You are on page 1of 7

l nteractions Between a

Zinc Dialkylphosphorodithioate and


Lubricating Oil Dispersants
NICHOLAS E. GALLOPOULOS and CHESTER K. MURPHY
General Motors Research Laboratories, Warren, Michigan

Direct infrared spectrophotometric evidence of interactions be- MDP-dispersant interactions. It was assumed that if the
tween lubricating oil dispersants and a zinc dialkylphosphorodi- changes in the infrared bands could be related to specific
thioate ( Z D P ) is presented. Increasing the concentration of the interactions between MDP and dispersants, the causes of
dispersants polyamino monoalkenylsuccinimide, barium thiophos- the effect of dispersants on the functional properties of
phonate, and basic barium dinonylbenzene sulfonate in a mineral MDP (i.e., anti-scuff, thermal stability) could be identi-
fied. Furthermore, the changes in the infrared bands were
oil containing 1.2% by weight of a Z D P decreased the intensity
recognized as important to the analysis of lubricants with
of the phosphorus-oxygen-carbon and phosphorus-sulfur infrared
infrared spectrophotometry. For these reasons, the effects
bands, and caused the appearance of a new band at 668 cm-l. of several typical lubricating oil dispersants on the infra-
The dispersants barium dinonylnaphthalene sulfonate, calcium red bands of a common MDP, zinc dialkylphosphorodi-
petroleum sulfonate, and alkaline petroleum sulfonate decreased the thioate (ZDP) were studied.
intensity of the phosphorus-sulfur bands only ajer the solutions
had aged, and independently of dispersant concentration.
EXPERIMENTAL
It is speculated that chemical reactions came these interactions
between the Z D P and the dispersants, and lhat ionic metal phos- Apparatus
phorodithioates areformed. The possibility of association, isomeric, All infrared spectra were recorded with a Perkin-Elmer
and complexation e m s is also explored. Regardless of the exact Model 337 spectrophotometer operating at a scanning
mechanism involved, these results should be valuable not only to speed of 1.2 cm-' per minute and at the "Normal" slit
analytical chemists, but also to lubricant technologists and re- program. The samples were contained in matched 0.1 mm
searchers. thick KBr cells.

Materials
INTRODUCTION
The zinc dialkylphosphorodithioate (ZDP), and the
Additive, synergistic, and antagonistic interactions seven dispersants studied are commercial automotive
have been reported for many combinations of the com- lubricant additives. Table 1 shows their approximate
mon lubricating oil additives. The ubiquitous metal chemical structure as deduced from infrared spectra, the
dialkylphosphorodithioates (MDP) are no exception. literature, and the elemental composition shown. Table
They act synergistically with chain-breaking oxidation 1 also identifies the additives by a code, lists the molecular
inhibitors in preventing oil oxidation (1). Their ability weight, and indicates the fraction of the active chemical
to prevent scuffing of moving metal parts is reduced (2), in the commercial product.1
but their thermal stability is increased (3)by the presence The solvent with which the ZDP-dispersant solutions
of metallic dispersants in the lubricant. were prepared was a mid-continent, solvent-extracted
Whereas the chemistry of MDP synergism with base stock with the properties shown in Table 2.
chain-breaking inhibitors has been studied ( I ) , the The concentration of the ZDP in the mineral oil was
chemical changes responsible for the interactions between always 1.04 gm/100 cc (1.2% by weight), whereas the
M D P and dispersants have not. The observation that the concentration of the dispersant ranged from zero to 21.3
infrared bands of MDP changed when certain dispersants gm/100 cc. These concentrations include the diluent oil.
were added to mineral oil solutions of MDP suggested The range of concentrations reflects commercial practice
that infrared spectrophotometry could be used to study in the formulation of automotive lubricants, but higher

Presented at the 25th ASLE Annual Meeting in Chicago, M a y 4-8, 1970 lThe remainder is a diluent oil.
1
TABLEI-ADDITIVES

ACTIVE
CHEMICAL COMMERCIAL
IN COMMERCIAL ADDITIVE
APPROXIMATE ADDITIVE, ELEMENTAL
APPROXIMATE MOLECULAR APPROXIMATE CONTENT,
CHEMICAL
NAME CODE MOLECULAR
STRUCTURE WEIGHT VOL. % WT. ?h

Zinc Dialkylphosphorodithioate ZDP Unknown

'2
Polyamino Monoalkenylsuccinimide PAMAS
I
R-CH-C

CH2-C
\ -
,N-Rr-(NH).

