TW200914604A - Lubrication oil compositions - Google Patents

Abstract

This invention relates to lubrication oil compositions comprising (i) an acid ester (monoester and/or diester) of polytrimethylene ether glycol; and (ii) a vegetable oil lubricant.

Description

200914604 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a composition comprising (1) a polytrimethylene ether glycol acid ester (monoester and/or diester); and (u) a vegetable oil lubricant . The invention is also directed to the use of such compositions as lubricating oils. This application is related to the following references: commonly owned U.S. Application No. 1 1/593,954, filed on November 7, 2006, entitled, PCT, POLYTRIMETHYLENE ETHER GLYCOL ESTERS " co-owned and concurrently filed with " U.S. Provisional Application No. 60/957J28 to LUBRICATION OIL COMPOSITIONS"; US Provisional Application No. 60/957,725, entitled "1' LUBRICATION OIL COMPOSITIONS", which is co-owned by the same application; US Provisional Application No. 60/957,716, entitled "LUBRICATION OIL COMPOSITIONS" [Prior Art] Certain monoesters and diesters of polytrimethylene ether glycol ("P03G ester") have certain properties It is suitable for use in a variety of fields, including the use as a lubricant, as disclosed in commonly-owned U.S. Patent Application Serial No. 1 1/593,954, the entire disclosure of which is incorporated herein by reference. This invention relates to specific lubricant compositions based on combinations of such P03G esters with vegetable oil lubricants. SUMMARY OF THE INVENTION In one embodiment, the present invention relates to one or more P03G esters and one or 134069.doc 200914604 various vegetable oil base lubricants, as appropriate, and one or more polytrimethylene ether glycols (&quot ; P03G") 盥 亦 玄 、 、 表 表 表 表 表 表 表 表 表 表 混合物 混合物 混合物 混合物 混合物 混合物 混合物 混合物Therefore, the present invention comprises a lubricating oil composition comprising a base fluid raw material comprising: + from (3) P〇3Gδθ fluid (a polytrimethylene which is fluid at ambient temperature) - # & mercapto ether-fermented ester); and (U) vegetable oil basic lubricant. When P03GS (and P03G (when used)) is based on biologically produced, 3-propanol, it provides a lubricant with extremely high reproducible content.

combination. [Embodiment] All technical and scientific terms used herein have the same meaning as commonly understood by those 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. Trademarks are shown in capital letters unless explicitly stated otherwise. All percentages, parts, ratios, etc., are by weight unless otherwise indicated. 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 disclose 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, a range of values is intended to include the 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 specific value of the 134069.doc 200914604. The use of the term "about" when describing the value or endpoint of a range is intended to include the particular value or endpoint referred to. The term "include", "","&" or any other variation thereof as used herein is intended to cover a non-exclusive include. For example, processes, methods, articles, or devices that comprise a list of components are not necessarily limited to the elements, but may include other components or methods, methods,

An element inherent in an article or device. In addition, unless expressly stated to the contrary, "or" is meant to be inclusive or non-exclusive. For example, any one of the items - the eight or two conditions: A is true (or exists) and 8 is false (or non-existent); A is false (or non-existent) and 8 is true (or The existence of "and A and B are true (or present). The elements and components used to describe the invention are used. This is for convenience only and gives the general meaning of the invention unless clearly meant otherwise. The description is to be understood as being inclusive or inclusive, and the singular Methods and materials equivalent to those of the methods and materials described herein can be used in the practice or testing of the present invention 'but suitable methods and materials are described herein. Base fluid materials:: indicated as 'lubricating oils for use in the present invention The base flow package of the composition is at ambient temperature (25. 〇 is the fluid p〇3Gg and the vegetable oil is basically I month. The base fluid raw material may also contain preferably at ambient temperature (2 is called I34069.doc 200914604 fluid) P03 G and / or other synthetic fluids Slip agents. The vegetable oil base lubricants suitable for use in the present invention are generally derived from plants and usually consist of triglycerides. In general, these are liquid at room temperature. Although many different parts of the plant produce oil, In practice, oil is typically extracted primarily from the seeds of oilseed plants, including edible and inedible oils, and includes, for example, high oleic sunflower oil, rapeseed oil, soybean oil, castor oil, and the like. And modified oils such as US65833〇2 (fatty acid vinegar) and I. Malchev ' "Piant_0il_Based Lubricants" (purchased from

Department of Plant Agriculture - Ontario Agriculture College > University of Guelph ^ 50 Stone Road W.. Guelph, Ontario, Canada NIG 2W1). Synthetic fluid auxiliary lubricants (except P03G and P03G esters) include lubricating oils such as hydrocarbon oils such as polybutene, polypropylene, propylene-isobutylene copolymers; polyoxyalkylene glycol polymers (except P〇3G) And other derivatives thereof, such as copolymers of ethylene oxide and propylene oxide; and esters of ditinoic acid with various alcohols, such as dibutyl adipate, di(2-ethylhexyl) sebacate, anti Dihexyl succinate, dioctyl sebacate, diisooctyl sebacate, diisononyl sebacate, dioctyl phthalate, dinonyl phthalate and linseed oil Acid dimer 2-ethylhexamethylene diacetate. In one embodiment, the binder comprises a plurality of P03G esters (or a mixture with p〇3G) (greater than 50% by weight 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 feedstock. /. Or 66 weight 〇 / 〇 above or about 75 weight. /. Or more than 75% by weight, or about 9% by weight or more, or about 95% by weight or more by weight of p〇3g ester 134069.doc 200914604 (or mixture). In another embodiment, the base comprises a substantial amount of vegetable oil base lubricant (greater than 50% by weight based on the weight of the base). In some embodiments, the binder may comprise from about 66% by weight or more by weight, or from about 75 weight percent, based on the total weight of the base fluid feedstock. / 〇 or more than 75% by weight, or about 9% by weight or more than 90% by weight, or about 95% by weight or more by weight of the vegetable oil base lubricant. In one embodiment, the weight ratio of the P03G/P03G ester in the base fluid feedstock is greater than 1:1 (P03G is the major component), or about 15:1 or 15:1 or greater, or about 2:1 or 2:1 or more, or about 5 ·· 1 or 5:1 or more, or about 20:1 or 20:1 or more. Further, the weight ratio is preferably about 25:1 or less than 25:1, or about 20:1 or less than 20:1 or about ι:ι or ι〇:ι or less. In another embodiment, the weight ratio of P03G ester/P03G in the base fluid feedstock is greater than 1:1 (P〇3G ester is the major component), or about 1.5:1 or 1.5:1 or more 'or about 2: 1 or 2:1 or more 'or about 5:1 or 5:1 or more, or about 20:1 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 1 〇:1 or less. In another embodiment, the weight ratio of P03G/P03G ester to the base fluid feedstock is about 1:1 (the weight of the two components is about equal). The lubricating oil composition preferably comprises a base oil feedstock in an amount of about 50% by weight or more by weight based on the total weight of the lubricating oil composition. In various embodiments, the lubricating oil can comprise about 75% by weight or 75% by weight based on the total weight of the lubricating oil composition. Above, or about 9 〇 weight y. Or a binder in an amount of 9% by weight or more, or about 95% by weight or more. 134069.doc 200914604 Monoesters and diesters of polytrimethylene ether glycols In some embodiments, the P03G ester comprises one or more compounds of formula (I):

