The Ad d itive/An t ist a t Int e ra ct io n in PoIy p ropy Ie ne

DALE DIECKMA", WAYNE NYBERG, DAN LOPEZ, and PAUL BARNES

PATCO Polymer Additives Division

American Ingredients Company
Kansas City, Missouri 641 1 1
Analytical and performance data demonstrate chemical interactions between
glycerol esters and various other additives, primarily acid neutralizers. This phe-
nomenon is pronounced when the additive is a strong base, like synthetic hydro-
talcite, or a metal carbovlate. The performance of lactate neutralizers is compared
to stearates and metal bases. Chemical reactions are proposed based on the ana-
lytical tests performed.

INTRODUCTION
hemical interactions between polymer additives
C have been recognized and documented when the
interaction was readily apparent (1-3). Such interac-
tions are usually observed visually (e.g., as color
change) or in the results of relatiuely precise tests,
such as a melt flow rate. When antistatic activity is the
measurement, however, a chemical interaction be-
tween the antistat and another additive could go, and
has gone, undetected for a long time.
The possibility of such an interaction came to our
attention when one of our polypropylene customers
couldn't find any antistat during a routine, quality
control, FTIR. Manufacturing records indicated it was
added to the polymer. It was subsequently determined
that this disappearance was coincident with a sub-
stantial increase in the acid neutralizer, a synthetic
hydrotalcite.
A quick test was created to determine if there was a
chemical interaction between synthetic hydrotalcite
neutralizer and mono/diglyceride antistat. Other
typical neutralizers, including lactic acid derivatives
(4,5),were then tested, as was a distilled monoglycer-
ide. When evidence of a chemical reaction was discov-
ered, polypropylene specimens with various additive
combinations were prepared and evaluated for static
dissipation. Further analytical testing was done to
better understand the chemistry of interaction. When
the neutralizer / antistat chemistry had been con-
firmed, testing was extended to other additives. This
paper describes the results of our investigation.
EXPERIMENTAL
Hot Plate Reactions-Series 1
A 50 ml beaker was charged with 16.8 g glycerol
ester and 3.2 g neutralizer. A Model PC-351, 120v,
615 w hot plate was set on high and allowed to come to
thermal equilibrium. The beaker was placed on the
hot plate and the contents stirred by hand with a glass
thermometer. When the temperature reached 220°C.
the mixture was taken off the hot plate and allowed to
cool to ambient temperature. The mixture was ana-
lyzed for glycerine and a-monoglyceride by periodic
acid titration.
Injection Molding
Compounding was done in a Prodex Henschel
model 2JSS. Compound was extruded using a Haake
Rheocord System 40 with a Rheomex 100: 3/4 inch,
25:l l / d , 3 : l compression ratio single stage mixing
screw. Hot melt was granulated with a Nelmor
G810VL with a '/S inch screen. Granulate was injec-
tion molded using a Boy 15R and a temperature pro-
file of: front zone 235°C. barrel 240°C mold 49"C, and
a cycle time of 38 sec.
Static Decay Testing
Injection molded specimens were tested a t Electro-
Tech Systems under NFPA 99 Static Decay Testing
Method 4046. The specimens were pre-conditioned for
68 hrs a t 20°C, 38%RH and tested a t 26"C, 50.8% RH.
Cutoff voltage was at 10% of 55 kv. Multiple values
of triplicate specimens were averaged for the final
results.
Programmable Hot Plate Reactions-Series 2
Thirty grams of glyceride and 5 g neutralizer were
added to a 250 ml Pyrex beaker and the contents
stirred 15 sec by hand using a spatula. The beaker
was then placed on a Cole Parmer 04644 Series Digital
Hot Plate/Stirrer, preheated to 385°C surface temper-
ature. Using the temperature probe, the sample was
hand stirred for 5 min and then removed from heat.
Final temperature was recorded. Final temperatures
averaged 205°C. Contents were poured into a sample
jar to await further analysis.

JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, MARCH 1996, Vol. 2, No. 1 57

 Dale Dieckmann et al.

Table 1. Additives.

Code Chemistry Trade Name Source

Neutralizers:
L-N neutral calcium lactate Pationic 1230 PATCO Polymer Additives
L-B basic calcium lactate Pationic 1240 PATCO Polymer Additives
SL-N neutral calcium stearoyl lactylate Pationic 930 PATCO Polymer Additives
SL-B basic calcium stearoyl lactylate Pationic 940 PATCO Polymer Additives
ZnO zinc oxide Kadox 15 NJ Zinc Company
ZnSt zinc stearate Polymer Grade Witco Chemical
Cast calcium stearate Polymer Grade Witco Chemical
SHT synthetic hydrotalcite DHT-4A Kyowa Chemical Company
Antistats:
DM distilled monoglyceride Pationic 901 PATCO Polymer Additives
M/D mono/diglyceride Pationic 1052 PATCO Polymer Additives
Other Additives:
NaB sodium Benzoate Na Benzoate Mallinckrodt Chemical
Perox 2,5-dimethyl-t-butyl peroxyhexane Peroxide D Aztec Chemical
A0 tetrakis[methane(3,5-di-t-butyl-4-hydroxyhydrocinnamate]methane lrganox 1010 Ciba-Geigy
Phos tris(2,4-di-t-butylphenyl) phosphite lrgafos 168 Ciba-Geigy

Table 2. Polypropylene Formulations (ppm). wavelength range from 4000 to 650 wave numbers.
Spectra were collected after a background, and the
All Runs: - 6501 PP (Himont)
1000 lrganox 1010 (Ciba-Geigy) background subtracted. CO, and water were also sub-
500 lrgafos 168 (Ciba-Geigy) tracted. Although spectral subtractions were performed
to further treat the spectral data, results were not con-
SHT Monoldiglyceride L-N sidered useful and are not reported in this paper.
1st Set: 0 5000 0
100 5000 0 Programmable Hot Plate Reactions-Series 3
300 5000 0
800 5000 0 Glyceride and additive, in the amounts noted in
2000 5000 0 Table 4, were added to a 250 ml Pyrex beaker and the
0 0 0 contents stirred 15 sec by hand using a spatula. The
2nd Set: 800 5000 beaker was then placed on a Cole Parmer 04644 Se-
0 5000 2000 ries Digital Hot Plate/Stirrer, preset to 250°C. Using
300 1000 0
the temperature probe, the sample was hand stirred
until it reached 200°C and then removed from the
heat. Contents of the beaker were saved for testing.
HPLC Control specimens of glyceride and additive were
The system comprised a Waters Liquid Chromato- similarly prepared, but just mixed until a uniform
graph Module I equipped with a normal phase Alltech melt was obtained. Contents of the beaker were saved
Silica-Based Lichrosphere 100 Diol5U 250 mm X 4.6 for testing.
mm column and a Varex ELSD MK 111 detector. The All the mixtures were analyzed for glycerine and
mobile phase composition was 25% IPA, 75% a-monoglyceride by periodic acid titration, and by
Iso-Octane while the stationary phase was 85% Iso- HPLC and FTIR.
Octane, 10% IPA, 5% Chloroform. A 50-mg sample
was weighed and brought to volume in a 100 ml volu- RESULTS
metric flask with the diluent. The solution was filtered
through a n Acrodisc LC PVDF 0.45 pm syringe filter. A Series 1
diluent run preceded all analyses. Gas flow rate was Titration: The first tests on the hot plate were run
1.50 slpm, drift tube 70°C, solvent pressure 12.0, and using a mono/diglyceride (M/D) antistat heated with
amount injected was 22.5 pg per injection volume of neutralizers SHT, CaSt. ZnSt, L-N, L-B, SL-N, and
45 p1. The data was processed by Millennium soft- SL-€3, respectively. Analytical results versus a calcu-
ware. The processing method employed here quanti- lated control value are shown in Figs. 1 and 2.
tates mono, di and triglycerides: It does not identify Maximum alpha-monoglyceride loss was observed
other chemicals, such a s glycerine, that elute at dif- for the metallic stearates (Fig. 1 ) . Analysis showed
ferent times. substantial loss of monoglyceride in the presence of
strong base: SHT, L-B, SL-B. The neutral stearoyl lac-
FTIR
tylate SL-N retained most of its monoglyceride compo-
Samples were analyzed using a Nicolet 550 FTIR nent, and the neutral lactate, L-N, demonstrated al-
Spectrometer. The method employed a single bounce most zero loss of this important antistat component.
HATR (Horizontal Attenuated Total Reflectance) sam- Glycerine increase was also measured [Fig. 2). The
pling accessory that uses a ZnSe crystal operating in a greatest increase in glycerine was observed for the

