EP2510043A1 - Dérivés polyéther d'acides gras hydroxy secondaires et leurs dérivés - Google Patents

Dérivés polyéther d'acides gras hydroxy secondaires et leurs dérivés

Info

Publication number
EP2510043A1
EP2510043A1 EP09795613A EP09795613A EP2510043A1 EP 2510043 A1 EP2510043 A1 EP 2510043A1 EP 09795613 A EP09795613 A EP 09795613A EP 09795613 A EP09795613 A EP 09795613A EP 2510043 A1 EP2510043 A1 EP 2510043A1
Authority
EP
European Patent Office
Prior art keywords
polyether
carbon atoms
fatty acid
compound
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09795613A
Other languages
German (de)
English (en)
Inventor
Johan Thoen
Jean-Paul Masy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP2510043A1 publication Critical patent/EP2510043A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • 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
    • C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride groups
    • 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
    • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group

Definitions

  • This invention relates to derivatives of hydrogenated castor oil and their use in polyurethanes, lubricants and other functional fluids. More specifically, the invention relates to polyethers of hydrogenated castor oil and derivatives thereof.
  • Castor oil-based lubricants have an advantage of being based on renewable resources, but a disadvantage of having limited thermal oxidative stability because of triglyceride bonds and unsaturated compounds. Furthermore natural oils like castor oil have a high level of linear saturated materials that appear to adversely affect pour point performance (for example, increase it from -5 degrees centigrade ( Q C) to +5 Q C) when present in a lubricant or other functional fluid.
  • Isolated hydroxy-substituted fatty acids or combinations thereof may be obtained from natural oils either directly such as ricinoleic acid (1 2-hydroxyocta- decenoic acid (1 2-HODA)) from castor oil, or by derivation such as production of 1 2-hydroxy stearic acid (1 2-HSA) from hydroxyoctadecanoic acid.
  • Esters of such acids, particularly esters of 1 2-HODA have known utility in lubricants, but these esters are usually linear polyesters or even salts of the acids.
  • Such esters are generally linear rather than short chain branched, that is having branches of less than ( ⁇ ) 1 2 carbon atoms (Ci 2 ).
  • each hydroxy fatty acid is reacted with the hydroxyl group of the previous fatty acid in a linear chain.
  • Linear polyesters of this nature have limitations in viscosity, pour point and thermo- oxidative stability. Frequently there are free hydroxyl groups which tend to further react resulting in viscosity increase.
  • branched derivative of a fatty acid preferably of 1 2-HSA, effective as a lubricant or functional fluid and based primarily on renewable resources, but which overcomes disadvantages of linear polyesters and triglyceride castor oil based lubricants.
  • the branched derivative preferably has at least one of (a) good friction properties as indicated by a "low" coefficient of friction determined using Stribeck curves as established on a PCS MTM Minitraction machine of ⁇ 0.07, preferably at most ( ⁇ ) 0.06, more preferably ⁇ 0.05; (b) a low pour point, that is a pour point of ⁇ 0 ° C measured in accord with
  • this invention includes a compound that is a polyether of a saturated monobasic secondary hydroxyl fatty acid, preferably 1 2-HSA.
  • the polyether is optionally formed from a derivative of the fatty acid, for instance an ester of the fatty acid, most preferably methyl 12-hydroxy stearate (M-12-HS), to provide a monobasic secondary hydroxy fatty acid moiety.
  • the monobasic secondary hydroxy fatty acid moiety optionally comes from any compound capable of introducing such a moiety, for instance a monobasic secondary hydroxy fatty acid, anhydride, chloride or ester thereof, and is, independently, most preferably a 12-HSA moiety.
  • this invention includes compositions comprising derivatives of polyethers of such saturated fatty acids, wherein hydroxyl groups are capped, and wherein a resulting polyether is reacted with a polyhydric alcohol to form a polyester of the polyether or a combination thereof.
  • the alkylene oxide has no more than one alkyl group and is represented by
  • the polyether may be structurally represented by Formula 1 :
  • this invention includes a process comprising a step of (1 ) contacting a saturated secondary hydroxy monobasic fatty acid or derivative thereof with an alkylene oxide in the presence of a double metal cyanide (DMC) catalyst to form a polyether of the fatty acid or derivative.