II

Ri-C—Ο—Q—Ο—R 2 (丨), where Q represents the residue of the polytrimethylene ether glycol after removal of the hydroxyl group, R 2 is Η or R 3 CO, and each of 1 及 and 尺 3 Individually substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic or cycloaliphatic organic having 4 to 40 carbon atoms, preferably at least 6 carbon atoms, more preferably at least 8 carbon atoms Group. In some embodiments, each of I and R3 has 20 or fewer carbon atoms, and in some embodiments has 10 or fewer carbon atoms. In some preferred embodiments, each of Ri and R3 has 8 carbon atoms. The P03G ester is preferably formed by polycondensation of a hydroxyl group-containing monomer (a monomer having 2 or more hydroxyl groups) mainly comprising 1,3-propanediol to form P03G (as disclosed in further detail below), followed by a monocarboxylic acid. The acid (or equivalent) is esterified to be prepared as disclosed in U.S. Patent Application Serial No. 1 1/593,954, the entire disclosure of which is incorporated herein by reference. The ester preferably comprises from about 50% to 100% by weight, more preferably from about 75% to 100% by weight of the diester and from 0 to about 50% by weight, more preferably from 0 to about 25% by weight, based on the total weight of the ester. Preferably, the monoesters and diesters are esters of 2-ethylhexanoic acid. The P〇3G used to prepare the ester does not require a P03G co-component with the base fluid feedstock 134069.doc -10 - 200914604 The same. Polytrimethylene ether glycol (P〇3G) For the purposes of the present invention, P03G is an oligomeric or polymeric ether diol wherein at least 50% of the repeating units are trimethylene ether units. More preferably , about 75% to 100%, more preferably about 90% to 1%, and even more preferably about 99% to 100% of the repeating early is the Sanya sulfhydryl Preferably, P03G is prepared by polycondensing a monomer comprising ruthenium, 3-propylene glycol, preferably in the presence of an acidic catalyst, thereby producing a polymerization comprising a _(CH2CH2CH20)- linkage (eg, a trimethylene ether repeating unit). Or a copolymer. As indicated above, 'at least 50% of the repeating units are trisinodecyl 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 Approximately 10 ppm of sulfur. In addition to the diazide unit, there may be minor amounts of other units, such as other polyalkylene ether repeating units. In the context of this disclosure, the term M polytrimethylene ether Glycol " covers P03G prepared from substantially pure 1,3-propanediol and their oligomers and polymers containing up to about 50% by weight of comonomer (including those below). The 1,3-propanediol of P03G can be obtained by any of various well-known chemical routes or by a biochemical conversion route. Preferred routes are, for example, US 5015789 ' US 5276201, US 5284979, US 5334778, US 5364984, US 5364987, US 56333 62, US 5,686,276, US 5,821,092, US 5,962,745, US 6,140,543, US 623,251 1, US 6,235,948, US 6,277,289, US 6,297,408, US 6,331,264, US 6,342,646, US 70,380, 922, US 70, 843 411, US 7098368, 134069.doc 200914604 US 7009082 and US Said in 20050069997A1. Preferably, '3,3-propanediol is obtained by biochemical method from a renewable source ("Bipropanediol obtained by biological method". A particularly preferred source of 1,3-propanediol is via a fermentation process. Regenerating biological sources. As an illustrative example of a starting material from a renewable source, the biochemical pathway of 1,3-propanediol (PDO) has been described, which is utilized by biology and

Raw materials derived from renewable resources (such as corn raw materials). For example, Klebsiella (C. sphaeroides) is found to be able to convert glycerol to 1 in CVw's heart and Lactobacillus (1). , a strain of 3-propanediol. The technique is disclosed in several publications, including us 5633362, us 5686276, and US 5821092. US 5821〇92 discloses a biologically produced H-propylene glycol from glycerol using recombinant organisms. The process consists of E. coli dW transformed with a heterologous pdu diol dehydratase gene specific for 1,2 propanol. The transformed E. coli is grown in the presence of glycerol as a carbon source and The growth medium separates hydrazine, 3-propanediol. Since both bacteria and yeast can convert glucose (such as corn sugar) or other carbohydrates to glycerol, the processes disclosed in the publications provide I,3-propanediol monomer. A source that is fast, inexpensive, and environmentally expensive. = The u_propanediol obtained by biological methods, such as those produced by the above-mentioned formula, contains the raw materials from the composition used to produce propylene glycol. The plant has the same effect. In this way, it is preferably applied to the present invention, and the biologically obtained 1,3-propanediol is only available in the form of a scorpion. Regeneration of carbon, while fossilized stone or petroleum-based carbon. Therefore, using 134069.doc 200914604 biologically obtained 1,3-propanediol P03G and vinegar based on it have less impact on the ring & The hydrazine used in the composition, 3-propanediol does not consume the decreasing fossil fuel, and releases the carbon back to the atmosphere after degradation to be used again for the plant. Thus, the compositions of the present invention can be characterized as containing petroleum-based A similar composition of the second fermentation is relatively natural and has less environmental impact.

