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WO2009129292A1 - Esters de polyol et procédé de fabrication de ceux-ci - Google Patents

Esters de polyol et procédé de fabrication de ceux-ci Download PDF

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Publication number
WO2009129292A1
WO2009129292A1 PCT/US2009/040635 US2009040635W WO2009129292A1 WO 2009129292 A1 WO2009129292 A1 WO 2009129292A1 US 2009040635 W US2009040635 W US 2009040635W WO 2009129292 A1 WO2009129292 A1 WO 2009129292A1
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Prior art keywords
polyol
polyether
oil
polyol ester
fatty acid
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English (en)
Inventor
Henri Gruenbauer
Michael Meerbote
Johan Thoen
Hanno Van Der Wal
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups

Definitions

  • This invention relates to improved methods for producing polyols and related materials from vegetable or renewable feedstocks.
  • Polyols with OH functionalities other than 3 can be made using technology claimed by The Dow Chemical Company in WO 2004/096744, WO2004/096882 and WO2004/096883.
  • This technology essentially teaches a complex, four-step process: methanolysis, hydroformylation, hydrogenation and polymerization. The process does not integrate into a product polyol backbone any unsaturated fatty acids, whether they come from the natural oil or result from the hydrogenation step, thereby producing a mixture of chemically divergent species.
  • this invention is a process for producing polyol esters from natural oils or derivatives thereof.
  • the process comprises steps: (i) Subjecting an admixture that comprises (a) a natural oil component consisting essentially of at least one natural oil or derivative thereof having at least one ( ⁇ ) hydroxyl group, and a solubility parameter ⁇ (a), each such oil or derivative thereof hereinafter also referred to as "hydroxylated triglyceride"; and (b) a polyether component consisting essentially of at least one polyether polyol having a boiling point above that of glycerin and having a solubility parameter ⁇ (b); wherein
  • this invention includes a polyol ester comprising structural elements derived from (a) hydroxylated triglycerides having hydroxyl groups and (b) polyether polyols having a number averaged molecular weight of at least 92 Daltons, wherein (a) constitutes at least ( ⁇ ) 50 weight percent (wt percent), more preferably ⁇ 60 wt percent, most preferably ⁇ 70 wt percent, each wt percent being based upon total polyol ester weight.
  • the polyol esters preferably have an OH-functionality of from 3 to 8.
  • the polyol ester may be capped such that at least one, preferably all, of the polyol ester's hydroxyl groups are capped (reacted) with an alkylene oxide or an acid group that has from two carbon atoms to 18 carbon atoms (C 2 -Ci 8 ).
  • the above polyol esters and capped polyol esters have utility in a variety of compositions or applications including, but not limited to elastomers, coatings, adhesives, sealants, and foams as well as functional fluids lubricants, surfactants, wetting agents, dispersing agents, power transmission fluids, oil and gas exploration fluids, industrial and institutional cleaning, metal working fluids, and quenchants.
  • Initiator means a compound having ⁇ one active hydrogen group, that is, ⁇ one functional group having a hydrogen atom or an atom such as oxygen, sulfur or nitrogen, which is sufficiently active to react with an alkylene oxide.
  • Initiators include such compounds as, water, ethylene glycol, or propylene glycol, glycerol, sorbitol or combinations thereof.
  • Polyether polyol refers to a reaction product of an initiator and an alkylene oxide (for example, ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO) or a combination thereof.
  • alkylene oxide for example, ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO) or a combination thereof.
  • Polyol ester means a product of a transesterification reaction between a polyether polyol and a one natural oil or derivative of a natural oil wherein an ester group linking a glycerine moiety and at least one fatty acid moiety in a hydroxylated triglyceride is replaced by an ester linkage between the oxygen of a hydroxyl group on the polyether polyol and the fatty acid moiety from the natural oil.
  • Natural oil refers to animal and vegetable oils, preferably vegetable oils.
  • vegetable and animal oils include, but are not limited to, castor oil, soybean oil, safflower oil, linseed oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, fish oil, or a blend of any of these oils.
  • petroleum or mineral oils are distinguished from natural oils.
  • Natural oil or derivative thereof refers to a natural oil as previously discussed or any substance, compound or combination thereof chemically or physically, preferably chemically, derivable from a natural oil.
  • Natural oil moiety refers to a molecule or, preferably, a part of a molecule which is derived from or derivable from a natural oil.
  • Structural element means a portion of a molecule comprising ⁇ two atoms bonded to each other within that portion and ⁇ one atom bonded to ⁇ one atom not in that portion but in the molecule.
