KR20100061813A - Lubrication oil compositions - Google Patents

Abstract

This invention relates to compositions comprising a base fluid stock comprising a PTEEG fluid (a poly(trimethylene-ethylene ether) glycol that is a fluid at ambient temperature) and an additive package comprising certain specified additive combinations, and lubrication oils containing the compositions.

Description

Lubricant composition {LUBRICATION OIL COMPOSITIONS}

Cross Reference with Related Application

This application is filed on November 7, 2006 and is co-owned by Applicant of US Patent Application No. 11 / 593,954 entitled "POLYTRIMETHYLENE ETHER GLYCOL ESTERS"; United States Provisional Patent Application No. 60 / 957,716, filed concurrently with this application and titled "LUBRICATION OIL COMPOSITIONS"; US Provisional Patent Application No. 60 / 957,725, filed concurrently with this application and titled "LUBRICATION OIL COMPOSITIONS," US Pat. And US Provisional Patent Application No. 60 / 957,722 (Internal Reference: CL3887), filed concurrently with the present application and entitled "LUBRICATION OIL COMPOSITIONS".

The present invention relates to a composition comprising an additive package comprising (i) poly (trimethylene-ethylene ether) glycol, and (ii) a specified specified combination of additives, and a lubricating oil comprising said composition.

Certain polytrimethylene ether glycols (“PO3G”), and their mono- and diesters (“PO3G esters”), including but not limited to poly (trimethylene-ethylene ether) glycols are co-owned US Patent No. 7179769, and US Patent Application No. 11 / 593,954, filed Nov. 7, 2006, entitled " POLYTRIMETHYLENE ETHER GLYCOL ESTERS, " Has properties that make them useful in a variety of fields.

Because of these properties, it is desirable to formulate lubricant compositions based on PO3G and PO3G esters.

The present invention relates to compositions based on the combination of certain types of PO3G (poly (trimethylene-ethylene ether) glycol -PTEEG) with certain additive combinations, which have properties which make them particularly suitable for lubrication end use.

In one embodiment, a lubricant composition is provided comprising (i) a base fluid stock comprising PTEEG that is a fluid at ambient temperature and (ii) an additive package, wherein the additive package comprises

(a) an antiwear additive package comprising from about 0.5 to about 2.0 wt% (based on total composition weight) of a mixture comprising an amine phosphate antiwear additive and a phosphorothionate antiwear additive, and

(b) about 0.1 to about 0.5 wt.% (based on total composition weight) of an additive that acts as an extreme pressure additive, as an antioxidant additive, or as an extreme pressure additive and an antioxidant additive. In a preferred embodiment, the additive acting as extreme pressure additive, as antioxidant additive, or as extreme pressure additive and antioxidant additive is methylene bis (dialkyldithiocarbamate).

If PTEEG is based on biologically produced 1,3-propanediol, lubricant compositions with a very high renewable content can be provided.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

Except where explicitly noted, trade names are indicated in capital letters.

Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.

When an amount, concentration, or other value or parameter is given as a list of ranges, preferred ranges, or preferred upper and preferred lower limits, this means that any upper range limit or preferred value and any lower range limit, whether or not a range is disclosed separately, or It is to be understood that all ranges formed in any pair of preferred values are disclosed in detail. When listing a range of numerical values herein, unless stated otherwise, the range is intended to include its endpoints and all integers and fractions within that range. The definition of a range is not intended to limit the scope of the invention to the specific values listed.

When the term "about" is used to describe an endpoint of a value or range, it is to be understood that the disclosure includes the specific value or endpoint mentioned.

As used herein, the terms “comprises”, “comprising”, “comprises”, “comprising”, “have”, “having” or any other variation thereof includes non-exclusive inclusions. I want to cover it. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to such elements, and may not be explicitly listed or include other elements inherent to such process, method, article, or apparatus. It may be. Moreover, unless expressly stated to the contrary, "or" refers to a comprehensive 'or' and not an exclusive 'or'. For example, condition A or B is met by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is True (or present), and both A and B are true (or present).

The use of the indefinite article "a" or "an" is employed to describe the elements and components of the present invention. This is done merely for convenience and to give a general sense of the invention. This description should be understood to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

The materials, methods, and examples herein are illustrative only and are not intended to be limiting except as specifically stated. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

Base fluid stock

As indicated above, the base fluid stock for use in the lubricating oil composition of the present invention comprises PTEEG, which is a fluid at ambient temperature (25 ° C.). The base fluid stock may also include other natural and / or synthetic fluid co-lubricants.

Examples of natural fluid co-lubricants include vegetable oil based lubricants, which are generally derived from plants and generally consist of triglycerides. Usually they are liquid at room temperature. Many different parts of plants can produce oil, but in practice the oil is generally extracted primarily from the seeds of oilseed plants. These oils include both edible and non-edible oils, for example sunflower oil, rapeseed oil, soybean oil, castor oil, etc., which have a high content of oleic acid, and US Pat. No. 6583302 (fatty acid ester) and I. Malchev, "Plant-Oil-Based Lubricants"] (Part-Oil-Based Lubricants, Canada) 1 Department of Plant Aggregation, Ontario Academy of Arts, University of Guelph, Guelph Stone Road W. 50, Ontario1 Modified oils such as those disclosed in Agriculture, Ontario Agriculture College, University of Guelph).

Synthetic fluid co-lubricants (other than PO3G and PO3G esters) include lubricating oils such as hydrocarbon oils such as polybutylene, polypropylene, propylene-isobutylene copolymers; Polyoxyalkylene glycol polymers (other than PO3G) and derivatives thereof such as ethylene oxide and propylene oxide copolymers; And esters of various alcohols with dicarboxylic acids such as dibutyl adipate, di (2-ethylhexyl) sebacate, di-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, 2-ethylhexyl diesters of dioctyl phthalate, didecyl phthalate, and linoleic acid dimers.

PO3Gs other than PTEEG as well as PO3G esters (including but not limited to esters of PTEEG) can generally be used as synthetic fluid co-lubricants as well.

Preferably, the base stock comprises a major amount (greater than 50 wt% by weight of the base stock) of PTEEG. In some embodiments, the base stock may comprise PTEEG in an amount of at least about 66 wt%, or at least about 75 wt%, or at least about 90 wt%, or at least about 95 wt%, based on the total weight of the base fluid stock. . In some preferred embodiments, the base fluid stock comprises only (or substantially only) PTEEG.

Some of the PTEEG may be replaced with PTEEG esters and the amounts mentioned above may be for a combination of PTEEG + PTEEG esters. In one embodiment, the weight ratio of PTEEG / PTEEG ester in the base fluid stock is at least 1: 1, or greater than 1: 1 (PTEEG is the major component), or at least about 1.5: 1, or at least about 2: 1, or about 5: 1 or greater, or about 20: 1 or greater. In addition, this weight ratio is preferably about 25: 1 or less, or about 20: 1 or less, or about 10: 1 or less.

