TW200918661A - Lubrication oil compositions - Google Patents

Abstract

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

Description

200918661 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition comprising (1) poly(trimethylene-ethyl ether) diol and (ii) an additive composite package comprising certain specified additive combinations and A full lubricating oil containing the compositions. This application is related to the following reference: commonly owned U.S. Application No. 11/593,954 entitled "POLYTRIMETHYLENE ETHER GLYCOL ESTERS", filed November 7, 2006, co-owned; "LUBRICATION OIL COMPOSITIONS" US Provisional Application No. 60/957, 7 16; commonly owned US Provisional Application No. 60/957,725 (internal reference CL3886) entitled "LUBRICATION OIL COMPOSITIONS" And co-owned U.S. Provisional Application No. 60/957,722, entitled "LUBRICATION OIL COMPOSITIONS" (internal reference CL3887). [Prior Art] ^ Certain polytrimethylene ether glycols ("P03G") (including (but not limited to) poly(trimethylene-extended ethyl ether) diol) and its monoesters and diesters ("P03G esters") have certain properties that make them suitable for use in a variety of applications. Including the use of lubricants, such as US 7179769, co-owned, and US application entitled "POLYTRIMETHYLENE ETHER GLYCOL ESTERS", filed on November 7, 2006 It is disclosed in the No. 11/593,954. Because of these characteristics, it is desirable to formulate a lubricant composition based on P03G and P03G esters. 134067.doc 200918661 [Summary of the Invention] The present invention relates to a specific type of P03G (poly (Sanya) A combination of methyl-extended ethyl-)-fermentation-PTEEG) in combination with a particular additive, the compositions having properties that make them particularly suitable for lubricating end uses. In one embodiment, 'providing a lubricating oil a composition comprising (1) a base fluid feedstock comprising PTEEG fluid at ambient temperature and (ii) an additive composite package comprising: (a) an antiwear additive composite package comprising from about 5% by weight to About 2.0% by weight (based on the total weight of the composition) comprising a mixture of a phosphate amine antiwear additive and a phosphorothionate antiwear additive, and (b) from about 0.1% to about 0.5% by weight (by composition) The total weight of the additive acts as an extreme pressure additive, an antioxidant additive or an extreme pressure additive and an antioxidant additive. In a preferred embodiment, it acts as an extreme pressure additive, an antioxidant additive. Extreme pressure additive or additives of antioxidant additives is methylene bis (dialkyldithiocarbamate urethane). When PTEEG is based on a biologically produced i-, 3-propanediol, a lubricant composition having a very high reproducible content can be provided. [Embodiment] All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains, unless otherwise defined. In case of conflict, the present specification (including definitions) will prevail. ‘,, ' Unless otherwise stated, the trademarks are displayed in capital letters. All percentages, parts, ratios, etc., are by weight 134067.doc 200918661 unless otherwise stated. When a quantity, a concentration, or other value or parameter is given by a range, a preferred range, or a list of upper and lower preferred values, this should be understood to specifically exclude any range of upper or preferred values and any range. All ranges formed by any pair of lower or preferred values are independent of whether the ranges are disclosed separately. Unless otherwise stated, when a range of values are recited herein, the range is intended to include its endpoints and all integers and fractions within the range. When a range is defined, the scope of the invention is not intended to be limited to the particular value. When the term "about" is used to describe a value or an endpoint of the range, the disclosure is to be understood to include the particular value or endpoint. The term "includes,," includes ",, has " or any other variation thereof as used herein to cover a non-exclusive include. For example, a process, method, article or device comprising a list of components. They are not necessarily limited to the elements of the invention, and may include other elements that are not specifically listed or elements that are inherent to such processes, methods, articles, or devices. In addition, unless expressly stated to the contrary, "or" Or not exclusive or. For example, any of the following satisfies the A4B condition: A is true (or exists) and 0 is false (or non-existent); A is false (or non-existent) and b True (or exist); and eight and B are true (or present). Use, "," is used to describe the elements and components of the present invention. This is for convenience only and gives the general meaning of the invention. This description should be understood to include one or at least one and singular and plural. 134067.doc 200918661 The materials, methods, and examples herein are illustrative only and are not intended to be limiting unless otherwise indicated. Although methods and materials similar or equivalent to those of the methods and materials described herein can be used in the practice or testing of the present invention, suitable squares & and ## are described herein. The basic fluid feedstock as indicated above does not apply to the base fluid feedstock of the lubricating oil composition of the present invention comprising pteeg at ambient temperature (25t) Ts fluid. The base stock may also contain other natural and/or synthetic fluid auxiliary lubricants. Examples of natural fluid auxiliary lubricants include 4 vegetable oil based lubricants which are often derived from plants and which are typically composed of triglycerides. Generally, these are liquid at room temperature. Although many different parts of the plant produce oil, in practice the oil is typically extracted primarily from the seeds of the oilseed plants. Such oils include edible and inedible oils and include, for example, high oleic sunflower oil, rapeseed oil, soybean oil, castor oil and the like, as well as modified oils such as US6583302 (fatty acid esters) and L Maichev,"plant 〇il Based

Lubricants" (purchased from Department of Plant Agriculture, 0ntari〇

Agriculture College, University of Guelph, 50 Stone Road W., Guelph, Ontario, Canada NIG 2W1). Synthetic fluid auxiliary lubricants (except P〇3G and P〇3G esters) include lubricating oils such as hydrocarbon oils such as polybutene, polypropylene, propylene-isobutylene copolymers; polyoxyalkylene glycol polymers (except P03G) and its derivatives, such as copolymers of ethylene oxide and propylene oxide; and esters of dicarboxylic acids with various alcohols, such as dibutyl adipate, di(2-ethylhexyl) sebacate , di-hexyl fumarate, dioctyl sebacate, diisosaccharide azelaic acid, bismuth

134067.doc Q 200918661 Diisodecyl phthalate, dioctyl phthalate, dinonyl phthalate and 2-ethylhexyl dimer of linoleic acid dimer. P03G and P〇3G esters other than PTEEG are usually (including but not limited to) PTEEG vinegar and can also be used as a synthetic fluid auxiliary lubricant. Ο

