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Patented Sept. 18, 1951 2568,426 UNITED STATES PATENT OFFICE 2,568,426 CONDENSATION PRODUCTS FROM POL ETHYLENC-UNSATURATED ALDEBY DE ADDUCTs, DERVATIVES THEREOF, AND METHODS FOR PRODUCING THE SAME Richard R. Whetstone, Orinda, William J. Raab, Berkeley, and Seaver A. Ballard, Orinda, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application June 6, 1949, Serial No. 9,484 23 Claims. (C. 260-23) This invention relates to new compositions of present in the said adducts condense together matter and to methods for their preparation. to form an ester linkage. These novel condensas More particularly, the invention relates to novel tion products have been found to possess many condensation products prepared from adducts of unexpected beneficial properties which enable the unsaturated aldehydes and polyethylenic con said products to be utilized for many important pounds, to valuable derivatives prepared there industrial applications described hereinafter. from, and to methods for producing the same. The adducts utilized in the preparation of the Specifically, the invention provides new and novel condensation products comprise the re particularly useful condensation products which action products of alphabeta-ethylenically un are prepared by treating adducts of alpha,beta O saturated aldehydes and derivatives of polyethyl ethylenically unsaturated aldehydes and deriva enic acids. As used throughout the specification tives of polyethylenic acids with an ester-type and claims the expression "alphabeta-ethyleni condensation catalyst, such as aluminum isopro cally unsatured aldehydes' is meant to include poxide. The invention further provides valuable all those aldehydes having a formyl group at derivatives which may be prepared from the 5 tached to an aliphatic carbon atom which in above-described condensation products. turn is joined through an ethylenic double bond It is an object of the invention to provide new to another aliphatic carbon atom. The remain and useful condensation products from adducts ing bonds of the aliphatic carbon atoms in the of unsaturated aldehydes and polyethylenic con ethylenic linkage may be attached to saturated pounds. It is a further object to provide 20 or unsaturated aliphatic, allicyclic or aromatic novel condensation products from adducts of radicals, which in turn may be further subst alphabeta-ethylenically unsaturated aldehydes tuted with non-interfering substituents, such as and derivatives of polyethylenic acids. It is a halogen atoms, ether radicals and the like. Ex further object to provide novel condensation amples of these aldehydes are acrolein, methac products from the above-described adducts which 25 rolein, crotonaldehyde, cinnamaldehyde, 2-pen possess many unexpected properties enabling the tenal, 2,4-pentadiena, 2,5,7-Octatriena, 2-pen said products to be used for many important in ten-1,5-dial, 4-phenyl-2-hexenal, 4-cyclohexyl-2- dustrial applications. It is a further object to heptenal, 3-chlorophenyl-2,5-octadenal, 3-cy provide novel condensation products from the clo-pentenyl-2-hexena, -cyclohexene-1-carbox above-described adducts which possess Superior aldehyde, l-cyclopentene-1-carboxaldehyde, 3,4- air-drying properties. It is a further object to 30 dihydro-1,2-pyran-6-carboxaldehyde, 5,6 - dihy provide novel condensation products which are dro-1,2-pyran-3-carboxaldehyde, 2,6 - dimethyl useful as plasticizers for natural and Synthetic 5,6-dihydro-1,2-pyran - 3 - carboxaldehyde, and resins. It is a further object to provide valuable furfural. derivatives prepared from the above-described Particularly preferred aldehydes are the novel condensation products. It is a further ob 35 alpha,beta - ethylenically unsaturated aliphatic ject to provide a process for the preparation of aldehydes, preferably containing from 3 to 12 the above-described novel condensation products carbon atoms, such as acrolein, methacrolein, 2 and derivatives thereof. Other objects and ad pentenal, 2-hexenal, 2-methyl-2-pentenal, 3 vantages of the invention will be apparent from 40 butyl-2- butenal, 2-butenyl-2-pentena, 3,5-di the following detailed description thereof. ethyl-2-octenal, 2-dodecenal, and 4-propenyl-2,5- It has now been discovered that new and par heptadienal. ticularly useful condensation products may be The polyethylenic compounds utilized in the obtained by treating adducts of alphabeta production of the adducts of the above-described ethylenically unsaturated aldehydes, Such as 45 unsaturated aldehydes comprise the derivatives acrollein, and derivatives of polyethylenic acids, of polyethylenic acids. As used throughout the preferably acids having at least two ethylenic specification and claims the expression "poly linkages