The biologically obtained 1,3-propanediol, P03G and P03G esters can be distinguished from similar compounds produced from petrochemical or fossil fuel carbon by dual carbon isotope fingerprinting. The method effectively distinguishes between chemically identical substances' and resolves the carbon in the copolymer based on the source of growth (and possibly age) of the biosphere (plant) component. The isotopes mc and nc provide additional information for this problem. Radiocarbon dating (i4c) with a nuclear half-life of 5730 clearly allows for the analysis of specimen carbon between fossil ("dead") and biosphere ("live") materials (Currie, LA "Source Apportionment of Atmospheric Particles , "Characterization of EnvironmentaJ Particles, J, Buffle and HP van Leeuwen Editor, 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 14C 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, 573 0 is the half-life of radiocarbon, and Eight and Aq are specific 14C activities of samples and modern standards (Hsieh, Y., Soil Sci. 134069.doc 13 200914604

Soc. Am J., 56, 460, (1992)). However, due to atmospheric nuclear testing since 195 及 and fossil fuel combustion since 850, 14匸 obtained the second geochemical time characteristic. 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 about 1.2x1 (T12 steady-state (atmospheric) baseline isotope ratio (14C/12C), where the relaxation half-life is 7-10 years. The half-life cannot be understood literally; instead, the detailed atmospheric nuclear input/decay function must be used to track changes in the atmosphere and biosphere i4c 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. The results can be measured by accelerator mass spectrometry (AMS), and the results are given in , , , , , , , , , , , , , , , , fM is based on the National Institute of Standards and Technology (NIST) Standard Reference Materials (Standard Reference Materia SRM) 499〇B and 4990C (referred to as oxalic acid standards 1€(^1 and 11(^ respectively) 11) Definition. The basic definition refers to the 14C/12C isotope ratio of 0.95 by ( (refer to ad i95〇p which is roughly equal to the decay-corrected industrial revolutionary wood. For the current living biosphere (plant matter), fM = 1.1. The stable carbon isotope ratio (13C/12C) provides a complementary source of source identification and analysis. The meaning of the given biosourced material is the result of the 13c/12c ratio of atmospheric carbon dioxide in fixed carbon dioxide, and also reflects the accuracy. There are also regional changes in the metabolic path. Petroleum* plants (broadleaf trees), t plants (grass) and marine carbonates all show significant differences in 13C/12C and corresponding values. In addition, the lipid substances of q and a plants The results of the analysis differed from those derived from the carbohydrate components of the same plant due to the generation of 134069.doc •14·200914604. In the range of measurement accuracy, i3c The positional fractionation effect shows a large change. For the present invention, the most significant of the isotope fractionation effects is the photosynthetic mechanism. The main reason for the difference in carbon isotope ratio in plants is the photosynthetic carbon metabolic pathway in plants, especially primary carboxylation (also That is, the difference in the reactions that occur during the initial atmospheric fixation is closely related. The two major classes of plants are those with the C3" (or the Cavin-Bens〇n) photosynthetic cycle and both "C4" (or Hatch-Slack) Photosynthetic cycle. C3 plants (such as broad-leaved trees and conifers) are mainly in temperate climate zones. In a plant, 'primary c〇2 immobilization or carboxylation involves enzymes Nuclear network sugar-1,5-bisphosphate carboxylase, and the first stable product is a 3-carbon compound. On the other hand, 'C4 plants include plants such as tropical grass, corn and sugar cane. In q plants, 'is another Another carboxylation reaction of the enzyme phosphoenol-pyruvate carboxylase is a primary carboxylation reaction. The first stable carbon compound is 4-carbonic acid, followed by decarboxylation of 4-hydrogen acid. thus C〇2 is re-fixed by C3 cycle. Both C4 and C3 plants exhibit a range of "c/12c isotope ratios, but typical values are per mil (C0 about -10 to -14 and per mil (c3) )_21 to _26 (Weber et al., J. Agric. Food Chem., 45, 2942 (1997)). Coal and oil are usually within the scope of this latter. The 13C measurement scale was originally defined by the zero set by the pee dee belemnite (PDB) limestone, and its value is given in parts per thousand deviations from the substance. The "§13c" value is in parts per thousand (mils per mil) (abbreviation %) and is calculated as follows: 134069.doc 15 200914604 χίοοο% 13 (13c/12c) sample-(13c/12c) standard The δ Cs (13c/12c) standard has been developed in collaboration with IAEA, USGS, NIST and other selected international isotope laboratories to develop a range of alternative RMs due to the depletion of the PDB reference material (RM). The expression is δ13 (:.) The C〇2 is measured by high-precision stable ratio mass spectrometry (IRMS) for molecular ions of masses 44, 45 and 46. Therefore, it is obtained by biological methods. The 1,3-propanediol 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 double carbon isotope fingerprints, thereby indicating the new composition of the substance. The ability of such products is beneficial for the commercial tracking of such substances. For example, products containing "new" and "old" carbon isotope profiles can be distinguished from products made only from 'old' materials. Therefore, the substance of the present invention can be used in business Based on its unique profile and tracked for the purpose of confirming competitiveness, determining the shelf life and especially for assessing environmental impacts. Preferably, the 1,3-propanediol used as a reactant or as a component of the reactants is borrowed. The purity should be greater than about 99% by weight and more preferably greater than about 99.9% by weight as determined by gas chromatography analysis. Particularly preferred are purified as disclosed in US Pat. No. 7,703,092, US Pat. No. 7,098, 368, US Pat. 3-propanediol and P03G prepared therefrom as disclosed in US 20050020805 A1. Purified 1,3-propanediol preferably has the following characteristics: (1) UV absorption at 220 nm is less than about 0.200, and at 250 nm The UV absorption is less than about 0.075, and the UV absorption at 275 nm is 134069.doc •16-200914604 is less than about 0.075; and/or (2) L*a*b*"b*” is less than about 〇.i5 (ASTM D6290) and having an absorbance at 270 nm of less than about 0.075; and/or (3) a peroxide composition of less than about 1 〇 ppm; and/or (4) as measured by gas chromatography 'less than about 4 〇〇 ppm, more preferably less than • about 300 ppm and more preferably less than about 150 ppm The concentration of total organic impurities (organic compounds other than 1,3-propanediol). The starting materials used to prepare P〇3G will depend on the desired p〇3G, starting material availability, catalyst, equipment, etc. And contains "1,3-propanediol reactants." "1,3-propanediol reactant" means i-, 3-propanediol, and oligomers and prepolymers of preferred 1,3-propanediol having a degree of polymerization of from 2 to 9, and mixtures thereof. In some cases, it may be desirable to use up to 1% or more than 5% by weight of the low molecular weight polymer (where available). Accordingly, preferably, the starting material comprises 1,3 -propanediol and its dimers and trimers. More preferably, the starting material contains about 9% by weight or more than 9% by weight of the 1,3-propanediol reactant and more preferably 99% by weight or 99% by weight or more. , 3-propanediol. P03G can be prepared by a variety of processes known in the art, such as those disclosed in U.S. Patent No. 6,977,291 and U.S. Patent No. 6,720,459. The preferred process is described in U.S. Patent No. 7,074,969, U.S. Patent No. 7,157,607, U.S. Pat. As indicated above, in addition to the trimethylene ether unit, P〇3G may contain less than one other polyalkylene ether repeating unit. Thus, the monomer used to prepare the polytrimethylene diol may contain up to 5 134 134069.doc -17- 200914604 heavy oxime in addition to the 1,3-propanediol reactant. (preferably about 20% by weight or less, preferably 2% by weight or less, more preferably about 1% by weight or less, and more preferably about 2% by weight or less, based on the p-comonomer polyol. Comonomer polyols include aliphatic: alcohols such as ethylene glycol, hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, hydrazine, 10· Decylene glycol, 1,12-dodecanediol, ^3,4,4,5,5-^. 252,3,3,454,5,5-, va-l,6-e, diol and 3 ,3,4,4,5,5,6,6,7,7,8,8 9,9,1〇,1〇_六敦112_12

