AU602280B2 - Functional fluids and lubricants having improved water tolerance - Google Patents

Description

6022 8 Q 10 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Application Number: Lodged: Int. Class -Complete Specification Lodged: Accepted: Published: Priority: Related Art: Name of Applicant: Address of Applt!ant Actual Inventor: Address for Service: EXXON RESEARCH AND ENGINEERING COMPANY ARGUS CHEMICAL CORPORATION and P.O. Box 390, Florham Park, New Jersey 07932, United States of America and Brooklyn, New York, United States of America, respectively LAWRENCE ROBERT BRECKER, OTTO ERNEST LOEFFLER, CHARLES ABRAMOFF, WILLIAM KENNETH CLEVELAND and SUSAN JEAN WOSATKA EDWD. WATERS SONS, QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: FUNCTIONAL FLUIDS AND LUBRICANTS HAVING IMPROVED WATER

TOLERANCE

The fcllowing statement is a full description of this invention, including the best method of performing it known to l -I j i respectively are the actual inventors of the invention

I'

FUNCTIONAL FLUIDS AND LUBRICANTS HAVING IMPROVED WATER

TOLERANCE

1 This invention relates to functional fluids and 2 lubric3nts which exhibit improved water tolerance pro- 3 percies. More particularly, the invention relates to 4 mineral oil or synthetic oil based functional fluid compositions which contain effective amounts of certain 6 oil-soluble, alkoxypoiyethyleneoxy mono- or di-acid 7 phosphite ester additives, which additives are highly 8 effective in improving the water tolerance properties of 't 9 such compositions.

10 U.S. Patent No. 2,280,450 describes hydrocarbon 11 oils of improved resistance to corrosion containing a small j 12 amount of a substantially stable oil-soluble water-in- 13 soluble reaction product of tricresyl phosphite and octyl C I 14 phenoxyethanol. The mole ratio of tricresyl phosphite to octyl phenoxyethanol varies from 1:1 to about 1:2.5. The t 16 reaction product iu described as a complex ester of 17 phosphorous acid, which m-~y or may nst contain unreacted 18 octyl phenoxyethanol. The product is not however an acid 19 phosphite, and it is not suggested that the water tolerance of the resulting composition is improved-.

21 U.S. Patent No. 3,583,915 provides industrial 22 fluid compositions and lubricant compositions containing 23 improved load-carrying additives, including a diorgano 24 hydrogen phosphonate in which at least one organic group is an aliphatic group containing at least fourteen carbon 26 atoms in admixture with an active sulfur compound.

27 U.S. Patent No.3,652,410 provides multifunctional 28 lubricant additive compositions and lubricating oils 29 containing, among other things, an organic acid phosphate 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 mineral oil soluble or dis- 33 persible basic detergent, a mineral oil antioxidant, a 34 sulfurized fat, or an alkyl sulfide or alkyl polysulfide.

L 4 1 2 3 4 6 7 8 9 10 rc C e I 11 12 13 14 16 S 17 S 18 19 21 U.S. Patent No. 4,346,148 and U.S. Patent No.

4,358,509 describe reaction products of alkoxylated alkyl phenol and a phosphorus trihalide which are included in lubricating compositions useful in metal-working operations, imparting corrosion resistance, extreme pressure properties, and protection against wear of working parts.

U.S. Patent No. 3,115,465 provides antioxidant combinations for organic materials, including lubricants, comprising an oil-soluble phosphite ester having the formula:

R

1 0 R20 P wherein R 1 and R 2 are alkyl, alkoxyalkyl, haloalkyl, cycloalkyl, halocycloalkyl, aralkyl, aryl, alkaryl, haloaryl or haloalkaryl radicals and R 3 is hydrogen or one of the aforesaid radicals; and from about 0.01 to about preferably 0.25 to by weight based on the oil of a methylene bis-phenol having the formula: R4 R4 HO- 0 CH 2 0 OH wherein R 4 is an alkyl group containing 3 to 12 carbon atoms, the group being branched on its alpha carbon atom, and R 5 is an alkyl group of 1 to 12 carbon atoms.

None of the foregoing references disclose the improvement in water tolerance properties achieved in accordance with the present invention. Water compatibility is a highly significant property of functional fluids and lubricants, which, under severe conditions, come into contact with water and in the absence of acceptable water tolerance properties the fluid will have its lubricating and power transmission properties substantially reduced.

The specifications of many equipment manufacturers require ii ii,.

I F .14 i t i i i i i

I

ic j i I iY l#

IT

CC I

C.C

C Ce C (i 3 1 that the fluids and lubricants used thUrein have certain 2 water tolerance properties, for example, fluids for use in 3 agricultural machinery, such as traci'or fluids.

