Патент USA US3069383код для вставки
United States Patent ‘()?tice 3,069,373 Patented Dec. 18, 1962 2 2 3,069,373 is sometimes possible to attain the desired hydrophobic character of a conversion system by simply building up MODIFICATION OF POLYEPOXKDE CONVERSION SYSTEMS WHTH PETROLEUM RESIN-PHENOL ADDITION PRUDUCTS extremely high molecular weights, although this method is not always applicable. The other method is that ‘of building into the overall polymeric structure suf?cient hydrophobic material to repel attraction of water mole cules by the polar linkages used in polymerizing this Sylvan Owen Greeniee, 343 Laurel Drive, West Lafayette, Ind. No Drawing. Filed Mar. 21, 1960, Ser. No. 16,150 17 Claims. (Cl. 260-28) system to the insoluble, infusible state. If molecules of water can make appreciable contact with polar linkages This invention relates to phenol addition products of 10 in the conversion system, the water then acts as a solvent unsaturated petroleum resins, reactive mixtures of such for many elements of deterioration such as oxygen, alkali, - y, products with polyepoxide, and conversion products of acids, and salts which will in time destroy the organic ma such mixtures. terials. On the other hand, if the overall polymeric struc While chemically resistant, infusible, insoluble materials ture is of such hydrophobic character that water cannot may be prepared from properly formulated polyepoxide 15 make contact with the polar groups, regardless of how conversion products, many of these formulations based on sensitive these groups might be to reaction with water or the commercial polyepoxides leave much to be desired in p , the other elements which would be solubilized by water, resistance to aqueous systems. Such weakness, for ex~ deterioration of the organic material does not occur. ample, to boiling water and other aqueous systems is often One of the desirable means of introducing the hydro exhibited by protective coatings prepared from the reac 20 phobic character to conversion systems would be that tion of commercial polyepoxide resins with polyamines of introducing hydrocarbon structure which contains rela containing active‘ hydrogen directly attached to nitrogen ' tively few polar linkages in the nature of non-carbon link or with the widely used amino-amides, such as the com ages. It is, however, often di?icult to ?nd a means of in mercial products known as “Versamids” prepared from troducing large portions of hydrocarbon structures into long chain polymerized vegetable oil acids and aliphatic ' the conversion systems due to the lack of proper func tionality being present in the hydrocarbon materials. Another di?iculty encountered in introducing the hydro phobic type hydrocarbon material into such conversion polyamines. Such systems which convert to infusible, in soluble materials through the reaction of an epoxide, group with an active hydrogen directly attached to a nitrogen of an amide or amine group result in amide or systems as the polyepoxide conversion mixtures is that of amine linkages in the tri~dimensional polymer resulting simple cases of the reaction of ethylamine with diepoxy obtaining proper miscibility of all ingredients with each other. It is accordingly a primary object of the invention to butane and acetamid with diepoxy butane, provide novel hydroxyphenylated unsaturated petroleum ' from the conversion reaction. To illustrate, consider the 35 resins effective, in admixture with polyepoxides to pro vide hydrophobic conversion systems. It is an additional object of the invention to provide a method for the preparation of novel hydroxyphenylated unsaturated petroleum resins. It is a more speci?c object of the invention to provide a method eifective to increase the degree or extent of hy droxyphenylation of unsaturated petroleum resins. It is an additional primary object of the invention to Although the foregoing formulae illustrate the reac— tions of amides and amines with polyepoxides, in com— mercial practice the amines and amino-amides are more complex in that they contain a large number of nitrogen attached hydrogen groups per molecule-the number of active hydrogens per molecule normally being at least three and usually many more than three. It is well known that the carbon-nitrogen linkage forming a part of the polymeric structure of the conversion products is one of the more hydrophilic linkages and in order to give satis-' factory resistance to aqueous systems