  • the process also includes a step (2) capping the resulting polyether, or alternatively, contacting a resulting polyether with a polyhydric alcohol, or both.
  • DMC double metal cyanide
  • this invention includes a compound or composition that is or comprises a reaction product of a saturated secondary hydroxyl monobasic fatty acid or derivative thereof and an alkylene oxide formed in the presence of a DMC catalyst. Capped and polyester derivatives of such reaction products are also included in this invention.
  • This invention further includes compositions (for example, functional fluids) comprising at least one of the above compounds, which fluids are preferably plasticizers, lubricants, power transmission fluids, solvents or surfactants.
  • the invention also includes polyols which are or comprise such compounds or compounds derived from such compounds and polyurethanes that are reaction products of such polyols as well as articles made from such polyurethanes.
  • “Friction properties” designates an ability to ameliorate effects of friction between surfaces at least one of which is moving with respect to the other and can be measured using an instrument designed for such measurements, for instance, a PCS Instruments (MTM2 Minitraction Machine) commercially available from PCS Instruments Ltd, London, UK. Measurement conditions preferably include slide-roll- ratio (SRR) 50 percent, load 50 Newtons (N), speed 100 millimeters per second (mm/sec), and temperature 40°C in which a steel ball (3/4 inch (1 .9 centimeters (cm))) is rotated on a steel disc)
  • Weight properties indicates an ability to reduce wearing of two objects in contact with each other, at least one of which is moving with respect to the other, and is also measured by an instrument such as that used to measure friction properties.
  • Pul point refers to a temperature at which a material solidifies as measured in accord with ASTM D97.
  • Thermal oxidative stability means resistance to deterioration in the presence of heat (at least ( ⁇ ) 95 °C) and oxygen measured in accord with
  • Polyether designates a compound having ⁇ two ether oxygen atoms separated by a hydrocarbyl group. Preferably, it is the reaction product of ⁇ two moles of an alkylene oxide with a hydroxyl group of another compound.
  • Alkylene oxide refers to an organic compound having an epoxide group.
  • Polyhydric alcohol designates an organic compound having ⁇ two hydroxyl groups.
  • Fatty acid means a long-chain carboxylic acid, with chain length of ⁇ 4 carbon atoms. Typical fatty acids have chain lengths of 4 to 18 carbon atoms (C - Cis), though some have longer chains. Linear, branched, or cyclic aliphatic groups may be attached to the long chain. Fatty acid residues may be saturated or unsaturated, and optionally have functional groups in addition to the acid group.
  • Hydroxy fatty acid designates a fatty acid having ⁇ one hydroxyl group, preferably a secondary hydroxyl group.
  • the hydroxyl group is optionally present in the acid as obtained from a natural oil or is introduced by chemical reaction such as by reaction at a double bond, for instance, by epoxidation, reaction with a compound such as maleic anhydride, by oxidation, by reaction with water such as blown oils where moist air is used in the presence of a catalyst such as cobalt, by epoxidation with propylene oxide or higher alkylene oxide, by reaction with aqueous perchloric acid or hydrogen peroxide and the like.
  • “Monobasic hydroxy fatty acid” designates a fatty acid that has one carboxyl group.
  • Capping agent or “capping reagent” refers to any compound capable of reacting with a hydroxyl group such that the hydroxyl group's active hydrogen atom is replaced by a group not having a reactive hydrogen atom, that is, not having an active hydrogen or having a functional group which is not sufficiently reactive to have appreciable detrimental effects in intended end uses.
  • Exemplary and preferred capping reagents include carboxylic esters, anhydrides, chlorides or acids that lack alcohol or amine functionality.
  • Suitable capping agents include short chain carboxylic acids, their anhydrides, their chlorides and their alkyl esters of wherein the carboxylic acid or derivative thereof has two to eighteen carbon atoms (C-2 -Cis), 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 C 10 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 C 10 carboxylic acids), and even more preferably one or more carboxylic acids or methyl esters of such carboxylic acids.
  • capping agents are epoxides having ⁇ 4 carbon atoms, preferably ⁇ 8 carbon atoms.
  • Such epoxides are preferably linear or branched alkyl-oxiranes like n-alkyloxiranes, 2-ethylalkyloxiranes and 2,3- butyloxiranes and combinations thereof.