4 In accordance with the presefnt invention there have been discovered improved functional 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

RIO--[CH

2

CH

2 0]x 12

P-OH

13

R

2 14 wherein: 15 R 1 is alkyl or alkenyl and R 2 is OH, alkoxy, 16 oxy-alkenyl, or R1O[CH2CH20]x, in which the total number of 17 carborn atoms in the alkyl, alkenyl, alkoxy or oxyalkenyl 18 groups is about 8 to 36; and x is a number (which can be a 19 whole number or a fractional number) representing the 20 average number of [CH 2 CH20] groups, and ranges from about 2 21 to about 4. Preferred phosphite additives are those 22 wherein x is 2, 2.5, 3.5 or 4.

23 In R, and R2, alkyl and alkenyl groups 24 include octyl, 2-ethyl hexyl, isooctyl, tertiary-octyl, nonyl, isononyl, tertiary-nonyl, secondary-nonyl, decyil, 26 isodecyl, undecyl, dodecyl, tridecyl, palmityl, stearyl, 27 and isostearyl; octenyl, nonenyl, decenyl, dodecen;l, 28 oleyl, linoleyl and linolenyl.

29 Acid phosphites according to the invention 30 includL di(octyl di(ethyleneoxy)) phosphite, di(isooctyl 31 tri-(ethyleneoxy)) phosphite, di(2-ethylhexyl-tetra(ethy- 32 leneoxy)) phosphite, di(nonyl-di(ethyleneoxy)) phosphite, 33 di(isodecyl-tri(ethyleneoxy)) phosphite, di(palmityl-tetra- 34 (ethyleneoxy))"phosphite, di(stearyl tri(ethyleneoxy)) phosphite, octyl di(ethyleneoxy) phosphite, stearyl 36 di(ethyleneoxy) phosphite, and octyl(tri(ethyleneoxy))- 0 1 t 1 iii ii

Y

i1.

;iij i.

;:a ii t 4 1 nonyl(tetra(ethyleneoxy)) phosphite; octyl di(ethylene- 2 oxy))octyl phosphite, isooctyl tri-(ethyleneoxy) oleyl 3 phosphite, 2-ethylhexyl-tetra(ethyleneoxy) decyl phosphite, 4 nonyl-di(ethyleneoxy) nonyl phosphite, isodecyl-tri(ethyleneoxy) linoleyl phosphite, palmityl-tetra(ethyleneoxy) 6 stearyl phosphite, stearyl-tri(ethyleneoxy) stearyl 7 phosphite, octyl di(ethyleneqxy) stearyl phosphite, stearyl S 8 di(ethyleneoxy) oleyl phosphite, and octyl tri(ethyleneoxy) 9 nonyl phosphite.

S 10 The oil-soluble phosphite ester additive of this 11 invention will provide effective water tolerance properties 12 to a wide variety of functional fluid and lubricating 13 compositions and these include hydraulic fluids, compressor 14 oils, pump oils, tractor fluids and universal tractor fluid compositions, gear oils, hydrostatic transmission oils, 16 power shift transmission fluids and the like. Such 17 functional fluids and lubricating cc~positions will also 18 contain a number of conventional additives in amounts as 19 required to provide their normal attendant functions. fich 20 additives include viscosity modifiers or viscosity index 21 improvers, corrosion inhibitors, oxidation inhibitors, S 22 friction modifiers, dispersants, demulsifiers, anti-foam 23 agents, anti-wear agents, pour point depressants, seal 24 swellants and other special purpose additives.

25 Typical vicosity modifiers include polyiso- 26 butylene, ethylene-propylene copolymers, polymethacrylates, 27styrene-acrylic ester copolymers and vinyl monomer un- 28 saturated dicarboxylic acid (or ester) copolymers.

29 Corrosion inhibitors include zinc dialkyl dithiophosphates and phosphosulfurized hydrocarbons and reaction products 31thereof with alkaline earth metal oxides or hydroxides, 32 preferably in the presence of alkyl phenols or alkyl phenol 33thioethers. Oxidation inhibitors are illustrated by 34alkaline earth metal salts of alkyl (C 5

-C

1 2 phenol

I

1.

;i ct (t c c r.7 Il CC 16 17 eprc 18 aC 1 19 21 22 23 24 26 27 28 29 31 32 33 34 36 37 Dispersants are well known in the art and include oil-Soluble alkenyl succinimides, eqg. the reaction products of polyisobutenyl succinic anhydrides with ethylene amines and borated derivatives. Exemplary pour point depressants are C 8

-C

1 8 dialkylfumarate/vinyl acetate copolymers, polymethacrylates and wax-naphthalene condensation products. Anti-foam agents are typically polysiloxane materials such as silicone oil and polydimethyl siloxane; .anti-wear agents include zinc dialkyl (or diaryl) dithiophosphates and magnesium sulfonates. Seal swellants are typified by mineral oils that provoke swelling, Cg-C 1 3 aliphatic alcohols and C 1 0

-C

6 0 hydrocarbon esters having 2-4 ester linkages such as dihexylphthalate.

