Patented May 13, 1952 2,596,235

UNITED STATES PATENT OFFICE 2,596,235 TERPENE-PHENOLIC REACTION PRODUCT Lyle M. Geiger, Edgewood, Pa., assignor to The Neville Company, Pittsburgh, Fa, a corporation of Pennsylvania, ------No Drawing. Application October 2, 1947, Serial No. 7,594 Claims. (C. 260-69) 1. 2 This invention relates particularly to a novel Other objects will appear hereinafter. product, made by the interaction of ordinary The term 'solubility in alcohol' as used herein phenol and natural cyclic terpenes and which and in the claims refers to the ability to coola, is characterized by reactivity with drying oils and 20 per cent by weight solution of the material by alcohol solubility, and this application is a 5 in anhydrous methyl, ethyl, propyl or isopropyl continuation-in-part of my copending applica alcohol to 5° C. without precipitation. The 20 tion Serial No. 561,818, filed November 3, 1944, per cent concentration refers, of course, to a now abandoned. Solution containing that amount of solute at Terpene-phenol resins have been used widely normal room temperatures. This standard is in paints, varnishes, lacquers, adhesives, and 0. applied because experience has shown that a other coating compositions. The practice in mere trace of alcohol-insoluble polymer material making such resins has been to treat a mixture will be precipitated under these conditions. of a terpene and a phenol with a catalyst that he foregoing objects of the invention are promotes condensation and polymerization re attained, as I have discovered, by effecting reac actions. A wide variety of terpenes have been tion between a natural cyclic terpene and ordi used for this purpose such, for example, as alpha nary phenol, under the influence of a condensa pinene, beta pinene, limonene, dipentene, and tion catalyst while observing certain critical turpentine or turpentine fractions. Similarly, factors. A variety of condensation catalysts, various phenols have been applied to this end, such as those well known in the art, examples examples being ordinary phenol, cresols, the of which will appear hereinafter, may be used, naphthols, and various substituted phenols. The depending on the mol ratio of phenol to terpene. catalysts that have been used for this purpose A feature is that the phenol is to be used in at include various acids, such as sulfuric, oxalic, least slight molar excess over the terpene; excess phosphoric, and sulfonic acids; metallic chlorides of phenol over that proportion may be, and for Such as those of zinc, aluminum or iron; the certain purposes is preferably, used. As I have halogens; and boron trifluoride, either as such discovered, the use of a molar excess of natural or in the form of molecular compounds with cyclic terpene reduces the alcohol solubility of organic acids, ethers, alcohols or phenols. the products. The resins produced in that manner are all characterized by solubility in aromatic hydro I have discovered, and the invention is predi carbon solvents, and they show a wide variety of cated in part on this also, that it is essential to properties, ranging from oily liquids to hard, allthe ofterpene, the embodiments preferably slowlyof the and invention progressively, to add brittle resins. Disadvantageously, however, all to a previously prepared mixture, Suspension, of them are insoluble in alcohols, such as meth dispersion or solution of the condensation catar anol, ethanol, propanol, and the like, and they 3.5 iyst in phenol, heated to an appropriate tem tend to be quite dark colored. Likewise, they perature. Other ways, or orders, of mixing the are not reactive with drying oils. reactants and the catalyst result in products of A primary object of the present invention is impaired alcohol solubility. Thus, mixing the to provide a novel reaction product of ordinary reactants and catalyst in the required quantities phenol (C6H5OH) and natural cyclic terpenes 40 and heating, or adding the catalyst at once or in that is characterized by the capability of exist portions, to a mixture of the reactants, results ing in both a stable, crystalline state and also in in products of very poor or nil alcohol solubility, a metastable resinous state, by being soluble in alcohol, and by unique reactivity with drying oils produced.and the unique product of the invention is not to provide varnish and related coating compo The terpene may be added to a simple Suspen sitions of especially desirable properties, both sion or solution of the catalyst in the phenol. technical and economic. - However, in some instances the viscosity of the A further object is to provide a simple and ef reaction body may rise rapidly as the concentra ficacious method of making the product of the tion of reaction product increases with the ne product of the foregoing object. 