  • Epichlorohydrin, methyl chloride, dimethyl sulfate, sodium methoxide and other compounds known in the art to react with hydroxyl groups to produce ethers are among other alternative capping agents.
  • Moiety and structural element refer to a portion of a molecule comprising ⁇ two atoms bonded to each other within a structural element and ⁇ one atom bonded to ⁇ one other atom in the molecule.
  • the moiety or 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 thereof.
  • the compound of some aspects of this invention is a reaction product of an alkylene oxide and a saturated monobasic secondary hydroxy fatty acid or mixture of such acids. Reactant stoichiometry is such that every hydroxyl group on the saturated monobasic hydroxyl fatty acid molecule reacts with ⁇ two molecules of alkylene oxide (sequentially) to form a polyether.
  • the compound has, at its core, a molecular moiety from a saturated secondary hydroxyl monobasic fatty acid.
  • Saturated monobasic secondary hydroxy fatty acids are commercially available.
  • Other fatty acids that have a secondary hydroxyl group for example, those derived from Lesquerella seeds, are also useful. See Kleiman, R. "Chemistry of New Industrial Oilseed Crops" p. 1 96-203, in: J. Janick and J.E. Simon (eds.), Advances in New Crops, Timber Press, Portland, OR (1990).
  • 12 HSA (hereinafter exemplary of saturated monobasic secondary hydroxyl fatty acids) is preferably used as a derivative thereof, preferably as an anhydride, a halide or, more preferably, an ester, most preferably the methyl ester, methyl 12-hydroxy stearate (M12HS).
  • M12HS is preferably reacted with (that is alkoxylated by) an alkylene oxide (for example, ethylene oxide (EO), propylene oxide (PO), or a combination thereof) to form a corresponding polyether at the molecular site of the hydroxyl group.
  • an alkylene oxide for example, ethylene oxide (EO), propylene oxide (PO), or a combination thereof
  • Any alkylene oxide having an epoxide group sufficiently reactive to react with the hydroxide group on M12HS such that the epoxide ring is opened, forming an ether group at the fatty acid hydroxyl group and another hydroxyl group for further reaction with additional alkylene oxide from the epoxide oxygen is suitable for use in practicing various aspects of this invention.
  • they are optionally used in admixture to form a random polyether structure or in sequence to form a block polyether structure.
  • pure ethylene oxide or mixtures of propylene oxide and ethylene oxide having a high proportion of ethylene oxide are preferably added as a terminal block or used for the entire polyether chain, such that the polyether chains bonded to the M12HS have ⁇ 50 mole percent, more preferably ⁇ 70 mol percent, most preferably ⁇ 90 mol percent of primary OH terminal groups.
  • at least terminal block of polyether residues derive from propylene oxide to give a secondary hydroxyl group. More preferably the polyether molecular structure is formed from propylene oxide alone.
  • propylene oxide is at least 50 wt percent, more preferably at least 60 wt percent and most preferably at least 70 wt percent of the combination of alkylene oxides.
  • the molar ratio of M12HS to alkylene oxide is preferably ⁇ 1 :30, more preferably ⁇ 1 :20 and most preferably ⁇ 1 :10; independently the ratio is preferably ⁇ 1 :1 , more preferably ⁇ 1 :5 and most preferably ⁇ 1 :7.
  • DMC catalysts are preferred because ester bonds of the M1 2HS are subject to fewer secondary reactions when a DMC catalysis used.
  • DMC catalysis is well within the skill in the art as illustrated by such patent references as U.S. Pat. Nos. 3,404, 109, 3,829,505, 3,941 ,849 and
  • Alkoxylation of the M1 2HS is carried out under reaction conditions effective to form a polyether molecular structure at the site of the secondary hydroxyl group on the M1 2HS.
  • reaction conditions effective to form a polyether molecular structure at the site of the secondary hydroxyl group on the M1 2HS.
  • Such processes are within the skill in the art as exemplified by WO-A 97/29146 and WO-A 98/03571 .
  • the reaction is suitably batch or continuous or a combination thereof.
  • Such conditions preferably include contact of the M1 2HS and an alkylene oxide in the presence of a DMC catalyst in a reactor under a pressure that is preferably ⁇ 0.1 Bar (10 kilopascals (kPa)), more preferably ⁇ 0.5 Bar (50 kPa), most preferably ⁇ 1 .0 Bar (100 kPa), and independently preferably ⁇ 15 Bar (1500 kPa), more preferably ⁇ 10 Bar (1 ,000 kPa), most preferably ⁇ 5 Bar (500 kPa).
  • kPa kilopascals
  • reaction temperatures are usually ⁇ 20 °C, preferably ⁇ 90 °C, more preferably ⁇ 100°C, most preferably ⁇ 1 20 °C, and independently preferably ⁇ 200 °C, more preferably ⁇ 180 °C, most preferably ⁇ 160 °C.
