JP2010523797A - Capped polyester polyol lubricant composition - Google Patents

Abstract

  The present invention relates to various polyester polyol lubricant compositions (some of which are capped) containing two or more chemically linked ester components, at least one of which is derived from seed oil or vegetable oil. And their preparation. The compositions of the present invention are in the case of no pour point depressant, either when the composition does not include an initiator component or when the composition includes an initiator that is not a dendritic initiator component. A pour point temperature of -10 degrees Celsius or less and a viscosity at 25 degrees Celsius in the range of 40 centipoise (0.04 Pascal seconds) to 2000 centipoise (2 Pascal seconds), and the composition is dendritic With a pour point initiator component, with no pour point depressant in the range of −5 ° C. pour point temperature and in the range of 40 centipoise (0.04 Pascal second) to 8000 centipoise (8 Pascal second). It has a viscosity of 25 degrees Celsius. The present invention also relates to a process for removing at least a portion of the saturates from the composition.

Description

  This application claims the benefit of US Provisional Patent Application No. 60 / 922,476 (filed Apr. 9, 2007).

  The present invention generally relates to capped polyester polyol lubricant compositions. More specifically, the present invention relates to a capped polyester polyol lubricant composition based on a renewable raw material source (eg, seed oil or vegetable oil, whether or not genetically modified). . The present invention more particularly relates to a capped polyester polyol composition in which the renewable source is alkanolated, hydroformylated and reduced seed oil or vegetable oil.

  “Bio-lubricants”, ie, lubricants that are not derived from oil or natural gas, but rather based on renewable resources (eg, seed oil or vegetable oil), have a small overall global lubricant demand. , One of the growing areas. Due to the observation that bio-lubricants are readily biodegradable, have low toxicity, and do not appear to be harmful to aquatic and surrounding vegetation, various bio-lubricants are sensitive to the environment. In application, it is particularly supported, for example, in marine, forestry or agricultural lubricants. In at least partial recognition of such observations, Germany and Austria have banned the use of mineral oil in loss-of-total lubrication applications (eg, chainsaw lubrication), and Portugal and Belgium have used biodegradable lubricants in outboard engines. Commanded to use. Hydrolytic stability, oxidative stability and low temperature properties (including pour point) compared to synthetic lubricants derived from petroleum or natural gas (eg polyol polyesters, polyalkylene glycols and poly (α-olefins) etc.) The technical performance shortcomings of unmodified seed oils with respect to limit the growth of such seed oils as biolubricants. For example, in cold climates (temperatures below −10 ° C. (degrees Celsius)), vegetable oils tend to solidify more easily than petroleum-based products and thus have a relatively high flow (from 0 ° C. to −20 ° C.). Has a point temperature. By adding a pour point depressant to the vegetable oil, a composition having a pour point temperature lower than the pour point temperature of the net (no additive) vegetable oil is obtained.

  US Pat. No. 5,335,471 discloses the use of methacrylate and styrene / maleic anhydride interpolymers as pour point depressant additives for seed oil lubricants.

  US Pat. No. 5,413,725 teaches the use of the same interpolymer as a pour point depressant additive for seed oil lubricants derived from high oleic acid containing feedstocks.

  US Pat. No. 4,243,818 discloses “hydroformylation” in column 5, lines 8 to 12 as the preparation of aldehydes from unsaturated compounds by reaction with hydrogen and carbon monoxide in the presence of a catalyst. Define. A preferred unsaturated compound is oleyl alcohol according to column 5, lines 36-38, but linoleyl alcohol or linolenyl alcohol can also be used as the unsaturated compound. In column 9, lines 52-58, the '818 patent uses an acid halide (such as acryloyl chloride) to convert the alcohol to its corresponding unsaturated ester (such as acrylate or methacrylate). Teach that.

  As used throughout this specification, the various definitions given in this paragraph, in subsequent paragraphs, or elsewhere in this specification are the meanings given to them when first defined. Have

  When a range is described herein as in the range of 2-10, both endpoints of the range (eg, 2 and 10) are included within the range unless specifically excluded otherwise It is.

  The first aspect of the present invention is a capped polyester polyol lubricant composition, which can be (a) directly or (b) indirectly via an initiator component as required. Hydroxyl percentages, each of which is in the range of 0.1 weight percent to 2 weight percent (each weight percent based on the composition weight), including at least two ester components that are chemically linked to each other; and A saturated hydrocarbon content of 12 or more carbon atoms in the range of 0 weight percent to 32 weight percent (each weight percent based on the composition weight), 40 centipoise (cps) (0.04 Pascal second) (Pa.s)) to 2000 cps (2 Pa.s), and also has a viscosity at 25 degrees Celsius and a pour point of -10 degrees Celsius or less.

  A second aspect of the invention is a polyester polyol lubricant composition, the composition comprising a plurality of ester components that are chemically linked to each other indirectly via a dendritic initiator component, Hydroxyl percentages in the range of weight percent to 31 weight percent (each weight percent based on the composition weight) and saturated carbonization of 12 or more carbon atoms in the range of 0 weight percent to 32 weight percent It has a hydrogen content (each weight percent based on the composition weight), a viscosity at 25 degrees Celsius that is in the range of 40 centipoise to 8000 centipoise, and a pour point of -5 degrees Celsius or less. The dendritic initiator component is preferably derived from a dendritic base product or an alkoxylated form thereof.

  The polyester polyol lubricant composition of the present invention has utility as, for example, hydraulic oil, whether or not capped. A variety of hydraulic oils are used in a variety of equipment common to a variety of industrial fields, including mining, steel, die casting and food processing, as well as forestry and offshore facilities. Furthermore, such lubricant compositions also have potential utility in the automotive field, for example as engine oils, transmission fluids and gear oils, or as components of such oils or fluids (in various applications). Fluids such as gear oils, transmission fluids, engine oils and compressor fluids). Those skilled in the art of lubricant compositions will readily appreciate other suitable end use applications for the lubricant compositions of the present invention.

A third aspect of the present invention is a method for preparing a polyester polyol lubricant composition, in particular the capped polyester polyol lubricant composition of the first aspect, which comprises:
a. The reaction mixture comprising monomer (preferably alkanolated, hydroformylated and reduced seed oil), capping agent, catalyst, and initiator, if necessary, is in the range of 170 degrees Celsius to 200 degrees Celsius. Subjecting to elevated temperature to convert at least a portion of the reaction mixture to capped polyester polyol and volatile by-products; and b. Including simultaneously removing at least a portion of the volatile by-products.

A fourth aspect of the present invention is a method for preparing a polyester polyol lubricant composition, in particular a polyester polyol lubricant composition of the second aspect, which comprises:
a. Bring the reaction mixture containing monomer (preferably alkanolated, hydroformylated and reduced seed oil), catalyst, and initiator, if necessary, to an elevated temperature that is in the range of 170 degrees Celsius to 200 degrees Celsius. Providing to convert at least a portion of the reaction mixture into a polyester polyol and a volatile by-product; and b. Including simultaneously removing at least a portion of the volatile by-products.