in conjugated relationship, with an ethylenic acid' is meant to include those organic ester-type condensation catalyst, such as alum acids possessing at least two ethylenic linkages, inum isopropoxide, wherein the aldehyde groups SO i. e. a double bond between two aliphatic carbon 2,568,426 3 4. atoms, in their molecule. The ethylenic link at least 12 carbon atoms and aliphatic alcohols ages may be contained in an open-chain or cyclic containing from 1 to 10 carbon atoms, and dry structure, and the free bonds of the aliphatic ing oils the acid residue of which contains at carbon atoms present in the said linkages may least 30% of the open-chain polyethylenic acids be attached to aliphatic, allicyclic or aromatic containing at least 12 carbon atoms, the acids radicals which may be further substituted if de described in each of the foregoing members sired with non-interfering substituents, such as having at least two of the ethylenic linkages in halogen atoms, ether radicals, ester radicals, and conjugated relationship. Examples of this par the like. As described above the preferred ticularly preferred group of derivatives are tung polyethylenic acids are those having at least O oil, Oiticica oll, po-yOak oil, methyl elaeostearate, tWO of their ethylenic linkages in conjugated butyl icanate, methallyl 9,11-octadecadienoate, relationship, i. e. possessing the structure glycol 7,9-octadecadienoate, octyl abietate, glycerol dielaeoStearate, glycerol 6,8,11-penta decatrilenoate, and alyl 7,9-octadecadienoate. Somewhere in the acid molecule. Examples of s The adducts of the unsaturated aldehydes and these acids are 5,7-decadienoic acid, 6,8,11 the derivatives of the polyethylenic acids may be pentadecatrienoic acid, 7,9-dodecadienoic acid, prepared by any suitable method. They are pref 9,11-octadecadienoic acid, 5.79-octadecatrienoic erably prepared by merely heating acid deriva acid, 5,7-Octadecadienoic acid, 5,7-hexadecadi tives and the aldehydes together in a suitable cons enoic acid, 5,7,13,15-eicOSatetrenoic acid, 1,3- 20 tainer. No catalyst need be employed to effect cyclopentadienyl-4-pentanoic acid, 1,3-cyclo this reaction, but if desired, Substances such as hexadienyl-5-octanoic acid, 4,7-dichloro-9,11 toluene Sulfonic acid, benzoic acid, hydrochloric Octadecadienoic acid, 3-acetoxy-6,8-pentadeca acid, Zinc chloride, stannic chloride, and the like dienoic acid, rosin acids as abietic acid, 1 in amounts varying from .1% to 5% by weight, pimaric acid, and the like. 25 may be utilized. The proportions of acid derivas Derivatives of the polyethylenic acids used in tives and aldehydes employed in the reaction may producing the adducts of the unsaturated al Vary Over a considerable range. The aidehydes dehydes are those obtained by replacing the hy are usually employed in excess as Such con drogen atom or hydroxyl group in the carboxyl pounds are normally quite volatile and more group or carboxyl groups of the acids with suit 30 easily removed from the reaction mixture. Satis able Substituents, SO as to form, for example, factory results are obtained, however, when the salts, amides, esters, and the like, of the 'said reactants are employed in equal molar quantities acids. Examples of Such derivatives are sodium Or when an excess of the polyolefin is employed, 5,7-decadienoate, potassium 6,8-11-pentadeca Preferably, the acid derivative and the aldehyde trienoate, sodium abietate, sodium pimarate, 35 are reacted in a molar ratio varying from 1.5:1 to abietamide, ethyl alpha-elaeostearate, butyl 1:3, respectively. beta-thioelaeOStearate, butyl beta-elaeostearate, The temperature employed in the reaction may amyl icanate, methallyl 9,11-octadecadienoate, also vary Over a considerable range. In most ethyl thio-abietate, cyclohexyl 5,7,9,12-octadeca cases, the temperature Will vary from about 50 tetrenoate, phenyl 7,9-octadecadienoate, glycol C. to about 300° C., with a preferred range vary bis(7,9-octadecadienoate), glycerol bis(elaeoste ing from 70° C. to 200° C. Higher or lower tem arate), and glycerol 6,8,11-pentadecatrienoate. peratures may be employed, however, if desired or Preferred. derivatives to be reacted with the necessary. Atmospheric, Superatmospheric, or unsaturated aldehydes are the esters of poly Subatmospheric pressures may be utilized. ethylenic acids having at least two of their The reaction may be accomplished in the pres ethylenic linkages in conjugated relationship 45 ence or absence of diluents or solvents. If so and Organic compounds containing esterifiable Wents are employed, it is preferred to utilize inert hydroxyl groups, such as methyl alcohol, ethyl Organic compounds, such as benzene, toluene, alcohol, butyl alcohol, isoamyl alcohol, hexyl al Xylene, cyclohexanone, and mixtures thereof.