Preferably, the binder comprises a substantial amount of PTEEG (greater than 50 weight percent per gram based on the weight of the binder). In some embodiments, the binder can comprise about 66 weight based on the total weight of the base fluid feed. /. Or 66% by weight or more, or about 75% by weight or 75% by weight. Above, or about 9% by weight or more than 9% by weight, or about 95% by weight or more than 95% by weight of pTEEG. In some preferred embodiments, the basic fluid feedstock contains only (or substantially only) PTEEG. A portion of the PTEEG can be replaced with a pTEEG ester, and the amounts mentioned above can be used in combination with PTEEG plus pTEEG ester. In one embodiment, PTEEG/PTEEG S is intended to have a weight ratio of substantially 1 : 丨 or greater than 1:1 (PTEEG is the primary component), or about 1 5:1 or greater than 1.5:1, or about 2:1 or 2:1 or more, or about 5:1 or 5:1 or more, or about 2〇:1 or 2〇:1 or more. Further, the weight ratio is preferably about 25:1 or 25:1 or less, or about 20:1 or 20:1 or less or about 10:1 or less. The lubricating oil composition preferably comprises about 5 Torr and/or based on the total weight of the lubricating oil composition. Or a base oil raw material in an amount of 50% by weight or more. In various embodiments, the lubricating oil may comprise about 75 weights 〇/〇 or more than 75% by weight or about 9% by weight or more, or about 95% by weight, based on the total weight of the lubricating oil composition. Or 95 to reset the amount of the base above %. General purpose polytrimethylene decanediol (p〇3G) For the purposes of the present invention, P03G (including PTEEG) is a polymeric or polymeric ether 134067.doc • 10-200918661 diol' wherein at least 50% of the repeating units are Trimethylene ether unit. P03G is preferably prepared by polycondensing a monomer comprising 1,3-propanediol preferably in the presence of an acidic catalyst, thereby producing a polymer containing a -(ch2ch2ch2o)-bond (eg, a trimethylene ether repeating unit) or Copolymer. As indicated above, at least 50% of the repeating units are trimethylene ether units. When a sulfur-based acidic catalyst such as sulfuric acid is used to prepare P03G, the resulting product preferably contains less than about 20 ppm, more preferably less than about 1 〇 ppm of sulfur. In addition to the dimethylene ether oxime, there may be minor amounts of other units, such as other polyalkylene ether repeating units. In the context of the present disclosure, the term "polytrimethylene ether glycol" encompasses P03G prepared from substantially pure 1,3-propanediol and contains up to about 50 weights. /. The oligomers and polymers of the comonomers (including PTEEG and others described below). For PTEEG, the other polyalkylene ether repeating units are mainly exo-ethylation units. The 1,3-propanediol used to prepare P03G can be obtained by any of a variety of well known chemical routes or by biochemical conversion routes. Preferred methods are as follows: (for example, Q) US5015789, US5276201, US5284979, US5334778, US5364984, US5364987, US5633362, US5686276, US5821092, US5962745, US6140543, US6232511, US6235948, US6277289, US6297408, US6331264, US6342646, US7038092, US7084311, US7098368, US7009082 And as described in US20050069997A1. Preferably, the 1,3-propanediol is biochemically derived from a renewable source, a biologically derived "1,3-propanediol". A particularly preferred source of 1,3-propanediol is the use of a renewable biological source via a fermentation process. Illustrative example of a starting material of origin '134067.doc 11 200918661 describes a biochemical pathway of 1,3-propanediol (PDO) that utilizes raw materials (such as corn raw materials) produced from biological and renewable resources. It is found that Klebsiella (ΑΓ/ehW/a), bacterium of the genus C. citrinum (Cz7r〇^cier), Clostridium (C/(10), and Lactobacillus (10)) can convert glycerol into 1 , a strain of 3-propanediol. The disclosure of the technology is disclosed in several publications, including US Pat. No. 5,633,362, US Pat. No. 5,686,276, and No. 21,92, wherein US Pat. No. 5,821,92 discloses the use of recombinant organisms to produce 1,3 from glycerol by biological dry processes. - a process for propylene glycol. The process has a large intestine rod (10) transformed with a heterologous diol dehydratase gene specific for 1,2-propanediol. The transformed Escherichia coli is grown in the presence of glycerol as a carbon source and Self-growth medium U3_propanediol. Since bacteria and yeast can convert glucose (such as corn sugar) or other carbohydrates into glycerol, the processes disclosed in the publications provide fast, inexpensive, and environmentally friendly propylene glycol precursors. Source. The process produced by the biologically derived process, containing from the above / and m 3 from the composition of the plant used to produce 1) 3 - C = material and atmospheric carbon dioxide Carbon in this way, compared to == in the case of the current day and month, the heart biological method (4) carbon, not fossil fuel-based or petroleum-based carbon. Therefore, the use of the environment and the phenolic coffee and based on it Vinegar on the ring == influence 'This system is used in the composition... Two: The fossil burning and the non-gas in which the shoulder consumption is gradually decreasing is used again for the plant. Therefore, the carbon is released back to the large and contains petroleum-based A similar group of alcohols: = The object can be characterized by a sub-day that is more natural and has less environmental impact. 134067.doc 12 200918661

The biologically obtained 1,3-propanediol, p〇3G and p〇3G esters can be distinguished from similar compounds produced by petrochemical sources or fossil fuel carbon by double slave isotope fingerprinting. The method effectively distinguishes between chemically identical materials and resolves the carbon in the copolymer based on the source of growth (and possibly age) of the biosphere (plant) component. The isotope i4C adds additional information to the problem. Radiocarbon dating (mc) with a nuclear half-life of 5730 clearly allows for the analysis of specimen carbon between fossils ("dead") and biosphere ("live") materials (Currie, LA "Source Apportionment of Atmospheric Particles, '' Characterization of Environmental Particles, edited by J. Buffle and HP van Leeuwen, IUPAC Environmental Analytical Chemistry Series (Lewis Publishers, Inc) Vol. 1 Part 1 (1992) 3-74). The basic assumption in radiocarbon dating is that the constancy of C concentration in the atmosphere causes the constancy of i4c in living organisms. When processing an isolated sample, the age of the sample can be roughly inferred by the following relationship: t = (-5730 / 0.693) ln (A / A 〇), where t = age, 5730 is the half-life of radiocarbon, and eight And ~ respectively for the sample and modern standard specific i4c^m (Hsieh, Y., s〇n Sci. St) C.

Am J., 56, 460, (1992)). However, due to atmospheric nuclear testing since 1950 and fossil fuel combustion since 1850, ιγ obtained the second geochemical time characteristics. Its concentration in the atmosphere C〇2 and therefore in the living biosphere is approximately doubled during the peak of the nuclear test (in the mid-1960s). Thereafter, it gradually returns to a steady-state (atmospheric) baseline of about l_2xi 〇·12. I34067.doc •13· 200918661 Isotope ratio (14c/12c) 'The approximate relaxation half-life' (relaxati〇n half· life) is 7 -10 years. (The latter half-life cannot be understood literally; instead, a detailed atmospheric nuclear input/decay function must be used to track changes in the atmosphere and the biosphere 14C since the beginning of the nuclear era). It is this 14C time feature of the biosphere that supports the annual dating of the new biosphere carbon. 14C can be measured by Accelerator Mass Spectrometry (AMS) and the results are given in "Modern Carbon Fractions" (fM). fM is based on the National Institute of Standards and Technology (Nati〇nal).

