Document 0GNvzrqYaEyZBEg208ZrVJ6k
"7 -
ORGANIC CHEMICALS DIVISION
RESEA
Special ReporvOf$Ofel8
c&t Cx
MCS 153 Transfer Report
Transfer to Organic Development
Job No. 4013
January 7 1963
Written by. J. D. Sullivan
MONSANTO CHEMICAL COMPANY ORGANIC CHEMICALS DIVISION
ST. LOUIS RESEARCH DEPARTMENT
s.V
Special Repor
18
MCS 155 Transfer Report
Transfer to Organic Development
Job No. 4013
January 7 1963
Written by: J. D. Sullivan
MONS 0210^1
DISTRIBUTION
1. File 2. K. L. McHugh 3. W. R. Richard, Jr. iv. Duplicate File
6. J. D. Sullivan 7. R. E. Hatton - Development Department 8. L. R. Stark 9. L. E. Klein - Development Department 10. Extra 11. Extra 12. Extra
This report contains confidential Information which la the property of the Monsanto Chemical Company and which shall be disclosed only to duly authorized persons. The recipient Is held accountable for the filing and safe custody of the report, which must be returned on demand.
HONS 021092
J J0\0'0. o.o.o O'.O'O'U' UHHUI-JI oivjuji f
INDEX
rage
'jj'ji'jJrvi
A. INTRODUCTION ...........................................
B. CHEMISTRY.......................................................
1. Degree of Polymerization . . .
2, Addition of Reactants
..,
a Stepwise Polymerization. .
b. Batcnwlse Polymerization .
C. PROPERTIES OF MCS 153..........................
1. Fluid Properties ....... a. Viscosity ............................... b. Pour Point .............................. c. Viscosity Index Study. . .
2. Quality Tests ...............................
3. Physical Properties......................
a. Densities ............................... b. Specific Heat..........................
4. Electrical Properties.................
a. Dielectric Constanta . . . b. Power Factor .......................... c. Specific Resistivity . . .
5- Flammability .............................. a. AIT ............................................ b. Flash Point.............................. c. Fire Point ............................... d. High Pressure S)ray Test . e. Hot Manifold Teat.................
f. Molten Metal Ignition Test
6. Lubricity............................................ a. Four-Ball Test ...................... b. Timken Wear Test ................. c* Shear Stability.................
7. Performance Tests ...................... a. Oxldatlon-Corro3lon Test b. Foam Tests ..............................
c. Rust Tests .............................. d. Emulsion Tests ......................
Q. Heat StabilityTest3........................................................................
9. Toxicity......................................................................................................................................
10. Patent Status. .*..........................
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HONS 021093
1
A. INTRODUCTION
This report is an attempt to bring together In one place all
of the pertinent technology on the preparation and use of
MCS 153- The publication of this report will formally transfer the responsibility for this product from the Research Department to the Organic Development Department.
Although OS 81, Monsanto's synthetic steam turbine lubricant,
has served as a suitable gas turbine fluid, the lower vis cosity MCS 153 la desirable to facilitate start-upa at low temperatures. MCS 153 la a shear stable functional fluid having the following formulation:
Aroclor 1242
Aroclor 1232 Trlcresyl phosphate (TCP) Poly(Oxybutylene-MDI) Dlol (PH-139) N-Phenyl-a-Naphthylamine (PAN)
DC-200 Silicone
75.31* 12.84%
10.00%
1.8o% 0.05% 50 ppm
PH-139 la a shear stable viscosity Index Improver prepared by the reaction of polyoxybutylene dlol (B-2000) with methylene dl--phenylene Isocyanate (MDX). This la a "long sought after"
development in functional fluid research and its utility may be
visualized beyond the current gas-turbine application. Shear stability la imperative for hydraulic fluids of the Aroclor and the Pydraul serlee and would prove extremely advantageous In the Skydrcl fluids used In the aircraft Industry.
An intensive effort was made to design a shear stable viscosity Index improver which did not cause eaulslfloatlon when the
formulation was mixed with water. Non-emulsifying fluids are not a requirement for the gaa-turblne application but It Is an Important property for fluids which could be contaminated by water by mechanical failures such as In steam turbine or ship board installations. Water washing followed by dehydration, is becoming a popular method for recovering used hydraulic fluids and Increasing emphasis is being placed on formulations which will not emulsify in contact with water.