  • the structural element preferably retains structural characteristics, at least structural skeleton of its chemical source.
  • Renewable resource refers to annually renewable resources such as compounds of animal and plant origin as distinguished from, for instance, petroleum or mineral oils and derivatives.
  • Natural oil content “weight contribution of renewable resource,” “renewable resource content,” “renewable content” “renewable” and “weight contribution from natural oil” all refer to that weight percentage of subject matter derived from plant or animal oil or fat as its origin, based on total weight of said subject matter.
  • Active hydrogen functionality refers to number of active hydrogen atoms, that is, hydrogen atoms available for reaction, more reactive than the hydrogen atoms on carbon. Determine active hydrogen functionality using the Zerewitinoff test published in J. Amer. Chem. Soc. 49(1927) p3181 .
  • a functional group having at least one active hydrogen atom is referred to as an "active hydrogen group” and include hydroxyl groups, amine groups, sulfides and combinations thereof
  • solubility parameter refers to a property, represented by ⁇ , used within the art of organic, physical and polymer chemistry to describe the solubility of organic compounds in other organic compounds or solvents. Calculate ⁇ from fragment contributions published in the art (see, for example, Handbook of
  • Transesterification vessel refers to any reaction vessel in which a transesterification reaction takes place, preferably in which mixing and transesterification take place.
  • Closed loop denotes any device for conveying liquid that can be isolated from atmospheric oxygen.
  • Exemplary closed loops include tubing, piping, connectors, or a combination thereof.
  • Evaporator denotes equipment effective for vaporizing at least one liquid, especially for separating said liquid(s) from a liquid or semi-liquid mixture.
  • Evaporators include, for instance, falling film evaporators, rotary evaporators, vapor-liquid separators and the like as well as thin film evaporators.
  • Capping agent or “capping reagent” refers to any compound capable of reacting with a hydroxyl group such that the active hydrogen atom of the hydroxyl group is replaced by a group not having an active hydrogen atom.
  • Exemplary and preferred capping reagents include, for instance, esters, anhydrides or carboxylic acids that lack alcohol or amine functionality.
  • Suitable capping agents include short chain carboxylic acids, their anhydrides and their alkyl esters of wherein the carboxylic acid or derivative thereof has two to eighteen carbon atoms (C 2 -Ci 8 ), advantageously six to twelve carbon atoms (C 6 -Ci 2 ), preferably six to ten carbon atoms (C 6 -Ci 0 ), more preferably short chain carboxylic acids or short chain lower alkyl esters of C 8 and Ci 0 carboxylic acids, mixtures of two or more of such carboxylic acids or lower alkyl esters (for example, a mixture of short chain lower carboxylic acids or short chain lower alkyl esters of C 8 and Ci 0 carboxylic acids), and even more preferably one or more carboxylic acids or methyl esters of such carboxylic acids.
  • Number average molecular weight is a measure of average chain length of a polymer based on monomer repeating unit units per chain and is calculated from the molecular weight distribution curve measured by gel permeation chromatography (GPC).
  • Weight average molecular weight is a measure of average chain length based on a weighted average and is calculated from the molecular weight distribution curve measured by GPC.
  • Molecular weight distribution (MWD) or polydispersity is Mw/Mn and is a measure of the similarity of molecular weights in a sample of polymer.
  • references to the Periodic Table of the Elements herein refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 2003. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
  • a hydroxylated triglyceride is suitably any triglyceride of any fatty acid or derivative thereof having ⁇ one hydroxyl group (for example, ricinoleic acid).
  • the triglyceride is a natural oil such as castor oil, rapeseed oil, sunflower oil, soy oil, or Kamala oil.
  • the triglyceride is a derivative of a natural oil such as hydrogenated castor oil, blown castor oil, dehydrated castor oil, or a combination thereof.
  • the natural oil is optionally reacted with other materials within the skill in the art for forming derivatives of natural oils. Derivatives of natural oils so formed include hydroxy fatty acid derivatives, fatty acids derivatives, fatty alcohols and combinations thereof.
  • polyether polyols include such compounds as a reaction product of an alkoxylating agent with an active hydrogen initiator.
  • Preferred alkoxylating agents include C 2 to C 8 epoxides. More preferred alkoxylating agents include ethylene oxide, propylene oxide or combinations thereof, most preferably propylene oxide.
  • Active hydrogen initiators suitable for alkoxylation include any alkoxylateable active hydrogen compound, for instance polyols, polyamines and aminoalcohols.