Alkane: alcohol; m aliphatic diol, such as U4, hexanediol, (tetra) hexane dimethanol and isosorbide; "hydroxyl compounds, such as glycerol, trimethylol, and "pentaerythritol." comonomer II A preferred group of alcohols is selected from the group consisting of 'ethylene glycol, 2-methyl decanediol, 2-dimethyl _, alcohol 2,2-ethylidene, 3_ Propylene glycol, 2-ethyl-2 (hydroxymethyl R3-propanediol, C6_CiQ diol (such as ^-hexanediol, octyl diol and U 〇-nonanediol) and isosorbide and mixtures thereof. , 3-propanediol is particularly preferred - the alcohol is ethylene glycol, and the C6_Ci decanediol may also be especially. A preferred p〇3G containing a comonomer is poly(trimethylene-extension) a diol, such as described in (iv) 00 Side View A. Preferably, the poly(tris-ethylidene) diol is acid-catalyzed by 5 〇 mol% to about mol% (preferably about 6 〇 mol% to about 98 mol%, and more preferably (four) mol% to about 98 mol%) 1,3_prop: alcohol and at most chicken ears to about 1 mol _ good for (four) moor % to about 2 mol%, and more preferably about 3Q mol% to about #耳%) ethylene glycol Polycondensation is used to prepare. Preferably, the p〇3G after purification is substantially free of acidic catalyst end groups, 134069.doc -18·200914604 but may contain a very low content in the range of from about 0.003 to about 0.03 meq/g. Saturated end groups, mainly allyl end groups. It is believed that such P03G comprises (having essentially consist of) compounds having the following formulae (II) and (III): HO-((CH2)30)m_H ( II) HO-((CH2)3-0)mCH2CH=CH2 (III), wherein m is within a range such that Μη (number average molecular weight) is in the range of from about 200 to about 10,000, wherein formula (III) The compound is present in an amount such that the allyl end group (preferably all unsaturated ends or end groups) is present in an amount ranging from about 0.003 to about 0.03 () meq/g. Preferred P03G suitable for use in the present invention has at least Preferably, at least about 500, more preferably at least about 500 and more preferably at least about 1000 (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 2500. P03G blending may also be used. For example, P03G may comprise a blend of higher and lower molecular weight P〇3G, preferably wherein the higher score The amount of P03G has a number average molecular weight of from about 1 Torr to about 5,000, and the lower molecular weight P 〇 3G has a number average molecular weight of from about 200 to about 950. The Μ 掺 掺 G G G G G G G G 较佳 较佳 较佳Preferably, the P03G used herein is generally polydisperse having a polydispersity of preferably from about 1.0 to about 2.2, more preferably from about 1.2 to about 2.2, and still more preferably from about 1.5 to about 2.1 (ie, Mw/Mn). Polydispersity can be adjusted by using a blend of P〇3G. P〇3G suitable for use in the present invention preferably has a color value of less than about 1 〇〇 APHA and more preferably less than about 50 APHA. The viscosity of p〇3G is preferably greater than the viscosity of P〇3G ester. At 40 ° C, the preferred viscosity is about 10 〇 (^ or 10 〇 cS or more. 134069.doc • 19· 200914604 Acid and equivalent Sa is formed by acid and / or equivalent (preferably The reaction of the monocarboxylic acid and/or the equivalent) is carried out. The early acid equivalent "quote" means a compound which is substantially mono-acid-like when reacted with a polymeric diol, as is generally familiar with For the purposes of the present invention, the mono-inferior acid equivalents include, for example, mono-acidified vinegar and brewed derivatives, such as acid complexes (e.g., acid chloride anhydride. Preferably, the use has a monobasic acid of the formula R_CO〇H, wherein r is a substituted or unsubstituted group, a lipid organic moiety containing 6 to 4 carbon atoms, a mixture of different monocarboxylic acids and/or equivalents. Suitably, as indicated above, the monocarboxylic acid (or equivalent) may be an aromatic, aliphatic or cyclic steroid. In this regard, the aromatic "mono-acid is a hindrance in the thiol and benzene ring systems Single-repulsive acid that is connected to a wide range of days, such as the following monoterpene acids. "Alipo" is a single group of acids that are attached to a fully saturated carbon atom or a portion of the diatomic linkage of the acid. If the carbon atom is in the ring, then the aliphatic ". The horse per monocarboxylic acid (or equivalent) may contain any substituent or combination thereof (such as guanamine, amine) , a carbonyl group, a hydroxyl group, a hydroxyl group, etc.) as long as the substituents do not interfere with the esterification reaction or do not adversely affect the properties of the donor product. The monocarboxylic acid and the equivalent may be derived from Any source, but dry and live from the source of Tianzhu or biological sources. ..., to 134069.doc •20· 200914604 The following acids and their derivatives are particularly preferred: lauric acid, myristic acid, picking acid, hard Fatty acid, arachidic acid, benzoic acid, octanoic acid, sinapic acid, palm oil such as ·, fifteen-burning acid, heptadecanoic acid, nineteen acid, linoleic acid, arachidonic acid, oleic acid, valeric acid, Acid, citric 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. Equivalent ester, from about loot to about 275t, preferably about 125^

