DE2006807A1 - Lubricant mixtures - Google Patents

Description

DR. JUR. DfPL-CHEM. WALTER BEIL ■ '- ■

ALFREDHOSPPEMER X

DR. JUR. DiPL-CMEM H.-1 WOLFF ~ "

DR. JUR. HANS CHR. ROPE

023FRANKFURTAMMAIN-UOCMSr.

ADO0NSRASSE5 -

Our Kr. 16.112

The Procter St Gamble Company Cincinnati, Ohio, V.St.A.

Lubricant mixtures.

The present invention relates to lubricant mixtures, .die Contain a unique base fluid for lubricants and an antioxidant. These Lubricant blends have acceptable flash points, freezing points and loading properties so that they can be used as Lubricants for jet machines can be used.

Dipropylene glycol dipelargonate was used as the base liquid sold for synthetic lubricant mixtures. This Material has a flash point that is too low for example with lubricant mixtures for jet machines to be used because at high temperatures too much of the liquid is lost through evaporation would go. Further, since dipropylene glycol dipelargonate has a very low pour point, it solidifies when it does is kept at temperatures at which it is liquid lead

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should practice.

The present invention relates to lubricant mixtures containing the fatty acid diesters of tripropylene glycol which each fatty acid portion has about 6 to 10 carbon atoms, ■ preferably contains from 7 to 9 carbon atoms, and

0.001 to about 5 # of an antioxidant which is a Mixture of ρ, ρ'-dioctyldiphenylamine and N-phenyl-1,2,3 »4— tetrahydro-2-naphthylamine is included.

The unique base fluid for lubricants. '. this mixture is a fatty acid diester from Tripro -

^ pylene glycol. Have fatty acid diesters of dipropylene glycol

^ Flashpoints that are too low to be used as lubricants for

the latest in jet machines to be used and dipropylene glycol and tetrapropylene glycol diesters solidify when used at low temperatures, e.g., about -54 ° C being held. Also, there are diesters of tripropylene glycol, the; two fatty acid residues with about 6 carbon atoms or less, decomposed under extreme temperature conditions, and esters, the fatty acids with 10 or contain more carbon atoms tend to have high pour points. For use as a lubricant for nozzle machines it is therefore necessary that diesters of tripropylene glycol are used in which the fat is fe contain acids from about 6 to about 10 carbon atoms,

and in which only minor amounts of the fatty acids contain either 6 or 10 carbon atoms. Small amounts of C -, -, - and higher fatty acids can be present in the diesters but in general they should be avoided. Synthetic fatty acids can also be used will.

Suitable tripropylene glycol diesters are described in the following examples. Other reason -

10 9 8 30/1677

Liquids for lubricants can also be used together with the specific, unique base fluids for lubricants according to the invention. .... _: ,

The tripropylene glycol diester, which serves as the base material for the lubricant according to the invention, appears to be too unstable to be at the high temperatures due to the hydrogen atom bonded to a tertiary carbon atom of the tripropylene glycol chain. _: ,. J temperatures of the latest jet machines to be used alone. To therefore the Tripropyl englycoi diester, in one. To use lubricant for a jet engine is a must. to incorporate an effective antioxidant.

Antioxidants are, well "known lubricant additives. The" preferred antioxidant is a _; · =

Mixture of p'jp'-dioctyldiphehylamine and li-phenyl-l, 2,3,4-

tetrahydro-2-naphthylamine .. Das li-Phenyl-ljg. ^ jA-teträ - ^

hydro-2-naphthylamine should be around 30 to BO ^a / o>. the mixture, preferably et _(wa 50 'to 70. fy, make up. Preferably these two amines are in a ratio of two parts P.P ■■ ■.' .- dioctyldiphenylamine to three parts of N-phenyl-i

1,2,3t4-tetrahydro-2-naphthylamine can be used. One, Preferred Concentration. des Antioxidatio ^ nsmi.t ^ e ^ qi ^ l. is, »,.-.-.- with about.A:,; 5 wt .- ^ .., based on the lubricant r- ■ mixed, and, a preferred B, erei, ch is about 0.1: to.

