# US 4,395,351 A · Polyether-based thickeners with additives for increased efficiency in aqueous systems > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,395,351 A - Document ID: US4395351A - Status: Granted - Kind: A - Application number: 06/252,165 - Filed: 1981-04-08 - Granted: 1983-07-26 - Earliest claimed: 1979-10-22 - Inventors: Ronald L. Camp - Web page: https://patentgrep.com/patent/US4395351A ## CPC - C10M 173/02: not containing mineral or fatty oils - C10M 2201/02: Water - C10M 2209/107: of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 - C10M 2215/04: having amino groups bound to acyclic or cycloaliphatic carbon atoms - C10M 2215/042: containing hydroxy groups; Alkoxylated derivatives thereof - C10M 2215/044: having cycloaliphatic groups - C10M 2215/22: Heterocyclic nitrogen compounds - C10M 2215/221: Six-membered rings containing nitrogen and carbon only - C10M 2215/225: the rings containing both nitrogen and oxygen - C10M 2215/226: Morpholines - C10M 2215/26: Amines - C10M 2215/30: Heterocyclic compounds - C10M 2221/043: Polyoxyalkylene ethers with a thioether group - C10M 2223/04: Phosphate esters - C10M 2223/042: Metal salts thereof - C10M 2223/043: Ammonium or amine salts thereof - C10M 2225/00: Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions - C10M 2225/02: Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds - C10N 2040/08: Hydraulic fluids, e.g. brake-fluids - C10N 2050/01: {Emulsions, colloids, or micelles} - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract Polyether-based thickeners for aqueous systems, said polyethers having molecular weights of about 1000 to about 25,000 which are modified by reaction with at least one glycidyl ether having a carbon chain length of about 12 to about 18 carbon atoms, exhibit increased thickening efficiency in the presence of certain organic additives. These are ethoxylated phosphate esters or mixtures of said esters with water-soluble amines. The polyethers contain about 1 to about 20 percent by weight, based upon the weight of the liquid polyether, of a glycidyl ether. Polyether-based thickeners containing an ethoxylated phosphate ester, or said ester in admixture with a water-soluble amine, and thickened aqueous compositions are disclosed together with processes for the preparation of thickened aqueous systems. The polyether-based thickeners of the invention are particularly useful for thickening water or water-glycol mixtures which are useful as hydraulic fluids. ## Claims ### Claim 1 A polyether-based thickener for an aqueous system comprising in admixture: A. a polyether having a molecular weight of about 1000 to about 25,000 which is selected from the group consisting of (1) polyethers prepared by reacting a mixture of ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-containing aliphatic or alkyl aromatic compound containing no more than one active hydrogen and about 12 to about 18 aliphatic carbon atoms and at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based upon the total weight of said polyether, and (2) polyethers prepared by reacting ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen compound containing no more than one active hydrogen and about 12 to about 18 aliphatic carbon atoms to prepare a heteric or block copolymer and further reacting said copolymer with at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based on the total weight of said thickener, and (3) polyethers prepared by reacting (a) ethylene oxide and at least one glycidyl ether with at least one active hydrogen compound containing no more than one active hydrogen to prepare a heteric copolymer or (b) ethylene oxide with at least one active hydrogen compound containing at no more than one active hydrogen to prepare a homopolymer and further reacting said homopolymer with at least one glycidyl ether, said glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said active hydrogen compound is an aliphatic or alkylaromatic compound containing about 12 to about 18 aliphatic carbon atoms and said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based on the total weight of said thickener, and about 10 to about 35 percent by weight based upon the total weight of said polyether polyol-based thickener of: B. a mixture of a water-soluble amine and an ethoxylated phosphate ester, or an ethoxylated phosphate ester, wherein said phosphate ester is selected from the group consisting of ##STR2## and mixtures thereof, wherein EO is ethylene oxide; R is selected from the group consisting of linear or branched chain alkyl groups having about 6 to about 30 carbon atoms, and aryl or alkylaryl groups wherein said arylalkyl groups have about 6 to about 30 carbon atoms; X is selected from the group consisting of the residue of hydrogen, ammonia, an amine, an alkali or alkaline earth metal and mixtures thereof; and n is a number from 1 to 50. ### Claim 2 (depends on 1) The thickener of claim 1 wherein said polyether is prepared by copolymerizing a mixture of said reactants to produce a heteric copolymer and wherein said mixture includes said water-soluble amine and said phosphate ester in the proportion by weight of about 20 to about 50 percent of said amine and about 80 to about 50 percent by weight of said phosphate ester based upon the total weight of said amine and phosphate ester. ### Claim 3 (depends on 1) The thickener of claim 1 wherein said polyether is prepared by copolymerizing a mixture of ethylene oxide and at least one of said lower alkylene oxides to produce a heteric copolymer intermediate and subsequently reacting said intermediate with at least one of said glycidyl ether. ### Claim 4 (depends on 3) The thickener of claim 3 wherein said lower alkylene oxides are selected from the group consisting of propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide and tetrahydrofuran and wherein the proportion of ethylene oxide in said polyether is at least 10 percent by weight of the total weight of said thickener. ### Claim 5 (depends on 4) The thickener of claim 4 wherein the proportion of ethylene oxide to said lower alkylene oxides is from about 70 to about 90 percent by weight of ethylene oxide to about 30 to about 10 percent by weight of the said lower alkylene oxides and said active hydrogen containing compound is an aliphatic monohydric alcohol. ### Claim 6 (depends on 5) The thickener of claim 5 wherein said monohydric alcohol is selected from the group consisting of alkane monoalcohols, alkene monoalcohols, and alkyne monoalcohols. ### Claim 7 (depends on 6) The thickener of claim 6 wherein said glycidyl ether has