Патент USA US2130740код для вставки
' Patented Sept. 20, 1938 2,130,140 i -. UNITED? STATES PATENT OFFICE 2,130,740 mm ‘AL HYDBOGENATEDrnonuomo ss'rsas 0FAND METHOD OF oonor. Del., assignor ' ‘ Humphrey, Wilmington, Irvin W. to Hercules Powder Company, Wilmington, DeL, a oorporation‘o! Delaware No Drawing. Application August so, 1933, ' Serial No. some; . . 46 Claims- (CL 280-400)‘ Thus. for example, a rosin ester, as ethyl abie- ‘ Thislinventi'on relates to esters of hydrogenat ed abietyl alcohol and method of producing. - The esters contemplated by this invention will be produced from fully or partially hydrogenated tate, in solution in ethyl alcohol is heated with metallic sodium and the abietyl alcohol formed is recovered. The abietyl alcohol is then treat ed with hydrogen at elevated temperature and, 5 abietyl ‘alcohol, as, for example, dihydro and ' pressure in the presence of a base metal hy'dro- ‘ 5 tetrahydro abietyl alcohol or their mixtures, by genation catalyst as nickel, cobalt, copper chro- f reaction with an organic acid or, an equivalent mite, etc., or at lower temperatures in the pres- “ therefor according to the method contemplated ‘ ence of a noble metal catalyst as platinum, pal ladium, etc. ' For example,the abietyl alcohol 10 by this invention. = More speci?cally in producing esters in ac-‘ may be hydrogenated by treatment with hydro cordance with this invention abietyl alcohol may gen ata temperature of 125-225’ .C., and under be first hydrogenated to the desired degree and ' a hydrogen pressure of about 5-400, atmospheres, then esteri?ed with an organioacid or equiv in the‘ presence of a nickelhydrogenation cata . alent by heating with or without the use of‘ an esteri?'cation- catalyst. >Or' the abietyl alcohol 15 may first be esteri?ed with the organic acid, and the abietyl ester so formed hydrogenated to tion of a mixture oi dihydro- and tet'rahydro abietyl alcohol by addition of hydrogen to the abietyl alcohol. The the desired degree. The hydrogenated abietyl proportion alcohol may also be prepared directly by the hydrogenation and reduction 0! the abietyl 20' -group to the-alcohol group of abietic acid or its r , lyst. Such procedure will result in the produc esters. is } increased with'increase oi the pressure used 50. above about 100 atmospheres. - ' . Alternatively, for example, the‘ hydrogenated‘ abietyl alcohol may be produced by reducing . In proceeding to the practical-adaptation oi , the. ester group of, for example, hydrogenated ' this invention theabietyl alcohol may. be pro- ' ethyl butyl or methyl abietate to the alcohol 35 ' as for example group with ‘hydrogen, ata temperature of about . ducedby any suitable method, 225-325° C., under-pressure of 80-1000 atmos ple, ethyl or methyl abietate, in amonohydric pheres and in the presence of, a conversion cata \ nickel chromite. aliphatic alcohol, for example, ethyl or butyl ‘lyst such as copper-chromite, alcohol, heating the solution with metallic so‘ etc. If desired hydrogenated rosin, dihydro dium, diluting the solution with water, distilling . abietic acid, tetrahydroabietic acid, or- their mix of the low boiling alcohol, and ?nally extracting -; tureamay be converted into dihydro- or tetra the abietyl alcohol iormed by means of a water hydro-abietyl alcohol or mixtures ‘thereof simi immiscible solvent, as benzene." Hydrogenationn larly. The rosin ester, rosin, or abietic ‘acid may‘ be ?rst hydrogenated by contacting with a= of the abietyl-alcohol so produced ‘may be ‘ac complished .byany oi the well known methods ' base metalI hydrogenation catalyst as nickel, cop- ‘ ‘for the’ hydrogenation of unsaturated com per-chromite, cobalt, etc., at a temperature of about 150-225“ C. and under about 10-500 at- ” Hydrogenated abietyl alcohol may also be ob- .mospheres hydrogen pressure, yielding ' either tained by reducing the carboxyl group of hydro dlhYdI'O-r and tetrahydro-abietate esters or di genated abietic acid to a primary‘ alcohol group hydro- and~tetrahydro-abietic acid. ' . > _ ‘ by dissolving an ester of abietic acid, for exam-. pounds. , , , _ , e . 4.0. ‘by treatment oi hydrogenated abietic‘ acid, or’ ~ The esters contempla ‘ by this invention may rosin, or anester of hydrogenated abietic acid vhe formed by‘ reacting partially or fully hydroe genated abietyl alcohol with an ‘organic acid, with hydrogen ‘under pressure of say about 70 ‘ ‘at anjelevated temperature of ' 1000 atmospheres say about 225-350’ C., in the presence or ‘a’ cata ' lyst, such as, , for.