50 cessity for using excessive power to maintain the 2,596,285 3 4 agitation necessary for adequate distribution of oil reactive product of this invention may be pro the catalyst. Such increase in viscosity likewise duced from ordinary phenol and alpha pinene may make separation of the catalyst from the re by observing the factors described above. In action body difficult. Generally speaking, there stead of alpha pinene, any of the other natural - fore, it is preferable to use an inert diluent Such, cyclic terpenes and their derivatives, or naturally for example, as petroleum benzine or an aro occurring combinations of such terpenes, may be matic hydrocarbon solvent. The phenol may be used. Thus beta pinene, the gum, Wood or Sull initially dissolved in such a diluent and the cata phate turpentines of commerce, which are mix lyst suspended or dispersed in the Solution. Or, tures of the stated natural cyclic terpenes, and di if preferred, the diluent may be added, all at 0 pentene are typical of the raw materials advan once, or progressively, as the reaction proceeds tageously used in the preparation of this oil re or after it has been completed. active product. After the reaction has been completed the The temperature of the reaction varies With catalyst is separated, suitably by filtration, and the catalyst used, suitably from 45 to 65 C. the reaction product is recovered as described With boron trifluoride and its active complexes hereinafter, as exemplified by the various ex to from 80 to 110° C. With activated clayS; it may amples. Vary also with the terpene, e. g., With pure COm More in detail, the novel product that con pounds such as alpha, or beta pinene lower ten stitutes an outstanding feature of the invention peratures suffice than With mixtures of natural and Which is reactive With the drying oils, is 20 terpenes, such as turpentines, which in Some in Soluble in alcohol by the test described above, stances may be reacted at, e. g., 150 to 180° C. and shows the rather unusual property of exist Although the temperature applied is not critical, ing reversibly in both the crystalline and also a generally speaking, low temperatures result in resinous form. low reaction speed while excessively high ten In this invention ordinary phenol is reacted 25 peratures may cause the product to be darker With a natural cyclic terpene, using at least a than is the case with lower temperatures. slight molar excess of phenol and a condensation The product may be recovered as a resinous catalyst. With about 1.1 mol, or slightly more, body by distilling off solvent, if used, and residual of phenol per mol of terpene this oil-reactive unreacted phenol and terpene. In trying to puri product is produced preferably by activated clay 30 fy the product by recrystallization from aroma Condensation catalyst. Such, for example, as that tic hydrocarbons, or from mixtures of aromatic sold as 'Superfiltrol.' and aliphatic hydrocarbons, it was found that The commercially available activated clays the compound does not always crystallize readily contain appreciable quantities of water in the from these solutions, and that when forced out aS-received condition, and it is essential to this 35 of solution by the addition of larger quantities aspect of the invention that these activated clays of low-boiling petroleum hydrocarbons, the be used in that normal moist, or wet, condition. compound is precipitated in the form of a soft, That is, if they are subjected to artificial dry resinous, noncrystalline mass, from which it is ing prior to use they do not produce the desired very dificult to obtain pure crystals, even after alcohol-soluble and oil-reactive product because 40 standing at low temperatures. I have found, in that case they preferentially produce simple however, that the compound of my invention polyterpene polymers so that the primary phe is very readily crystallized from mixtures of nolic modification reaction suffers, with conse dilute ethyl alcohol, e.g., equal parts of ethanol quent impairment of alcohol solubility and oil and water, and very pure products, forming per reactivity. fectly White crystals of sharp melting point I find that for many purposes the use of such (98° C.) are obtained after repeated crystalliza moist activated clay in an amount approximately tions. Another simple process for obtaining pure 10 per cent by weight of the terpene used suffices Crystals from a mixture containing the product to produce Satisfactory results. As is usually in impure form is to extract the resinous mixture the case, however, appreciable variations in the 50 With a dilute aqueous alkali solution and to pre amount of catalyst used are permissible without cipitate the compound by the addition of dilute influencing greatly the properties of the final hydrochloric acid, followed by recrystallization product. Of course, there should be enough cat from dilute alcohol. Similarly, when the crystal alyst to produce the desired product at an eco line product is heated above the melting point, nomically satisfactory rate; likewise, too much recrystallization does not occur readily upon catalyst is undesirable, economically, because