New Dibenzoate Plasticizer Blends for PVC Applications

William D. Arendt, Emily L. McBride, Rebecca D. Hanes

Emerald Performance Materials, 1296 Third Street, NW, Kalama, WA 98625

Dibenzoates plasticizers are well-established and are nonphthalate plasticizers [3, 4]. In addition to these plasti-
used in PVC applications. Chemically, these plasticiz- cizers, renewable, sustainable, green types of plasticizers
ers are non-phthalates and function well as high-sol-
vating. In the past, new benzoates, dibenzoate blends,
also contend for the GP plasticizer market. An example
and grades were developed to keep pace with formu- of one type is based on castor oil [5]. Others are based on
lators’ needs. More recently, a new generation of soybean oil [6].
dibenzoate triblend platform has been developed to Although these phthalate alternatives are viable, they
offer formulators an improved high solvator to comple- do not always give the performance desired in vinyl com-
ment general purpose plasticizer performance. A basic
plastisol evaluation protocol was utilized to help deter-
positions, particularly in plastisols (i.e., poor compatibil-
mine how to formulate with these new blends. In addi- ity, slow speed, high gel temperatures, less gel strength).
tion to the basic data that were developed, examples As is always the case, often performance can be adjusted
of performance in starting plastisol formulations are by the blends of plasticizers. There are limits to this
shown. J. VINYL ADDIT. TECHNOL., 20:137–142, 2014. V
C 2014
approach, however [7, 8].
Society of Plastics Engineers
Just as for GP plasticizers, there is a need for higher
solvator phthalate alternatives for PVC applications. Clas-
sically, butyl benzyl phthalate (BBP) has been the plasti-
BACKGROUND
cizer of choice when a high solvator was required. Di-n-
One of the best things about polyvinyl chloride (PVC) butyl phthalate and DIBP have also been used in the role
is its versatility. PVC can be formulated to a tremendous of higher solvators. Dibenzoates have also been classi-
number of applications. For flexible applications of PVC, cally used as high solvators. Diethylene glycol dibenzoate
plasticizers are the additives that provide this versatility. (DEGDB) and dipropylene glycol dibenzoate (DPGDB)
Plasticizer production is around 12 billion pounds per and blends thereof have principally been used and have
year [1]. Although there is tremendous pressure from a been used as nonphthalates before there was such a thing
regulatory standpoint on the use of phthalate plasticizers, as a need for a nonphthalate. However, newer nonphtha-
each year this versatile class of plasticizers accounts for late types such as dibutyl terephthalate (DBTP) [9] and
the largest number of pounds of plasticizer used. Di-2- N-alkyl pyrrolidones [10] have been proposed as high sol-
ethylhexyl phthalate (DOP) still accounts for about half vator alternatives. An epoxidized propylene glycol dis-
of the pounds of plasticizer consumed [1]. However, oyate [6] has also been proposed as a high solvating
health and environmental issues loom over the usage of alternative to phthalates as was isononyl benzyl-1,2-
phthalates, primarily in the European Union and the cyclohexane dicarboxylic acid ester [11].
United States [2]. As indicated above, historically, DEGDB, DPGDB,
There is therefore a need for phthalate alternatives. and blends of these two esters have been used in the vinyl
The focus of the development of phthalate alternatives industry. DEGDB is an excellent plasticizer, but because
has been primarily on general purpose (GP)-type plasti- of its high freeze point, blends with plasticizers such as
cizers. Currently, there two types of plasticizers that are DPGDB were developed to capitalize on the utility of
contending for replacement of DOP and diisononyl DEGDB. Several years ago, a blend of DEGDB, DPGDB,
phthalate (DINP). Di-2-ethylhexyl terephthalate (DOTP, and triethylene glycol dibenzoate was introduced as a
which, although still is a phthalate, is not an ortho-phthal- high solvating dibenzoate blend with good handling char-
ate) and diisononyl-1,2-cyclohexane dicarboxylic acid acteristics [12].
ester (DIDC) are considered to be next-generation GP In response to continued needs in the PVC industry,
two new dibenzoate blends and a new grade of a glycol
dibenzoate were developed. One is a new blend of
Correspondence to: William D. Arendt; DEGDB and DPGDB (X-250), and another is a new gly-
e-mail: [email protected] col dibenzoate grade (X-100). The last in this series is a
Presented at ANTEC 2012 in Orlando, Florida.
DOI 10.1002/vnl.21343
new blend of three dibenzoates (X-20) designed for
Published online in Wiley Online Library (wileyonlinelibrary.com). vinyl from a new blend platform introduced early in
C 2014 Society of Plastics Engineers
V 2011 [13].

