3,223,680 United States Patent 0 ” 1C6 Patented Dec. 14, 1965

1 2 These and further objects of the invention will become 3,223,680 apparent or be described as the speci?cation proceeds. POLYESTERS 0F OLEFINIC ALCOHOLS AND The esters used as intermediates in preparing the resins COMPLEX ACIDS AND THEIR POLYMER of this invention are prepared with facility by known IZEI) PRODUCTS esteri?cation methods and conditions. It is only neces Walter E. Kramer, Niles, Ill., assignor, by mesne assign sary to place the complex acids and the selected ole?nic ments, to Union Oil Company of California, Los Arl alcohol in a reaction vessel and heat same at least to the geles, Calif., a corporation of California No Drawing. Filed Dec. 30, 1960, Ser. No. 79,505 melting point of the reactants, and/or to a temperature 2 Claims. (Cl. 260-75) suf?cient to drive off the water of esteri?cation from the 10 reaction mass. Any solvent which is inert with either re This invention relates to novel thermosetting resins actants or the products may be used as the solvent to re prepared from polycarboxylic acids derived from solvent move water as the reaction proceeds. The use of a cat extracts obtained in the solvent extraction of mineral lub alyst is optional. ricating oils by reaction with monohydric and dihydric When employing monohydric alcohols to prepare the ole?nic alcohols under esteri?cation conditions and ester intermediates from which the resins of this inven polymerizing the resulting complex unsaturated polyesters tion are prepared, an alcohol/acid molar ratio of about at their double bonds. 2/ 1 is used and a monomeric unsaturated diester results. Polyester resins derived from unsaturated dicarboxylic The molecular weight and properties of the resulting poly acids and saturated monohydric or dihydric alcohols are ester intermediate, and consequently those of the resin, known in the prior art. The resins of this invention can be controlled when using dihydric alcohols in a num differ therefrom in that they are derived by polymerization ber of Ways. First, an alcohol/acid molar ratio greater from unsaturated polyesters prepared from unsaturated than 1/ 1 leads to intermediate polyesters of relatively low mon-ohydric or dihydric alcohols and complex polynuclear molecular weight, with the molecular weight of the poly aromatic di- and polycarboxylic acids. The nature of esters being inversely proportional to the alcohol/acid the complex acids from which the resins of this invention 25 mole ratio. are prepared also differentiates the ?nal resin product A second feature of this invention is the ?nding that from the resins of the prior art. higher esteri?cation temperatures result in intermediate It becomes, therefore, a primary object of this invention polyesters having relatively low molecular weights, while to provide a new class of thermosetting resins derived low temperatures result in polyesters having high molec from unsaturated di- and polyesters prepared by esterify 30 ular weights. The molecular weight of the polyester is ing the complex mixed di- and polycarboxylic acids hav proportional to the degree of esteri?cation. A third fea ing nuclei predominating in polynuclear aromatic alkyl ture is the discovery that the choice and concentration aryl con?gurations with known mono_ or dihydric unsatu of catalyst affect the molecular weight. These and other rated alcohols and polymerizing the resulting unsaturated features will be explained as the description of the inven esters. 35 tion proceeds. Another object of this invention is to provide a new The complex, polynuclear, aromatic, and alkaromatic class of thermosetting resins derived from solvent extracts di- and polycarboxylic acids, used to prepare the novel obtained in the manufacture of mineral lubricating oils. thermosetting resins of this invention, are derived by met An object of this invention is to provide a new class of alation, carbonation and acidi?cation of a source of com thermosetting resins from unsaturated esters and poly 40 plex, polynuclear, aromatic nuclei. These complex acids may be prepared by the prior art methods of metalation esters. Another object of this invention is to provide polymers and carbonation or the process of copending applications of monomeric diesters having the formula, Serial Numbers 819,932, now US. Patent No. 3,128,302, issued April 7, 1964, and 79,661, now U.S. Patent No. 45 3,153,087, issued October 13, 1964. Since the preferred source material, namely, solvent extracts from the manu facture of mineral lubricating