it cooling, but Super-cooled melts appear to exist merely adds to the cost of the product. for long periods of time, in a metastable, resinous My tests show that other condensation cata form, Without showing crystallization phenom lysts, typified by those known in the art, may be ena. The product is thus obtainable in metas used With higher mol ratios of phenol to the ter 60 table, resinous and in stable, crystalline form, pene. Thus, at ratios of 2 mols or more, say 3 convertible one to the other. or 4 mols, of phenol to terpene, there may be The same. melting point (98 C.) has been ob used the various Friedel-Crafts catalysts such, tained by reacting a number of natural cyclic for example, as aluminum chloride, zinc chloride terpenes With phenol, using various catalysts, and other metallic chlorides, or acids, e. g. sul 65 thus showing identity of the products obtained, furic acid, that act as condensing agents. At and as far as I am aware it is produced from any these higher mol ratios the best results are to be latural cyclic terpene. had, however, by the use of boron trifluoride or An elementary analysis carried out on a puri any of the wide variety of its molecular com fied product made from phenol and alpha pinene plexes with ethers, esters, organic acids and 70 pointed to the formula C11H14O, corresponding phenols. These complexes are equivalent to each to the simplest molecular weight of 162. From other in being merely carriers of BF3; inert sol the freezing point depression in benzene a molec vents for BF3 might be used but they give off ular Weight of 325.0 was calculated. This made corrosive fumes. it apparent that two phenol molecules had con As an example, the novel alcohol soluble and densed with a single terpene molecule, and from 2,596,235 5. 6 its properties as well as from its formation re dissolved in 91 grams of WM&P naphtha were actions, I consider the product to be cis 1-8 bis added gradually over a period of 1 hour. The (parahydroxyphenyl) menthane: reaction was allowed to continue for another hour, after which the catalyst was removed by filtration. The reaction mixture was subjected to steam distillation and the resultant resinous HC CH product was dissolved in benzene and allowed to. Stand. Overnight, after which crystallization oc C C curred. Total yield 29 parts. E. 0 Eacample. No. 6 Hic?* CEa-(Don 103 parts of phenol (1.1 mol) were heated at The following examples of preparing this oil 90° C. with 15 parts of 'Superfiltrol' clay, while reactive product of my invention are given as 5. being agitated. 136 parts of beta pinene (1 mol) illustrative of practical, simple and economical dissolved in 91 parts of WM&P naphtha were WayS. Of producing the product from readily added gradually over a period of 2 hours. The reaction was allowed to continue for an additional available raw materials in commercial quantities, 30 minutes. The catalyst was then removed by but are in no way, restrictive, filtration and the solution subjected to steam Eacample No. 1 20 distillation. The resultant resinous product was 188 parts of phenol (1.1 mol) and 28 parts of dissolved in benzene and allowed to Stand Over "Superfiltrol' clay were heated at 90° to 95° C., night, after which crystallization occurred. The While being agitated. 136 parts of turpentine total yield was 44 parts. (1 mol) dissolved in 91 parts of WM&P naphtha, Similar results are obtainable from larger scale were added gradually over a period of 140 min Operation. utes. The reaction was permitted to continue Eacample No. 7 another 60 minutes, after which the catalyst was 1342 pounds of phenol, 715 pounds of petro removed by filtration. The solution was allowed leuil benzine as a diluent, and 175 pounds of to stand-overnight, after which crystallization oc 30 'Superfiltrol' clay were heated, with agitation, Curred. The yield obtained was 89.5 parts. at 80 to 90° C. while adding 1943 pounds of alpha Eaccingle No. 2 pinene over a period of 8% hours. Agitation and 103 parts of phenol (1.1 mol) and 15 parts of in eating at the teiiaperature stated were continued "Superfiltrol' clay were heated at 90° C., while for 2% hours longer. (Jpon filtration and distil being agitated. 136 parts of dipentene (1 rol) 35 lation to renowe in reacted naterials and the dissolved in 91 parts of WIM&P naphtha, were diluent there were obtained 1948 pounds of prod added gradually over a period of 2 hours. The !ct of which 507 pounds were a resin of 96° C. reaction was permitted to continue for another 2inelting point ( cube-in-mercury), of a pale color, 30 minutes, after which the catalyst was removed 40 and soluble in isopropanol without precipitation by filtration. The solution was allowed to stand at 3 C. he renainder was 1441 pounds of a overnight, after, which crystallization occurred. lethanol-soluble Stean distilliable oil which The yield obtained was 55 parts. boiled entirely above 300° C. at atmospheric pressure and had a specific gravity of 0.998 at Eacagmple No. 3 30.6/5.6° C. 188 parts of phenol (2 mois) and 9.4 parts of 45 Eaca 12ple No. 8 a boron trifluoride-phenol complex containing 30 per cent by weight of BF3 were heated at 55° C. In this case 244 pounds of phenol, 387 pounds while being agitated. 