‘ ‘ example, copper; chromite, to. . all as is more fully dis nickel chromite, e, _ or equivalently with an organic anhydride, or certain organic acid compounds, as organic, acid chlorides, acid esters, etc. The organic acid or equivalent. may ,be- aromatic, hydroaromatic,' closed in my application vfor United ‘States Let- " he'terooyclic, or aliphatic. and may :be monobasio - ' ters Patent, Serial Number 004,859. ?led April. this application is a continuaé 12, 1932, of which tion in part; The hydrogenated abietyl alcohol‘ ' oi dihydroe or tetrahy so'produced will consist droabietyl alcohol-or a mixture thereof depend ing upon the exact conditions ‘of temperature andpressure employed. or polybasic. As illustrative, the organic acid 501 or equivalent may, for example, be acetic, butyric, propionic, valeric, iuroic, benzoic, cinnamic, oleic, palmitic, stearic, lauri , linoleic; linolenic, abietic, dihydro abietic, tetra- ‘ - salicylic, lactic, hydro 1abietic, pimaric, \ricinoleic, 'dihydroxy 5s 2 , 2,130,740 stearic', glycollic, formic, naphthenic. anisic, at any operable temperature and pressure. Any .capric, tetrahydro-furoic acid, caprylic, cerotic, pyruvic, naphthoic,'sorbic, hydrosorbic, carnau temperature, including room temperature, which ‘ bio, mellissic, margaric, toluic, erucic, levulinic, myristic?monylic, sativic, undecylenic, alpha or beta-elaeostearic, 10 etc.,~ or 'mixtures I " thereof; - adipic, citric, citraconic, maleic, malic,» tartaric, sebacic, succinic, terep thalic, phthalic, itaconic, sirably at temperatures say within about the malonic, oxalic, glutaric, suberic, camphoronic, ' range 150°-300° C., and generally fairly rapidly methyl succinic, terephthalic, azelaic, ~aconitic, tricarballylic, diphenic, fumaric, naphthalic, acids present in copal and kauri, and pyromel erally be completed, when using the temperatures indicated, within about 2-15 hours depending upon the temperature, catalyst, reactivity of the acidic groups in acid esters as mono-methyl suc acid, and proportion of reagents. cinate, alpha-terpinene monobutyl maleate, the The reagents may be heated in any desired pro monoethyl maleate of methyl abietate, the'di methyl maleate of abietic acid, the monomethyl 20 ester of alpha-pinene-maleic anhydride, mono ethyl phthalate, etc., may be esteri?ed with hy " drogenated abietyl alcohol. at 175-225” C., under atmospheric pressure, while, desirably, permitting the water produced in the reaction to escape. The reaction will gen litic, etc., or mixtures thereof. Substituted. or ganic acids as monochlor acetic, dichlor acetic, 15 nitrobenzoic, etc., may be used.. likewise the 25 will not decompose the reagents or the product, under the pressure conditions prevailing and at which the reaction will proceed, in other words, various reaction temperatures may be used. Generally speaking, the reaction will proceed de portion, but usually itwill be found e?icient to react the hydrogenated abietyl alcohol and an organic acid or equivalent in about the desired 20 chemically equivalent reacting proportions form As indicated, or ing neutral or acid esters from polybasic acids. ganic anhydrides, as acetic, phthalic, maleic, suc cinic, etc. anhydrides, or addition products of maleic anhydride to unsaturated compounds, as As speci?cally illustrative of the _ practical adaptation of the method in accordance with this invention for the production of the product con 25 templated, for example, 9 parts by weight of hy terpinene-maleic anhydride, dipentene-maleic anhydride, abietic-acid-maleic anhydride, abie drogenated abietyl alcohol, say comprising a mix tyl-alcohol maleic anhydride, 'butadiene-maleic ture of dihydro and tetrahydro abietyl alcohol, 30 anhydride, pinene-m leic anhydride etc. may be Since hydrogenated abietyl alcohol is high used. - ' is heated at about 200° C., for about 8 hours with - 1.8 parts of succinic acid, using an air condenser 30 hydrogenated abietyl alcohol will be converted to permit the removal of water of reaction. The boiling, the esters may generally be produced without the useof acatalyst, especially when the organic acid is also comparably non-volatile, ’ as is the case, for example, with abietic, hydro genated abietic, succinic, stearic, palmitic, etc., acids. However, it is frequently desirable to em ploy‘ a catalyst- and when such is used, for ex ~ample, 1-8% byI weight of dry hydrogen chloride 40 or concentrated hydrochloric acid, less than 1% of concentrated sulphuric acid, anhydrous zinc chloride, small