the overall polymer provide a highly hydrophobic polyepoxide conversion system. It is a further important object of the invention, to provide a reactive mixture of polyepoxides with phenol addition products of petroleum resins which are con vertible to infusible, insoluble products characterized .by excellent resistance to aqueous systems. It is an additional object of the invention to provide a polyepoxide conversion system characterized by hydro carbon structures of a type and in an amount requisite to render such systems hydrophobic. It is a more speci?c object of the invention to provide must possess su?icient hydrophobic portions to more than 55 reactive mixtures of hydroxyphenylated, petroleum resins neutralize the hydrophilic character of the carbon-nitrogen linkages. In many of the epoxide converting systems consisting of the reaction of polyepoxides with catalysts or with other active hydrogen coupling compounds, the products also lack in the requisite overall hydrophobic 60 with polyepoxides which constitute highly hydrophobic polyepoxide conversion systems characterized by physical properties requisite for application as protective coatings, character to give the desired resistance to aqueous sys_ It is an additional object of the invention to provide terns. To illustrate, the conversion products prepared by catalytic polymerization of aliphatic polyepoxides are conversion products of polyepoxide and hydroxyphenyl ated petroleum resins. impregnants, adhesives and molded objects. usually subject to some deterioration as is often exhibited It has now been found that certain resinous phenol ad by a Whitening of the surface when exposed to boiling 65 dition products of unsaturated petroleum resins possess water. It is generally known in the art that in order to prevent unusually high hydrophobic character, possess complete miscibility with commercial polyepoxide conversion sys deterioration of protective coatings, and plastic objects tems and co~react into the polyepoxide conversion sys in general which are to be exposed to the atmosphere, tems through reaction of the phenolic hydroxyl group the plastic system must be of such hydrophobic character 70 with a portion of the epoxide groups so as to give highly that water is not absorbed by the polymeric structure hydrophobic polyepoxide conversion systems possessing through attraction of one of the chemical linkages. It desirable physical characteristics required for applica 3,069,873 3 tions as protective coatings, adhesives, impregnants and molded objects. The hydroxyphenylated petroleum resins contemplated Reinhold, New York, 1947, pages 296-301. Such ma terials are thought to contain unsaturated allocyclic hy drocarbon structures which account for the fairly high degree of unsaturation. The unsaturated petroleum resi dues are essentially a by-product of petroleum re?ning, by the invention are prepared by the reaction of a phenol -. selected from the group consisting of the monohydric phenols and the dihydric phenols having at least one un substituted ortho or para portion on an aromatic nucleus are readily available at a price of 2;? to about 10¢ per pound and are offered to the market under trade names on the basis of speci?cations which are normally restrict “to which a phenolic hydroxyl group is attached with an ed to physical data and percent unsaturation. Such ma unsaturated'petroleum resin having an iodine value of from about 100 to about 500, an average molecular 10 terials vary from a heavy semi-?owing oil. consistency to high melting solids and usually are very dark in color weight of from about 250 to about 2500 and containing although some of the commercial versions now available anaverage of at least two double bonds per molecule, said material containing at least about 2.5% phenolic are of light color. 7 ' I Illustrative unsaturated petroleum residues ‘are de Vhydroxyl ‘by weight, an average of at least about 0.75 phenolic hydroxyl groups per molecule and a total phenol 15 seribed in Table I entitled “Unsaturated Petroleum I-Iy- : addition of at least about 8% by weight. Preferred hydroxyphenylated petroleum resins con drocarbon Resins.” It will be noted that the examples illustrated in the table have iodine values ranging from 119 to 475, molecular weights ranging from 300 to_690, 7, _ tain atleast about 3.5% by weight phenolic hydroxyl. ‘ Hypdroxyphenyl modi?ed petroleum resins containing 7% and ole?n double bonds per molecule ranging from 2.76 or more phenolic hydroxyl by weight are readily pre 20 to 6.37. Iodine value (or number) as used in tabulating , pared, for example, by utilization of dihydric phenols this data represents the grams of’ iodine absorbed per 100 grams ole?n._ The number of double bonds per I such as resorcinol. The hydroxyphenylated petroleum ‘ resinsvof particular signi?cance accordingly are charac molecule would then equal‘ ‘terized bya range offrom about 3.5% to about 10% by Iodine valuegx ‘mnwt weight phenolic hydroxyl. 