136 parts of gun turpen of petroleum benzine diluent, and 125 pounds of tine (1 mol) dissolved in 9.4 parts of WMi&E “Superfiltro' were heated and agitated as before naphtha, Were added gradually over a period of 5) while adding il 55 pounds of alpha pinene during 90 minutes. The reaction was cointinued for air. 2/2 hours. Resin and oil were obtained as before. other 30 rainutes after Which the mixture \vaS the resin Weighed 441 pounds, showed a melting agitated with 25 parts of Attapulgus clay, a point of 107 C., was of pale color, and was soluble fuller's earth. The mixture was filtered and al in isopropanol Without precipitation at 3 C. The 55 oil weighed 850 pounds, distilled wholly above 300 lowed to stand overnight, after which crystalliza C. at atmospheric pressure, was soluble in meth tion occurred. The yield obtained was 109 parts. anol, and had a specific gravity of 0.985 at Eacample No. 4 30.6/15.6° C. 188 parts of phenol (2 mols) and 10 parts of In the foregoing examples the clay catalyst a boron trifluoride-ethyl ether complex contain 60 was used in its as-received, Iloist condition. ing 30 per cent by weight of BF3 were heated at The reaction product produced in accordance 55° C. 136 parts of dipentene (1 mol) dissolved With the foregoing embodiment and examples is in 91 parts of WM&P naphtha, were added gradu soluble in alcohols according to the test described. ally over a period of 45 minutes. The reaction above, as well as in aromatic hydrocarbons, and was allowed to continue for another 4 hours, 65 in dilute aqueous solutions of alkalies. It is, how after which 25 parts of Attapulgus clay were ever, insoluble in low boiling petroleum hydro added. The mixture was filtered and the solution carbons, such as petroleum ether and petroleum was allowed to stand overnight, after which Crys benzine. Likewise, when recovered in the form tallization occurred. The yield obtained WaS of resin it is convertible, as described above, to 14.9% parts, 70 he thermodynamically stable crystalline state. This novel product is insoluble. in drying oils, Eaconi ple. No. 5 but an important and unique characteristic is 103 parts of phenol (1.1 mol) were heated at that it will react, chemically with drying oils upon 90° C. with 15 parts of “Superfiltrol' clay, while heating the mixture at a suitably elevated ten being agitated. 136 parts of alpha pinene (1 mol) 75 perature. i he thus modified drying oils acquire 2,596,285. 7 8. thereby very valuable new properties, making it As indicated above, although the maximum possible to provide improved varnishes, lacquers, ratio of cis 1-8 bis (parahydroxyphenyl) men paints and the like coating materials, as described thane to drying oils is essentially the same for all more fully in a copending application directed of the oils, the cooking temperature varies. thereto, Serial No. 777,593, filed October 2, 1947, The crystalline compound of my invention, as now U. S. Patent 2,588,821, issued March 11, 1952. described above, may be made by procedures other It is also possible to condense this condensation than that just discussed. Such other procedures product further with formaldehyde to produce are less direct and hence less economical but they valuable resins. give a better insight into the chemical mechanism A considerable variety of drying oils, typified by O of its formation. Thus, by reacting cis-dipentene linseed, oiticica, tung (China-wood), sunflower, hydrochloride, obtained by reaction of 1-8 cineole dehydrated castor oils, and other drying oils used with hydrochloric acid and acetic acid at lower for making coating compositions may be modified temperatures, with phenol in the presence of a chemically by reaction at elevated temperatures Friedel-Crafts catalyst such as aluminum chloride with the aforesaid cis 1-8 bis (parahydroxy S or zinc chloride, cis 1-8bis (parahydroxyphenyl) phenyl) menthane to provide products that may menthane is formed, which is clearly distin be formulated into coating compositions that are guished from the considerably higher melting characterized by highly improved characteristics. trans compound formed under similar conditions The exact temperature necessary for reaction from trans-dipentene hydrochloride and phenol. varies with the drying oil used. When properly 20 It is to be understood that the term 'activated processed in this way the reaction product is a clay' as used in the claims refers to the clay in perfectly homogeneous liquid that is productive its commercial moist condition. of films of similar characteristics and which is According to the provisions of the patent productive of coating formulations of greatly im statutes, I have explained the principle and mode proved characteristics, now to be described. 