oils, does not lend itself wherein R is the complex residue or nuclei or di- and to economical production of the desired complex acids poly carboxylic acids prepared from complex aromatic, using the prior art methods, the preferred methods of polynuclear compounds, R’ is hydrogen, or an alkyl, aryl, 50 preparation set forth in said copending applications will alkaryl, aralkyl, cycloparaf?nic, or hydroxy-substituted be described and the properties of the acids set forth as alkyl, aryl, alkaryl, cycloparaf?nic, or aralkyl radical, and examples. The details of these processes as described in n is one or greater. said copending applications are incorporated herein by Another object of this invention is to provide polymers reference. of dimeric and higher polyesters represented by the for 55 One procedure is to react about 30 parts of a petroleum mulas, fraction rich in complex polynuclear aromatics, as ex-' empli?ed by solvents extracts, with -1 to 5 parts of an alkali metal, such as sodium, potassium, cesium, lithium, and rubidium, and their mixtures and amalgams, at a 60 temperature of about —60‘° to 80° C. in the presence of a reaction solvent such as dimethyl glycol ether, dimethyl ether, methylakyl ethers, dialkyl glycol ethers, tetrahydro furan, methylal, and trimethylamine. The formation of the adduct is promoted by shearing, agitation, providing 65 an excess of alkali metal, using a pre-formed dispersion The ——CH=CH— portion of the molecule may be of the alkali metal in an inert solvent, or using a pre -—-CEC—. formed dispersion of the alkali metal in a portion or all An object of this invention is to provide polymerized of the solvent extract. These techniques overcome the polyester resins predominating in two or more combined induction period of the reaction due to impurities, in or polymerized esters of the Formulae I, II, III, and IV. 70 cluding sulfur compounds present therein, which tend to An object of this invention is to provide a method of coat the alkali metal particles and prevent the reaction preparing polyesters of Formulae I, II, III, and IV. or prolong the induction period. A brook?eld counter~ I 3,223,680 3 4 rotating stirrer is used to give ‘continuous shearing and The starting material for the reaction to prepare the expose fresh metal surfaces during the reaction. Color complex acids may be any complex polynuclear, and/ or ‘changes indicate the progress of the reaction. heterocyclic aromatic from synthetic or nat The alkali-metal adduct thus formed is either separated ural sources. A preferred and unique source of aromatic or left in the unreacted oil, and the mixture is treated starting material comprises petroleum fractions rich in with excess gaseous or solid carbon dioxide at tempera more complex polynuclear aromatic , not tures ranging from about —20° C. to —80° C., causing only because the dibasic or polybasic acid products there a discharge of the color. This forms the alkali-metal salt from have unique properties, but also because the tech of the complex acid which, upon acidi?cation with a niques outlined herein are particularly adapted to process mineral acid, yields the desired complex, polynuclear _ ing these more complex and resistant source materials. polycarboxylic acids in good yields. To illustrate, the Illustrating the preferred and novel starting materials is following non-limiting examples are given. the class‘known as solvent extracts from the manufacture EXAMPLE I of mineral lubricating oils, which solvent extracts are rich in complex, polynuclear, aryl, ailkaryl, condensed ring 100 gms. of extract oi'l No. 19 (Table I) from the 15 and heterocyclic nuclei forming the organic portion of preparation of 170 vis., 100 V.I. neutral oil, dissolved in the dibasic or polybasic carboxylic acids of this invention. 675 cc. of dry tetrahydrofuran was reacted with agitation Solvent extracts from the manufacture of bright stock and at 10° to 30° C. with 8.3 gms. of metallic sodium in the neutral lubricating oils are particular examples of such form of 1%6" cubes. After 25 minutes, adduct-formation fractions rich in complex aromatic compounds obtained ‘began and a strong color change took place. The product 20 as by-products from the solvent re?ning of mineral oils. was cooled to ——60° C. while an excess of carbon dioxide For example, a preferred source of the above-de?ned gas was introduced, resulting in a discharge of the color complex hydrocarbons comprises the extracts obtained in without precipitation. The 5.1 gms. of unreacted sodium solvent