\b

Basic Barium Dinonylnaphthalene BBDNS


Sulfonate BaOH

Barium Dinonylnaphthalene BDNS


Sulfonate

Barium Thiophosphonate BTP Unknown

12-!l
Alkaline Calcium Petroleum ACPS Unknown 50
Sulfonate

Calcium Petroleum Sulfonate CPS Unknown 50

P~l~alkylmethacrylate-N-
vinyl-2-pyrrolidone Copolymer PAM-VP

C=O
0

Notc: K denotes alkyl groups.

dispersant concentrations were used whenever the detec- shown in Fig. 1, in which the bonds corresponding to the
tion of dispersant effects was difficult. characteristic infrared bands of ZDP are identifiedon the
basis of previous studies (4). Notice that the shoulder at
668 cm-' is labeled unknown and that it became a band
Procedure as intense as the 652 cm-I P=S band .as dispersant
To determine if a dispersant and the ZDP interacted, concentration was increased. Such changes in'tlie inten-
the differential infrared spectrum of ZDP was obtained sity of this unknown as well as of the P-0-c;and P=S
in the conventional manner in the range from 1200 to bands were considered indications that a dispersant was
400 cm-l. This range contains the characteristic ZDP interacting with the ZDP. The intensity changes were
bands. treated quantitatively by computing the absorbance (A)
Typical differential spectra obtained in this manner are of each band. of interest according to Beer's Law and the
Interactions between a Zinc Dialkylphorodithioate and Lubricating Oil Dispersants

conventional baseline technique (5).To compensate for


TABLE
2-BASE STOCK PROPERTIES any variations of cell thickness, the absorbance was di-
Viscosity, cs vided by the cell thickness in mm.
100" F Differential infrared spectra of solutions containing
210" F different ,amounts of dispersant were recorded immedi-
Viscosity Index ately after each solution was prepared, and after it had
aged for several days or weeks at room temperature in
Hydrocarbon Composition, wt. %
covered bottles. Thus, not only effects of dispersant con-
Paraffins
Aromatics centration, but also effects of aging were investigated.
Naphthenes
Sulfur, Wt. % Precision
Several independent differential spectra were recorded
from the same solution during the same day to determine
the precision of the spectrophotometric measurements
shown in Table 3 for dispersant-free ZDP solutions, and
in Table 4 for solutions of constant ZDP, but varying
dispersant concentration.
Some of the solutions were prepared more than once
and spectra were obtained from each individual prepa-
ration. The precision of the absorbance measurement in
these cases was equal to that shown in Tables 3 and 4.
The poor precision of the 668 cm-' band measurements
l p\- o - c I glla) cc. ZDP PLUS
1.04CONCENTRATIO~S
from dispersant-free solutions is due to the very low
intensity of the 668 cm-l band (shoulder) in these solu-
tions. The intensification of this band in the dispersant-
containing solutions increases the precision of the meas-
urements to that of the other bands.
Because the precision of the results is acceptable, and
for simplicity, only the average of the repeated determi-
Fig. I-Differential Spectra of ZDP and ZDP-PAMAS Solutions. nations will be shown.

3-PRECISION
TABLE OF INFRARED BAND INTENSITY MEASUREMENTS
ZDP Solutions-No Dispersant Present

P-0-C P=S (652 cm-1) P=S (635 cm-1) P-S 668 cm-I
ZDP CONC.,
m/100cc A/mm AA/mm, % A/mm AA/mm, % A/mm AA/mm, % A/mm AA/rnm, % A/mm AA/mm, %

Note: AA/mm, % is the percent difference between determinations.

TABLE
4-PRECISION OF INFRARED BAND INTENSITY MEASUREMENTS
1.04 gm/ 100 cc ZDP Solutions Containing PAMAS Dispersant
P-0-C P=S (652 cm-') P=S (635 cm-1) P-S 668 cm-1
PAMAS CONC.,
RESULTS

*+
For convenience, the dispersants have been arbitrarily
classified into three categories according to whether they
changed the ZDP bands, and whether the change was
immediate or occurred only after the solutions had aged.
A change in the ZDP bands was judged significant and
indicative of interactions with the dispersants, only if the
absorbance of the band changed substantially more than
would be expected from the precision of the measure-
ments. A qualitative assessment of any changes in band
shapes was also included in this judgment.