The method of either the third aspect or the fourth aspect preferably further comprises a plurality of successive precursor steps for preparing such alkanolated, hydroformylated and reduced seed oil (monomer). Including, but this sequential precursor process in turn,
a1. The seed oil is alkanolated, and the glyceride present in the seed oil has a linear or branched structure and contains from ₁ carbon atom (C ₁ ) to 15 carbon atoms (C ₁₅ ). Converting to a mixture of saturated and unsaturated fatty acid esters of alkanols;
a2. Hydroformylating a mixture of saturated and unsaturated fatty acid esters to convert said mixture to an aldehyde or mixture of aldehydes; and a3. The aldehyde or mixture of aldehydes is reduced in a hydrogen atmosphere with the aid of a hydrogenation catalyst, and the aldehyde or mixture of aldehydes is converted to an alcohol composition of a hydroxymethyl-substituted fatty acid or a hydroxymethyl-substituted fatty acid ester. Including converting.

  Step a2. Preferably with a solubilized Group VIII transition metal-organophosphine ligand complex catalyst, and optionally together with a solubilized free organophosphine metal salt ligand, a non-aqueous reaction medium Done in

  As used herein, “monomer” refers to a compound that has both alcohol functionality and either acid or ester functionality. Preferred monomers include alkanolated, hydroformylated and reduced seed oil.

  A fifth aspect of the present invention is a method for removing at least a portion of a saturate from the capped polyester polyol lubricant composition of the first aspect or the polyester polyol lubricant composition of the second aspect. In such cases, such a process may be used under reduced pressure to separate a heated feedstock stream that is a capped polyester polyol lubricant composition or a polyester polyol lubricant composition into a saturate concentrate portion and a saturate reduction residue. Feeding a wiped thin film evaporator to be operated. The feed stream is preferably heated to a temperature that is in the range of 90 degrees Celsius to 150 degrees Celsius, and the reduced pressure is preferably in the range of 0.01 millimeter mercury to 1 millimeter mercury. In one preferred variant of the fifth aspect, the saturate-reducing stream resulting from one pass of the wiped thin film evaporator is used as a heated feed feed stream for the next pass of the wiped thin film evaporator, This further reduces the saturate content of the saturate-reduced stream.

As used herein, “capping agent” refers to an ester or carboxylic acid that has no alcohol functionality. Suitable capping agents include short chain carboxylic acids or short chain lower alkyl esters of carboxylic acids of 6 to 12 carbon atoms (C ₆ -C ₁₂ ), preferably 6 to 10 carbon atoms (C Short chain carboxylic acids or short chain lower alkyl esters of carboxylic acids of _{6 to} C ₁₀ ), more preferably short chain carboxylic acids or short chain lower alkyl esters of C ₈ carboxylic acids and C ₁₀ carboxylic acids, such carboxylic acids Or a mixture of two or more lower alkyl esters (eg, a mixture of short chain lower carboxylic acids or short chain lower alkyl esters of C ₈ carboxylic acids and C ₁₀ carboxylic acids), even more preferably such carboxylic acids Of one or more carboxylic acids or methyl esters.

  References to the Periodic Table of Elements herein are found in CRC Press, Inc. Reference must be made to the Periodic Table of Elements, published in 2003 and copyrighted. Similarly, any reference to a family (one or more) shall be to a family (one or more) reflected in this periodic table using the IUPAC system for numbering the family.

  Unless otherwise stated, or implicit from the context, or customary in the art, all parts and percentages are based on weight. For purposes of US patent practice, the contents of any patents, patent applications, or publications referred to herein are not inconsistent with, inter alia, synthetic techniques, definitions (any definition provided herein). To the extent), and with respect to disclosure of general knowledge in the field, this specification is hereby incorporated by reference in its entirety (or its equivalent US counterpart is so incorporated by reference).

  The term “comprising” and its derivatives are not intended to exclude the presence of any additional components, steps or procedures, regardless of whether any additional components, steps or procedures are disclosed herein. For the avoidance of doubt, all compositions claimed herein by use of the term “comprising” are intended to be (whether polymeric or not) unless stated otherwise. Any further additives, adjuvants or compounds may be included, if any. In contrast, the term “consisting essentially of” excludes from the scope of any subsequent enumeration any other components, steps or procedures, except those not essential for operability. The term “consisting of” excludes any component, step or procedure not specifically delineated or listed. The term “or (or)” refers to the listed items individually, as well as in any combination, unless otherwise stated.

  The expression of temperature can be either in degrees Fahrenheit (° F.) with its equivalent value in degrees Celsius (° C.), or more typically simply in degrees Celsius (° C.).

  The preparation of alkanolated, hydroformylated and reduced seed oil (sometimes referred to as “ester alcohol”) involves three successive steps: alkanolysis, hydroformylation and reduction. Alkanolysis (also known as transesterification) converts the glycerides present in seed oil into a mixture of saturated and unsaturated fatty acid esters of alkanols. Those skilled in the art understand that glycerides can be difficult to process and separate, and that transesterification of such glycerides results in a mixture that is more suitable for chemical conversion and separation. .

Alkanols (sometimes referred to as “lower alkanols”) can have a linear or branched structure and typically contain from 1 to about 15 carbon atoms (C ₁ -C ₁₅ ). And preferably contains 1 to 8 carbon atoms (C _{1 to} C ₈ ), more preferably 1 to 4 carbon atoms (C _{1 to} C ₄ ). Particularly suitable alkanols include methanol, ethanol and isopropanol, with methanol being preferred. The carbon atoms in the alcohol segment of the alkanol can be substituted with various substituents provided such substituents do not interfere with processing and downstream applications.

  Choose any known direct esterification method or known transesterification methodology by condensing the alcohol moiety in one molecule and the carboxylic acid moiety in a different molecule, with the consequent elimination of water Methanolysis and ethanolysis are described in, for example, Patent Cooperation Treaty Application (WO) 2001/012581, German Patent Application Publication (DE) 199090878, Brazilian Patent Application Publication (Br) No. 953081 and US Patents No. 3,210,325 (these teachings are incorporated herein to the maximum extent permitted by law). Typically, in such a process, a lower alkanol is contacted with an alkali metal, preferably sodium or potassium, at a temperature in the range of about 30 ° C. to about 100 ° C. to prepare the corresponding metal alkoxide. It is done. Thereafter, seed oil is added to the metal alkoxide to form a reaction mixture, and the reaction mixture is heated to a temperature in the range of about 30 ° C. to about 100 ° C. to achieve transesterification. Separation of the transesterified crude product from the reaction mixture can involve a variety of standard techniques, for example, phase separation, extraction, distillation, or a combination of two or more standard techniques. Can do.

  If it is chosen to use a mixture of fatty acids rather than fatty acid esters, seed oil can be hydrolyzed to its constituent fatty acids using conventional techniques. Such acids can be easily esterified by conventional techniques, provided that esterification results in water as a byproduct.

  United States Patent Application Publication (USPAP) No. 2006/0193802, the teachings of which are incorporated herein by reference, particularly the teachings in paragraphs [0037] to [0042] emphasize the hydroformylation under non-water conditions. Thus, hydroformylation is discussed. US 2006/0193802 also refers to US Pat. No. 4,731,486 and US Pat. No. 4,633,021, in particular US Pat. No. 4,731,486, Those teachings are incorporated by reference.

Generally speaking, when hydroformylation is carried out in the present invention, a fatty acid ester or a mixture of fatty acids (preferably a fatty acid ester or fatty acid derived from seed oil), a fatty acid ester or fatty acid as an aldehyde or a mixture of aldehydes. under conditions sufficient to convert, solubilized group VIII (periodic table of the elements, front cover, CRC Handbook of Chemistry and Physics, 77 th Edition, 1996~1997) a transition metal - organic phosphine ligand complex Together with carbon monoxide (CO) and hydrogen (H ₂ ) in a non-aqueous reaction medium, together with a solubilized free organophosphine metal salt ligand, if necessary. As used herein, “non-aqueous reaction medium” means a reaction medium that is substantially free of water. In other words, any water that may be present is present in a small amount such that hydroformylation is not characterized as including a separate aqueous or aqueous phase in addition to the organic phase. “Free organic phosphine metal salt ligand” means that the organic phosphine metal salt ligand is not complexed, that is, the organic phosphine metal salt ligand is not bound to or bound to the Group VIII transition metal. Means not.