  • Exemplary active hydrogen initiators include neopentylglycol; 1 ,2- propylene glycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerol; alkanediols such as 1 ,6-hexanediol; 2,5-hexanediol; 1 ,4-butanediol; 1 ,4- cyclohexane diol; ethylene glycol; diethylene glycol; triethylene glycol; polytetramethyleneglycol and derivatives thereof; 9(1 )-hydroxymethyloctadecanol, 1 ,4-bishydroxymethylcyclohexane; 8,8- bis(hydroxymethyl)tricyclo[5,2,1 ,02,6]decene; dimerol alcohol (a 36 carbon diol available from Henkel Corporation); hydrogenated bisphenol; 9,9(10,10)- bishydroxymethyloctadecanol
  • Exemplary polyamine active hydrogen initiators include ethylene diamine; neopentyldiamine, 1 ,6-diaminohexane; bisaminomethyltricyclodecane; bisaminocyclohexane; diethylene triamine; bis-3-aminopropyl methylamine; triethylene tetraamine and bis(aminoalkyl)alkylamines.
  • Exemplary aminoalcohols include ethanolamine, diethanolamine, and triethanolamine.
  • Other useful active hydrogen initiators that are optionally used include polyols, polyamines or aminoalcohols described in U.S. Patent Nos. 4,216,344; 4,243,818 and 4,348,543 and British Pat. No. 1 ,043,507.
  • the active hydrogen initiator is selected from a group consisting of neopentylglycol, trimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, propoxylated pentaerythritol, butanol, sorbitol, sucrose, glycerol, ethoxylated glycerol, propoxylated glycerol, diethanolamine, 1 ,2-propylene glycol, 1 ,6-hexanediol, 2,5-hexanediol, 1 ,4-cyclohexane diol, 1 ,4-butanediol, ethylene glycol, diethylene glycol, triethylene glycol, sucrose, bis-3-aminopropyl methylamine, propylene glycol, ethylene diamine, diethylene triamine, 9(1 )- hydroxymethyloctadecanol, 1 ,
  • the active hydrogen initiator is selected from butanol, ethylene glycol, propylene glycol, glycerine, sorbitol, sucrose, alkanolamines, aromatic amines like ortho-toluene diamine or combinations thereof.
  • Alkoxylation of an active hydrogen initiator to form a polyether initiator useful in the practice of the invention is well within the skill in the art, for instance as taught by "Chemistry And Technology of Surfactants” from Richard J. Farn, published by Blackwell Publishing, 2006 or by "Polyols for Polyurethanes" by M. Ionescu, published by Rapra Technology, 2005.
  • Alkoxylation forms at least one polyether chain in the polyether initiator.
  • oxide moieties for example, ethylene oxide (EO) and propylene oxide (PO)
  • EO ethylene oxide
  • PO propylene oxide
  • the polyether polyol preferably has a boiling point sufficiently above that of glycerin that it does not distill out with glycerin that is removed from a reaction mixture.
  • the polyether polyol preferably has a boiling point at process conditions of ⁇ 5 degrees centigrade ( 0 C), more preferably ⁇ 15 °C, most preferably ⁇ 30 °C higher than the boiling point of glycerine.
  • the polyether polyol preferably has a molecular weight of ⁇ 92 Daltons, more preferably ⁇ 150 Daltons, most preferably ⁇ 300 Daltons.
  • the polyether polyol is optionally very large, for instance, having a molecular weight of 12,000 Daltons, smaller polyether polyols are preferred in most instances to allow use of a larger relative weight contribution of renewable resource.
  • the polyether polyol preferably has a molecular weight of ⁇ 1500 Daltons, more preferably ⁇ 1000 Daltons.
  • the polyether polyol preferably has a functionality ⁇ 1 , more preferably ⁇ 2, most preferably ⁇ 3 and, independently, preferably ⁇ 8, more preferably ⁇ 6, with more specific preferences corresponding to a preferred functionality for an intended use.
  • the polyether polyol or mixture thereof (polyol component b) is preferably sufficiently compatible (as determined by solubility parameters) with the hydroxylated triglyceride or combination thereof (natural oil component a) with which it is reacted in the process of the invention that they do not readily separate.
  • solubility parameters of the polyol component and natural oil component as measured on the MPa 1/2 scale, differ by advantageously by ⁇ 2 MPa 1/2 , preferably ⁇ 1 .5 MPa 1/2 , more preferably ⁇ 1 MPa 1/2 , most preferably ⁇ 0.5 MPa 1/2 .