The oil-soluble phosphite ester additive of this invention will be present in amounts effective to provide acceptable water tolerance properties to the particular composition and the desired amount will vary according to the service conditions but generally the additives of this invention will be present in an amount of about 0.05 to by weight, based on the weight of the total lubricating oil or functional fluid composition and preferably from about 0.2 to 2% by weight percent.

Typical base oils for such functional fluids and lubricating compositions include a wide variety of hydrocarbon mineral oils such as naphthene base, paraffin base and mixtures thereof having a lubricating viscosity range of about 34 to 45 Saybolt Universal Seconds (SUS) at 35 0

C.

Examples of synthetic oils useful in the compositions of the present invention include olefin oligomers, alkylated aromatics, polybutene oils, cycloaliphatic compounds, dibasic acid esaers, polyol esters, polyglycerol fluids, phosphate esters, silicone oils and halogenated hydrocarbon fluids and -i.xtures thereof.

The following examples illustrate the preferred embodiments of the oil soluble phosphite ester additives of this invention: (EO refers to ethylene oxide) r 1 EXAMPLE I 2 Di(C9-Ci1 alkyl_2.5 EO) phosphite 3 159.Bg of' triphenyl phosphite and 405g of 4 (mixed alkyl(oxyethylene) 2 .5 alcohols, the alkyl having from nine to eleven carbon atoms, and 0.6g of K 2 C0 3 were 6 heated at 85 0 C for three hours. Vacuum was then apriied (6 7 mm) with heating to a maximum temperature of 170* ,o 8 'remove pheno'l. The weight of volati).os collected was 9 150.9g~ (theory 145.8). To the transeaterified nrauct 15.63g of" phosphorous acid was added with agitation and the Cr 11 mixture heated to 85 0 C for 5 hours with agitation, giving 12 clear reaction product having the formula: 13 (C 9 11 Hl 9 23 0 -[CH 2

CH

2 0J 2 5

P

.C 9 1

H

1 9 2 3 )0-C H 2 CH 2 0] 2 16 EXAMPLE 11 17 Di(C 12 -Cli)alkyl-3E0) phosphite was prepared from triphenyl 18 phosphite and (.1ixed alkyl(oxyethylene)-t alcohols, 19 the& alkyl having from eleven to fifteen carbon atoms)using tUie procedure of Example J1. The compound has the formula: 21 (C 1 2 1 5

H

2 5 3 0- )0 -(CH 2

CH

2

O]

3

PO

22P-

H

23 C 2-1 1 0 CH2CH201 24 Control A Di(C 1 2- C15~ alkyl-7E0) phosphite was prepared from 26 triphenyl phosphite (9701), and mixed C 1 2 -C1 5 (oxyethylene) 7 27 alcohols using the procedure of Example I. The compound has 28 the formula: 29 (Cl?- 1 5 11 2 5 0-(CH- 2 CH2] 7

P-OH

31 (C 1 2-1 5i125-31 )-O-CH 2

CH-

2 0] 7 7 Control B 2 Ethoxyllated nonyl phenol (9.5E0) ph Qsphite wa~s prepared 3 from triphenyl phosphite and ethoxylate:! nonyiphenol using 4 the procedure of Example I. The compound has the formula:

C

9 H 1 9

-O-[CH

2

CH

2 0] 9 6 P 0H 7 C 9 H 9 8 EXAMPLE III 9 Mono( C9_1i 1 akyl 2 .5E0) mono oleyl phosphite was prepared f rom triphenyl phosphite (mixed alkyl oxyethytlene) 2 11 alcohols, the alkyl having from nine to eleven carbon 12 atoms), and oleyl alcohol using the procedure of Example 1.

13 The compound has the formula- 1.4 (C 9 1 1

H

1 9 2 3

(CH

2

CH

2 0 2 5

P-OH

16 Cl 1 8

H

3 t rO

A

17 18 19 21 Typical functional fluids or lubricating corn-, position of the present invention will contain a number of conventional additives in typical amounts as required to provide their normal sttendant functions. Such additive components and their usual ranges are set forth below.

