(19) & (11) EP 2 407 444 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 18.01.2012 Bulletin 2012/03 C07C 29/16 (2006.01) C07C 31/133 (2006.01) C07C 45/53 (2006.01) C07C 49/413 (2006.01) (2006.01) (2006.01) (21) Application number: 11173087.5 C07C 51/31 C07C 53/126 (22) Date of filing: 18.03.2009 (84) Designated Contracting States: (72) Inventor: Rajendran, Gurusamy AT BE BG CH CY CZ DE DK EE ES FI FR GB GR League City, TX 77573 (US) HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR (74) Representative: Cockerton, Bruce Roger Carpmaels & Ransford (30) Priority: 19.03.2008 US 37861 P One Southampton Row London (62) Document number(s) of the earlier application(s) in WC1B 5HA (GB) accordance with Art. 76 EPC: 09721453.0 / 2 257 516 Remarks: This application was filed on 07-07-2011 as a (71) Applicant: Invista Technologies S.a r.l. divisional application to the application mentioned 9000 St. Gallen (CH) under INID code 62. (54) Process for the preparation of dodecanedioic acid (57) The present disclosure provides processes for the preparation of dodecanedioic acid (DDDA) EP 2 407 444 A2 Printed by Jouve, 75001 PARIS (FR) EP 2 407 444 A2 Description CROSS-REFERENCE TO RELATED APPLICATION 5 [0001] This application claims priority to U.S. provisional application entitled, "CYCLODODECATRIENE AND CHEM- ICAL PROCESS", having serial number 61/037,861, filed on March 19, 2008, which is entirely incorporated herein by reference. FIELD OF THE INVENTION 10 [0002] The disclosure herein relates to a process for forming a mixture containing dodecanedioic acid (DDDA). BACKGROUND 15 [0003] It is known to produce dodecanedioic acid (DDDA) using a chemical process starting with the conversion of 1,3-butadiene (trimerization) to 1,5,9-cyclododecatriene (CDDT). This trimerization process employs a Ziegler-Natta catalyst (TiCl4 and aluminum chloride) and mild 70 to 80°C conditions at ca. 2 bar pressure absolute. Followed by reduction of the CDDT to cyclododecane using hydrogen and Raney Nickel catalyst at 170 to 180°C and 26 - 28 bar pressure absolute, the cyclododecane is oxidized with air to a mixture comprising cyclododecanol (CDDA) and cyclodo- 20 decanone (CDDK) in the presence of a boric acid catalyst at 160 to 180°C and 1 - 2 bar pressure absolute. The CDDK and CDDA mixture contains about 80-90% CDDA and 10-20% CDDK. This mixture is oxidized using nitric acid and catalysts comprising copper and vanadium to obtain a mixture comprising DDDA. SUMMARY 25 [0004] Briefly described, embodiments of this disclosure include processes of making dodecanedioic acid (DDDA), and the like. One exemplary process for making dodecanedioic acid, among others, includes: contacting 1,3-butadiene with a first catalyst and forming cyclododeca-1,5,9-triene; oxidizing the cyclododeca-1,5,9-triene using an oxygen con- taining reagent to form epoxycyclododeca-5,9-diene, converting the epoxycyclododeca-5,9-diene into a first mixture 30 comprising cyclododecanol and cyclododecanone; and contacting the first mixture with reactants comprising a third catalyst and nitric acid to form a second mixture comprising dodecanedioic acid. [0005] One exemplary process for making laurolactone, among others, includes: providing a reaction vessel including a solution of cyclododecanone (CDDK) that is dissolved in about an equal weight of an acid anhydride; providing to the vessel an acid catalyst in an amount effective to promote the reaction, wherein the acid catalyst is selected on the basis 35 of its pKa such that its pKa is about 0 to about 5; and introducing hydrogen peroxide to the reaction vessel to promote the Baeyer-Villiger oxidation, wherein about 20% or more of the cyclododecanone (CDDK) is converted to laurolactone. [0006] One exemplary process for making laurolactone, among others, includes: contacting 1,3- butadiene with a first catalyst and forming cyclododeca-1,5,9-triene; oxidizing the cyclododeca-1,5,9-triene using an oxygen containing rea- gent to form epoxycyclododeca-5,9-diene, converting the epoxycyclododeca-5,9-diene into a first mixture comprising 40 cyclododecanol and cyclododecanone; disposing the cyclododecanone (CDDK) from the first mixture in a reaction vessel, wherein the CDDK is dissolved in about an equal weight of an acid anhydride; providing to the vessel an acid catalyst in an amount effective to promote the reaction, wherein the acid catalyst is selected on the basis of its pK a such that its pKa is about 0 to about 5; and introducing hydrogen peroxide to the reaction vessel to promote the Baeyer-Villiger oxidation, wherein about 20% or more of the (CDDK) is converted to laurolactone. 