58 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, MARCH 1996, Voi. 2, No. 1

 The AdditivelAntistat Interaction in Polypropylene
Free Glycerlne
Dmtliiad Monogtycari&Sb~l
10.0 -r---
I 1
3 6.0
8
.a
4.0

2.0

0.0
SHT Cast ZnSt L-N L-B SL-N SL-B L-N SHT
Neutralizers Neulralbrs

Fig. 1 Fig. 4

Free Glycerlne
MonoiDlgtywrideSari#* 1
specimens containing the SHT neutralizer in combi-
10.0 nation with M/D antistat. This work was designed to
--1
~

correlate polymer performance to the chemical

8.0 changes seen in the beaker, and validate the original
FTIR observation.
.I 6.0
.a
-
Figure 5 shows a progressive loss of antistatic pro-
tection with increasing levels of the highly basic neu-
4.0 ~

tralizer SHT. For comparison, the effect of no antistat

is also shown. Several additional data points were
2.0 -
obtained, shown in Fig. 6. This graph demonstrates
repeatability from the first static tests: 800 ppm SHT
0.0 ~

SHT Cast ZnSt L-N L-B
NeUtmllzers
Fig. 2
strong bases: SHT, L-B, SL-B. The metallic stearates
showed intermediate increases in glycerine. The neu-
tral products based on lactic acid chemistry showed
virtually no change.
Two neutralizers were selected for hot plate tests
with a distilled monoglyceride (DM),as shown in Figs.
3 and 4. NeutraZ calcium lactate, L-N, showed very
little loss of monoglyceride or increase in glycerine
versus the control. SHT, however, demonstrated a
substantial loss in alpha-mono content and a n in-
crease in glycerine.
Static Tests: Clear evidence of chemical reaction
between SHT and glycerol antistat having been discov-
ered, static testing was performed on polypropylene
SL-N SL-B with 5000 ppm M/D. It further shows that 2000 pprn
L-N, neutral calcium lactate, does not inhibit the an-
tistat protection provided by 5000 ppm M/D antistat
in the manner of SHT. It further appears that a t lower
addition levels (300SHT, 1000 M/D), the hydrotalcite
neutralizer adversely affects the antistat.
Series 2
More in-the-beaker reactions were carried out, now
using a programmable hot plate. Resultant mixtures
were analyzed by HPLC and FTIR, looking for further
information about these chemical reactions. A large
set of neutralizers was tested with a high purity DM
antistat (97.3%mono content). A subset of these neu-
tralizers was tested with a M/D antistat (59.6%mono
content).
HPLC: Glycerol esters are prone to rearrangement.
Distilled monoglycerides are susceptible to the most
chemical change, as they are moved far from their

L-N SHT
Neutralin

Fig. 3 Fig. 5

JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, MARCH 1996, Vol. 2, No. I 59

 D a l e Dieckrnann e t al.
static Decav llme f d Mono
Glycerides by HPLC
~- MonolDiglywrid. Soria 2
1.4 75- C m d Mono
1.2 61 59.8