P03G is contacted with a monocarboxylic acid at a temperature in the range of about 250 ° C, preferably in the presence of an inert gas. The process can be carried out under atmospheric pressure or under vacuum. Water is formed during the contacting and it can be removed in an inert gas stream or under vacuum to drive the reaction to completion. In order to promote the reaction between P03G and (iv), a acetification catalyst is usually used, and a mineral acid catalyst is preferred. Examples of inorganic acid catalysts include, but are not limited to, sulfuric acid, hydrochloric acid, phosphoric acid, hydroiodic acid, and heterogeneous catalysts such as zeolites, heteropolyacids, macroporous resins, and ion exchange resins. Preferably, the self-catalyzed acid catalyst is selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid and hydroiodic acid. A particularly preferred inorganic acid catalyst is sulfuric acid. The weight % used is preferably from about 〇_〇1% by weight to about 1% to about 5% by weight, and more catalyst may be the reaction mixture, preferably the reaction mixture. 1 weight 0.2% by weight to About 2% by weight. A ratio of a carboxylic acid or a derivative thereof to a diol hydroxyl group can be used. The preferred ratio of the acid disk base is from about 3:1 to about 1:2, wherein the ratio of 屮皇', m, and 甲 can be adjusted to change the ratio of the saponin to the diester. In general, horses favor diester production 134069.doc •21 _ 200914604 students' use ratios slightly larger than 1:1. To facilitate monoester production, a ratio of acid to hydroxyl of 0.5:1 or less than 0.5:1 is used. A preferred method of esterification comprises polycondensing a propylene glycol reactant into a polytrimethylene ether glycol using a mineral acid catalyst. Then, a carboxylic acid is added and esterified without isolating and purifying P03G. In this process, the etherification or polycondensation of the hydrazine, 3 - propylene glycol reactant to form a polytrimethylene ether glycol is carried out using an acid catalyst as disclosed in U.S. Patent No. 6,977,291 and U.S. Patent No. 6,720,459. The etherification reaction can also be carried out using a polycondensation catalyst containing an acid and a base as described in JP 2004-182974A. The polycondensation or etherification reaction is continued until the desired molecule I' is reached and then a calculated amount of the mono-acid is added to the reaction mixture. Continue to react' while removing water by-products. At this stage, the esterification and etherification reactions can be carried out on the same day. Therefore, in the preferred esterification process, an acid catalyst for polycondensing the diol is also used for esterification. If necessary, additional esterification catalysts may be added during the esterification stage. The viscosity (molecular weight) of the resulting product in this procedure is controlled by the time of addition of the carboxylic acid. In an alternative procedure, the esterification reaction can be carried out on purified p〇3G by addition of a S-catalyst and a carboxylic acid, followed by heating and removal of water. The viscosity of the resulting product in this procedure is primarily a function of the molecular weight of P〇3G used. Regardless of the procedure followed by the ® 1 procedure, any field product is removed after the esterification step, and then the remaining catalyst residue of the polycondensation and/or esterification reaction is removed to obtain stability (especially at elevated temperatures) The ester product. This can be achieved by hydrolyzing the crude ester product via water treatment at about 80 c to about 1 ° C. 134069.doc • 22- 200914604 is sufficient for the residual acid to be aged without significantly affecting the carboxylate. to realise. Required: η* ^ 源 from the catalyst can vary from about 1 hour to about 8 hours. If the hydrolysis is carried out under pressure, ^ ^ is J. This is the temperature and the corresponding shorter time. In this regard, t „ Η 1 depends on the product, the product may contain a combination of two, early S or diester and monoester, 々 夂 夂 置 acid catalyst, unreacted lean acid and diol. The hydrolyzed polycondensate is further purified by known conventional techniques (such as water washing, alkali neutralization, filtration, and/or kiln & mountain), to remove water, acid catalyst And unreacted carboxylic acid. Not > The diol and acid catalyst of the bismuth can be removed, for example, by washing the strip with deionized water. Alternatively, for example, by deionized water or aqueous solution. Washing (4) removing the unreacted slow acid by vacuum stripping. The following steps are followed by _ or multiple water washing steps to remove the acid catalyst, and drying (preferably under vacuum) to obtain the (4) product. Any unreacted mono-acid used to remove unreacted alcohol may also be removed in a water wash, but may also be removed by washing with an aqueous base or by vacuum stripping. Production 16 can be further separated by splitting under reduced pressure to separate low molecular weight esters. Proton NMR and wavelength 乂 ray ray can be used. Spectroscopic methods to identify and quantify any residual catalyst (such as sulfur) present in the polymer. Protons can, for example, identify the sulfate groups present in the polymer chain, and wavelength X-ray fluorescence can be used. The total sulfur (inorganic and organic sulfur) present in the polymer is determined. The vinegar prepared by the above process is substantially free of sulfur and is therefore suitable for high temperature applications. Preferably, the p〇3G ester after purification is substantially non-acidic. The catalyst end group 'but may contain a very low content of from about 〇〇〇3 to about me03 meq/g. 134069.doc -23- 200914604 of the unsaturated end group 'mainly allyl end group. It can be considered P〇3G g| comprises (or consists essentially of) compounds having the following formulae (IV) and (V):