The lubricating oil composition preferably comprises the base oil stock in an amount of at least 50 wt% based on the total weight of the lubricating oil composition. In various embodiments, the lubricant can include the base stock in an amount of at least about 75 wt%, or at least about 90 wt%, or at least about 95 wt%, based on the total weight of the lubricant composition.

Polytrimethylene  Ether glycol ( PO3G )

PO3G (including PTEEG) for the purposes of the present invention is an oligomeric or polymeric ether glycol wherein at least 50% of the repeat units are trimethylene ether units.

PO3G preferably polycondenses monomers comprising 1,3-propanediol in the presence of an acid catalyst and thus to bond-(CH ₂ CH ₂ CH ₂ O)-bonds (e.g. trimethylene ether repeat units) It is prepared by producing a polymer or copolymer comprising. As indicated above, at least 50% of the repeat units are trimethylene ether units.

When sulfur-based acid catalysts (such as sulfuric acid) are used to prepare PO3G, the product obtained preferably contains less than about 20 ppm sulfur, more preferably less than about 10 ppm sulfur.

In addition to trimethylene ether units, smaller amounts of other units, such as other polyalkylene ether repeat units, may be present. In the context of the present disclosure, the term “polytrimethylene ether glycol” refers to oligomers and polymers (including PTEEG and others described below) comprising up to about 50% by weight of comonomers, as well as essentially pure 1,3- Also included is PO3G made from propanediol.

In the case of PTEEG, other polyalkylene ether repeat units are the predominant ethylene ether units.

The 1,3-propanediol used in the preparation of PO3G can be obtained by any of a variety of well known chemical routes or by biochemical transformation routes. Preferred routes are described, for example, in U.S. Pat.No. 51578989, U.S. Pat. No. 5276201, U.S. Pat.No. 5,249,793, U.S. Patent No. 5334778, U.S. Patent No. 536984, U.S. Pat. Patent 5686276, United States Patent 5821092, United States Patent 5962745, United States Patent 6140543, United States Patent 6262311, United States Patent 6,592,48, United States Patent 62,40889, United States Patent 6297408, United States Patent 6331264, U.S. Pat.No. 6634646, U.S. Pat.No.7038092, U.S. Pat.No.7084311, U.S. Pat.7098368, U.S. Pat.No.7009082, and U.S. Patent Application Publication No. 20050069997A1. Preferably, 1,3-propanediol is obtained biochemically from a renewable source ("biologically-derived" 1,3-propanediol).

Particularly preferred sources of 1,3-propanediol are by fermentation processes using renewable biological sources. As an illustrative example of a starting material from a renewable source, a biochemical pathway for 1,3-propanediol (PDO) has been disclosed that utilizes feed materials generated from biological and renewable resources such as corn feed materials. . For example, bacterial strains capable of converting glycerol to 1,3-propanediol include Klebsiella spp., Citrobacter spp., Clostridium spp. And Lactobacillus. Found in species. This technique is disclosed in several publications, including US Pat. No. 5633362, US Pat. No. 5686276, and US Pat. No. 5821092. U. S. Patent No. 5821092 discloses a process for biologically preparing 1,3-propanediol from glycerol, in particular using recombinant microorganisms. The method is a transformed E. coli transformed with a heterologous pdu diol dehydratase gene having specificity for 1,2-propanediol. E. coli bacteria. Transformed Tooth. E. coli is incubated in the presence of glycerol as carbon source and 1,3-propanediol is isolated from the growth medium. Because both bacteria and yeast can convert glucose (eg corn sugar) or other carbohydrates to glycerol, the methods disclosed in these publications are fast, inexpensive and environmentally reliable 1,3-propanedie Provide all monomer sources.

Biologically-derived 1,3-propanediol, such as prepared by the methods described and mentioned above, is introduced into the atmosphere by plants, which constitutes a feedstock for the production of 1,3-propanediol. Carbon from carbon dioxide. In this way, biologically derived 1,3-propanediol preferred for use in the context of the present invention contains only renewable carbon and does not include fossil fuel-based or petroleum-based carbon. Therefore, PO3Gs based thereon using biologically derived 1,3-propane diols have less impact on the environment because the 1,3-propane diols used in the compositions are reducing fossil fuels. It does not deplete and releases more carbon back to the atmosphere for plant use once again upon decomposition. Thus, the compositions of the present invention may be characterized by more natural and less environmental impact than similar compositions containing petroleum based glycols.

Biologically derived 1,3-propanediol, PO3G and PO3G esters can be distinguished from similar compounds that are produced from petrochemical sources or from fossil fuel carbon by double carbon-isotopic finger printing. This method usefully distinguishes chemically identical materials and distributes carbon in the copolymer by a source (and possibly years) of growth of the biosphere (plant) component. Isotopes, ¹⁴ C and ¹³ C, provide complementary information on these matters. The radiocarbon dating isotope ( ¹⁴ C) with a nuclear half-life of 5730 makes it possible to distribute sample carbon between fossil ("dead") and biosphere ("live") feedstocks (Currie , LA "Source Apportionment of Atmospheric Particles," Characterization of Environmental Particles, J. Buffle and HP van Leeuwen, Eds., 1 of Vol. I of the IUPAC Environmental Analytical Chemistry Series (Lewis Publishers, Inc) (1992) 3-74 )]. The basic assumption in radiocarbon dating is that homeostasis of ¹⁴ C concentrations in the atmosphere leads to ¹⁴ C homeostasis in living organisms. When processing an isolated sample, the age of the sample can be approximated by the following relationship:

t = (-5730 / 0.693) ln (A / A ₀ )

Where t is the age, 5730 is the half-life of the radiocarbon, and A and A ₀ are ¹⁴ C inertness of the sample and the modern standard, respectively (Hsieh, Y., Soil Sci. Soc. Am J., 56, 460, (1992)]. However, due to atmospheric nuclear testing since 1950 and the burning of fossil fuels since 1850, ¹⁴ C has obtained a second geochemical time characteristic. His concentration in atmospheric CO ₂ , and hence in the living biosphere, doubled at the nuclear test peak in the mid-1960s. Subsequent plot This gradually returned to the steady-state, cosmic (air) baseline isotope ratio ( ¹⁴ C / ¹² C), approximately 1.2 × 10 ^-12 , with rough relaxation The “half life” was 7 to 10 years. (The latter half-life should not be taken literally, but rather should use the above-described atmospheric nuclear inflow / decay function to track changes in the atmosphere and ¹⁴ C of the atmosphere since the beginning of the nuclear age). It is this latter biosphere ¹⁴ C time characteristic that offers the possibility of recent annual dating of biosphere carbon. ¹⁴ C can be measured by accelerator mass spectrometry (AMS), and the results are given in units of "fraction of modern carbon" (f _M ). f _M is defined by the National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) 4990B and 4990C, known as oxalic acid standards HOxI and HOxII, respectively. The basic definition relates to 0.95 times the HOxI (based on AD 1950) of the ¹⁴ C / ¹² C isotope ratio. This is approximately equivalent to pre-collapsing-corrected industrial revolution wood. For the current living biosphere (plant material), f _M ≒ 1.1.

