CA1238034A

CA1238034A - Functional fluids and lubricants having improved water tolerance

Info

Publication number: CA1238034A
Application number: CA000453467A
Authority: CA
Inventors: Lawrence R. Brecker; Otto E. Loeffler; Charles Abramoff; William K. Cleveland; Susan J. Wosatka
Original assignee: Argus Chemical Corp; Exxon Research and Engineering Co
Current assignee: Argus Chemical Corp; ExxonMobil Technology and Engineering Co
Priority date: 1983-05-10
Filing date: 1984-05-03
Publication date: 1988-06-14
Also published as: EP0125144A3; JPS59230093A; AU2772889A; EP0125144A2; EP0125144B1; AU602280B2; DE3480097D1; AU2785984A

Abstract

ABSTRACT OF THE DISCLOSURE
There are disclosed functional fluids and lubricating compositions containing a minor amount of an oil-soluble alkoxypolyethyleneoxy acid phosphite ester additive which provides improved water tolerance properties to the compositions.

Description

3~a TOLERANCE
1 ~his invention relates to func~ional fluids and

2 lubricants which exhibit improv0d water tolerance pro-

3 perties. More particularly, the invention relates to

4 mineral oil or synthetic oil based functional fluid com-

5 positions which contain effective amounts of certain

6 oil-soluble, alkoxypolyethyleneoxy mono- or di-acid

7 phosphite ester additives, which additives are highly

8 effective in improving the water tolerance properties of

9 such compositions.
U.S. Patent No. 2,280~450 describes hydrocarbon lloils oF improved resistance to corrosion containing a small 12 amount of a substantially stable oil-soluble water--in-13 soluble reaction product of tricresyl phosphite and octyl 14 phenoxyethanol. The mole ratio of tricresyl phosphitc to 15 octyl phenoxyethanol varies from 1:1 to about 1:2.5. The 16 reaction product i9 described as a complex ester of 17 phosphorous acid, which may or may not contain unreacted 18 octyl phenoxyethanol. The product is not however an acid 19 phosphite, and it is not suggested that the water tolerance 20 of the resulting composition is improved 21 U~S a Patent No. 3,583,915 provides industrial 22 fluid compositions and lubricant compositions containing 23 improved load-carrying additives, including a diorgano 24 hydrogen phosphonake in which at least one organic group is 25 an aliphatic group containing at least fourteen carbon 26 atoms in admixture with an active sulfur compound.
27 U.5. Patent No.3,652,410 provides multifunctional 28 lubricant additive compositions and lubricating oils 2~ containing, among other things, an organic scid phosphate 30 or organic phosphite containing at least one alkyl or 31 alkenyl group having from about 12 to about 24 carbon 32 atoms. Also present is a rnineral oil soluble or dis-33 persible basic deterqent, a mineral oil antioxidant, a 34 sulfurized fat, or an alkyl sulfide or alkyl polysulfide.

.

_ 2 _ 1 U,S~ Patent No. 4,346,148 and U.S. Patent No.
2 4,358,503 describe reaction products of alkoxylated alkyl 3 phenol and a phosphorus trihalide which are included i~
4 lubricating compositions useful in metal-working opera-tions, imparting corrosion resistance, extreme pressure 6 properties, and protection against wear of working parts.
7 U.S0 Patent No. 3,115,465 provides antioxidant 8 combinations for organic materials, including lubricants, g ~omprising an oil-soluble phosphite ester haviny the

10 fl~rmula

11 ' ~1~

12 R20 ~ P

13 R30

14 wherein R1 and R2 are alkyl, alkoxyalkyl, haloalkyl, cycloalkyl, halocycloalkyl, aralkyl, aryl, alkaryl, 16 haloaryl or haloalkaryl radicals and R3 is hydrogen or one 17 of the aforesaid radicals; and from about 0.01 to about 5, 1~ preferably 0.25 to 2%, by weight based on the oil of a 19 methylerle bis-phenol having the ~ormula:

.., . J,_ 1 21 H0- ~ C~2 ~ _~H

23 wherein R4 is an alkyl group containing 3 to 12 carbon 24 atoms, ths group b~ing branched on its alpha carbon atom~
25 and R5 is an alkyl group of 1 to 12 carbon atoms.
26 None of ths foregoing references disclose the 27 improvement in water tolerance properties achieved in 28 accordance with the present invention. Water compatibility 29 is a highly significant property o~ functional fluids and 30 lubricants, which, under severe conditions~ come into 31 contsct w.ith water and in the absence of acceptable water 32 tolerance properties the fluid will have its lubricating 33 and power transmission properties substantially reduced.
34 The speciFications of many equipment manufacturers require ~238039L