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2014

 TABLE 1. Formulation, basic screen. TABLE 2. Spread coating starting formulation.

Raw material phr % Raw material phr %

Dispersion resin 100 58 Dispersion resin (Geon 121A) 75 44.9

(GeonV R 121A) Blending resin (Geon 217) 25 15
Plasticizer 70 40 Plasticizer 45 26.9
Heat stabilizer 3 2 Isodecyl benzoate 10 6
(MarkV R 1221) Viscosity control additive 5 3
Heat stabilizer (Mark 1221) 3 1.8
phr, parts by weight per hundred parts of resin. Epoxidized soybean oil 4 2.4

One feature of the X-20 blend is a lower freeze point than

most commercial dibenzoate blends containing DEGDB. PVC without interference with other additives (other than
Almost all newer commercial dibenzoate blends will contain the required heat stabilizer).
DEGDB as the basis of the blend due to the excellent solva- In addition to presenting the basic performance data,
tion of this plasticizer and the drive for economics. However, two specific examples of use of a high solvator are pre-
DEGDB in its pure form freezes above normal room tempera- sented. One is a flooring wear layer or spread coating-
ture (28 C). The freeze points of the experimental triblends type formula and the other is a starting plastisol screen
and diblends (initial onset of freezing) and of a commercial ink formula. The formulas are listed in Tables 2 and 3.
competitive plasticizer blend are as follows: The basic screen considers the four basic performance
parameters: compatibility, efficiency, permanence, and
 X-20: 14 C processability. The specific examples examine basic char-
 X-250: 112 C acteristics used to indicate performance. Viscosity, rheol-
 Commercial competitive dibenzoate blend similar to X- ogy, gel/fusion characteristics, and staining were
250: 112 C determined on the starting spread coating formula. Gel/
 X-100 (propylene glycol dibenzoate): does not typically fusion and rheology were determined on the starting
crystallize, but instead forms a glassy solid. (This plasti- screen ink formulation.
cizer, like others, does not crystallize but solidifies to a
glassy-like solid as the temperature is lowered.)
EXPERIMENTAL
Therefore, handling dibenzoate blends with DEGDB
can be a potential issue compared with many other Plastisol and Vinyl Preparation
phthalate esters. A lower freeze point is preferable.
The purpose of this work was to introduce the new diben- The plastisols used in the basic screen were prepared
zoate grade and dibenzoate blends for use in PVC applications in a Hobart Model N-50 mixer. A 10-min mix at Speed 1
with a focus on creating the best high-solvating nonphthalate was used. A high-speed disperser was used to prepare the
plasticizers for use in the plastisols of the future. plastisols in the specific examples (10-min mix cycle).
All of the plastisols were deaerated at 1 mm Hg until
they were as air-free as possible.
EVALUATION The vinyl for the basic screen was fused in a 1.27-mm-
High solvators are often used in plastisol formulations thick closed mold at 177 C for 10 min in a Blue M oven.
for speed and other performance characteristics. Based on Vinyl for stain testing was fused in a Mathis oven at a
that fact, the first evaluation of the new dibenzoate and thickness of 0.5 mm with an air flow rate of 1,500 rpm.
new blends was conducted in plastisols. Table 1 lists the
simple plastisol formulation used to evaluate the plasticiz- Tests
ers initially. The following plasticizers were used in the
Plastisol Deaeration. After the plastisol was mixed, the
evaluation (in whole or in part):
degree and ease of deaeration were determined. About 10
 DINP;
 BBP; TABLE 3. Plastisol screen ink, starting formulation.
 DOTP;
Raw material phr %
 DIDC;
 DBTP; Dispersion resin 100 30.5
 N-C8-C10 alkyl pyrrolidone (300) (Geon 121A)
 X-20 dibenzoate proprietary triblend; Plasticizer 100 30.5
 X-250 dibenzoate blend tailored to the PVC industry; Diluent plasticizer, 6 1.8
 X-100 new grade of propylene glycol dibenzoate. (isodecyl benzoate)
Dispersant (BYKV R 1148) 2 0.1
CaCO3 60 18.3
The concept with the basic plastisol evaluation was to
TiO2 60 18.3
provide only the interactions of the plasticizers with the