Class I Dispersants
The first class encompasses three widely different types
of dispersants-polyamino monoalkenylsuccinimide
(PAMAS), basic barium dinonylnaphthalene sulfonate
(BBDNS), and barium thiophosphonate (BTP). These
affected the infrared bands of ZDP immediately after the
solutions were prepared.
Figure 2 shows the effect of PAMAS on the absorbance
of the ZDP bands. The intensity of the P-0-C
the 635 cm-I P=S bands steadily decreased as the con-
centration of PAMAS increased. The 652 cm-l P=S and
the P-S bands remained essentially unchanged, whereas
the unknown band at 668 cm-l increased as the concen-
tration of PAMAS increased. These band intensity
changes were accompanied by pronounced band shape
changes as shown in Fig. 1. At the higher PAMAS con-
centrations the P-0-C band broadened considerably
and shifted to a lower frequency, the P=S band at 635
cm-[ became a rather weak shoulder, and the 652 cm-I
P=S band also broadened and tended to merge with the
668 cm-' band which was intensified considerably.
The band intensity changes caused by BBDNS are
shown in Fig. 3. The results are similar to those with

Z
s
g
E

f5
0.

V)
m
u

Fig. 2-The
3.5

3.0

2.5

2.0

1.5

1.0

0.5

0
o

\
-

,-

I\*-*-
17
e<t>$-?
0
I

I
o<iz"
-. .>
2
O\O

P - S 1652 on-1)

3
and

-
l

0
P
P - 0o

4
-C

CONCENTRATION OF P A M A S lgllW ccl


-
E

P-S
(635 cm-f)

Effects of PAMAS on the Intensity of the Characteristic


Infrared Bands of ZDP.
I

5 6
6
0

d
E
E

, 2.0
Z

0:
0

Fig. 3-The
3.5

3.0 /

1.5

0.5

o
o

2.5 -

PAMAS for the P-0-C


0

0
5

-
\o

, \ . - . .•
0.5
,
\

- "

and P=S bands, but both


P=S bands decreased in intensity as the BBDNS' con-
,
1.0

The data for BTP are not shown because they. generally

6 60
z
23
Lo
f
=4 0

Fig. 4-The
20

0-.
1100 1000
, ,

I
V

, ,

900
, ,
-
parallel those of BBDNS. However, the following differ-
ences between BTP and BBDNS were observed: the
absorbance of the P-0-C band decreased to a final
value of only 2.5/mm, and not as rapidly; both P=S
bands gradually decreased in intensity, and without ap-

100

80

BOO
FREQUENCY (cM-')
-

,
o

.
-

CONCENTRATION OF BBDNS (g1100 cc)

centration increased. This decrease was rapid at the lower


concentration ranges, but leveled off at BBDNS concen-
trations greater than about 0.6 gm/100 cc. Conversely,
the intensity of the 668 cm-l band rapidly increased at
concentrations up to 0.6 gm/100 cc, after which a plateau
was reached. As shown in Fig. 4 band shapes were not
altered drastically in this system. At higher concentrations
of BBDNS, the two P=S bands were not as sharply
shaped because their intensity decreased, whereas the
intensity of the 668 cm-l band increased substantially.
P-So

1.5

Effect of BBDNS on the Intensity of the Characteristic


Infrared Bands of ZDP.

-
o

Effect of BBDNS on the Differential Spectrum of ZDP.


I
2.0
P.

CONCENTRATIONS
l.M gllW cc ZDP PLUS

........

700
P-0-C

668 cm'l

0 g11W cc BBDNS
1.45 gllW cc BBDNS
2.83 gllW cc BBDNS

600
1652 crn-l)

p = S ,(635

I
2.5
-1

500
3.0
Interactions between a Zinc Dialkylphorodithioate and Lubricating Oil Dispersants 5

preciable leveling off at the higher BTP concentrations;


the absorbance of the 668 cm-I band steadily increased
to the same final value of 0.8/mm. Band shape changes
with BTP were similar to those observed with BBDNS.
There were subtle differences in the effects caused by
the three Class I dispersants, but since they all produced
the same limiting absorbance per mm for the 668 cm-l
band, and showed no effect of aging, the causes respon-
sible for the absorbance change are apparently similar.