A stable carbon isotope ratio ( ¹³ C / ¹² C) provides a complementary pathway for source identification and allocation. Given biological supplied (biosourced) material of ¹³ C / ¹² C ratio is the result of ¹³ C / ¹² C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C ₃ plants (leafy plants), C ₄ plants (the grasses), and marine carbonates all show significant differences in ¹³ C / ¹² C and corresponding δ ¹³ C values. Indicates. Moreover, lipid substances of C ₃ and C ₄ plants are analyzed differently from substances derived from carbohydrate components of the same plant as a result of metabolic pathways. Within the precision of the measurement, ¹³ C exhibits large variation due to isotope fractionation effects, the most important of which is the photosynthetic mechanism in the present invention. The main cause of the difference in carbon isotope ratios in plants is closely related to the carbon metabolic pathways by photosynthesis in plants, in particular the reactions occurring during primary carboxylation, ie the differences in the initial fixation of atmospheric CO _{2 in} the atmosphere. Related. Two large classes of plants include those comprising the "C ₃ " (or Calvin-Benson) photosynthesis cycle, and the "C ₄ " (or Hatch-Slack) photosynthesis cycles. There are things to do. C ₃ plants, such as hardwoods and conifers, are dominant in temperate climates. In C ₃ plants, the primary CO ₂ immobilization or carboxylation reaction comprises a ribulose-1,5-diphosphate carboxylase enzyme and the first stable product is a C3 compound. C ₄ plants, on the other hand, include plants such as tropical grasses, corn and sugar cane. In C ₄ plants, a further carboxylation reaction involving another enzyme, phosphphenol-pyruvate carboxylase, is a primary carboxylation reaction. The stable first carbon compound is tetracarboxylic acid, which is then decarboxylated. The CO ₂ thus released is redefined by the C ₃ cycle.

Both C ₄ and C ₃ plants exhibit a range of ¹³ C / ¹² C isotope ratios, but typical values are about -10 to -14 per mil (C ₄ ) and -21 to -26 permill ( C ₃ ) (Weber et al., J. Agric. Food Chem., 45, 2942 (1997)). Coal and petroleum are generally within this latter range. ^{The 13} C measurement scale was originally defined as 0, set by pee dee belemnite (PDB) limestone, where values are given in units of percent deviation from this material. The value "δ ¹³ C" is in milliseconds (per mille), abbreviated as% and is calculated as follows:

Since the PDB reference material (RM) has been exhausted, a series of alternative RMs have been developed in cooperation with IAEA, USGS, NIST and other selected international isotope laboratories. The notation for per mille deviation from PDB is δ ¹³ C. The measurement is carried out at CO ₂ by high precision and stable ratio mass spectrometry (IRMS) for molecular ions of mass 44, 45 and 46.

Therefore, a composition containing biologically derived 1,3-propanediol, and biologically derived 1,3-propanediol, has its petroleum based on ¹⁴ C (f _M ) and double carbon-isotopic fingerprinting. It can be completely distinguished from chemically derived counterparts, which represent a new composition of matter. The ability to distinguish these products is beneficial for tracking these materials commercially. For example, a product that includes both "new" and "old" carbon isotope profiles can be distinguished from products made only of "old" materials. Thus, the materials of the present invention can be pursued commercially on the basis of their unique profile and for determining the shelf life for the purpose of defining competition, and in particular for the assessment of environmental impacts.

Preferably, 1,3-propanediol used as a reactant or as a component of a reactant is more than about 99% pure by weight and more preferably greater than about 99.9% by weight as determined by gas chromatography analysis. will be. Purified 1,3-propanediol disclosed in U.S. Patent No. 7080982, U.S. Pat.7098368, U.S. Patent No. 7084311, and U.S. Patent Application Publication No. 20050069997A1, and prepared therefrom. PO3G is particularly preferred.

Purified 1,3-propanediol preferably has the following properties:

(1) an ultraviolet absorbance of less than about 0.200 at 220 nm, and less than about 0.075 at 250 nm, and less than about 0.075 at 275 nm; And / or

(2) a composition having L * a * b * having a “b *” color value of less than about 0.15 (ASTM D6290) and having an absorbance of less than about 0.075 at 270 nm; And / or

(3) less than about 10 ppm peroxide composition; And / or

(4) less than about 400 ppm, more preferably less than about 300 ppm, and even more preferably less than about 150 ppm total organic impurities (organic compounds other than 1,3-propanediol, as measured by gas chromatography). A) concentration.

Starting materials for the production of PO3G will depend on the desired PO3G, availability of starting materials, catalysts, equipment and the like and include "1,3-propanediol reactants". "1,3-propanediol reactant" means oligomers and prepolymers of 1,3-propanediol, and 1,3-propanediol, preferably having a degree of polymerization of 2 to 9, and mixtures thereof. In some instances, it may be desirable to use up to 10% or more low molecular weight oligomers when available. Thus, preferably the starting material comprises 1,3-propanediol and its dimers and trimers. Particularly preferred starting materials consist of at least about 90% by weight of 1,3-propanediol, and more preferably at least about 99% by weight of 1,3-propanediol, based on the weight of the 1,3-propanediol reactant. .

PO3G can be prepared through a number of methods known in the art, such as those disclosed in US Pat. No. 6977291 and US Pat. Preferred methods are disclosed in US Pat. No. 70,999,697,077607, US Pat. No. 7,716,045, and US Pat.

As indicated above, PO3G may include lesser amounts of other polyalkylene ether repeating units in addition to trimethylene ether units. Thus, monomers for use in the production of PO3G may contain up to 50% by weight of comonomer polyols in addition to the 1,3-propanediol reactant. Suitable comonomer polyols for use in the process include aliphatic diols such as ethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3,3,4,4,5,5-hexafluro-1,5-pentanediol, 2,2,3, 3,4,4,5,5-octafluoro-1,6-hexanediol, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9 , 10,10-hexadecafluoro-1,12-dodecanediol; Alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbide; And polyhydroxy compounds such as glycerol, trimethylolpropane, and pentaerythritol. Preferred groups of comonomer diols are ethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propane Diol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, C ₆ -C ₁₀ diol (eg 1,6-hexanediol, 1,8-octanediol And 1,10-decanediol) and isosorbide, and mixtures thereof. Particularly preferred diols other than 1,3-propanediol are ethylene glycol, and C ₆ -C ₁₀ diols may also be particularly useful.

