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WO2011075343A1 - Coiffage par de l'oxyde d'éthylène d'hydroxyl polyols secondaires - Google Patents

Coiffage par de l'oxyde d'éthylène d'hydroxyl polyols secondaires Download PDF

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WO2011075343A1
WO2011075343A1 PCT/US2010/059175 US2010059175W WO2011075343A1 WO 2011075343 A1 WO2011075343 A1 WO 2011075343A1 US 2010059175 W US2010059175 W US 2010059175W WO 2011075343 A1 WO2011075343 A1 WO 2011075343A1
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Prior art keywords
polyol
polyether
ester
polyester polyol
hydroxyl functionality
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Pavel Shutov
Jorge Jimenez
Hanno Van Der Wal
Francois Casati
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G65/26—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
    • C08G65/2642—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
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2672—Nitrogen or compounds thereof
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • C08G2650/24—Polymeric initiators

Definitions

  • the invention relates to a conversion of secondary hydroxyl compounds to primary hydroxyl compounds.
  • it relates to a process for converting secondary hydroxyl compounds to half acid esters and subsequently to primary hydroxyl alkoxo ester compounds while concurrently capping with ethylene oxide.
  • Secondary hydroxyl group -containing polyols may be used in some polyurethane formulations, but are often less desired than primary hydroxyl group- containing compounds, particularly for certain specialized polyurethane applications.
  • Secondary hydroxyl group-containing compounds are not as reactive as primary hydroxyl group-containing compounds, and their use in slabstock or molded flexible foam polyurethane formulations often results in foam densification or unacceptably long cycle times, making them frequently unsuitable for such applications.
  • the secondary hydroxyl group-containing compounds may also increase costs by requiring higher catalyst levels, and may be undesirably hydrophobic, poorly miscible in formulations with other polyols and/or additives, produce foams with poorer insulation and thermal properties, and decrease fire retardancy capability.
  • researchers have sought methods of efficiently converting secondary chain ends to primary chain ends.
  • Still other methods have included, for example, a process disclosed in U.S. Patent 4,487,853, wherein a 2- to 8-functional polyether polyol having an equivalent weight from 500 Da to 10,000 Da is reacted with a cyclic organic acid anhydride to form a half acid ester, and ethylene oxide is then added in the presence of an amine or oxide or salt of a divalent metal catalyst.
  • U.S. Patent 4,582,926 describes a process of reacting a secondary hydroxyl capped polyol with a carboxylic acid anhydride to form a carboxylic acid half ester in the presence of an amine catalyst, then oxyalkylating the carboxylic acid half ester with alkylene oxide in the presence of a phosphine catalyst.
  • an alkylene oxide is reacted with a half acid ester obtained by the reaction of a secondary hydroxyl capped polyol with an unsaturated acid anhydride. This reaction is either uncatalyzed or trialkylamine catalyzed.
  • U.S. Patent 5,145,883 discloses polyester ether polyol obtained by co-polymerizing poly-carboxylic-acid anhydride and alkylene oxide with an initiator in presence of a double metal cyanide catalyst. The content of poly-carboxylic-acid anhydride in the polyester ether polyol is from 10 to 50 weight percent.
  • the initiator is a secondary hydroxyl-capped polyether polyol with a hydroxyl number of not more than 160.
  • the capping level may be less than desired, with the result that products may contain a higher than desired level of uncapped acid and/or include a significant amount of transesterification by-products, including cyclic esters, uncapped secondary hydroxyls, and fully-esterified chain-ends resulting in higher number average molecular weights (Mn) and reduced polyol functionality.
  • Another problem may be broader than desired polydispersities and functionality distributions, and the amount of ethylene oxide required may be higher than desired and/or lead to an increase in overall polyol hydrophilicity. All of these problems may tend to reduce certain properties of a final polyurethane prepared therefrom.
  • Such properties may include, for example, cure rate, wet compression set, flame lamination properties, thermal insulation, demold expansion, polyol miscibility, thermal stability, and flame retardancy.
