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Patented‘ov. 5, i946 _' 5410,425 . ST *5. ~ 2,410,425 ORGANIC POLYBASIC ACID POLYESTER/S 0F “HYDROIHYDRGNORPQLYCYCLOTENTADIENES Herman A. Bruson, Philadelphia, Pa., assignor to ' The Resinous Products & Chemical Company, Philadelphia, Pa, a corporation of Delaware No'Drawing. Application March 13, 1944, Serial No. 526,313 6 Claims. (Cl. 260-475) 2 This invention relates to polyesters of organic ' mént products of a polycarboxylic acid and di cyclopentadiene. They are esters of hydroxy polycarboxylic acids and hydroxydihydronorpoly cyclopentadienes. More speci?cally, this inven dihydronordicyclopentadiene and a polycarbox- ' tion deals with polyesters of said acids and hy ylic acid and have the general formula: droxydihydronordicyclopentadiene. 6. These new esters possess the unique property of absorbing oxygen from the air to form prod ucts which are insoluble in water and organic solvents. They are particularly useful as coating materials, serving in this respect as drying oils which have been modi?ed with resins. These esters may be- prepared in several dif ferent ways. One method is to reactat least two Coo; 0 H_\il_1 . Zion-l‘‘m C 1 wherein, ‘as before, R is the organic residue of a poiycarboxylic acid, 11. is a small integer of two or more,‘ and Cal-I4 is a propylene group which mols of dicyclopentadiene with one mol of an ‘organic poiycarboxylic acid, advantageously in 15 in conjunction with the adjoining carbon atoms the presence of an acidic condensing agent such as boron tri?uoride, as described, in copending forms a cyclopenteno group. The functional carboxyl group is attached tothe dihydronordi application ‘Serial No. 476,639, ?led February 20, 1943, of which the present application is a con- ‘ tinuation-in~part, whereby addition of each car boxyl group to the endomethylene cycle of the cyclodienyl ring system at a secondary carbon atom ?anked by a methylene group and by a 20 tertiary carbon atom in an endoethylene cyclo pentano group which carries the said propenylene .group forming a cyclopenteno ring therewith. neous molecular rearrangement of the latter to Theaddition of a polycarboxylic acid to di the nordicyclopentadienyl ring system, thus: cyclopentadiene having'two double bonds and one as endomethylene cycle per molecule voccurs readily at temperatures from about 50° C. to about 145° C‘.,‘ a \ H dicyclopentadiene is accompanied by a simulta- . on - ' although temperatures both somewhat higher and - mooon). +1» 51 lower may be used. It is sometimes desirable, but not ‘essential, to use an organic solvent, such as benzene, toluene, xylene; ethylene dichloride, or ” other organic solvent, in which case the reaction H may be effected under re?ux. _ Small amounts of acidic condensing agents promote the formation of the desired polyesters. The most e?'ective are boron tri?uoride and itsv coordination complexes, such asv those formed with boron’ trifluoride and oxygenated com-» pounds, including aldehydes, ketones, ethers, esters, alcohols, and carboxylic acids, typified by BF3.2CH3CHO, BF‘3.C2I~I5OC2H5, BF: .CHaC‘OOCzI-Is, BFs.CH3CQCH3, BFaCiI-l'sOH etc. The catalyst or CH calms CH _ may be removed from the reaction mixture by washing with water or mildly alkaline solutions, ‘such as aqueous sodium carbonate solutions. db wherein R is the organic residue of a polycar boxylic acidnand n is an integer of at least two. The ?rst formula given for the products is more probable, di?ering from the second only in ' the position of the double bond of the terminal 50 cyclopenteno group relative to the position of the functional substituent in the opposite terminal . cycle, an endoethylene cyclopentano group. The products as thus obtained may be regarded from one point of view as addition-rearrange The reaction product may be‘dried with-con ventional drying agents, or water may be removed therefrom by distillation of a solvent. The prod uct may be further purified by treatment with activated clays or charcoal and/or distillation under reduced pressure in many