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UNITED STATES PATENT OFFICE 2,688,627 DCYCLOPENTADENE CARBOXYFLIC ACDS Charles A

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UNITED STATES PATENT OFFICE 2,688,627 DCYCLOPENTADENE CARBOXYFLIC ACDS Charles A Patented Sept. 7, 1954 2,688,627 UNITED STATES PATENT OFFICE 2,688,627 DCYCLOPENTADENE CARBOXYFLIC ACDS Charles A. Cohen, Roselle Park, Louis A. Mikeska, Westfield, and Frederick Knoth, Jr., Sayreville, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application May 8, 1952, Serial No. 286,834 13 Claims. (C. 260-429) 1. 2 This invention relates to novel dicyclopenta- diene is used as the starting material. In the diene carboxylic acids and to a process for pro- case of pure dicyclopentadiene the hydrogenation ducing the same. Specifically, this invention re- product is 9,10-dihydrodicyclopentadiene boiling lates to tetrahydrodicyclopentadiene carboxylic at 177° to 178° C., at atmospheric pressure and acids and process for producing these products. 5 inelts at 50 to 50.5° C. On titration with bromine In the practice of this invention the starting it absorbs bromine in an amount equal to 119 material is Substantially pure dicyclopentadiene centigrams of bromine per gram. The mixed Or a copolymer of methyl cyclopentadiene and products of hydrogenation are liquid at Ordinary cyclopentadiene (hereinafter referred to as temperature due to the mutual depression of the methyldicyclopentadiene) or a dimer made from 10 melting point. methyl cyclopentadiene (hereinafter referred to For purposes of purification and elimination of as dimethyldicyclopentadiene) or mixtures of two any unhydrogenated dimers present in the crude or more of these products normally found in dihydro product it is desirable but not necessary petroleum refinery streams originating from to distill the crude hydrogenation product at at either vapor phase, gas phase, or steam cracking 15 mospheric or higher preSSure So as to crack any processes. The production of the starting mate- unhydrogenated material to monomers which Will rials and methods of concentrating these dinners boil between 40 and 75° C. and thus effect a sepa is not an intrinsic part of this invention. For ration of a pure dihydro dimer which is stable most purposes, 60 to 90% alpha-dicyclopenta- against cracking when distilled at atmospheric diene available commercially Will Suffice. It is a 20 pressure. primary object of this invention to convert the The next stage in the preparation of these acids individual or mixed dimers to the tetrahydro- is to ester-CXonate the dihydro derivative to a carboxylic acids by a series of reactions involving carbaikoxy derivative of the tetrahydro dimer. hydrogenation to the dihydro derivative, ester- This is effected by bringing into intimate mixture OXOnation of the dihydro derivative, and hy- 25 in a pressure resistant vessel capable of having drolysis or Sagonification of the ester to the cor- its contents agitated, the dihydro derivative and responding acid. an excess of a monohydric aliphatic alcohol in the The hydrogenation of the dicyclopentadiene or presence of a cobalt catalyst while Subjecting the alkyl Substituted dicyclopentadiene to the dihydro contents of the vessel to a pressure of carbon derivative is effected by means of ordinary hy- 3G monoxide at a pressure of preferably 3000 pounds drogen in the presence of catalysts such as Raney per square inch gauge and a temperature of pref nickel, nickel on kieseguhr or other supporting erably 150° C. medium, or noble metal catalysts such as plati- The monohydric alcohol may be any aliphatic num oxide and the like. Temperatures for the alcohol of from one to 12 carbon atoms, pref hydrogenation may be from ambient temperatures erably 1 to 3 carbon atoms, and may be a normal to about 100° C. and pressures may be from one 3) primary alcohol, a branched primary alcohol, or atmosphere to as high as 1000 pounds per Square a secondary alcohol. Examples of these alcohols inch pressure. The upper limit expressed is not are methanol, ethanol, isopropanol, isooctyl alco limiting. Hydrogenation may be accomplished on hol, dodecanol, etc. Since the primary purpose the raw material as such or in the presence of an of the process is to recover the acids, it is of ad inert, diluent and solvent. On hydrogenation vantage to use the lowest molecular weight alco to the dihydro derivative two hydrogen atoms hol available and for this reason methanol is the enter the ring in the 9,10 position as shown in preferred alcohol. The quantity of alcohol to be the Structural formula, below: used in this reaction should be in excess of at 6 6 45 least One molar equivalent of the dihydro nate 10 N 01 rial utilized in the reaction and is preferably pres 7 CH, -- Ha - ent in a volume ratio of three parts of alcohol to 9 2 one of the dihydro material. Under these condi N-1N/ 8 3. tions, a large part of the dihydro product is solu 50 ble in the alcohol but is not completely so. It has Dicyclopentadiene Dihydrodicyclopentadiene been found that complete solubility of the re to give 9-10 dihydro dicyclopentadiene or a actants in the alcohol phase is not necessary for mono- or dialkyl substituted dicyclopentadiene Successful operation of the reaction. depending on whether pure dicyclopentadiene, a The cobalt catalyst used in this reaction may be mono alkyl derivative, or a dialkyl dicyclopenta- 5 5 present preferably in a concentration of between 2,688,627 3 4. 