Class II Dispersants
Three other dispersants affected the infrared bands of
ZDP only after their solutions had aged. The effect was
essentially the same at all dispersant concentrations stud-
ied; therefore, it will be illustrated with the results ob-
tained with only one of these concentrations. The effect
of aging was neither as intense nor as uniform as that 0 1 I I
of dispersant concentration shown in the previous section. 0 10 M 30 40 50 60
Figure 5 shows that alkaline calcium petroleum sulfo- TlME AFTER BLENDING IOAYSI

nate (ACPS) had an aging effect parallel to that of dis-


Fig. 6-The Effect of Aging on the Intensity of the Characteristic Infrared
persant concentration. The P-0-C and the two P=S Bands of ZDP. 23.1 g/100 cc CPS.
bands decreased, the P-S band did not change, and the
668 cm-I band increased in intensity.
Figure 6 shows the results with calcium petroleum
sulfonate (CPS). Only the 668 cm-l and P=S (635 cm-')
Class I1 dispersants did not alter the shape of the ZDP
bands seem to be affected appreciably by storage time.
bands.
The intensity of the former increased, whereas that of the
latter decreased. Class 111 Dis~ersants
Data for barium dinonylnaphthalene sulfonate
This class comprises the dispersants which in no way
(BDNS) are not shown because its effects were small and
affected the infrared bands of ZDP. Only the polyalkyl-
similar to those caused by CPS and ACPS.
methacrylate-N-vinyl-2-pyrrolidone copolymer (PAM-
It may be significant that the final absorbance per mm
VP) was found to belong to this class. Concentrations of
measured for the 668 cm-I band with ACPS and CPS
PAM-VP as high as 4.42 gm/100 cc were tested, and
is about 0.8. This is equal to that measured at the highest
neither the shape nor the intensity of the infrared bands
concentrations of Class I dispersants. The absorbance per
of ZDP was altered.
mm obtained with BDNS after 42 days of storage was
only 0.4.
DISCUSSION

The results were obtained with commercial materials


of unknown purity and not well defined chemical struc-
ture. In addition, extensive studies of the infrared spectra
of MDP (4) have failed to identify, precisely, the origin
of the two P=S bands (652 and 635 cm-l) of ZDP and
of the 668 cm-l band. Therefore, interpretation of the
results in terms of the molecular structure of the dis-
persants will be avoided. However, it appears that addi-
tion of the dispersants to ZDP solutions cause one or more
of the following: a) disturbance of either the rotational
isomerism or association equilibrium of ZDP; b) forma-
tion of ZDP-dispersant complexes; c) reactions of ZDP
with the dispersants. These explanations are best con-
668cm-I

0.5
['lNlo
./;
/

S 1635 c m - l l
O
P * S 1652 cm-l,
sidered after a discussion of spectra-structure correlations
of ZDP with particular attention to the bands of 652,
0 - P 635, and 668 cm-l.
P-S
0 1 I I I I
0 10 20 M 40 M W Spectra-Structure Correlations
TlME AFTER BLENDING IDAYSI
The conventional molecular structure for MDP, and
Fig. 5-The Effect of Aging on the Intensity of the Characteristic Infrared the ionic and covalent resonance hybrid structures pro-
Bands of ZDP. 3.07 g/100 cc ACPS. posed by Gallopoulos (4) are, respectively
"" ' M "P'
/ \ /
RO S
\ / \
S
OR

OR,
[rRo,Q 1 M and I(Ro);p<L
M.