25 ' 254X 100 TheVhydro/xyphenylated petroleum resins also pref '_erably.__contain an average of at least about 1.5 phenolic lhydroxyhgroups per molecule. 7 An appropriate range is ‘,‘from about 1.5 to about 10 phenolic hydroxyl groups per molecule. The quantity 254 is the molecular weight of iodine. :The equivalent weight to ole?n group equals 25 4 X l 00 Iodine value 30 >1(he-preferred'hydroxyphenylated resins also contain Rat‘ least about 153%, and appropriately from about 15% The limits on iodine value, molecular weight and num to about 50% total phenol addition. The hydroxyphenylated petroleum resins contemplated ;,,_by the invention may be classi?ed in two categories. A ber of double bonds per molecule as tabulatedin the 35 table are not all inclusive of the operable unsaturated .1 ‘?rst category is‘used per se to effect conversion of poly petroleum resins. Petroleum resins of somewhat higher molecular weight than those reported in the table are epoxide to infusible products. Inasmuch as the hydroxy available. The contemplated petroleum residues are characterized by iodine values within the range 'of 100 to tively low equivalent weight, resins containing only two 40 500, molecular weight Within the range of 250 to 2500 phenolic hydroxyl groups per molecule can frequently and of ole?n content amounting to at least two double _ phenylated petroleum resins are characterized by a rela .» be utilized to effect conversion of polyepoxides. Hydroxy phenylated petroleum resins preferred for polyepoxide bonds per molecule. . > conversion contain at least 2.5 phenolic hydroxyl groups In the following examples, the “Hydropolymer'-’-~oil is a low-cost, low-molecular-weight (M.W. about 300) permolecule. ethylene polymer produced as a coproduct in the manu - . .1 vHydroxyphenylated petroleum resins of the second category contain less than about two phenolic hydroxyl '' groups permolecule and hence are ineffective alone to . convert polyepoxide. Such materials do, however, co facture of ethyl chloride by the Ethyl Corporation. It is brown in color but can be distilled to give lighter frac tions. This product consists mainly [of cyclic ole?nic structures having an average of two- or more double . react to be chemically bound into converted polyepoxide 50,. bonds per molecule. A substantial portionof these 'systems' and are effective to impart hydrophobic char acter to such systems. .. .. .. The, hydroxyphenylated . . _ resins contemplated by this -' invention are fundamentally distinguishable from the I previously known materials designated as “phenolated petroleum resins” described in “Experiment 8” of Patent 7 2,319,386.- Attempts to duplicate such experiment with wthe petroleum resins contemplated by this speci?cation . for the'most part resulted in gel formation. The only ' phenolated derivatives formed were obtained in quite 60 low yields and were characterized by a hydroxyl content of less than-two percent by Weight. Such products do -- , not uniformily co-react inepoxide conversion systems, and hence fall outside the scope of this invention. The unsaturated petroleum resins contemplated for =_ use in formation of the phenol addition products em ‘ braced by the invention are know to the art. Such resins . may-be: derived from cracking petroleum and from acid 3’ polymerization of petroleum fractions. The cracking of double bonds are arranged‘in conjugated diene systems, suggesting possible uses as a polymerizable material in inks, core oils, drying oils, and surface coatings.,_ Hydro oolymer oil alone dries to a hard, non-tacky, resinous ?lm. . I TYPICAL PROPERTIES OF “HYDROPOLYMER” ‘ Flash point, ° F. OIL (Cleveland I Firepoint, ‘’ F. (Cleveland Open » natureof such unsaturated hydrocarbons is very complex, H l- . . . l 1 Cup) ___________________ _. 203-215 (95-l02° C.) API gravity at 60/60° F ____ _. 23-24 Speci?c gravity ____________ _.. 