test tubes. Add to each test t u b e two to
three drops of the isolated plasticizer a n d a d r o p of concen-
120 PAINT AND COATING TESTING MANUAL
trated sulfuric acid. Heat the contents in an oil bath at 160~
for several minutes. Cool and add 2 mL of distilled water and
2 mL of 10% sodium hydroxide solution and stir. The pres-
ence of phthalate is indicated by a pronounced green fluores-
cence in the tube with resorcinol, and the tube with phenol
will be red.
PERFORMANCE PROPERTIES
Compatibility
Compatibility is the ability of two or more substances to
mix together without objectionable separation [12]. In the
case of plasticizers, it is primarily a measure of the solvency
or strength of positive interactions between the plasticizer
and the polymer which attract them together.
Solvency is the extent (or amount) of interaction of plasti-
cizer or solvent molecules at the surface of a polymer particle;
a solid solution results when the polymer and plasticizer--
and possibly additional reagents--become molecularly ho-
mogeneous. The degree to which a homogeneous solution, or
miscibility, is stable is a function of the plasticizer/polymer
interactions when in the presence of other reagents employed
in the coating formulation; it must be recognized that the
presence of these additional reagents can compete with the
polymer/plasticizer interactions. The rule of thumb "like dis-
solves like" applies, but more specific knowledge is required
to avoid results that appear to be anomalous.
Dried polymeric coatings may be considered as solid solu-
tions; the limits of miscibility are impacted by all of the
reagents that become components of the coating--those in-
tentionally added, as well as inadvertent contaminates and/or
degradation products formed in the coating process. When
plasticizers are employed, they have a major effect on com-
patibility, primarily due to the level, or concentration, used in
the polymer. If we accept the definition of a solution as a
homogeneous mixture of two or more types of molecules,
then "solvency" is a measure of a given solvent or plasticizer
to homogenize and interact with a given polymer. Quantifica-
tion of this "interaction" has been elusive; scales which have
been devised are capable of measuring only gross differences.
Observations of phase separation of plasticizer/polymer have
been more finite than that predicted in many cases, while on
the other hand, observations of symptoms (compatibility) are
incapable of separating "solvency" from other interfering
mechanisms that are concurrent, such as diffusibility.
Hansen publications [13-14] define the total solubility pa-
rameters of polymers, solvents, and other reagents as a func-
tion of three component parameters:
)kT = (~t~ + ~tp2 -{- }~)1/2, ( c a l / c m 3 ) l / 2
where
hr = total solubility parameter,
hd = dispersion parameter,
hp = polarity parameter, and
hh = hydrogen bonding parameter.
The location of polymers and other non-ionic reagents may
be defined on this three-dimensional grid. Hansen states that
it may be assumed that the closer a plasticizer lies to the
center of the polymer solubility space of a polymer, the more
compatible it will be with the given polymer. Many materials
have been characterized in this fashion. Exxon Chemical
Company has developed a computerized capability to define
the location of various solvents and plasticizers relative to
that of various polymers; it is called the CO-ACT| program
and contains information on more than 1200 resins, solvents,
and plasticizers [15].
Compatibility data for different plasticizer resin systems
are available in various publications [1,16-17]. The plasticiz-
ers are usually presented as compatible, incompatible, or
partially compatible with the resins. These data are often not
useful due to incomplete description of the resin or a lack of
standard approach in the test and reporting of observations.
Where Hansen parameters are available for the plasticizers
and resins, comparison of three-dimensional Hansen solubil-
ity parameters provide a better measure of compatibility as
described earlier. Table 3 lists generalized examples of plasti-
cizers and their compatibility with various coating resins.
Permanence
"Reactive" plasticizers are specialty types designed to self-
polymerize or graft onto the polymeric resin during the
curing process. But, in most cases, plasticizers do not chemi-
cally react with the polymer. They function by an overall
solvating action that is less strong than that of a good solvent,
but stronger than that of incompatible reagents such as lubri-
cants. This interaction imparts a slight effect on plasticizer
"permanence," or more properly "transience." One of two fac-
tors are generally the controlling influence over loss of plasti-
cizer:
9 Rate of diffusion of plasticizer from the resin bulk to the
surface.
9 Rate of loss of plasticizer from the surface.
The slowest rate of the two is the controlling factor under
any specific set of conditions. Volatility and extraction by
aqueous reagents are generally surface-controlled losses,
while rate of diffusion controls loss under oil immersion and
similar tests. The subject is very complex [1-2], but one may
consider plasticizer vapor pressure as a key predictor of vola-
tile loss, while diffusion-controlled losses are improved with
plasticizers of higher molecular weight and branchiness in
the chemical structure.
Resistance to washing is typically characterized as a func-
tion of thermal and/or humidity cycling exposures. This is a
measure of the aging resistance of the plasticized polymeric
coating.
Low-Temperature Properties
(3) Some applications require flexibility and impact resistance
at low temperatures. This property may be significantly im-
proved at increased plasticizer levels, as well as being a func-
tion of the plasticizer type [1 ]. For example, at approximately
50 PHR, plasticizer in poly(vinyl chloride) phthalates of lin-
ear alcohols impart about - 10~ improvement in low-tem-
perature brittleness over branched, DOP-type, phthalate
plasticizer. Dialkyl adipates, however, impart about -25~
improvement over the brittleness value of DOP-plasticized
PVC as measured by ASTM Test Method for Brittleness Tem-
perature of Plastics and Elastomers by Impact (D 746).
 CHAPTER 17---PLASTICIZERS 121