Of the viscosity Index Improvers prepared and tested, the most effeotlve polymers, which also gave non-emulslfylng fluids upon
fonnulatlon, were ones prepared from polybutylene glyoole (B-2000) and MDI. However, this polymer (PH-139) prepared in the plant from production size lots of B-2000 and MDI caused
the resulting MCS 153 formulation to emulsify In contact with water. This emulsifying tendency was traced definitely to a contaminant, other than moisture and free acid. In the poly butylene glycol. Purifying this dlol by customary techniques, prior to polymerization, failed to give non-emulslfylng formulations.
HONS 021094
MCS 15? was marketed as a gas-turbine lubricant but this problem will have to be resolvea before FH-139 can be used in formulations whose applications require non-emulslfylng fluids.
CHEMISTRY
The general equation for the preparation of FH-139 Is as follows;
(X + l)H0{C4HB0)nC4He0H
N.---------
The reaction temperature for the polymerization is 70* to 85*C.
1. Degree of Polymerization
Although much higher molecular weights were attained in this
polymerization reaction, limiting the chain lengths of
FH-139 to the minimum viscosity requirements of gas turbine applications increased the chances of shear stability and non-emulslflcatlon cf the resulting MCS 153- Difficulties
would be encountered In the production of higher molecular
weight polymers because of the low fluidity of the products and the selection of a suitable solvent or diluent which would not Inhibit the polymerization. Since FH-139 was slated for a vlacoalty index improver in Aroclor type fluids, It was felt that high molecular weight polymers could be easily handled by reacting MDI and the dlol In a solution of the appropriate Aroclor. However, Aroclor inhibits the DOlymerization and the reaction cannot be carried out in .ais medium without the aid of a catalyst. On the other nand, the polymerization proceeds smoothly In benzene without a catalyst. The use of polymerization catalysts In the reaction of MDI with the dlol resulted in gel polymers which were insoluble In the fluid base stocks.
If the polymer contains terminal Isocyanate groups, they
will react readily when the fluid comes in contact with
water and result in severe emulsions. Likewise, water
must be excluded from the reaction of MDI with the dlol
since the resulting urea groups would serve as terminators
for the polymerization. Acid Impurities In the starting
materials will inhibit the complete polymerization of MDI
and the dlol.
'
MONS 021095
2, Adaitlon of Reactants
a. Stepwise Polymerisation - In order to obtain the desired polymerization, the aiol ana MDI were addea In definite Increments to supply the required excesses
of each reactant, for various time intervals, auring tne reaction period. Specifically, two moles cf KDI were added to one mole of the dlol to form a poly-
oxyalkylene dllsocyanate. This dllsocyanate was
reacted with two more moles of the aiol to form a poly(oxyalkylene urethane} dlol. The cycle was
repeated until a polymeric dlol, having an approximate molecular weight of 10,000, was obtained.
b. Satchwise Polymerization - If the total MDI and polyglycoi required were "added at the same time in a single reaction mixture, the desired order of polymerization cannot be attained even with prolonged heating. Under these conditions, the molecular weight of the polymer did not reach Its maximum and optimum viscosity Index improvement of the resulting formu lation was not obtained.
PROPERTIES OF MCS 153
1. Fluid Properties
Table I lists the pour point, along with the viscosities of MCS 155 at various temperatures. Similar results are listed for 05-81, Monsanto's current steam turbine lubri
cant, for comparative purposes.
Table I
a. Viscosity (cs)
MCS 153
OS cl
b. Pour Point
at 20*F at 40*F at 60 *F at 100*F at 150*F
at I75'P at 210*F
3,681.0 468.6 120.0 22.6 10.7 *9 3.2
0'F
200,000 3,200
-
34
-
5- 5 3.1
+ 20?
In Table lc are listed viscosities of numerous formulatiora
In which the shear stable viscosity Index improver (PH-159; was added to various Monsanto base stock fluids.
MONS 021056
Table 1c
c. Viscosity Index Stuay
Monsanto's Base Stock Fluids
Arcelor 1242, S-409 " " + 45 PH-139
TCP " + 4% FH-139
Tetralkyl Urea " " + 4J8 FH-139
100*F Vis.