Ο

Institute of Standards and Technology, NIST) Standard Reference Material (SRM) 4990B and 499〇c (referred to as oxalic acid standards! 1 plus 1 and 11 plus 11 respectively). The basic definition refers to the 4C/i2C isotope ratio of 〇95 times H〇xI (refer to AD 195〇). This is roughly equal to the pre-industrial wood that was decay-corrected. For the current living biosphere (plant matter), fM = 1 · 1. Stable Carbon Isotope Ratios C) Provide complementary pathways for source identification and analysis. The 13c/12c ratio in the given biosourced material is the result of the 丨3C/12c ratio in atmospheric carbon dioxide at fixed carbon dioxide and also reflects the precise metabolic pathway. There are also regional changes. Oil, C3 plants (broadleaf trees, plants (grass) and marine carbonates show 13C/12C and corresponding fc values'. In addition, the analysis results of lipid substances in C3 and C4 plants are due to the metabolic pathway The carbohydrate content of the same plant is different. Within the range of measurement accuracy, 3C shows a large change due to the isotope fractionation effect. For the Taigong _, the moon and the S, the most significant of the isotope fractionation effects: photosynthetic mechanism The main reason for the difference in carbon isotope ratios in plants is closely related to the difference in the plant's carbon-metabolic pathway, especially the primary grouping (ie, the initial atmospheric co2 134067.doc 14 200918661 疋). The majority are those who have a "CV (or Calvin-Benson) photosynthetic cycle and have a "CV' (or Hatch-Slack) photosynthetic cycle C3 plants (such as broad-leaved trees and conifers) are mainly in the temperate climate zone. In the A plant, the 'primary C〇2 fixation or carboxylation reaction involves the enzyme ribulose-1,5-bisphosphate carboxylase, and the first The stable product is 3_ Compounds. On the other hand, C4 plants include plants such as tropical grass, corn, and sugar cane. In C4 plants, another dephosphorylation reaction involving another enzyme, phosphoenol-pyruvate carboxylase, is a primary carboxylation reaction. The first stable carbon compound is 4_carbon acid, and then the hydrocarbon is decarboxylated. The CO2 thus released is re-fixed by C3 cycle. Both C4 and C3 plants exhibit a certain range of nc/ 12c isotope ratio, but typical values are about -10 to -14 per mil (C4) and per mil ((:3)_21 to _26 (|Py, et al., J. Agric. Food Chem., 45, 2942 (1997)). Coal and oil usually fall within the scope of this. The nc measurement scale was originally defined by the zero of the pee dee belemnite (PDB) limestone to define its value with the substance. The fraction of each thousand deviation is given. The value is in parts per thousand (per mil) (abbreviation %) and is calculated as follows: (-χ1000°/〇 because the reference material (RM) has been consumed 4, it has been developed in cooperation with Deputy A, USGS, NIST and other selected international isotope laboratories - a series of replacement RM. For each with PDB The mil bias is expressed as a measure of CO 2 by high-precision stable ratio mass spectrometry of molecular ions of masses 44, 45, and 46. 134067.doc 15 200918661 (stable ratio mass spectrometry, IRMS) The 1,3-propanediol obtained by the method and the composition comprising the biologically obtained 1,3-propanediol can be completely distinguished from the petrochemical source counterpart based on the 14C (fM) and the double carbon isotope fingerprint, thereby indicating the substance New composition. The ability to distinguish between these products is beneficial for the commercial tracking of such substances. For example, a product containing a "new π and "old" carbon isotope profile can be distinguished from a product made only from "old" materials. Thus, the materials of the present invention can be commercially based on A unique overview and tracking for the purpose of confirming competitiveness, determining C's release and especially for assessing environmental impact. Preferably, 1,3-propanediol used as a reactant or as a component of the reactants Purified by gas chromatography analysis should have a purity of greater than about 99% by weight and more preferably greater than about 99.9% by weight. Particularly preferred are purified 1,3-propanediols as disclosed in US Pat. No. 7,038,092, US Pat. No. 7,098,368, US Pat. P03G prepared therefrom as disclosed in US20050020805A1. Purified 1,3-propanediol preferably has the following characteristics: 〇(1) has a UV absorption of less than about 0.200 at 220 nm and an ultraviolet absorption of less than about 0.075 at 250 nm. And the UV absorption at 275 nm is less than about 0.075; and/or (2) the L*a*b*"b*" color value is less than about 0.15 (ASTM D6290) and the absorbance at 270 nm is less than about 0.075. ; and / or (3) less than about 10 ppm The peroxide composition; and/or (4) total organic impurities (excluding 1) of less than about 400 ppm, more preferably less than about 300 ppm, and more preferably less than about 150 ppm as measured by gas chromatography. , 3 - Propylene 134067.doc • 16· 200918661 Organic compounds other than alcohol) concentration.

The starting materials used to prepare P03G will depend on the desired P03G, starting material availability, catalyst, equipment, etc. and will include "1,3-propanediol reactant". "1,3·propanediol reactant" means i-, 3-propanediol, and oligomers and prepolymers of preferred 1,3-propanediol having a degree of polymerization of 2 to 9, and mixtures thereof. In some cases, it may be desirable to use up to 10% or more of the low molecular weight oligomer (where it is available). Accordingly, preferably, the starting material comprises 1,3-propanediol and dimers and trimers thereof. More preferably, the starting material contains about 9% by weight or 9 Å by weight based on the weight of the 1,3-propanediol reactant. The above 1,3-propanediol, and more preferably 99% by weight or 99% by weight or more of 1,3 - propylene glycol. P03G can be prepared by a variety of processes known in the art, such as those disclosed in U.S. Patent No. 6,977,729 and U.S. Patent No. 6,672,459. The preferred processes are as described above in U.S. Patent Nos. 7,074,969, US Pat. No. 7,157,607, U.S. Patent No. 7,716,045, and U.S. Patent No. 7,174,046. As indicated above, P03G may contain, in addition to the tris-decyl ether unit, a greater amount of other extended excipient ether repeating units. Thus, the monomer used to prepare p〇3G may contain up to 5% by weight of the comonomer polyol in addition to the 1,3-propanediol reactant. Comonomer polyols suitable for use in the process include aliphatic monoalcohols such as ethylene glycol, 丨'6·hexanediol, 丨'h-heptanediol, 1,8-octanediol, 1,9-壬diol 1,1〇-nonanediol, 1,12-dodecanediol, 3,3,4,4,5,5-hexa,% pentatriol, 2,23,3,4, 4,5,5_/U,6j ^-81^3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10--1-alkane Alcohol; cycloaliphatic diol, such as M_cyclohexanediol, "4•cyclohexane II 134067.doc -17· 200918661 methanol and isosorbide; "base group compounds, such as glycerol, trimethyl ketone And a preferred group of isoprene 1-4 comonomer diols are selected from the group consisting of ethylene glycol, 2-methyl-hydrazine propylene glycol, 22 dimethyl propylene glycol, 2,2-diethyl Base {3-propanediol, 2-ethyl-2 side methyl)·1,3·propanediol, cvc decanediol (such as hydrazine, 6-hexanediol, octyl octanediol and U0-decanediol) And isosorbide and mixtures thereof. In addition to hydrazine, 3 propylene glycol, a particularly preferred diol is ethylene glycol, and C6_C10 diol may also be particularly suitable.

Suitable PTEEGs suitable for use in the present invention are, for example, as described in U.S. Patent 4, 4, 3, 95,. Preferably, PTEEG is from 50 mole % to about 99 mole % by acid catalysis (preferably from about 60 mole % to about 98 mole %, and more preferably from about 7 mole % to about 98) Mohr, 3-propylene glycol and up to 5 mole % to about i mole % (preferably from about 40 mole % to about 2 mole %, and more preferably from about 3 mole % to about two moles) Preferably, the purified PTEEG is substantially free of acidic catalyst end groups, but may contain very low levels ranging from about 〇〇〇3 to about me3 meq/g. Unsaturated end groups, mainly allyl end groups. Such PTEEGs are considered to comprise (substantially consist of) compounds having the following formulae (I) and (II): H0-((CH2)30) m((CH2)20)nH (I) H0-((CH2)3-0)m((CH2)20)nCH2CH=CH2 (II), where m and η are within a certain range to make [^11] The average molecular weight) is in the range of from about 2 Torr to about 10,000, wherein the compound of the formula (ΙΠ) is present in an amount such that the allyl end group (preferably all unsaturated ends or end groups) is about 〇〇〇3 to Amounts in the range of about 0.03 meq/g are present. 134067.doc -18- 200918661 PTEE G may be a random or block copolymer, and formula (I) and formula (II) are intended to cover both variants. Preferred P〇3G (PTEEG) suitable for use in the present invention has at least about 250, more preferably at least about 1000 and more preferably at least about 2000 数量 (number average molecular weight). Μη is preferably less than about 10,000, more preferably less than about 5,000, and still more preferably less than about 3.500. A blend of P03G may also be used. For example, P03G A blend of higher and lower molecular weight Ρ03G may be included, preferably wherein the higher molecular weight P〇3G has a number average molecular weight of from about 1000 to about 5,000, and the lower molecular weight P03G has from about 200 to about 950. The number average molecular weight. The Μ η of the ΡΟ 3 G is preferably still within the above range. P03G preferably used herein is generally polydisperse, preferably having from about 1_0 to about 2.2, more preferably about 1.2 to Polydispersity (i.e., Mw/Mn) of from about 2.2 and more preferably from about 1.5 to about 2.1. Polydispersity can be adjusted by using a blend of P03G. P03G suitable for use in the present invention preferably has less than about 100 APHA. And more preferably less than about 50 APHA, and preferably about 1 〇〇 cS or 100 cS at 40 ° C P03G Ester In some embodiments, the P03G ester comprises one or more compounds of formula (III): 〇R1-C-Ο-Q-Ο-R2 (III) wherein Q represents the removal of hydroxyl groups by P03G Subsequent residues, R2 is hydrazine or R3CO, 134067.doc -19- 200918661 and each of Ri and Rs is independently 4 to carbon atoms, preferably at least 6 carbon atoms, more preferably at least 8 A substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic or cycloaliphatic organic group of a carbon atom. In the second embodiment, each of 'R丨 and r3 has 2 or less carbon atoms, and in some embodiments, 10 or less carbon atoms. In some preferred embodiments, each of Ri and R3 has 8 carbon atoms. P〇3GSa is preferably formed by polycondensation of a hydroxyl group-containing monomer mainly comprising 1,3-propanediol (3 monomers having 2 or more hydroxyl groups) to form p(1)g (as disclosed below), and a monodecanoic acid (or equivalent) esterification to prepare, such as 2〇〇6年丨J月

