(19) TZZ ¥¥ZZ_T (11) EP 2 633 008 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 211/00 (2006.01) 20.03.2019 Bulletin 2019/12 (86) International application number: (21) Application number: 11838497.3 PCT/US2011/057595 (22) Date of filing: 25.10.2011 (87) International publication number: WO 2012/061092 (10.05.2012 Gazette 2012/19) (54) ALKOXYLATED FATTY ESTERS AND DERIVATIVES FROM NATURAL OIL METATHESIS ALKOXYLIERTE FETTESTER UND DERIVATE AUS EINER ERDÖLMETATHESE ESTERS GRAS ALCOXYLÉS ET DÉRIVÉS À PARTIR DE LA MÉTATHÈSE D’HUILES NATURELLES (84) Designated Contracting States: • HOLLAND, Brian AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Deerfield GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO IL 60015 (US) PL PT RO RS SE SI SK SM TR • MALEC, Andrew, D. Chicago (30) Priority: 25.10.2010 US 406556 P IL 60657 (US) 25.10.2010 US 406570 P • MASTERS, Ronald, A. 25.10.2010 US 406547 P Glenview IL 60025 (US) (43) Date of publication of application: • MURPHY, Dennis, S. 04.09.2013 Bulletin 2013/36 Libertyville IL 60048 (US) (73) Proprietor: Stepan Company •SKELTON,Patti Northfield, Illinois 60093 (US) Winder GA 30680 (US) (72) Inventors: • SOOK, Brian • ALLEN, Dave, R. Lawrenceville Chicago GA 30045 (US) IL 60610 (US) • WIESTER, Michael •ALONSO,Marcos Chicago Chicago IL 60625 (US) IL 60645-4922 (US) • WOLFE, Patrick, Shane • BERNHARDT, Randal, J. Palatine Antioch IL 60074 (US) IL 60002 (US) • BROWN, Aaron (74) Representative: Müller, Christian Stefan Gerd Chicago ZSP Patentanwälte PartG mbB IL 60645 (US) Hansastraße 32 • BUCHEK, Kelly 80686 München (DE) Hoffman Estates IL 60169 (US) (56) References cited: • GANGULY-MINK, Sangeeta EP-A1- 2 446 743 WO-A2-2012/061103 Chicago DE-A1- 19 755 559 US-A- 6 103 770 IL 60646 (US) US-A1- 2007 118 916 US-A1- 2007 187 301 US-A1- 2009 031 614 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 633 008 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 633 008 B1 • DATABASECA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; COHEN, L. ET AL: "Identification of the products from the sulfonation of an oleic acid methyl ester", XP002736898, retrieved from STN Database accession no. 2008:1091468 & COHEN, L. ET AL: "Identification of the products from the sulfonation of an oleic acid methyl ester", TENSIDE,SURFACTANTS, DETERGENTS ,45(4), 178-181 CODEN: TSDEES; ISSN: 0932-3414, 2008, DOI: 10.3139/113.100373 10.3139/113.100373 2 EP 2 633 008 B1 Description FIELD OF THE INVENTION 5 [0001] The invention relates to alkoxylated fatty esters and derivatives thereof that originate from renewable resources, particularly natural oils and their metathesis products. BACKGROUND OF THE INVENTION 10 [0002] Alkoxylated fatty esters are normally manufactured by inserting of one or more alkylene oxide units, usually ethylene oxide (EO), between the oxygen and CH3 portions of a methoxy group of a methyl ester using mixed oxide catalysts, typically magnesium-containing oxides (see, e.g., U.S. Pat. Nos. 5,817,844, 6,184,400, and 6,504,061). They can also be made by esterifying fatty acids (or transesterifying fatty esters of lower alcohols) with alkoxylated alcohols. In yet another method, the alkoxylated fatty esters can be made by alkoxylating fatty acids with alkylene oxides, followed 15 by etherification of the terminal hydroxyl group. [0003] The performance characteristics of alkoxylated fatty esters will depend on the nature of the starting fatty methyl ester or fatty acid and the proportion, kind, and distribution of oxyalkylene groups. Alkoxylated fatty esters are valuable as nonionic surfactants and as additives for a wide variety of end-use applications, including, for example agricultural uses (see U.S. Pat. No. 6,068,849 and U.S. Pat. Appl. Publ. Nos. 2007/0032382 and 2008/0175930), hard surface 20 cleaners (U.S. Pat. No. 7,270,131 and 5,386,045), laundry detergent boosters (U.S. Pat. No. 7,098,175), and other detergent applications (U.S. Pat. Nos. 6,303,564, 6,395,694, and 5,753,606). [0004] The fatty acids or esters used to make alkoxylated fatty esters and derivatives thereof are usually made by hydrolysis or transesterification of triglycerides, which are typically animal or vegetable fats. Consequently, the fatty portion of the acid or ester will typically have 6-22 carbons with a mixture of saturated and internally unsaturated chains. 