  • solubility parameter values of 4 Mpa 1/2 or less would lead to miscible liquids whereas differences larger than 4 Mpa 1/2 would give immiscible liquids. Based on this knowledge, one would expect any effect of the difference in solubility parameters between hydroxylated triglycerides and polyether polyols to manifest at differences -in an absolute sense- of less than 4 Mpa 1/2 units in solubility parameter. Surprisingly, in the practice of the current invention, smaller absolute differences in solubility parameter between triglyceride and polyether polyol component result in a more homogenous product mixture than is observed with larger absolute differences in the solubility parameters.
  • Absolute differences greater than about 2, more particularly absolute differences greater than about 1 .5, most particularly less than about 1 , even less than about 0.5 MPa 1/2 show a tendency toward more homogenous products. It is believed that these smaller absolute differences in solubility parameters result in product mixtures much closer to ideal homogeneous character. Additionally, practice of the invention results in removal of small product molecules such as fatty acids or dimers of fatty acids not reactive with the polyether polyol, which are preferably distilled away with the glycerine. This, too, helps achieve product mixtures that are more homogenous (less chemically diverse) than those achieved by practice of other processes that would superficially appear to result in similar products.
  • Products of the process of the invention preferably also have fewer variations in the numbers of these functional groups and structural elements (structural diversity) and associated smaller molecular weight distributions than have products of similar processes wherein the differences between solubility parameters of the polyether polyol and the hydroxylated triglyceride are greater, advantageously greater than about 2 preferably greater than about 1 .5, more preferably greater than 1 , most preferably greater than about 0.5 MPa 1/2 .
  • a stoichiometric ratio (ratio of equivalents, where a triglyceride has a functionality of 3) of polyether polyol to hydroxylated triglyceride is preferably ⁇ 1 :1 , more preferably ⁇ 1 :2, most preferably ⁇ 1 :3 and independently advantageously ⁇ 1 :12, preferably ⁇ 1 :8, more preferably ⁇ 1 :6, most preferably ⁇ 1 :3.
  • ratios preferably result in an equivalent weight of preferably ⁇ 250, more preferably ⁇ 500, most preferably ⁇ 750, and independently preferably ⁇ 4000, more preferably ⁇ 2000, and most preferably ⁇ 1500 with corresponding molecular weights of preferably ⁇ 500 Daltons, more preferably at ⁇ 1 100 Daltons, and most preferably ⁇ 1875 Daltons, and independently preferably ⁇ 32,000 Daltons, more preferably ⁇ 12,000 Daltons, and most preferably ⁇ 9,000 Daltons.
  • a resulting polyol ester has its hydroxyl functionality determined by number of active hydrogen groups, preferably hydroxyl groups, on the hydroxylated triglyceride and polyether polyol component, stoichiometry and extent of reaction.
  • a stoichiometric ratio is close to one, on average, each terminal hydroxyl group on a polyether polyol is expected to esterify such that an ester is formed with one natural oil moiety.
  • the hydroxyl functionality of the resulting polyol ester is then that of the hydroxyl functionality of the polyether polyol component, if the fatty acid units of the hydroxylated triglyceride all have a functionality of 1.
  • Hydroxylated fatty acids having a hydroxyl functionality of greater than 1 result in greater functionalities in the product. For instance, when a trifunctional polyether polyol is reacted with castor oil at a stoichiometric ratio of 1 , the resulting polyol ester has an average hydroxyl functionality of 3 because each polyether polyol hydroxyl group is esterified with one ricinoleic acid moiety, which moiety has one hydroxyl group. When a stoichiometric excess of natural oil component is used, a polyester chain of more than one natural oil moiety forms on each hydroxyl group of the polyether polyol.
  • the final hydroxyl functionality of the polyol ester is ⁇ 2 preferably ⁇ 3, and more preferably ⁇ 8, most preferably ⁇ 6, depending on the intended final use of the product.
  • functionalities of ⁇ 2, preferably ⁇ 2.2 and most preferably ⁇ 2.5, and independently preferably ⁇ 8, more preferably ⁇ 6 are particularly useful in making flexible foams.
  • M3 (M2-f2) + (M1 -92) * (n1/n2)
  • n is the number of moles
  • M is Mn, preferably as calculated from atoms in the ideal structure.
  • EW is equivalent weight
  • f is hydroxyl functionality
  • 1 represents that of the hydroxylated triglyceride, 2 that of the polyether polyol and 3 that of the product.