  • the invention provides a process for preparing a polyol having primary hydroxyl functionality, comprising the steps of (a) reacting a polyether polyol, a polyester polyol, polyether-ester polyol or a polyether-polyester polyol, having predominantly secondary hydroxyl functionality, with a cyclic anhydride of a polycarboxylic acid, under conditions such that a half acid ester is formed; and (b) reacting the half acid ester with ethylene oxide, under conditions such that a polyether- ester polyol, a polyester polyol or a polyether-polyester polyol, having primary hydroxyl functionality, is formed; provided that both steps are carried out in the presence of an amine catalyst and a double metal cyanide catalyst.
  • the invention provides a polyol having primary hydroxyl functionality prepared by a process comprising the steps of (a) reacting a polyether polyol, a polyester polyol, polyether-ester polyol or a polyether-polyester polyol, having predominantly secondary hydroxyl functionality, with a cyclic anhydride of a polycarboxylic acid, under conditions such that a half acid ester is formed; and (b) reacting the half acid ester with ethylene oxide, under conditions such that a polyether-ester polyol, a polyester polyol or a polyether-polyester polyol, having primary hydroxyl functionality, is formed; provided that both steps are carried out in the presence of an amine catalyst and a double metal cyanide catalyst.
  • the invention provides a polyurethane product prepared by a process comprising reacting an organic polyisocyanate and a polyol having primary hydroxyl functionality prepared by a process including the steps of (a) reacting a polyether polyol, a polyester polyol, polyether-ester polyol or a polyether- polyester polyol, having predominantly secondary hydroxyl functionality, with a cyclic anhydride of a polycarboxylic acid, under conditions such that a half acid ester is formed; and (b) reacting the half acid ester with ethylene oxide, under conditions such that a polyether-ester polyol, a polyester polyol or a polyether-polyester polyol, having primary hydroxyl functionality, is formed; provided that both steps are carried out in the presence of an amine catalyst and a double metal cyanide catalyst.
  • the present invention provides a method of converting a secondary hydroxyl capped polyol into a polyether-ester polyol having a desired level of primary hydroxyl capping.
  • Such capping may, in certain non-limiting embodiments, range from 10 percent to 95 percent, based on the weight of the starting secondary hydroxyl capped polyol.
  • the method is one which requires less ethylene oxide than prior art methods, thereby producing a product which, when used to formulate polyurethanes, may contribute to desirable improvements in several properties of those polyurethanes while being less expensive to produce.
  • the polyols produced by the present invention are well suited for the production of flexible polyurethane foam.
  • the starting material for the inventive method may include any polyether polyol, polyester polyol, or polyether-ester polyol or polyether-polyester polyol which comprises one or more secondary hydroxyl end-groups per molecule, provided that such secondary hydroxyl end-groups predominate.
  • predominate and “predominantly” are meant herein that more than 50 percent of the end-groups per molecule are secondary hydroxyls, while the remaining portion, if any, may be primary hydroxyl groups and/or other types of terminal isocyanate reactive groups, such as carboxyl groups, that do not interfere with the inventive process.
  • Such starting polyol may be selected from, for example, any polyols conventionally employed in the production of polyurethanes, and blends thereof, which preferably have an equivalent weight ranging from 50 daltons (Da) to 10,000 Da. In certain particular embodiments the equivalent weight ranges from 200 to 8,000 Da, and in other particular embodiments it ranges from 500 Da to 3,000 Da.
  • Preparation of such predominantly secondary hydroxyl capped polyols may be by, for example, KOH catalyzed propoxylation of a polyhydric alcohol with 1 to 9 hydroxy groups, an organic amine or aminoalcohol with from 1 to 9 active hydrogen atoms; double metal cyanide complex (DMC) catalyzed propoxylation of a polyol derived from natural resources, such as castor oil, that are epoxidized and/or maleated ring-opened with a functional compound natural oil, or any other natural oil modified to introduce active hydrogen containing moieties, suitable for further alkoxylation; or a mono- or polycarboxylic acid, an alkoxo ester, or a half acid ester prepared from a polyhydric alcohol with from 0 to 8 carboxy groups and/or from 1 to 9 hydroxy groups.
  • DMC double metal cyanide complex
  • Such polymerizations may be carried out by methods well-known to those skilled in the art, generally in the presence of one or more polymerization catalysts and at elevated temperatures in order to facilitate the reaction.
  • Another method of preparation of the starting polyol is by polymerization of other epoxides in addition to propylene oxide, such as butylene oxide, styrene oxide or ethylene oxide, in the presence of a catalyst, such as a DMC complex catalyst, with an active hydrogen-containing compound as the polyol initiator.