138 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2014 DOI 10.1002/vnl

 TABLE 4. Performance properties, basic formulation.

Property X-20 X-250 X-100 DINP DIDC DOTP DBTP 300 BBP

Compatibility
Loop, RT to 28 days C C C C C C PC PC C
Roll, 60 C for 3 days C C C C (Sl) I I C C C
Efficiency
Shore A, 10 s 67 66 66 70 67 70 62 52 65
Tensile parameters
Tensile at break, MPa 18.8 21.3 18.6 17.9 16.4 12.7 12.6 11.4 18.8
100% modulus, MPa 6.4 7.2 8.5 7.7 7.3 5.7 3 3.8 6.8
Elongation, % 390 350 280 390 340 280 460 410 340
Permanence
Extraction
Heptane, 24 h, % 22.1 22.2 21.4 237 241 241 28.9 29.0 22.9
1% soap, 24 h, % 26.2 26.3 23.9 21.6 21.8 21.7 24.5 211.2 23.5
Peanut oil, 24 h, % 21.2 21.4 20.6 25.5 211.4 28.7 24.2 26.3 21.4
Act. char. vol., 70 C
1 day, % 24.0 24.2 24.4 21.6 21.4 21.7 27.0 23.9 22.3
3 day, % 26.4 26.9 27.6 22 22 22.1 214.8 28.1 23.9
7 day, % 29.1 28.8 212.5 22.5 22.8 22.6 223.9 216.3 26.1
14 day, % 212.0 210.7 218.6 23.1 24. 23.4 229.8 224.7 210.0
21 day, % 214.7 212.3 222.7 23.7 25.1 24.3 231.7 229.3 213.3
28 day, % 216.1 213.7 224.2 24.2 26.1 24.9 232.4 231.3 216.2
Processability
Viscosity, Brookfield RVT,
20 rpm, 23 C
Initial, 1 h, mPas 3,740 3,720 3,120 2,070 1,060 1,630 1,390 25,150 1,980
1 day, mPas 4,800 5,800 4,200 2,380 1,270 1,860 2,880 Gel 4,230
28 day, mPas 5,500 5,880 7,380 2,830 2,020 2,670 7,200 Gel 4,620
Gel temperature,  C 56 58 59 90 111 102 57 – 59
Foam/break, s 13/50 9/53 12/>300 6/100 5/135 5/134 13/150 7/150 19/86
Heat stability
Minutes to first color 8 8 8 10 12 12 8 <6 8
Minutes to brown 14 12 14 16 18 18 16 6 16

mL of plastisol was placed in a vacuum cylinder and a 1- then placed in an oven at 60 C for 3 days. Compatibility
mm Hg vacuum was applied. Height of the increase in was judged on the degree of exudation in sum.
milliliters was divided by the starting volume and that
value was reported. The time to foam break was also Efficiency. Shore A (ASTM D-2240); tensile (ASTM
noted. D-638), type IV die and 50.8 cm/min pull-rate.

Viscosity and Rheology. A low-shear, Brookfield RVT, Permanence. Extraction resistance (ASTM D-1239)
20 rpm, 10 revolution reading (ASTM D-1823) was was measured. Extractants used were peanut oil (24 h of
employed. For high-shear measurements, a TA AR2000ex exposure at room temperature [RT]), 1% Ivory soap solu-
was used. Parallel plates were set at appropriate gaps tion (24 h at 50 C followed by 4 h dry at 50 C), and
(350 mm). Shear to 1,000 s21 was measured.

TABLE 5. Gel/fusion curve data.

