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Wo 2010/085712 A2 (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 29 July 2010 (29.07.2010) WO 2010/085712 A2 (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07C 57/16 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) Number: International Application CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US20 10/02 1894 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 22 January 2010 (22.01 .2010) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (25) Filing Language: English NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, (26) Publication Language: English SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/146,545 22 January 2009 (22.01 .2009) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, DRATHS CORPORATION [US/US]; 2367 Science ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, Parkway, Suite 2, Okemos, MI 48864 (US). TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, (72) Inventors; and MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM, (75) Inventors/Applicants (for US only): FROST, John, W. TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, [US/US]; 1621 Dobie Circle, Okemos, MI 48824 (US). ML, MR, NE, SN, TD, TG). MILLIS, James [US/US]; 2360 Yuman Lane N, Ply mouth, MN 55447 (US). TANG, Zhenyu [CN/US]; 4495 Published: Heritage Avenue, Apt A2, Okemos, MI 48864 (US). — without international search report and to be republished (74) Agent: CAMACHO, Jennifer, A.; Proskauer Rose, LLP, upon receipt of that report (Rule 48.2(gf) One International Place, Boston, MA 02 110 (US). (54) Title: METHODS FOR PRODUCING DODECANEDIOIC ACID AND DERIVATIVES THEREOF (57) Abstract: Methods for producing biosourced dodecanedioic acid and compositions comprising biosourced dodecanedioic acid are provided. In some embodiments, the method comprises first forming muconic acid bio- logically from a renewable carbon source, reducing the muconic acid to hexenedioic acid, and then reacting the hexenedioic acid with an unsaturat ed fatty acid, typically a ∆9 unsaturated fatty acid, in a metathesis reaction to produce dodecenedioic acid. Dodecenedioic acid is then reduced to do decanedioic acid. Dodecanedioic acid is can be used to form polymers, such as polyamides. Examples of polyamides include nylon, such as nylon 6,12. Nylon 6,12 can be formed by reacting dodecanedioic acid with 1,6- hexamethylene diamine. METHODS FOR PRODUCING DODECANEDIOIC ACID AND DERIVATIVES THEREOF RELATED APPLICATIONS [001] This application claims the benefit of U.S. Provisional Application No. 61/146,545, filed January 22, 2009, which application is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION [002] The invention relates generally to the production of dodecanedioic acid from renewable feedstock and subsequent uses thereof, such as for forming polyamides. BACKGROUND OF THE INVENTION [003] Nylon is a generic designation for a family of synthetic thermoplastic polyamides that are used to make fabrics, musical strings, rope, screws and gears, to name just a few examples. Nylon is available with fillers too, such as glass- and molybdenum sulfϊde-fϊ lled variants. [004] Nylon 6 is the most common commercial grade of molded nylon. The numerical suffix specifies the numbers of carbon atoms donated by the monomers; the diamine first and the diacid second. For nylon 6,6, the diamine typically is hexamethylenediamine and the diacid is adipic acid. Each of these monomers donates 6 carbons to the polymer chain. [005] Another example of a useful nylon is nylon 6,12, which is a copolymer of a 6-carbon diamine and a 12-carbon dicarboxylic acid. One method for making nylon 6,12 comprises forming a polycondensation product of 1,6-hexamethylene diamine and dodecanedioic acid. For commercial production of such polymeric materials, the starting materials are virtually solely obtained from hydrocarbon sources. [006] Dodecanedioic acid is thus a very important chemical. It is used in a variety of industrial applications, such as plasticizers for polymers, epoxy curing agents, adhesive and powder coatings, engineering plastics, perfumery and pharmaceutical products, etc. Annually, 15,000,000,000 pounds of dodecanedioic acid are synthesized from petrochemical feedstock. Such petrochemical feedstocks are a predominantly depleting natural resource, and the use of such feedstocks has been linked to detrimental changes to the environment on a global scale. [007] Such feedstock materials useful