0.9l0-0.915 Iodine number (Modi?ed . Wijs) ___________________ __ 430-475 Acid number (mg. KOH/ gm. oil) ___________________ __ 1 Ash, weight percent _______ __¢ 0.005—0.0l4 petroleum-ordinarily yields gasoline which contains ap 70 Viscosity, SSU, at 100° F_____ 80-90 .preciable amounts .of polymerizable unsaturates which must be removed in order to stabilize the gasoline. The g Open Cup) _____________ _. 180-190 (82-88” C.) Non-volatile residue content, Weight percent (by ASTM method D154-43) ________ _. 55 ,widelyvariedkand not’ completely de?ned as indicated by Wakeman, The Chemistry of Commercial Plastics, 75 Englerdi'st?lation data: 13,069,373 6 The invention generally contemplates hydroXyphenyl _ _ Temperature ated petroleum resins from all the various monohydric Percent distilled and drhydric phenols. The essential feature of the phe oR 2-. - 15 o g' nohc reactant is the hydroxyl group hence the presence 5 of the other substituents on the aromatic ring structure 100 1s lmmaterial. Representative preferred phenols include phenol; the alkyl phenols such as ortho-, meta-, and para 212 ____ __ gg- ?g 40: 480 249 2% 2g? 32% 10 cresol; ortho-, meta-, and para-ethyl phenol; ortho-, meta-, 70 ' cresol; ortho-, meta-, and paraethyl phenol; ortho-, meta-, 564 and para-propyl and isopropyl phenol; ortho-, meta-, and 296 gg and para-phenyl phenol; xylenol; resorcinol; methyl re ‘382 sorcinol; alpha napthol; and beta napthol. - Hydroxyphenylated unsaturated petroleum resins are , Cracking temperature’ The PDQ 40 -s d f 1 - d 1 fl . h d carbon 2h :1 compose no polilmefnzeh o e tmc ya a5: s S r produced 1n accordance with the method of the invention 10 by addition of the phenol reactant to the ole?nrc double bonds of the resin. As indicated by the ensuing examples g} are geélerzl ybcy‘zilc m claralc er Dan '1'[ is appropriate to utilize in the reaction mixture at least ‘n Tag :23? E111 91116 b0“ 6 out Per mdo ecu 6‘ fry‘ about three equivalents of the phenol reactant per each 2131310; ddptrimaln y01 ymevazpotra ionfartlh oXiggena “tmé‘ equivalent of hydroxyphenyl in the hydroxyphenylated Co i da duona updy . mtg“? do . e oygenilrg 20 petroleum resin product. Preferably from about 4 to m (211130;:l In S efJekftocfct? 1121.135) u in ar_ cull)? F2168 ' T F about 10 equivalents of the phenol reactant are so utilized. cal 0 irt‘fv 1%)f tie relied‘ 15 cm ‘Se? u ' yp ' ln'the reaction of phenols with unsaturated petroleum - Pr P T165 "1 1 P0 Ym r M Speci?c gravity of 60° F __________ -- 7 residues, it appears that the phenol is nuclear alkylated ___-9,554 _ ,_ vby addition at the ole?n group. In most cases a part of Flash (C.O.C.), deg. F _______________ __‘__-_-_ Fire (C.O.C.), deg. F ______________________ __ 195 '2‘) the phenol adds to the Ole?n bond by direct addition to 205 form a phenyl ether group. The reaction to form phenyl Viscosity, SUS/IOO deg. F _____ _.__-__ ________ __ Viscosity, SUS/ZlO deg. F __________________ __ Pour point, deg. F _________________________ -_ Bromine number __________________________ .... Iodine number ____________________________ __ Solids content (ASTM D154-43), percent ____ __ Initial boiling point, deg. F __________________ __ 230 44 ‘ ‘ l’ ' ether groups in conjunction with hydroxyphenylation has 'proven to be bene?cial to the characteristics of the modi -35 3,0 ?ed resins in that their miscibility with both the resinous 80 and’ the nonresinous polyepoxides is greatly enhanced 220 thereby. The enhanced miscibility through the pres 6.8 ence of the phenyl ether groups appears to introduce no 375 physical or chemical Weakness as the phenyl ether group 35 is very stable toward heat and chemical reactivity. ' l The ‘Pahalez T651118 emPIPYed 111 the eXamPIFS are unsaturated hydrocarbon resins the characteristics of a Various types of unsaturanon account for the reported iodine vahles of the petroleum resirm only a portion > of such unsaturation is receptive to phenol alkylation pursuant to the invention. To provide a more accurate 40 measure of the phenol alkylation receptivity of the var which are given below! Panarcz Panarez 220-220 ______ -_ 210-225. ____ ._ 3-210 Panarez 6.210 . 7.210 . . 1ous petroleum resins, the max1mum degree of phenol allcylation under the conditions of the invention was de termined, and the weight of each resin which adds one Speci?cations: Softening point,°F. lodmenumber'wija Color, coal tar, mac. 200-220. 