  • n2 is the number of moles of polyether polyol, which according to Formula 1 is equal to the number of moles of product n3.
  • the product mixtures produced by practice of the process of the invention vary less from the average or fully reacted product than do products of other processes wherein the difference between solubility parameters of the hydroxylated triglyceride and the polyether polyol are greater than (>) 2 MPa 1/2 .
  • the reaction temperature employed is, for example, a function of the reactants and catalyst as well as the pressure, but the reaction temperature is preferably ⁇ 150 °C, more preferably ⁇ 180 °C, most preferably ⁇ 200 °C, to preferably ⁇ 250 °C, more preferably ⁇ 220 °C, and most preferably ⁇ 210 °C when the pressure is below 1 .0 millibar (mbar) (100 Pascals (Pa)). For instance, a pressure of 26 mbar (2600 Pascals) and a temperature of 182 °C are sufficient to remove vaporized high purity glycerin from a reaction mixture while leaving the product polyol ester in a liquid phase.
  • mbar millibar
  • a pressure of 26 mbar (2600 Pascals) and a temperature of 182 °C are sufficient to remove vaporized high purity glycerin from a reaction mixture while leaving the product polyol ester in a liquid phase.
  • a pressure below atmospheric is needed to assist in volatilizing the glycerin at temperatures below those that could result in deterioration of some choices of reactants.
  • the pressure is preferably a vacuum, that is, a pressure below ( ⁇ ) 200 Pa, preferably ⁇ 150 Pa, more preferably ⁇ 100 Pa.
  • the catalyst is any catalyst within the skill in the art for use in catalyzing transesterification, preferably at the preferred temperatures previously outlined.
  • Such catalysts include tin, titanium, zinc, cobalt, carbonate catalysts (for example, potassium carbonate (K 2 CO 3 ), sodium carbonate (NaHCO 3 ), or lithium carbonate (LiCO 3 )), other bases (for example, sodium hydroxide (NaOH) or potassium hydroxide (KOH)) and combinations thereof.
  • Organometallic catalysts particularly those of tin and titanium are preferred.
  • the tin catalyst is optionally any tin transesterification catalyst such as those known in the art.
  • Exemplary tin catalysts include tin (II) octanoate, tin (II) 2-ethylheptanoate, dibutyl tin (IV) dilaurate, and other tin catalysts which are similarly functionalized.
  • the tin catalyst is tin (II) octanoate, tin (II) 2-ethylheptanoate, or dibutyl tin (IV) dilaurate or combination thereof.
  • the titanium catalyst is optionally any titanium catalyst effective for transesterification, such as those known in the art.
  • titanium catalysts include titanium tetraisopropoxide, titanium tetraisobutoxide, or any appropriately functionalized titanium (IV) alkoxide.
  • the titanium catalyst is titanium tetraisopropoxide.
  • the carbonates the lithium salt is more preferred.
  • the amount of catalyst is preferably at least a minimum amount sufficient to effect a reaction between the polyether polyol component and natural oil component and form the polyol ester at a desirable rate. The amount of catalyst depends, for example, on the particular type of catalyst and reactants.
  • the amount of catalyst is advantageously ⁇ 100 parts by weight per million parts by weight (ppm), preferably ⁇ 250 ppm, more preferably ⁇ 500 ppm, and most preferably ⁇ 1000 ppm, in each case based on total weight of reactants. Considerations other than operability determine any preference for upper limits. While more is operable, even suitable, such considerations as cost of the catalyst or necessity of deactivating or removing excess indicate that, in most cases, an amount of catalyst would be preferably ⁇ 2500 ppm, more preferably ⁇ 2000 ppm, most preferably ⁇ 1500 ppm, based on total weight of reactants.
  • Reaction time similarly, depends on such variables as temperature, vacuum, kind of catalyst and catalyst concentration. In most instances, the time is ⁇ 10 minutes to ⁇ 24 hours. Preferably, the reaction time is ⁇ 15 minutes, more preferably ⁇ 30 minutes, more preferably ⁇ 1 hour to preferably ⁇ 12 hours, more preferably ⁇ 9 hours and most preferably ⁇ 5 hours.
  • the polyol esters described herein may be used with any additives known in the art for production of polyurethane polymers.
  • additives include blowing agents, catalysts, surfactants, cell openers, colorants, fillers, load bearing enhancement additives such as copolymer polyols, water, internal mold releases, antistatic agents, and antimicrobial agents.