It is believed that the ρ, ρ'-dioetyldiphenyl- (1) as an inhibitor of door-free radicals ,, (2), as; dispergie

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rendes agent and (3) acts as a secondary base. It is believed that the N-phenyl-1,2,3 ^ -tetrahydro-2-naphthylamine acts primarily as a base to neutralize any acid generated during storage or use. Other materials that serve the same functions can either be wholly or partially in place of the aforementioned components of the anti-oxidation mixture be replaced.

Other additives that can be added to the lubricant mixtures according to the invention, belonging. "Ren agents for improving the viscosity index, means" to reduce the pour point, dispersing agents, agents for preventing wear (anti-wear additives), etc metal deactivators ..

These agents for improving the viscosity index are normally used in a concentration of about 0.01 to 2 wt .- ^ j based on the lubricant mixture, used. Suitable agents are, for example, polyisobutenes, polymethacrylates, vinyl acetate-fumaric acid ester copolymers and polyacrylates.

The means for lowering the pouring point are ■ * those in a concentration of about 0.01 to 2 wt .- #,

based on the lubricant mixture. Appropriate Nice agents for lowering the pour point are the agents listed above for improving the viscosity index, alk.ylated waxes, naphthalenes, poly methacrylates and alkylated wax phenols.

The metal deactivators (anti-corrosion additives) are normally used in a concentration of about 0.001 to 0.5 wt .- ^, based on the lubricant

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ORfGfNAL INSPECTED

mixture, used. Suitable metal deactivators are, for example, disalicylidene-l ^ -diaminopropane, benzoguanamine and N-alkyl- and Mngalkyl-substituted benzoguanamines, Thioureas, octadecylamine, quinizarine, quinolines, phenylaeridine, hexamethylenetetramine, thiobenzamide, Benzothiadol and imidazolines

The anti-wear agents are normally used at a concentration of from about 0.01 to 5 wt .- ^, based on the lubricant mixture, used. Suitable additives to prevent wear are Tricresyl phosphate, organic phosphites and long chain Methylenediphosphonate ester. '-

Dispersants are usually used in a

Concentration of about 0.01 to 2 wt .- ^, based on the lubricant mixture is used. Suitable dispersing Means are the means given above for Improvement of the viscosity index, mixed polymers of methacrylates ?! or acrylates, N-substituted long chain Alkenyl succinimides, high molecular weight esters or Polyester and vinyl acetate-fumaric acid ester copolymers.

Other suitable additives are used in Canadian Patent 792 739 described that as a reference is used for the present application.

. ' ■: ■■ ■!

The essential fatty acid diesters of tripropylene. Glycols can be combined with other known lubricant base fluids to improve their properties. In a broader sense, the other base liquid can either be a petroleum hydrocarbon, a fatty acid triglyceride, a synthetic liquid (fluid), an aqueous base liquid (based) or mixtures thereof. Petroleum hydrocarbons include - , / include mineral oil (e.g. light solvents, neutral oils,

■■ '- ■; 109830/1677 -

heavy, clear and refined fractions as well as residues containing asphalt), fats and waxes. The base fluids of the lubricants can also include suspensions of graphite in oils. Synthetic liquids are, for example, disparate materials such as polymerized olefins, organic carbonates, organic esters and / or ethers, polyglycols, silicones, modified organic substances (halogenated, phosphated, sulfurized substances, etc.). Polymers such as alkyl methacrylate polymers and synthetic resins such as resins obtained by esterifying polyhydric alcohols with polycarboxylic acids. Examples of base materials that can be used in the practice of the present invention are shown in U.S. Patents 2,599,761, 2,725,359, 2,767,142, 2,882,228, 2,956,952, 2,993,859, 3,296, and 3,357 920 described. Other suitable lubricant base materials are in the "Encyclopedia of Chemical Technology", Kirk-Othmer, 2nd Edition, Volume 12, pages 557-616, especially pages 576-582, edited by Interscience Publishers, 1967, mentioned. Further examples of base materials of metalworking lubricants are given in "Metal Working Lubricants" by ELH Bastian, 1st Edition, McGraw-Hill Book Co., Inc., 1951. All of the above patents and publications, including the literature cited, serve as a basis of reference for the present invention.