Component V.I. Im,,,rover Corrosion Inhibitor Oxidation Inhibitor Dispersant Pour Point Depressant Anti-foam Agent Anti-wear Agent Seal Sweliant Friction Modifier Mineral Oil Base Concentration Range (Vol. 1-15 0.01-2 0.01-2 0.2-10 0.01-1 0.001-0.1 0.01-5 0.01-1 0.1-5 Balance 1

-F

i;i r 1

;;I

i i ii i_ t i

E

BI ia 1 2 3 4 6 7 8 9 S 11 12 13 14 15 16 17 18 19 20 21 22 23 24 26 27 28 29 31 32 33 34 The foregoing composition is referred to as Base Fluid and a tractor hydraulic fluid corresponding to the Base Fluid was evaluated for water tolerance with various additives as set forth below. The mineral oil used in the Base Fluid had a kinematic viscosity of 69.8 centistokes at 37.8 0

C

and 14.5 centistokes at 98.9 0

C.

The test used was the International Harvester Water Tolerance Test IH BT-7; January, 1980 contained in the International Harvester Engineering Materials Specification for Combination Hydraulic and Transmission Fluid.

The test is described as follows: APPARATUS REQUIRED Mechanical paint shaker, Red Devil No. 30 or equivalent.

118 ml bottle with cap.

Graduated cylinder, 100 ml.

100 ml centrifuge tube according to ASTH Designation D 2273-67.

Pipette or syringe capable of delivering 1.0 ml.

Stopper to fit centrifuge tube.

PROCEDUR.E

Add 1 ml distilled water to 99 ml hydrocarbon oil in the 118 ml bottle.

Shake the prepared sample for 5 minutes in the mechanical shaker.

Transfer immediately to the 100 ml centrifuge tube, Stopper and let the agitated solutions stand undisturbed in a vertical position for 168 hours (7 days at 70 to 80°F, 21 to 27°C), then examine for emulsion, water, clearness and sediment.

REPORT

Level of emulsion, water and sediment to the nearest 0.1 ml.

The clearness or turbidity of the solution.

-~W~IIP~WL

9 EXAMPLE IV The results of evaluations are tabulated below in the Table. The data include comparisons with Control A, Control B and two commercially available Surfactants A (sorbitan oleate) and B (ethoxylated fatty acid eater of sorbitol anhydride). All additives were employed in the same Base Fluid at concentration of 1% by weight.

Table Water Tolerance Results 9 11 12 13 14 16 17 Additive Tests Results

H

2 0 Interface Oil Appearance None 0.2 0.5 Ex I 0 0 Ex II 0 0 Control

A

1-2.5 Control

B

Haze Haze Surfactant A 0.45 0 Surfactant B' 3.4 0 Haze clear Clear Haze Clear Haze i i ?j I r 18 Emulsions, sediment and haze present 19 Note: The test is unsatisfactory if the total ml of H 2 0 20 and interface is 0.2 or greater. The oil appearance 21 should be clear and free of haze.

L t s i

Claims (10)

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: RIO-CH 2 CH 2 CH0] P-O H R2 wherein: R1 is alkyl or alkenyl; and R 2 is OH, alkoxy, oxy- alkenyl or RIaCCH 2 CH20O], in which the total number of carbon atoms in the alkyl, alkenyl, alkoxy or oxyalkenyl groups is 8 to 36, and x is a number representing the average number of [CH 2 CH20] groups and is within the *range from--r 2 to 4. v

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

3. A composition according to claim i in which x is

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

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

7. A composition according toLcaizs 1-6 in which Rl is alkyl having from nine to eleven carbon atoms. c4 composition according to laims 1-6 in which R1 is alkyl having from twelve to fifteen carbon atoms. 3. A composition according to claim 1 in which the phcphtte ester is C 9 11 H19- 23 -0-[CH 2 CH 2 0]2.5 .P-OH C -llH 9 -23-o-[CH2H20]J2 and the oil is a hydrocarbon mineral oil. A composition according to claim 1 in which the phosphite ester is C1 2 -15SH 2 5 -31-O-[CH 2 CH20J3 P-OH C 1 2-1 5 H 2 5 3 1 2 CH 2 0 3 and the'oil is a hydrocarbofi mineral oil.

11. A composition according to claim 1 in which the phosphite ester is (C 9 -llH 1 9 2 3 )-O-CH 2 CH 2 01 P-OH C 1 8 H 3 5 0

12. A tractor fluid composition according to claims 1-11.

13. A composition according toclaims 1-12 in which the amount of the additive is within the range from 0.05 5% by weight of the oil. i 1 0 12

14. A hydrocarbon oil composition according toj claims 1-12 in which the amount of the additive is within the range from 0.2 to 2% by weight of the oil. DATED this 4th day ofJanuary 1989. EXXON RESEARCH AND ENGINEERING COMPANY and ARGUS CHEMICAL CORPORATION 2a C C C i i I ii is i i i T ii1 EDWD. WATERS SONS PATENT ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000. I