Suitable PTEEGs for use in the present invention are disclosed, for example, in US Patent Application Publication No. 20040030095A1. Preferred PTEEG is 50 to about 99 mole% (preferably about 60 to about 98 mole%, and more preferably about 70 to about 98 mole%) of 1,3-propanediol and up to 50 to about 1 mole% (Preferably from about 40 to about 2 mol%, and more preferably from about 30 to about 2 mol%) by acid catalyzed polycondensation of ethylene glycol.

Preferably, the PTEEG after purification has essentially no acid catalyst end groups, but may comprise very low levels of unsaturated end groups, mainly allyl end groups, in the range of about 0.003 to about 0.03 meq / g. Such PTEEGs can be considered to include (comprised essentially of) compounds having the formulas (I) and (II):

[Formula I]

HO-((CH ₂ ) ₃ O) _m ((CH ₂ ) ₂ O) _n -H

[Formula II]

HO-((CH ₂ ) ₃ -O) _m ((CH ₂ ) ₂ O) _n CH ₂ CH = CH ₂

Wherein m and n are in a range such that Mn (number average molecular weight) is within the range of about 200 to about 10000, wherein the compound of Formula III has an allyl end group (preferably all unsaturated ends or end groups) It is present in an amount such that it is present in the range of 0.003 to about 0.03 meq / g.

PTEEGs can be random or block copolymers, and formulas I and II are intended to cover variants of both.

Preferred PO3G (including PTEEG) for use in the present invention has a Mn (number average molecular weight) of at least about 250, more preferably at least about 1000, and even more preferably at least about 2000. Mn is preferably less than about 10000, more preferably less than about 5000, and even more preferably less than about 3500. Blends of PO3G can also be used. For example, PO3G may comprise a blend of higher and lower molecular weight PO3G, preferably higher molecular weight PO3G has a number average molecular weight of about 1000 to about 5000, and lower molecular weight PO3G It has a number average molecular weight of about 200 to about 950. The Mn of blended PO3G will preferably still be within the above mentioned range.

PO3Gs preferred for use in the present invention typically have a polydispersity (ie, Mw / m) of preferably from about 1.0 to about 2.2, more preferably from about 1.2 to about 2.2, and even more preferably from about 1.5 to about 2.1. Mn) and is polydisperse. Polydispersity can be adjusted using a blend of PO3G.

PO3G for use in the present invention preferably has a color value of less than about 100 APHA, and more preferably less than about 50 APHA, and a viscosity of preferably at least about 100 cS at 40 ° C.

PO3G ester

In some embodiments, the PO3G ester comprises one or more compounds of formula III:

[Formula III]

Wherein Q represents the residue of PO3G after removal of the hydroxyl group, R ₂ is H or R ₃ CO, each of R ₁ and R ₃ is individually 4 to 40 carbon atoms, preferably at least 6 carbon atoms, More preferably, it is a substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic, or alicyclic organic group containing at least eight carbon atoms. In some embodiments, each of R ₁ and R ₃ has up to 20 carbon atoms, and in some embodiments up to 10 carbon atoms. In some preferred embodiments, each of R ₁ and R ₃ has 8 carbon atoms.

PO3G esters are disclosed in US Patent Application No. 11 / 593,954, filed Nov. 7, 2006 and entitled " POLYTRIMETHYLENE ETHER GLYCOL ESTERS " The hydroxyl group-containing monomer (monomer containing two or more hydroxyl groups) comprising 3-propanediol is polycondensed to form PO3G (as described above) and then monocarboxylic acid (or equivalent) It is prepared by esterification.

The PO3G esters so prepared are preferably about 50 to 100% by weight, more preferably about 75 to 100% by weight diester and 0 to about 50% by weight, more preferably 0 to about 25, based on the total weight of the esters Composition comprising% by weight of monoester. Preferably the mono- and diesters are esters of 2-ethylhexanoic acid.

The PO3G used for preparing the ester does not need to be identical to the PO3G co-component of the base fluid stock.

Acid and equivalent

The esterification of PO3G is carried out by reaction with acids and / or equivalents, preferably monocarboxylic acids and / or equivalents.

"Monocarboxylic acid equivalent" means a compound that substantially acts like a monocarboxylic acid in the reaction with polymer glycols and diols, as generally recognized by those skilled in the art. Monocarboxylic acid equivalents for the purposes of the present invention include, for example, esters of monocarboxylic acids, and ester-forming derivatives such as acid halides (eg acid chlorides) and anhydrides.

Preferably, monocarboxylic acids having the formula R-COOH are used, wherein R is a substituted or unsubstituted aromatic, aliphatic or alicyclic organic moiety containing 6 to 40 carbon atoms.

Mixtures of different monocarboxylic acids and / or equivalents are also suitable.

As indicated above, the monocarboxylic acid (or equivalent) may be aromatic, aliphatic or cycloaliphatic. In this regard, “aromatic” monocarboxylic acids are monocarboxylic acids in which a carboxyl group is attached to a carbon atom in a benzene ring system such as those mentioned below. An "aliphatic" monocarboxylic acid is a monocarboxylic acid having a carboxyl group attached to a carbon atom that is fully saturated or to a carbon atom that is part of an olefinic double bond. If the carbon atom is in the ring, the equivalent is "alicyclic".

Monocarboxylic acids (or equivalents) are any substituents or combinations thereof (e.g., amides, amines, carbonyls, halides) unless the substituents do not interfere with the esterification reaction or adversely affect the properties of the resulting ester product. , Functional groups such as hydroxyl, and the like).

Monocarboxylic acids and equivalents may be from any source, but are preferably derived from or are bio-derived from natural sources.

Particular preference is given to the following acids and derivatives thereof: lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benzoic acid, caprylic acid, erucic acid, palmitic acid, pentadecanoic acid, heptadecanoic acid, Nonadecanoic acid, linoleic acid, arachidonic acid, oleic acid, valeric acid, caproic acid, capric acid, and 2-ethylhexanoic acid, and mixtures thereof. Particularly preferred acids or derivatives thereof are 2-ethylhexanoic acid, benzoic acid, stearic acid, lauric acid and oleic acid.

Esterification method

For ester preparation, PO3G may be contacted with the monocarboxylic acid (s), preferably in the presence of an inert gas, at a temperature ranging from about 100 ° C to about 275 ° C, preferably from about 125 ° C to about 250 ° C. . The method can be carried out at atmospheric pressure or under vacuum. Water is formed during the contact and can be removed in an inert gas stream or under vacuum to induce the completion of the reaction.

Esterification catalysts are generally used to promote the reaction of PO3G with carboxylic acids, preferably photocatalysts. Examples of photoacid catalysts include, but are not limited to, sulfuric acid, hydrochloric acid, phosphoric acid, hydroiodic acid, and heterogeneous catalysts such as zeolites, heteropolyacids, amberlysts, and ion exchange resins. Preferred esterification acid catalysts are selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid and hydroiodic acid. Particularly preferred photocatalysts are sulfuric acid.