cases. The compounds formed are esters from one molecule of an organic polycarboxylic acid and at least two molecules of hydroxydihydronordi cyclopentadiene. Another method is to esterify one molecule of 2,410,425 with at least two molecules of hydroxydihydro , nordicyclopentadiene, a new alcohol obtained by the hydration-rearrangement reaction of dicyclo pentadiene with water in the presence of sulfuric acid, as described in copending application Serial lead, cobalt, manganese, and other polyvalent metals supplying siccative action, and of carbox No. 476,645, filed February 20, 1943, the formation ' ylic acids imparting oil-solubility to the salt, in ' of which may be represented as follows: I CH2" .4 admixed with at least one oxidation catalyst. The oxidation catalysts include peroxides, such as benzoyl peroxide, tert. butyl hydroperoxide, or lauroyl peroxide, and metallic driers, such as the oil-soluble salts of heavy metals, typi?ed by the organic polycarboxylic acid or its anhydride eluding naphthenic acids, long-chained fatty 10 acids such as .linolelo and linolenic, and ether acids, such as butoxyacetic or octyloxyacetlc acids. Mixtures of peroxides and metallic driers are par ticularly e?icacious. When coating compositions comprising the 15 polyesters of this invention and an oxidation cat alyst are applied to surfaces which are then ex posed to air or preferably baked at 130° C. to 190° (3., they are converted to hard, tough ?lms, which are substantially insoluble in all common organic 20 solvents and are highly water-resistant and non porous. When used in ?nishes on metal, excep tional adhesion is obtained, and treated metal sheets ?nished with a baked coating may be ?exed without cracking or breaking of the ?lm. Since the new esters are compatible with nitro 25 cellulose as well as with the natural drying oils, for example, linseed, tung, soyabean, oiticica, and ?sh oils, as well as with many natural and‘ syn thetic resins, they may be used for the prepara Hydroxydihydronordicyclopentadlene may thus 30 tion of a wide variety of coating and plastic com positions. be represented by the formula: The following examples illustrate the prepara tion and properties of these esters: Example 1 Fifty-nine grams of diethyl carbonate was mixed with 150 grams of hydroxydihydronorcy ,clopentadiene and one gram of sodium was added. The resulting mixture was heated in a still under wherein C3114 is a propenylene group which in such conditions that the temperature of the va conjunction with the adjoining carbon atoms 40 por did not exceed 90° C. About 33 grams of dis forms a cyclopenteno group as oneiterminal cycle. ' Still another method for the preparation of the esters of this invention is based upon trans‘esteri tillate was taken off between 80° and 85° C. The . pressure was then reduced and distillation con tinues until no more ethyl alcohol was obtained. iication or ester interchange. According to this Thereupon, the still residue was distilled under method, an ester :of a polycarboxylic acid and an 45 reduced pressure. The fraction boiling between - alcohol of lower molecular weight than hydroxy 200° and 240° C. at 3 mm. was a pale yellow vis dihydronordicyclopentadiene is heated with hy droxydihydronordicyclopentadiene in the pres cous oil, amounting to 61 grams, which upon re- . ence of a catalyst, such as sodium ethylate or sul analysis agreed with the formula for di-(dihy distillation boiled at 217°~220° C./2.5 mm. furic acid, and the alcohol of lower molecular 50 dronordicyclopentadienyl) carbonate, Its ‘ ' - weight displaced. Thus, by displacing at least two molecules of a lower molecular weight alcohol It possessed the following constants: ND25 1.5288; _ with hydroxydihydronordicyclopentadiene, there may be prepared polyesters of said acid and said compound which contain only these components 55 or which contain these components in addition to _ Particularly useful polyesters are derived from carbonic, oxalic, malonic, succinic, maleic, fu ‘ ‘a The above ester was mixed with such amounts of lead, cobalt, and manganese naphthenates as siccatives that 0.50% of lead, 0.02% of cobalt, and 0.02% of manganese by weight, respectively, were present in the mixture. A ?lm of this composi another alcoholic residue or other alcoholic resi dues. d4“ 1.0216. 