re?ning mineral oils, particularly lubricating oil was removed, the tetrahydrofuran was vacuum-stripped, fractions. These extracts, hereinafter referred to as sol and the remaining liquid combined with ether and water 25 vent extracts, are obtained as the extract or solvent phase washed. Acidi?cation of the aqueous phase and further when lubricating oils are re?ned by treatment with a se ether washing resulted in the recovery of free acids. lective solvent having an a?inity for aromatic and sulfur About 11% of the solvent extract had reacted. The acid compounds. The complex hydrocarbons removed by this product had an indicated average molecular weight of re?ning treatment often contain appreciable amounts of 686, a saponi?cation value of 171, and a calculated equiv 30 combined sulfur, nitrogen and oxygen. These complex alent weight of 328, indicating 2.11 carboxyl groups per hydrocarbons contain a predominance of polynuclear molecule. rings of aromatic structure, and of condensed con?gura EXAMPLE II tions having hydrocarbon substituent groups attached 100 gms. of extract oil No. 19 (Table I) and 675 ml. thereto as side chains. These starting materials are of a of dry tetrahydrofuran were charged to a one-liter, 3 35 generally viscous nature, have low viscosity indices, low necked ?ask equipped with a stirrer, thermometer, pres resistance to oxidation, and are considered to be deleteri sure-equalized drop-funnel, gas inlet with rotometer, and ous in lubricating oils. Heretofore, these aromatic ex gas outlet. A dry nitrogen atmosphere was maintained tracts have been regarded as waste products, and because in the ?ask. Approximately 100 gms. of Alundum balls they are exceedingly complicated mixtures of complex (a proprietary product comprising white fused alumina compounds, including various sulfur-, oxygen-, and nitro containing 99% A1203 with traces of sodium, iron, titania gen-containing compounds, they have not been used suc and silica), 5/16" in diameter, were charged and agitation cessfully in preparing petrochemicals or as sources of hy started. The solution was cooled to —20° C. and 8.3 drocarbon reactants or starting materials. gms. of sodium as a 20% dispersion in were The starting materials used are adequately described added. After an induction period of about 5 minutes, the as those aromatic materials separated from mineral lubri solution was warmed, and at —7° C. the reaction began; cating oils and their fractions (i.e., those aromatics ob in 17 minutes it was proceeding rapidly. An excess of tained in the manufacture and re?ning of neutral oils and dry carbon dioxide was added at —180° C. over a period bright stocks during treatment with a selective solvent of 78 minutes. The reaction mass was worked up as in designed to extract the predominantly aromatic materials Example I after the excess sodium was destroyed with 50 from the paraf?nic materials). Solvent extracts resulting water. About 15% of the extract oil reacted, and 22.5 from the treatment of mineral lubricating oils for the gms. of acid were recovered having a saponi?cation value purpose of separating non-aromatic hydrocarbons (the of 241, indicating an equivalent‘weight of 233. The acid ra?inate and ?nished oil) from the aromatic hydrocar product contained 2.8% sulfur. bons (the extract and waste product) may be used and 55 are preferred as starting materials. EXAMPLE III Since the general process of re?ning mineral lubricat The process of Example II was repeated producing ing oils in which solvent extracts are obtained is well complex acids having a saponi?cation value of 323, indi known, it is only necessary for present purposes to de cated equivalent weight of 173, indicated average molecu scribe a typical procedure for obtaining same and give lar weight (cryoscopic) of 600, and containing 3.0% 60 some examples by Way of illustration. sulfur. The ratio of molecular weight to equivalent In a typical operation, desalted crude oil is ?rst charged weight was 3.4, indicating a mixture containing acids to a distillation unit Where straight-run gasoline, two with more than two carboxyl groups per molecule. grades of naphtha, kerosine, and virgin distillate are taken off, leaving a reduced crude residue. The reduced EXAMPLE IV 65 crude is continuously charged to a vacuum distillation The various recovered acids of application Serial No. unit where three lubricating oil distillates are taken off 819,932, illustrated in Table II therein, are further ex as side streams, a light distillate is taken off as overhead, amples