The amount of catalyst used may be from about 0.01% to about 10% by weight of the reaction mixture, preferably from 0.1% to about 5% by weight of the reaction mixture, and more preferably from about 0.2% to about 2% by weight. .

Any ratio of carboxylic acid or derivatives thereof to glycol hydroxyl groups can be used. Preferred ratios of acid to hydroxyl groups are from about 3: 1 to about 1: 2, where the ratio can be adjusted to shift the ratio of monoester to diester in the product. Generally a slightly higher ratio than 1: 1 is used to favor the production of diesters. In order to favor the production of monoesters, an acid to hydroxyl ratio of 0.5: 1 or less is used.

Preferred methods for esterification include polycondensing the 1,3-propanediol reactant to PO3G using a photocatalyst, followed by addition of the carboxylic acid, and esterification without isolation and purification of PO3G. In this process, etherification or polycondensation of 1,3-propanediol reactants to form PO3G is carried out using acid catalysts as disclosed in US Pat. Nos. 6,772,792 and 6720459. The etherification reaction can also be carried out using a polycondensation catalyst containing both acid and base as disclosed in Japanese Patent Application Laid-open No. 2004-182974A. The polycondensation or etherification reaction continues until the desired molecular weight is reached, then the calculated amount of monocarboxylic acid is added to the reaction mixture. The reaction continues while the water by-products are removed. In this step both esterification and etherification reactions occur simultaneously. Thus, the acid catalyst used for the polycondensation of diols in this preferred esterification process is also used for esterification. If desired, additional esterification catalyst may be added in the esterification step.

In this procedure, the viscosity (molecular weight) of the product obtained is controlled by the time point at which the carboxylic acid is added.

In an alternative procedure, the esterification reaction can be carried out by addition of esterification catalyst and carboxylic acid in purified PO3G, followed by heating and removal of water. In this procedure, the viscosity of the product obtained is primarily a function of the molecular weight of PO3G used.

Regardless of which esterification procedure is followed, any by-products are removed after the esterification step, followed by residual catalyst residues from the polycondensation and / or esterification to obtain a particularly stable ester product at high temperatures. This can be achieved by hydrolysis of the crude ester product by treatment with water at about 80 ° C. to about 100 ° C. for a time sufficient to hydrolyze any residual acid ester derived from the catalyst without significantly affecting the carboxylic acid ester. have. The time required may vary from about 1 to about 8 hours. If hydrolysis is carried out under pressure, higher temperatures and corresponding shorter times are possible. At this point the product may contain diesters, monoesters or combinations of diesters and monoesters, and small amounts of acid catalysts, unreacted carboxylic acids and diols depending on the reaction conditions. Hydrolyzed polymers are further purified to remove water, acid catalysts and unreacted carboxylic acids by known conventional techniques such as water washing, base neutralization, filtration and / or distillation. Unreacted diol and acid catalyst can be removed, for example, by washing with deionized water. Unreacted carboxylic acid can also be removed, for example, with deionized water or an aqueous base solution, or by vacuum stripping.

It is generally washed once or more with water to remove the acid catalyst after hydrolysis and preferably dried under vacuum to afford the ester product. Water washing also serves to remove unreacted diols. Any unreacted monocarboxylic acid present can also be removed in a water wash, but can also be removed by washing with an aqueous base or by vacuum stripping.

If desired, the product can be further fractionated by fractional distillation under reduced pressure to isolate low molecular weight esters.

Proton NMR and wavelength X-ray fluorescence spectroscopy can be used to identify and quantify any residual catalyst (eg, sulfur) present in the polymer. Proton NMR can identify, for example, sulfate ester groups present in the polymer chain, and wavelength x-ray fluorescence can determine the total sulfur (inorganic and organic sulfur) present in the polymer. The esters of the present invention produced by the process disclosed above are virtually sulfur free and therefore useful for high temperature applications.

Preferably, the PO3G esters after purification have essentially no acid catalytic end groups, but may comprise very low levels of unsaturated end groups, mainly allyl end groups, in the range of about 0.003 to about 0.03 meq / g. Such PO3G esters may be considered to consist essentially of comprising compounds having the formulas IV and V:

[Formula IV]

R ₁ -C (O) -O-((CH ₂ ) ₃ O) _m ((CH ₂ ) ₂ O) _n -R ₂

[Formula V]

R ₁ -C (O) -O-((CH ₂ ) ₃ -O) _m ((CH ₂ ) ₂ O) _n CH ₂ CH = CH ₂

Wherein R ₂ is H or R ₃ C (O); Each of R ₁ and R ₃ is a substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic, or alicyclic organic group containing individually 6 to 40 carbon atoms; m and n are in the range such that Mn is in the range of about 200 to about 10000; The compound of formula III is present in an amount such that allyl end groups (preferably all unsaturated end or end groups) are present in the range of about 0.003 to about 0.03 meq / g.

Preferably, the PO3G ester has a viscosity less than the viscosity of PO3G. Preferred viscosities of the PO 3 G esters range from about 20 cS to about 150 cS at 40 ° C., more preferably about 100 cS or less.

Other preferred properties of the PO3G esters can be determined based on the preferences described above for the intrinsic PO3G. For example, the preferred molecular weight and polydispersity are based on the preferred molecular weight and polydispersity of the PO3G component of the ester.

Common additives

The synthetic lubricating oil composition according to the invention comprises a mixture of a base stock and one or more additives, wherein each additive is, for example, hydraulic fluid, gear oil, brake fluid, compressor lubricant, fabric and calender lubricant, metalworking, refrigeration Lubricants, two-cycle engine lubricants and / or crankcase lubricants are used for the purpose of improving the performance and properties of the base stock in their intended use.

Additives can generally be added in amounts based on the type of additive and the level of additive effect desired, which can generally be determined by one skilled in the art.

Preferably the additive is miscible in either or both of PO3G and PO3G esters.

Preferably, the lubricant additive (s) comprise at least one of ashless dispersants, metal cleaners, viscosity modifiers, antiwear agents, antioxidants, friction modifiers, pour point depressants, antifoams, corrosion inhibitors, anti-emulsifiers, rust inhibitors and mixtures thereof.

When the lubricant composition is used as a refrigeration lubricant, the lubricant additive (s) are preferably extreme pressure and antiwear additives, oxidation and thermal stability improvers, corrosion inhibitors, viscosity index improvers, pour point depressants, floc point depressants, cleaning agents At least one of an antifoaming agent, a viscosity modifier, and a mixture thereof.

The use of any one or more of the specified additives, alone or in combination with one or more of the remaining specified additives, is intended to be within the scope of the present invention. It is also within the scope of the present invention to use more than one of any specified additives, for example one or more friction modifiers, alone or in combination with one or more of the other specified additives, for example in combination with one or more corrosion inhibitors. .

Individual additives may be incorporated into the base stock in any convenient manner. Thus, each of the components can be added directly to the base stock by dispersing or dissolving it in the base stock at a desired concentration level. Such blending can occur at ambient or elevated temperature.