  • Preferred surfactants include those made commercially available by Crompton Corporation under trade designation L26 or other polyol pendant chains grafted with a silicone moiety.
  • the polyol esters described herein form polyurethane foams made with a wide range of water concentrations.
  • the water concentrations range from preferably 1 part by weight (pbw) water per hundred pbw polyol, more preferably ⁇ 2 pbw water per 100 pbw polyol, most preferably ⁇ 4 pbw water per 100 pbw polyol, to advantageously 10 pbw water per 100 pbw polyol, preferably ⁇ 9 pbw water per 100 pbw polyol, more preferably ⁇ 8 pbw water per 100 pbw polyol and most preferably ⁇ 6 pbw water per 100 pbw polyol.
  • the polyol esters described herein also particularly useful in bio- lubricants, that is, lubricants based upon renewable resources such as seed oils and vegetable oils rather than from petroleum or natural gas.
  • Bio-lubricants are particularly important in environmentally sensitive applications such as marine, forestry or agricultural lubricants, especially because they are believed to be readily biodegrade, and appear not to harm aquatic organisms and surrounding vegetation.
  • Bio-lubricants without or with reduced numbers of free hydroxyl groups are preferred in most situations over bio-lubricants with a greater number of free hydroxyl groups..
  • Carboxylic acid capping occurs via known esterification or transesterification reactions, for example, by using acidic or basic catalysts for esterification, and transesterification catalysts described herein for production of polyol esters for transesterification.
  • Temperatures used for capping reactions are conveniently ⁇ 70 °C, preferably ⁇ 100 °C, more preferably ⁇ 120 °C independently to preferably ⁇ 230 °C, more preferably ⁇ 200 °C, most preferably ⁇ 180 °C at atmospheric pressure. While capping optionally occurs simultaneously with the formation of the polyol ethers according to the practice of the invention, it preferably occurs in a separate step in order to improve product homogeneity relative to simultaneous capping.
  • the capped polyol esters described herein find use in such products as lubricants and power transmission fluids. For instance, they optionally replace at least a portion of the petroleum or mineral oils frequently used in such fluids.
  • the capped polyol esters are also useful in or as lubricants, surfactants, wetting agents, dispersing agents, power transmission fluids, oil and gas exploration fluids, industrial and institutional cleaning, metal working fluids, quenchants and combinations thereof.
  • the polyether polyesters are useful alone or in combination with other materials such as oils, polyolefins, other functional fluids, cleaners, or lubricating materials.
  • the polyol esters are useful with synthetic lubricants such as polyalkylene glycols (PAG), polyol ethers (POE), and poly (alpha-olefins) (PAO), and with mineral oils.
  • the capped polyol esters described herein have a hydroxyl percentage that is preferably ⁇ 0.1 wt percent, more preferably ⁇ 0.2 wt percent and, most preferably ⁇ 0.3 wt percent and independently ⁇ 2 wt percent, more preferably ⁇ 1 wt percent, most preferably ⁇ 0.7 wt percent, each wt percent being based upon capped polyol ester weight as measured in accord with American Society for Testing and Materials (ASTM) D4272-94d. Achieving a hydroxyl percentage of 0 wt percent, while technically possible, is very expensive.
  • the polyol esters, especially the capped polyol esters, described herein also have a 12 carbon atom and higher carbon number saturated hydrocarbon content that is preferably ⁇ 0 wt percent, more preferably ⁇ 0.1 wt percent and, most preferably ⁇ 0.2 wt percent, and independently preferably ⁇ 32 wt percent, more preferably ⁇ 10 wt percent, most preferably ⁇ 2 wt percent, each wt percent being based upon polyol ester or capped polyol ester weight, whichever is appropriate.
  • a lower saturated hydrocarbon content is better than a higher saturated hydrocarbon content as composition pour point tends to increase with increasing saturated hydrocarbon content as determined by the procedures of ASTM D97.
  • the polyol esters especially the capped polyol esters, described herein, have a viscosity at 25 °C that is preferably ⁇ 40 centipoises (cps) (0.04 Pascal second (Pa.s)), more preferably ⁇ 50 cps (0.05 Pa.s), still more preferably ⁇ 75 cps (0.075 Pa.s) and even more preferably ⁇ 100 cps (0.1 Pa.s) independently preferably ⁇ 2000 cps (2 Pa.s), more preferably ⁇ 1500 cps (1 .5 Pa.s), still more preferably ⁇ 1000 cps (1 Pascal Pa.s), and even more preferably, ⁇ 800 cps (0.8 Pa.s).