10.0
Heilweil (6) concluded that M D P in solution exist as
a n equilibrium between internal chelate monomers and -
d

oligomers with structures: E 8.0 -


YI
a
\
d

6
N
6.0 -
B
2
t
4.0 -
Z
\ s BTP
S-P=S
/ \
Internal Chelate Oligomer
(dimer)
I
IV v DISPERSANT CONCENTRATION (gllW CC)

Fig. 7-The Effect of Dispersant Concentration on the Ratio of the


None of these structures account for the doublet 652- Intensities of the P==S Infrared Bands of ZDP.
635 cm-', (4) but if it is postulated that for the covalent
salts the equilibrium includes free structures such as I or
111, then the 652 cm-I member of the doublet could be
increased as the concentration of dispersant increased.
assigned to the P=S (P=S) bond of structure I or 111,
This indicates that any association or isomeric equilib-
whereas the 635 cm-' member would be due to the P=S
rium was disturbed, but does not explain either the
P r S ) bond of structures I V or V. The coordination in
changes in the P-0-C band, or the increase in the
structures IV and V could weaken the P=S bond and
intensity of the 668 cm-l band.
therefore lower its frequency from 652 to 635 cm-l.
Association or isomerism considerations do not apply
Alternately the doublet 652-635 cm-I could arise from
to Class I1 dispersants because, as Fig. 8 shows, the ratio
a n equilibrium of rotational isomers about the P-S bond
of the intensities of the 652 cm-' and 635 cm-I bands
as suggested by Zumuna. (7) Most likely the higher fre-
did not change'with solution age.
quency band would belong to the isomer in which the
Complexes between the dispersants and ZDP could
P=S bond is farthest from the metal atom, whereas the
form easily. For example, the amino groups of PAMAS
lower frequency band would be assigned to the P=S
could coordinate with ZDP, much like dodecyl amine
bond closest to the metal atom, because proximity of the
coordinated with a ZDP. (6) It is unlikely, however, that
P=S bond to the metal atom would weaken the bond
complexation would affect the P-0-C bond, although
and lower its frequency.
the P=S bonds could be disturbed, and new bonds could
To evaluate changes in association and isomeric equi-
be formed. Apparently, complex formation alone would
librium, the ratio of intensities of the two P=S bands
not account for the effects observed with Class I dis-
can be examined. In either case, disturbance of the equi-
persants.
librium would change the ratio, whereas interactions
With Class I1 dispersants, one could speculate that the
which do not alter the equilibrium would not change the
668 cm-I band develops because complexes are formed,
ratio.
From previous work (4) it is known that the 668 cm-l
band cannot be assigned to structures I, 111, IV, or V.
If it is assumed, however, that the band is related to ZDP,
then it is possible to assign it to the antisymmetric vibra-
tion of the thiophosphorylate anion of structure 11. (4)
In other words, it is postulated that the commercial
product used contains not only the covalent ZDP, but
also an ionic metal phosphorodithioate.
0
-0 CPS 5.2 g l l W CC
8--* ACPS 0.76 g11M CC
Association, Isomerization, and *----* BDNS 1.33 g11W cc
Complexation Effects
I
Adding dispersants to ZDP solutions would tend to 0 10 20 30 40 M 60
shift any association or isomeric equilibrium which might TIME AFTER BLENDING (DAYS)

exist. For Class 1 dispersants, Fig. 7 shows that the ratio Fig. 8-The Effect of Aging on the Ratio of the Intensities of the P=S
of intensities of the two P=S bands (652 cm-'/635 cm-') Infrared Bands of ZDP.
Interactions between a Zinc Dialkylphorodithioate and Lubricating Oil Dispersants 7