45 DETAILED DESCRIPTION [0007] Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology 50 used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims. [0008] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the 55 preferred methods and materials are now described. [0009] All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are 2 EP 2 407 444 A2 cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admissi on that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed. [0010] Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of chemistry, chem- 5 ical engineering, and the like, which are within the skill of the art. Such techniques are explained fully in the literature. [0011] It must be noted that, as used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a support" includes a plurality of supports. In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless a contrary intention is apparent. 10 Discussion [0012] Embodiments of the present disclosure provide for a process for making dodecanedioic acid (DDDA). Embod- iments of the present disclosure may have certain advantages in energy consumption versus other methods. In general, 15 embodiments of the present disclosure require less energy in the conversion of cyclododeca-1,5,9-triene to cyclodo- decanol (CDDA) or cyclododecanone (CDDK) in comparison to a process disclosed by Welton in his U.S. Patent Number 3,607,948 (assigned to E. I. du Pont de Nemours and Co.); the disclosure of Welton are herein incorporated by reference in their entirety. [0013] In general, embodiments of this disclosure relate to processes for the preparation of dodecanedioic acid (DDDA) 20 by oxidizing cyclododeca-1,5,9-triene with an oxygen containing reagent to form epoxycyclododeca-5,9-diene, forming a mixture containing cyclododecanol and cyclododecanone, and oxidizing the mixture with nitric acid to form a DDDA containing mixture of diacids. [0014] Embodiments of this disclosure relate to processes of chemical transformation employing the steps of polym- erizing (trimerization) of 1,3-butadiene to cyclododeca-1,5,9-triene, which is subsequently oxidized to form epoxycy- 25 clododeca-5,9-diene. Then, epoxycyclododeca-5,9-diene is converted by selective reduction and/or rearrangement to a first mixture containing cyclododecanol (CDDA) and cyclododecanone (CDDK). Next, the first mixture is oxidized to a second mixture comprising dodecanedioic acid (DDDA). Reduction of the cyclododeca-1,5,9-triene (CDDT) to cy- clododecane with hydrogen over a heterogeneous Raney Nickel catalyst is not performed in this process and no catalyst is employed in the intermediate steps of this transformation as compared with the known method of employing air 30 oxidation in the presence of boric acid. Ways to perform the oxidation of cyclododeca- 1,5,9-triene to the epoxycyclodo- deca-5,9-diene are known from T. Sridharet al. (Department of Chemical Engineering, Monash University, Victoria 3800, Australia) found in Ind. Eng. Chem. Res., 46 (10), 3057 -3062, 2007 "Uncatalyzed Oxidation of 1,5,9-Cyclodo- decatriene with Molecular Oxygen." [0015] In an embodiment, the process includes contacting 3-butadiene (BD) with a first Ziegler-Natta type catalyst 35 effective for trimerizing BD and forming cyclododeca-1,5,9-triene (CDDT). Next, the process includes oxidizing the cyclododeca-1,5,9-triene (CDDT), using an oxygen containing reagent, to form epoxycyclododeca- 5,9-diene (ECDDD). In an embodiment, the oxidization can be conducted in the presence of a second catalyst. Subsequently, the process includes converting epoxycyclododeca- 5,9-diene (ECDDD) into a first mixture comprising cyclododecanol (CDDA) ( e.g., about 30% to 70% of the first mixture) and cyclododecanone (CDDK) ( e.g., about 70% to 30% of the first mixture).