  Paragraph [0038] of US Patent Application Publication No. 2006/0193802 describes group VIII transition metals as iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd ), Osmium (Os), iridium (Ir), platinum (Pt), and mixtures thereof. Preferred Group VIII transition metals include Rh, Ru, Co and Ir, with Rh and Co being more preferred and Rh being most preferred. When the preferred amount of Group VIII transition metal is calculated as free metal, the amount ranges from 10 parts by weight / million parts by weight (ppm) to 1000 ppm, and the amount in the range of about 10 ppm to about 800 ppm is free metal. Preferred for calculated Rh.

  Paragraph [0039] of US 2006/0193802 contains teachings on organophosphine metal salt ligands wherein the organophosphine metal salt ligand comprises a monosulfonated metal salt of a tertiary phosphine. Note that it includes. Paragraph [0039] refers to US Pat. No. 4,731,486 for non-limiting examples of such ligands. Examples of preferred ligands include triphenylphosphine, diphenylcyclohexylphosphine, phenyldicyclohexylphosphine, tricyclohexylphosphine, diphenylisopropylphosphine, phenyldiisopropylphosphine, diphenyl-t-butylphosphine and phenyl-di-t-butylphosphine mono Sulfonated metal salt derivatives are included, and phenyl dicyclohexylphosphine derivatives are particularly preferred.

  Paragraph [0040] of US 2006/0193802 discloses suitable organic solubilizers, see the teachings of US Pat. No. 5,180,854 and US Pat. No. 4,731,486. To capture. US Pat. No. 5,180,854 shows organic solubilizers including amides, glycols, sulfoxides, sulfones and mixtures thereof. U.S. Pat. No. 4,731,486 discloses alkylene oxide oligomers having an average molecular weight of 150 to 10,000 or more, as well as organic nonionic surfactant monools having an average molecular weight of at least 300, and water solubility. Figure 2 shows an alcohol alkoxylate containing both a (polar) group and an oil-soluble (non-polar) group (which is available under the trade name TERGITOL ™).

  Additional references for hydroformylation (the teachings of which are incorporated herein by reference) include US Pat. No. 4,243,818. When used, step a. Precursor steps preceding the above include sufficient hydroformylation to functionalize or react with greater than zero percent of unsaturation in the starting material to 100 percent of such unsaturation. Hydroformylation is preferably sufficient to react with at least (≧) 20 percent (%) of unsaturation, more preferably sufficient to react with ≧ 50% of unsaturation, Most preferably it is sufficient to react with ≧ 80%.

  Still other references discussing hydroformylation (the teachings of which are incorporated herein to the maximum extent permitted by law) include US Pat. No. 4,423,162 (especially column 3, line 50). Column 4, line 36), U.S. Patent No. 4,723,047, Canadian Patent Application (CA) No. 2,162,083, International Publication No. 2004/096744, U.S. Patent No. 4,496,487. US Pat. No. 4,216,343, US Pat. No. 4,216,344, US Pat. No. 4,304,945 and US Pat. No. 4,229,562.

  U.S. Patent Application Publication No. 2006/0193802, previously incorporated herein by reference, lists exemplary vegetable oils and plant seed oils in paragraph [0030]. Such oils include palm oil, palm kernel oil, castor oil, soybean oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, canola oil, safflower oil, linseed oil, sunflower oil; high oleic acid oil For example, high oleic sunflower oil, high oleic safflower oil, high oleic corn oil, high oleic rapeseed oil, high oleic soybean oil and high oleic cottonseed oil; Body, as well as mixtures thereof. Preferred oils include soybean oil (both natural and genetically modified soybean oil), sunflower oil (including high oleic sunflower oil), and canola oil (including high oleic canola oil). High oleic oils, particularly high oleic oils having a saturated hydrocarbon content of 12 or more carbon atoms in the range of 0 weight percent to 32 weight percent, specifically carbon numbers of 12 or more carbon atoms High oleic oils with a saturated hydrocarbon content of less than 10 weight percent tend to have greater thermal oxidative stability and lower pour points than their natural oil counterparts (eg, high oleic sunflower oil versus natural Sunflower oil).

  US Patent Application Publication No. 2006/0193802 also discusses the reduction or hydrogenation of aldehydes (hydroformylated or formyl substituted fatty acids or fatty acid esters) to alcohols in paragraph [0047]. In general, in hydrogenation, formyl-substituted fatty acids and / or formyl-substituted fatty acid esters are used to convert formyl-substituted acids and / or esters to hydroxymethyl-substituted fatty acids or alcohol compositions of fatty acid esters. Under sufficient conditions, it is placed in contact with a hydrogen source in the presence of a hydrogenation catalyst. Sources of hydrogen include pure hydrogen as well as hydrogen that is diluted with non-reactive gases such as nitrogen, helium, argon, or saturated hydrocarbons. The hydrogenation catalyst typically comprises a metal selected from Group VIII, Group IB or Group IIB of the Periodic Table of Elements described above. Exemplary metals include Pd, Pt, Rh, Ni, copper (Cu), zinc (Zn), and mixtures thereof. The metal can be supplied as a Raney metal or as a supported metal in a suitable catalyst support such as carbon or silica. The hydrogenation temperature ranges from 50 ° C to 250 ° C. The hydrogenation pressure preferably ranges from 50 pounds per square inch gauge (psig) (345 kilopascals (kPa)) to 1,000 psig (6895 kPa).

  The capped polyester polyol lubricant composition of the present invention can be directly or indirectly through an initiator component (also known as such part of the initiator incorporated into the capped polyester polyol). In particular, it comprises at least two ester components that are chemically linked to each other. The capped polyester polyol lubricant composition of the present invention has several features or performance parameters that help one skilled in the art to match such composition to the desired lubricant application.

  The polyester polyol lubricant composition of the present invention, as well as its capped analog, is known directly or as the initiator component (which is also known as such part of the initiator incorporated into the polyester polyol). A number of ester components that are chemically linked to each other either indirectly, and to help those skilled in the art to match such compositions to the desired lubricant application. It has these characteristics or performance parameters.

  The composition of the first aspect of the present invention can comprise an initiator component that is different from the dendritic initiator component, whether capped or not, preferably It actually contains an initiator component that is different from the agent component. Such compositions preferably have a hydroxyl percentage that is in the range of 0.1 weight percent (wt%) to 2 wt%, more preferably a hydroxyl percentage that is in the range of 0.2 wt% to 1 wt%. And even more preferably having a hydroxyl percentage in the range of 0.3 wt% to 0.7 wt% (each wt% based on the composition weight). The composition of the second aspect of the present invention, whether capped or uncapped, is preferably not capped, but includes a dendritic initiator component. Such compositions preferably have a hydroxyl percentage that is in the range of 0.1 wt% to 31 wt%, more preferably a hydroxyl percentage that is in the range of 10 wt% to 31 wt% (each wt% Based on composition weight). While it is technically possible to achieve a hydroxy percentage of 0 weight percent, it is very expensive and counterproductive from a lubricity standpoint. Lubricity is a complex function of viscosity and hydroxyl content, and similarly viscosity is a function of molecular weight and hydroxyl percentage. As such, hydroxyl content within the above range favorably affects both lubricity and viscosity, and so does at a reasonable cost.