of polycarboxylic acids to be used to prepare the and a residuum is withdrawn from the bottom of the thermosetting resins of this invention. tower. The residuum is charged to a propane-deasphalt 70 ing unit wherein propane dissolves the desirable 1ubricat~ EXAMPLE V ing oil constituents and leaves the asphaltic materials. A typical vacuum residuum charge to the'propane-deasphalt The various polycarboxylic acid products described in ing unit may have an API gravity of 12.9°, viscosity SUS Runs 12 through 47 of application Serial No. 79,661 are at 210° F. of 1249, ?ash 585° F., ?re 650° F., vC.R. of further examples of acids that may be used. 75 13.9 weight percent, and may be black in color. The 3,223,680 5 5 deasphalted oil may have an API gravity of 215° to The solvent extracts from lubricating oils used as start 21.8°, viscosity SUS at 210° F. of 165-175, NPA color ing materials for this invention have the following gen 6-7, ?ash 575° F., ?re 650° F., and OR. of 1.7-2.0. The eral properties and characteristics: deasphalted oil and various lubricating oil distillates from Table II the reduced crude are subjected to solvent extraction for the separation of non-aromatic from aromatic constitu Characteristic: Range of value ents prior to use. The re?ned oil or “ra?inate” from the Gravity, °API ______7.3-18.3 extraction processes is used per se, or as blending stock, Gravity, Sp, 60/60” F ______09446-10195 for lubricating oils, and the solvent extract, predominat Viscosity, SUS @ 100° F. _____ 250-25,000 (ext.) ing in complex aromatic constituents, is distinctively use Viscosity, SUS ((2 130° F. ______140-19,000 ful in accordance with this invention. Viscosity, SUS @ 210° F ______200-1500 For example, a crude oil from an East Texas ?eld, with Viscosity index ______—101-+39 an API gravity of 33.1, was topped to remove such light Pour point (max) ______+35-100 fractions as gasoline, naphtha, kerosine, and a light lubri Color, NPA ______+2-5D cating distillate. The vacuum residue was a reduced 15 Molecular Weight, average (above 300) __ 320-750 crude, having a viscosity of 1251 SUS at 210° F., 2.2 per Boiling point (initial), °F. ______300-1000 cent sulfur, and an API gravity of 12.6. After propane Boiling point (end), °F. ______400-1200 deasphalting, the oil had a viscosity of 174 SUS at 210° Sulfur, percent wt. ______1.9-4.5 F., and an API gravity of 21.7. This deasphalted oil was Sulfur compounds, percent wt. ______20-50 treated with phenol to produce a rat?nate from which an 20 Aromatics and thio compounds ______50-90 aviation lubricating oil could be prepared. The oil ex Thio compounds ______14-40 tracted by phenol treatment, after removal of phenol, is Neutral aromatic hydrocarbons ______40-51 ready for use as the starting material in accordance with Av. number of rings/means arom. mol. ____ 1.7-3.5 this invention. H/C wt. ratio ______O.116-0.136 Solvents other than phenol may be used to obtain the 25 H/C atom ratio, Whole sample ______1383-1622 extraction product used in accordance with this invention, H/C atom ratio, aromatic portion ___ 1.289-1.500 for example, liquid sulfur dioxide, nitrobenzene, 2,2’ Nearest empirical formula ______C22H30-C44H66 dichloroethyl ether, ehlorophenol, trichloroethylene, cre sylic acid, pyridine, furfural, or the Duo-Sol solution (a The speci?c gravities of the extracts in general increase with increase in the viscosity of the raf?nate at a constant proprietary composition comprising liquid propane and 30 cresol) may be used. When using phenol, it is possible viscosity index. Stated otherwise, the speci?c gravities to vary the characteristics of the extract and rai?nate of these extracts increase with decrease in viscosity in products considerably by adjustment of the amount of dex of the ra?inate at a constant viscosity. For the pro water present. A raf?uate of relatively low viscosity in duction of 100:5 V.I. neutral oils, the viscosities of the dex can be obtained by using a water solution of phenol extracts increase with increase in stated viscositics of the during the extraction, and a rat?nate of high viscosity neutral oils (ra?inates). The pour points of extracts index can be obtained by using anhydrous phenol. Fol are high and are affected by changes in the depth of ex lowing are the physical characteristics of typical extract traction. The sulfur contents are also affected by the products, from lubricating oil stocks derived from various depth of extraction. The solvent extracts are charac crude oils and other source hydrocarbon materials, which 40 tcrized by containing aromatic and heterocyelic com may be used in accordance with this invention. pounds in the range of 75-98%, the remainder being