Alternatively, all or part of the additives may be blended into a concentrate or additive package and subsequently blended into a base stock to produce a finished lubricant. Concentrates will typically be formulated to contain an appropriate amount of additive (s) to provide the desired concentration in the formulation when the concentrate is combined with a predetermined amount of base lubricant.

Non-limiting and illustrative examples of various additives follow.

Ashless dispersants include a polymeric hydrocarbon backbone having functional groups that can associate with the particles to be dispersed. Typically, dispersants often comprise amine, alcohol, amide and / or ester polar moieties attached to the polymer backbone via a crosslinking group. Ashless dispersants are, for example, salts, esters, amino-esters, amides, imides and oxazolines of long chain hydrocarbon substituted mono- and dicarboxylic acids and / or anhydrides thereof, thiocarboxylate derivatives of long chain hydrocarbons, directly Long chain aliphatic hydrocarbons with attached polyamines, and Mannich condensation products formed by condensing long chain substituted phenols with formaldehyde and polyalkylene polyamines.

Viscosity modifiers (VMs) function to impart high and low temperature operability to the lubricant. The VM used may have a single function above, or may be multifunctional.

Multifunctional viscosity modifiers that also function as dispersants are also known. Exemplary viscosity modifiers include copolymers of polyisobutylene, ethylene and propylene with higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, Interpolymers of styrene and acrylic esters and partially hydrogenated copolymers of styrene / isoprene, styrene / butadiene, and isoprene / butadiene, and isoprene / divinylbenzene and isoprene and butadiene Partially hydrogenated homopolymers of ene.

Metal-containing or ash-forming cleaners function as cleaners to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. The cleaning agent generally comprises a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salt may contain a substantially stoichiometric amount of metal where it is usually described as a normal or neutral salt and typically has a total base of 0 to about 80, as can be measured by ASTM D-2896. (total base number, TBN). It is possible to include large amounts of metal bases by reacting excess metal compounds such as oxides or hydroxides with acidic gases such as carbon dioxide. The resulting overbased detergent comprises a neutralized detergent as the outer layer of the metal base (eg carbonate) micelle. Such overbased detergents may have about 150 or more, and typically about 250 to about 450 or more TBN.

Exemplary cleaning agents are neutral and overbased sulfonates, phenates, sulfided phenates, thiophosphonates, salicylates of metals, in particular alkali metals or alkaline earth metals such as sodium, potassium, lithium, calcium and magnesium, And naphthenates and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium, which may be present in both detergents used in lubricants, and mixtures of calcium and / or magnesium and sodium. Particularly convenient metal cleaners are neutral and overbased calcium sulfonate having a TBN of about 20 to about 450, and neutral and overbased calcium phenates and sulfide phenates having a TBN of about 50 to about 450.

Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidants. The metal may be an alkali metal or an alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. Most commonly zinc salts are used in lubricating oils in amounts of about 0.1 to about 10 wt%, preferably about 0.2 to about 2 wt%, based on the total weight of the lubricating oil composition. Zinc salts can be prepared according to the known art by first reacting at least one alcohol or phenol with P ₂ S ₅ to form dihydrocarbyl dithiophosphoric acid (DDPA) and then neutralizing the formed DDPA with a zinc compound. For example, dithiophosphoric acid can be prepared by reacting a mixture of primary and secondary alcohols. Alternatively, a plurality of dithiophosphoric acid may be prepared, wherein the hydrocarbyl group on one dithiophosphoric acid is entirely secondary in character and the hydrocarbyl group on another dithiophosphoric acid is entirely in character It may be primary. Any basic or neutral zinc compound can be used to prepare the zinc salt, but the oxides, hydroxides and carbonates of interest are most commonly used. Commercial additives frequently contain excess zinc due to the use of excess basic zinc compounds in the neutralization reaction.

However, in one embodiment, the lubricating oil composition is preferably substantially free of zinc.

Oxidation inhibitors or antioxidants reduce the tendency of base stocks to deteriorate in use, which can be demonstrated by oxidative products such as sludge and varnish-like deposits on metal surfaces and by increasing viscosity. Such oxidation inhibitors are alkaline earth metal salts of hindered phenols, preferably alkylphenolthioesters with C ₅ to C ₁₂ alkyl side chains, calcium nonylphenol sulfides, ashless soluble phenates and sulfide phenates, phosphosulfurized or sulfided hydrocarbons. , Phosphorus esters, metal thiocarbamates, oil soluble copper compounds disclosed in US Pat. No. 4,088,890, and molybdenum containing compounds.

Friction modifiers may be included to improve fuel economy. Oil-soluble alkoxylated mono- and di-amines are well known to improve boundary layer lubrication. The amines can be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halide, metaborate, boric acid or mono-, di- or tri-alkyl borates.

Other friction modifiers are known. Among these are esters formed by reacting carboxylic acids and anhydrides with alkanols. Other conventional friction modifiers generally consist of polar end groups (eg, carboxyl or hydroxyl) covalently bonded to the lipophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are disclosed in US Pat. No. 4,702,850. An example of another conventional friction modifier is organometallic molybdenum.

Exemplary rust inhibitors are selected from the group of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids.

Copper and lead bearing corrosion inhibitors may also be used. Typically such compounds are thiadiazole polysulfides containing 5 to 50 carbon atoms, derivatives thereof and polymers thereof. Another additive is thio- and polythio-sulfenamides of thiadiazoles, such as those disclosed in British Patent No. 1560830. Benzotriazole derivatives also belong to this class of additives.

Illustrative examples of anti-emulsifying ingredients are disclosed in European Patent Application Publication No. 0330522. This is obtained by reacting an adduct obtained by reacting bis-epoxide with a polyhydric alcohol and alkylene oxide.

Pour point depressants, also known as lubricant improvers, lower the minimum temperature at which fluid can flow or be poured. Such additives are well known. Typical of these additives which improve the low temperature fluidity of the fluids are C ₈ and C ₁₈ dialkyl fumarate / vinyl acetate copolymers, polyalkylmethacrylates and the like.

Foaming control can be provided by many compounds, including antifoams of polysiloxane-based, for example, silicone oils or polydimethyl siloxanes.

Some of the aforementioned additives can provide a number of effects; Thus, for example, a single additive can act as a dispersant-oxidation inhibitor. This approach is well known and requires no further explanation.

Illustrative and non-limiting examples of additives specific for use in compression refrigeration systems are as follows.

Extreme pressure additives are known to those skilled in the art and are used to protect metal surfaces in applications that occur under relatively very high pressures. Exemplary extreme pressure and antiwear additives include phosphates, phosphate esters (bicresyl phosphates), phosphites, thiophosphates (zinc diorganodithiophosphates) chlorinated waxes, sulfided fats and olefins, organic lead compounds, fatty acids, molybdenum complexes, halogen substitutions Organosilicon compounds, borates, organic esters, halogen-substituted phosphorus compounds, sulfide Diels Alder adducts, organic sulfides, compounds containing chlorine and sulfur, metal salts of organic acids.