Other esters of polyols and monobasic acids, such as Cg-C ₁ p-fatty acid polyesters of ethylene glycol, poly ethylene glycol, propylene glycol, other polypropylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane and are particularly preferred for sole hon mixtures (1.) Pentaerythritol, (2nd) eater

B 7 7

BAO ORIGtNAL

Acids, such as esters from Gg-Gtp fatty acid alcohols (normal, branched and secondary alcohols) and adipine, azelaine and / or sebacic acid and (3 ·) complex esters, such as poly-. ester of polyalkylene glycol and dibasic acid, the in the end position, either a monobasic acid or a have monohydric alcohol. . · - .. '. -

Two groups of lubricant masterbatches are. This includes materials that meet the requirements of military regulations MIL-L-7808 G .. and MIL-L-23699A. The first regulation (MIL-L-7808G) requires a low pour point and good wear properties ., The Gg-G-vQ fatty acid diesters of ulripropylene glycol are superior base fluids for lubricants for the production of lubricant mixtures that meet these "regulations, which require a low pour point and good abrasion properties. Small amounts, usually less than 50 % , of dibasic acids, e.g. dioctyl adipate O'jiir di- (2-ether vJhexvl) -sebacate, can be used together with the überlet: oneii tripropvlenglycbldiestei'n. The ErnaltHn ^ n üetani erraittelgemische can economically i: cner-Lei ii, but 'nind' they are not as good as lube mi itui'k'emir.ohe; who only entertain the Tripropyl Glycol diesters . th. -..-. ■■ - ■ .-> ■■ -

The second version (M1L-1 / -23.6699A) requires "a low evaporation rate, higher viscosity and a higher degree of heat resistance than the triprecipylene glycol diester itself is obtained. Palis however, small amounts, usually less than about 50%, of the tripropylene diesters of such liquids as trimethylolpropane tripel agonate or PentaerVthrittetraester,

830 / 167T

BATH ORIGINAL

as described, for example, in U.S. Patent 3,360,465 (which serves as a reference for the present application) are added, one can use the Lower the pour point of the lubricant mixture and improve its wear properties without increasing the degree of evaporation and the viscosity to one no longer reduce acceptable value.

The present blends are unique for use as lubricants in modern jet engines suitable. The mixtures according to the invention and also longer-chain acid esters are also improved to achieve ver Results as lubricants for crankcases of automobiles, transmission fluids, low-temperature greases, Sintered bearing sealants, steam turbine lubricants, textile lubricants, metal polishing lubricants (especially for aluminum), brake fluids, lubricants for metalworking, Lubricants for vacuum pumps, lubricants for two- and four-stroke machines, such as lawn mowers, lubricants for closed lubrication systems, hydraulic fluids in general and automotive and truck turbine engines (automotive and truck turbine engines.).

The following examples serve to illustrate the invention and are not intended to limit the scope thereof.

Example. 1:

In this and the following examples, all pouring points were determined according to ASTM D97. The corrosion and Oxidation resistance tests were a modification of the

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- Federal Standard 791 Process, Method 5308, "at the the tests were carried out at a temperature of 175 C. became. The evaporation test was carried out in accordance with ASTM D 972.

The following describes a tripropyl glycol diester in which the fatty acids have the following approximate distribution: C ₆ -4%; O _Q - 55 1 ° \ ⁰ Io " ⁴⁰ ^ ^{and G} 12 ~ ¹ ^ ' ^{compared with the} same tripropylene glycol diester in a lubricant mixture which contains 1.5 $ of an antioxidant package, which consists of 40% p .p'-Oioctyldiphenylamine and 60 $ li-Phenyl- -

1,2,3,4-tetrahydro-2-naphthylamine. Yy

Ai oxidation-erosion test (175 ° C).