about 14 to about 18 carbon atoms, said alkane monoalcohol is selected from the group consisting of at least one of stearyl alcohol, lauryl alcohol, myristyl alcohol, and cetyl alcohol, the ratio of said monoalcohol to said glycidyl ether is about 1:5 to about 1:15 and wherein said phosphate ester is the ester of two moles of phosphorus pentoxide and one mole of the condensation product of one mole of oleyl alcohol and 4 moles of ethylene oxide. ### Claim 8 (depends on 7) The thickener of claim 7 wherein said monoalcohol is stearyl alcohol, said lower alkylene oxide is propylene oxide, and said water-soluble amine is ethanolamine. ### Claim 9 (depends on 1) The thickener of claim 1 wherein said polyether is prepared by sequentially reacting ethylene oxide with at least one of said lower alkylene oxides to produce a block copolymer intermediate and subsequently reacting said intermediate with at least one of said glycidyl ether. ### Claim 10 The process of thickening an aqueous system comprising the addition of an effective thickening amount of a polyether-based thickening agent to said aqueous system, said polyether-based thickening agent comprising in admixture: A. a polyether having a molecular weight of about 1000 to about 25,000, which is selected from the group consisting of (1) polyethers prepared by reacting a mixture of ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen-containing aliphatic or alkylaromatic compound containing no more than one active hydrogen and about 12 to about 18 carbon atoms and at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based upon the total weight of said polyether, (2) polyethers prepared by reacting ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen compound containing no more than one active hydrogen and about 12 to about 18 aliphatic carbon atoms to prepare a heteric or block copolymer and further reacting said copolymer with at least one glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based on the total weight of said thickener, and (3) polyethers prepared by reacting (a) ethylene oxide and at least one glycidyl ether with at least one active hydrogen compound containing no more than one active hydrogen to prepare a heteric copolymer or (b) ethylene oxide with at least one active hydrogen compound containing no more than one active hydrogen to prepare a homopolymer and further reacting said homopolymer with at least one glycidyl ether, said glycidyl ether having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said glycidyl ether is present in the amount of about 1 to about 20 percent by weight based on the total weight of said thickener, and about 10 to about 35 percent by weight based upon the total weight of said polyether-based thickener of: B. a mixture of a water-soluble amine and an ethoxylated phosphate ester, or an ethoxylated phosphate ester, wherein said phosphate ester is selected from the group consisting of ##STR3## and mixtures thereof, wherein EO is ethylene oxide; R is selected from the group consisting of linear or branched chain alkyl groups having about 6 to about 30 carbon atoms, and aryl or alkylaryl groups wherein said arylalkyl groups have about 6 to about 30 carbon atoms; X is selected from the group consisting of the residue of hydrogen, ammonia, an amine, an alkali or alkaline earth metal and mixtures thereof; and n is a number from 1 to 50. ### Claim 11 (depends on 10) The process of claim 10 wherein said polyether is a liquid heteric copolymer prepared by copolymerizing a mixture of said ethylene oxide with at least one of said lower alkylene oxides, at least one of said active hydrogen containing compound, and at least one of said glycidyl ethers and wherein said phosphate ester is the ester of the reaction of two moles of phosphorus pentoxide with one mole of the condensation product of one mole of oleyl alcohol and four moles of ethylene oxide. ### Claim 12 (depends on 10) The process of claim 10 wherein said polyether is prepared by polymerizing a mixture of ethylene oxide and at least one of said lower alkylene oxides to prepare a liquid heteric copolymer intermediate which is subsequently capped with said glycidyl ether. ### Claim 13 (depends on 10) The process of claim 10 wherein said polyether thickening agent is the reaction product of the sequential polymerization of ethylene oxide and at least one of said lower alkylene oxides to prepare an intermediate which is subsequently capped with said glycidyl ether. ### Claim 14 (depends on 10) The process of claim 10 wherein said ethylene oxide is present in said polyether in an amount of at least 50 percent by weight of the weight of said polyether and said lower alkylene oxide is selected from the group consisting of propylene oxide, the butylene oxides, tetrahydrofuran, and mixtures thereof. ### Claim 15 (depends on 14) The process of claim 14 wherein the proportion of said ethylene oxide to said lower alkylene oxide in said polyether is in the amount of about 70 to about 90 percent by weight, said lower alkylene oxide is present in the amount of about 30 to about 10 percent by weight and said active hydrogen containing compound is an aliphatic monohydric alcohol. ### Claim 16 (depends on 15) The process of claim 15 wherein said monohydric alcohol is selected from the group consisting of alkane monoalcohols, alkene monoalcohols, and alkyne monoalcohols. ### Claim 17 (depends on 16) The process of claim 16 wherein said monohydric alcohol is selected from the group consisting of at least one of stearyl alcohol, lauryl alcohol, myristyl alcohol, and cetyl alcohol and wherein said phosphate ester is the ester of two moles of phosphorus pentoxide and one mole of the condensation product of one mole of oleyl alcohol and four moles of ethylene oxide. ### Claim 18 (depends on 17) The process of claim 17 wherein the ratio of said monoalcohol to said glycidyl ether is 1:5 to 1:15 on a molar basis. ### Claim 19 (depends on 16) The process of claim 16 wherein said aqueous system comprises water or a mixture of water and ethylene glycol. ### Claim 20 (depends on 19) The process of claim 19 wherein said polyether is a liquid at ambient temperatures, and said polyether is prepared by the heteric polymerization of a mixture of ethylene oxide and propylene oxide with stearyl alcohol as initiator to produce an intermediate heteric copolymer which is subsequently capped with said glycidyl ether, having about 14 to about 18 aliphatic carbon atoms in the chain, to produce a polyether having a molecular weight of about 1000 to about 10,000 and wherein said amine is ethanolamine.