United States Patent 19 11 Patent Number: 5,892,123 Anderson Et Al

USOO5892.123A United States Patent 19 11 Patent Number: 5,892,123 Anderson et al. (45) Date of Patent: Apr. 6, 1999

54 PROCESS FOR REPRODUCING A MIXTURE 56) References Cited CONTAINING CYCLODODECANONE AND CYCLODODECANOL U.S. PATENT DOCUMENTS

75 Inventors: Howard Wayne Anderson, Hockessin; 4,465,861 8/1984 Hermollin ------568/342

James Bernard Sieja, Newark, both of 4,568,769 2/1986 Yashima ------568/342 Del. FOREIGN PATENT DOCUMENTS 73 Assignee: E. I. du Pont de Nemours and 1032390 6/1966 United Kingdom. Company, Wilmington, Del. 21 Appl. No.: 17,784 Primary Examiner Shailendra Kumar ASSistant Examiner Sreeni Padmanabhan 22 Filed: Feb. 3, 1998 57 ABSTRACT 51 Int. Cl...... C07C 45/53; CO7C 35/08 52 U.S. Cl...... 568/361; 568/342; 568/344; A method is disclosed for catalytically decomposing 568/821 cyclododecyl hydroperoxide into cyclododecanone and 58 Field of Search ...... 568/342,835, cyclododecanol using a chromium catalyst. 568/798, 385,578, 361, 821, 375,832, 344 7 Claims, No Drawings 5,892,123 1 2 PROCESS FOR REPRODUCING AMIXTURE cyclododecane, is decomposed to cyclododecanone (K) and CONTAINING CYCLODODECANONE AND cyclododecanol (A) in the presence of a chromium catalyst. CYCLODODECANOL Cyclododecyl hydroperoxide may be obtained by oxida tion of cyclododecane. Air oxidation is the preferred BACKGROUND OF THE INVENTION method. This may be performed by bubbling air through Cyclododecanone (K) and cyclododecanol (A) are inter cyclododecane at a temperature of about 145 C. to about mediates in the production of nylon-12 and 1,12 180° C. Normally conversion is about 10%. The resulting dodecanedioic acid (DDDA). The air oxidation of oxidation product is a Solution which contains unreacted cyclododecane produces a mixture containing K, A and a cyclo do de cane, cyclo do decyl hydrop eroxide, significant amount of cyclododecyl hydroperoxide (P). The cyclododecanone, cyclododecanol, and other impurities. P can be decomposed into more K and A. Aboron compound The resulting oxidation product Solution is then treated may be used as a catalyst for the decomposition; See UK with a chromium catalyst to decompose the cyclododecyl Patent No. 1,032,390. hydroperoxide to cyclododecanone and cyclododecanol. U.S. Pat. No. 4,465,861 discloses a process for the This chromium-catalyzed process gives a product which is conversion of cyclohexyl hydroperoxide to a mixture of 15 rich in cyclododecanone (K) relative to cyclododecanol (A). cyclohexanone and cyclohexanol using, among others, a Salt Although ratios of K to A as high as 25 have been observed, of chromium, Such as chromium octoate, and a Stabilizing typical K to A ratios are 5 to 10. agent. Cyclohexyl hydroperoxide can be made from the The chromium catalyst may be any chromium Salt Soluble oxidation of cyclohexane. The Oxidation results in a reaction in cyclododecane, a non-polar medium. Examples of Such mixture containing cyclohexanone, cyclohexanol, cyclo homogeneous (i.e., Soluble) catalysts include chromium hexyl hydroperoxide, unreacted cyclohexane, as well as Octoate, chromium naphthenate, chromium laurate, and Some water and acids. Before the cyclohexyl hydroperoxide chromium ethylhexanoate. Chromium Salts of fatty acids in this reaction mixture can be decomposed with a chro which are Soluble in hydrocarbon Solvents are particularly mium catalyst to provide more cyclohexanone and preferred. The catalyst may also be heterogeneous (i.e., cyclohexanol, the acids must be washed away with water, 25 and Substantially all the water-both that produced during insoluble). The chromium may be contained on an ion cyclohexanone oxidation and that used to wash away the eXchange resin. Examples of these include Sulfonic acid acids-must be removed. Typical cyclohexanone and cyclo resins Such as Amberlist 15, Amberlist XN-100, DoweX hexanol production from peroxide decomposition results in M-31, and DoweX DR-2030. Amberlist is a trademark of