Ri-C(0)-0-((CH2)30)m-R2 (IV)

Ri-C(0)-0-((CH2)3-〇)mCH2CH=CH2 (V), where R2 is Η or RsCCO); each of 1^ and 尺3 alone contains 6 to 40 a substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic or cycloaliphatic organic group of carbon atoms; the claws are within a range such that Mn is in the range of from about 200 to about 3,000; The compound is present in an amount such that the dilute propyl end group (preferably all unsaturated ends or end groups) is present in an amount ranging from about 〇〇〇3 to about 0.03 meq/g. Preferably, the P03G ester has a viscosity that is less than the viscosity of P〇3G (if used). The preferred viscosity of P03G is from about 2 〇 cS to about 〇5 〇 β at 4 〇〇 c and more preferably about 100 or less 〇〇 cS. Based on the above preferences for P03G itself, other preferred properties of the p〇3G ester can be determined. For example, the preferred molecular weight and polydispersity are based on the preferred molecular weight and polydispersity of the known P03 G component. Additives The synthetic lubricating oil compositions of the present invention comprise a fastener of a binder and one or more additives, wherein each additive is used in an application to improve the binder (eg, as a hydraulic fluid, gear oil, brake fluid, compressor lubrication) It is used for the purpose of the performance and characteristics of the agent, the spinning Q port and the calender lubricant, the metal working fluid, the cold, the East lubricant, the two-stroke engine, and/or the crankcase lubricant. 134069.doc •24· 200914604; Ice additives can usually be added in amounts determined by the skilled artisan based on the type of additive and the desired level of additive effect.

II 'Additives can be miscible in one of P03G and P03G esters or both 〇 - 0Λ. -7* — 丄上έ 'This means that the additive used when it is miscible in the diol will be It is miscible to some extent and will be at least to some extent miscible in oil when it is miscible in the ester. Preferably, the lubricating oil additive comprises at least one of the following: ashless knives, metal cleaners, viscosity modifiers, antiwear agents, antioxidants, friction modifiers, pour point depressants, defoaming Agents, corrosion inhibitors, deemulsifiers, anti-caries agents and mixtures thereof. 1 When the lubricating oil composition is used as a freezing lubricant, the lubricating oil additive is preferably at least one of the following: extreme pressure and anti-wear additives, oxidation and thermal stability improver, rot #inhibitor, viscosity index improvement Agents, pour point depressants, flocculation point depressants, detergents, defoamers, viscosity modifiers, and mixtures thereof. The use of any one or more of the specified additives, either alone or in combination with one or more of the remaining specified additives, is intended to be within the scope of the invention. It is also within the scope of the invention to use one or more of any of the specified additives (e.g., one or more friction modifiers), either alone or in combination with - or a plurality of other specified additives (e.g., in combination with - or a plurality of narcotics). Individual additives can be incorporated into the binder in any convenient manner. Thus, each of these components can be added to the binder directly by dispersing or dissolving it in the binder at the desired concentration level. The blending can be carried out at ambient temperature or at ambient temperature. 134069.doc -25- 200914604 or all or some of these additives may be blended into a concentrate or additive additive package and 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 backbone having functional groups capable of binding to the particles to be dispersed. Typically the dispersant comprises an amine, alcohol, guanamine and/or ester polar moiety which is typically attached to the polymer backbone via a bridging group. 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, esters, amino esters, decylamines, retannings, and hydrazines, long-chain hydrocarbons. a thiorexic acid ester derivative, a long-chain aliphatic hydrocarbon directly linked thereto, and a Mannich condensation product formed by condensation of a long-chain substituted phenol with formaldehyde and a polyalkylene polyamine. 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 alpha-olefins, polydecyl acrylates, polyalkyl methacrylates, mercapto acrylate copolymers, unsaturated dicarboxylic acids and Copolymer of vinyl compound, interpolymer of styrene and acrylate, and partial hydrogenation copolymerization of styrene/isoprene, styrene/butadiene and isoprene/butene And a partially hydrogenated homopolymer of dibutyl and isoprene and isoprene/divinylbenzene. Metal- or ash-forming detergents act as both cleaners to reduce or remove deposits. 134069.doc •26- 200914604 also acts as an acid neutralizer or anti-recording agent, thereby reducing wear and decay. • Long 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 of from about 8 Torr as measured by ASTM D-2896. Value (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 yfj-inspective cleaner comprises a neutralized detergent as a metallocene (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, phenolates, sulfonated salts, thiophosphonates, salicylates and naphthenates, and other oil-soluble metals (especially metals or alkaline earth metals) For example, sodium, potassium, bell, mom and magnesium) tartrate. 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 highly detectable TBN (/δ黄酸妈' and TBN from about 50 to about 45 0 neutral and overbased phenol calcium and benzene sulfide Salts are used. • Metal salts of dihydrocarbyl dithiophosphates are commonly used as antiwear agents and antioxidants. - Metals can be metal or alkaline earth metals, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. The salt is most commonly used in lubricating oils in an amount of from about 〇·i by weight, based on the total weight of the lubricating oil composition, to about 1% by weight, preferably from about 0.2% by weight to about 2% by weight. The dihydrocarbyl dithiophosphoric acid (DDPA) can be first formed by reacting one or more alcohols or phenols with P2Ss, and 134069.doc •27·200914604, followed by neutralization with zinc compounds, according to known techniques. For example, the first generation phosphonium can be prepared by reacting a mixture of a first alcohol and a second alcohol, or 'a plurality of dithio acid can be prepared, and the nicotine in the middle is It is completely second in nature and the hydrocarbon group on the other is completely in nature. Grade: For the preparation of zinc salt, any can be used. Authentic or neutral zinc compounds, but most commonly oxides, hydroxides and carbonates. Commercial additives usually 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 the oxidation inhibitor or the antioxidant to reduce the tendency of the binder to deteriorate during use, such as by oxidation of the product (such as on a metal surface) Slag and varnish-like deposits) and as evidenced by increased viscosity. The oxidation inhibitors include an alkaline earth metal sulfonated calcium sulphate, an ashless oil-soluble phenolate, a sulphurized phenolate, a phosphorus sulphide or a sulphide sulphate, preferably a hindered phenol preferably having an alkyl phenol thioester of a CS to C12 alkyl side chain. Phosphate esters, 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 adducts or reactions with boron compounds such as boron oxide, functional boron, metaborate, boric acid or monoalkyl borate, dialkyl borate or trialkyl borate. The product form is used. Other friction modifiers are known. Among these are esters formed by reacting a carboxylic acid and an acid anhydride with an alkanol. Other conventional friction modifiers typically consist of a polar end group (e.g., a carboxyl group or a hydroxyl group) covalently bonded to a lipophilic double bond. Esters of carboxylic acids and anhydrides with alkanols are described in 134,069.doc -28-200914604 US 4,702,850. Another example of a conventional friction modifier is organometallic molybdenum. Illustrative rust inhibitors are selected from the group consisting of nonionic polyoxyalkylene alkyl 7G alcohols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids. Corrosion inhibitors containing copper and lead can also be used. Usually, the compounds are thiadiazole polysulfides having 5 to 50 carbon atoms, derivatives thereof and polymers thereof. Other additives are thiadiazole thiosulfinamide and polythiosulfin