U.S. Patent Application Serial No. 1 1/593,954, the entire disclosure of which is incorporated herein by reference. The P03G vinegar thus prepared preferably contains about 5 Å by weight based on the total weight of the ester. A composition of up to 100% by weight, more preferably from about 75% by weight to just wt% of the diester and from 0 to about 50% by weight, more preferably from about 25% by weight of the monoester. Preferably, the monoesters and diesters are esters of 2-ethylhexanoic acid. The P〇3G used to prepare the vinegar does not need to be the same as the p〇3G co-component of the basic fluid feedstock. Acids and Equivalents The esterification of P〇3G is carried out by reaction with an acid and/or an equivalent (preferably a monocarboxylic acid and/or an equivalent). "Single-acid equivalents" means a compound that is substantially ruthenium-like when reacted with a polymeric diol' as is generally recognized by those of ordinary skill in the art. For the purposes of the present invention, monocarboxylic acid equivalents include, for example, ester and ester forming derivatives of monocarboxylic acids 134067.doc • 20-200918661, such as acid dentates (eg, acid chlorides) and acid livers 0 Preferably, a monocarboxylic acid having the formula R_COOH wherein R is a substituted or unsubstituted aromatic 1 group or a cycloaliphatic organic moiety having 6 to 40 carbon atoms is used. Mixtures of different monoterpenic acids and/or equivalents are also suitable. As indicated above, the monocarboxylic acid (or equivalent) can be an aromatic, aliphatic or cycloaliphatic group. In this regard, the 'monomeric' monocarboxylic acid is bonded to a carbon atom in the benzene ring system, such as the following monocarboxylic acids. The "aliphatic" monocarboxylic acid is a slow base and fully saturated. a carbon atom that is attached to or linked to a carbon atom that is part of a double bond of a woman's cigarette. If the carbon atom is in the ring, the effect is "cycloaliphatic". The monocarboxylic acid (or equivalent) may contain Any substituent or combination thereof (such as a functional group such as a guanamine, an amine, a "halogen, a thiol group, etc.") as long as the substituents do not interfere with the esterification reaction or adversely affect the properties of the resulting ester product. The mono-acids and equivalents may be derived from any source, and the preferred acids are derived from natural or biological sources. The following acids and derivatives are particularly preferred: lauric acid, myristic acid, palmitic acid, stearic acid, Arachidonic acid, benzoic acid, octanoic acid, sinapic acid, tartaric acid, fifteen-burning acid, heptadecanoic acid, cinnamic acid, linoleic acid, peanut tetrabasic acid, oil quinone, valeric acid, caproic acid, hydrazine Acid and 2-ethylhexanoic acid and mixtures thereof. Particularly preferred acid or its derivative is 2-ethylhexanoic acid, benzene Acid, hard moon acid, lauric acid and oleic acid. 134067.doc 200918661 The esterification process for preparing the ester can be about 1 〇〇C> c ^ ^ about 275 C, preferably about 125 t: to, (10) C At a temperature within the dry perimeter, it is preferred to contact 〇3G with an earlier acid in the presence of an inert gas. The process can be formulated under atmospheric force or under vacuum. Water is formed during contact and can be The reaction is carried out in an inert gas stream or under vacuum to drive the reaction to completion. To promote the reaction of P03G with a carboxylic acid, a acetation catalyst, preferably a mineral acid catalyst, is generally used. Examples of inorganic acid catalysts include, but are not limited to, sulfuric acid, Hydrochloric acid, squaric acid, hydrogen sulphate and heterogeneous catalysts, such as fossil, heteropoly acid, macroporous resin and ion exchange resin. Preferably, the acetal acid preparation agent is selected from the group consisting of sulfuric acid, scaly acid, hydrochloric acid and hydromoxic acid. The preferred inorganic acid catalyst is sulfuric acid. The amount of the catalyst used may be from about 〇.% by weight to about 1 〇 by weight of the reaction mixture, preferably from about 5% by weight to about 5% by weight of the reaction mixture. And more preferably about 0.2% by weight to About 2 weights 〇 / 0. Any ratio of carboxylic acid or its derivative to diol hydroxyl group can be used. A preferred ratio of acid to hydroxyl group is from about 3:1 to about 1:2, wherein the ratio can be adjusted to change the product The ratio of monoester to diester. In general, to facilitate diester production, a ratio of slightly more than 1:1 is used. To facilitate monoester production, a ratio of acid to hydroxyl of 0.5:1 or less is used. A preferred method of acetalization comprises polycondensation of a ruthenium, 3-propanediol reactant to P〇3G using a mineral acid catalyst, followed by addition of a carboxylic acid and esterification without isolation and purification of p〇3G. The etherification or polycondensation of the U3_propylene glycol reactant to form the P03G system is carried out using an acid catalyst as disclosed in U.S. Patent 6,977,291 and U.S. Patent 6,720,459, the disclosure of which is incorporated herein by reference. The keying reaction can also be carried out using an acid-containing sizing agent such as jp _ 182974A. The reaction is continued to be polycondensed or squashed until the desired molecular weight is reached, and a calculated amount of monoacid is then added to the reaction mixture. The reaction is continued while the water by-product is removed. At this stage, the acetation (four) reaction proceeds simultaneously. Therefore, it is preferred herein that the acid catalyst for polycondensing the diol is also used for acetification, and other esterification catalysts may be added during the esterification stage. In this procedure, the viscosity (molecular weight) of the resulting product is controlled by the time of addition of tracing. In an alternative procedure, the acetification reaction can be carried out on purified P03G by adding an esterification catalyst and tareric acid, followed by heating and removal of water. In this procedure, the viscosity of the resulting product is primarily a function of the molecular weight used. Regardless of the procedure followed by the acetalization process, any by-products are removed after the _chemical step and the remaining catalyzed residue of the polycondensation and/or esterification reaction is subsequently removed to obtain stability (especially at elevated temperatures) ) § product. This can be borrowed from about 80 C to about 1 〇〇. The crude vinegar product is hydrolyzed by treatment with water for a time sufficient to hydrolyze any residual acid ester derived from the catalyst without significantly affecting the acid retardation. The time required can vary from about 丨 hours to about 8 hours. If the hydrolysis is carried out under pressure, it may be a higher temperature and a correspondingly shorter time. In this regard, depending on the reaction conditions, the product may contain a combination of diacetic acid, monoacetic acid or diacetic acid and monoacetic acid' and a small amount of acid catalyst, unreacted toxaic acid and diol. The hydrolyzed polymer is further purified by known techniques (such as water washing, alkali neutralization, percolation and/or distillation) to remove water, 134067.doc -23-200918661 acid catalyst and unreacted carboxylic acid . The unreacted diol and acid catalyst can be removed, for example, by washing with deionized water. Unreacted carboxylic acid can also be removed, for example, by washing with deionized water or an aqueous solution or by vacuum stripping. The hydrolysis is typically followed by one or more water washing steps to remove the acid catalyst, and drying (preferably under vacuum) to obtain the ester product. Washing is also used to remove unreacted diol. Any unreacted monocarboxylic acid present may also be removed in a water wash' but may 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 separate the low molecular weight. Proton NMR and wavelength chirped ray spectroscopy can be used to identify and quantify any residual catalyst (such as sulfur) present in the polymer. The proton Nmr can, for example, identify the sulfate groups present in the polymer chain, and the wavelength χ-ray glory method can determine the total sulfur (inorganic and organic sulfur) present in the polymer. The ester prepared by the above process of the present invention is substantially free of sulfur and is therefore suitable for use in high, high-quality fields. Preferably, the P〇3G ester after purification is substantially free of acidic catalyst end groups' It may contain very low levels of unsaturated end groups in the range of from about 〇003 to about me3 meq/g, primarily allyl end groups. The p〇3G ester may be considered to comprise a compound having the following formulae (IV) and (V) consisting essentially of: R.-C(0)-0-((CH2)30)m((CH2) ) 20) n-R2 (IV)