but speculation about the kinds of complexes is not pos- reliance on one ZDP band is diminishkd in favor of
sible because of inadequate data. examination of all pertinent bands. However, this proce-
dure still does not guarantee that the measurements re-
Chemical Reactions flect the concentration of ZDP, and are not confused by
Reactions between Class I dispersants and ZDP would the presence of some new species formed by interaction
explain all the observations and would be consistent with of dispersants and ZDP.
the rapid and pronounced effect of the dispersants on the
infrared bands of ZDP. Because the P-S band was, not SUMMARY AND CONCLUSIONS
affected, it appears that only those portions of ZDP
containing the P-0-C and P=S bonds were involved The addition of certain dispersants to mineral oil solu-
in reactions. In particular, reactions and the consequent tions of a zinc dialkylphosphorodithioate (ZDP) changed
generation of new species in the ZDP-PAMAS system are the infrared spectra of ZDP. Increasing the concentration
very likely because as shown in Figs. 1 and 2, not only of three Class I dispersants, polyamino monoalkenylsuc-
the intensity, but also the shape and position of both the cinimide (PAMAS), basic barium dinonylnaphthalene
P-0-C and the P=S bands were affected. Apparently sulfonate (BBDNS), and barium thiophosphonate (BTP)
the new species still contain P-0-C bonds, but in a progressively and immediately decreased the intensity of
different environment. In addition, if the 668 cm-l band the P-0-C and P=S ZDP bands, but increased the
is assigned to ionic MDP, then it must be concluded that intensity of a n unknown band at 668 cm-l. Three Class
chemical reactions between Class I dispersants and ZDP I1 dispersants, barium dinonylnaphthalene sulfonate
produce some ionic phosphorodithioates. (BDNS), calcium petroleum sulfonate (CPS), and alka-
Assignment of the 668 cm-I band to ionic MDP and line calcium petroleum sulfonate (ACPS) decreased the
the increase of the intensity of this band to 0.8/mm for intensity only of the P=S ZDP bands, and increased the
five of the six Class I and I1 disperants, is consistent with intensity of the 668 cm-l band; however, these effects
the supposition that ionic MDP was also formed with were independent of dispersant concentration, but de-
Class I1 dispersants. It is postulated that the metal atom pendent on the age of the solution. A seventh dispersant,
in these new ionic MDP was supplied by the metal atoms a copolymer of polyalkylmethacrylate-N-vinyl-2-pyrroli-
of Class I1 dispersants. done (PAM-VP), did not affect the bands of ZDP in any
It should be recognized that the previous discussion is manner.
speculative, and that all the concepts examined may be It is likely that chemical reactions occur between ZDP
responsible to some degree, and simultaneously, for the and the dispersants. For Class I1 dispersants the reactions
phenomena observed. probably lead to ionic metal phosphorodithioates,
whereas for Class I dispersants additional unknown spe-
cies must be formed. It is also possible that association,
SIGNIFICANCE rotational isomerism, and complexation effects are super-
The data strongly indicate that the species in solutions imposed on the chemical reactions.
of ZDP and dispersants are not the same as those in
solutions of either ZDP or dispersants alone. Therefore, REFERENCES
it is not surprising that previous investigators have found (I) Kennedy, G. W., and Patterson, W. L., Jr., "Kinetic Studies of
the antagonistic and synergistic effects described in the Petroleum Antioxidants," Industrial and Engineering Chemist7y, 48,
Introduction. The chemistry of these effects still remains 1917-1924 (1956).
(2) Quilty, C. J., and Martin, P., Jr., "The Effect of Anti-Wear Addi-
undefined, but this paper has proven that strong chemical tives on the Lubrication Properties of Corrosion Preventive Oils,"
interactions exist in dispersant-ZDP systems. More refined Lubrication Engineering, 25, 240-245 (1969).
investigations with pure, well defined materials must be (3) Gallopoulos, N. E., "Thermal Decomposition of Metal Dialkyl-
dithiophosphate Oil Blends," ASLE Transactions, 7, 55-63 (1964).
conducted to elucidate the chemistry of these antagonistic (4) Gallopoulos, N. E., "Infrared Spectra and Structural Features of
and synergistic effects, and to adequately explain the Salts of 0,O'-DialkylphosphorodithioicAcid," Preprints, Division of
observations described in this paper. Petroleum Chemistry, Inc., ACS, Vol. 11, No. 3, 21-37 (1966).
(5) Potts, W. J., Jr., "Chemical Infrared Spectroscopy," John Wiley
The information in this paper also indicates that cali- & Sons, Inc., New York, Vol. I, 1963, pp. 155-1 70.
bration curves for infrared analysis of lubricants must be (6) Heilweil, I. J., "Association Studies of Metal 0,O'-Dialkylphos-
constructed from solutions as nearly identical in compo- phorodithioates," Preprints, Division of Petroleum Chemistry, Inc.,
ACS, Vol. 10, No. 4-D, 19-31 (1965).
sition to the lubricant under analysis as possible. Even (7) Zumuna, K. Y., et. al., "Infrared Absorption Spectra of Metal
then, reliable analytical information will be obtained if Dialkyldithiophosphates," Neftekhimia, 5, 629-635 (1965).

You might also like