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(12) United States Patent (10) Patent No.: US 8,129,563 B2 Schmitt Et Al

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(12) United States Patent (10) Patent No.: US 8,129,563 B2 Schmitt Et Al USOO8129563B2 (12) United States Patent (10) Patent No.: US 8,129,563 B2 Schmitt et al. (45) Date of Patent: Mar. 6, 2012 (54) METHOD FOR SYNTHESIZING ALLYL (51) Int. Cl. METHACRYLATE C07C 67/02 (2006.01) C07C 69/52 (2006.01) (75) Inventors: Bardo Schmitt, Mainz-Kastel (DE); Guido Protzmann, Bensheim (DE); (52) U.S. Cl. ........................................ 560/217:560/225 Thorben Schuetz, Seeheim-Jugenheim (58) Field of Classification Search ........................ None (DE); Harald Trauthwein, Buerstadt See application file for complete search history. (DE); Reinhold Martin, Bad Koenig (DE); Joachim Knebel, (56) References Cited Alsbach-Haehnlein (DE); Ingo Sander, Min Hang District (CN); Klaus U.S. PATENT DOCUMENTS Gottmann, Heppenheim (DE); Thomas 4,202,990 A * 5/1980 Murakami et al. ............ 560,217 Kehr, Muehltal (DE); Dieter Bathen, 5,856,611 A * 1/1999 Schlaefer et al. ............. 585,520 Duisburg (DE); Christian Maul, 6,639,099 B1 10/2003 Knebel et al. Neustadt a.d.W. (DE) 2002/0123643 A1* 9, 2002 Paul .............................. 560,217 FOREIGN PATENT DOCUMENTS (73) Assignee: Evonik Roehm GmbH, Darmstadt (DE) EP 1 O78913 2, 2001 (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 OTHER PUBLICATIONS U.S.C. 154(b) by 130 days. U.S. Appl. No. 12/667,822, filed Jan. 5, 2010, Knebel, et al. U.S. Appl. No. 12/667,538, filed Jan. 4, 2010, Knebel, et al. (21) Appl. No.: 12/667,604 U.S. Appl. No. 12/667,599, filed Jan. 4, 2010, Protzmann, et al. (22) PCT Filed: May 8, 2008 * cited by examiner (86). PCT No.: PCT/EP2008/055669 Primary Examiner — Karl J. Puttlitz Spivak, S371 (c)(1), (74) Attorney, Agent, or Firm — Oblon, (2), (4) Date: Jan. 4, 2010 McClelland, Maier & Neustadt, L.L.P. (87) PCT Pub. No.: WO2009/003746 (57) ABSTRACT PCT Pub. Date: Jan. 8, 2009 The present invention relates to a process for preparing allyl methacrylate, comprising the reaction of allyl alcohol with an (65) Prior Publication Data ester of methacrylic acid, wherein the reaction is catalyzed by Zirconium acetylacetonate. The process according to the US 2010/O185OO9A1 Jul. 22, 2010 invention enables particularly favorable preparation of allyl (30) Foreign Application Priority Data methacrylate with a very high purity. Jul. 5, 2007 (DE) ......................... 10 2007 O31 468 26 Claims, No Drawings US 8,129,563 B2 1. 2 METHOD FOR SYNTHESIZING ALLYL Appropriate modifications to the processes according to the METHACRYLATE invention are protected in the dependent claims referring back to claim 1. The present invention relates to processes for preparing The present invention accordingly provides a process for allyl methacrylate. preparing allyl methacrylate, comprising the reaction of allyl Allyl methacrylate serves, interalia, as an intermediate for alcohol with an ester of methacrylic acid, wherein the reac preparing silyl-containing methacrylates. Accordingly, Vari tion is catalysed by Zirconium acetylacetonate. ous methods of obtaining this compound are known. These As a result, it is possible in an unforeseeable manner to include especially processes in which allyl alcohol is reacted provide a process for preparing allyl methacrylate in which with methacrylates, for example methyl methacrylate or ethyl 10 the product is obtained with a very high purity. Surprisingly, the product obtained contains only very Small amounts of methacrylate. To improve the yield and the selectivity of the allyl alcohol and/or water. reaction, different catalysts can be used. Furthermore, the process according to the invention For example, acids or bases can be used to catalyse the enables particularly selective preparation of allyl methacry transesterification. Such reactions are detailed, for example, 15 late. in CN 1410412 or DE 34.23 441. When these catalysts are Moreover, the process according to the invention can be used, however, side reactions have to be expected, for performed simply and inexpensively, while the product can example Michael addition, which reduces both the purity of be obtained in high yields and, viewed overall, with low the allyl methacrylate desired and the yield. energy consumption. Furthermore, the reaction can be per According to the publication.JP 11222461, the transesteri formed especially without nitrogen-containing polymeriza fication of methyl methacrylate with allyl alcohol can be tion inhibitors. catalysed by titanium alkoxides. In this case, nitrogen-con According to the invention, allyl methacrylate is prepared. taining polymerization inhibitors in particular are used, Allyl methacrylate (propenyl 2-methylpropenoate) has been which, though, are undesired in the allyl methacrylate. known