60 tion was formed on a glass plate and allowed to ‘maric, chloromaleic, glutaric, e,a-diethy1 glutaric, itaconic, adipic, pimelic, suberic, azelaic, sebacic, dry in the air at room temperature. After forty phthalic, 3,6 - endomethylene-1,2,3,6-tetrahydro an oleoresinous varnish was obtained. eight hours, a hard, dry, colorless film resembling phthalic, A3-tetrahydrophthalic, tartaric, malic', Example 2 be prepared from other polycarboxylic acids, such A mixture of 36.5 grams of adipic acid, 90 grams of hydroxydihydronordicyclopentadiene, 120 citric, and tricarballylic acids. Esters may also 65 as 'v-alkyl-v-carboxypimelic acids, delta-ketonic tetracarboxylic acids (of. United States Patent _' grams of benzene, and 0.5 gram of sulfuric acid , (95%) was stirred and boiled under a're?ux con 2,329,432) , and the carbocyclic, compounds in which two to six p-carboxyethyl groups are joined 70 denser attached to a water trap for six hours un til no more water distilled over with the benzene. , to unsaturated carbocycles (cf. United States Pat The product was cooled, washed several times ent No. 2,339,218) . with cold water, then with dilute sodium carbon The new esters are advantageously used as ve ate solution, followed by a water wash. The ben- ' hicles in preparing paintsyvarnishes, and similar coating materials. For this purpose, they may be 75 zone was evaporated ed and the excess hydroxy 2,410,425 dihydronordicyclopentadiene vacuo. , distilled oil in dronordicyclopentadiene, and 1.5 grams of con centrated sulfuric acid was boiled under a re?ux condenser attached to a water trap for three 1 The residual oil consisted essentially of di (dihydronordicyclopentadienyl) adipate, hours, during which time 8.5 grams of water was collected in the trap. The reaction product was C10H13—OCO—CH2CH2CH2CH2COO—C10H13 Upon distillation in high vacuo, it boiled between cooled to room temperature ‘and stirred for sev eral hours with ?ve grams of powdered calcium ‘250° and 270°C. at 3 mm. and formed a pale hydroxide. Thev mixture was ?ltered and the yellow oil which crystallized on standing. After recrystallization from ethanol, it formed color less crystals melting at.75°-77." C. clear ?ltrate distilled at 3 mm. until the benzenev and excess hydroxydihydronordicyclopentadiene had been stripped oil‘. A solution of the above ester in ‘benzene was ' - The residual product, consisting of di-(dihy mixed with lead, cobalt, and manganese naphe dronordicyclopentadienyl) maleate,‘was a thick thenates to give a composition containing 0.25% oil. When heated in the air at 190°-200° C., it of lead, 0.02% of cobalt, and 0.02% of man 15 rapidly polymerizes to a hard re'sin.- Films of ganese on the weight of the ester. A ?lm of this the oil dry by oxidation in the air. solution was baked on a steel panel for one hour A solution of equal parts of the above ester at 150° C. to yield a hard, varnish-like coating. and linseed oil was mixed with 0.50% of lead, 0.02% of cobalt,‘ and 0.02% of manganese in the Ewample 3 form of the corresponding naphthenate driers, 20 A mixture of 180 grams of hydroxydihydronor and ?lms of this solution baked on steel plate dicyclopentadiene, 59 grams ofsuccinic acid, 200 at 150° C. forone to two hours. Hard, adherent, grams of benzene, and one gram of sulfuric acid tough, mar-proof coatings were obtained. ' (95%) was boiled under a re?ux condenser at Example 6 tached to a water trap for six and one-half hours, at which time 18 grams of water had been 25 A mixture of 178 grams of sebacic acid, 531 collected. The product was then cooled and .grams of hydroxydihydronordicyclopentadiene, mixed with ten. grams of calcium hydroxide. 