Exemplary oxidation and thermal stability improvers include sterically hindered phenols (BHT), aromatic amines, dithiophosphates, phosphites, sulfides and metal salts of dithio acids.

Exemplary corrosion inhibitors include organic acids, organic amines, organic phosphates, organic alcohols, metal sulfonates and organic phosphites.

The viscosity index is a measure of viscosity change with temperature, and a large number suggests that the viscosity change with temperature is minimal. In view of the high viscosity index of the lubricant composition of the present invention, it is possible to prepare a lubricant composition without a viscosity index improver. However, there may be applications where it is desirable to further improve the viscosity index. Exemplary viscosity index improvers include polyisobutylene, polymethacrylate and polyalkylstyrene.

Exemplary pour point and / or mica point depressants include polymethacrylate ethylene-vinyl acetate copolymers, succinic acid-olefin copolymers, ethylene-alpha olefin copolymers, and Friedel-Crafts of wax and naphthalene or phenol. ) Condensation products.

Exemplary cleaning agents include sulfonates, long chain alkyl substituted aromatic sulfonic acids, phosphonates, thiophosphonates, phenolates, metal salts of alkyl phenols, alkyl sulfides, alkylphenol-aldehyde condensation products, metal salts of substituted salicylates, Copolymers comprising polyester bonds such as N-substituted oligomers or polymers from the reaction products of unsaturated anhydrides and amines and vinyl acetate-maleic anhydride copolymers.

Exemplary antifoams include silicone polymers.

Exemplary viscosity modifiers include polyisobutylene, polymethacrylates, polyalkylstyrenes, naphthenic oils, alkylbenzene oils, paraffinic oils, polyesters, polyvinylchlorides and polyphosphates.

In the present invention, the additive (s) must be at least partially miscible (greater than about 50% by weight) in the base stock. In general, this means that the additive used will be useful at least to some extent and preferably to a considerable extent.

Thus the lubricating oil composition should preferably be a substantially homogeneous mixture and substantially free of sedimentation or phase separation of the components.

The lubricating oil composition preferably comprises the additive in an amount of less than about 50 wt% based on the total weight of the lubricating oil composition. In various embodiments, the lubricant can include additives in an amount of about 25 wt% or less, or about 10 wt% or less, or about 5 wt% or less, based on the total weight of the lubricant composition.

Specific additive package

In some embodiments, the lubricating oil composition contains an additive package comprising a combination of at least three different additives (wt% based on total composition weight):

(a) a wear resistant additive package comprising about 0.5 to about 2.0 wt% of a mixture comprising an amine phosphate antiwear additive and a phosphorothioate antiwear additive, and

(b) about 0.05 to about 0.5 wt% of methylene bis (dialkyldithiocarbamate). Methylene bis (dialkyldithiocarbamate) may function as extreme pressure additive and / or antioxidant.

In another embodiment, the wear resistant additive package in the lubricating oil composition contains about 0.5 to about 1.0 wt% of a mixture comprising an amine phosphate antiwear additive and a phosphorothionate antiwear additive.

In another embodiment, the additive package contains about 0.1 to about 0.3 wt% of methylene bis (dialkyldithiocarbamate).

In a preferred embodiment, the lubricating oil composition further comprises one or more of the following (wt% is based on the total composition weight):

(c) about 0.05 to about 2.0 wt%, or alternatively about 0.05 to about 1.0 wt%, or alternatively about 0.1 to about 0.5 wt% tolutriazole antioxidant / metal deactivator additive; And / or

(d) about 0.05 to about 1.0 wt%, or alternatively about 0.1 to about 1.0 wt%, or alternatively about 0.1 to about 0.75, selected from the group consisting of hindered amine antioxidants, hindered phenol antioxidants, and mixtures thereof wt% primary antioxidant additive package, and / or

(e) about 0.05 to about 0.3 wt%, or alternatively about 0.05 to about 0.2 wt% calcium sulfonate corrosion inhibitor; And / or

(f) about 0.01 to about 2.0 wt%, or alternatively about 0.05 to about 1.0 wt%, or alternatively about 0.1 to about 0.5 wt% of a thiadiazole metal inert and disulfide metal inert, or That combination.

Gear / Hydraulic Lubricants

A preferred use of the lubricating composition of the present invention is as a gear / hydraulic lubricant. Exemplary formulations for such lubricants are as follows (wt% based on total composition):

(a) about 90 to 99 wt%, or alternatively about 95 to about 98.5 wt%, PTEEG fluid at ambient temperature, or a mixture of PTEEG and PTEEG esters fluid at ambient temperature;

(b) a wear resistant additive package comprising from about 0.5 to about 2.0 wt%, or alternatively from about 0.5 to about 1.0 wt% of a mixture comprising an amine phosphate antiwear additive and a phosphorothionate antiwear additive;

(c) about 0.05 to about 0.5 wt%, or alternatively about 0.1 to about 0.3 wt% methylene bis (dialkyldithiocarbamate) extreme pressure / antioxidant additives;

(d) 0 to about 2.0 wt%, or alternatively about 0.05 to about 2.0 wt%, or alternatively about 0.05 to about 1.0 wt%, or alternatively about 0.1 to about 0.5 wt% tolutriazole Antioxidant / metal deactivator additives;

(e) 0 to about 1.0 wt%, or alternatively about 0.05 to about 1.0 wt%, or alternatively about 0.1 to about 1.0 wt%, or alternatively about 0.1 to about 0.75 wt%, hindered amine oxidation A primary antioxidant additive package selected from the group consisting of antioxidants, hindered phenolic antioxidants and mixtures thereof,

(f) 0 to about 0.3 wt%, or alternatively about 0.05 to about 0.3 wt%, or alternatively about 0.05 to about 0.2 wt% calcium sulfonate corrosion inhibitor; And / or

(g) 0 to about 2.0 wt%, or alternatively about 0.01 to about 2.0 wt%, or alternatively about 0.05 to about 1.0 wt%, or alternatively about 0.1 to about 0.5 wt% of thiadiazole metal One or a combination of inerts and disulfide metal inerts.

EXAMPLE

Unless otherwise indicated, all parts, percentages, etc., are by weight.

ASTM method D445-83 and ASTM method D792-91 were used to determine the kinematic viscosity and density of the polymer, respectively.

Additional ASTM methods were used as listed in the table below.

The materials of the invention were tested with or without lubricant additive packages. The package used during the test included the components listed in Table 1.