for some time and has the CAS number 96-05-9. Moreover, publication JP-01-258642 describes the reac 25 To prepare allyl methacrylate, in accordance with the tion of methyl methacrylate with allyl alcohol in the presence invention, allyl alcohol (2-propen-1-ol) is used, which is of titanium alkoxides. In this case, oxygen-containing poly obtainable commercially, for example, from Lyondell. The merization inhibitors are used. CAS number of allyl alcohol is 107-18-6. Furthermore, publication DE 28 05 702 describes the According to the present invention, allyl alcohol is reacted preparation of esters of unsaturated carboxylic acids. To 30 with an ester of methacrylic acid. Particularly suitable meth catalyse the reactions described, it is possible in particular to acrylates are formed especially from alcohols having 1 to 4 use compounds which contain zirconium and/or calcium. The carbon atoms. These include especially methanol, ethanol, particularly suitable catalysts include especially Zirconium n-propanol, isopropanol, n-butanol and tert-butanol. Particu acetylacetonate. However, the preparation of allyl methacry lar preference is given to using especially ethyl methacrylate late is not described explicitly. The reactions lead to high 35 or methyl methacrylate, very particular preference being yields of approx. 98% based on the alcohol used. However, it given to methyl methacrylate. is evident from this that the product contains considerable The weight ratio of allyl alcohol to the ester of methacrylic amounts of by-products. acid is preferably in the range of 1:1.5 to 1:10, more prefer The preparation of silyl-containing methacrylates from ably 1:2.5 to 1:5 and most preferably in the range of 1:3 to 1:4. allyl alcohol requires a very high purity of the reactants, since 40 Too Small an ester excess can reduce the reaction rate; too impurities, for example allyl alcohol and water, can deacti great an ester excess is economically unviable, since it vate the Pt catalyst used for the synthesis of the silane meth reduces the utilizable tank volume. acrylate. Nitrogen-containing secondary components are dis According to the invention, Zirconium acetylacetonate is ruptive in the same way. Allyl methacrylate, which is sold used to catalyse the present transesterification. The CAS commercially as a reactant for these purposes, must therefore 45 number of zirconium acetylacetonate is 17501-44-9. The not contain more than 200 ppm of allyl alcohol, a minimum preparation of Zirconium acetylacetonate from acetylacetone content of allyl alcohol being desirable. In order to satisfy (pentane-2,4-dione) and Zirconium compounds is described, these requirements, the products obtained according to the for example, in Houben-Weyl, Methoden der organischen prior art must be purified in a complicated manner. Chemie Methods of Organic Chemistry, 4th Edition, Vol. In view of the prior art, it was an object of the present 50 VI/2, 1963, pages 53-55 and 58 to 61, and also in A. E. invention to provide a process for preparing allyl methacry Martell, M. Calvin, “Die Chemie der Metallchelatverbindun late, in which the product is obtained with a very high purity. gen” The chemistry of the metal-chelate compounds In particular, the allyl methacrylate obtained should contain (1958). Advantageously, it is possible to use 0.2 to 5 mmol. only very small amounts of allyl alcohol and/or water. more preferably 0.5 to 2 mmol, of zirconium acetylacetonate It was a further object of the invention to provide a process 55 per mole of allyl alcohol. The catalyst can also be prepared in in which allyl methacrylate can be obtained very selectively. situ, in which case the starting materials can be added before Furthermore, it was an object of the present invention to or during the transesterification of the reaction mixture. provide processes for preparing allyl methacrylate which can The reaction can be effected at elevated or reduced pres be performed simply and inexpensively. At the same time, the Sure. In a particularly appropriate modification of the present product should be obtained in maximum yields and, viewed 60 invention, the transesterification can be performed at a pres overall, with minimum energy consumption. Furthermore, sure in the range of 200 to 2000 mbar, more preferably in the the reaction should be performable especially without nitro range of 500 to 1300 mbar. gen-containing polymerization inhibitors. The reaction temperature may, especially depending on the These objects and further objects which are not stated pressure, likewise be within a wide range. In a preferred explicitly but which are immediately derivable or discernible 65 embodiment of the present invention, the reaction is effected from the connections discussed herein by way of introduction preferably at a temperature in the range of 80°C. to 120°
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