Table l SOURCES AND PHYSICAL CHARACTERISTICS OF SOLVENT EXTRACTS

Ext. API Sp. Gr. vis/100° Vis/130° vis/210° ° F. ° F. Iodine Per- Per No. Crude Source Solvent Grav. at 10° F. F. F. F. V.I. Pour Flash Fire No. cent cent (Wijs) .R. Sulfur

11.1 ______15. 4 ______12. 6 14. 6 l5. 4 ______1 13. 7 8. 6 10. 5 ______

10.2 ______

10__,__ Texas ______Furiural ______._ 13.0 11_____ Penn _ Ohiorcx ______.1 12.2 12 ______._ Nitrobenzene... 10.0 ‘ Propane cresol. _ 14. 4 13.6 13.6 8.9 14.9 13.5 5. 76 2. 36 11.1 0. 42 2. 7 13.7 5. 5 2. 3 7.8 0. 86 3. 2 7.3 7. 7 3. 0 ______-- 1. 1 2. 75 17.6 0. 1 2. 0 13.7 5. 5 2. 3 11.1 0. 4 2. 7 7.7 0. 86 3. 2 7.3 ______7. 7 3. 0

Extract No. 41 was obtained in the production 0185 vis neutral, has an average molecular weight of 300, and contained 76.8% aromatics (by the silica gel procedure) . Extract No. 42 was obtained in the production of 150 vis Bright Stock, has an average molecular weight of 590, and contained 86% aromatics, 14% satu rates, 86.2% carbon, 11.4% hydrogen, and averaged 3.3 aromatic rings per aromatic molecule. Extract No. 43 was obtained in the production of 170 vis neutral, has an average molecular weight of 340, contained 84.1% aromatics, 15.9% saturates, 86.4% carbon, 10.7% hydrogen and averaged 2.7 aromatic rings per aromatic molecule. Extract. N o. 44 was obtained in the production of 200 vis neutral, has an average molecular weight 0134.0, contained 87% aromatics, and 13% saturates. Extract No. 45 was obtained in the production of 160 vis Bright Stock, contained 92% aromatics and 8% saturates. 3,223,680 7 -8 principally saturates, or material behaving as saturates, Despite the size of the acid molecules the linkages through together with a minor proportion of up to about 7% of or between the carboxyl groups are about the same as organic acids. The organic acids present are not sus those of phthalic and terephthalic acids. A portion of ceptible to extraction by the use of aqueous strong caus the aromatic rings or condensed aromatic rings is prob tic because of the solubility of the alkali metal salts of ably further condensed with naphthenic rings to form the acids in the oil. Little or no asphaltic material is con?gurations similar to the steroid ring system. Extract present in solvent extracts and they contain essentially dibasic acids from solvent extracts obtained in the pro no materials volatile at room temperature. duction of bright stocks probably contain more highly The complexity of the types of compounds present, as condensed aromatic structures. Most of the sulfur (1.9 based on these analyses, is illustrated by the following to 3.2% or 4.5% total sulfur being present) is in the table: form of heterocyclic rings With carbon associated with Table III both the aromatic type and naphthenic type structures ESTIMATED CHEMICAL COMPOSITION OF SOLVENT present. Only trace amounts of the sulfur are present EXTRACTS NOS. 19, 2'1, 43, AND 44 OF TABLE I as high-molecular-weight aliphatic sul?des. The nitro Type of compound: Approx. percent 15 gen content of distilled solvent extracts is 0.01 to 0.04%. in the Extract Analysis for the types of carbon linkages as percent Ca Saturated hydrocarbons ______12.5 (carbon atoms in aromatic con?guration), percent Cn Mononuclear aromatics: (carbon atoms in naphthenic con?guration) and percent Substituted ______25.0 Cp (carbon atoms in paraf?nic con?guration) gives re Dinuclear aromatics: 20 sults ranging from about 30-40% C,,, 20-35% C1) and Substituted ______30.0 31-47% C‘p using the method of Kurty, King, Stout, Par Trinuclear aromatics: tikian and Skrabek (Anal. Chem. 28, 1928 (1956)). The Substituted ______10.0 polybasic acids used in preparing the polymerized poly Substituted ______5.0 ester resins have acid numbers (1948 Method) of from Tetranuclear aromatics: 25 200-300, M.P. 80-90° C., bromine number 16-24, sul Substituted chrysenes ______00.5 fur 1.7-2.3%, are deep red in color, transparent in thin Substituted benzphenanthrenes ______0.2 sheets and contain 2-6% unsaponi?ables. They are solu Substituted ______0.2 ble in ethyl ether, acetone, methyl ethyl ketone, tetrahy Pentanuclear aromatics: drofuran, , toluene, and xylene. 