amounts of phosphoric acid, or a small percentage of paratoluene sulphonic acid, benzene sulphonic acid, acid sodium sulphate, 45 boric anhydride, etc., or mixtures thereof will be found satisfactory. into an ester of low acidity. v As a further illustration, v21 parts of hydro genated abietyl alcohol is allowed to react with 35 80 parts of acetic anhydride, containing 4 parts of sulphuric acid as a catalyst, at room tempera ture, for three days. The resultant ester will show only a few‘ percent of unreacted alcohol. As a further illustration‘, 10 parts of hydro 40 genated abietyl alcohol are-heated with» 10 parts _ of hydrogenated rosin for 5 hours at 250°-260° C., and then for 5 more hours at 260°-280° C. The resultant ester is a hydrogenated abietyl hy droabietate. . The esters in accordance with this invention If desired in carrying out the method conteme‘ plated a relatively low boiling water irmniscible are usually amorphous compounds. Sometimes solvent for the ester product, as benzene, toluene, they are'very viscous liquids but are more gen 50 carbon tetrachloride, etc., may be used to assist erally solids with melting points varying from about 50 to 100". C. (dro-pmethod). When con in the removalof the water of reaction. ditions are such as to effect a high degree of 50 In the practical adaptation of the method em v bodying this invention for production of the es _ ters contemplated, generally speaking the hydro genated abietyl alcohol, as dihydro or tetrahydro abietyl alcohol,’ or a mixture thereof, will be reacted by heating with an organic acid, ‘or equivalently an organic anhydride, or acid com pound of an organic acid, as an acid ester, with 60 or without-use of a catalyst and/or a low boil ing water immiscible solvent to facilitate the removal of water of reaction. On completion of esteri?cation the acid number varies from 5 to 25. . They are in general more readily saponi?ed thanv esters of abietic acid. Esters of hydrogenated abietyl alcohol are more resistant to discolora 55 tion on aging than esters of non-hydrogenated abietyl alcohol. They have thiocyanate values Oif from 0 to about 40 depending upon the de gree of hydrogenation of the unsaturated bonds of the abietyl alcohol, and exhibit much lower. iodin . values than those of the corresponding non-hydrogenated abietyl esters. Their proper ties also depend upon the purity of the hydro vent, as benzene, toluene; etc., and the solution washed with aqueous alkali, to remove excess acid with ?nal evaporation of the solvent. If a ‘volatile organic acid, ‘such ‘as, for exam ple, acetic acid, etc., be used the esteri?cation .may be ‘carried out bypassing an excess of the vvolatile acid into the heated hydrogenated abietyl alcohol. The excess acid may be removed along with the water‘ of reaction by distillation. 75 In proceeding, the reaction may be carriedv out genated abietyl alcohol used. ' The prbducts in accordance with this invention 65'. will be found variously adaptable for use in the commercial arts as, for example, ingredients in coating compositions, as lacquer, varnishes, etc., or‘ in plastic compositions. The products in ac cordance with this invention may be advanta-' 70 geously used in such compositions to replace in whole or in part other resins heretofore used for such purposes. ‘This application is~?1ed as a continuation in 75 . . 3 1 2,180,740 a resin acid in the presence or heat at a reaction part of an application for United States patent for method of producing abietyl alcohol and product, ?led by me April 12, 1932, Serial Num ber 604,859. ' temperature. ' ~ which in- ‘ 25. The method of forming an ester _ cludes reacting hydrogenated abietyl alcohol with a fatty acid in the presence of heat at a reaction ' What I claim and desire to protect by Letters Patent 1. Anis:organic carboxylic acid ester of hydro genated abietyl alcohol. I ' cludes reacting hydrogenated abietyl alcohol ‘ with phthalic acid in the presence of heat at a - reaction temperature. 10' 27. The method of forming an ester'which in genated abietyl alcohol. 3. A dibasic carboxylic acid ester of hydrogen ated abietyl alcohol. ' . 