2,907,738 United States Patent \ .j Patented Oct. 3, 1959 1 2 dibasic acids would also give polymerization in which the natural resin acid ester becomes an intimate part ‘ 2,907,738 of the ?nal polymer chemical composition. Such esteri ‘MIXED RESIN ACID ESTERS OF 4,4-BIS(47 ?cation reactions involving the phenolic hydroxyl groups HYDROXYARYL) PENTANOIC ACID 01 would conveniently be carried out by heating with a mix ture of the dibasic acid and acetic anhydride. Sylvan 0. Greenlee, Racine, Wis., assignor to The hydroxyaryl—substituted aliphatic acids contem~ S. C. Johnson & Son, Inc., Racine, Wis. plated for use in preparing the desired resinous poly No Drawing. Application June 30,1955 hydric phenols have two hydroxyphenyl groups attached ‘ Serial No.‘ 519,279’ 10 to a single carbon atom. The preparation of these sub~ stituted acids may be most conveniently carried out by 9 Claims. (Cl. 260-24)‘ condensing a keto-acid with the desired phenol. Expe rience in the preparation of bisphenols and related com pounds indicates that the carbonyl group of the keto This invention relates to new compositions which are 15 acid must be located next to a terminal carbon atom in ‘mixed esters of‘polyhydric alcohols, natural resin,acids, order to obtain satisfactory yields. A terminal carbon and hydroxyaryl-substituted aliphatic acids. atom as used herein refers to primary carbon atoms An object of this invention is to produce new com other ‘than the carboxyl carbon atom of the keto-acid. positions from natural resin acids, polyhydric alcohols Prior applications, Serial Nos. 464,607 and 489,300, and hydroxyaryl-substituted aliphatic acids which are 20 ?led October 25, 1954, and February 18, 1955, respec~ valuable as intermediates in the production of other more tively, disclose a number of illustrative compounds suit complex compositions. able for use as the hydroxyaryl-substituted acid, and Another object of this invention is to produce new methods of preparing'the same. These materials, which compositions of the hereinbefore described ‘character are referred to for convenience as Diphenolic Acid, or which are valuable in the manufacture of more complex 25 DPA a trademark of S. C. Johnson & Son, Inc., com~ reaction products having unusually good chemical resist- , prise the condensation products of levulinic acid and ance, hardness, gloss, etc. . phenol, substituted phenols or mixtures thereof. It is These and other objects and advantages ‘are attained to be understood that the phenolic nuclei of the ,Diphe ' by the present invention,‘ various novel features of which nolic Acid may be substituted with any groups which will become more fully apparent from the following 30 will not interfere with the esteri?cation reactions. For description, with particular‘reference to speci?c exam example, the nuclei may be alkylated as disclosed in ples which are to be considered as illustrative only. Serial No. 489,300 or they may be halogenated. The The compositions of this invention, being esters of Diphenolic Acid derived from 1 mol of levulinic acid polyhydric alcohols and mixtures of natural resin acids and 2 mols of phenol is particularly advantageous in and hydroxyaryl-substituted aliphatic acids, are relatively that it may be readily prepared to a high degree of high molecular weight resinous polyhydric phenols. The purity, whereas the use of substituted phenols, such as number of phenolic groups per molecule. are dependent the alkylated products, usually results in. mixed compo on the number of alcoholic hydroxyl groups present in sitions which are less readily puri?ed. On the other the polyhydric alcohol esteri?ed, as well as on the hand, there are cases Where the Diphenolic Acid derived amounts and proportions of natural resin acid and from alkylated phenols are more desirable than those hydroxyaryl-substituted aliphatic acid used in the prep derived from the nonalkylated product on the basis that aration of the esteri?ed product. the alkyl groups tend to give better organic solvent solu The mixed esters of this invention combine ‘within bility, ‘?exibility, and better water resistance. the same chemical molecule natural resin acid esters and The natural resin acids which