  • DMC compounds are well known as catalysts for epoxide polymerization. These catalysts are often highly active, have relatively high surface areas, typically within the range of from 50 to 200 square meters per gram (m 2 /g), and may produce polyether polyols, in particular, that have lower unsaturation when compared with otherwise similar polyols made using basic (KOH) catalysis.
  • the catalysts can be used to make a variety of polymer products, including polyether, polyester, and polyether- ester polyols.
  • a DMC compound may comprise a reaction product of a water-soluble metal salt and a water-soluble metal cyanide salt.
  • a water-soluble metal salt may have the general formula
  • M may be selected from Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(rV), W(VI), Cu(II), and Cr(III). It may be desirable in some embodiments for M to be selected from Zn(II), Fe(II), Co(II), and ⁇ ( ⁇ ).
  • X may be an anion selected from the group including halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate.
  • the value of n may be from 1 to 3 and satisfy the valence state of M.
  • Examples of a suitable metal salt may include, without limitation, zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate, and combinations thereof.
  • a water-soluble metal cyanide salt may have the general formula
  • M' may be selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), V(V), and combinations thereof, and CN is cyanide. It may be desirable in some embodiments for M' to be selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), Ni(II), and combinations thereof.
  • Y be an alkali metal ion or alkaline earth metal ion
  • A may be an ion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate.
  • a and b are integers equal to or greater than 1.
  • the sum of the charges of a, b, and c balances the charge of M' .
  • Examples of a suitable metal cyanide salt may include, without limitation, potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), lithium hexacyano-cobaltate(III), and combinations thereof.
  • a solid DMC catalyst that is useful for epoxide polymerizations generally may include an organic complexing agent, often of a relatively low molecular weight and often containing a heteroatom.
  • an organic complexing agent often of a relatively low molecular weight and often containing a heteroatom.
  • the complexing agent may be added during preparation and/or immediately following precipitation of the catalyst, and is frequently employed in excess. Examples of some suitable complexing agents are described in greater detail in U.S. Patents 5,158,922; 3,427,256; 3,427,334; and 3,278,459; which are incorporated herein by reference in their entireties.
  • Such complexing agents may include alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, polyether polyols and combinations thereof.
  • the complexing agent may include, without limitation, a water-soluble aliphatic alcohol selected from ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol, and tert-butyl alcohol (t-butanol) may be preferred in certain applications.
  • the selected complexing agent may be an ether, such as glyme (dimethoxyethane) or diglyme.
  • aqueous solutions of zinc chloride (in excess amount) and potassium hexacyanocobaltate may be combined by simple mixing.
  • the resulting precipitate of zinc hexacyanocobaltate is then mixed with aqueous glyme.
  • the active DMC catalyst obtained has the formula:
  • DMC compounds prepared in the absence of a complexing agent are highly crystalline, as shown by X-ray diffraction analysis, and are inactive for expoxide polymerization, but may still be, along with the highly crystalline DMC compounds prepared with a complexing agent, useful in the process of the present invention.
  • DMC catalysts include both crystalline and amorphous components.
  • these DMC catalysts which are generally prepared by simple mixing, still contain at least 35 weight percent of highly crystalline DMC compound.
  • there are some conventional DMC compounds, useful for epoxide polymerizations which contain less than 30 weight percent of the highly crystalline component.
  • Examples of DMC compounds useful both in epoxide polymerizations, to prepare the starting secondary hydroxyl group-containing compound and in the conversion process of the present invention may include zinc hexacyanocobaltate(III), zinc hexacyanoferrate(III), zinc hexacyanoferrate(III)zinc hexacyanoferrate(II), nickel(II) hexacyanoferrate(II), cobalt(II) hexacyano-cobaltate(III), and the like. In certain embodiments, it may be particularly desirable to use zinc hexacyanocobaltate(III). Further examples are listed in U.S. Patent 5,158,922, which is incorporated herein by reference in its entirety.
  • a solid DMC catalyst may include from 5 to 80 weight percent, based on the total amount of catalyst, of a polyether. For example, it may be desirable to include from 10 to 70 weight percent of the polyether. In other embodiments it may be desirable to include from 15 to 60 weight percent of the polyether.