1.o

!i:::
0.4
0.2
nn
u.u
NOSHTI 5000MD 2MX)LN I5000MD SOOSHT i lOOOMD
ppm Additive8
ITri L-N SHT Cast
I !Di Neutrdizan
Fig. 6 kl Mono
Fig. 8
equilibrium proportions when they are distilled. Fig-
ure 7 displays the mono/di/ triglyceride proportions of Table 3. FTlR Inspection DM Reactions.
the heated mixtures as determined by HPLC, and Peak
compares them to the mono content of the starting Neutralizer (cm-’) Interpretation
DM antistat. The least amount of rearrangement was -
SHT
observed for L-N, the neutral calcium lactate, followed ZnO -
by the neutral stearoyl lactylate, SL-N. Other neutral- L-N -
izers followed in this order: SHT < ZnO < L-B < L-B 3650 missing Free basicity consumed in
Cast < SL-B < ZnSt. As expected, the M/D tests in reaction or dehydrated.
Series 2 showed less dramatic change (Fig. 8 ) , but 1544,1452 Ca stearate formed by reaction.
SL-N -
with results in the same order: L-N < SHT < Cast. SL-B 3650 missing Free basicity consumed in
FTIR: Spectra were obtained for all Series 2 DM hot reaction or dehydrated.
plate mixtures. Although computer spectral subtrac- 1556,1 1 21 Ca stearate formed by reaction.
Cast -
tions were performed, those results were inconclusive. -
ZnSt
Spectra were visually inspected for the presence and
absence of key peaks ( T a b l e 3 ) . In most cases, all
peaks were readily attributable to the starting mate- numerous neutralizers, testing was extended to other
rials or were subject to ambiguous interpretation. Ev- common additives (Table 4 ) . T e s t s were again con-
idence of ester rearrangement was virtually impossi- ducted using a monoldiglyceride and a distilled mono-
ble to detect because of the close similarities among glyceride. Because the ratio of antistat to “other additive”
glycerol ester spectra, and the small levels of some of varied, our experimental results are compared to the
the predicted components. However, both basic lactic analysis of melt-blended controls. Figures 9 through 14
neutralizers showed evidence of free base reacting show the 200°C mixtures (bars) versus melt-blended
with antistat. controls (line).Where there is a significant gap between
Series 3 bar and line, chemical interaction is assumed.
M I D (Figs. 9-1 1): The alpha-mono titration showed
Because of the substantial chemical changes that minor loss for peroxide and A 0 samples. However,
were seen in antistat chemistry in the presence of because these minor losses were not confirmed by
HPLC, some interference in the titration has been as-
Glyceridesby HPLC sumed. There was zero change for the No Add and
100 phosphite samples. The glycerine titration and HPLC
show zero change in the- no additive, the phosphite,

i 75
GMS
Table 4. Series 3 Mixtures.
Other Additive
409 M/D 509 NaB
I 525
O 409 M/D 309 Perox
409 M/D lOOg A 0
409 M/D 509 Phos
0 40g M/D None
L-N SL-N SHT ZnO L-8 Cast SL-8 ZnSt 409 DM 509 NaB
Nautrdtzan
ITn 40g DM 309 Perox
n DI 409 DM lOOg A 0
a Mono 409 DM 509 Phos
409 DM None
Ftg. 7

60 JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, MARCH 1996, Vol. 2, No. 1

 The AdditivelAntistat Interaction in Polypropylene
Alpha-Monoglyceride Alpha Monoglyceride
MonolDigbycerideSeries 3 Dlshlled MonoglycendeSeries 3

60 I - - -_
I
50 80

zg40 g
I 60
230
a"
220
4s 40
20
10

0 0
NoAdd NaB Perox A0 Phos NoAdd NaB Perox A0 Phos
Additives Additive

Fig. 9 Fig. 12

Free Glycenne
Distilled Momglycenae Series3
-
10 -

"
NoAdd NaB Perox A0 Phos NoAdd NaB Perox A0 Phos
Additive Additives

Fig. 10 Fig. 13

Glycerides b y HPLC Glycerides by HPLC

Distilled Monaglyceoue Series 3
MonolDlgtycendeSenes 3
100
---07 1
80

f
0
2
6o
40
20

NoAdd NaB Perox A0 Phos

Additive
NoAdd NaB Perox A0 Phos
Additive
Tri n Di L Mono
Tri Di Mono Fig. 14
Fig. 1 1