30 Perylene ______0.01 The alcohols used to prepare the esters of this inven Sulfur components i‘, oxygen compounds etc __ 16.5 tion are mono-, or dihydric, ole?nic or acetylenic alcohols i‘ Mainly heterocyclic compounds. The average mol. wt. of of the formulae: Extracts 19 and 21 is 340, and that of Extract 20 is 590. Any portion of the reactive aromatic constituents 35 in solvent extracts may be isolated therefrom, or from other sources, to be used as starting materials for the R1—(‘3=(|1—(CHOH)mCH=CH——R2 reaction in accordance with this invention. For example, and solvent extracts may be distilled and selected fractions H thereof used as the starting materials. The content of 40 reactive, complex, polynuclear, aromatic compounds and HO—R1—(lJ=CH(CH2)n—-CHzO1-I heterocyclics present in solvent extracts, as illustrating wherein R1 and R2 are hydrogen or a hydrocarbon radical the preferred source material, may vary depending on having from 1 to 20 carbon atoms which may be in the the type of solvent, the extraction process applied, and form of alkyl, aryl, alkaryl, aralkyl, cycloalkaryl, hydroxy alkyl, hydroxy- groups, n is zero to 10, m has the mineral oil treated, although the general types of 45 compounds present in the extract are not so varied. Ex a value of 1 or 2 and the ole?nic bonds may be acetylenic. tracts containing from about 30% to 90% of poly Examples include allyl alcohol, crotyl alcohol, isocrotyl nuclear aromatics and heterocyclics of aromatic nature alcohol, methyl vinyl carbinol, 2-pentene-1, 3-pentene-1 represent a preferred type of starting material. ol, 4-pentene-1-ol, 3-pentene-2-ol, 4-pentene-2-ol, 2-meth yl-2-butene-1-ol, 2-methyl-3-butene-1-ol, 2-hexene-1-ol, 2 In addition to the general physical and chemical prop 50 erties of the solvent extracts given in Table II, these start— heptene-l-ol, 2-octene-1-ol, 3-octene-1—ol, 4-octene~1-ol, ing materials may be further characterized by the fact that 2-nonene-1-ol, 3-nonene-1-ol, 4-nonene-1-ol, S-decene-l their average molecular Weight is about 320 to 600, the o1, 6-decene-1-ol, 7-decene-1-ol, 7-dodecene-1-ol, 8-un boiling point (initial) is between 300 to 1000° F., the end decene-l-ol, 9-tetradecene-1-ol, 10-heptadecene-1-ol, 9-oc boiling point is between 400 to 1200° F., and they may 55 tadecene-l-ol, 9--octacene-2-ol, 2-eicosene-1-ol, 3-eico exhibit pour points as high as 100° F. Chemically, the sene-l-ol, 3-eicosene-2-ol, propargyl alcohol, 2--1 extracts may contain 1.9 to 4.5% wt. of sulfur, exhibit ol, 3-butyne~1—ol, 3-butyne-2-ol, 2--1-ol, 3-pen a H/C wt. ratio of 0.116 to 0.136, a H/C atom ratio of tyne-l-ol, 4-pentyne-1-ol, 3-pentyne-2-ol, 4-pentyne-2-ol, 1.383 to 1.622, a H/C atom ratio, based only on the aro 2-butene-1,4-diol, 2-butyne-1,4-diol, 2-pentyne-1-ol, 1 pentyne-3-ol, 1-pentyne-4-ol, dimethylethenylcarbinol, 2 matic portion, of 1.289 to 1.500, and the nearest empir 60 ical formula is C22H30 to CMHSS. The extracts may con -l-ol, 3-hexyne-1-ol, n-propylethynyl carbinol, 2 tain from about 15% to 50% by weight of sulfur com methyl-4-pentyne - 2 - ol, methylethylethynylcarbinol, 4 pounds, and 30% to 90% by weight of aromatic and thio methyl-2-pentyne-1,4-diol, 2--1-ol, 3-heptyne-1-ol, compounds. Many of these characteristics, particularly 5-methyl-3 -hexyne-2 - o1, methyl-n-propylethynylcarbinol, the chemical characteristics, carry over into the polym 65 4,4-dimethyl-2-pentyn-1-o1,_ diethylethynylcarbinol, meth erized polynuclear polyesters of this invention. ylethylpropynylcarbinol, 2,5-heptadiyne-4-ol, 2--1 Without limiting the invention, the characteristics of ol, 3-octyne-1-ol, 3-octyne-2-ol, 3,5-octadiene-2,7-diol, the products of this invention as in?uenced by the com methyl-t-butylethynylcarbinol, 2,5- dimethyl-3-hexyn-2,5 plex acids are further disclosed as thus far evaluated. diol, 3-nonyne-2-ol, methyl-n-amyl ethynylcarbinol, and The di- and polycarboxylic acids used are mixtures of 70 diisopropylethynylcarbinol to includes the series acids of the dihydronaphthalene, dihydrophenanthrene, HOCH2(CH2)n'—-CEC(CH2)n~CH2OH and dihydroanthracene types averaging in molecular and Weight from about 375 to 450 having several alkyl groups HOCH2(CH2)nCH:CI-I(CH2),,,CH2OH in each aromatic nucleus wherein the sum of the carbon Where in each instance 11:0, 1, 2, 3 etc. up to 10 or more atoms in the alkyl substituents varies between 15 to 22. 