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PATENT OFFICE 2,101,820 PROCESS for the PREPARATION of POLYMERIZABLE UNSATURATED COM POUNDS John C

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PATENT OFFICE 2,101,820 PROCESS for the PREPARATION of POLYMERIZABLE UNSATURATED COM POUNDS John C Patented Dec. 7, 1937 2,101,820 UNITED STATES PATENT OFFICE 2,101,820 PROCESS FOR THE PREPARATION OF POLYMERIZABLE UNSATURATED COM POUNDS John C. Woodhouse, Wilmington, Del, assignor to E. I. du Pont de Nemours & Company, Will mington, Del, a corporation of Delaware No Drawing. Application December 5, 1933, Serial No. 701,053 10 Claims. (Cl. 260-106) This invention relates to a process for the prep included under the term aryl include benzyl, aration of unsaturated polymerizable organic naphthyl, and analogous aryl compounds. It will compounds and more particularly to the prepara be appreciated by those skilled in this art that tion of Such compounds from Saturated organic altho the Substitutions in the X and Y positions 5 compounds containing an isopropyl radical at Will alter the reaction rates and in many in 5 tached to a carbonyl group which likewise carries stances the by-products resulting from the de a hydrogen, hydroxy, aryl, or aralkyl group. hydrogenation, these substitutions are to be given An object of the present invention is to provide but secondary consideration for, generally speak an improved process for the preparation of poly ing, if the compound to be dehydrogenated has the O merizable unsaturated aliphatic and/or aromatic basic formula 10 organic compounds. Another object of the in vention is to provide an improved process for the chi-qi- - O preparation of esters of the unsaturated mono it may be dehydrogenated to an unsaturated poly carboxylic aliphatic organic acids. Another ob merizable compound. ject of the invention is to provide an improved The compounds containing an isobutyryl group, 15 process for the preparation of methacrylic acid. such, for example, as isobutyric acid, isobutyralde A further object of the invention is to provide a hyde, or an alkyl ester of isobutyric acid, such, process for the preparation of polymerizable esters for example, as methyl isobutyrate, ethyl iso of the unsaturated monocarboxylic aliphatic Or butyrate and the higher esters thereof, are par ganic acids from aliphatic or aromatic organic ticularly well suited for dehydrogenation in ac 20 compounds containing an isopropyl radical at cord with my process in which corresponding tached to a carbonyl group which likewise carries unsaturated polymerizable compounds are ob a hydrogen, a hydroxy, an alkyl, or an aryl group. tained; that is from isobutyryl aldehyde there is A further object of the invention is to provide obtained an alpha methylacrolein which may be a process for the preparation of the methyl ester directly polymerized or which may be oxidized 25 of methacrylic acid including the steps of catalyti and then esterified to the polymerizable meth cally dehydrogenating a compound containing an acrylate; from isobutyric acid, methacrylic acid iscbutyryl group and Subsequently converting the which may be esterified to the ester; and in some thus obtained oxygenated compound to an alkyl instances from the alkyl esters of isobutyric acid ester of methacrylic acid. Other objects and ad the corresponding alkyl methacrylates are ob 30 Vantages Will hereinafter appear. tained directly. I usually prefer to convert the Waluable polymerizable unsaturated compounds unsaturated compounds, if in the form of an are produced by dehydrogenation in accord with aldehyde or acid, to the ester prior to polymer my invention and Substantially as indicated by ization. M the equation: Polymerization may be effected by any of the 35 customary processes such, for example, as by heating, submitting the unsaturated compound X Y X Y to ultraViolet light, etc. Heat and/or light treat in which X may be an alkyl or aryl group and ment may be augmented by the addition of per 4) Y may be hydrogen, or a hydroxyl, alkoxy, aryl, oxides, if desired. 40 alkyl, or aralkyl group. Thus by substituting an The dehydrogenation of the above compounds I alkyl group Such as methyl, ethyl, propyl or a prefer, generally, to effect in the vapor phase. higher group for X and hydrogen for Y - iso Isobutyraldehyde, for example, is vaporized and butyryl aldehyde, 2-methyl butyryl, aldehyde, passed at a temperature within the range of and analogous aldehydes are indicated; these 200-500 C., over a suitable dehydrogenation 45 - compounds being dehydrogenated to alpha catalyst. The dehydrogenation may be conducted methyl acrolein, alpha-ethyl acrolein, respective also under elevated pressures, although usually ly, etc.; by the substitution of a hydroxyl group I prefer to carry out the reaction under atmos in lieu of hydrogen there would result 2-methyl pheric pressure. A number of dehydrogenation propionic acid, 2-ethyl propionic acid, etc., which catalysts may be employed for the treatment of upon dehydrogenation would be converted re isobutyryl containing compounds and the other spectively to methacrylic and ethylacrylic acids. compounds indicated above including, for ex The specific groups included under alkoxy cover, ample, nickel, copper, platinum, etc., the com for example, methoxy, ethoxy, propoxy and the pound catalysts such as copper-zinc-cadmium, 5 5 higher alkyloxy compounds, while the compounds copper chromite, and like well known catalysts. 