  • Such polyether may, in some embodiments, have an average of from 1 to 9 hydroxyl functionalities.
  • a polyether polyol may have a number average molecular weight of from 200 to 10,000.
  • a polyether polyol may be made by polymerizing an epoxide in the presence of an active hydrogen-containing initiator and a basic, acidic, or organometallic catalyst (for example, a DMC catalyst), in some embodiments.
  • Examples of a polyether polyol may include, without limitation, poly(propylene glycol)s, poly(ethylene glycol)s , ethylene oxide-capped poly(oxypropylene) polyols, mixed ethylene oxide/propylene oxide polyols, butylene oxide polymers, butylene oxide copolymers with ethylene oxide and/or propylene oxide, polytetramethylene ether glycols, and combinations thereof.
  • Examples of a polyether polyol may include, without limitation, tripropylene glycol, triethylene glycol, tetrapropylene glycol, tetraethylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, monoalkyl and dialkyl ethers of glycols and poly(alkylene glycol)s, and combinations thereof.
  • poly(propylene glycol)s and poly(ethylene glycol)s having number average molecular weights within the range of from 150 to 500 may be used.
  • An organic complexing agent and a polyether may be used in a double metal cyanide catalyst.
  • a DMC catalyst may be fully described, in some embodiments, by the following formula:
  • 1 is at least one metal ion selected from the group consisting of Zn 2+ , Fe 2+ ,
  • M 2 is at least one metal ion selected from the group consisting of Fe 2 Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr + , Cr 3+ , Rh 3+ , Ru 2+ , and Ir 3+ ;
  • a and X are each, independently of one another, an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrogensulfate, phosphate, dihydrogenphosphate, hydrogenphosphate and hydrogencarbonate;
  • L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands having a pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphanes, phosphonates and phosphates;
  • k is a fraction or integer greater than or equal to zero
  • P is an organic additive
  • a, b, c, d, g and n are selected such that the compound of Formula 4 is electrically neutral, with c being able to be 0;
  • e is the number of ligand molecules and is a fraction or integer equal to or greater than 0;
  • f and h are each, independently of one another, a fraction or integer equal to or greater than 0.
  • Examples of an organic additive P may include, without limitation, polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylamide-comaleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co- acrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co- styrene), oxazoline polymers, polyalkylenimines, maleic acid and maleic anhydride copolymers, hydroxyethylcellulose, polyacetates, ionic
  • polyether polyols are made by the reaction of epoxides (oxiranes) with active hydrogen-containing starter compounds, while polyester polyols are made by the polycondensation of multifunctional carboxylic acids and hydroxyl compounds.
  • Use of propylene oxide to extend the polyols results in mainly (90 to 95 percent by weight) secondary capped materials, while use of combinations of propylene oxide and ethylene oxide results in species that include both primary and secondary hydroxyl groups, with the molar ratio of the two alkoxides helping to determine the proportion of secondary versus primary end capping.
  • the amount of the ethylene oxide in the mixed feed is, in certain preferred embodiments, not higher than 75 percent of the total number of moles, in order to avoid broad polydispersity and heterogeneity of the resulting product.
  • primary hydroxyl level in the resulting polyol may, in some embodiments, be preferably not higher than 70 percent.
  • a desired polyol which is predominantly secondary hydroxyl-capped is reacted, preferably at a temperature ranging from 90 degrees Celsius (°C) to 180°C, with a cyclic anhydride of a polycarboxylic acid.
  • the temperature ranges from 120°C to 150°C, and in other particular embodiments, it ranges from 130°C to 140°C.
  • the cyclic anhydride of a polycarboxylic acid may be prepared, in general, by the dehydrogenation of the given polycarboxylic acid, though methods involving oxidation or carbonylation may be used, depending on the character of the polycarboxylic acid.
  • maleic anhydride may be produced by the oxidation of butane, but it is still a cyclic anhydride of a polycarboxylic acid (maleic acid).
  • phthalic anhydride can be produced by catalytic oxidation of o-xylene.
  • Other useful acids that may be used as starting materials to prepare the anhydride may include, but are not limited to, succinic acid, maleic acid, phthalic acid, and combinations thereof.
  • This first-step reaction is desirably carried out in the presence of an amine catalyst and a DMC catalyst.