75 and n'=0, 1, 2, 3 etc. up to 10 or more. 3,223,680 9 10 Other aliphatic ole?nic alcohols include divinylcarbinol, the use of higher esteri?cation temperatures results in 2,4-hexadiene-l-ol, 1,5-hexadiene-3-ol, 1,3-hexadiene-5-ol, intermediate polyesters of relatively low molecular weights l,5-hexdiene-3,4-diol, 2-methyl-3-pentene-2-ol, 4-methyl and low esteri?cation temperatures in the order of 100 to 3-pentene-2-ol, 2-methyl-4-pentene-2-ol, 4-methyl-4-pen 200° C. produces polyesters having high molecular tene-Z-ol, isopropinylvinylcarbinol, 2,2-dimethyl-3-butene weights, i.e., the molecular weight of the polyester is in 1-01, 4-heptene-l, 6-heptene-1-ol, 3-heptene-2-ol, 4-hep versely proportional to the esteri?cation temperature. tene-3-ol, 2sheptene-4~ol, 1,5-heptadiene-4-ol, 2-methyl-4 Other ways of controlling the molecular weight and hexene-3-ol, 3-methyl-5-hexene-3-ol, S-methyl-l-hexene properties of the polymerized resins of this invention are 5-ol, vinylisobutenylcarbinol, 2,4-dimethyl-3-pentene-2-ol, choice and concentration of the polymerization catalyst 2-isopropyl-3~hydroxy-l~butene, cis-2-octene-l~ol, trans-2 and the use of “chain-breakers” such as hydroquinone. octene-l-ol, 1-octene-4-ol, 2,4,6-octatriene-1-ol, Z-methyl The polyester intermediates are prepared by conven 6-heptene-2-ol, 6-methyl-2-heptene-6-ol, 6-methyl-3-hep tional esteri?cation methods, with or without a catalyst. tene-6-ol, cis—2,5-dimethyl-3~hexene-2,S-diol, 8-nonene-l Any of the known esteri?cation catalysts may be used ol, 4,6-dimethyl-1-heptene-4-ol, citronellol (from rose to speed up the reaction, such as sulfuric acid, other oil), rhodinol, phytol, dipropenyl glycol, 4,6-dimethyl 15 mineral acids, boron trifluoride or other Lewis acids. The 1,5-heptadiene-4-ol, w-undecylenyl alcohol, oleyl alcohol, preferred method of ester synthesis involves re?uxing and linoleyl alcohol. about 1 mole of the complex polycarboxylic acids with The alicyclic ole?nic alcohols such as 2-cyclopentenol, about 2 to 2.5 moles of the mono- or dihydric ole?nic 2-cyclohexenol, 1~methyl-2-cyclohexenol, 2-(1-cyclopen alcohol. A diluent such as an inert solvent may be tenyl)-ethanol, l-vinyl-l-cyclopentanol, l-methyl-Z-cyclo 20 used when convenient for lowering the re?ux tempera pentenyl-l-carbinol, methyl~l-cyclopentenylcarbinol, ,8-(1 ture and removing water as an azeotropic mixture. The cyclohexenyl) -ethanol, 1 - allylcyclopentanol, ethyl-1 ester product is then washed in the usual manner to cyclopentenyl-carbinol, 4-n-propyl-2-cyclohexenol (cryp remove ‘any residual acid and subjected to distillation tol), 4-(2’-cyclopentenyl)-l-butanol, l-methallylcyclo at reduced pressure (about 1 mm.) to remove excess pentanol, and trans-2-cyclohexenylcyclohexanol can be 25 alcohol and any moisture that may be present. The used. reaction can be carried out at temperatures ranging ‘from The aromatic ole?nic alcohols and phenols such as 100° to 200° C. When an excess of ole?nic alcohol is O-vinylphenol, cinnamyl alcohol, phenylvinyl carbinol, used, that is alcohol/acid molar ratios in excess of 1/ l, O-allylphenol, O-propenylphenol, phenylpropenyl car a substantially neutral ester and ?nal resin is obtained binol, methyl-ot-styrylcarbinol, methyl-?-styryl carbinol, which tends to be soluble in water and organic solvents, phenylisobutylenecarbinol, l-(ot-naphthyl)-3-butene-1-ol, but is alkali resistant. When an alcohol/acid molar O-cinnamylphenol, 2-hydroxymethyl stilbene can be used. ratio of less than 1/1, an acidic resin is obtained which The alicyclic and aromatic acetylenic alcohols such as is subject to deterioration by contact with alkali. l-ethynylcyclopentanol, l-ethynylcyclohexanol, l-ethynyl The polymerization reaction is also carried out by cycloheptanol, 4-cyclopentyl-2-butyne-1~ol, phenylethynyl conventional methods using a small amount, less than carbinol, l-phenyl-l-butyne-3-ol, 1-phenyl-1-butyne4-ol, 2% of an initiator such as a Lewis acid, a peroxide or and diphenylethynylcarbinol can also be used. a trace amount of an alkali metal. The reaction pro As seen from the foregoing examples, R1 and R2 in ceeds of its own accord, beginning at room temperature Formulae I, II, III and IV may be hydrogen, an alkyl, and gradually becoming exothermic. Means may be pro aryl, alkaryl, aralkyl, cyclopara?inic radical or a hydroxy vided to control the exothermic reaction temperature so alkyl, hydroxylaryl, hydroxyalkaryl, hydroxyaralkyl or as not to exceed 200° C. One procedure is to dissolve hydroxycycloparal?nic radical, containing up to 20 car the esters in a suitable solvent and add methyl ethyl bon atoms and —CH=CH— may be —-CEC—- (acety ketone peroxide and subsequently cobalt naphthenate or lenic). Examples of alkyl groups include methyl, ethyl, dimethyl aniline slowly with ‘agitation. The esters may propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, 45 be incorporated in paints or other