cyclohexanone to cyclohexanol ratioS of about 3. Rhom and Haas. DoweX is a trademark of Dow. Because it is expensive to dispose of boron-containing Typically the homogeneous chromium catalyst is present waste from commercial operations, there is a need for a in a concentration of 0.5 to 10 ppm, most preferably 1 to 4 process for the conversion of cyclododecane to DDDA that ppm. based on the total reaction mixture. does not use a boron compound to facilitate the decompo Pressure is not an important factor. Typically, the Sition of cyclododecyl hydroperoxide. There is also a need 35 cyclododecyl hydroperoxide decomposition is conducted at to decompose cyclododecyl hydroperoxide in a manner that atmospheric pressure for ease and cost of operation. Typical results in a high ratio of K to A. Cyclododecanone (K) is a reaction temperatures are 80 to 165 C., preferably 100 to more valuable product than cyclododecanol (A): cyclodode 120° C. canone can be converted to the corresponding lactam and Optionally, the decomposition portion of the process of ultimately to nylon-12, and cyclododecanone can also be 40 the present invention can be run in the presence of air which used cost-efficiently to produce DDDA, since it is already results in high K/A ratioS and conversion of Some unreacted partially oxidized from A. Finally, there is a need to be able cyclododecane to K and A. to catalytically decompose cyclododecyl hydroperoxide The present process does not require that the cyclodode without the need to wash away acids formed during cane oxidation product be washed with water to remove cyclododecane oxidation and without the need to remove 45 acids or that water be removed from the oxidation product Water. before addition of the chromium catalyst. SUMMARY OF THE INVENTION EXAMPLES These needs are met by the present invention which is a proceSS for producing a mixture containing cyclodode 50 The following nonlimiting examples illustrate the present canone and cyclododecanol, comprising oxidizing invention. cyclododecane to provide a reaction mixture containing Example 1 cyclododecyl hydroperoxide and contacting the reaction mixture with a chromium catalyst. This example shows the need to wash cyclohexane oxi It has been found that when a chromium catalyst is used 55 date (but not cyclododecane oxidate) prior to hydroperoxide in accordance with the present invention, there is a Surpris decomposition by a chromium catalyst. ing increase in the ratio of K to A, based on ratioS typically The reactor consisted of a 50 ml round-bottomed flask obtained from cyclohexyl hydroperoxide decomposition. It equipped with a condenser topped with a nitrogen tee, also has been found that, unlike cyclohexane oxidation Teflon(R) stirring bar, thermocouple, and a Teflon(R)-coated product, cyclododecane oxidation product may be treated 60 rubber Septum for catalyst injection and Sample removal. with a chromium catalyst without the need to wash the The flask was charged with 12 grams of oxidate containing oxidation product with water, and without the need to about 0.12 grams of an internal Standard (tetradecane for remove the water. cyclohexane oxidate, hexacosane for cyclododecane oxidate), and brought to temperature. A Zero time sample DETAILED DESCRIPTION 65 was removed when the Solution reached the desired tem In accordance with the present invention, the cyclodode perature (79. C.), and was analyzed, after Sillylation, by gas cyl hydroperoxide (P), resulting from the oxidation of chromatography using a Hewlett Packard HP 50 capillary 5,892,123 3 4 column. 