for the production of nylon have therefore limited availability and are subject to substantial price fluctuations. As a result, there has been a growing interest and need for alternative methods to produce dodecanedioic acid as well as polyamides that are renewable, sustainable and less harmful for the environment. SUMMARY OF THE INVENTION [008] Aspects of the invention relate to the production of useful commercial product, such as polyamides, starting with materials produced by a biological process from renewable feedstock, as opposed to using starting materials derived from non-renewable feedstock such as petroleum or other fossil carbon resources. Aspects of the invention relates more particularly to the production of dicarboxylic acid, as well as derivatives thereof, from renewable biomass-derived carbon source. More particularly, some aspects of the invention relate to the production of dodecanedioic acid, as well as precursors and derivatives thereof, from renewable biomass-derived carbon source. More specifically, the methods of the invention make use of a metathesis step with olefinic compounds in order to produce biosourced dicarboxylic acid such as dodecanedioic acid from renewable biosourced feedstock. The resulting renewable dodecanedioic acid can be separated from other products of the metathesis reaction and from any remaining starting materials. Dodecanedioic acid and derivatives thereof have utility in the production of polyamides and other polymers. [009] In some aspects, the invention provides a method of producing first muconic acid biologically from renewable feedstock. In preferred embodiments, the muconic acid is reduced to an isomer or isomers of hexenedioic acid. Reduction of the muconic acid can be performed using methods known in the art such as a zinc halide reagent, electrochemical reduction, or selective hydrogenation. The hexenedioic acid may be present as a derivative such as an ester, amide, or salt. [0010] In some embodiments, the hexenedioic acid is reacted with an unsaturated fatty acid in a metathesis reaction to produce dodecenedioic acid, which is then reduced to dodecanedioic acid. The reaction typically involves using a metathesis catalyst, such as a Grubbs catalyst, including benzylidene-bis(tricyclohexylphosphine)dichlororuthenium or benzylidene[1,3- bis(2,4,6- trimethylphenyl)-2- imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium. [0011] Forming muconic acid biologically may comprise forming the muconic acid bacterially using prokaryotes belonging to the genera Escherichia, Klebsiella, Corynebacterium, Brevibacterium, Arthrobacter, Bacillus, Pseudomonas, Streptomyces, Staphylococcus, or Serratia, or by using yeasts of the genus Saccharomyces or Schizosaccharomyces. [0012] Muconic acid is reduced to an isomer of hexenedioic acid, such as 3-hexenedioic acid, using any suitable reagent. One suitable reagent is a zinc halide reagent, such as zinc chloride in pyridine. [0013] The hexenedioic acid or derivative thereof is reacted with an unsaturated fatty acid to form an unsaturated dicarboxylic acid or derivative thereof. In preferred embodiments, the unsaturated fatty acid is first reacted in a self metathesis reaction to produce ∆9 octadecenedioic acid. ∆9 octadecenedioic acid then reacts with the hexenedioic acid to produce dodecenedioic acid. Preferably, the unsaturated fatty acid is a ∆9 unsaturated fatty acid. Examples, without limitation, of the ∆9 unsaturated fatty acid include myristoleic acid, palmitoleic acid, elaidic acid, and oleic acid. The unsaturated dicarboxylic acid or derivative thereof which is produced by the metathesis reaction can then be reduced to a saturated dicarboxylic acid. In preferred embodiments, the unsaturated dicarboxylic acid which is formed is dodecenedioic acid is then reduced to its saturated analog dodecanedioic acid. This can be accomplished by, for example, hydrogenating the dodecenedioic acid using a precious metal hydrogenation catalyst. [0014] In another embodiment, the ∆9 unsaturated fatty acid is first transformed to the symmetric ∆9 unsaturated dicarboxylic acid octadecenedioic acid via a self-metathesis reaction. The symmetric ∆9 octadecenedioic acid can then be used in a cross-metathesis reaction with the symmetric 3-hexenedioic acid to give the desired dodecenedioic acid as a single product of the metathesis reaction. [0015] In some embodiments, the dodecanedioic acid is used for forming polymers,
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