17.2 36.0
31.66 62.18
51.48 78.56
210*F Vis. VI
2.35 -273 4.6l - 3 2
4.159 - 33 7 691 * 95 3
7.465 + 1110.77 + 121
FH-118 " +4j6 FH-139
Santicizer 140 " + 4* FH-139
FH-1Q2-2 " + 4j( FH-139
47.1 81.58
17-66 34.05
10.91 19-15
7.41 + 125 11.97 + 132
3.258 + 20.0 6.379 +142.0
2.960 + 141 4,877 + 184
Santicizer 141 " " + 45 FH-139
9.955 2.431 + 62.3 20.07 4.48? +156 0
OS-59 n + 4* FH-139
Dlbutyl Phenyl Phosphate " + 45 FH-139
6.791 6.956
4.166 3.472
2.254 + 156 2.298 + 158
1.440 + 86.8 2 708 + 176
Diphenyl Sulphide " h + 45 FH-139
2.00
1.16 + 121
5.800 2.234 + 199
Unfortunately, PH-139 is Insoluble In hydrocarbon oil and cannot be utilized in that application.
Quality Teste
These tests are analytical determinations for trace con tamination.
MCS 153
OS cl
a. Neutralization 'Jumber (typical) b Water, % by weight, maximum
0.07 0.10
0.0/
C 10
HONS 0210^7
3. Physical Properties
The following table lists the densities of MCS 153 at various temperatures along with the specific heat of this fluid at
17'?.
a. Density
Temperature
Om/ml
20'F 60F
100'F 210*F
1.3663 1.3*52 1.32*7
1.267*
MCS 153
OS 51
Specific Heat at 11'?, BTU/lb./'P
0.30
0.31
4. Electrical Properties
Table II lists dielectric constants, power factors and specific resistivities for MCS 133, OS 3l, DTE Oil 797 and Cellulube 220.
Table II
MCS 153 OS 81 DTE 797 Cell. 220
a. Dielectric Constant at 25*C
at 60 cps at 1000 cps
6.52 5-9*
5.95 2.22 5-8* 2.2*
6.91
b. Power Factor (*) at 25*C
at 60 cps at 1000 cps
52-0 3.*5
17.6
0
1.08 0
17-5
c. Specific Resistivity
I ohm-cm)
1 0 lO 13
at 25*C
1.7x10# 50x10s l.*xlOii 2.0x1Ct
at 100*C
2,0x10 3-3x10 3-9x10 8.6x10
Dielectric constants and power factors were measured at 60 and 1000 cycles per second at room temperature {25C) Specific resistivity measurements were made at 25 C and 100*C with a megohm triage.
MO NS G21O90
o.
5. Flammability
The following flammability tests show that MCS 153 Is
fire retardant despite the Incorporation of FH-1J9 Into the formulation.
Is
1"
MCS 153
a. AIT
1130*F
1260F
b- Flaah Point (C.O.C.)
360F
385'f
c. Fire Point (C.O.C.)
56o*F
66o*F
d. High Pressure Spray Test
~TAH5~?15P51---------
Does not flash or bum
Does not flash or
burn
e. Hot Manifold Teat
--(AMS 315051------
Intermittent flashing on tube, does not carry flame to pan (130O*P)
No flashing at 1300P
f. Molten Metal Ignition Test
Intermittent ignition, self-ex tinguishing.
Plashes by spark, selfextlngulshlng.
Does not Ignite.
Plashes by spark, self extinguishing
6. Lubricity
The following table compares the lubricating properties of MCS 153 to OS 81.
a. Pour-Ball 'Wear
OS 81
MCS 153
at 167*F, 1 Hr. 626 RFM
Steal 4 Kg. on 10 Kg.
Steel 40 Kg.
Stell-on-Brass 10 Kg.
b. Timken T*75.Z.
0.27 mm 0.55 mm
0.21 mm 0.23 mm 0.53 mm
I. 25 mm
0.92 mm
30 lbs. Passed aq lbs. Passed
II, 350
11,760
HONS 021099
c. Shear Stability
FH-139 In for-iulatior.s of Aroclor and/or trlcresyl phosphate are exceptionally shear stable. After twelve (12) passes through the Diesel Injector, the viscosity of the fluid is decreased by only 0.5^6.
Ferformance Tests
a. Oxidation-Corrosion Test
For purposes of comparison, MCS 153 is compared to the 7800 type fluid specifications along with OS 8l and WS-3777, an Esso candidate for a 9236 type fluid
The following table lists the results of comparable oxidation and corrosion tests after a 72 hour retention time at 347*F per Mil-L-73o8c.