  • Reaction time depends on such parameters as concentration of reactants, pressure and temperature. In a batch reaction, reaction times are preferably ⁇ two hours, more preferably ⁇ three hours, most ⁇ five hours, and independently preferably ⁇ 10 hours, more preferably ⁇ eight hours.
  • a solvent is optionally used, such as toluene, tetrahydrofuran (THF) or a combination thereof.
  • THF tetrahydrofuran
  • convenient amounts are often preferably ⁇ 10 wt percent, more preferably ⁇ 8 wt percent, most preferably ⁇ 5 wt percent, and independently preferably ⁇ 30 wt percent, more preferably ⁇ 20 wt percent, most preferably ⁇ 1 5 wt percent, each wt percent being based on expected weight of end product.
  • Catalyst concentration is selected to achieve control of the formation of the polyether.
  • catalyst concentration is often preferably ⁇ 20 parts by weight per million parts by weight (ppm), more preferably ⁇ 100 ppm, and independently preferably ⁇ 500 ppm, more preferably ⁇ 300 ppm, most preferably ⁇ 150 ppm (parts per million by weight) based on total amount of end product expected to be produced.
  • the reaction product of M12HS and alkylene oxide is a fatty acid, anhydride or ester as previously described having a polyether group or moiety on the carbon of the original hydroxyl group, in the case of M12HS, on the 12 carbon.
  • the polyether moiety is terminated by a hydroxyl group which is primary if the last alkylene oxide added is ethylene oxide or secondary if the alkylene oxide has more than two carbon atoms.
  • This reaction product is referred to herein as a polyether fatty acid or alkoxylated fatty acid, although those skilled in the art will recognize that the acid is optionally in the form of the anhydride or ester, that is, the same form as the starting material.
  • the product is referred to herein as 12-polyether methyl stearate or alkoxylated M12HS.
  • the polyether fatty acids are compounds of some aspects of this invention.
  • the polyether fatty acid is optionally, but preferably, further reacted with a polyhydric alcohol or polyhydric alcohol mixture.
  • a polyhydric alcohol or polyhydric alcohol mixture examples include trimethylolpropane (TMP), pentaerythritol (PE), dipentaerythritol (DPE), neopentyl glycol (NPG), 2-methyl-2-propyl-1 ,3-propanediol (MPPD) and combinations thereof.
  • TMPPD trimethylolpropane
  • the polyhydric alcohol has an average of ⁇ two hydroxyl groups, preferably ⁇ three hydroxyl groups, more preferably ⁇ four hydroxyl groups, and independently preferably ⁇ eight hydroxyl groups, more preferably ⁇ six hydroxyl groups, and most preferably ⁇ five hydroxyl groups.
  • the polyhydric alcohol preferably has an average equivalent weight of ⁇ 24 Daltons, preferably ⁇ 30 Daltons, more preferably ⁇ 52 Daltons, and independently preferably ⁇ 100 Daltons, more preferably ⁇ 90 Daltons, and most preferably ⁇ 80 Daltons.
  • the hydroxyl groups on the polyhydric alcohol are esterified with the carboxyl group of the polyether fatty acid.
  • the reaction is a simple esterification. If the polyether fatty acid is in the form of an ester such as the methyl ester, M12HS, the reaction is a transesterification. See Oleochemical Manufacture and Applications, Frank D. Gunstone and Richard J. Hamilton, ISBN 1 -84127-21 9-1 , Sheffield Academic Press Ltd, Sheffield S1 1 9 AS United Kingdom for a discussion of esterification and transesterification reactions.
  • esterification contact the polyether fatty acid or its anhydride and the polyhydric alcohol, preferably in the presence of an acidic or basic catalyst, under reaction conditions sufficient to result in formation of an ester between the acid and hydroxyl groups.
  • Temperatures conveniently are ⁇ 1 50 °C, preferably ⁇ 1 70 °C, more preferably ⁇ 190 °C independently to preferably ⁇ 240 ⁇ , more preferably ⁇ 220 °C, most preferably ⁇ 200 °C at atmospheric pressure.
  • the pressure is conveniently atmospheric pressure, but lower pressures are also useful, for instance, the pressure is preferably ⁇ 20 (hPa), preferably ⁇ 30 hPa, more preferably ⁇ 50 hPa independently to preferably ⁇ 200 hPa, more preferably ⁇ 150 hPa, most preferably ⁇ 100 hPa.
  • the amount of catalyst is preferably ⁇ 100 ppm, preferably ⁇ 200 ppm, more preferably ⁇ 400 ppm independently to preferably ⁇ 3000 ppm, more preferably ⁇ 2000 ppm, most preferably ⁇ 1000 ppm, based on total weight of reactants.
  • Reaction time depends on such variables as temperature, pressure, type of catalyst and catalyst concentration. In most instances, the time is ⁇ 240 minutes.