110 grams of ethylene dichloride, and 1.5 grams This mixture was stirred for several hours and of concentrated sulfuric acid was boiled for two ?ltered. The ?ltrate was evaporated to dryness. hoursunder a re?ux condenser attached to a The product, consisting essentially of di-(dihy water trap until 33 cc. of water had been col dronordicyclopentadienyl) succinate crystallized lected. The product was cooled, stirred for two on standing. After recrystallization from meth hours with ?ve grams of powdered lime, ?ltered, anol, it formed colorless crystals melting at ' and the clear ?ltrate evaporated to dryness. The 100° C. . .\ 35 ' residual oil was heated in vacuo to strip off the Example 4;‘ excess of the alcohol used. The ?nal product (a) A mixture of 66 grams oi dicyclopenta diene, 22.5 grams of anhydrous oxalic acid, and was a thick oil consisting essentially of di-(dihy- dronordicyclopentadieneyl) -sebacate. A solution was prepared by ,mixing this ester 75 grams of tetrachlorethane was stirred and boiled under re?ux at 135°~140° C. for ?ve hours. 40 with driers to give a composition containing 0.5% The product was cooled, washed with water, with dilute soda solution until free from acidity, and again with water. The liquid was dried and then evaporated under reduced pressure to re of lead, 0.03% of cobalt, and 0.03% of manga nese in the form of their naphthenates. A ?lm of this solution was formed on a steel plate and baked for two hours at 135°-150° C. A hard, move the tetrachlorethane. The residual dark, 45 tough, adherent, mar-proof ?lm of excellent quality was thus obtained. viscous product consisted essentially of crude di-(dihydronordicyclopentadienyl) oxalate. The In the same manner as described in Example - 6. the phthalic acid ester of dihydronordicyclo _ yield was '75 grams. (b) A mixture of 126 grams of oxalic acid pentadienyl phthalate is obtained as a thick oil dihydrate, 380 grams of hydroxydihydronordi 50 by using 150 grams of phthalic anhydride in place of the sebacic acid. When mixed with driers as cyclopentadiene, 200 grams of benzene, and one described above, it gives a hard ?lm when baked gram of 98% sulfuric acid was stirred and boiled for two hours at 150° C. under a re?ux condenser attached to a water The corresponding tartaric acid, tricarballylic trap. At the end of three and one-half hours of boiling, '74 cc. of water had been separated in 55 acid, citric acid, 3,6-endomethylene-1,2,3,6-tet the trap, indicating that the esteri?cation was rahyd'rophthalic acid polyesters of hydroxydihy complete. The product was cooled to room tem perature and stirred for a half hour with ten grams of powdered calcium hydroxide and ?ve pared. They are thick, autoxidizable, polymer grams of water to destroy free acidity. The 60 precipitate which was formed was ?ltered off and the filtrate heated in vacuo up to a vapor _ temperature of 200° C./2 mm. to distill there from the excess of alcohol. The residue, con sisting of a black thick syrup, was mixed with an 65 dronordicyclopentadiene can be similarly pre izable oils useful for the preparation of coatings. The po1y-dihydronorpolycyclopentadienyl es~ ters of a polycarboxylic acid may be represented by the general formula: a melting point of 83°-85° C. ' .4.» l CHzl if C i R 000- n_'_- A mixture of 49 grams of maleic anhydride, 70 grams of benzene, 302 grams of hydroxydihy 75 3 ' ls. _l -C: ' v Example 5 ‘ OH equal volume of petroleum ether and chilled, whereupon the crude oxalate crystallized out and was ‘?ltered, off. After recrystallization from petroleum ether, the di-dihydronordicyclopenta dienyl oxalate formed colorless crystals having _ wherein R. and n have the same signi?cance as above and m is a number from zero to three, in clusive. ' . 2,410,425 7 dicyclopentadiene or the alcohol derived there from by addition of water and rearrangement to the norcyclopentadienyl system is used, there being further'characterized by having the car boxylic ester groups attached to a terminal cycle from the rearranged dicyclopentadiene at a sec ' may be used with similar results higher polycy ' clopentadienes or mixtures of dicyclopentadiene ondary carbon atom thereof, the opposite termi nal cycle thereofv being a flve-membered ring and higher crystalline polycyclopentadienes hav containing one ole?nic linkage. 