  • cps centipoises
  • compositions have a pour point that is preferably ⁇ (lower in temperature) -10 °C, more preferably ⁇ -20 °C, still more preferably, ⁇ -25 °C and most preferably ⁇ -30 °C.
  • KV kinematic viscosity
  • cSt centistokes
  • m 2 /sec square meters per second
  • polyol ester lubricant compositions of the present invention are optionally admixed with an amount of one or more of the seed or vegetable oils disclosed herein.
  • the amount of such seed or vegetable oils is ⁇ 1 wt percent, preferably ⁇ 10 wt percent and more preferably ⁇ 30 wt percent, and independently ⁇ 90 wt percent, preferably ⁇ 80 wt percent, more preferably ⁇ 70 wt percent, in each instance based upon combined weight of uncapped or capped polyol ester lubricant composition and seed or vegetable oil.
  • PE-1 is a polyether polyol having a functionality of 3, and a number averaged molecular weight of 625 Daltons.
  • PE-2 is a polyether polyol prepared by alkoxylating a glycerine initiator with 8 moles of butylene oxide (BO) per mole of initiator to a final theoretical molecular weight of
  • PE-3 is a capped polyether polyol prepared by endcapping PE-2 with 4 moles of
  • PE-4 is a polyether polyol obtained by alkoxylating a glycerine initiator with 8 moles of propylene oxide (PO) per mole of initiator to a final molecular weight of 556
  • PE-5 is a capped polyether polyol prepared by alkoxylating PE-4 with 4 moles of
  • PE-6 is a polyether polyol obtained by alkoxylating a sorbitol initiator with 14 moles of BO per mole of initiator to a final molecular weight of 1 190 Daltons.
  • PE-7 is a capped polyether polyol obtained by endcapping PE-6 with 7.9 moles of
  • PE-8 is a polyether polyol obtained by alkoxylating a sorbitol initiator with 14 moles of PO per mole of initiator to a final molecular weight of 994 Daltons.
  • PE-9 is a capped polyether polyol obtained by endcapping PE-8 with 7.9 moles of
  • Table 1 summarizes characteristics, including solubility parameters, for PE-1 through PE-9.
  • Table 2 gives an overview of examples using the polyether polyols of Table 1 .
  • molecular weights of the polyols calculated from hydroxyl number data in Table 2 are in satisfactory agreement with GPC measurements using standard equipment.
  • Polydispersities range from 1 .25 to 1 .40.
  • Example 17-20 For each of Examples 17-20, replicate Example 1 using an initiator as shown in Table 2, but substitute a hydroformylated high oleic canola oil for the castor oil of Example 1 .
  • a hydroformylation reactor (Parr pressure reactor, 300 cubic centimeters (cc)) with a dip tube to feed syngas (CO + H 2 ) to the bottom of the reactor, and further equipped with internal coils for controlled water cooling, and with addition cylinders for addition of substrate or water into the reactor under pressure.
  • the reactor is also equipped with a high pressure cylinder (600 cc, 6000 pounds per square inch absolute (psia)/41 .4 megapascals (MPa)) for pressurization with syngas or any other gas to be fed into the reactor.
  • ⁇ absolute difference in calculated solubility parameter between polyether polyol and triglyceride
  • %REN percent by weight of renewable materials assuming all glycerine is distilled off In addition, sorbitol and glycerine are assumed to be of renewable origin
  • MW molecular weight, (OH#) determined from hydroxyl number, (ideal) calculated from structural formula of ideal product
  • ELSD for instance, the detector commercially available from Sedere Sa
  • Examples 1 -16 use the same hydroxylated triglyceride as Comparative Sample A and are more homogeneous in that they have a main peak, sometimes with a shoulder or a small peak in a more hydrophobic area (left side of chromatograms).