Ri-C(0)-〇-((CH2)3-〇)m((CH2)20)nCH2CH=CH2 (V), where R·2 is Η or 1<:(0); heart and ruler 3 Each of which is individually substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic or cycloaliphatic organic group containing from 6 to 134067.doc •24 to 200918661 4 carbon atoms; And η are within a range such that Mn is in the range of from about 200 to about loooo; and wherein the compound of formula (ΠΙ) is present in a quantitative amount such that the allyl end group (preferably all unsaturated ends or end groups) is about An amount in the range of from 〇〇〇3 to about 0.03 meq/g is present. Preferably, 'P03GS has a viscosity less than P03G. The preferred viscosity of the p〇3G ester is 40. (: at about 20 cS to about Within the range of 150 cS, and more preferably about 100 CS or 1 〇〇 c § below. Based on the above preferences for P03G itself, other preferred properties of the p〇3G ester can be determined. For example, preferred molecular weight And polydispersity is based on the preferred molecular weight and polydispersity of the P03G component of the ester. General Purpose Additives The synthetic lubricating oil compositions of the present invention comprise a mixture of a binder and one or more additives, each of which is added. The agent is used to improve the base material (for example, as hydraulic fluid, gear oil, brake fluid, compressor lubricant, textile ° and calender lubricant, metalworking fluid, refrigeration lubricant, two-stroke engine lubricant) And / or crankcase lubricants are used for the purpose of performance and characteristics. The additive it can often be added in an amount which can usually be determined by a person skilled in the art based on the type of additive and the desired effect of the additive effect. Preferably, the additive It may be miscible in one or both of P〇3G and P〇3G ester. Preferably, the lubricating oil additive comprises at least one of the following: an ashless dispersant, a metal detergent, a viscosity modifier Antiwear agent, anti-oxidation 134067.doc -25- 200918661 agent, friction modifier, pour point depressant emulsifier, antiscaling agent and mixtures thereof...., residual inhibitor, deodorized lubricating oil composition When chilling lubricants, the following items are included. 丨, one μ oil additive is better 赦 a a ω · t • Extreme and anti-wear additives, oxy- fen thermal stability improver, corrosion inhibition 丨 emulsification And lowering agent Flocculation: nr 11夂' and a number of improvers, pour point (four) I pour point depressant, detergent, a mixture. 1 viscosity modifier and its use alone or in combination with - 戋 multi-box 4 eve other specified additives Any one-night fingertip additive sounds belong to life. It belongs to the mouth of the invention. It can be used alone or with - or a variety of J: Detective, 夭4, Μ Μ history or preparation combination) It is also within the scope of the invention to treat any of the above specified additives (e.g., one or more wipe modifiers). Individual additives can be incorporated into the human base in any convenient manner. Thus, 1 = two: each can be added to the base directly by dispersing it at the desired concentration level or = = base. The blending can be carried out at ambient temperature or under Southern im. Alternatively, all or some of the additives may be blended into a concentrate or an additive package' subsequently blended into the base to prepare a finished lubricant. The concentrate will typically be formulated to contain an appropriate amount of additive to provide the desired concentration in the formulation when the concentrate is combined with a predetermined amount of the base lubricant. Non-limiting, illustrative examples of various additives are as follows. The ashless dispersant comprises a polymeric tobacco backbone having functional groups capable of binding to the particles to be dispersed. Typically, the dispersant comprises an amine, alcohol, amine and/or ester polar moiety that is attached to the polymer backbone, typically via a bridge 134067.doc • 26-200918661. The ashless dispersant may, for example, be selected from the group consisting of long chain hydrocarbon-substituted monocarboxylic acids and salts of dicarboxylic acids and/or anhydrides thereof, known as decylamine, quinoneimine and hydrazine. a long-chain aliphatic hydrocarbon directly linked thereto by a thiol, a long-chain hydrocarbon, and a Mannich formed by condensation of a long-chain substituted hydrazine with formaldehyde and a polyalkylene polyamine. Mannich condensation product. The viscosity modifier (VM) functions to impart high temperature and low temperature operability to the lubricating oil. The VM used may have a single function or may have multiple functions. Multifunctional viscosity modifiers which also act as dispersants are also known. Illustrative viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene with high carbon olefins, polymethacrylates, polyalkyl methacrylates, mercapto acrylate copolymers, unsaturated dicarboxylic acids Copolymer with vinyl compound, interpolymer of styrene and acrylate, and partially hydrogenated copolymer of styrene/isoprene, styrene/butadiene and isoprene/butadiene, and Partially hydrogenated homopolymer of dienes and isoprene and isoprene/divinylbenzene. Metal- or ash-forming detergents act as both cleaners to reduce or remove deposits and also act as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents typically comprise a polar head and a long hydrophobic tail, wherein the polar head comprises a metal salt of an acid organic compound. The salts may contain a substantially stoichiometric amount of a metal, which is generally described as a normal or neutral salt, and will generally have a total base number of from about 80 to about 80 as measured by ASTM D-2896. (TBN). It is possible to include a large metal test by reacting an excess of a metal compound such as an oxide or a hydroxide with an acid gas such as carbon dioxide. The resulting highly detrimental cleaner comprises a neutralized cleaner as a gold 134067.doc 200918661 genus (e.g., carbonate) micelle outer layer. The overbased detergents can have a TBN of about 150 or more and typically from about 250 to about 450 or more. Illustrative cleaners include neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates and naphthenates, and other oil-soluble metals (especially metals or soils) For example, sodium, potassium, bell, about and town) carboxylates. The most commonly used metals are calcium and magnesium, which may be present in the detergent used in the lubricant; and calcium and/or a mixture of magnesium and sodium. Particularly convenient metal cleaners are from about 20 to about 450 neutral and overbased calcium sulfonates having a TBN, and from about 50 to about 450 neutral and overbased phenolic and sulfurized phenates of TBN. A metal salt of a dihydrocarbyl dithiophosphate is generally used as an antiwear agent and an antioxidant. The metal may be an alkali metal or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, copper or copper. The zinc salt is most commonly used in a full lubricating oil in an amount of from about 0.1% by weight to about 10% by weight, preferably from about 0.2% by weight to about 2% by weight, based on the total weight of the lubricating oil composition. It can be prepared according to known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA) by first reacting one or more alcohols or phenols with pzS5 and subsequently neutralizing the formed DDPA with a zinc compound. For example, dithiophosphoric acid can be prepared by reacting a mixture of a first alcohol and a second alcohol. Alternatively, a plurality of dithiophosphoric acids may be prepared, one of which is completely second in nature and the other of which is completely first in nature. For the preparation of zinc salts, any basic or neutral zinc compound can be used, but oxides, hydroxides and carbonates are most commonly employed. Commercial additives typically contain an excess of zinc due to the use of excess zinc compounds in the reaction. However, in one embodiment, the lubricating oil composition preferably does not substantially contain 134067.doc -28-200918661 zinc. The oxidation inhibitor or antioxidant reduces the tendency of the binder to deteriorate during use, as evidenced by oxidation products such as sludge and varnish-like deposits on the metal surface and by viscosity growth. The oxidation inhibitors include hindered oxime, alkaline earth metal salts of alkyl phenol thioesters preferably having a C5 to c! 2 alkyl side chain, nonyl phenol calcium sulfide, ashless oil soluble phenates, and sulfurized phenates, phosphorus Sulfurized or sulfurized hydrocarbons, ester-filled, metal thioamino phthalates, oil-soluble copper compounds as described in U.S. Patent 4,867,890, and molybdenum-containing compounds.