  • the DMC catalyst may be selected from any described hereinabove.
  • the amine catalyst may be selected from any effective amine, but such may typically include the N-arkylmorpholines, N-alkyl-alkanolamines, aminoalcohols, ⁇ , ⁇ -dialkylcyclohexylamines, alkylamines where the alkyl groups are methyl, ethyl, propyl, butyl and isomeric forms thereof, and heterocyclic amines.
  • Typical but non- limiting specific examples thereof are 1-methyl-imidazole, triethylenediamine, tetramethylethylenediamine, bis(2-dimethyl-aminoethyl)ether, triethanolamine, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, ⁇ , ⁇ -dimethyl-cyclohexylamine, N-ethyl-morpholine, 2-methylpropanediamine, methyltriethylene-diamine, 2,4,6-tri-dimethyl- aminomethyl)phenol, ⁇ , ⁇ ' ,N"-tris(dimethylaminopropyl)-sym-hexahydrotriazine, and combinations thereof.
  • a preferred group of tertiary amines comprises 1-methyl- imidazole, bis(2-dimethyl-aminoethyl)ether, dimethylcyclo-hexylamine, N,N-dimefhyl- ethanolamine, triethylenediamine, triethylamine, triisopropylamine, 2,4,6- tri(dimethylaminomethyl)-phenol, ⁇ , ⁇ ', ⁇ -ethylmorpholine, and combinations thereof.
  • the result of the reaction of the starting polyol with the cyclic anhydride of a polycarboxylic acid is the half acid ester product.
  • This reaction may be shown formulaically by the following first reaction sequence example, wherein a secondary hydroxyl-containing polyether polyol, prepared by the propoxylation of n-butanol, is reacted with one equivalent of succinic anhydride in the presence of 1000 parts per million (ppm) of 1-methylimidazole catalyst at 150°C for two hours, to form the corresponding half acid ester.
  • Step 1
  • time for this first step may vary from 1 hour to 4 hours for commercial practicability; the amine catalyst amount may range from 100 parts per million (ppm) to 10,000 ppm, though it is preferred that an amount from 100 ppm to 1,000 ppm be employed; and the DMC catalyst amount may range from 10 ppm to 1,000 ppm, though it is preferred that an amount from 10 ppm to 50 ppm be employed.
  • the half acid ester is determined, by proton nuclear magnetic resonance ⁇ H-NMR) spectroscopy, to be approximately 85 percent to 95 percent acid- capped in the reaction sequence hereinabove.
  • a second step may be carried out.
  • the half acid ether-ester is reacted, preferably at a temperature from 50°C to 150°C, with ethylene oxide.
  • the reaction is again carried out in the presence of an amine catalyst and a DMC catalyst, which may be independently the same as, or different from, the catalysts used in the first step.
  • an amine catalyst and a DMC catalyst which may be independently the same as, or different from, the catalysts used in the first step.
  • the second step may be represented by the second reaction sequence, shown hereinbelow.
  • the identification of reactants, product, catalyst, catalyst concentration, temperature and time are included only for illustrative, not limitative, purpose.
  • the half acid ester is converted to the primary hydroxyl capped polyether polyol by reaction with ethylene oxide in the presence of 50 ppm of the DMC catalyst, at 140°C, as follows.
  • reaction sequence may be carried out on a batch, semi-batch, or continuous basis.
  • Time for the second step may range from 0.5 to 2 hours, and in certain embodiments may be, for commercial practicability, from 0.5 to 1 hour.
  • the final polyol may be characterized as a primary hydroxyl alkoxo ester compound, which may be alternatively characterized as a polyether-ester polyol, a polyester polyol or a polyether-polyester polyol having primary hydroxyl capping.
  • the amount of primary hydroxyl capping may vary from 10 percent to 95 percent in certain particular and non-limiting embodiments. Control of the percent primary hydroxyl capping achieved, that is, of the conversion rate from secondary to primary capping, will depend upon the relative amount of the cyclic anhydride in comparison with the amount of hydroxyl groups in the starting hydroxyl-capped polyol.
  • Such may range from 0.1: 1 to 1 : 1, cyclic anhydride:hydroxyl groups in the starting polyol.