0.1 and 5.0 Weight percent as metal based on the The acids prepared by the process described dihydro product and is added to the reaction nix above are novel and have many useful proper ture either in the form of finely powdered cobalt ties not hereinbefore shown by products of sini metal or as cobalt carbonyl or as a cobalt Salt lar molecular Weight. In performance chara,c- of an organic acid readily soluble in at least one terstics they are best approached by the naph of the reaction materials Such as the alcohol or thenic acids isolated by alkali extraction from dihydro material. For this purpose we use cobalt certain gas oils, but suffer from none of the acetate, cobalt oleate, cobalt naphthenate or the drawbacks of these naphthenic acids in that the cobalt Salt of the novel acids forming the subject naphthenic acids are odoriferous to an unde of this invention. 0 sirable degree, possess poor color initially, and The reaction as set forth hereinbefore is run become worse in storage and contain appreciable under the conditions set forth until at least one quantities of reactive sulfur compounds which molar equivalent of carbon monoxide has been interfere seriously with their extended use. absorbed as indicated by pressure drop. On cool ihese new acids readily form oil- and hydrocar ing and removing the reaction mixture from the bon-soluble salts of all of the heavy metals and pressure vessel, there is obtained a mixture Com accordingly are a suitable material for the pro prising excess alcohol and the alkyl ester of the duction of paint driers such as the cobalt, lead tetrahydrodicyclopentadiene carboxylic acid cor and manganese salts, and in addition are Suitable responding to the alcohol employed in the reac for the production of hydrocarbon-Soluble cop tion. The point of attachment of the carboxyl 20 per and zinc salts which are of the utmost in group to the dicyclopentadiene ring is in the 1 or portance for the treatment of textiles, leather, 2 position as shown in the structural formula, and other material exposed to humid climatic below: conditions. The zinc salt in addition to use in fungicides, mildew preventatives and in paints 1.N COOR 1N 25 is also suitable for incorporation into lubricant CH CI compositions where they act as inhibitors. It is within the province of this invention to utilize l l"Uloor these acids for any uses where the naphthenic Ester of tetrahydrodicyclo- Ester of tetrahydrodicyclo acids have hitherto been used, since a unique pentadiene 1: Carboxylic Acid pentadiene 2: Carboxylic Acid 30 feature of the acids described in this invention In the case of pure dihydrodicyclopentadiene and is their ability to readily form oil and hydrocar methanol, the methyl ester may be readily Sepa bon-soluble derivatives of metal salts. The acids rated from excess methanol by distillation. The may further be esterified with other alcohols or methyl esters of the mixture of the 1- and 2 glycols to form plasticizers, Synthetic lubricants carboxylic acids boils at 97 to 99 C. at 2 mm. 35 and the like. They are capable of rendering preSSure and shows On analytical Saponification, basic dyes, namely, those containing an aimino a saponification equivalent equal to 288 mgm. group, which are normally water soluble in the KOHAgm. With the conditions shown above a form of their salts with inorganic acids, oil or yield of 78 mole percent of the ester was obtained hydrocarbon-soluble by reaction of the basic dye in a typical run based on the quantity of dihydro 40 With this acid. alpha-dicyclopentadiene charged to the pressure Wessel. Eacample 1-ox-Dicyclopentadiene For recovering the corresponding acids these Commercially available dicyclopentadiene esters are then hydrolyzed by Conventional meth which . On analysis was found to contain (ex ods such as the use of moderately dilute acids, pressed as monomer) 75% of cyclopentadiene Such as 20% Sulfuric acid used. With or without and 15% methyl cyclopentadiene was cracked in the addition of an agent capable of depressing the liquid phase by distillation under a fraction the interfacial tension such as mahogany Sul atting tower containing 30 plates. Using a re fonates, Twitchell agents and the like. Or, the flux ratio of 15:1 rejected any methyl cyclo esters may be Saponified in Conventional nan pentadiene formed during the Cracking process ner by means of an excess of alkali. In the case and substantially pure cyclopentadiene boiling at of the former method the acids are obtained di 40-40.5° C.
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