Friction modifiers can be included to improve fuel economy. It is well known that oil-soluble alkoxylated monoamines and diamines improve the boundary layer lubricity. The amines may be used as such or in combination with a boron compound such as boron oxide, boron boride, metaborate, boric acid or oleic acid monoalkyl vinegar, rotten acid dialkyl vinegar or acid-cutting trialkyl vinegar. Used as a substance or as a reaction product. Other friction modifiers are known. Among these, there are vinegar formed by reacting (iv) acid and acid with an alkanol. Other conventional friction modifiers typically consist of polar end groups (e.g., sulfhydryl or hydroxy) covalently bonded to the oleophilic hydrocarbon chain. The brain 7 〇 285 描述 describes several acids and anhydrides and vinegar. Another example of a conventional friction modifier is organometallic molybdenum. + The lunar anti-recording agent is selected from the group consisting of non-ionic polyoxyalkylene extended calcinol and its ester, polyoxyalkylene extended (four) and anionic burning base acid. = Use copper and wrong rot # inhibitor. Usually, the sulphide, its derivatives and its poly-I, the additive is thiadisulfide thiosulfinamide and polythiol amide, and the (four) κ 丨 (4) Etc. 134067.doc -29- 200918661 Also pertaining to such additives. j. Emulsifying components - illustrative examples are as described in Panel A, Side 522. The ruthenium is made by diluting the oxidizing agent with Obtained by the reaction of the polyol adduct. The pour point depressant (or known as the turbid oil improver) reduces the flow of the fluid or: the lowest temperature at which it is poured. These additives are well known to us. The low temperature flow is pure and the other additives are deducted and ~2 炫基反丁归·- vinegar/acetic acid B, saying 妒-U take this β

Vinyl ruthenium copolymer, polyalkyl methacrylate, and the like. Foam control may be provided by a variety of compounds including polyoxyalkylene type defoaming "e.g., eucalyptus or polydimethyl siloxane" - some of the above additives may provide a variety of effects; thus, for example, a single additive may act as a dispersant - oxidation Inhibitors. This method is well known and need not be described in further detail. Illustrative, non-limiting examples of additives specifically for use in compression refrigeration systems are as follows.

Extreme pressure additives are known to those skilled in the art and are used to provide protection to metal surfaces in applications where relative pole pressure occurs. Illustrative extreme pressure and anti-wear additives include phosphate, phosphate (diphenyl phenyl phosphate), phosphite, thiophosphate (zinc dithiophosphate) gasification wax, sulfurized fat and olefin, organic lead Compounds, fatty acids, molybdenum complexes, elemental substituted organotelluric compounds, borate, organic esters, phosphine-substituted phosphorus compounds, sulfurized Diels Alder adducts, organosulfides, compounds containing chlorine and sulfur, organic acids Metal salt. 134067.doc -30. 200918661 w S Oxidation and thermal stability improvers include sterically hindered phenol (bht), aromatic amines, dithiophosphates, phosphites, sulfides and metal salts of dithioacids. Said month I. Raw corrosion inhibitors include organic acids, organic amines, organic phosphates, organic alcohols, I sulfonates & organic phosphites. The number of viscosities is a measure of the change in point with temperature, and the high value indicates that the viscosity changes minimally with temperature. In view of the high viscosity of the lubricating oil composition of the present invention, there is a lubricating oil composition which can be formulated with a non-viscosity index improver. However, there is a desire to further improve the viscosity index. Illustrative viscosity index improvers include polyisobutylene, polymethacrylate, and polyalkyl styrene. Illustrative pour point and/or flocculation point depressants include polydecyl acrylate ethylene-vinyl acetate copolymers, succinyl amide copolymers, ethylene _α olefin copolymers, and waxes with naphthalene or phenol - Cladding condensate (Friedel_