  • the molar amount of ethylene oxide incorporated in the second step is generally closely comparable to the molar amount of the cyclic anhydride of a polycarboxylic acid used in the first step of the process, no matter how large an excess of ethylene oxide is used for the reaction. Desirably this ratio is from 1.05:1 to 1.5: 1, ethylene oxide:cyclic anhydride of a polycarboxylic acid.
  • Any unreacted polycarboxylic acid anhydride (generally, not more than 10 percent of the total amount of anhydride taken for the first step), that may have remained from the first step, will be incorporated together with the ethylene oxide into the polyol chain end-capping, forming primary hydroxyl-capped alternating polyester. If ethylene oxide is used in an amount such that its molar amount is less than that of the half acid ester, corresponding unreacted acidity will remain in the polyol.
  • a small amount of ethylene oxide in the amount of less than 5 percent by weight, may effectively convert a polyether polyol containing more than 50 percent of secondary hydroxyl functionality, based on total functionality, into a polyether-ester polyol containing more than 90 percent of primary hydroxyl functionality, based on total functionality.
  • the remaining acidity of the product polyol is generally low (less than 1 mg/g as KOH). Additional polyol post-treatment may be introduced to neutralize this remaining acidity, for instance, addition of equimolar amounts of epoxy resins or amines/aminoalcohols.
  • the process of the invention represents a cost savings as well as a final product offering reduced hydrophilicity and miscibility problems, and also improved reactivity. These advantages may translate into better quality polyurethanes made therefrom, particularly as to properties such as cure rate, wet compression set, flame lamination properties, thermal insulation, demold expansion, thermal stability, and flame retardancy.
  • a DMC catalyst is synthesized by adding, in a three-necked, round- bottomed flask 11.1 grams (g) (0.033 moles (mol)) K 3 Co(CN) 6 , 453 g (25.17 mol) water (H2O), and 58.5 g (0.789 mol) t-butanol and stirring at more than 200 revolutions per minute (rpm) for 30 minutes at 30°C.
  • a mixture of 114 g (0.836 mol) ZnCl 2 and 114 g (6.33 mol) H 2 0 is then added at a rate of 5 milliliters per minute (mL/min).
  • the precipitate is dried for 16 hours (hr) at 20-30 millibar (mbar) (2-3 kilopascals, kPa) at 50°C.
  • the product is then milled in a mortar to break up any agglomerates, and the catalyst, approximately 15 g, is obtained as a fine white powder.
  • the catalyst is then analyzed for the metals cobalt, potassium, and zinc using X-Ray Fluorescence (XRF) and Inductively Coupled Plasma Emission Spectrometry (ICP-ES) in an aqua regia (nitro-hydrochloric acid) digest.
  • XRF X-Ray Fluorescence
  • ICP-ES Inductively Coupled Plasma Emission Spectrometry
  • the elemental composition is found to be as follows: Potassium, 0.31 weight percent; zinc, 25.2 weight percent; cobalt, 11.1028 weight percent; potassium/cobalt, 0.028 weight percent; and water, 7.0489 weight percent.
  • Activation of the catalyst is observed within 2 minutes following completion of the feed by an abrupt pressure drop in the reactor.
  • the PO feed is resumed and 760 g PO are fed to the reactor at a feed rate of 15 g/min.
  • a 0.5 hr digestion time is allowed upon the end of the second PO feed.
  • the product is stripped of unreacted PO via vacuum for 0.5 hr at 100°C. A colorless liquid is obtained.
  • the product has the following properties: hydroxyl number 56.2 mg/g KOH, water 205 ppm, unsaturation 0.003 meq/g, viscosity at 25°C 107 centistokes (cSt).
  • N-methylimidazole About 0.975 g (1000 ppm by weight) of N-methylimidazole is added to a mixture of 885 g of an n-butanol-initiated monol, polypropylene oxide polyether polyol, prepared similarly as described in the "Polyether Polyol Preparation" section hereinabove (but having as properties: hydroxyl number 56.6 mg/g KOH, water 410 ppm, unsaturation 0.0071 meq/g, viscosity at 25°C 110 centistokes (cSt)), which also contains the DMC catalyst used to prepare the polyol, and 89.4 g of crystalline succinic anhydride (99 percent purity) in a 1 liter laboratory Pyrex glass esterification reactor.