140(min_)____ 1400mm ’ mole or phenol was calculated 9. Color, Gardner, max. T Mild numherymun do were denominated as the _ - :The values so derived alkylatlon equ1va]ent weight ' ‘ ‘ ‘ of each resin and are reported in the ensumg Table II. 1' ypica inspections: Softening point, ° F. 210. Iodine number .... ._ 160. Color, coal tar _____ -. 7. 223x332?“ ---- r- 10 N41 égéci?c gravi-t—y-,-éb—/. 9.09. . N11. Trace Trace Trace Petroleum resin Qic?n t1 Alkj'lation eqmvalcn panapol 3E ________________________________ ‘_ . Sapom?catron num- heft-sh 50 Log-L Pounds/gallon at 60° - Table II rppaaaa'fngta' CleandeinhIn” cm‘r'grt" Clear,‘ dark inspection. yellow. amber. brown. 100 eqmmlcnt 125 Panarcz 8-210. 113 330 Panarez 6_21D_ _ _ 17;, 240 12g 5 253 A 55 gem“ 121F528“ “‘ Ydmmlymeml -------------------------- -- 1Weight of resin per ole?nic double bond as determined from the iodine value of the resin. Table I UNSA’I‘URATED PETROLEUM HYDROCARBON RESINS Calcu Petroleum residue and supplier Percent non- Iodine value on nonvolatile Soft. pt. or vise. volatile Velsicol Ell-52S (Velsicol Chemical Corporation) ____ -- 200 300-400 2. 76 Vclsicol M-144 (Vclsicoi Chemical Corporation). 87. 5 5.0 poises, 9 parts to 1 in toluene... . 170 300-400 2. 34 55 68 0.5 poise ________________________ .. 1.32 poi‘ s_.__ _ _ 430-475 2‘20 Panapol 3E (Amoco Chemical Corporation). 83 148 poiscs. 3.0 pulses at 9 parts to 1 of toluene. . 253 590-600 6. 37 31.6 poises .............................. .123.2 poises ...................... .. 93-105 C (ASTM D36-26) ........ -99-107 0 (ASTM D36-26) ...... _. 93-105 0 (ASTM D36-26) ...... .. 119 19% 220 145 160 590-690 590-090 690 590 670 3.00 4. 88 6.10 3.36 4. 20 CTLA polymer (Enjay Company Incorporated) .... _. 95 81 100 100 100 94 75-80 0 (ball and ring) ________________________ .- range lated average double bonds per mol Hvdropolymer oil (Ethyl Corporation) ...... -_ PDQ-40 (Sun Oil Company) __________ _. Panapol 5C (Amoco Chemical Corporation). Panapol 5D (Amoco Chemical Corporation)... Panarez 3-210 (Amoco Chemical Corporation). Panarez 6-210 (Amoco Chemical Corporation). Panarez 7-210 (Amoco Chemical Corporation)... 100 Molecular weight . . . _ 3.5 poises, 0 parts to l in toluene ............... -. ‘.300 5. 34 ____________________ .. 240 .................... ._ 3,069,373 7 8 phenol per each mol to be added as a hydroxyphenyl group are employed. An examination of infra-red ab A salient feature of the process of the invention re sides in the discovery that the relative degree of hydroxy sorption data on the B133 catalyzed products shows that ~phenylation is a function of the phenol concentration in the hydroxyphenyl groups contain both ortho- and para the reaction mixture. The alkylation of phenol with substituted structures. Panapol 3E in the presence of boron tri?uoride is di Aluminum chloride, iron chloride and antimony chlo* verted predominantly to hydroxyphenylation as the pro ride are comparable in activity with boron trifluoride and portion of phenol in the reaction mixture is increased are employed in a similar manner to give comparable above about two mols per alkylation equivalent of the results. Maximum hydroxyphenylation is achieved when resin. about four mols of phenol per alkylation equivalent of 10 Aluminum phenoxide has also ‘been found‘to ‘be an vex cellent catalyst for the hydroxyphenylation of unsaturated resin is utilized. This is representative of a phenomenon petroleum residues. The aluminum phenoxide catalyst which generally characterizes the phenol alkylation re desirably is formed by adding aluminum turnings or foil actions of the invention as the speci?c phenol and resin to the phenol to be used in the reaction, and heating with reactants and catalysts are varied. Accordingly one as agitation at 150° C. to 250° C., depending on the par pect of ‘the invention contemplates utilization of at least ticular phenol employed, until all of the aluminum is dis about twice the amount of phenol theoretically required solved. Desirably, aluminum is employed in an amount by the alkylation equivalent of the resin reactant to ef between 0.1% and 5% by weight of the unsaturated pe fect predominantly hydroxyphenylation. troleum residue. Reactions employing an aluminum Catalysts which may be employed in accordance with phenoxide catalyst desirably are carried out in the tem the invention in the production of hydroxyphenylated 20 perature range of 50° C. to 300° C., depending on the petroleum resins include Lewis acid type catalysts such as combination of