There was zero change for the No Add and phosphite

the A 0 and the peroxide mixtures. The sodium ben-
zoate mixture, however, loses approximately 20% of
its alpha-mono (a 10%decrease),and gains 1.5%glyc-
erine. HPLC shows significant conversion of mono-
glyceride to diglyceride. No noticeable changes were
seen in the FTIR for any mixture.
DM (Figs. 12-1 4): The alpha-mono titration showed
some loss for the peroxide and A 0 samples. However,
because these losses were not confirmed by HPLC,
some interference in the titration has been assumed.
samples. The glycerine titration shows zero change in
the no additive, the AO, the peroxide and the phos-
phite mixtures. The HPLC shows no loss in mono
content for the no additive, the AO, the peroxide and
the phosphite mixtures. Again, the sodium benzoate
mixture loses approximately 20% of its alpha-mono (a
20% decrease), and gains 3% glycerine. HPLC shows
significant conversion of monoglyceride to diglyceride.
No noticeable changes were seen in the FTIR for any
mixture.

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, MARCH 1996, Vol. 2, No. 1 61

 Dale Dieckmann et al.

DISCUSSION
Chemical interactions with glycerol ester antistats
vary according to the chemistry of the co-additive.
Nonmetallic additives have little or no interaction in
these experiments. Metallic additives appear to be
more aggressive when they are 1) more soluble, and
2) more basic. Very basic neutralizers result in sub-
stantial glycerine by-product, in addition to ester re-
distribution. Very soluble neutralizers show substan-
tial redistribution, but less glycerine generation.
These observations, in addition to the FTIR results,
suggest the following (unbalanced) reactions:
M(0H)z + CH~(OH)CH(OH)CH~(OOCR)
base monoglyceride
CONCLUSIONS
Other additives can react with glycerol ester anti-
stats, resulting in diminished performance of the an-
tistat. The additives most likely to react are acid neu-
tralizers, although a significant reaction with sodium
benzoate was discovered. Additives with higher ba-
sicity and greater solubility in polymer and antistat
are more destructive. Chemically neutral products
based on lactic acid chemistry offer safe, nonreac-
tive alternatives to metallic stearates a n d synthetic
hydrotalcites.
ACKNOWLEDGMENTS

+ M(0OCR)Z + CHz(OH)CH(OH)CH~(OH) Thanks to Wayne Nyberg and Paul Barnes for their
salt glycerine FTIR and HPLC work, respectively, as well as for
and their excellent sample preparation. Also, thanks to
Dan Lopez for his exacting polymer preparation and
M(0OCR)z + CHz(OH)CHloH)CHz(OOCR) testing.
soluble salt monoglyceride

CH,(OH)CH(OH)CHz(OH) REFERENCES
glycerine

+ CHz(OH)CH(OH)CHz(OOCR) 1 . G. J. Klender et al., SPE ANTEC Tech. Papers, 3 1 , 989

monoglyceride
(1985).
+ CHz(OH)CH(OOCR)CH,(OOCR) 2. G. Kletecka, paper presented at Polyolefins VII Interna-
diglyceride tional Conference, pp. 254-73 (February 1991).
+ CHz(OOCR)CH(OOCR)CHz(OOCR) 3. R. E. Asay, paper presented at Polyolefins V Interna-
tional Conference, pp. 210-23 [February 1987).
triglyceride

+ M(O0CR)z 4. D. Dieckmann, paper presented at Polyolefins XI11 Inter-

soluble salt national Conference, pp. 462-93 (February 1993).
5. D. Dieckmann, Plastics Engineering, September 1991,
R = -C17H35 M = metal p. 39.

62 JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, MARCH 1996, Vol. 2, No. 1