  • the mixture is flushed with nitrogen (N 2 ) and heated in an N 2 atmosphere at 150°C for 1 hr and at 170°C for 1 hr with stirring.
  • the reactor is cooled to room temperature. A
  • This liquid has the following properties: hydroxyl value 11.1 mg KOH/g; acid value 54.7 mg KOH/g; total unsaturation 0.04 meq/g; water 640 ppm; viscosity at 25°C 331 cSt; ⁇ -NMR: 86 percent of all chains are acid-capped.
  • An amount, 50 g, of EO (1.14 mol, 1.5 eq/acid function) is fed to the reactor at once, giving a maximum pressure of 5 bar (500 kPa).
  • the immediate reaction is accompanied by a visible exotherm.
  • the mixture is allowed to digest for 1 hr following completion of the feed.
  • the product is stripped of unreacted EO in vacuum for 1 hr at 100°C. A colorless liquid is obtained.
  • the properties of the final product are as follows: hydroxyl value: 60.6 mg KOH/g; acid value: 0.55 mg KOH/g; total unsaturation: 0.0069 meq/g; water 650 ppm; viscosity at 25°C 265 cSt. 1 H+ 13 C-NMR: 1 percent of all chains are half acid ester- capped; 85 percent of all chains are primary hydroxyl EO-capped; 14 percent are secondary hydroxyl PO-capped.
  • This liquid, the intermediate product has the following properties: hydroxyl value 13.0 mg KOH/g; acid value 52.9 mg KOH/g; total unsaturation 0.0028 meq/g; water 340 ppm; viscosity at 25°C 333 cSt; 'H+ ⁇ C-NMR: 75 percent of all chains are acid-capped.
  • An amount, 836 g, of the intermediate product is placed into a 6-liter laboratory stainless steel alkoxylation reactor.
  • the reaction mixture is flushed several times with 3.5 bar (350 kPa) nitrogen (N 2 ) pressure with stirring at 300 ppm, and vacuum is applied for 5 minutes to the reactor at ambient temperature, followed by addition of 1.6 bar (160 kPa) of N 2 pressure.
  • the reactor is thermostated at 140°C with stirring.
  • An amount, 58 g, of ethylene oxide (EO) (1.32 mol, 1.5 eq/acid function) is fed to the reactor at once, giving a maximum pressure of 3.7 bar (370 kPa).
  • the immediate reaction is accompanied by a visible exotherm.
  • the mixture is allowed to digest for 17 hr following completion of the feed.
  • the product is stripped of unreacted EO in vacuum for 1 hr at 100°C. A colorless liquid is obtained.
  • the properties of the final product are as follows: hydroxyl value: 41.6 mg KOH/g; acid value: 13.6 mg KOH/g; total unsaturation: 0.001 meq/g; water 430 ppm; viscosity at 25°C 226 cSt. ⁇ + ⁇ C-NMR: 24.6 percent of all chains are half acid ester- capped; 39 percent of all chains are primary hydroxyl EO-capped; 30 percent are secondary hydroxyl PO-capped; and 6.4 percent of all chains are EO-capped and doubly-esterified.

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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)
  • Toxicology (AREA)
  • Polyethers (AREA)

Abstract

L'invention porte sur un procédé pour convertir un polyol coiffé par hydroxyle secondaire en un polyol coiffé par hydroxyle primaire. Ce procédé consiste à faire réagir un polyéther polyol, un polyester polyol ou un polyéther-ester polyol avec un anhydride cyclique d'un acide polycarboxylique, pour former un hémiacide ester, en faisant suivre par la réaction de l'hémiacide ester avec de l'oxyde d'éthylène, afin de former un polyester polyol ou un polyéther-polyester polyol. Les deux étapes sont effectuées en présence d'un catalyseur amine et d'un catalyseur complexe cyanure métallique double. Le procédé offre une fonctionnalité hydroxyle primaire élevée (par exemple, jusqu'à 95 pour cent, sur la base de la fonctionnalité totale) avec de faibles quantités d'oxyde d'éthylène comme réactif (par exemple, inférieures à 5 pour cent en poids).