residue, phenol and catalyst used, the de boron tri?uoride, aluminum chloride, iron chloride, and sired characteristics of the ?nal product, and the de antimony chloride and also aluminum phenoxide and the composition temperature of the organic components of various aluminum alkoxides such as aluminum methox the reaction mixture. Where ‘the presence of'the small amounts of aluminum compounds are not harmful to a product in which the hydroxyphenylated material is to ‘be used, no puri?ca ide, aluminum ethoxide, aluminum propoxide, aluminum .isopropoxide and the like. Conversion of such alkoxides ‘to the phenoxide is likely as an excess of the more acidic phenol is present in the reaction mixtures contemplated. Boron trifluoride, aluminum chloride, and aluminum phenoxide are the preferred catalysts. Of the Lewis acid type catalysts, boron tri?uoride has 30 been found to be particularly convenient. Boron tri?uo ride can be utilized in relatively small amounts either as ‘the gas or one of the liquid adduc'ts such as the ether vadduct or the phenol adduct. Regardless of which fonn is used, the boron tri?uoride would likely form the ad dition product with phenol in the reaction mixture. When boron tri?uoride is present in the ‘reaction mixture tion of the reaction product is required. If desired, the catalytic activity may be stopped by neutralizing the aluminum phenoxide with an acid such as a mineral acid ‘or acetic acid. The aluminum may be conveniently re moved by washing the product (usually solvent solution) with hot water, and adding a sufficient quantity of neu tralizing acid to convert the aluminum to a water soluble salt. As with ‘the phenol addition products prepared in the presence of BB,» catalyst, the volatile materials in cluding unreacted phenol conveniently may be removed by distillation under reduced pressure while heating the in ‘catalytic quantities. it is sometimes convenient to carry pot residual product to keep it su?iciently liquid to facili out the phenol addition reaction in the presence of an 40 tate agitation throughout the stripping process. "organic vsolvent such as toluene, xylene, or dichlorodiethyl An examination of infra red absorption data on the ether; however, if the polymer is su?iciently low in vis cosity a ‘solvent is not required. The boron triliuoride “catalyst may be conveniently removed at the end of the reaction period by adding water to the reaction mixture. The water apparently hydrolyzes the boron tri?uoride thereby terminating its activity. The hydrolyzed boron tri?uoride may then be removed by washing the product with hot water. The washing process is also facilitated by having the polymeric reaction mixture dissolved in an . organic solvent. In certain preparations it has been found advantageous to merely add a small amount of water to the reaction mixture at the end of the reaction period, mix thoroughly with ‘heating and stirring, and ?nally remove the water by distillation along with the unreacted phenol and the organic solvent if a solvent has been used. In the preparation of the phenol addition products using boron tri?uoride catalyst, it has been found de sirable to carry out the reaction of the unsaturated pe troleum resin with the phenol in the temperature range of about 25° C. to 300° 0., preferably about 50° C. to about 200° C. The temperature and reaction time varies with the particular combination of phenol and unsatu rated petroleum resin used as well as the ?nal properties desired in the phenol addition product. In general, it has been found that best results are ob tained when boron trifluoride is employed in a quantity of at least 0.5% by weight of the unsaturated polymer employed. Excellent results are obtained when boron tri fluoride is used in quantities of 0.5% to 5% by weight of the unsaturated polymer. aluminum phenoxide catalyzed products establishes that the hydroxyphenyl groups comprise both ortho and para alkylation materials with a predominance of the ortho structure. As with the BE», catalyst the aluminum phen oxide catalyst gives a good balance between hydroxy phenylation and phenyl ether formation, thus enhancing miscibility with hydrocarbon solvents and polyepoxides, and good reactivity with the e'po'xide groups. The hydroxyphenylated petroleum resins useful in the invention frequently demonstrate molecular weights and melting or softening points which are substantially higher than might be anticipated from the basic reactions