. . (l) volume- (2) total acid

loss φ re number

Tripropylene glycol diester *

(TPG) .- '. 23 24

Tripropylene glycol diester and

Antioxidant 2 0.55

(3) Corrosion tendency (weight loss,
.2

Al Mg Cu steel Ag

TPG too bad to be carried out too

"will

TPG + antioxidant 0.00 0.008 0.188 0.015 0.008

B. Evaporation, %, 6 l / 2h at .204 ' ⁰ O

TPG 57

TPG + antioxidant. '.

medium '15 _; ■ - ■ .- '. -

1 0 9 8 3 ii / 167 7

- ίο -

! ν TPG alone had excessive material

\ lust in both the oxidation-corrosion and % ·, the evaporation test and the acid number was excessively high, whereas in the antioxidant system in both

Tests a minimal loss occurred and the acid value rose. was acceptable. From the above data it can be seen that the antioxidant surprisingly ·; essential for the good effect of the mixture in terms of Corrosion, evaporation and acid number is.

f 'The pouring points for various diesters of poly-

Fe alkylene glycols were determined as follows:

Pouring point diester

( ⁰ O

(1) tripropylene glycol dilaurate -32

(2) tripropylene glycol dicaprate -51

(3) tripropylene glycol dipelargonate -68

(4) tripropylene glycol dicaprylate -73

(5) tripropylene glycol diheptanoate -73

(6) Mixture of (2) and (4) in the ratio

*, -. 50: 50-62

^ (7) Tripropylene glycol diester, in which the fatty acyl content, arbitrarily distributed, is about 4 $ C ₆ , 55 # C ₈ , 40 # C _iQ and

1 io C ₁₂ is. -67

(8) (3), made with synthetic

Fatty acids -65

\ (9) Tripropylene glycol killers with arbitrary

borrowed (random.) CV-Ij'ettsäurem -hA

(10) Jüiethyleneglycolu LpeLar ^ onat f- I, b7

(11) Diethylene glycol pelargonate (from synthetic

I.iachen fatty acids produced) - ^ m

9; Γί = - / Ι Π 7 7

BATH ORIGINAL

Diester

Semolina purfct

(12) Triethylene glycol dipelargonate

(13) (12), with synthetic fatty acids

manufactured- ^

(14) Tetraethylene glycol dip elargonate

(15) (14), with synthetic fatty acids manufactured

(16) tripropylene glycol dibenzoate

(17) Dipropylene glycol dicaprate

(18) Tetrapropylene glycol diester (n-Gg-C ₁ Q-fatty acids average ^G 8.6 ^

(19) Tripropyl engly c oi diester fatty acids average C.

-9.44

-20.56 -3.89

-28.89

-17.78 -59.44

-48.33 -65

The diester 17, 18 and 19 for 72 hours at -54 C were maintained, the diesters 17 and 18 were found currency "rend d _(r diester 19 zurüekbehielt a viscosity of about 9,200 centipoise This shows unusual viscosity stability of the diester according to the invention. at low temperatures compared to dipropylene glycol and tetra propylene glycol analogues 51 in the Diesters 17-iy.Biese Diesters 17-19 were also acceptable when performing the Ryder gearbox tests, in which values of 375 kg / cm (2,100 ppi), 446.5 kg / cm (2,500 ppi) and * 517.9 kg / cm (-2 »900. Ppi) were achieved * These materials also have viscosity indices of 130, 143 and 30»

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As can be seen from the above data, many compounds have the essential Tiapropylene glycol diesters of the present invention are quite similar, surprisingly higher pour points, despite the fact that the diesters of the invention have higher molecular weights. It's surprising that the diesters according to the invention have as many of the good properties of their own that are required for the base fluids which are used for the production of lubricant mixtures are suitable for use in the advanced jet machines.

It should be noted that the pour points for diesters of tripropylene glycol are lower than those for the corresponding diesters of dipropylene glycol, tetrapropylene glycol and polyethylene glycols.

Example 2:

The blends listed below are excellent lubricants. The antioxidant in everyone Mixture is the mixture of the antioxidant of the example 1.