1 that the fluids and lubricants used therein have certain ~ water tolerance properties, for example, fluids for use in 3 agricultural machinery, such as tractor fluids.
- In accordance with the present invention there ' have been discovered improved ~un~tional fluids and 6 lubricating compositions comprising a major amount of a 7 synthetic or mineral oil of lubricating viscosity and an -8 amount, effective to improve the water tolerance properties 9 of the composition, of an oil-soluble alkoxypolyethyleneoxy 10 acid phosphite ester additive oF the formula:
11 R10--~cH2cH2~x 12 ~ P-OH

lL~herein:
R1 is alkyl or alkenyl and R2 .is ûH, alkoxy, 16 oxy-alkenyl, or R10[CH2CH2û]x, in ~Ihich the total number of 17 carbon atoms in the alkyl, alkenyl, alkoxy or oxyalkenyl 13 groups is about 8 to 36; and x is a number (which can be a 19 ~hole number or a fractional number) representing the . j 20 average number of ~CH2CH20~ groups, and ranges from about 2 21 to about 4~ Preferred phosphite additives are those 22 ~herein x is 2, 2.5, 3.5 or 4.
23 In Rl and ~2' alkyl and al~enyl groups 24 include octyl9 2 ethyl hexyl, isooctyl, tertiary-octyl, 2; nonyl, isononyl, tertiary-nonyl, secondary-nonyl, decyl, 26 isodecyl, undecyl, dodecyl, tridecyl, palmityl, stearyl, 27 and isostearyl; octenyl, nonenyl, decenyl, dodecenyl, 28 oleyl, linoleyl and linolenyl.
2~ Acid phosphites according to the invention 30 include di(octyl di(ethyleneoxy)) phosphite, ai(isooctyl 31 tri-~ethyleneoxy)) phosphite, di(2-ethylhexyl-tetra(ethy-2 leneoxy)) phosphite, di(nonyl-di(ethyleneoxy)) phosphite, ;i.i'isodecyl-tri(ethyleneoxy)) phosphite, di(palmityl-tetra , (ethyleneoxy)) phosphite, di(stearyl tri(ethyleneoxv)) phosphite, octyl di(ethyleneoxy) phosphite, stearyl di(ethyleneoxy~ phosphite, and octyl(tri(ethy1eneoxy))-' 1:

~ D34~

l nonyl(tetra(ethyleneoxy)) phosphite; octyl di(ethylene 2 oxy))octyl phosphite, isooctyl tri-(ethyleneoxy~ oleyl 3 phospnite, 2-ethylhexyl-tetra(ethyleneoxy) decyl phosphite, 4 nonyl-di(ethyleneoxy) nonyl phosphite, isodecyl-tri(ethy-leneoxy) linoleyl phosphite, palmityl-tetra(ethyleneoxy) 6 stearyl phosphite, stearyl-tri(ethyleneoxy) stçaryl 7 phosphite, octyl di(ethyleneoxy) stearyl phosphite, stearyl 8 di(ethyleneoxy) oleyl phosphite, and octyl tri(ethyleneoxy) 9 nonyl phosphite.
The oil-soluble phosphite ester additive of this 11 invention will provide effective water tolerance properties 12 to a wide Yariety of functional fluid and lubricating 13 co~positions and these include hydraulic fluids, compressor 14 oils, pump oils, tractor fluids and universal tractor fluid

15 compositiDns, gear ~ils, hydrostatic transmission-oils,

16 power shift transmission fluid~ and the like. Such

17 functional fluids and lubricating compositions will also

18 contain a number of conventional additives in amounts as

19 required to provide their normal attendant functions. Such

20 sdditives include viscosity modifiers or vi9c09ity index

21 improvers, corrosion inhibitors, oxidation inhibitors~

22 friction modifiers, dispersants, demulsifiers, anti-foam

23 agents, anti-wear agents, pour point depressants, seal

24 swellants and other special purpose additives.

Typical viscosity modifiers include polyiso-26butylene, ethylene-propylene copolymers, polymethacrylates, 27styreneacrylic esteE copolymers and vinyl monomer un 23saturated dicarboxylic acid (or ester) copolymers.
29Corrosion inhibitors include ~inc dialkyl dithiophosphates 30and phosphosulfuri~ed hydrocarbons and reaction proaucts 31thereof with alkaline earth metal oxides or hydroxides, 32preferably in the presence of alkyl phenols or alkyl phenol thioethers. Oxidation inhibitors are illustrated by alkaline earth metal salts of alkyl (Cs-C12) phenol - 3sthioethers.