Indoleamines such as those described in UK 1560830. Benzotriazole derivatives = also belong to such additives. An illustrative example of one of the emulsification components is as described in Ep_A_〇33〇522. This is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bisepoxide with a poly S alcohol. Pour point depressants (or lubricant modifiers) reduce the minimum temperature at which a fluid can flow or can be dumped. These additives are well known to us. Typical additives for improving the low temperature fluidity of fluids are: (8 and cls dialkyl fumarate / vinyl acetate copolymer, polyalkyl methacrylate: and the like. In view of the lubrication of the present invention The low pour point of the oil composition, there is a lubricating oil composition that can be formulated without a pour point depressant. However, there may be a Greek; further reduction of the application of the lower pour point. The bead control is comprised of a polylithic eve. A plurality of compounds of an oxy-squeeze type antifoaming agent (for example, Shihe methyl oxane) are provided. Thus, for example, a single addition of the method is well known to the human body and some of the above additives may provide various effect additives to act as Dispersant-oxidation inhibitor. No further details are required. 134069.doc -29- 200914604 Illustrative, non-limiting examples of additives specifically for use in compression refrigeration systems are as follows. Illustrative extreme pressure and antiwear additives include phosphates, phosphoric acid Ester (diphenyl phenyl phosphate), phosphite, thiophosphate (zinc dithiophosphate) gasification wax, sulfurized fat and olefin, organic lead compound, fatty acid 'molybdenum complex, Substituted organic antimony compound, borate, organic ester, functional compound substituted with a functional element, sulfurized Diels Alder adduct, organic sulfide, compound containing chlorine and sulfur, metal salt of organic acid. Illustrative oxidation and thermal stability The improver includes sterically hindered phenol (BHT), aromatic amine, dithiophosphate, phosphite, sulfide and metal salt of dithio acid. Illustrative corrosion inhibitors include organic acids, organic amines, organic Filler, organic alcohol, metal sulfonate and organic phosphite. Viscosity index is a measure of viscosity as a function of temperature, and high values indicate that the viscosity changes minimally with temperature. In view of the high viscosity index of the lubricating oil composition of the present invention It is possible to formulate a lubricating oil composition without a viscosity index improver. However, there may be applications for further improvement of the viscosity index. The illustrative viscosity index improvers include polyisobutylene, polymethacrylic acid, and polyphenylene. Ethylene. Descriptive pour point and / or flocculation point reducing agent includes polymethyl acrylate vinegar ethylene oxime ethylene copolymer, amber 5 leucine - dilute smoke copolymer Ethylene _ "_ dilute olefin copolymer and (iv) naphthalene cut the Friedel Crafts condensation _ g (Μ #

Crafts condensation) product. Illustrative detergents include aromatic sulfonated sulfonic acid-only salts substituted with long-chain alkyl groups 134069.doc -30- 200914604 Acids, phosphonates, thiophosphonates, phenates, metal salts of alkylphenols, hospitals a base sulfide, an alkylphenol-aldehyde condensation product, a metal salt of a substituted salicylate, an N-substituted oligomer or polymer from a reaction product of an unsaturated acid needle and an amine, and a polyester bond a copolymer such as a vinyl acetate-cis succinic anhydride copolymer. An illustrative antifoaming agent is a siloxane polymer. Illustrative viscosity modifiers include polyisobutylene, polymethacrylate, polyalkylene styrene, ring burn oil, alkyl benzene oil, eucalyptus oil, polyester, polyvinyl chloride, and polyphosphate. In the present invention, the lubricating oil additive should be at least partially (greater than about 5% by weight) miscible in the base. In general, this means that the additives used are at least to some extent, and are preferably soluble in esters and vegetable oils to a large extent. 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 less than the total weight of the lubricating oil composition.