  • the reaction time is ⁇ 500 minutes, more preferably ⁇ 450 minutes, more preferably ⁇ seven hours to preferably ⁇ 90 hours, more preferably ⁇ 40 hours and most preferably ⁇ 20 hours.
  • Hydrocarbons are optionally used as entrainment agents to facilitate removal of volatile components from a (trans)esterification reaction.
  • Useful hydrocarbons include aliphatic and aromatic hydrocarbons such as iso- octane, toluene, xylene and combinations thereof.
  • Catalysts include tin, titanium, zinc, or cobalt catalysts, carbonate catalysts (for instance, potassium carbonate (K 2 C0 3 ), sodium carbonate (NaHC0 3 ), or, preferably, lithium carbonate (LiC0 3 )), or other bases (for example, sodium hydroxide (NaOH) or potassium hydroxide (KOH)) or a combination thereof.
  • Organometallic catalysts particularly those of tin and titanium are preferred.
  • Exemplary tin catalysts include tin (I I) octanoate, tin (II) 2-ethylheptanoate, dibutyl tin (IV) dilaurate, and other tin catalysts which are similarly functionalized.
  • Exemplary titanium catalysts include tetra-n-butyl titanate, titanium tetraisopropoxide, titanium tetraisobutoxide, or any appropriately functionalized titanium (IV) alkoxide.
  • the catalyst is present in an amount effective to result in the reaction between the acid ester and hydroxyl group to form the resulting ester at a desirable rate.
  • the amount depends, for example, on type of catalyst and reactants.
  • the amount of catalyst is advantageously ⁇ 100 ppm, preferably ⁇ 250 ppm, more preferably ⁇ 500 ppm, and most preferably ⁇ 1 000 ppm based on total weight of reactants. Considerations other than operability determine any preference for upper limits.
  • an amount of catalyst would be preferably ⁇ 2500 ppm, more preferably ⁇ 2000 ppm, most preferably ⁇ 1500 ppm, based on total weight of reactants.
  • reaction times, temperatures and pressures are preferably the same as those disclosed above for esterification.
  • the reaction time is dependent on such variables as temperature, pressure, type of catalyst and catalyst concentration.
  • the molar ratio of polyether fatty acid to hydroxyl groups on the polyhydric alcohol is ⁇ 1 .1 /1 .0, more preferably ⁇ 1 .05/1 .0 and most preferably ⁇ 1 .01 /1 .0 and independently preferably ⁇ 0.90/1 .0, more preferably ⁇ 0.95/1 .0, most preferably ⁇ 1 .0/1 .0 to avoid unreacted hydroxyl groups on the polyhydric alcohol.
  • the product of the reaction between a polyether fatty acid and a polyhydric alcohol has as many ester groups as there are hydroxyl groups on the polyhydric alcohol, and is, therefore, referred to herein as a "polyether fatty polyester”.
  • the polyether fatty polyester has as many hydroxyl groups on polyether chains as there are hydroxyl groups on the polyhydric alcohol to each react with a M1 2HS.
  • the polyether fatty polyester is a polyol.
  • it is useful in making polyurethanes or other polymers by reacting the polyether fatty polyester with such monomers as polyisocyanates, for instance toluene diisocyanate, methylene diphenyl diisocyanate, and polymers thereof. Preselect the number of hydroxyl groups on the polyether fatty polyester by choosing a polyhydric alcohol of desired functionality. Similarly, preselect percentage of primary and secondary hydroxyl groups by choice of alkylene oxide in making the polyether chain of the polyether fatty polyester.
  • the polyurethanes find use in application such as flexible foams, rigid foams, coating, elastomers, and adhesives.
  • the above polyols are also useful in making copolymer thermoplastic resins, in thermoset epoxy applications or as surfactants, solvents, oils of lubricating viscosity, heat transfer fluids, and power transmission fluids.
  • functional fluids such as lubricants, power transmission fluids, heat transfer fluids, thickening agents, surfactants, solvents, and plasticizers
  • Capping is a reaction of an active functional group on the polyether fatty acid derivative (preferably ester) or polyether fatty polyester, particularly a hydroxyl group with another molecule such that there is no longer a reactive functional group (preferably hydroxyl group).
  • Free hydroxyl groups are preferably capped by reaction with monobasic alkyl carboxylic acid capping agents, that is the acid or an acid derivative reactive with the hydroxyl group, preferably the acid, anhydride or ester form.
  • the capping agent may be an epoxide that results in a hindered hydroxyl group.
  • the capping agent may also be epichlorohydrin which reacts with a hydroxyl group under conditions effective to produce a glycidyl ether, preferably at a temperature of ⁇ 80 °C and ⁇ 1 20 °C, independently preferably a pressure of ⁇ 50 kPa and ⁇ 5000 kPa, independently preferably at concentrations of epichlorohydrin to free hydroxyl group of ⁇ 1 .0/1 .05 and ⁇ 1 .0/1 .10, and independently preferably for a time of ⁇ two hours and ⁇ five hours.