Crafts condensation) product. Illustrative detergents include acid salt, aromatic acid extended by long chain alkyl groups, phosphonates, thiophosphonates, phenates, metal salts of alkyl phenols, alkyl sulfides, alkyl phenols - An aldehyde condensation product, a metal salt of a substituted salicylate, an N-substituted merging polymer or polymer derived from a reaction product of an unsaturated acid anhydride and an amine, and a copolymer having a polyester bond (such as ethylene glycol) _ Maleic anhydride copolymer). An illustrative antifoaming agent is a siloxane polymer. Illustrative viscosity modifiers include polyisobutylene, polymethacrylate, polyalkyl styrene, naphthenic oil, alkyl benzene oil, eucalyptus oil, polyester, polygas 134067.doc •31 200918661 olefin And polyphosphates. In the present invention, the additive should be at least partially (greater than about 50% by weight) miscible in the binder. In general, this means that the additives used are at least to some extent, and preferably are generally oil soluble. Accordingly, the lubricating oil composition should preferably be a substantially homogeneous mixture wherein the components are substantially free of settling or phase separation. The lubricating oil composition preferably comprises an additive in an amount of less than 50% by weight based on the total weight of the lubricating oil composition. In various embodiments, the lubricating oil may comprise about 25% by weight or less by weight, or about 10% by weight or less, or about 5% by weight or 5% by weight, based on the total weight of the lubricating oil composition. The following amounts of additives. Specific Additive Composite Package In some embodiments, the lubricating oil composition contains an additive composite package (wt% by weight of the total composition) comprising a combination of at least three different additives: (a) an antiwear additive composite package comprising about 0.5 5% by weight to about 2.0% by weight of a mixture comprising a phosphate amine antiwear additive and a phosphorothioate antiwear additive, and (b) from about 5% by weight to about 0.5% by weight of a fluorenyl bis(dialkyl group) Dithioamino phthalate). Methylene bis(dialkyldithioamino phthalate) can be used as an extreme pressure additive and/or an antioxidant. In an alternative embodiment, the antiwear additive composite in the lubricating oil composition comprises from about 0.5% to about 1% by weight of a mixture comprising a phosphate amine antiwear additive and a thioate antiwear additive. 134067.doc -32· 200918661 In an alternative embodiment, the additive composite comprises about (from about 5% by weight to about 3% by weight of methylene bis(dioxadithiocarbamic acid vinegar). In a preferred embodiment, the lubricating oil composition additionally comprises one or more of the following (% by weight based on the total weight of the composition) (c) from about 0.05% by weight to about 2% by weight, or about 〇〇 5% by weight to: 1.0% by weight, or from about 1% by weight to about 5% by weight. The benzotriazole anti-emulsifier/metal deactivator additive; and/or (4) from about 0.05% by weight to about 1% by weight , or about."% by weight to about 1.0% by weight 'or about 5% by weight to about 75% by weight of the main antioxidant additive package selected from the group consisting of: a hindered amine antioxidant, blocked a phenolic antioxidant and mixtures thereof, and/or 0) from about 0.05 by weight; from about 1% to about 3% by weight, or from about 5% by weight to about 0.2% by weight of a calcium sulfonate corrosion inhibitor; and/or (f) from about 0% by weight to about 2.0% by weight, or from about 5% by weight to about 1.0% by weight, or about 0% "% by weight to about 5% by weight of the bismuth metal passivator and the disulfide metal passivating agent or combination. Gear / hydraulic lake slip agent The preferred use of the lubricant composition of the present invention is as a gear / Hydraulic Lubricants. Exemplary formulations of such lubricants are as follows (% by weight based on total composition): (a) from about 90 weights 。/. to 99 weight% ❶, or from about 95% to about 98.5% by weight a pTEEG that is fluid at ambient temperature, or a mixture of 1> and a PTEEG ester that is fluid at ambient temperature; (b) an antiwear additive composite package comprising from about 0.5% to about 2 weights 134067.doc •33- 200918661 Amount %' or from about 0.5% by weight to about 1.% by weight of a mixture comprising a phosphate amine antiwear additive and a phosphorothioate antiwear additive; (c) from about 0.05% by weight to about 0.5% % by weight, or about 11. 1% by weight to about 0.3% by weight of hydrazine/bisindole bis(dialkyldithiocarbamate) extreme pressure/antioxidant additive; (d) 〇 to about 2.0 weight %, or from about 0.05% to about 2.0% by weight, or from about 0.05% to about 1% by weight %, or about 〇. 1 重量./〇 to about 0.5% by weight of benzotriazole antioxidant/metal deactivator additive; (e) from about 5% by weight to about 1.0% by weight, or from about 0.05% by weight to about 1 · 〇 weight ° / ° 'or about 1. 1 weight ° / ❶ to about 1.0% by weight, or about 1. 1% by weight to about 0.75 weight ° /. selected from the group consisting of the following main antioxidant Additive compound package: hindered amine antioxidant, hindered phenol antioxidant and mixtures thereof, (f) from about 〇 to about 3% by weight, or about 〇. /〇 to about 0. 3 wt% or about 0.05 wt. Up to about 2% by weight of a calcium sulfonate corrosion inhibitor; and/or (g) 〇 to about 2.0% by weight, or about o. oi% by weight to about 2.0% by weight, or about 0.05% by weight to about 1·〇 weight. /. Or one or a combination of about 5% by weight to about 0.5% by weight of the thiadiazole metal deactivator and the disulfide metal deactivator. EXAMPLES Unless otherwise stated, all parts, percentages, etc. are by weight. The dynamic viscosity and density of the polymer were determined using ASTM method D445-83 and ASTM method D792-91, respectively. 134067.doc -34- 200918661 Other ASTM methods used are listed in the table below. The materials of the present invention were tested with and without a lubricating oil additive composite package. The complex used during the test contained the components listed in Table 1. Table 1

Additive description function available from IRGALUBE® TPPT Triphenyl thiophosphate, usually containing 9% phosphorus and 9.4% sulfur antiwear/extreme pressure agent Ciba Specialty Chemicals, Tarrytown, NY VANLUBE® 7723 methylene bis (dibutyl bis) Thioamine phthalate) Acute antioxidants and extreme pressure agents RT Vanderbilt Company Inc., Norwalk, CT VANLUBE® 887E Tolutriazole Antioxidant RT Vanderbilt Company Inc., Norwalk, CT PANA Phenyl α-naphthylamine Oxidizing Agent Akrochem, Akron, OH VANLUBE® RD Polymerization 1,2-Dihydro-2,2,4-Trimethylquinoline Antioxidant RT Vanderbilt Co., Inc., Norwalk, CT IRGANOX® 1135 Hindered Phenol Antioxidant Ciba Specialty Chemicals, Tarrytown, NY IRGALUBE® 349 Amine Phosphate Mixture and Corrosion Inhibitor Ciba Specialty Chemicals, Tarrytown, NY VANLUBE® 8912E Calcium Sulfate Rust Preventive Agent RT Vanderbilt Company Inc., Norwalk, CT CUVAN® 826 2,5-II Mercapto-1,3,4-thiadiazole derivative f-etch inhibitor $metal passivation L#j RT Vanderbilt Company, Inc., Norwalk, CT IRGACORE® L12 corrosion inhibitor Ciba Specialty Chemicals, Tarrytown, NY Polydimethylsiloxane polymer 200cSt defoamer Dow Coming, Midland, MI LUBRIZOL 889D Ester Copolymer - Defoamer The Lubrizol Corporation, Wickliffe, OH 134067.doc 35· 200918661 Examples 1-5 Examples 1-5 The solid components (in the form of granules) are blended in the form listed in Table 2 by stirring the mixture at 50 ° C or at room temperature in a sealed can on a can roller mill for 2 to 3 days. It was prepared by PTEEG (prepared using 25 mol ethylene glycol). The solid form in particulate form helps to avoid entrainment of air that causes excessive foaming when using the powder form. When the mixture was prepared in an open can, a nitrogen atmosphere was used. A liquid additive is added to the premix blend to ensure that no solid particles are not dissolved. Table 2 summarizes the composition of the examples. Table 2: Examples 1-5 Example 1 Example 2 Example 3 Example 4 Example 5 Polydimethylsiloxane polymer 0.005 0.0025 0.0025 Lubrizol 889D 0.05 0.05 Vanlube® 7723 0.3 0.3 0.2 0.3 0.3 Vanlube® 887E 0.4 0.4 0.3 0.4 0.4 Irganox ® 1135 0.2 0.2 0.2 0 Irgalube® TPPT 0.5 0.5 0.5 0.5 0.5 Irgalube® 349 0.4 0.4 0.4 0.4 0.4 Vanlube® 8912E 0.1 0 PANA 0.5 0 Vanlube® RD 0.25 0.25 0.5 0.5 Irgacore® L12 0.1 0 CUVAN® 826 0.1 0.1 0.1 0.1 0.1 PTEEG (Mn, SEC/GPC) 98.3 (993) 97.85 (1093) 97.95 (1093) 97 (1040) 97.8 (993) 134067.doc -36- 200918661 The compositions of the examples are made for the establishment of industrially Tests required to accept the standard specifications for anti-wear gears/hydraulic oils. The results are shown in Tables 3 and 4. Table 3: Lubricant Characteristics of Examples 1-5 ASTM Example 1 Example 2 Example 3 Example 4 Example 5 Viscosity Index D-2270 207 206 208 203 Pour Point, °c D-97 -45 -45 -48 -42 -48 Flash point, °c D-92 272 288 286 302 294 Four-ball wear scar, mm D-4172 0.3 0.37 0.4 0.59 0.45 Friction coefficient D-4172 0.042 0.033 0.032 0.044 0.051 Load wear index D-2783 50.13 61.5 77 77 42.28 Maximum no card Bite load (wear marks, mm) D-2783 126 (·49) 160 (.52) 200 (.54) 200 (.52) 100 (.43) Maximum card bit load (wear marks, mm) D-2783 160 Kg (2.78) No or no 160kg (2.37) Welding load, kg D-2783 200 200 250 250 200 Falex pin and V block (Falex Pin and V block) maximum load, lb D-3233 4250 3000 3000 4250 3500 134067.doc -37- 200918661 Table 4 - Oxidation and Corrosion Test Results (ASTM D4636-190C-24h) Characteristic Example 1 Example 2 Example 3 Example 4 Example 5 Viscosity Change -11.7 1.49 0.97 6.731 6.5 Acid Value Change (Mg/ KOH/g) 0.7 0.07 0.09 0.3 0.3 Viscosity, initial at 40 ° C, cSt 195.1 234.8 238.3 208.1 198.1 cSt 172.2 238.3 240.6 222.1 210.9 Total Acid # Initial, mg KOH/g 0.22 0.25 0.25 0.42 0.21 , mg KOH/g 0.92 0.32 0.34 0.72 0.51 Copper rot # Dull-lb Dull-lb Dull-lb Dull-lb Dull-lb Example 1 compared to other examples Contains a minimum amount of antioxidant (as shown in Table 2). This lubricant showed signs of thermal degradation during oxidation and corrosion testing (ASTM D4636) as shown by a decrease in viscosity (-11.7%) and a significant change in acid value (0.7) after 24 hours of operation at 190 °C (eg Table 4)). However, this composition is tested by a very low four-ball wear mark (0.3 mm-ASTM D4172-40 kgjj200 rpm at 75 ° C) and a Falex pin and V-block test (maximum load 4250 lb-ASTM D3233) The figure shows excellent wear and load bearing properties (as shown in Table 3). Example 2 contains a composite antioxidant containing, in addition to the second antioxidant (VANLUBE® 7723, dithiocarbamate), a hindered amine (VANLUBE® RD, 0-25% by weight) and hindered phenol (IRGANOX® 1135). , 0.2% by weight of the main antioxidant. As tested by ASTM D4636, this lubricant exhibits minimal viscosity changes and negligible acid value changes. Example 3 contained calcium sulfonate (VANLUBE® 8912E, 0.1% by weight). As with 134067.doc -38- 200918661, this additive composite package exhibits excellent load carrying characteristics as shown by the high "load wear index" (77), although it also contains a lower number of VANLUBE® 7723. Example 4 and Example 5 of 5% by weight or more of hindered amines (VANLUBE® RD and PANA) showed a high viscosity increase compared to the example containing 0.255% by weight of VANLUBE® RD, but all of them were like Falek The high load-bearing characteristics are indicated by the load (Table 3). The negative effects of anti-wear properties were also observed in the case of more than 0.5% hindered amine (in the absence of VANLUBE® RD "four-ball wear "lowest) ° A low "coefficient of friction is observed when the VANLUBE® RD content is 0-25% by weight (regardless of other components). The compositions of the present invention provide high load carrying capacity (Farex load > 3000 lb - Table 3), low friction and wear coefficient. Again, as shown by these examples, the combination of hindered phenol and hindered amine antioxidant provides the best results for oxidation and thermal stability, corrosion resistance and anti-money properties (copper rot -1 b). The composition containing 0.25 wt% VANLUBE® RD (hindered amine) and 0.2 wt% IRGANOX® 11 3 5 (obstructed) is in terms of oxidation and rot resistance test - ASTM D 4636 (190 ° C - 24 h) Shows the minimum viscosity and acid value change. 134067.doc -39-