The following amounts of additives. Instance

The ASTM method was used to determine the number average molecular weight (Mn). D445-83 and ASTM Method D792-91 to measure 134069.doc *31 - 200914604 Kinetic Viscosity and Density of Polymers The properties of various binder fluids for σ-incorporated are shown in the table below. Polytrimity OB® Wanma Oil---- Polytrimethylene Termethylene Glycol Poly(trimethylene-extended ethylenyl)diol'---- Polytrimethylene ether diacetate 2-hexanoic acid Molecular weight _ ester 1026 1245 1150 510 Density at 40 ° C 0.9627 1.0164 1.0315 0.9575 Viscosity at 40 ° C, cP '---- 245 320 211 ~~ 23.2 Viscosity, at ioo °c, cP 18.1 47.1 32.2 5.07 Viscosity Index 87 216 204 177 '--

Example = root blending =: = each:. Base (4)... Example 1 50/50 compound of castor oil and P〇3G homopolymer Example 2% of sesame oil and P03G copolymer 5〇/5〇#Household example 3 Castor oil and P03G ester 50/50 Blend Example 4 Castor Oil / P03G Homopolymer / P03G 33/33/33 Blend Example 5 Castor Oil / P03G Copolymer / P03G Ester 33/33/33 Blend Density at 40° C under 0.9891 ^3 0.951 0.9714 0.9757 ^95 59 107 88.6 Viscosity, at 40 ° C, cP viscosity, at 10 CTC, cP 257 29.7 8.4 15.7 13.3 Viscosity index 161 〆, 127 166 161 • 32- 134069.doc 200914604 Examples 6 A lubricating composition was prepared by adding the following additives to the blend composition of Example 4. Base fluid blend 97.3% IRGALUBE® TPPT 0.40% VANLUBE® 7723 0.30% VANLUBE® 887E 0.20% PANA 0.40% VANLUBE® RD 0.80% IRGALUBE® 349 0.40% CUVAN® 826 0.10% 134069.doc -33-

Claims (1)

200914604 X. Patent application scope: 1. A lubricating oil composition comprising: a base material comprising a polytrimethylene ether glycol acid ester at ambient temperature and a vegetable oil μ"11·/Tian Benben lubricant. 2. The lubricating oil composition of claim 1, wherein the additional sentence comprises one or more lubricating oil additives, wherein the amount of the base fluid raw material in the lubricating oil composition is the total weight of the lubricating oil composition. It is calculated to be about 5% by weight or more than 5% by weight. (Ί 3. > The lubricating oil composition of claim 2, wherein the amount of the base fluid raw material in the lubricating oil composition is about Μ by weight or more than 75% by weight based on the total weight of the lubricating oil composition 4. The lubricating oil composition of claim 3, wherein the amount of the base fluid material in the lubricating oil composition is about 95% by weight or more by weight based on the total weight of the lubricating oil composition. The lubricating oil composition of the present invention, wherein the base fluid raw material additionally comprises a polytrimethylene ether glycol which is a fluid at a temperature of a component. V. 6. The lubricating oil composition of claim 1 wherein The base fluid feedstock consists essentially of the acid ester of the polydialkylene ether glycol and the base oil of the vegetable oil. 1A. The lubricating oil composition of claim 1, wherein the base fluid raw material is substantially comprised of The polytrimethylene glycol diol, the polytrimethylene ether glycol and the vegetable oil base lubricant composition. 8. The lubricating oil composition of the invention, wherein the polytrimethylene ether glycol / the weight of the polydialkylene ether glycol in the base fluid feedstock 134069.doc 200914604 The ratio is 1:1 or 1:1. 9. The lubricating oil composition of claim 5, wherein the decyl ester of the polytrimethylene ether glycol / the polytrimethylene ether glycol The lubricating oil composition of the base fluid of claim 1, wherein the acid composition of the polytrimethylene propylene glycol is the acid. The weight of the ester comprises from about 5% by weight to about 1% by weight of diacetin, and from 0 to about 50% by weight of the monoester. II. The lubricating oil composition of claim 1, wherein the polytrimethylene sulfonate The acid ester of the alcohol is an acid ester of a monocarboxylic acid and/or an equivalent. The lubricating oil composition of claim 11, wherein the monocarboxylic acid has the formula RC〇〇H' wherein R is 6 to 40 A substituted or unsubstituted aromatic, aliphatic or cycloaliphatic organic moiety of the carbon atom. The lubricating oil composition of claim 1, wherein the acid ester of the polytrimethylene glycol comprises a Or a plurality of compounds of the formula (I): wherein Q represents a residue of the polytrimethylene glycol in the removal of the hydroxyl group, R·2 is Η or R_3CO, and each of 1 and 3 is separate a substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic or cycloaliphatic organic group containing from 6 to 40 carbon atoms. 14. The lubricating oil composition of claim 1, wherein The acid ester has a number average molecular weight based on a polytrimethylene sulfonate diol having a number average molecular weight of at least about 250 to less than about 10,000. 134069.doc 200914604 15 16 17. 18. 19. 20. 21. 22. 23. A lubricating oil composition, wherein the acid ester is prepared from a biologically produced 1,3-propanediol. The lubricating oil composition of claim 5 wherein the polytrimethylene ether glycol has at least about 250 To a number average molecular weight of less than about 丨〇〇〇〇. The lubricating oil composition of claim 1, wherein the repeating unit of "% to 1 ()%) in the polytrimethylene diol is a trimethylene ring unit. The claimed item is a lubricating oil composition wherein the polytrimethylene glycol comprises a trimethylene ether unit and a minor amount of other polyoxyalkylene ether repeating units. A lubricating oil composition as claimed in claim 1, wherein the polytrimethylene (tetra)diol is prepared from a biologically produced hydrazine, propylene glycol. A lubricating oil composition as claimed, which additionally comprises (iv) an oil additive comprising at least one selected from the group consisting of: an ashless dispersant, a metal cleaner, a point modification, an antiwear agent, an antioxidant, a friction Modifier, 4 shells '3 reducer, deodorizer/bag, corrosion inhibitor, deemulsifier and rust inhibitor. The lubricating oil composition of claim 20, wherein the lubricating oil additive is at least 50% miscible in the base fluid material. The lubricating oil composition of claim 1, wherein the lubricating oil composition is a mixture of substantially uniform sentences, wherein the components are substantially free of sedimentation or phase separation. The lubricating oil composition of claim 1, wherein the base fluid material comprises greater than 50% by weight of the § hai vegetable oil base lubricant. 134069.doc 200914604 VII. 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 reveal the best indication of the characteristics of the invention. Chemical formula: I ; 〇II R "C-Ο-Q-Ο-R2 (I) 134069.doc