OS 81 MCS 153 WS-3777 7808C
Viscosity Initial
100 zoo
viscosity Change ff
122
Acid
Metal Attack
Change H& A1
Cu
wt. Loss
II
34.5 3-15 17-9
1.9 0.14 .01 03 03 -.11 -.01 3.4
22.9 3.28 -4.9 -13.7 0.15 .02 .02 .02 -.34 -.10 8.1
52-3 10.4 -4.3 - 5.9 0.54 .02 .02 .03 102 .01 2.3
11. 3.
-5 to
2.0 + .2 + .2 + .2 + .4 1-2
+15
No sludge or cocing was observed in the MCS 153 formu
lation after th< test was terminated.
-
The following tible lists the results of oxidation corrosion tests on MCS 153 and OS 81 at 250*F for
168 hours.
os 81
MCS 153
etal Attack, M-/cm:
M;
A1
Fj Ci CD/Fe
0
-0.01
-0.01
-0.05 -0.04
-0.C1
-0.01
0
-0.04
-0.01
lscosity: 100*F Initial 100*P Final Change
210*F Initial 210*F Final % Change
34.51 cs. 35.48 cs. +2.8
3.15 cs. 3.11 cs. -1.3
22.55 C3 24.71 C 3
+9.b
3.24 3.31 *2.1
MONS 021100
8.
OS 8l
HCS 15?
Acidity: Initial, TAN Pinal, TAN
0.07 0.09
0.07 0.05
b. Foam Tests (ASTll D392}
The following table lists the foaming characteristics
of MCS 153 and OS 8l.
MCS 153
0S-31
75*F Tendency (foam after 5 min. air
100 ml.
10 ml
blowing)
Stability (time to collapse)
200 sec.
10 sec
200*F Tendency Stability
0 ml.
0 ml. --
75*F after 200*7 Tendency Stability
50 ml. 40 sec.
20 ml. 20 sec
o. Runt Teats (ASTM D665)
The cylindrical specimens removed from these tests were equivalent for ICS 153 and OS 81. Furthermore, both of these were comparable to coupons exposed to an uninhibited petroleum oil under similar test conditions.
d. Emulsion Tests (ASTM D1401)
The emulsification properties of a fluid is measured by the ability of the formulation to separate from
an equal amount of water, in a half an hour at 135*0, after the mixture has been thoroughly agitated for five minutes at that temperature. Both OS 81 and MCS 153 are rated as non-emulsifying fluids by this test.
OS 81 SmuT*.' Fluid TTTP
MCS 153 Emui. r'luia H2P
0 40 ml. 40 ml.
0 ml. 44 ml. 36 ml.
Although most additives, especially viscosity index
improvers. Increase the tendencies of synthetic formulations to emulsify with water, FH-139 la rated as s non-emulsifying, shear stable, viscosity
index improver.
HONS Oil101
9.
8. Heat Stability
Laboratory teats showed that large moleoular weight polymers (20,000 to 30,000) made from MDX and polyalkylene glycols degraded when heated for prolonged periods above 200*F. On the other hand, lower mole cular weight (approximately 10,000) polymers are still effective viscosity index Improvers and are more thermally stable. In addition to shear stability and non-emulslflcatlon, this thermal characteristic of the polymer was another reason for limiting the chain length of the FH-139 going into the MCS 153 formu lation. Table III (see page 10) lists the changes in viscosity and acidity in MCS 153 and OS 8l after long retention times in a severe (static) oven test at 300*F.
It will be noted that the acid build-ups and viscosity increases were only moderate at temperatures well in excess of the operating temperaturea of a gas turbine -
9. Toxicity
The toxicity of MCS 153 1 unknown at present, but it is anticipated that this fluid will prove to be relatively non-toxic and non-lrrltatlng to the skin.
10. Patent Status
A disclosure (No. 2*51) has been filed by the Organic Division to cover tne use of polyrsers, made from polyglycols and diisocyanate, as shear stable, nonemulslfylng viscosity index improvers for various fluid base stocks.
2-25-63
J. D. Sullivan HONS 021102
TABU III
AfUr 120 Hrs.
Fluid
IM'1-fir--
F F W(
TOB*- Jl "gnr~ % F Chant* r Chaw NN
W"----1-----TTT" -% -
F Chaw F Change NN
KC3 153 20.6 3-2* .07 21.1 '6.6 2.96 -e.i .09 20.7 -6.0 2*> *e.7 0. lo
OS 8l >*5 3.15 .07 35.3 >2.2 3.13 -0.6 .07 35-2 +2.0 3.2J .0.9 0 09
HONS 02U3
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