- ' ~3~

1 Dispersants ars well known in the art and include 2 oil-~oluble alkenyl succinimides, e~g. the reaction products of 3 polyisobut~yl succinic anhydrides with ethylene amines 4 and borated derivatives. Exemplary pour point depressants are Cg-C1g dialkylFumarate/vinyl acetate copolymers~
6 polymethacrylates and wax-naphthalene condensation 7 products. Anti-foam agents are typically polyslloxane 8 rnaterials such as silicone oil and polydimethyl siloxane;
9 anti-~ear agents include zinc dialkyl (or diaryl) dithio-10 phosphates and magnesium sulfonates. Seal swellants are 11 typified by mineral oils that provoke swelling, Cg-C13 12 aliphatic alcohols and C10-c60 hydrocarbon esters having 13 2-4 ester linkages such as dihexylphthalate.

The oil-soluble phosphite ester additive of this 16 invention will be present in amounts effective to provide 17 acceptable water tolerance properties to the particular 1~ composition and the desired amount will vary according to 19 the service conditions but generally the additives of this 2Q invention will be present in an amount of about O.û5 to 5O
21 by weiyht, based on the ~eight of the total lubricatin~ oil 22 or functional fluid composition and preferably from about 23 û.2 to 2,o by weight percent.
24 Typical base oils for such functional fluids and lubricating compositions include a wide variety Df hydro-26 carbon mineral oils such as naphthene base, paraffin base 27 and mixtures thereof having a lubricating viscosity range 28 of about 34 to 45 Saybolt Universal Seconds (SUS) at 35C.
29 Examples o~ synthetic oils useful in the compositions of the present invention include olefin oligomers, alkylated 31 aromatics, polybutene oils, cycloaliphatic compounds, 32 dibasic acid esters, polyol esters, polyglycerol fluids, 33 pllospllate esters, silicone oils and halogenated hydrocarbon 34 fluids and mixtures thereof.
The Following examples illustrate the preferred 36 embodiments of the oil soluble phosphite ester additives oF
37 this invention: (Eo refers to etllylene oxide) ~313~3~

l EXAMPLE I
2 ~
3 159089 of triphenyl phosphite (97~) and 4059 of 4 (mixed alkyl(oxyethylene)z.s alcohols, t:he alkyl having from nine tu eleven carbon atoms, and 0.69 of K2C03 were 6 heatPd at 85~C ~or three hours. Vacuum was then applied (6 7 mm) with heating to a maximum temperature of 170C to 8 remove phenol. The weight of vol~tiles collected was 9 150.99 (theory 145.8). To the transesterified product lO 15.639 of phosphorous acid was added with agitation and the ll mixture heated to 85C for 5 hours with agitation, giving 12 clear reaction product having the formula:

13 (Cg_~1H1g_23)- 0 -[CH2CH20]2.5 14 ~ P-OH
(C9-11H19-23)- 0 [CH2CH20]2.5 ~

17 Di(C12-C1salkyl-3EO) phosphite was prepared from triphenyl 18 phosphite (97~), and (mixed alkyl(oxyethylene)3 alcohols, l9 the alkyl having from eleven to fifteen caroon atoms)using the procedure of Example I. The compound has the formula:

21 (C12-15H25-31)- 0 -[CH2CH20]3 22 ~ P-OH
23 (C12-15H25-31)- 0 -(CH2CH20]3 24 Control A
Di(C12- C~s alkyl-7EO) phosehite was prepared from 26 triphenyl phosphite (97'), and mixed C12-C1s (oxyethylene)7 27 alcohols using the procedure of Example I~ The compound has 28 the formula:

29 (C12-15H25 31)~ - [CH2CH20~7 P-OH
31 (C12-15H25_31) - -[CH2CH20]7 ~3~ 3~

l Control B
2 ~ was prepared 3 from triphenyl phosphite and ethoxylated nonylphenol using the procedure of Example I. The compound ha~s the formula:

C9H19-- ~ _ o_~CH2CH20]9.5___~_ 6 ~ P-O~
7 C9H19 - O _ O- tCH~CH20]9.5 ~

g Mono(Cg_11 àlkyl 2.5EO) mono oleyl ehos~ite was prepared lO from triphenyl phosphite ((mixed alkyl oxyethylene)2 5 ll alcohols~ the alkyl having from nine to eleven carbon 12 atoms), and oleyl alcohol using the procedure of Example I.
13 The compound has the formula:

14 (C9-11~19-23)~ O- [CH2CH2û~2.s _____~ P-OH
16 C18H35 ~
17 Typical functional fluids or lubricating com--l8 position of the present invention will contain a number of l9 conventional additives in typical amounts as required to 20 provide their normal attendant Functions. Such additive 21 components and their usual ranges are set forth below.