con templated. Some reactions which account for such vari ations as well as hydroxyphenyl content of the ?nal phenol addition products are -'(a) the polymerization of the ole?n double bond in the presence of a catalyst for alkylation and (b) the reaction of one phenol molecule with two double bonds of the unsaturated petroleum The phenol might, for example, form some di alkylation product as well as the monoalltylatio-n ma terial and thus unite two molecules of the petroleum 60 resin. resin thereby doubling the molecular weight as calculated without considering such side reaction. The side reaction of ole?n polymerization in the presence of the alkylation catalyst would result in increasing the molecular weight of the ?nal product. Since phenyl ether formation is possible with the contemplated catalyst, an etheri?cation of phenol groups already attached to the unsaturated pe troleum residue through hydroxyphenylation may occur. Such reaction would also contribute to an increase in mo— lecular weight. The detailed procedure followed in preparing the phe When employing boron tri?uoride catalyst, optimum nol addition products of the petroleum residues using results are obtained when a stoichiometric excess of phenolis present. Desirably, as much as 2 to 3 mols of 75 BFa catalyst as reported in Table Ill is ‘given as follows: 3,069,373 10 The phenol dissolved in the indicated solvent (if sol to the speci?ed reaction temperature. With all washed vent is used) and the BF3 ether catalyst are placed into a batches, suf?cient acid is added to convert the aluminum 3-neck ?ask provided with a thermometer, a mechanical to a water soluble salt. In cases where the batches are not agitator, a one-liter dropping funnel, an electrical heating washed, the aluminum may remain as the phenoxide or it mantle and a pan of tap water to be used for cooling the may be neutralized with an acid such as acetic acid so that reaction if necessary. The reaction mixture is raised to the aluminum would remain in the product as aluminum the indicated reaction temperature, and addition of the acetate. unsaturated petroleum residue dissolved in the indicated Illustrative preparations of the phenol addition prod solvent (if a solvent is used) was begun. The addition of ucts of unsaturated petroleum resins in accordance with the unsaturated petroleum residue is at such rate that the 10 the foregoing procedures are described in Table III en' temperature does not rise above the desired reaction tem titled “Preparation of Hydroxyphenylated Petroleum perature from exothermic reaction heat. This addition is Resins” under Examples 1 through 27. normally carried out over a period of 10-30 minutes ap The hydroxyl content of the products identi?ed in plying heat if necessary or cooling the ?ask externally Table III was determined by reaction with acetyl chloride with a pan of tap water if required to hold the reaction and titrating with alkali. An acetyl chloride-toluene solu temperature. \At the end of the reaction period, toluene tion was prepared by mixing 1.5 mols acetyl chloride with or xylene in an amount approximately equal to the weight dry toluene to make one liter of solution. Into a 250 ml. of the reaction mixture is added slowly through the con iodine ?ask was pipetted 10 ml. of the acetyl chloride denser. In case solvent has been used in the reaction mix toluene reagent and the ?ask chilled in ice water followed ture then this solvent takes the place of a part or all of the 20 by the addition of 2 ml. of pyridine. The ?ask was solvent required in the washing operation. The solvent tightly stoppered and shaken to form a paste. Add the solution cooled to below 90° C. is then washed with water sample as a 50% solution in toluene in such quantity that by heating with continuous agitation for 10—l5 minutes at there remains in excess 0.5 mol of acetyl chloride for 80° C. and allowed to separate into Water and organic . each mol reacted. Gently heat the ?ask for 20 minutes layers. In case layering is not satisfactory because of 25 in a water bath held at about 60° C. When ?rst placing emulsi?cation, 20-50 ml. of acetic acid are added to the the ?ask in the bath, momentarily remove the stopper to wash. The water layer is removed and the washing with expel any pressure and reseat ?rmly. Shake the ?ask 80° C. tap water repeated two more times. In some cases 100 ml. of water are added to hydrolyze the B133 as a several times during the