  • epichlorohydrin which reacts with a hydroxyl group under conditions effective to produce a glycidyl ether, preferably at a temperature of ⁇ 80 °C and ⁇ 1 20 °C, independently preferably a pressure of ⁇ 50 kPa and ⁇ 5000 kPa, independently preferably at concentrations of epichlorohydrin to free hydroxyl group of ⁇ 1 .0/1
  • the hydroxyl groups of the polyether fatty polyester of the invention may be capped with methyl groups, for example, as disclosed in such references as U.S. Pat. No. 4,587,365 or EP-B 0 302 487. It is advisable to carry out the reaction at a temperature of ⁇ 60 °C, preferably ⁇ 80 °C and independently ⁇ 120 °C, preferably ⁇ 100 °C. In this case, the end capping reaction is a
  • Williamson's ether synthesis which occurs in the presence of at least stoichiometric quantities of a strong base, for example an alkali metal hydroxide or alkoxide.
  • a strong base for example an alkali metal hydroxide or alkoxide.
  • the alkoxylated hydroxy-fatty acid ester, the base and the methylating agent in a molar ratio of approximately 1 :1 (that is, preferably a ratio of from 1 .05 to 2.0 moles of base to 1 .05 to 2.0 moles of methylating agent).
  • the polyether fatty polyester or polyether fatty acid derivative has a free carboxylic acid or anhydride group, it is also preferably reacted to form the ester.
  • the ester is formed before alkoxylation.
  • the capped polyether fatty polyesters described herein differ from art recognized end-capped fatty alcohol polyglycol ethers, so-called “mixed ethers" (for example, as described by R. Piorr in Fat Sci. Technol. 89, 1 06 (1987)) used as low-foaming surfactants. These products are generally butyl-end-capped nonionic surfactants. See ,for example, EP-A 0 124 81 5, EP-B 0 303 928, EP-B 0 324 340, EP-A 0 420 802, DE-A 39 28 600 and DE-C 42 43 643.
  • the capped polyether fatty polyesters described herein have both ether and ester functionality and are branched as illustrated in Formula 1 above.
  • the capped polyether fatty polyesters differ from methyl-end-capped methyl mixed ethers normally prepared by reaction of corresponding fatty alcohol polyglycol ethers with methyl halides as disclosed in U.S. Pat. No. 4,587,365, or dimethyl sulfate as in EP-B 0 302 487.
  • the molar ratio of monobasic alkyl carboxylic acid capping agent to polyether fatty polyester is preferably ⁇ 1 /1 , more preferably ⁇ 1 .01 /1 to minimize presence of free hydroxyl groups in the final product, and independently preferably ⁇ 2.0/1 , most preferably ⁇ 1 .05/1 .
  • Molar ratios like 2.0/1 are used to speed the reaction, but require removal of excess of unreacted acid or anhydride by, for instance, distillation.
  • the capped polyether fatty polyesters correspond to Formula 1 above except that the terminal H on the molecular moiety represented by 0(CH 2 -CHR 1 " 0) X H is replaced by R 2 to form 0(CH 2 -CHR 1 O) x R 2 , wherein the structure of R 2 varies with the capping agent and is the molecular moiety introduced by the capping agent.
  • R 2 is a methyl group.
  • R 2 is -CR R 5 -CR 6 R 7 -OH where R 4 , R 5 , R 6 and R 7 are each independently H or a hydrocarbyl group of ⁇ one carbon atom and preferably ⁇ two carbon atoms, to ⁇ 10 carbon atoms, preferably ⁇ 6 carbon atoms, wherein the sum of the carbon atoms in R 4 , R 5 , R 6 and R 7 is ⁇ two carbon atoms, preferably ⁇ four carbon atoms, more preferably ⁇ six carbon atoms and independently ⁇ 10 carbon atoms, and preferably ⁇ 8 carbon atoms.
  • R 2 is 1 -oxy-2,3-epoxypropane.
  • capped polyether fatty acid esters and capped polyether fatty polyesters are useful as functional fluids.
  • the capped product preferably has at least one of friction properties as indicated by a low coefficient of friction of preferably ⁇ 0.07, more preferably ⁇ 0.06, most preferably ⁇ 0.05; pour point at a temperature of ⁇ 0°C, preferably ⁇ -5 °C; viscosity of preferably ⁇ 200 °C, more preferably ⁇ 150°C, most preferably ⁇ 100 cSt at a temperature of 40 °C; or thermal oxidative stability preferably ⁇ five mg KOH/g, more preferably ⁇ two mg KOH/g as measured by acid number change. All these properties are measured by standard tests disclosed herein.
  • Example 1 Formation of a Polyether Fatty Acid Ester Starting with Methyl 12- Hydroxy Stearate
  • the reactor contents constitute an oily product that has a viscosity of 35 megapascals.second (mPa.s) at 50 °C as determined by the procedures of International Standards Organization (ISO) 321 9 and an OH-value of 92.8 mgKOH/g as determined by the procedures of ASTM D4272-94d, which
  • the oily product has a viscosity of 96.7 centistokes (cSt) (98.9