22 ~ Concentration Ran~_(Vol- ~?
23 V.I. Improver 1-15 24 Corrosion Inhibitor 0.01-2

25 3xidation Inhibitor ~.01-2

26 Dispersant 0.2-10

27 Pour Point Depressant 0.01~-1

28 Anti-foam Agent0.001-0.1

29 Anti-wear Agent 0.01-5

30 Seal Swellant 0.01-1

31 Friction Modifier 0.1-5

32 Mineral Oil 8aseBalance ~23l!3~3~

l The foregoing composition is referred to as Base Fluid and 2 a tractor hydraulic fluid corresponding to the Base Fluid 3 was evaluated for water tolerance with various additives as 4 set forth below. The mineral oil used in the Base Fluid had a kinematic viscosity of 69.8 centistokes at 37.8C
6 and 14.5 centistokes at 98.9C.
7 The test used was the International Harvester 8 Water Tolerance Test IH BT-7; January, 1980 contained in 9 the International Harvester Engineering Materials SpeciFi-lO cation for Combination Hydraulic and Transmission Fluid.
ll The test is described as follows 13 (1) Mechanical paint shaker, Red Devil No. 3û or equiva-14 lent.
(2) 118 ml bottle with cap.
16 (3) Graduated cylinder, 100 ml.
17 (4) 100 ml centrifuge tube according to AST~`l Designation D
I8 2273-67.
19 (5) Pipette or syringe capable of delivering 1.0 ml.
(6) Stopper to fit centrifuge tube.
21 PRûCE~URE
22 (1) Add 1 ml distilled water to 99 ml hydrocarbon oil 23 in the 118 ml bottle.
24 (2) Shake the prepared sample for 5 minutes in the 25 mechanical shaker~
26 (3) Transfer immediately to the 10û ml centrifuge 27 tube~
28 (4) Stopper and let the agitated solutions stand 29 undisturbed in a vertical position for 168 hours (7 days at 30 70 to 80F, 21 to 27~C), then examine for emulsion, water, 31 clearness and sediment.

33 (1) Level of emulsion, water and sediment to the ~4 nearest 0.1 ml.
t2) The clearness or turbidity oF the solution.

~3~3~3~

l EXAMPLE IV
___ 2 The results of evaluations are tabulated beloN in 3 the Table. The data include comparisons with Control A, 4 Control B and two commercially available Surfactants A
5 (sorbitan oleate) and B (ethoxylated fatty acid ester of 6 sorbitol anhydride). All additives were employed in the 7 ~ame Base Fluid at concentration of 1~ oy weight.

8 Table - Water Talerance Results 9 Additive Sur- Sur-1l ~estsControl Control fac- fac-12 Results None Ex I Ex II A B tant A tant 8 13 H20 0.2 0 0 1 2.5 *D.45 3.4 14 Inter- 0.5 0 0 * * O O
lS face 16 Oil Ap-17 pearance Haze clear Clear Haze Haze Clear Haze 18 * Emulsions, sediment and haze present 19 Note: The test is unsatisfactory if the total ml of H2û
and interface is 0.2 or greater. The oil appearance 21should be clear and free of haze.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A functional fluid composition comprising a major amount of a synthetic or mineral oil of lubricating viscosity and an amount, effective to improve the water tolerance properties of the composition, of an oil soluble phosphite ester additive of the formula:
wherein:
R1 is alkyl or alkenyl; and R2 is OH, alkoxy, oxy-alkenyl or R1O[CH2CH2O]x, in which the total number of carbon atoms in the alkyl, alkenyl, alkoxy or oxyalkenyl groups is about 8 to 36, and x is a number representing the average number of [CH2CH2O] groups and is within the range from about 2 to about 4.

2. A composition according to claim 1 in which x is 7.

3. A composition according to claim 1 in which x is 2.5.

4. A composition according to claim 1 in which x is 3.

5. A composition according to claim 1 in which x is 3.5.

6. A composition according to claim 1 in which x is 4.

7. A composition according to claims 1-3 in which R1 is alkyl having from nine to eleven carbon atoms.

8. A composition according to claims 1-3 in which R1 is alkyl having from twelve to fifteen carbon atoms.

9. A composition according to claim 1 in which the phosphite ester is and the oil is a hydrocarbon mineral oil.

10. A composition according to claim 1 in which the phosphite ester is and the oil is a hydrocarbon mineral oil.

11. A composition according to claim 1 in which the phosphite ester is

12. A tractor fluid composition according to claims 1-3.

13. A composition according to claims 1-3 in which the amount of the additive is within the range from about 0.05 to about 5% by weight of the oil.

14. A hydrocarbon oil composition according to claims 1-3 in which the amount of the additive is within the range from about 0.2 to about 2% by weight of the oil.