  The composition of the present invention also preferably has a saturated hydrocarbon content of 12 or more carbon atoms in the range of 0 wt% to 32 wt%, more preferably in the range of 0.1 wt% to 10 wt%. The content of saturated hydrocarbons having 12 or more carbon atoms, and more preferably the content of saturated hydrocarbons having 12 or more carbon atoms within the range of 0.2 wt% to 2 wt% A quantity (each wt% based on the composition weight). As a general rule, lower saturated hydrocarbon content is better than larger saturated hydrocarbon content because the pour point of the composition tends to increase with increasing saturated hydrocarbon content.

  In addition, the composition of the first aspect is preferably from at least 40 centipoise (cps) (0.04 Pascal second (Pa.s)), more preferably from at least 50 cps (0.05 Pa.s), and even more. Preferably at least 75 cps (0.075 Pa.s), even more preferably at least 100 cps (0.1 Pa.s), up to 2000 cps (2 Pa.s), more preferably up to 1500 cps (1.5 Pa.s), and further More preferably, it has a viscosity at 25 ° C. of up to 1000 cps (1 Pa.s), even more preferably up to 800 cps (0.8 Pa.s). Furthermore, the composition of the first aspect preferably has a pour point that is −10 ° C. or less, more preferably has a pour point that is −20 ° C. or less, and even more preferably −25 ° C. or less. It has a pour point, and most preferably has a pour point of -30 ° C or lower. The expression “or less” means lower in temperature. For example, −15 ° C. is less than −10 ° C.

  As a control, the composition of the second aspect preferably has a viscosity at 25 ° C. that is in the range of 40 centipoise (cps) (0.04 Pascal second (Pa.s)) to 8000 cps (8 Pa.s). And more preferably has a viscosity at 25 ° C. within the range of 1000 cps (1 Pa.s) to 7800 cps (7.8 Pa.s), even more preferably 50 cps (0.05 Pa.s) to 7500 cps (7 And a viscosity at 25 ° C. within the range of 5 Pa.s). Furthermore, the composition of the first embodiment preferably has a pour point that is −5 ° C. or lower, more preferably −7 ° C. or lower.

  Those skilled in the art recognize that the pour point of the composition can be altered by the addition of conventional pour point depressants, such as polyalkyl methacrylates and styrene / maleic anhydride interpolymers. Those of ordinary skill in the art will also note that an amount of pour point depressant greater than about 2 wt%, based on the total weight of the composition (including pour point depressant), typically results in minimal further improvement in pour point, It is also recognized that it actually increases the cost of the composition.

  The composition preferably has a viscosity index or VI determined as detailed below, which is greater than 120, more preferably greater than 140, even more preferably greater than 150. VIs over 400 are known but rare. Those skilled in the art recognize that VI indicates how the viscosity of a lubricant varies with temperature. For example, a low VI (e.g., 100) will cause the viscosity of the fluid to change significantly when the fluid is used to lubricate one piece of equipment that operates over a wide range of temperatures (e.g., 20C to 100C). Suggest to do. Those skilled in the art also recognize that as VI increases, lubricant performance also tends to improve. Based on that recognition, those skilled in the art prefer higher VI values (eg, 150) over lower VI values (eg, 100). For comparison, typical lubricant VI ranges are: Mineral oil = 95 to 105; poly α-olefin = 120 to 140; synthetic ester = 120 to 200, and polyalkylene glycol = 170 to 300.

  The polyester polyol lubricant composition of the present invention need not include an initiator component that links at least two ester components, whether capped or uncapped, but preferably at least two It actually contains an initiator component that links the ester components. The initiator component of the composition of the first aspect of the present invention is derived from the initiator used in the method of the second aspect of the present invention. When present, the initiator reacts with a portion of the alkanolated, hydroformylated and reduced seed oil (preferably the reactive ester portion of the alkanolated, hydroformylated and reduced seed oil). It has at least two reactive sites, preferably pendant hydroxyl groups or terminal hydroxyl groups. When making capped polyester polyol lubricant compositions, the capping agent similarly reacts with the same or different portions of the alkanolated, hydroformylated and reduced seed oil.

Suitable initiators from which the initiator component is derived can be represented by the formula R— (OH) _n , where R is a linear alkyl component, a branched alkyl component, or a cyclic alkyl component, and n is 0 An integer in the range of ~ 64, preferably an integer in the range of 1 to 64, with very satisfactory results from the group n consisting of 2, 3, 6, 12, 16, 32 and 64 Obtained when the integer is selected. Particularly preferred results occur when n is an integer in the range of 1 to 32, preferably for the composition of the first aspect, n is an integer selected from the group consisting of 2, 3 and 6. Or for the composition of the second aspect, when n is an integer selected from the group consisting of 12, 16, 32 and 64. R preferably contains 1 to 6 carbon atoms (C ₁ -C ₆ ), more preferably 1 to less than 6 carbon atoms.

“N” in the formula R— (OH) _n can also be considered to represent the number of reactive sites. No initiator component is present in the capped polyester polyol lubricant composition of the first aspect or the polyester polyol lubricant composition of the second aspect, and no initiator is used in the method of the third or fourth aspect. If not, n is effectively equal to zero. Suitable initiators include neopentyl glycol (NPG), butanediol, hexanediol, cyclohexanediol, isomers of cyclohexanediol, isomers of cyclohexanedimethanol, hydroquinone bis (2-hydroxyethyl) ether, glycerin, ethoxylation Glycerin (eg, IP-625, which is commercially available from The Dow Chemical Company), trimethylolpropane, sorbitol, hyperbranched products or dendrites commercially available under the trade name BOLTORN® from Perstorp Including, but not limited to, one or more of the shaped base products. For example, BOLTORN® H20 has an n value of 16 and a nominal weight average molecular weight (M _w ) of 1,750, and BOLTORN® H2003 has an n value of 12 and an M _w of 2,300. BOLTORN® H2004 has an n value of 6 and _Mw of 3,100, BOLTORN® H30 has an n value of 32 and _Mw of 3,600, and BOLTORN® ) H40 has an n value of 64 and _Mw of 7,300. The present invention need not be limited to any particular initiator, and those skilled in the art will readily select a suitable initiator that will provide performance comparable to the initiator specifically identified herein. can do.

  In column 1, lines 21-55, US Pat. No. 6,627,720 (Campbell et al.) Discusses “hyperbranched polymers” where the hyperbranched polymer is further reacted to produce the final product. It is described as a material consisting of highly branched polymer chains that often contain a large number of reactive groups that may be useful for. One important property of hyperbranched polymers is their low viscosity compared to less highly branched polymers of similar molecular weight.

  Particularly mention that hyperbranched polymers can be classified as either dendrimers or random hyperbranched polymers. Dendrimers originate from a central location that results in branching as the polymer grows outward, thereby resulting in a relatively highly symmetric structure. Tight control of reaction conditions and stoichiometry is required to produce dendrimers. Random hyperbranched polymers can be more easily obtained from standard polymerization reactions. Campbell et al. Teach that the methods used for the production of random hyperbranched polymers usually require a separate post-polymerization step that reacts the functional groups present in different polymer chains to produce branching.