Gel/Fusion. TA AR2000ex in oscillatory mode was
used to determine the plastisol gel/fusion characteristics. Initial Gel peak
Parallel plates were set at appropriate gaps (600 mm) for inflection G0 3 G00
this test. temperature, cross

Plasticizer C Temp.,  C G0 , Pa temp.,  C

Gel Temperature. A hot bench-type test was used to X-20 63 91 1.2 3 106 168
determine gel temperatures. A thin bead of a plastisol X-250 60 91 1.0 3 106 168
was applied to a temperature gradient plate and, after 3 X-100 60 81 1.2 3 106 165
min, the temperature where the plastisol stopped flowing DINP 79 126 3.6 3 105 179
DIDC 107 139 2.2 3 105 181
after the cut was determined to be the gel point. DOTP 81 129 2.9 3 105 177
DBTP 59 87 9.3 3 105 167
Compatibility. Loop test (ASTM D-3291); roll test - a 300 47 71 3.5 3 105 158
BBP 61 86 1.1 3 106 167
tight loop of vinyl was rolled with absorbent paper and

DOI 10.1002/vnl JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2014 139

 FIG. 3. Rheology of spread layer. [Color figure can be viewed in the
FIG. 1. Rheology basic screen of dibenzoates. [Color figure can be online issue, which is available at wileyonlinelibrary.com.]
viewed in the online issue, which is available at wileyonlinelibrary.
com.]
blends are more compatible with vinyl than the GP non-
heptane (24 h at RT, followed by 4 h dry at 50 C). Acti-  phthalates. This result may be surprising about DOTP as
vated charcoal volatility (ASTM D-1203) was measured the Small’s solubility parameter for DOP is 8.8 Hilde-
at 1, 3, 7, 14, 21, and 28 days. brands, which is the same as that calculated for DOTP.
However, ortho- versus para-positioning of the ester
groups on the unsaturated ring does make a difference.
Heat Stability. Testing was conducted in a Mathis oven
Data confirm that DOTP is not as compatible with vinyl
at 195 C with a blower speed of 1,500 rpm at the test
as DOP. DINP is compatible with a Small’s solubility
intervals indicated in Table 4. First yellowing and then
parameter of 8.9 Hildebrands. DIDC, the saturated ver-
brown are noted.
sion of DINP, has a solubility parameter of about 8.2;
therefore, it is no surprise that it is not as compatible as
Stain Testing. A 1% solution of oil brown dye dis- may be desired.
solved in mineral spirits was used as the stainant. The The viscosity and rheology of dibenzoate plastisols are
stainant was applied to the vinyl and left in place with a not near as desirable as that of a GP type, but X-20 plas-
tissue for 30 min. The stainant was wiped from the vinyl; tisol exhibits some interesting viscosity characteristics. It
the vinyl was wiped with clean mineral spirits, and pic- was lower than expected (see Fig. 1). This characteristic
tures were taken to record. may well lend to easier formulation of plastisols with a
high solvator-type plasticizer. Of the plasticizers tested,
RESULTS AND DISCUSSION the 300 was particularly poor in viscosity stability. The
300 samples started out high in viscosity and gelled
overnight.
Basic Screen
The results of the basic screen are listed in Tables 4
and 5 and Figs. 1 and 2. The experimental dibenzoate

FIG. 4. Gel/fusion curve of spread layer plastisol. [Color figure can be

FIG. 2. Basic screen gel/fusion curves. [Color figure can be viewed in viewed in the online issue, which is available at wileyonlinelibrary.
the online issue, which is available at wileyonlinelibrary.com.] com.]

140 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2014 DOI 10.1002/vnl

FIG. 5. Staining data. [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]