Examples 1-5

Examples 1-5 are PTEEGs with Mn shown in Table 2 by stirring at 50 ° C. or rotating the mixture in a closed bottle in a jar roller mill at room temperature over a period of 2 to 3 days. Prepared by blending solid components (in pellet form) in (prepared with 25 mol% ethylene glycol). The pellet form of the solid components has helped to avoid air entrapment that occurs when powder forms are used and leads to excessive foaming. If the mixture was prepared in an open bottle, a nitrogen atmosphere was used. Liquid additives were added to the premixed blend to ensure that the solid particles did not remain undissolved. Table 2 below summarizes the composition of these examples.

The compositions of the examples were subjected to the tests necessary to establish a standard specification for an industrially acceptable wear resistant gear / hydraulic oil. The results are shown in Tables 3 and 4.

Example 1 contained the least amount of antioxidant compared to the other examples (as shown in Table 2). This lubricant was used during the oxidation and corrosion test (ASTM D4636) (as shown in Table 4) as indicated by the viscosity drop (-11.7%) and significant change in acid value (0.7) after operation for 24 hours at 190 ° C. A sign of thermal decomposition was shown. However, this composition is exhibited by a very low four-ball wear trace (0.3 mm-ASTM D4172-40 kg, 1200 rpm at 75 ° C.) and a Palex pin and V-block test (maximum load 1923 kg (4250 lbs) -ASTM D3233). Excellent wear and load transfer characteristics (as shown in Table 3) were shown.

Example 2 contains hindered amines, halves (R) (0.25 wt%) and hindered phenols, Irganox (R) 1135 in addition to the secondary antioxidant VANRUBE 7723 (dithiocarbamate) Antioxidant package containing primary antioxidant, including (0.2 wt%). The lubricant showed a negligible change in acid value and little change in viscosity when tested by ASTM D4636.

Example 3 contained calcium sulfonate (Banrube® 8912E, 0.1 wt%). At the same time, this additive package exhibits excellent load transfer properties as indicated by the high "load wear index" (77) despite the fact that it contains a smaller amount of half-ruve® 7723.

Examples 4 and 5, containing 0.5 wt% or more of hindered amines (Banrube® RD and PANA), although both exhibit high load transfer characteristics as indicated by the Palex load (Table 3) and showed a higher viscosity increase compared to the Examples containing 0.25 wt% Van Lube® RD.

A negative effect on the wear properties was also observed when containing more than 0.5% of hindered amines (lowest "four-ball wear" in the absence of half-ruve® RD).

Regardless of the other components, a low "friction coefficient" was observed at a half-rube® RD level of 0.25 wt%.

The composition of the present invention provides high load carrying capacity (3000 lbs)-Table 3), low friction and wear coefficient.

In addition, antioxidant combinations of hindered phenols and hindered amines provided the best results for oxidation and thermal stability, corrosion and rust resistance (copper corrosion-1b) as shown in the examples.

Compositions containing 0.25 wt% Van Lube® RD (hindered amine) and 0.2 wt% Irganox ® 1135 (hindered phenol) were subjected to oxidation and corrosion stability tests -ASTM D 4636, 190 ° C -24h. The minimum viscosity and acid value change were shown.

Claims (19)

(i) a base fluid stock comprising poly (trimethylene-ethylene ether) glycol fluid at ambient temperature, and
(ii) a wear resistant additive package comprising from about 0.5 to about 2.0 wt% (based on total composition weight) of a mixture comprising (a) an amine phosphate antiwear additive and a phosphorothionate antiwear additive, and
(b) an additive package comprising from about 0.1 to about 0.5 wt.% (based on the total composition weight) of an additive that acts as an extreme pressure additive, as an antioxidant additive, or as an extreme pressure additive and an antioxidant additive
Lubricating oil composition comprising a. The lubricating oil composition of claim 1, wherein the additive acting as an extreme pressure additive, as an antioxidant additive, or as an extreme pressure additive and an antioxidant additive is methylene bis (dialkyldithiocarbamate). The lubricating oil composition of claim 1, wherein the additive package further comprises at least one selected from the group consisting of:
(c) about 0.05 to about 2.0 wt% tolutriazole antioxidant / metal deactivator additive;
(d) about 0.05 to about 1.0 wt% of a primary antioxidant additive package selected from the group consisting of hindered amine antioxidants, hindered phenol antioxidants, and mixtures thereof,
(e) about 0.05 to about 0.3 wt% calcium sulfonate corrosion inhibitor; And
(f) at least one selected from thiadiazole metal inerts and disulfide metal inerts from about 0.01 to about 2.0 wt%. The lubricating oil composition of claim 3, wherein the additive package comprises about 0.1 to about 0.5 wt% of tolutriazole antioxidant / metal deactivator additive. The lubricating oil composition of claim 3, wherein the additive package comprises about 0.1 to about 0.75 wt% of a primary antioxidant additive package selected from the group consisting of hindered amine antioxidants, hindered phenol antioxidants, and mixtures thereof. The lubricating oil composition of claim 3, wherein the additive package comprises about 0.05 to about 0.2 wt% calcium sulfonate corrosion inhibitor. The lubricating oil composition of claim 3, wherein the additive package comprises from about 0.1 to about 0.5 wt% of at least one selected from a thiadiazole metal deactivator and a disulfide metal deactivator. The lubricating oil composition of claim 1, wherein the additive package further comprises tolutriazole antioxidant / metal deactivator additive in an amount of about 0.05 to about 2.0 wt% (based on total composition weight). The additive package of claim 1, wherein the additive package further comprises about 0.05 to about 1.0 wt% (based on total composition weight) of the primary antioxidant additive package selected from the group consisting of hindered amine antioxidants, hindered phenol antioxidants, and mixtures thereof. Lubricant composition. The lubricant of claim 1, wherein the additive package further comprises about 0.01 to about 2.0 wt% (based on total composition weight) of one or a combination of calcium sulfonate corrosion inhibitor, thiadiazole metal inert and disulfide metal inert. Composition. The lubricant composition of claim 1, wherein the base fluid stock is at least about 50 wt% based on the total weight of the lubricant composition. The lubricant composition of claim 11, wherein the base fluid stock is at least about 75 wt% based on the total weight of the lubricant composition. The lubricant composition of claim 11, wherein the base fluid stock is at least about 95 wt% based on the total weight of the lubricant composition. The lubricating oil composition of claim 1, wherein the base fluid stock consists essentially of poly (trimethylene-ethylene ether) glycol. The lubricating oil composition of claim 1, wherein the base fluid stock comprises a mixture of poly (trimethylene-ethylene ether) glycol and poly (trimethylene-ethylene ether) glycol ester. The lubricant composition of claim 1, wherein the lubricant additive is at least 50% miscible in the base fluid stock. The lubricating oil composition of claim 1, which is a substantially uniform mixture substantially free of sedimentation or phase separation of the components. The lubricating oil of claim 1, wherein the poly (trimethylene-ethylene ether) glycol has a number average molecular weight of at least about 250 to less than about 10000. The lubricating oil composition of claim 1, wherein the poly (trimethylene-ethylene ether) glycol is prepared from biologically produced 1,3-propane diol.