PCT/US2010/059175 2009-12-17 2010-12-07 Coiffage par de l'oxyde d'éthylène d'hydroxyl polyols secondaires Ceased WO2011075343A1 (fr)

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US20120196999A1 (en) * 2009-07-03 2012-08-02 Bayer Materialscienceag Method for the production of polyether polyols comprising terminal primary hydroxyl groups
WO2012114357A1 (fr) 2011-02-23 2012-08-30 Council Of Scientific & Industrial Research Procédé de préparation de polyesters hyper-ramifiés
WO2018005056A1 (fr) * 2016-06-30 2018-01-04 Dow Global Technologies Llc Procédé de production de polyéther diols
KR20190024966A (ko) * 2016-06-30 2019-03-08 다우 글로벌 테크놀로지스 엘엘씨 불포화 모노올의 감소된 양으로 폴리에테르를 제조하는 방법
WO2021176212A1 (fr) * 2020-03-02 2021-09-10 Econic Technologies Ltd Procédé de préparation d'un copolymère séquencé de polyol
WO2021176211A1 (fr) * 2020-03-02 2021-09-10 Econic Technologies Ltd Copolymère séquencé de polyol
CN114262430A (zh) * 2021-11-30 2022-04-01 山东一诺威新材料有限公司 实心轮胎用二氧化碳基聚碳酸酯醚多元醇及其制备方法
CN116333250A (zh) * 2021-12-22 2023-06-27 长华化学科技股份有限公司 聚氨酯软质泡沫塑料、制备方法及其应用

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US20120196999A1 (en) * 2009-07-03 2012-08-02 Bayer Materialscienceag Method for the production of polyether polyols comprising terminal primary hydroxyl groups
US9029495B2 (en) * 2009-07-03 2015-05-12 Bayer Materialscience Ag Process for producing polyether polyols having primary hydroxyl end groups
WO2012114357A1 (fr) 2011-02-23 2012-08-30 Council Of Scientific & Industrial Research Procédé de préparation de polyesters hyper-ramifiés
KR102385163B1 (ko) 2016-06-30 2022-04-13 다우 글로벌 테크놀로지스 엘엘씨 불포화 모노올의 감소된 양으로 폴리에테르를 제조하는 방법
KR102387647B1 (ko) 2016-06-30 2022-04-19 다우 글로벌 테크놀로지스 엘엘씨 폴리에테르 디올 제조 공정
KR20190025927A (ko) * 2016-06-30 2019-03-12 다우 글로벌 테크놀로지스 엘엘씨 폴리에테르 디올 제조 공정
CN109563260A (zh) * 2016-06-30 2019-04-02 陶氏环球技术有限责任公司 用于制备聚醚二醇的方法
KR20190024966A (ko) * 2016-06-30 2019-03-08 다우 글로벌 테크놀로지스 엘엘씨 불포화 모노올의 감소된 양으로 폴리에테르를 제조하는 방법
WO2018005056A1 (fr) * 2016-06-30 2018-01-04 Dow Global Technologies Llc Procédé de production de polyéther diols
US11124604B2 (en) 2016-06-30 2021-09-21 Dow Global Technologies Llc Process for making polyether diols
CN109563260B (zh) * 2016-06-30 2021-10-15 陶氏环球技术有限责任公司 用于制备聚醚二醇的方法
WO2021176211A1 (fr) * 2020-03-02 2021-09-10 Econic Technologies Ltd Copolymère séquencé de polyol
WO2021176212A1 (fr) * 2020-03-02 2021-09-10 Econic Technologies Ltd Procédé de préparation d'un copolymère séquencé de polyol
CN115485317A (zh) * 2020-03-02 2022-12-16 艾柯尼克技术有限公司 多元醇嵌段共聚物的制备方法
CN115485316A (zh) * 2020-03-02 2022-12-16 艾柯尼克技术有限公司 多元醇嵌段共聚物
JP2023516667A (ja) * 2020-03-02 2023-04-20 エコニック テクノロジーズ リミテッド ポリオールブロックコポリマー
JP7735295B2 (ja) 2020-03-02 2025-09-08 エコニック テクノロジーズ リミテッド ポリオールブロックコポリマー
CN114262430A (zh) * 2021-11-30 2022-04-01 山东一诺威新材料有限公司 实心轮胎用二氧化碳基聚碳酸酯醚多元醇及其制备方法
CN116333250A (zh) * 2021-12-22 2023-06-27 长华化学科技股份有限公司 聚氨酯软质泡沫塑料、制备方法及其应用

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