50 microliters of chromium octoate Solution in Cr in the final solution was 5 ppm. About 0.2 ml samples toluene were added so that the final concentration of Cr in were removed at various times and analyzed by GC on a the solution was 5 ppm. About 0.2 ml samples were removed Hewlett Packard HP 50 capillary column after silylation. at various times and analyzed. The wt % K, A, P were The wt % K, A, P were determined. determined. The increase in K divided by the increase in A 5 To determine the effect of air on the results, when the melt is termed delta K/delta A in the Table 1. reached the desired temperature and a Zero time Sample was The oxidates were obtained from commercial facilities. taken, the nitrogen purge was replaced with an air purge. The The C6 (cyclohexane) washing procedure involved washing effect of the air is shown in Table 2, where it is shown that the C6 oxidate twice with 5% water for 30 min at 72°C. The the delta K/delta A ratio increased to 30-35 from 9-12. resulting phases were Separated and the organic phase was Since K is the more valuable product (for example, for dried with magnesium Sulfate. nylon-12 manufacture) the present invention is an economi It is clear from Table 1, that for chromium to be an cally attractive method for obtaining oxidate rich in K. effective cyclohexyl hydroperoxide decomposition catalyst, the cyclohexane oxidate must be washed with water. It is TABLE 2 also clear that C12 (cyclododecane) oxidate does not require 15 Oxidate water washing to obtain hydroperoxide conversions similar TIME 9%. K % A % P % P delta K identity/ to those obtained from washed C6 oxidate. It is also clear (MIN) Wt 9% COW delta A treatment that the delta K/delta A ratio obtained from C12 oxidate is O O.94 0.79 5.4 nitrogen higher than that from C6 oxidate. 15 5.0 1.1 O.8 85 12 3O 5.3 1.2 0.4 92 9.6 TABLE 1. 60 5.3 1.3 O.3 94 9.3 O 1.1 O.8 5.5 air Oxidate 15 5.6 O.92 O.7 87 31 TIME 9%. K % A % P % P delta K identity/ 3O 6.1 O.9 O.3 95 3O (MIN) Wt 9% COW delta A treatment 25 60 6.3 O.92 O.2 97 35 O 186 3.64 0.57 O C6/none 3O 1.95 3.82 O.65 O 60 1.98 3.86 0.59 O What is claimed is: 90 1.98 3.81 O.67 O 1. A process for producing a mixture containing O 2.O 3.81 O.63 O cyclododecanone (K) and cyclododecanol (A), comprising 3O 2.4 4.1 O.29 54 1.38 C6/washed 60 2.48 4.27 O.086 86 1.04 oxidizing cyclododecane to provide an oxidation product 90 2.53 4.33 O.O58 91 1.O containing cyclododecylhydroperoxide and an initial O 0.5 O.12 0.59 C12/none amount of K (K) and an initial amount of A (A) and 3O O.91 0.17 O.17 72 8.7 contacting the oxidation product with a chromium catalyst to 60 0.95 O.18 O.13 78 7.5 90 0.97 O.18 O.12 8O 7.8 35 provide a mixture containing a final amount of K (K) and a O 1.05 O.51 2.73 C12/none final amount of A (A) in which (K-K)/(A-A) is greater 3O 2.84 O.64 O.58 79 14.6 than about 5. 60 3.0 O.66 0.4 85 14.3 2. The process of claim 1 in which the chromium catalyst 90 3.1 O.67 O.37 87 13 is chromium Octoate. 3. The process of claim 1 in which the oxidation product 40 is contacted with the chromium catalyst in the presence of Example 2 Water. This example shows the effect of air on the delta K/delta 4. The process of claim 1 in which the oxidation product A ratio for a cyclododecane oxidate. is contacted with the chromium catalyst in the presence of The reactor consisted of a cylindrical glass tube about 2 air or nitrogen. cm in diameter by 11 cm long, containing a concentric inner 45 5. The process of claim 4 in which the oxidation product tube about 2 mm in diameter, which terminated in a 1 cm is contacted with the chromium catalyst in the presence of fritted tip near the bottom of the larger tube. It was charged a. with about 3 grams of C12 (cyclododecane) oxidate con 6. The process of claim 3 in which the oxidation product taining about 0.3 grams of internal Standard. The tube was is contacted with the chromium catalyst in the further immersed in an oil bath at the desired temperature. On 50 presence of air or nitrogen. melting, nitrogen was blown through the melt at a rate of 25 7. The process of claim 6 in which the oxidation product cc/min, which provided agitation. When the melt reached is contacted with the chromium catalyst in the presence of the desired temperature (90° C.), a sample was taken at time a. Zero, and a Solution of chromium octoate in toluene was injected into the melt So that the resulting concentration of