2 2,101,820 I shall now describe several examples illus hyde by passing it in the vapor phase over a trating my invention which, however, will be un copper-chromium-zinc-cadmium catalyst at a derstood to limit in no way the Operating cond temperature of approximately 400° C. tions, equivalents, or Scope thereof. 4. A process of preparing an alkyl ester of Eacample 1.-Substantially anhydrous isobutyr methacrylic acid which conprises dehydrogenat aldehyde was passed at atmospheric pressure and ing isobutyraldehyde by passing it in the vapor at a temperature of approximately 400° C. Over phase Over a dehydrogenation catalyst at a tem 100 cc. charge of 8-14 mesh copper-chromium perature between 200 and 500 C., and subse zinc-cadmium catalyst at a space velocity of ap quently Oxidizing and esterifying the alpha 0. proximately 145. The catalyst may be prepared methyl acrolein to an ester of methacrylic acid. 10 in accord with the patented process of Lazier, 5. In a process for the preparation of poly described in U. S. Patent No. 1,964,001. The exit merizable esters of methacrylic acid the step gas issuing from the catalytic reaction was led which comprises dehydrogenating isobutyralde thru a water condenser, and a cold trap cooled hyde at a temperature of between 200 and 500 5 in a solid carbon dioxide-methanol bath. The C. in the presence of a dehydrogenation catalyst. 5 exit gas was collected by displacement of water. 6. A process of preparing a methyl ester of A total condensate of 116 cc, was collected from methacrylic acid which comprises dehydro the dehydrogenation of a 1.31 mols of isobutyr genating isobutyraldehyde by passing it in the aldehyde which contained an appreciable quan vapor phase over a dehydrogenation catalyst at tity of alpha-methyl acrolein, which is readily a temperature between 200 and 500° C., and sub 20 converted to the methyl ester of methacrylic acid Sequently oxidizing the product and esterifying by oxidation followed by esterification-well the Oxidation product with methanol. known oxidation and esterification processes may 7. In a process for the preparation of poly be used. merizable unsaturated organic compounds select 25 Eacample 2.-After drying isobutyraldehyde ed from the group consisting of alpha-aryl and 25 over anhydrous calcium chloride and distilling, alpha-alkyl Substituted acrylic acid compounds the thus dehydrated isobutyraldehyde, boiling be the step which comprises dehydrogenating, in the tween 63-64 C., was passed over a catalyst simi presence of a dehydrogenation catalyst, a com lar to that disclosed in Example 1 at a tempera pound in accord with the following equation: 30 ture of approximately 464 C., a space velocity of 30 approximately 118, and at atmospheric pressure. 2CH-H--0-2CH---0+H, 36 cc, of condensate was collected from the pas k H. kh sage of .526 gram mol. Of the oldehyde in a man in which X is a radical selected from the group ner similar to that disclosed in Example i. The consisting of alkyl and aryl radicals. 35 condensate contained alpha-methyl acrolein, 8. In a process for the preparation of poly 35 which on treatment in the liquid phase With nerizable unsaturated organic compounds select potassium dichromate and dilute sulfuric acid ed from the group consisting of alpha-aryl and may be converted to methyl acrylic acid, which alpha-alkyl substituted acrylic acid compounds, in turn is esterified in the usual manner with an the step which comprises reacting a compound aliphatic alcohol to obtain an alkyl ester of having the basic formula: methacrylic acid. From a consideration of the above Specifica chi-gh- O tion, it will be realized that any modification or k h improvement of the process herein described will in which X is a radical selected from the group come within the scope of my invention without consisting of alkyl radicals and aryl radicals, in sacrificing any of the advantages that may be the presence of a dehydrogenating catalyst. 45 derived therefron. 9. In a process for the preparation of an alkyl I claim: ester of methacrylic acid, the steps which com 1. In a process for the preparation of poly prise dehydrogenating a compound selected from merizable esters of methacrylic acid, the step the group consisting of isobutyraldehyde, iso which comprises dehydrogenating 'at reaction butyric acid, and its esters by passing the com 50 temperature isobutyraldehyde to alpha methyl pound in the vapor phase over a dehydrogenation acrolein in the presence of a dehydrogenating catalyst at a temperature between 200 and 500° catalyst. C. 2. In a process for the preparation of poly 10. In a process for the preparation of poly merizable esters of methacrylic acid, the steps merizable esters of methacrylic acid, the steps which comprise dehydrogenating isobutyralde which comprise dehydrogenating a compound hyde to alpha-methyl acrolein at a temperature selected from the group consisting of isobutyral of 200-500° C., and in the presence of a dehydro dehyde, isobutyric acid and its esters by passing genation catalyst adapted to the reaction.
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