  If desired, the polyester polyol lubricant composition of the present invention may be capped as in the first aspect or not capped as in the second aspect. It can be enhanced by one or more predetermined amounts of seed oil or vegetable oil disclosed in the document. When present in the lubricant composition, such seed oil or vegetable oil typically constitutes an amount in the range of 1 wt% to 90 wt%, preferably in an amount in the range of 10 wt% to 80 wt%. And more preferably comprises an amount in the range of 30 wt% to 70 wt% (in each case based on the combined weight of the capped polyester polyol lubricant composition and the seed oil or vegetable oil).

  In the methods of the third and fourth aspects of the invention, a catalyst is included as part of the reaction mixture. The catalyst tends to reduce the activation energy and increase the esterification / transesterification reaction rate. Both acids and bases can be used as catalysts. Exemplary catalysts include II-tin catalysts such as bis (ethylhexanoic acid) stannous; IV-valent tin-based catalysts such as tin octoate, dibutyltin dilaurate, butyl stannic acid and dibutyl tin oxide; Sodium carbonate; metal alkoxides (eg, sodium methoxide, potassium methoxide, titanium propoxide or titanium isopropoxide); sodium hydroxide; potassium hydroxide; sodium carbonate; potassium carbonate; boron trifluoride; Including but not limited to zinc dichloride. Other known catalysts for direct polyesterification are based on antimony, germanium and titanium, especially for higher temperatures.

Analytical Procedure Kinematic viscosity at 40 ° C. and 100 ° C. (centistokes (cSt) and its metric equivalent (in units of square meters per second (m ² / second)), Stubber viscometer, American Society for Testing and Materials ( ASTM) D7042. Determined using kinematic viscosity, VI is calculated according to ASTM D2270.

  The pour point of the lubricant is measured according to ASTM D97-87.

  Thermogravimetric analysis (TGA) is used to evaluate the thermal oxidation stability of the lubricant material. For TGA evaluation, the lubricant sample was heated in the air stream at a rate of 10 ° C./min, and the weight loss of the lubricant was 2 percent (2%) weight loss, 5% weight loss and 50%. It includes recording the weight loss against temperature.

  The dynamic coefficient of friction is measured using an Optimol SRV (Schwingungen Reibung Verschliess) friction device comprising a steel plate and vibrating steel balls. Three drops of candidate lubricant fluid are placed on the plate and a sphere is placed on the plate, but the sphere is placed in three drops of candidate liquid. Over a 1 hour test period, a 200 Newton (N) load is applied to the sphere and to the plate at a right angle, with a vibration frequency of 50 Hertz (sphere on the plate) and 1 millimeter (1 mm) Use distance. The SRV coefficient of friction is determined at 30 ° C and 60 ° C.

  Use the same equipment, vibration frequency, vibration distance and temperature, but start with an additional load of 50N and increase the load to 100N every minute until the failure load is reached. The “breaking load” or “breaking limit” is equal to the additional load that the candidate fluid “breaks” (subject to a sudden increase in the coefficient of friction). Results are reported as the maximum load applied to the sphere before the fluid breaks.

  Candidate fluids are evaluated for wear scar and coefficient of friction (COF) determination according to ASTM D5183-95 using a FALEX ™ 4-ball thrust washer tester (Model TW80). Test parameters for fluid evaluation include a 60 minute test time, a speed of 1200 revolutions per minute (rpm), and an applied load of 90 pounds (40.9 kilograms (kg)). Measure torque using a load cell. After the test, the wear scar length is measured using a microscope with an eyepiece verticule. The coefficient of friction (COF) is calculated by multiplying the device dependent constant of 5.67 by the quotient determined by dividing the measured torque by the applied load.

  The following examples illustrate the invention but do not limit the invention. All parts and percentages are on a weight basis unless otherwise stated. All temperatures are in ° C. Examples (Examples) of the present invention are indicated by Arabic numerals and comparative examples (Comp Examples) are indicated by uppercase alphabetic characters. Unless otherwise stated herein, “room temperature” and “ambient temperature” are nominally 25 ° C.

General Procedure for Preparing Hydroformylated and Reduced Fatty Acid Methyl Esters Hydroformylation of fatty acid methyl ester While stirring the catalyst solution, 0.078 grams (g) of dicarbonylacetonatodium and 0.751 g of dicyclohexyl- (3-sulfonylphenyl) phosphine monosodium salt were added under nitrogen atmosphere. Prepare by dissolving in 53.893 g of n-methyl-2-pyrrolidinone.

  11.06 g of the catalyst solution is transferred to a nitrogen purged 100 ml stainless steel autoclave. The autoclave was pressurized to 200 psig (1,379 kPa) pressure set point with synthesis gas (1: 1 molar ratio of gaseous hydrogen and carbon monoxide) and the autoclave contents were adjusted to 700 rpm. With stirring using a mechanical stirrer operating at speed, heat to a temperature of 90 ° C. and maintain that temperature for 15 minutes. 38.98 g of soy methyl ester mixture (11 wt% methyl palmitate, 4 wt% methyl stearate, 25 wt% methyl oleate, 52 wt% methyl linoleate and 8 wt% with continued stirring at a temperature of 90 ° C. Methyl linolenate, each weight percent based on the total weight of the mixture). Sufficient fresh synthesis gas is added to pressurize the autoclave to a pressure set point of 400 psig (2,758 kPa). The reactor contents are maintained at a temperature of 90 ° C. for 22.5 hours under stirring at a pressure setting of 400 psig (2,758 kPa) to obtain an aldehyde product composition (to aldehyde). Conversion of mixed methyl ester, 84%).

  Sample volume of aldehyde product composition (1 μl sample injection volume of 1: 1 dilution in diglyme) was gas chromatographed (GC) using a HP-6890GC equipped with a DB-5 capillary column and a flame ionization detector (FID). ) For diglyme as internal standard. Direct calibration (by injection of known concentrations of standard) results in response factors for the following components: Methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl formyl stearate. Response factors for the dialdehyde and trialdehyde components of the aldehyde product composition are determined by hydroformylating a set volume of the natural product distribution of unsaturated fatty acid methyl esters. Using the known monoaldehyde response factor response factor (obtained from hydroformylating methyl oleate), the dialdehyde and trialdehyde response factors, along with the known monoaldehyde sample content, their respective integrals Determined based on signal intensity and mass difference. The estimated error using this technique is ± 1% for dialdehyde and ± 20% for trialdehyde.

The dimer and heavy weight concentrations were diluted with a sample of the aldehyde product composition (1 μl sample injection volume of a 1: 1 dilution in diglyme) and the diluted sample was added at a rate of temperature increase of 40 ° C./min. Determined by subjecting the HP6890 GC and ZB-1 capillary column operated over a temperature range of 100 ° C. to 350 ° C. to GC analysis used in conjunction with FID. The chromatogram from the GC analysis is divided into two regions (product region and heavy weight region), after which the GC measured peak area of the compound of interest is divided by the sum of all peak areas arising from the sample. The “normalized area percent” method is used. As used herein, “heavy weight” refers to a compound having a mass that exceeds the mass of the C ₂₀ ester.

  The sum of the areas under the GC peak for methyl oleate, methyl linoleate and methyl linolenate is compared before and after hydroformylation to determine percent conversion.

  The aldehyde composition consists of 14 wt% saturates (palmitate and stearate), 14 wt% unsaturated materials (eg unreacted methyl oleate and methyl linoleate), 40 wt% monoaldehyde, 30 wt% dialdehyde, Contains 1.8 wt% trialdehyde and 0.2 wt% weight (each wt% based on total weight of aldehyde product composition).