25 Depending on source, the fatty acid or ester often has a preponderance of C16 to C22 component. For instance, meth- anolysis of soybean oil provides the saturated methyl esters of palmitic (C 16) and stearic (C 18) acids and the unsaturated methyl esters of oleic (C 18 mono-unsaturated), linoleic (C 18 di-unsaturated), and α-linolenic (C18 tri-unsaturated) acids. The unsaturation in these acids has either exclusively or predominantly cis-configuration. [0005] Recent improvements in metathesis catalysts (see J.C. Mol, Green Chem. 4 (2002) 5) provide an opportunity 30 to generate reduced chain length, monounsaturated feedstocks, which are valuable for making detergents and sur- factants, from C 16 to C 22-rich natural oils such as soybean oil or palm oil. Soybean oil and palm oil can be more economical than, for example, coconut oil, which is a traditional starting material for making detergents. As Professor Mol explains, metathesis relies on conversion of olefins into new products by rupture and reformation of carbon-carbon double bonds mediated by transition metal carbene complexes. Self-metathesis of an unsaturated fatty ester can provide an equilibrium 35 mixture of starting material, an internally unsaturated hydrocarbon, and an unsaturated diester. For instance, methyl oleate (methyl cis-9-octadecenoate) is partially converted to 9-octadecene and dimethyl 9-octadecene-1,18-dioate, with both products consisting predominantly of the trans-isomer. Metathesis effectively isomerizes the cis-double bond of methyl oleate to give an equilibrium mixture of cis- and trans-isomers in both the "unconverted" starting material and the metathesis products, with the trans-isomers predominating. 40 [0006] Cross-metathesis of unsaturated fatty esters with olefins generates new olefins and new unsaturated esters that can have reduced chain length and that may be difficult to make otherwise. For instance, cross-metathesis of methyl oleate and 3-hexene provides 3-dodecene and methyl 9-dodecenoate (see also U.S. Pat. No. 4,545,941). Terminal olefins are particularly desirable synthetic targets, and Elevance Renewable Sciences, Inc. recently described an im- proved way to prepare them by cross-metathesis of an internal olefin and anα -olefin in the presence of a ruthenium 45 alkylidene catalyst (see U.S. Pat. Appl. Publ. No. 2010/0145086). A variety of cross-metathesis reactions involving an α-olefin and an unsaturated fatty ester (as the internal olefin source) are described. Thus, for example, reaction of soybean oil with propylene followed by hydrolysis gives, among other things, 1-decene, 2-undecenes, 9-decenoic acid, and 9-undecenoic acid. Despite the availability (from cross-metathesis of natural oils and olefins) of unsaturated fatty esters having reduced chain length and/or predominantly trans-configuration of the unsaturation, alkoxylated fatty esters 50 and their derivatives made from these feedstocks appear to be unknown. Moreover, alkoxylated fatty esters and their derivatives have not been made from the C18 unsaturated diesters that can be made readily by self-metathesis of a natural oil. [0007] In sum, traditional sources of fatty acids and esters used for making alkoxylated fatty esters and their derivatives generally have predominantly (or exclusively) cis-isomers and lack relatively short-chain (e.g., C 10 or C12) unsaturated 55 fatty portions. Metathesis chemistry provides an opportunity to generate precursors having shorter chains and mostly trans-isomers, which could impart improved performance when the precursors are converted to downstream composi- tions (e.g., in surfactants). New C18 difunctional alkoxylated fatty esters and derivatives are also potentially available from oil or C 10 unsaturated acid or ester self-metathesis. In addition to an expanded variety of precursors, the unsaturation 3 EP 2 633 008 B1 present in the precursors allows for further functionalization, e.g., by sulfonation or sulfitation. SUMMARY OF THE INVENTION 5 [0008] The invention relates to an alkoxylated fatty ester. In a first aspect, the present invention provides an alkoxylated fatty ester having the formula: 2 1 R -CO-O-(AO)n-R 10 1 2 3 1 wherein: R is C 1-C4 alkyl; AO is C 2-C4 oxyalkylene; R is R -CH=CH-(CH2)7- or R (AO)n-O-CO-(CH2)7-CH=CH-(CH2)7-; 3 R is hydrogen or C1-C7 alkyl; and n, which is the average number of oxyalkylene units, has a value within the range of 1 to 100; and 3 9 wherein when R is C1-C7 alkyl, the fatty ester has at least 1 mole % of trans-Δ unsaturation. [0009] The alkoxylatedfatty estermay comprise the reactionproduct ofa metathesis-derived C 10-C17 monounsaturated 15 acid, octadecene-1,18-dioic acid, or their ester derivatives with one or more alkylene oxides in the presence of an insertion catalyst to give an alkoxylated fatty ester. In one variant, the metathesis-derived 10C-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivative is reacted with a glycol ether or a glycol ether alkoxylate, optional ly in the presence of an esterification or transesterification catalyst, to give an alkoxylated fatty ester.