may be used with these a phenolic residue, the natural resin acid ester portion 45 hydroxyaryl-substituted acids in the co-esteri?cation of being similar to the natural resin acid portion present the polyhydric alcohols are illustrated by the commercial in the so-called ester gums which are natural resin acid grades of rosin and other natural-occurring acid resins, esters of polyhydric alcohols. This property renders the such as the kauri, copal, damar, and Congo gums. compositions of this invention particularly valuable in Typical commercial grades of rosin, for example, have the manufacture‘ of complex products such as coating 50 and molding compositions, where the natural resin acid acid values of, around 150-175. Acid values as used esters are desirable for the purpose of contributing hard herein are de?ned as the number of milligrams of KOH ness and gloss to the ?nished product. The phenolic required to neutralized the acid present in a one-gram residues present in the compositions and introduced by sample. Typical damar gums have acid values ranging the hydroxyaryl-substituted aliphatic acids contribute‘ re~ 55 from 18 to 60. Kauri gums have acid values of from active phenolic hydroxyl groups which for the most part 60-80, while copal gums have acid values in the range do not enter into the esteri?cation reaction used in the of 105-130. The essential composition or" all these preparation of the mixed ‘esters of this invention. These natural-occurring resin acids are cyclic terpenic type functional groups permit further reaction between the acids of which abietic acid is fairly typical. mixed esters of this invention and such materials as 60 The polyhydric alcohols may be the nonresinous type aldehydes, epoxides, and carboxylic acids to yield addi~ or the resinous type. These polyhydric alcohols, be tional complex products. Reaction with aldehydes, cause of their polyfunctionality, will esterify with natural either in' the presence or absence of other compounds resin acids and hydroxyaryl-substituted acids to give a capable of polymerization with aldehydes, gives com resinous phenolic product. Illustrative of the nonresin positions which are valuable constituents of protective 65 ous type polyhydric alcohols are such materials as ethyl coatings and‘ molding resins. Similarly, the phenolic ene glycol, polyethylene glycols, propylene glycol, poly hydroxyl groups of the phenolic residues‘ may be reacted propylene glycols, 1,3-butane diol, 2,5-pentane diol, with polyepoxide compositions to give highly polymer 1,6-hexane diol, neopentyl glycol, glycerol, erythritol, ized products containing within the same molecule the pentaerythritol, polypentaerythritols, sorbitol, mannitol, natural resin acid ester‘residues. Esteri?cation‘ of the 70 alpha methyl, glucoside, polyallyl alcohols, diethanol phenolic hydroxyl groups of the phenolic residue with amine, triethanolamine, and tetramethylol cyclohexanolZ 2,907,738 'i' 3 4 The resinous polyhydfie alcohols Which may be used Esteri?eation of either the nonresinous or resinous in the preparation of the subject esters may be illustrated polyhydric alcohols with Diphenolic Acid and natural by Such materials as the l'esinells Ieaetion Products of resin acids is conveniently carried out by direct heating bisttlehvdroxyphenyl)isopropylidene With ethylene ch10‘ at temperatures of from 190—275° C. under conditions Tohydr’iil . 61‘ glycerol mo?eehlofohydrin- The reaction 5 where the water produced during condensation is continu ef the ‘Same. dihydrie Phenol with ‘epichlorohydfln or ously removed as it is formed. In the case where ep g'll’eei'ol 'die'hlofohydfin gives resinous polyhydric a100- oxide groups of, for example, a resinous composition of H015 which ‘are Polymeric polyhydric alcohols and Which the Epon resin type produced by Shell Chemical Corpo in some cases. in‘ addition to the alcholic hydroxyl groups. ration are partially esteri?ed only to the, extent of one 'eollt'ai‘n ePOXide groups- (The epoxidereenwinihg PYOd- 10 carboxyl group reacting with one epoxide group, lower nets are 'well illustrated by the commercially availa le temperatures may be used and no water is formed since Epon resins marketed by Shell