  • the chromatogram of Comparative Sample A shows a main peak made up of many smaller overlapping peaks between 2.5 and 5 minutes and a relatively large peak at about 1 1 minutes which is absent from the other chromatograms. While the chromatograms of products of the invention usually indicate mixtures, the chromatogram of Comparative Sample A indicates many more separate compounds and much more difference in the hydrophilicity, thus functional nature, of the product in the presence of a large separate product peak at 1 1 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne la production d'esters de polyol à partir d'huiles naturelles ou de dérivés de celles-ci par : (i) la soumission d'un mélange qui comporte (a) un composant d'huile naturelle constitué essentiellement d'au moins une triglycéride hydroxylée ayant au moins un groupe hydroxyle, et un paramètre de solubilité (a), et (b) un composant de polyester constitué essentiellement d'au moins un polyol de polyester ayant un point d'ébullition au-dessus de celui de la glycérine et ayant un paramètre de solubilité (b); |(a) - (b)| étant tels que mesurés sur l'échelle allant de 0,5 MPa à environ 2,50 MPa au maximum, dans des conditions de transestérification utilisant au moins un catalyseur de transestérification; et (ii) l’élimination suffisante de glycérine pour entraîner la formation d'au moins un ester de polyol à partir du polyol de polyester et au moins un acide gras à partir de la triglycéride hydroxylée. Les esters de polyol, qu'ils soient à coiffe ou non, sont de manière caractéristique homogènes et peuvent être utilisés, par exemple dans des élastomères, des revêtements, des adhésifs, des agents d'étanchéité, des mousses, des fluides fonctionnels, des lubrifiants, des tensioactifs, des agents humectant, des agents de dispersion, des liquides hydrauliques, des fluides d'exploration de pétrole et de gaz, des produits de nettoyage industriel et institutionnel, des fluides de travail du métal et des produits de trempe.
PCT/US2009/040635 2008-04-18 2009-04-15 Esters de polyol et procédé de fabrication de ceux-ci Ceased WO2009129292A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016118399A1 (fr) * 2015-01-21 2016-07-28 3M Innovative Properties Company Adhésif polyuréthane résistant aux produits chimiques
WO2017052680A1 (fr) * 2015-09-21 2017-03-30 3M Innovative Properties Company Adhésif polyuréthanne résistant aux produits chimiques
WO2020062036A1 (fr) * 2018-09-28 2020-04-02 Dow Global Technologies Llc Composition de polyol
US11629273B2 (en) 2017-02-28 2023-04-18 3M Innovative Properties Company Polyurethane adhesive with chemical resistant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246285A (en) * 1975-10-20 1981-01-20 The Procter & Gamble Company Skin conditioning compositions containing guanidine inorganic salts
US5284980A (en) * 1992-10-26 1994-02-08 E. I. Du Pont De Nemours And Company Block copolyethers via oxonium coupling of poly(tetramethylene ether) glycols
WO1997023559A2 (fr) * 1995-12-14 1997-07-03 E.I. Du Pont De Nemours And Company Alcanolyse des esters de polyol de polyether par distillation reactive
US6730642B1 (en) * 2003-01-10 2004-05-04 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Extruded multiphase bars exhibiting artisan-crafted appearance
WO2004096882A1 (fr) * 2003-04-25 2004-11-11 Dow Global Technologies, Inc. Huile vegetale a base de polyols et polyurethannes conçus a partir de celle-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246285A (en) * 1975-10-20 1981-01-20 The Procter & Gamble Company Skin conditioning compositions containing guanidine inorganic salts
US5284980A (en) * 1992-10-26 1994-02-08 E. I. Du Pont De Nemours And Company Block copolyethers via oxonium coupling of poly(tetramethylene ether) glycols
WO1997023559A2 (fr) * 1995-12-14 1997-07-03 E.I. Du Pont De Nemours And Company Alcanolyse des esters de polyol de polyether par distillation reactive
US6730642B1 (en) * 2003-01-10 2004-05-04 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Extruded multiphase bars exhibiting artisan-crafted appearance
WO2004096882A1 (fr) * 2003-04-25 2004-11-11 Dow Global Technologies, Inc. Huile vegetale a base de polyols et polyurethannes conçus a partir de celle-ci

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016118399A1 (fr) * 2015-01-21 2016-07-28 3M Innovative Properties Company Adhésif polyuréthane résistant aux produits chimiques
US10301418B2 (en) 2015-01-21 2019-05-28 3M Innovative Properties Company Chemical resistant polyurethane adhesive
WO2017052680A1 (fr) * 2015-09-21 2017-03-30 3M Innovative Properties Company Adhésif polyuréthanne résistant aux produits chimiques
EP3792325A1 (fr) * 2015-09-21 2021-03-17 3M Innovative Properties Company Adhésif polyuréthane résistant aux produits chimiques
US11629273B2 (en) 2017-02-28 2023-04-18 3M Innovative Properties Company Polyurethane adhesive with chemical resistant
WO2020062036A1 (fr) * 2018-09-28 2020-04-02 Dow Global Technologies Llc Composition de polyol
US12024581B2 (en) 2018-09-28 2024-07-02 Dow Global Technologies Llc Polyol composition

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