Mixture of base material antioxidant

_Ä middle, %

(1) tripropylene glycol diesters having pettacyl groups with the following approximate arbitrary distribution: C ₆ -4 <&; C ₈ -55%; C ₁₀ -40% and G ₁₂ -I io

(TPGDE) 2.0

(2) tripropylene glycol dipelargonate

(TPGDP) 2.5

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mixture Base material Anti oxidation
medium, $ (3) Triprop vl englyeol di caprylate
(TPGDC) • 1.5 (4) Tripropyl englyeol diheptanoate
(TPGDH) 3.0 (5) Tripropylene glycol diaprat
(TPGD Caprat) 1.8 (6) Mixture of TPGDP and TPGDC (1st si) 2.6 (7) 30% TPGDE and

70% trimethylolpropane tripelar- j

gonat (TPT) 2.0 %

(8) 40% TPGDE and 60% pentaerythritol tetraester, the 20 io C ^ ₃ 45 ^. Cg, 15% Cq and 20 f » C ₁ Q-ACyI groups

(PTE) contains. ■ 1.5

(9) 20% TPGDE, 30 9 ^ TPT and 50% PTE 3.2

(10) 70 <fo TPGDE and 30 fo dioctyl adipate 2.9

(11) 80 io TPGDE and 20% di- (2-ethyl -. 'Hexyl) sebacate 4.1

(12) 35% TPGDE and 65% d'ea condensation product of polyethylene

glycol (n = 4) 'and adipic acid with Ä

terminal 2-ethylhexanol (ATCE) 3.0 · ^

(13) 25 and 75 io TPGDE i> of the Zonden- \ sationsproduktes of sebacic acid

'and polyethylene glycol (η = 5)'

with terminal pelargonic acid

(PTCE). 2.6

20%
PTCE TPGDE, 50 5 i PTE and 30% 2 , 4 20%
ATCE TPGDE, 50% PTE and 30% 1 ,8th. 1 G 9 β 3 tt I 1 6 7 7

- 14 -

Mixture of base material anti-oxidant , J ₀

(16) 30% TtGDE and £ 70 of the condensation product of sebacic acid and polypropylene glycol (n = 3) with terminal Caprylic acid (CTCE) 1.6

2.4

Dinonyl -

2.2

(17) TPGDE (18) 80 <fo TPGDE and 20
adipate example 3:

The following blends are excellent lubricants. The additives listed were added to the mixture of Example 1 are added and replace an equivalent amount of the base material. ''

Mixture additive additive,

1. Disalicylidene-1,2-diamine propane 0, OL 2. Benzoguanamine 0.00 ° 3. Thiourea 0, <1Y 4th N-butylbenzoguanamiη 0,.? 14 5. Octadecylainine 0.1 ?. 6th China tsarina 0.0. ^ 7th Quinoline 0.4 8th. Phenylacridine 0, < 9. Hexamethylente trami η 0.Λ1 10. Thiobenzamide 0, Lo 11. Benzothiazole 0, Λ < 12th Imidazoline 0.111 11. Mixture of Benzo, '.; uunain L ti and

TeLraocL.-idecylfliethyLeruiiphORphoiiat (1:10)

10 9 8 Ί ■ · ι IR 7 7

Mixture additive; 14th 15. 16. 17.

Mixture of quinazarin and tricresyl phosphate (i / 10)

Mixture of quinoline and naphthalene (lsi). '.; ■ - ■

Polymer of methacrylic acid esters (Acryloid 704)

Polymer of methacrylic acid esters (Acryloid 714)

Additive"

4th , 4 O • 8th O , 5 O , 6

Example 4;

The following blends are excellent lubricants. The base materials listed have been made in the specified quantities instead of the base material Example 1 used.

mixture Base material 1. Allyl laurate. . 2. Propyl propionate 3.- Trioctyl phosphate 4th Dibctyl carbonate 5. Isopropyl myristate 6, atearyl acetate 7th Uibutyl ether of ethylene glycol a. Glycerol 9. Naphthalene ", 10. Petroleum (petrolatum) 11. Paraffin wax 12th Mixture of naphthalene and xylene (1: 1)

10

v>

ao

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BATH

- 16 -

mixture Base material JL 15th Di ο c tylphthalate 8.5 14th Propylene glycol 7.2 15th Methyl ethyl ketone 4.6 16. Carnauba wax 9.2 17th tallow 4.1 18th Stearyl alcohol 12.5 19th $ 20 emulsion of sebum in water 90 * 20th Octyl tripropylene glycol ether 24 21st Mineral oil S.A.E. 10 15.1 22nd Rosin 2.6 25th Phenol-formaldehyde resin (1: 1):