Chemical Corporation) the reaction of the carboxyl group with the epoxide The preparation of these resinous polyhydric alcohols are group is that of direct addition with the formation of an described in US. Patents 2,456,408, 2,503,726, 2,615,008, ester-linkage and a free hydroxyl group. Since the Di '2,6'68,805, 2,668,807 and 2693,315- 15 phenolic Acid ‘and the polyhydric alcohols have boiling ‘ Other resinous polyhydri'c'alwhols which may be em- points which are in all cases above 190° C., the Water ployedwmay be illustrated by those which are prepared mayberemoved by permitting ittoyolatilize during es~ ‘by’ the'reaction of phenol-formaldehyde‘condensates with teriiication, Rgmoval of thelwam-vmayp also-be fad“ ‘chlorohydrins. For example, analkylphenol may be Con- tated by continuously bubblin'gthrou‘gh the reaction mix ‘dells'ed With formaldehyde, followed by treatment of 8m 20 ture during esteri?cation a stream of inert gas, such as alkaline solution of this intermediate methylol derivative carbon dioxideor nitrogen, It is also sometimes conven ‘With ‘3 ‘chlerohydrln, Such as glycerol'mollqehlorohydfini lent to. facilitate the water removal bycarrying out the to yield ‘after ‘condensation a Polymeric polyhydric aleo- reaction in a vessel provided. with condenser attached 'hol. This resinous polyhydric alcohol may then‘ be'used thereto through a water trap, adding ‘a su?icient amount in esteri?cation with the diphenolic acids to prepare the 25 of a volatile, water-insoluble. solvent to give re?ux at the subject resinous polyhydric phenols; ‘ esteri?cation temperature, continually removing the wa A typical formula for a composition herein described ter by lazeotropic distillation and permitting ‘the solvent may be illustrated by the ‘following reaction between equal to return to the reaction mixture after vhaving dropped the molar portions of ethylene glycol, abietic acid, and 4,4- water in the water trap. V bis(4-hydroxyphenyl)pentanoic acid. Abietic acid is the 30 The order of ‘addition, of the‘ various ingredients,’ Di "chief acid ingredient of commercial rosin and is typical phenolic Acid, resin acids, and polyhydric alcohols, to of the terpenic type acids present in the natural resin each other’may be varied. It is sometimes advantageous acids. to vary this order of addition to obtain optimum results

H3O GOZH \ /

HOG / onioniooin H20 /C\H/CH\’0 V on OHrOH heat C +l (1) ll -——> Ha / A + CHzOH ‘ ' g 50 on on,

CH3 0 on, H: no® onioniooionionioio on \c/ ‘ \ / ‘

-|- 21110 H1O C . I' . \("JH ona HiiG 0-0 011a \CHs 'Ha .

From the above formula it will be obvious that use of with the particular combination of ingredients used. In ‘more ‘complex polyhydric alcohols, such ‘as glycerol, the art of high temperature esteri?cation, it is sometimes pentaerythritol, and the polypentaerythritols, would give 60 advantageous to use certain’ esteri?cation catalysts, and higher molecular weight products in which the ratio of these'may be used in the preparation of the compositions Diphenolic Acid to natural resin acid may be varied of this invention. ' ‘ through wide ranges. It is understood that the composi- The ‘following examples will serve to illustrate this in tions obtained by co-esteri?cation of polyhydric 'alco- vention, however, 'it should be understood that the in hols with Diphenolic Acid and the natural resin acids 65 vention. is not intended to be limited thereby; In'the give ‘mixed products, including to some extent esteri?ca- examples, proportions expressed are parts by weight un— tion of the phenolic hydroxyl groups of Diphenolic Acid less otherwise indicated. . i ' I" with the carboxyl groups of diphenolic acid itself as well Examples I to VI illustrate the preparation ‘of ‘some as esteri?cation of the alcoholic 'hydroxyl groups by the polyhydric alcohol esters of inixtures‘of Diphenolic'Acid natural resin acids. For the most part, however, the more 70 and-natural resin acid esters. These reactions are in all reactive alcoholic hydroxyl groups of the‘ polyhydric ale cases ‘carried out in vessels provided with a thermometer, 'cohols tend-to-esterify to a greater extent than the phenol- a mechanical agitator, and a condenser attached through '10 hydroxyl