B. Hydrogenation An upflow tubular reactor is charged with a commercially available supported nickel catalyst (440 ml, Sud-Chemie C46-8-03). The reactor has an inlet containing two liquid feeds and one gas feed that come together before entering the reactor. The first liquid feed is a hydroformylated soy methyl ester mixture (eg, an aldehyde composition prepared according to “A. Hydroformylation of fatty acid methyl esters” detailed above, or 15 wt% saturates. , 36 wt% monoaldehyde, 46 wt% dialdehyde and 2 wt% trialdehyde (each wt% based on the first liquid feed weight). The second liquid feed consists of a recycle stream from hydrogenation of the hydroformylated soy methyl ester mixture. The first liquid feed enters the reactor at a flow rate of 5 grams / minute (g / minute). A second liquid feed enters the reactor at a flow rate of 19 g / min. Together these two liquid feeds provide an overall liquid hourly space velocity of 3.51 hr ⁻¹ . Gaseous hydrogen is fed to the reactor at a rate of 2,000 standard cubic centimeters per minute (sccm), which is equivalent to a gas hourly space velocity of 272 hr ⁻¹ , after which the reactor contents are obtained. Setting at 143 ° C. while maintaining the pressure in the reactor at a set point pressure of 830 pounds per square inch gauge (psig) (5,723 kPa) over a period determined by the desired functionality of the methyl hydroxyl functionalized fatty acid ester Heat to point temperature to convert the aldehyde product composition to an alcohol product composition.

  Dilute the sample volume (10 microliter (μl) injection volume of the 1:20 dilution in dioxane) and use the same equipment as the one used for analysis of the aldehyde product composition. Analyze against internal diglyme standard. Response factors are determined by direct calibration for methyl palmitate, methyl stearate, methyl formyl stearate and methyl hydroxymethyl stearate. Response coefficients for other components of the aldehyde product composition (eg, dialdehyde and trialdehyde) are described above in A.C. Determine using the same procedure outlined under hydroformylation.

  Percent conversion is calculated by comparing the methylformyl stearate peak area before and after hydrogenation.

  The concentration of dimer and heavy weight is determined using the same procedure outlined above for the determination of similar concentrations in the aldehyde product composition.

  Analysis of the alcohol product composition revealed that the alcohol product composition was 19.2 wt% saturate, 35.6 wt% monool, 38.8 wt% diol, 3.3 wt% triol, 2.6 wt% Of dimer heavy, 0.2 wt% lactone and 0.3 wt% ether (each wt% based on the total weight of the alcohol product composition).

C. Removal of saturates Removing at least a portion of the saturates from the product constitutes one of the preferred embodiments of the present invention. Although various saturate removal techniques can be used, one preferred means involves feeding the product stream to a wiped thin film evaporator. One skilled in the art recognizes that the level of component removal (in this case, saturate removal) involves the interaction of several factors (mainly pressure, flow rate and evaporator jacket temperature). Those skilled in the art also have operational parameter limits that are not present in the same general-purpose type equipment (eg, wiped thin film evaporators) on much larger scales, including commercial scales, for small or laboratory scale equipment. We recognize what may be, and in many cases, that such limitations are in fact. For a 2 inch (5.1 centimeter (cm)) wiped thin film evaporator (DSL-5 UIC GmbH), such factors include a jacket temperature of 90 ° C. to 150 ° C., preferably a jacket temperature of 110 ° C. A product flow rate of 0.3 kilogram / hour (kg / hr) and a reduced pressure of 0.01 millimeter mercury (mmHg) to 1 mmHg, preferably a reduced pressure of 0.1 mmHg to 0.3 mmHg. For larger scale devices, limit the thermal history of the product in the device to a level lower than that which would cause unacceptable amounts of undesired by-products (eg, heavy weight), If the product flow rate to the device is increased and / or the pressure is changed in a manner sufficient to still achieve the desired level of saturate removal, the jacket temperature can be as high as 300 ° C. Can be raised to temperature. Those skilled in the art will readily understand how to change factors based on scale changes without undue experimentation. The output from the wiped thin film evaporator, regardless of scale, has a reduced saturate content compared to the saturate content found in the product stream fed to the wiped thin film evaporator. If the saturate content remains above that desired for further processing, the use of the wiped thin film evaporator is simply repeated one or more times, but from the previous pass of the wiped thin film evaporator. The output is used as a heated stream fed to the wiped thin film evaporator to further reduce the saturate content. If desired, the monohydroxyl fatty acid methyl ester from the saturate-reduced stream is separated using the same equipment and procedure except that the temperature is increased to 150 ° C.

Even if the above process is initiated using a commercially available methyl ester product, one skilled in the art will recognize a mixture of alkyl esters, preferably lower alkyl (1 to 4 carbon atoms (C ₁ -C ₄ )). It is recognized that a mixture of esters, more preferably a mixture of methyl esters, can be produced by subjecting the seed oil to a conventional alkanolysis procedure using, for example, methanol. Such mixtures of alkyl esters (preferably methyl esters) can easily be substituted for commercial products without undue experimentation.

Examples 1 to 7
To a 2 liter (L) three-necked round bottom glass flask, a water-cooled condensation column is attached at one opening or mouth, and a gaseous nitrogen (N ₂ ) inlet tube is attached at a second opening or mouth. The third opening is fitted with a hermetically sealed mechanical stirrer or a plug when using a magnetic stirrer. At the top of the condensation column, N ₂ gas, possible to exit through a bubbler filled with mineral oil, and conform to bring the approximate quantification of the flow rate of Suipugasu passing flask gas Cover the outflow pipe.

  A polyol initiator, a fatty acid methyl ester derived from hydroformylated and reduced seed oil, and a short chain fatty acid methyol ester or short chain fatty acid together with a predetermined amount of catalyst (see Table 2) in a flask. Add. The catalyst is either dibutyltin dilaurate (DBTL) (IV valent tin (Sn (IV)) catalyst) or tin octoate (Sn (II) catalyst).

  The contents of the flask are heated to a temperature in the range of 160 ° C. to 200 ° C. with stirring to cause a reaction between the contents of the flask. Overhead adapter with cooling condenser (methanol (when short chain fatty acid methyl ester is used as the reactant) or water (when short chain fatty acid is used as the reactant)) from the heated and stirred flask contents. This is sometimes collected via a “short path distillation adapter” in a receiver flask connected in series between the condenser and the bubbler.

Samples of the reacting mixture are collected periodically and the molecular weight (number average (M _n ), weight average (M _w ) and z average (M _z )) of the product is measured by gel permeation chromatography to determine the molecular weight distribution Calculate (MWD or _Mw / _Mn ). (A) sample molecular weight reaching the determined molecular weight range to yield a typical lubricant viscosity, and (b) the reaction is stopped when a molecular weight increase initially less than 0.5% / hour occurs. Let

The hydroxyl (OH) content of the products was calibrated with a series of similar polyols whose OH content was measured according to ASTM D4273-83, from 3300 reciprocal centimeters (cm ⁻¹ ) to 3600 cm ⁻ Determined by Fourier transform infrared (FTIR) spectroscopy using OH resonance absorption between ¹ . The standard polyol has the following hydroxyl percentages: 0.36%, 0.75%, 1.7% and 2.0%. The absorbance of FTIR, when determined according to ASTM D4273-83, is linear over the range including the hydroxyl percentage when 0.996 is used as the square of the correlation coefficient. An alternative technique involves determining the hydroxyl number by titration according to ASTM D4274-05 (this is sometimes referred to as the “phthalic anhydride method”).