Claims (1)

200918661 X. Patent Application Range: 1. A lubricating oil composition comprising: (i) a basic fluid raw material comprising a poly(trimethylene-extended ethyl ether) glycol which is a fluid at ambient temperature and (ii) An additive composite package comprising: (a) an antiwear additive composite package comprising from about 0.5% to about 2% by weight (based on the total weight of the composition) comprising an amine phosphate antiwear additive and a phosphorothioate a mixture of antiwear additives, and (b) from about 0.1% by weight to about 5% by weight (based on the total weight of the composition) of an extreme pressure additive, an antioxidant additive or an additive to an extreme pressure additive and an antioxidant additive. 2. The lubricating oil composition of claim 1, wherein the additive serving as an extreme pressure additive, an antioxidant additive or an extreme pressure additive and an antioxidant additive is an anthracenyl bis(dialkyldithioamino phthalate) . 3. The lubricating oil composition of claim 1, wherein the additive composite package further comprises at least one selected from the group consisting of: (C) from about 0.05% to about 2.0% by weight of the benzotriazole antibiotic Oxidant/gold/deactivator additive; (d) from about 0. 5% by weight to about 1% by weight of the main antioxidant additive package selected from the group consisting of hindered amine antioxidants, hindered phenol resistant The oxidizing agent and mixtures thereof, (e) from about 0.5% by weight to about 3% by weight. /. a calcium sulfonate corrosion inhibitor; and (f) about 0.01 by weight. /. Up to about 2.0% by weight of at least one selected from the group consisting of thiadiazole metal passivators and disulfide metal passivators. 134067.doc 200918661. The lubricating oil composition of claim 3, wherein the additive composite package comprises from about 0.1% by weight to about 5% by weight of the hydrazine triazole antioxidant/metal passivator additive. The lubricating oil composition of claim 3 wherein the additive composite package comprises from about 0.1% by weight to about 〇75 weight. /. The primary antioxidant additive complex is selected from the group consisting of hindered amine antioxidants, hindered phenol antioxidants, and mixtures thereof. 6. The lubricating oil composition of claim 3, wherein the additive composite package comprises from about 0.05% by weight to about 0.2% by weight of a calcium sulfonate corrosion inhibitor. 7. The lubricating oil composition of claim 3, wherein the additive composite package comprises a spoon 0. 1 reset. Up to about 5% by weight of at least one selected from the group consisting of a thiadiazole metal purifying agent and a di-IL metal purifying agent. 8. The lubricating oil composition of claim 1, wherein the additive composite package additionally comprises from about 0.05% by weight to about 2.% by weight based on the total weight of the composition of the benzotriazole antioxidant/metal Passivator additive. 9. The lubricating oil composition of claim 1, wherein the additive composite package additionally comprises about 0.05 by weight. To about! 〇% by weight (based on the total weight of the composition) The main antioxidant additive package of the group consisting of the following components: a hindered amine antioxidant, a hindered phenol antioxidant, and a mixture thereof. I. The lubricating oil composition of the present invention, wherein the additive composite package further comprises from about 0.01% by weight to about 2.0% by weight. /. One or a combination of a sulphuric acid per sulphur inhibitor, a bismuth di(s) metal deactivator, and a disulfide metal clarifying agent (based on the total weight of the composition). II. The lubricating oil composition of the present invention wherein the basic fluid raw material is about 5% by weight or more by weight based on the total weight of the 134067.doc 200918661 moist alpha oil composition. 12. The lubricating oil composition of the present invention, wherein the base fluid material is about 75% by weight or more by weight based on the total weight of the lubricating oil composition. 13. The lubricating oil composition of claim 1, wherein the base fluid material is about 95% by weight or more by weight based on the total weight of the lubricating oil composition. 14. The lubricating oil composition of claim 3, wherein the base fluid material consists essentially of the poly(trimethylene-extended ethyl ether) diol. 15. The lubricating fluid composition of claimant, wherein the base fluid feedstock comprises a mixture of the poly(trimethylene-extended ethyl ether) glycol and the poly(trimethylene-extended ethyl ether) glycol ester. 16. The lubricating oil composition of the present invention, wherein the lubricating oil additive is at least 50% miscible in the base fluid material. </ RTI> A lubricating oil composition of the present invention, wherein the lubricating oil composition is a mixture of large average sentences, wherein the components are substantially free of sedimentation or phase separation. Wherein the 馘, -π τ 丞 _ 虼 ethyl 虼) - privately has an amount of at least about 250 to less than about 10,000 denier. The decene molecule 19. The lubricating oil composition of the claim ,, wherein the poly(trimethylene) diol is a biologically produced hydrazine, 3-propanediol to prepare diethyl 134067.doc 200918661 VII. The designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R1-C——Ο——Q——0——R2 (III) c 134067.doc