3. As a new compound, a di-(dihydronordicy clopentadienyl) ester of a dicarboxylic organic acid, said ester being the acid-catalyzed addition rearrangement product of a dicarboxylic acid and ing two double bonds per molecule. There may be prepared mixtures of crystalline di-, tri-, tet~ ra-, and penta-cyclopentadiene having two dou ble bonds and one to four endomethylene cycles per molecule. These undergo the same esterify ing reactions as pure dicyclopentadiene. Further details of the behavior of these polycyclopenta dienes are given in the patent application. The polyesters of the various hydroxydihydronorpoly cyclopentadienes of the type aforesaid all have the drying properties above described and are useful in coating compositions. F'rom'the foregoing, it can beseen that the dihydronordicyclopentadienyl polyesters of or ganic polycarboxylic acids are unique and valu able materials. They are particularly useful as dicyclopentadiene, said ester being further char acterized by having each carboxylic ester group attached to a terminal cycle from the rearranged dicyclopentadiene at a secondary carbon atom thereof, the opposite terminal cycle thereof be ing a five-membered ring containing one ole?nic linkage. 4. As a new compound, the di-(dihydronordi cyclopentadienyl) ester of maleic acid, said ester being the acid-catalyzed addition-rearrangement product of maleic acid and dicyclopentadiene. said ester being characterized by having each carboxylic ester group attached to a terminal cy varnishes or lacquers, either alone or with sic catives. They may be mixed in compositions with drying or semi-drying oils, alkyd resins, and other ?lmeforming materials. They may be blown and bodied to a viscous state. They may be mixed with other autoxidizable derivatives from pol'ycyclopentadiene, including the esters of hydroxydihydronordicyclopentadiene and unsat urated higher aliphatic acids which are claimed in copending application Serial No. 526,312, ?led on even date. I claim: 1 . 1. As a new compound, a polydihydronor cle from the rearranged dicyclopentadiene at a secondary carbon atom thereof, the opposite ter minal cycle thereof being a five-membered ring , containing one ole?nic linkage. 30 35 carboxylic ester group attached .to a, terminal cycle from the rearranged dicyclopentadiene at a - ' lyzed addition-rearrangement product of a poly basic carboxylic acid and a crystalline polycyclo pentadiene having two double bonds and one to four endomethylene cycles per molecule, said es“ ter being further characterized by having each carboxylic ester group attached to a terminal cy cle from the rearranged polycyclopentadiene at a secondary carbon atom thereof, the opposite terminal cycle thereof being a ?ve-membered ‘ 5. As a new compound, the di-(dihydronordi - cyclopentadienyl) ester of sebacic acid,.said ester being the acid-catalyzed addition-rearrangement product of sebacic acid and dicyclopentadiene, said ester being characterized by having each polycyclopentadienyl ester of a polybasic organic carboxylic acid, said ester being the acid-cata ring containing one ole?nic linkage. 8 addition-rearrangement product of a polybasic, carboxylic acid and dicyclopentadiene, said ester While in the above examples essentially pure . 2. Asa new compound, a polydihydronordicyg clopentadienyl ester of a polybasic organiccar boxylic acid, said ester being the acid-catalyzed 50. secondary carbon atom thereof, the opposite ter minal cycle thereof being a ?ve-membered ring containing one ole?nic linkage. 6. As a new compound, the di-(dihydronordi cyciopentadienyl) ester of phthalic acid, said es ter being the acid-catalyzed addition-rearrange _ment product of phthalic acid and dicyclopenta diene, said ester being characterized by having , each carboxylic ester group attached to a termi nal cycle from the rearranged dicyclopentadiene at a secondary carbon atom thereof, the oppo site terminal cycle thereoi’ being a ?ve-membered ring containing one ole?nlc linkage. A. ‘BRUISON.