  The viscosity of the product is measured by one of two techniques. One technique uses a Brookfield viscometer that uses a # 3 nozzle at 50 rpm. In the second technique, a standard funnel (NALGENE ™ with a 52 mm upper inner diameter (ID), a 21 mm foot length, and a drainage time of 8.0 cps / sec calibrated against standard silicone fluid). A constant time flow through a model 4260-0020 polyethylene funnel is used. The square of the correlation coefficient of viscosity against drainage time for this method is = 0.992.

  Table 1 below provides composition information for alkanolated, hydroformylated and reduced seed oils used as reactants. Monomers (alkanolated, hydroformylated and reduced seed oils), the “general procedure for preparing hydroformylated and reduced fatty acid methyl esters” detailed above in the methanolysis procedure described above. Use together to prepare. Monomer A, Monomer B, Monomer C and Monomer F are started with NATREON ™ high oleic sunflower oil, whereas Monomer D and Monomer G are started with soybean oil and Monomer E Is started with NATREON ™ high oleic canola oil. Monomer A, monomer B, monomer C, monomer D and monomer G all have reduced saturate levels as a result of saturate removal using the procedure detailed above. Monomer E and monomer F have unsaturated saturate levels due to omission of the saturate removal step. NATREON is a trade name of Dow AgroScience.

Table 2 below provides composition information regarding the contents of the flask for each example. In Example 1 and Examples 3 to 7, NPG is used as an initiator. In Example 2, no initiator is used. In Examples 1 to 2 and Examples 4 to 7, DBTL is used as a catalyst, and in Example 3, tin octoate is used as a catalyst. Examples 1 2, and, in Examples 5 to 7, a short-chain _(C 8 _{-C 10)} methyl ester (these from Peter Cremer NA, is commercially available under the trade designation ME C8-10 It is used there) as a capping agent, used in examples 3 4, from Peter Cremer NA, as a short-chain _(C 8 _{-C 10)} fatty acid capping agent sold under the trade designation FA C8-10 Is done.

Table 3 below summarizes selected physical properties and performance measurements of the reaction products for each of Examples 1-7. Table 3 shows the viscosity measurements at 25 ° C.

  The data shown in Tables 2 and 3 show that the lubricant composition of the present invention can function as a base fluid with very good lubricant properties. These lubricant compositions exhibit very good properties independent of the seed oil source and the presence or absence of the alcohol initiator. Examples 1 to 4 and 7 show very low pour points, which are typically significantly lower than seed oils or vegetable oils having pour points in the range of 0 ° C to -20 ° C. A pour point of −30 ° C. or lower (eg, −36 ° C.) is particularly useful as a lubricant for devices operating in very cold climates over extended periods of temperatures below −20 ° C. Furthermore, the data show that the pour point temperature of the lubricant composition is a function of the saturated stearate content of the composition and that by reducing such saturated stearate content, Also show a decline. In addition, Examples 1 to 4 have VI values greater than 160. On the other hand, typical mineral oil products typically have a VI value in the range of 95-105. As noted above, those skilled in the art prefer larger VI values over lower VI values. Those skilled in the art will particularly desire larger VI values for operating industrial and automotive equipment, and values greater than 150 are considered particularly desirable.

  The wear scar data in Table 3 also reveals that these lubricants have excellent film-forming properties, and lubricants that give a wear scar of less than 0.70 mm are considered good lubricants. . The COF data supports a good lubricant characterization (COF below 0.13 for good, COF below 0.10 for good).

Example 8
12.08 g (20 mmol (mmol)) of ethoxylated glycerin (IP-625, The Dow Chemical Company) and 2.2 g (20 mmol) of a hydroxyl-terminated dendritic initiator with 16 terminal hydroxyl groups (this is , Which is commercially available under the trade name BOLTORN® H-20 from Perstrop) using a 16: 1 molar ratio for IP-625: BOLTORN H-20. Prepare. Ethoxylated glycerin and hydroxyl-terminated dendritic initiator are charged into a clean, dry three-necked 250 ml glass round bottom flask equipped with a magnetic stir bar and rubber septum. One mouth of the flask (nominally “exit mouth”) is fitted with a short path condenser that allows hot water at 50 ° C. to flow from the recirculation bath apparatus to prevent an increase in saturates. Using a needle, a nitrogen atmosphere is introduced into the flask through the septum. The flask is sealed and degassed under a vacuum of 20 Torr (266.6 Pascals (Pa)) while heating the contents of the flask to 50 ° C. The flask contents are heated to a temperature of 150 ° C. using a temperature-controlled oil bath with external feedback while maintaining a constant flow of gaseous nitrogen while continuing to stir, and the flask contents are Hold at temperature for 1 hour.

  After 1 hour, 187 g of soy monomer mixture (see Table 4 below for composition) was added to the heated and stirred flask contents through the addition funnel, maintaining a nitrogen flow throughout the addition period. Add. The contents of the flask were heated to a temperature of 150 ° C. under a stream of nitrogen with continued stirring, maintained at that temperature for an additional 30 minutes, and 0.1 g of dibutyltin oxide (DBTO) was added as a catalyst, Heat the contents of the flask to a temperature of 190 ° C. where methanol (MeOH) begins to evolve rapidly.

The contents of the flask are maintained under nitrogen with continued stirring at a temperature of 190 ° C. for 5 hours. Cool the contents of the flask to a temperature of 50 ° C. The distillate from the flask is a clear colorless liquid (methanol or MeOH) with a small amount of white solid. The contents of the flask contain a reaction product having a hydroxyl content of 30.2 percent and a M _n of 3363.

Example 9
Example 8 is repeated but the content of hydroxyl-terminated dendritic initiator is increased to 4.4 g (2.5 mmol) to give an 8: 1 molar ratio for IP-625: BOLTORN H20. The reaction product has a hydroxyl content of 10.4 percent, a M _{n of} 5505, a viscosity (at 25 ° C.) of 7428 cps (7.4 Pa.s) and a pour point of −8 ° C.

Example 10
Example 8 is repeated but the content of hydroxyl-terminated dendritic initiator is increased to 8.8 g (5 mmol) to give a 4: 1 molar ratio for IP-625: BOLTORN H20. The reaction product has a hydroxyl content of 23.9 percent, a M _{n of} 4152, a viscosity (at 25 ° C.) of 4316 cps (4.3 Pa.s) and a pour point of −7 ° C.

Example 11
Repeating Example 8 increased the hydroxyl-terminated dendritic initiator content to 8.8 g (5 mmol) to give a 2: 1 molar ratio for IP-625: BOLTORN H20, and the ethoxylated glycerol The content is reduced to 6.04 g (10 mmol). The reaction product has a hydroxyl content of 30.4 percent and a M _n of 3179.

  The data presented in Examples 8-11 relates to the use of hyperbranched polyol initiators, specifically engineered molecules commercially available from Perstorp under the trade name BOLTORN. Although the reaction products of Examples 8-11 are not fully optimized for pour point and viscosity, they function as polyester polyol lubricant compositions, and such engineered molecules are When used in combination with other compatibilizers (eg, IP-625, etc.), it will prove useful in making such capped polyester polyol lubricant compositions.