Landscapes

  • 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)
  • Toxicology (AREA)
  • Lubricants (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un composé qui est un polyéther d'un acide gras hydroxylé secondaire, monobasique et saturé, de préférence le 12-hydroxy stéarate, ou un produit de réaction du polyéther avec un alcool polyvalent, un agent de coiffage ou une combinaison des deux. Le composé est préparé par la mise en contact d'un acide gras monobasique hydroxy saturé ou d'un dérivé de celui-ci avec un alcoolate en présence d'un catalyseur cyanure métallique, double, de telle sorte qu'un polyéther de l'acide gras est formé. Facultativement, une préparation comprend également une étape de coiffage du polyéther ou, en variante, de mise en contact du polyéther avec un alcool polyvalent.
EP09795613A 2009-12-09 2009-12-09 Dérivés polyéther d'acides gras hydroxy secondaires et leurs dérivés Withdrawn EP2510043A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2009/067326 WO2011071492A1 (fr) 2009-12-09 2009-12-09 Dérivés polyéther d'acides gras hydroxy secondaires et leurs dérivés

Publications (1)

Publication Number Publication Date
EP2510043A1 true EP2510043A1 (fr) 2012-10-17

Family

ID=42244496

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09795613A Withdrawn EP2510043A1 (fr) 2009-12-09 2009-12-09 Dérivés polyéther d'acides gras hydroxy secondaires et leurs dérivés

Country Status (3)

Country Link
EP (1) EP2510043A1 (fr)
CN (1) CN102656209A (fr)
WO (1) WO2011071492A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2861065B1 (fr) * 2012-06-18 2017-03-15 Basf Se Produits phytosanitaires contenant un alcoxylate à base de lactones
DE102013208328A1 (de) 2013-05-07 2014-11-13 Evonik Industries Ag Polyoxyalkylene mit seitenständigen langkettigen Acyloxyresten und Verfahren zu ihrer Herstellung mittels DMC-Katalysatoren
FR3097867B1 (fr) * 2019-06-25 2021-10-15 Inst Nat Polytechnique Toulouse Procédé de préparation d’un élastomère à partir d’un acide gras hydroxylé et élastomère obtenu par un tel procédé
CN112480999B (zh) * 2020-11-27 2022-09-06 广东石油化工学院 一种多功能导轨油