groups. These compositions are valuable in a water trap. Inert gas was bubbled through the reac form'ulating useful products ‘in the coatings, molding, tion mixtures throughout esteri?cation so as to remove and adhesive ?eld. “ ‘ l :75 water formed in the esteri?cation. ' 2,907,738 ‘5 6 ‘ Example I one composition useful in the manufacture of protective . A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl) coatings; It will be understood, of course, that the phen~ pentanoic acid, 330 parts of a ‘commercial “grade of rosin olic hydroxyl groups of themixed esters may be reacted having an acid value of 160, “and, _51 parts of glycerol with other materials‘such as‘ epoxides ‘or other acids, to was esteri?ed to an acid value of 16.2 to yield a hard, give various other ‘reaction products. These products resinous product having asoftening point of 95° C. The generally‘ possess ‘the “hardness and ,gloss characteristic softening points as used therein were obtained by Dur of natural resin esters and show other exceptional prop rans’ Mercury Method (Journal of Oil and Colour Chem erties such as ?exibility, chemical resistancaetc. ists Association, 12, 173-175 ‘[1929] ). Example VII Example 11 A mixture of 100 parts of the resinous product of A mixture of 143 parts of 4,4-bis(4-hydroxyphen Example I, 21 parts of 38% aqueous formaldehyde, .063 yl)pentanoic acid, 165 parts of commercial rosin, and part of oxalic acid and 17 parts of xylol was heated with 34 parts of ethylene ‘glycol was esteri?ed to an acid value continuous agitation for a period of 1 hour and 30 15 of 7 yielding a product having a softening point of 81° C. minutes at 95 ° C., after which the water layer was re moved by decantation. The organic resin layer was Example III heated with agitation to 105° C. at a reduced pressure In a reaction vessel provided with a mechanical agita ‘of around 30-40 mm. in order to remove the last traces of water. tor was placed 452 parts of bis(4-hydroxyphenyl)iso 20 propylidene dissolved in 1500 parts of water containing A mixture of 10 parts of this formaldehyde reaction 82 parts of sodium hydroxide. The temperature of the product and 10 parts of linseed oil was heated with agi continuously agitated solution was raised to 60° C. and tation for 30 minutes at 240-280° C. at which point 10 93 parts of epichlorohydrin was added slowly at 60-65 ° parts of China-wood oil was added and agitation con C. After addition of the epichlorohydrin was complete, tinued until the mixture had cooled to 228° C., and this the temperature was gradually raised to 95° C. and held temperature held for 15 minutes. This product was dis at this temperature for a period of 1 hour. A solution solved to 50% nonvolatile content in a solvent composed ' of 82 parts of sodium hydroxide dissolved in 500 cc. of of equal weights of xylol and a high boiling naphtha water was added, lowering the temperature to 73° C. at (boiling range 145-225° C. and an aniline point of 60° which point 161 parts of ethylene chlorohydrin was added 30 C. to a viscosity of A-3 Gardner-Holdt bubble viscom slowly over a period of 28 minutes. After all of the eter). This varnish was treated with 03% cobalt naph ethylene chlorohydrin had been added, the temperature thenate drier and 3% lead naphthenate drier based on ' was gradually raised to 95° C. and held for 1 hour. The nonvolatile content, to give a product which, when spread unreacted caustic was neutralized by adding 100 parts of in .002" wet ?lm thickness and air-dried overnight, gave 37% aqueous HCl and the product was washed several 35 a ?exible ?lm which withstood boiling water for a period times with hot water to remove the salt and excess HC]. of 1 hour. The product was ?nally dried by heating with agitation Example VIII giving 558 parts of a product having a softening point of 56° C. Replacing the resinous product of Example I with the resinous product of Example II in the reaction with for To the 558 parts of this polymeric polyhydric alcohol 40 maldehyde, and ?nal cooking with the drying oils, as in was added 360 parts of 4,4-bis(4-hydroxyphenyl)penta Example VII, gave a product which formed ?exible noic acid and 415 parts of a commercial grade of rosin