Example 12
Example 1 is repeated with several changes. First, 10 torr (1333.2 Pascal (Pa)) is added to the flask contents during the heating period to achieve a reaction between the flask contents. This vacuum achieves the removal of volatile condensation products (mainly methanol) generated during the reaction between the flask contents. Second, the alkanolated, hydroformylated and reduced seed oil is changed to a composition as shown in Table 5 below. Third, change the type and amount of capping agent (580.26 g). The capping agent is a mixture of 4.29 wt% C ₆ methyl ester, 52.88 wt% C ₈ methyl ester and 42.03 wt% C ₁₀ methyl ester (this is the trade name of ME810 from Cremer NA.) (Each wt% is based on the weight of the mixture). Fourth, 733.8 g ethoxylated glycerin (625 weight average molecular weight, commercially available from The Dow Chemical Company under the trade name IP ™ 625) is added as an initiator.

  The product has a weight average molecular weight of 1200, a viscosity at room temperature (25 ° C. for nominal purposes) of 207 cps (0.21 Pa.s), 0.36%% OH, 0.67 mm wear scar, 0.024 Having a pour point of -3 ° C and a viscosity index (VI) of 179.

  Example 12 shows that a capped polyester polyol lubricant composition representative of the present invention provides desirable lubricity properties based on small wear scars and low COF.

Claims (20)

  Optionally comprising (a) at least two ester components that are chemically linked to each other either directly or (b) indirectly via an initiator component, and 0.1 weight Hydroxyl percentages in the range of percent to 2 weight percent (each weight percent based on the composition weight) and saturated hydrocarbons of 12 or more carbon atoms in the range of 0 weight percent to 32 weight percent Capped polyester polyol lubricant having a content (each weight percent based on the composition weight), a viscosity at 25 degrees Celsius in the range of 40 centipoise to 2000 centipoise, and a pour point of -10 degrees Celsius or less Composition.   A plurality of ester components that are chemically linked to each other directly or indirectly through a dendritic initiator component derived from a dendritic base product or an alkoxylated product thereof, from 0.1 weight percent to Hydroxyl percentages in the range of 31 weight percent (each weight percent based on the composition weight) and saturated hydrocarbon content of 12 or more carbon atoms in the range of 0 weight percent to 32 weight percent A polyester polyol lubricant composition having a viscosity at 25 degrees Celsius in the range of 40 centipoise to 8000 centipoise (with each weight percent based on the composition weight) and a pour point of -5 degrees Celsius or less. Said initiator component is of the formula R— (OH) _n , where R is an n-alkyl component, a branched alkyl component or a cyclic alkyl component, and n is an integer in the range of 1 to 64. The composition according to claim 1 or 2, represented.   4. The composition of claim 3, wherein n is an integer selected from the group consisting of 2, 3, 6, 12, 16, 32, and 64.   4. The composition of claim 3, wherein the alkyl component contains from 1 to 6 carbon atoms.   The initiator component is neopentyl glycol (NPG), butanediol, hexanediol, cyclohexanediol, cyclohexanediol isomer, cyclohexanedimethanol isomer, hydroquinone bis (2-hydroxyethyl) ether, glycerin, trimethylolpropane 2. The composition of claim 1 derived from an initiator selected from the group consisting of: sorbitol, a dendritic base product, and an alkoxylated form of this group of elements.   The composition according to claim 1 or 2, wherein the saturated hydrocarbon content is in the range of 0.1 to 10 weight percent. Wherein one of the ester component is an ester alcohol or capping agent, the capping agent is a short chain _(C 6 _{~C 12)} methyl ester or short chain _(C 6 _{~C 12)} fatty fatty, claim 1 or 2 A composition according to 1.   The ester alcohol is an alkanolated, hydroformylated and reduced seed oil, which is castor oil, soybean oil, olive oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil The composition according to claim 8, which is at least one of a natural oil, a high oleic acid oil or a genetically modified oil selected from the group consisting of canola oil, safflower oil, linseed oil and sunflower oil. a. Subjecting the reaction mixture comprising alkanolated, hydroformylated and reduced seed oil, capping agent, catalyst, and, if necessary, an initiator to a high temperature that is in the range of 170 degrees Celsius to 200 degrees Celsius; Converting at least a portion of the reaction mixture into a capped polyester polyol and a volatile byproduct; and b. A method of preparing a polyester polyol lubricant composition comprising simultaneously removing at least a portion of a volatile byproduct. The method further comprises a plurality of successive precursor steps for preparing the alkanolated, hydroformylated and reduced seed oil, wherein the successive precursor steps are:
a1. The seed oil is alkanolized, and the glycerides present in the seed oil are converted into saturated fatty acid esters and unsaturated fatty acid esters of alkanols having a linear or branched structure and containing 1 to 15 carbon atoms. Converting to a mixture;
a2. Hydroformylating a mixture of saturated and unsaturated fatty acid esters to convert said mixture to an aldehyde or mixture of aldehydes; and a3. The aldehyde or mixture of aldehydes is reduced in a hydrogen atmosphere with the aid of a hydrogenation catalyst, and the aldehyde or mixture of aldehydes is converted to an alcohol composition of a hydroxymethyl-substituted fatty acid or a hydroxymethyl-substituted fatty acid ester. The method of claim 10, comprising converting.   Step a2. Is carried out in a non-aqueous reaction medium with a solubilized group VIII transition metal-organophosphine ligand complex catalyst and, if necessary, with a solubilized free organophosphine metal salt ligand. The method of claim 11. The method according to claim 10, wherein the cap agent is a methyl ester of a short chain (C ₆ -C ₁₂ ) fatty acid or a short chain (C ₆ -C ₁₂ ) fatty acid.   The catalyst is stannous bis (ethylhexanoate), stannous octoate, dibutyltin dilaurate, butylstannic acid, dibutyltin oxide, metal alkoxide, soluble mineral acid, sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide The metal alkoxide is selected from the group consisting of sodium methoxide, potassium methoxide, titanium propoxide or titanium isopropoxide, wherein the metal alkoxide is selected from the group consisting of boron trifluoride and zinc dichloride. the method of. The initiator is represented by the formula R— (OH) _n , wherein R is an n-alkyl component, a branched alkyl component or a cyclic alkyl component, and n is an integer in the range of 1 to 64. 11. The method of claim 10, wherein:   The initiator is neopentyl glycol (NPG), butanediol, hexanediol, cyclohexanediol, cyclohexanediol isomer, cyclohexanedimethanol isomer, hydroquinone bis (2-hydroxyethyl) ether, glycerin, trimethylolpropane, 11. The method of claim 10, wherein the method is selected from the group consisting of sorbitol, a dendritic base product, and an alkoxylated form of the substance.   Natural oil or high oleic acid oil wherein the seed oil is selected from the group consisting of castor oil, soybean oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, canola oil, safflower oil, linseed oil and sunflower oil Or the method of Claim 10 which is at least 1 sort (s) of genetically modified oil.   A method for removing at least a portion of a saturate from a capped polyester polyol lubricant composition according to claim 1 or a polyester polyol lubricant composition according to claim 2, comprising capping polyester polyol lubrication. A heated feedstock stream that is an agent composition or a polyester polyol lubricant composition is fed to a wiped thin film evaporator that is operated under reduced pressure to separate the feedstock feed stream into a saturate concentrate portion and a saturate reduction portion Including the method.   19. The method of claim 18, wherein the feed stream is heated to a temperature in the range of 90 degrees Celsius to 150 degrees Celsius, and the reduced pressure is in the range of 0.01 millimeter mercury to 1 millimeter mercury.   The saturate reduction stream resulting from one pass of the wiped thin film evaporator is used as the heated feed feed stream for the next pass of the wiped thin film evaporator, thereby reducing the saturate content of the saturate reduction stream. 20. A method according to claim 18 or 19, wherein the method is further reduced.