Molecular weight: 1200) 4.7

24. Lubricant (grease nut oil

that has been thickened with soap) 8.6 25th Isopropyl laurate 22nd 26th Mixture of isopropyl and Al
alcohol (1: 1) 3 27 Kerosene 14th 28. Turbine oil 12.9 29 40 # soybean oil emulsion
in water 80 50. Di (2-ethylhexyl) sebacate 21st 31. 10 $ suspension of graphite
in mineral oil SAE 10 70 32. Polyethylene glycol (molar weight: 1,800) 40 33. Polypropylene glycol (molar weight:
2,200) 30th 54. Octyl ether of polyethylene glycol
(Molecular weight: 4,000) 28 55. Di-2-ethylhexanoate of an ethylene

y y

glycol-propylene glycol mixture (1: 1; molecular weight: 6,000) 8.9

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Mixture 'basic material

36. stearyl stearate 11

37. Emulsion of 20 # cottonseed oil in water with 5 # alkyl

(G _11-15 ) -ρolyäthoxylat (9 mol) -

Emulsifier 70

38. Winterized and hardened soy bean oil

(I.V.8). 8th

39 · Naphthenic hydrocarbon oil 14 '- j

40. Fluorinated polypropylene (molecular weight: 1,000 10

41. HL-n-butyl phthalate 4

42. Mixture of di- (2-butoxyethyl) - '■ / -. azelate and dimethylcyolo hexyl) adipate 20

43 · · Condensation product of /

Propylene glycol, ethyl englycol, phthalic acid and SeTaaoic acid (3: 2: 1: 1) (molar weight: _f 2,000) 25

44. CQ-C ₁₀ -OxO-AlkOhOlester of phthalic acid. 26th

45.Butyl ether of polyethylene - ( glycol (molar weight -: 1,000) 9

46. Mixture of butyl ether from polypropyl englycol (Molgeiw. -: 1.600)

; and diisooethyl adipate 13

47. Dioctylpentadecane dicarboxylate 19

48., IM iaethylsilicone polymer (molar weight : 3,000) x 3

49. Mineral oil SAB 30; '"22

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Semic basic material

Petroleum wax

Kendall Base Oil (SAE 10)

Kendall Base Oil (SAE 10)

Kendall Base Oil (SAE 20)

Cottonseed oil

Bis (2-ethylhexyl) sebacate

Kendall Base Oil (SAE 10)

Bis (2-ethylhexyl) adipate

De cylde canoat

naphthalene

Bean oil

paraffin

17th

2 4 23 26 17.5 11.5 12.7 2.3

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Claims (6)

20Q68Q7 claims: 1. Lubricant mixture, characterized in that it contains a fatty acid _{diester of tripropylene glycol, each:} fatty acid content of about 6 to 1Q carbon atoms, and from about 0.001 to / 5 i ° of a mixture of ρ, ρ'-dioctyldiphenylamine and N-phenyl -1,2,3,4-tetxrahydro-2-naphthylamine as an antioxidant. Contains. 2. Mixture according to claim 1, characterized in that the ratio of pjp'-dioctyldiphenylamine to H-ehenyl-l, 2,3,4-tetrahydro-2-naphthylamine about 2: 3. 3. Mixture according to claim 2, characterized in that the amine mixture, based on the lubricant mixture, is present in an amount of 1.5% by weight. 4 · mixture na'ch claim 1, characterized in that 4 ^a / o of the Fettöäureanteile 6 Kohlenstoffatpme, 55%> of the fatty acid moieties 8 carbon atoms, about 40 # of Fettaäureariteile 10 carbon atoms and about 1 io the Fe ttfiä urea η parts 12 carbon atoms . 5. Mixture according to claim 1, characterized in that that the tripropylene glycol diesters Tripropylene Glycpldipelargonate mean. 1 09830/1 BAD ORlGfNAL 6. Mixture according to claim 1, characterized in that the tripropylene glycol diester Glycoldicaprylate mean. For: The Procter 4 _{Oamble Oompany} Lawyer 10 9 8 3 0/1677