TABLE 3--Plasticizers and their compatibility with coating resins.

Plasticizer CA CAB CN EC PMMA PS VAc VB PVC VC/VAc
Phthalates
DOP I C C C C C I P C C
DIOP I C C C C C C P C C
DINP P C C C C C C P C C
DIDP P C C C P C P P C C

Trimellitates
TOTM P C C C P C P P C C
TINTM P C C C P C P P C C

Phosphates
TCP C C C C P C C C C C
TOP P P C C I C I C C C

Acyclic esters
DOA P C C C P C P P C C
DINA P C C C P C P P C C
DOZ P C C C P C P P C C
DOS P C C C P C P P C C

Epoxidized
S o y b e a n oil I P C C I I I I C C
(2EH) tallate I C C C I I I C C C

Polyesters
Adipic/Diol P C C C P C P P C C
Phthalic/Diol P C C C P C P P C C
C = Compatible; P = Partially compatible; I = Incompatible.
RESINS
CA = Cellulose Acetate
CAB = Cellulose Acetate/Butyrate
CN = Cellulose Nitrate
EC = Ethyl Cellulose
PMMA = Methyl Methacrylate
PS = Polystyrene
VAc = Vinyl Acetate
VB = Vinyl Butyral; 19 wt% Vinyl Alcohol
PVC = Vinyl Chloride
VC/VAc = Vinyl Chloride/Vinyl Acetate Copolymer: 90/10
PLASTICIZERS
Phthalates
DOP = di(2-ethylhexyl)
DIOP = di(isooctyl)
DINP = di(isononyl)
DIDP = di(isodecyl)
Trimellitates
TOTM = tris(2-ethylhexyl)
TINTM = tfis(isononyl)
Acyclic Esters
DOA = di(2-ethylhexyl) adipate
DINA = di(isononyl) adipate
DOZ = di(2-ethylhexyl) azelate
DOS = di(2-ethylhexyl) sebacate
NOTE: Compatibility of plasticizers in specific polymers is a function of relative concentration (PHR), as well
as the presence of other formulating reagents and residuals present in polymers. The above ratings are
based on plasticizer levels typically used in coatings applications (<40 PHR).

Commercial coatings require the optimum choice of plasti- REFERENCES

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or modulus, permanence, and low-temperature properties.
Acknowledgments
The authors would like to acknowledge the contributions,
consultation, and review given by their co-workers Arthur D.
Earlywine and Thomas M. Larson.
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