4. An aromatic carboxylic acid ester of hydro cludes reacting hydrogenated abietyl alcohol with‘ hydrogenated abietic acid in the presence of heat at a reaction temperature. “ ‘ ‘ 28. A carboxylic acid ester of hydro-abietyl 15 genated abietyl alcohol. ' 5. An aliphatic carboxylic acid ester of hydro 15 ' 26. The method of forming an ester which in ’ 2. A monobasic carboxylic acid ester of hydro 10 temperature. alcohol. . I 29. A compound _ oi the genated abietyl alcohol. H general formula hydrogenated‘ abietyl Ab-eCI-I O-—R, where Ab stands for the. 6. A resin acid esterof hydrocarbon nucleus of ,hydroabietic acid, whilev alcohol. ' 7. A fatty acid ester of hydrogenated abietyl _ R stands for an organic radical of the alkyl, ‘alcohol. ' aralkyl, cycloalkyl or aryl series. ’ 30. The ester of hydroabietyl alcohol and an ' “a. The method of forming an ester which in cludes reacting hydrogenated abietyl alcohol with an organic carboxylic acid. acetic acid. 4 31. Hydroabietyl acetate. ‘ 25 32.. Hydroabletyl-hydroabietate. 9. The method of forming an ester which in 33. An ester of a polycarboxylic acid wherein the hydrogen of at least one carboxyl group is cludes reacting hydrogenated abietyl alcohol with 25 an acid organic carboxylic acid compound. 10. The method of forming .an ester which in 'replaced by the radical'of a hydroabietyl alcohol: a 34. A hydroabietyl phthalate. 35. The method which includes reacting in the 30 an organic carboxylic acid in the presence of cludes reacting hydrogenated abietyl alcohol with presence of heat a hydroxyl group of a hydro- . heat at a reaction temperature. _ o 11. The method of forming an ester which in genated abietyl alcohol with a carboxyl group derived from a carboxylic acid. 36..The method of producing an ester which cludes reacting hydrogenated abietyl alcohol with an organic carboxylic acid at a temperature of includes reacting in the presence of heat a hy 35 12. The method of forming an ester which in- _ droxyl group of a hydrogenated abietyl alcohol cludes reacting hydrogenated abietyl alcohol with a carboxyl group of a polycarboxylic acid. 37. The method of producing an ester which with an organic carboxylic acid-in the presence ' includes reacting in the presence of heat and in 40 of an esterification catalyst. the presence of a volatile water-immiscible sol 13. The method of forming an. ester which in cludes reacting abietyl alcohol vent for the ester product a hydroxyl group of with an organic carboxylic acid in the presence or hydrogenated abietyl alcohol with a carboxyl heat at a reaction temperature and in the pres group of a polycarboxylic acid. . about 150 to about 300° C. ence of an esteri?cation- catalyst. '38. Hydroabietyl phthalate. _ _ 39. The method of forming an ester which in 45 14. The method of forming an ester which in cludes reacting hydrogenated abietyl alcohol with cludes reacting hydrogenated abietyl alcohol with an organic carboxylic acid at a tempera 150 to about 300° C. and in the ' ture of about presence of an esteri?cation catalyst. 15. A polybasic carboxylic acid ester of hydro genated abietyl alcohol. " 16. A hydroxy carboxylic acid ester of hydro gena'ted abietyl alcohol. > - ' 1 19. A saturated‘carboxylicacid ester of hydro genated abietyl alcohol. 20. A su reacting hydroabietyl alcohol with a carboxylic acid compound under anhydrous conditions. .41. The method of forming an ester which in a carboxylic acid in the presence oi a dehydrating ' - ‘ cludes reacting a hydroxyl group of hydrogenated ylic acid. .4 _ ‘ _ I 43. The method of forming an ester which in 60' cludes reacting hydrogenated abietyl alcoholwith hydrogenated abietyl alcohol. . 21. A phthalic acid ‘ester of hydrogenated an organic polycarboxylic acid. '44.‘ An unsaturated. polycarboxylic acid .ester ' 22. A hydrogenated abietic acid ester of hydro‘ -_. of hydrogenated abietyl alcohol. genated abietyl alcohol. 65 o _ , 45. The method of forming an ester which in_- =65 23. The method oi‘forming an ester which in cludes reacting hydrogenated abietyl alcohol with cludes reacting hydrogenated abietyl alcohol an organic polycarboxylic acid. .' ' 46‘. A hydroxy ipolycarboxylic acid’ ester or with an organic carboxylic acid at a temperature of about 175° C. to about 225° C.‘ . - 24. The method‘ of forming an ester which in cludes reacting hydrogenated abietyl 10 a 42. The method of forming an ester which in . abietyl alcohol with a carboxyl group of va carbox- - 'stituted. carbonylic acid ester . ofv abietyl alcohol.‘ ester of hydroabietyl alcohol, which comprises agent. 18. An unsaturated carboxylic acid ester of hydrogenated abietyl alcohol. _ 40. The process of preparing a carboxylic acid cludes reacting hydrogenated abietyl alcohol with 1'7. A cyclic carboxylic acid ester of hydro?‘ genated abietyl alcohol. a carboxylic acid anhydride. alcohol with hydrogenated abietyl alcohol. ‘ _, IRVIN '