25 The reaction product is worked up in accord of practicing my invention, and have described ance with standard practice, as by the addition what I now consider to represent, its best embodi of any of the various resins used for such pur ment. However, I desire to have it understood poses, and this may be done before or after the that, Within the scope of the appended claims, the reaction, the product is Worked to desirable Con 30 invention may be practiced otherwise than as Sistency by the addition of any of the solvents, Specifically described. or volatile thinners, or combinations of them, I Cairn: commonly used in varnishes and related composi 1. That method which comprises heating ordi tions. Properly cooked drying oil bases produced ilary phenol (C6H5OH) in contact with a conden in this way by reaction with the aforesaid men 35 Sation catalyst, adding to the heated mixture a thane derivative will standi dilution with nineral inatural cyclic terpene, said phenol being present Spirits to non-volatile contents as low as 30 per in molar excess over said terpene, and separating cent and Subzero temperatures without precipita from the reaction mixture condensation product tion, characterized by existing reversibly in a resinous Experience has shown that although Small pro O form and in a crystalline form melting at 98° C. portions of the cis 1-8 bis (parahydroxy phenyl) after recrystallization from alcohol, by being re menthane relative to the drying oil are effective active With drying oils, and by complete solubility to produce Substantial improvement of film in alcohol as determined by the test described properties, the optimum improvement is had in herein, general at about 8.6 per cent by weight of the 2. That method which comprises heating a con inenthane derivative, based upon the oil, and that densation catalyst carried in a solution of ordi this amount should not be substantially exceeded. nary phenol (C6H5OH) in an inert solvent, adding An OutStanding feature is that of strong fortifi to the said heated material a natural cyclic cation of the drying oil as a result of the reaction terpene, Said phenol being present in molar excess described. In fact, dry films of compositions Over said terpene, and separating from the re made from this reaction product of drying oil action. Inixture condensation product character and the menthane derivative behave as though ized by existing reversibly in a resinous form and they contain from 40 to 100 per cent in Ore drying oil than they actually do. in a crystalline form melting at 98° C. after re Compositions made in this manner possess 55 Crystallization from alcohol, by being reactive other important characteristics. For instance, as With drying oils, and by complete solubility in compared With controls made from identical con alcohol as determined by the test described herein. Stituents but without this modification of the oil 3. A method according to claim 2 in which said by reaction with my new menthane derivative, terpene is a pinene. and varnishes made from the reaction product 60 4. A method according to clairn 2 in which said with drying oil show definite increase in protec terpene is turpentine. tive life, as in resistance to water, acid and salt 5. A method according to claim 2 said catalyst, spray, freedom from rust, adhesion to metal, and being activated clay. - resistance to checking. Also, improved gloss and 6. A method according to claim 2 said phenol fullness are inherent, especially on Wood, in coat 65 and pinene being present in substantially 1:1 to ings made from the drying oil reaction product. 2:1 molar proportions, and said catalyst being A further and particularly important feature is that compositions made from the drying oil boron trifluoride. menthane derivative reaction product show no 7. That method of preparing cis 1-8bis (para Skinning While at the same time drying time is not 70 hydroxy phenyl) menthane which comprises impeded. And, this modification of drying oils heating borontrifluoride in contact with ordinary does not result in after-yellowing; pale colored phenol (C6H5OH), adding to the said heated ma bases are produced by the reaction, and color terial a natural cyclic terpene, said phenol and fidelity in the formulation With pigments is pinene being present in 1:1 to2:1 molar propor aSSured. 75 tion, and Separating from the reaction mixture 2,596,285 9 10 said menthane melting at 98° C. after recrystal- Number Name Date lization from alcohol. 2,123,898 Honel et al. ------July 19, 1938 LYLE. M. GEIGER, 2,129,153 Schirm ------Sept. 6, 1938 - 2,145,369 Osterhof ------Jan. 31, 1939 REFERENCES CITED is 2,319,386 Carmody ------May 18, 1943 The following references are of record in the 2,343,845 Powers ------Mar. 7, 1944 file of this patent: OTHER REFERENCES UNITED STATES PATENTS Zinke et al., Jour, fur Prak. Chem, vol. 156, Number Name Date 97-100 (1940). 1,469,709 Wuyts ------Oct. 2, 1923 Martin, Paint Manufacture, vol. 15, 30-32 (1945),