air-dried ?lms which withstood boiling water for a period having an acid value of 160, and the resulting mixture of 1 hour. esteri?ed to an acid value of 6.4. The product had a softening point of 102° C. The mixed esters of this invention may be modi?ed to 45 some extent by incorporating with the esters other con Example IV stituents. These constituents maybe inert constituents such as ?llers, pigments, or certain plasticizers, or they A mixture of 143 parts of 4,4-bis(4-hydroxyphen may contain functional groups and enter into the esteri yl)pentanoic acid, 165 parts of commercial rosin, and 37 ?cation of the polyhydric alcohols with natural resin acids parts of pentaerythritol was esteri?ed to an acid value of 50 and hydroxyaryl-substituted acids so as to be chemically 7.5 to yield a product having a melting point of 126° C. carried by the mixed esters of this invention. It should be appreciated that while there are above Example V disclosed only a limited number of embodiments of this A mixture of 86 parts of 4,4-bis(4-hydroxyphenyl)pen invention, it is not intended to be restricted thereto, and tanoic acid, 101 parts of commercial rosin, and 174 55 that it is intended to cover all modi?cations of the in~ parts of Epon 1004 was esteri?ed to an acid value of vention which would be apparent to one skilled in the 12 giving a product having a softening point of 149° C. art and that come within the scope of the appended Epon 1004 is a resinous polyhydric alcohol containing claims. some epoxide and prepared from epichlorohydrin and It is claimed and desired to‘ secure by Letters Patent: bis(4-hydroxyphenyl)isopropylidene. Epon 1004 has a 60 1. A new composition of matter comprising the mixed softening point of 95-105° C. and an epoxide equivalent ester of a fusible polyhydric alcohol, a natural resin acid, weight of 870-1025 as speci?ed by its manufacturer, the and a pentanoic acid consisting essentially of 4,4 bis(4 Shell Chemical Corporation. hydroxyaryl) pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from sub Example VI 65 stituents other than alkyl groups of from 1-5 carbon atoms. A mixture of 174 parts of Epon 1004 ‘and 7101 parts of 2. The composition of claim 1 where the pentanoic commercial rosin was esteri?ed to an acid value of 19 acid consists essentially of 4,4 bis(4-hy~droxyaryl)pen at which point 86 parts of 4,4-bis(4-hydroxyphenyl)pen tanoic acid wherein the hydroxyaryl radical is a hydroxy tanoic acid was added and esteri?cation continued until 70 phenyl radical and is free from substituents other than an acid value of 139 was reached, giving a product hav alkyl groups of one carbon atom. ing a softening point of 131° C. I 3. The composition of claim 1 wherein the pentanoic The remaining examples illustrate the preparation of acid is 4,4 bis(4-hydroxyphenyl)pentanoic- acid. more complex products by the reaction of the mixed esters 4. The composition of claim 3 wherein the natural of this invention with formaldehyde, to produce a resin 75 resin acid is rosin. 5 2,907,738

. 5. The composition "of clai1n~§ whefe'in' the natui‘al 8. The composition of claim 3 'wherein the polyhydric alcohol 'is ethylene glycol. ’ '4 resin vacid. is abietic acid? _ 7 Q _ V ' v A 6. The composition-ofclaimj wherein the polyhydiiic v9-. The coinp'ositionbf ~clgirn 3 wherein the polyhydric alcohol is a polyglycidyl étheriofv a member of the group alcohol is péntaerythritbl; I ~ consisting ‘of polyhydrlic phenols and polyhydric alcohols. , 7. The composition of claim. 3-vwherein-the polyhydric 7 No references ‘cited. alcohol is.g1'ycei'~ol. . _' ' UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION ‘ Patent No. 2,907,738 Sylvan 0. Greenlee October 6, I959 It is hereby certified that err Patentof the shouldabove numbered patent requiri or appears in the-printed specification read as corrected below.ng correction and that the said Letters-

Column 2, line 52, for "neutralized" read —- neutralize -—; Acidcolumn -—; 3, lineline 68,25, forfor "d'‘"diphenolic acids" read -— Diphenolic iphenolic acid" read Signed and sealed thia 14th day of —— Diphenolic Acid ——. June 1960.

(SEAL) Attest: KARL "I1. AXLINE \ttesting Of?cer , ' CommissionerROBERT C. WATSONof Patents