coating materials and hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, caused to polymerize into protective coatings by the addi dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepta tion of metallic driers such as those of the cobalt and decyl, octadecyl, nonadecyl and eicosyl groups. The lead naphthenate series. The resins are useful as lami cyclopara?inic groups may be cyclopropyl, cyclobutyl, nating agents, shell-molding compounds and protective cyclopentyl, cyclohexyl, methyl cyclopentyl, and the like. coatings. Aryl and alkaryl groups include phenyl, naphthyl, anthryl, Other examples of feed materials that comprise a source tolyl, xylyl and the like groups. Any of the foregoing of related polynuclear aromatic compounds comprising may contain hydroxy groups to form the hydroxyl-con the nuclei of the acids are FCC recycle stock and com taining series. bined reformate polymers described in US. Patent No. The polymerized resin products of this invention are 55 3,153,087. In addition to the polymerizing catalyst dis softer, more pliable etc. than prior art resins prepared closed herein, other suitable catalysts are acetyl peroxide, from saturated monohydric or dihydric alcohols and cumene hydroperoxide, azo-bis-isobutyronitrile, as well unsaturated dicarboxylic acids. This is apparently due to as numerous other peroxy-type catalysts known in the art. the complex polynuclear group present in the polycar The embodiments of the invention in which an ex‘ boxylic acids derived from solvent extracts. As seen 60 clusive property or privilege is claimed are de?ned as from this description two types of esters, namely, those follows: prepared from monohydric ole?nic alcohols and those 1. A polymerized, cross-linked resin prepared by the prepared from dihydric ole?nic alcohols, are used to reaction under esteri?cation conditions of prepare the polymerized resin products of this invention. (1) a carboxylic acid prepared from solvent extracts When “monomeric” diesters are formed and polym 65 obtained in the solvent re?ning of mineral lubri erized, an alcohol/ acid molar ratio of about 2/1 is used cating oils using a solvent selective for aromatic and with dihydric alcohols the alcohol/ acid molar ratio compounds, by reaction of said solvent extracts with may be 1/1 to or as high as 5/1, and the molecular an alkali metal to form the alkali metal adduct, carbonation of said adduct to form the correspond weight of the polyester intermediate and consequently 70 that of the resin can be controlled. I have found that ing alkali metal salt of a carboxylic acid and acidi with an alcohol/ acid molar ratio of greater than 1/1, a ?cation of said salt to form the free acid character relatively low molecular weight intermediate polyester ized by having an average molecular weight of about results. The molecular weights of the polyesters are in 375 to 450, contain about 1.9 to about 4.5 weight versely proportional to the alcohol/ acid mole ratio. Also, 75 percent of combined sulfur and have an average of 3,223,680 11 12 ‘about 1.7 to 3.5 aromatic rings per mean aromatic 2,482,606 . 9/1949 Adelson ______260-468 molecule and 2,723,259 11/1955 Kurtz ______260—468 (2) an alcohol of the group consisting of monohydric 11/1959 ole?nic alcohols having 3 to 33 carbon atoms per 2,911,433 Jolly ______260—468 molecule, m-onohydric di-ole?nic alcohols having 5 2,965,587 12/1960 Rickert ______260—75 to 45 carbon atoms per molecule, dihydric diole 2,970,164 1/1961 Jezl ______260—75 ?nic alcohols having 6 to 46 carbon atoms per mole 3,056,773 10/1962 100 et al ______260—128 cule, dihydric ole?nic alcohols of 4 to 33 carbon 3,097,231 7/1963 Mills et al. ______260—468 atoms per molecule and the corresponding acet 3,128,302 4/1964 Martinek ______260—475 ylenic alcohols of said group using about 1 mole of 4/1964 said carboxylic acid to about 2 to 21/2 moles of said 3,129,192 Kramer et al ______260—75 alcohol at a temperature of about 100° to 200° C. OTHER REFERENCES to form the unsaturated ester and polymerizing said ester in the presence of a peroxide initiator. Conant et al.: J.A.C.S., vol. 50 (1928), pp. 542-550. 2. A polymerized, cross~linked resin in accordance with 15 Chat?eld: Varnish Constituents, 3rd Edition, Leonard claim 1 in which said peroxide initiator is methyl ethyl Hill Limited, London, 1953, 868 pages; pages 266—271 ketone peroxide. relied upon. References Cited by the Examiner LEON J. BERCOVITZ, Primary Examiner. UNITED STATES PATENTS 0 H.N. BURSTEIN, Examiner. 2,221,662 11/1940 Rothrock ______260—78.4