FIG. 6. Gel/fusion curve for screen ink. [Color figure can be viewed in
There are different ways to characterize solvator class the online issue, which is available at wileyonlinelibrary.com.]
in PVC. The TA AR2000ex rheometer in oscillatory
mode was used to generate gel/fusion characteristics for 15]. However, classic high solvators are often used in
the series plastisols. Table 5 lists the data and Fig. 2 illus- exactly the same way. This is well documented in the lit-
trates the curves that were developed. It is clear that all erature. The 300 really does not appear to be a plasticizer
of the dibenzoates, BBP, DBTP, and 300, are much better here but acts more like a solvent might. DBTP is also
solvators than all of the GP types, which also means that considered to be an additive for such applications as resil-
gaining full strength at lower temperatures is possible, ient flooring, similar to how di-n-butyl phthalate or DIBP
which translates to higher speed in production. The clas- has been used in the past [10].
sic gel point data also illustrate this point. Although the
300 was the most aggressive high solvator, very low gel
strength was developed. Examples
Dibenzoate blends are somewhat more efficient than
The starting spread coating formulation is a formula
DINP, but the other phthalates and high solvators were
for such applications as resilient floor wear layers, vinyl
somewhat more efficient than the dibenzoates. The X-100
leather cloth, or wall coverings. The formulation is shown
was the least efficient of the dibenzoates.
in Table 2. Figure 3 illustrates the excellent rheology and
As far as extraction and volatility are concerned, the
viscosity of X-20 in the formula. Figure 4 illustrates the
data indicated that GP plasticizers were extracted in mas-
excellent gel/fusion characteristics. Figure 5 shows the
sive quantities by solvent and oils but also extracted well
stain resistance of the vinyl plasticized with the X-100,
against water solutions. It was the opposite for the high
X-250, and X-20 compared with DINP and a DINP blend
solvators. Furthermore, GP types were less volatile than
with DIHP. All of the dibenzoates had excellent stain
the higher solvators. The 300 and DBT were very volatile
resistance to oil brown dye, which is an indicator of traf-
compared with the other high solvators tested. BBP was
fic staining. X-20 vinyl was the most stain resistant.
initially the lowest in volatility. Note that the activated
The starting plastisol screen formula is shown in Table 3.
charcoal test for volatility is generally run for only 1 day.
The X-20, DINP, and a 50:50 blend of X-20 and DINP were
This test was extended to 28 days in this evaluation to
show what happens as the plasticizers are exposed long-
term. Dibenzoate plasticizers always contain residual
reaction products that come off early with time. The data
indicated this. X-100 was somewhat different than this
and was somewhat more volatile than the dibenzoate
blends.
The dibenzoate vinyl samples and all of the high sol-
vator plasticized vinyl samples exhibited poorer heat sta-
bility than the GP plasticized samples. The 300 vinyl was
extremely poor in heat stability. It was even difficult to
fuse properly to prepare the 300 vinyl for testing without
degrading.
Overall the dibenzoates performed quite well versus
the other high solvators and were particularly so versus
the newer nonphthalate types, such as the N-alkyl pyrroli- FIG. 7. Rheology of starting screen ink formulations. [Color figure can
done (300). Granted, the 300 plasticizer is treated more be viewed in the online issue, which is available at wileyonlinelibrary.
as an additive to improve solvency and compatibility [14, com.]

DOI 10.1002/vnl JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2014 141

used as the plasticizers in this formulation. Note the excellent Rempala, Meaghan Jones, Melissa Schaffer, Paul Robideau,
rheology and viscosity in Fig. 6 and the good gel/fusion prop- and Chris Evoniuk
erties in Fig. 7 of the blend. High solvators can enhance the
performance of GP-type plasticizers in many ways. REFERENCES
1. C. Emanuel, “Plasticizer Market Update,” Society of Plastic
CONCLUSIONS Industry Vinyl Products Division 22nd Annual Vinyl Com-
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ACKNOWLEDGMENTS Eighth Annual Waterborne, High-Solids and Powder Coat-
ings Symposium, “New Dibenzoate Plasticizer/Coalescent
The authors thank Mr. Ed Gotch, president of Emerald Blends for Low VOC Coating Formulations,” DEStech Pub-
Kalama Chemical, for permission to publish. We also thank lications, Lancaster, PA, 419 (2011).
the following for their help in developing the data and prepa- 14. H. Kaytan, U.S. Patent Application 2007/0112104 A1
ration of the experimental plasticizers: Emily McBride, (2011).
Steve Roth, Rebecca Hanes, Debra Davidson, Pawel 15. H. Kaytan, U.S. Patent Application 2010/0216919 A1 (2010).

142 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY—2014 DOI 10.1002/vnl