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1063525A (en) 1963-02-14 1967-03-30 Gen Tire & Rubber Co Organic cyclic oxide polymers, their preparation and tires prepared therefrom
US3829505A (en) 1970-02-24 1974-08-13 Gen Tire & Rubber Co Polyethers and method for making the same
US3941849A (en) 1972-07-07 1976-03-02 The General Tire & Rubber Company Polyethers and method for making the same
DE3315951A1 (de) 1983-05-02 1984-11-08 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
US4587365A (en) 1984-10-29 1986-05-06 Basf Corporation Preparing capped polyoxyalkylene polyols
DE3726121A1 (de) 1987-08-06 1989-02-16 Basf Ag Veretherung von polyoxyalkylenderivaten
DE3727378A1 (de) 1987-08-17 1989-03-02 Henkel Kgaa Schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3800492A1 (de) 1988-01-11 1989-07-20 Henkel Kgaa Schaumbekaempfungsmittel fuer die herstellung und verarbeitung von nahrungsmitteln bzw. fuer fermentationsprozesse
DE3928600A1 (de) 1989-08-30 1991-03-07 Henkel Kgaa Schaumdaempfende mehrstoffgemische mit tensidcharakter fuer die maschinelle geschirr- und flaschenreinigung
DE59009494D1 (de) 1989-09-26 1995-09-14 Ciba Geigy Ag Wässriges, lagerstabiles, gering schäumendes Netzmittel.
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
DE4243643C1 (fr) 1992-12-22 1993-08-26 Henkel Kgaa, 4000 Duesseldorf, De
US5470813A (en) 1993-11-23 1995-11-28 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
US5712216A (en) 1995-05-15 1998-01-27 Arco Chemical Technology, L.P. Highly active double metal cyanide complex catalysts
US5482908A (en) 1994-09-08 1996-01-09 Arco Chemical Technology, L.P. Highly active double metal cyanide catalysts
US5545601A (en) 1995-08-22 1996-08-13 Arco Chemical Technology, L.P. Polyether-containing double metal cyanide catalysts
US5777177A (en) 1996-02-07 1998-07-07 Arco Chemical Technology, L.P. Preparation of double metal cyanide-catalyzed polyols by continuous addition of starter
US5627120A (en) 1996-04-19 1997-05-06 Arco Chemical Technology, L.P. Highly active double metal cyanide catalysts
US5689012A (en) 1996-07-18 1997-11-18 Arco Chemical Technology, L.P. Continuous preparation of low unsaturation polyoxyalkylene polyether polyols with continuous additon of starter
US5714428A (en) 1996-10-16 1998-02-03 Arco Chemical Technology, L.P. Double metal cyanide catalysts containing functionalized polymers
DE19905611A1 (de) 1999-02-11 2000-08-17 Bayer Ag Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen
DE10240186A1 (de) * 2002-08-28 2004-03-11 Basf Ag Verfahren zur Herstellung von emissionsarmen Polyurethan-Weichschaumstoffen
KR101315527B1 (ko) * 2004-10-26 2013-10-08 다우 글로벌 테크놀로지스 엘엘씨 활성 수소 함유 화합물의 알콕시화를 위한 개량된 방법 및그로부터 제조된 알콕시화 화합물
US20060229375A1 (en) * 2005-04-06 2006-10-12 Yu-Ling Hsiao Polyurethane foams made with alkoxylated vegetable oil hydroxylate
EP1792640A1 (fr) * 2005-12-02 2007-06-06 Wella Aktiengesellschaft Crème de coiffrage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011071492A1 *

Also Published As

Publication number Publication date
WO2011071492A1 (fr) 2011-06-16
CN102656209A (zh) 2012-09-05

Similar Documents

Publication Publication Date Title
US9783635B2 (en) Polyoxyalkylenes with pendant long-chain acyloxy groups and method for producing same using DMC catalysts
US20100317824A1 (en) Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof
US8580984B2 (en) Esters of secondary hydroxy fatty acid oligomers and preparation thereof
US20120041219A1 (en) Double esters and lubricants thereof
US20110213170A1 (en) Estolide derivatives useful as biolubricants
JP2010523797A (ja) キャップ化ポリエステルポリオール潤滑剤組成物
WO2011071492A1 (fr) Dérivés polyéther d'acides gras hydroxy secondaires et leurs dérivés
WO2013002910A1 (fr) Dérivés étholides utiles comme biolubrifiants
US20130289291A1 (en) Estolide derivatives prepared from triglycerides
CN113896879A (zh) 用于金属切削液的大粘度酯及其制备方法
JP5500977B2 (ja) 潤滑油基油およびその製造方法
JP2007217691A (ja) 狭い分子量分布を有するポリアルキレングリコール潤滑剤用基油
KR20140125736A (ko) 불포화 폴리카보네이트 디올, 이 폴리카보네이트 디올의 제조 방법 및 그것의 용도
WO2009129292A1 (fr) Esters de polyol et procédé de fabrication de ceux-ci
US20140011723A1 (en) Lubricant composition
EP0711332B1 (fr) Fluide de base pour lubrifiant
CN114585717A (zh) 经封端的烷氧基化的醇
US8153750B2 (en) Viscosity reducer for highly viscous polyols
US20020095021A1 (en) Water-soluble polyalkylene glycol oils having a high viscosity index and low aerosol toxicity
KR20010020433A (ko) 옥시알킬렌-개질된 폴리옥시부틸렌 알콜
US20240191025A1 (en) Novel polyethers on the basis of 2,3-epoxybutane and process for the preparation thereof
Lee et al. Preparation of polyester polyol from epoxidized palm olein
US4161482A (en) Production of polyols containing basic nitrogen
JPH02269198A (ja) 潤滑油組成物
GB1572913A (en) Production of polyols containing basic nitrogen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120709

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130422

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140109

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140717

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20141128