heating period. Remove from replacement for the three washings. The ?ask is then pro the water bath and chill in ice water. Add 25 ml. of dis tilled water and shake well. Add a few drops of phenol vided with a salt-ice-bath cooled receiver and the mixture phthalein indicator and titrate with 0.5 N methanolic heated with rapid agitation until the pot temperature KOH. reaches 150~l60° C. at which point the pressure is re duced to 15-20 mm. of mercury by using a water pump. The batch is held about 15 minutes at this pressure keep ing the pot temperature at ISO-250° C. depending on the are made for any free acidity of the sample and any al coholic hydroxyl content of the basic polyene used in A blank is run in a similar manner. Corrections preparation of the hydroxyphenylated composition. softening point of the ?nal product (softening points as used throughout this description are determined by Dur ran’s Mercury Method, Journal of Oil and Colour Chem ists’ Association, 12, 173-5 ). In order to keep 40 Percent OH the hydroxyphenylated petroleum residues sufficiently from the percent hydroxyl and as tabulated refers to the’ percent hydroxyphenyl or hydroxycresyl depending on the ?uid for good agitation, the pot temperature at this stage is maintained at an estimated 50° C. above the softening __ml. for blank——rnl. for sampleX N of KOH><17X100 grams of sampleX 100 The percent hydroxyphenyl (--¢OH) was calculated point of the ?nal product. The receiving ?ask is then con speci?c phenol used. The percent by Weight addition of phenol minus that nected to a vacuum pump and the pressure reduced to 1-5 added as hydroxyphenyl is represented as phenyl ether mm. of mercury holding this pressure for 10-15 minutes, (¢O--), speci?c to the phenol used as with the hydroxy holding the pot temperature of the constantly agitated phenyl value. The calculated minimum molecular weight represents product at a temperature estimated to be 50° C. above the softening point. The product is poured into a suit able container and allowed to cool. 50 a minimum as it did not take into consideration side re The general procedure used in preparing the phenol addition products of the unsaturated petroleum resins using aluminum phenoxide catalyst as reported in Table III differs from the above procedure for BF3 preparation actions which tend to increase molecular weights, but merely took into consideration the percent by weight added phenol to the original average molecular weight reported by the supplier on the unsaturated petroleum residue. as follows: The aluminum foil or turnings are dissolved in the phe nol at a temperature of 150-250" C. as necessary for the speci?c phenol after which the pot temperature is adjusted The calculated minimum number of phenolic hydroxyl groups per molecule is based on the analytically deter mined hydroxyl content. and the calculated minimum molecular weight. Table III PREPARATION OF HYDROXY PHENYLA’I‘ED PETROLEUM RESINS Ex. Grams phenol and ml. solvent Grams polyene and ml. solvent No. Mols phenol] Catalyst/100 g. eq. polyene polyene Hours at; ° C. Grams product 750 o-crcsol ____________________ _195 o-crcsol _________ -_ 500 (N.V.) Panapol 3E __________ _. 125 (N.V.) Panapol 313.. 1.39 1. 45 1.00 g. A1____ 1.04 g. A1,..- 645; o-crcsol, 525 xylen 365 (N .V.) Panapol 3E__ 1. 65 3.42 ml. BFg-ether... 2.5 at 100-1 230 (N.V ) PDQ-40 _____ __ 5.0 2.17 g. Al __________ __ 212 (N.V.) CTLA polymer 5.0 2.36 g. A] _______________ __ o ________ __ 293 1. 36 1,080 o-cresol _______ __ _____do ___________ __ 564 phenol, 525 xvle 365 (N.V.) Panapol 3E_. _ . 3 at 2 at; 250 ___ 3 at 190-195... 850 213 576 293 3.40 ml. BEE-ether"- 2.5 at 100-105-.. 560 415 (NlVJ Panapol 3E 2. 58 1.20 g. A1 __________ __ 1.5 at 180-185.._ 250 (N.V.) Panapol 3E _.___do _______________ __ 4. 25 4. 25 3.2 g. Al __________ .- 3 at 250 __________________ __ 10.0 ml. BFa-ether... ] at 100-105, 2at 120-125 __ 671 372 403 200 (N.V.) Panapol 31]-. _ 226 Panarez 3-210 ________________ __ 28" phenol _____________________ .. 439 Velsicol EL 528, 337 aromatic 10.00 1.0 0.87 105 __________ __ 355 8.85 ml. BEE-ether"- lat 100-105, 2at120~125 0.68 g. A1 __________ __ 1 at 12.5 ml. BITE-ether... 6 at 28c 53 1. 11 Table Ill-Continued PREPARATION OF HYDROXY PHENYLATED PETROLEUM RESINS—Continued Mols phenol] Er. Grams phenol and ml. solvent Grams polycne and mi. solvent 13..... 188 phenol _____________________ __ 254 Velsicol E1. 528 ______________ .. 226 Panarez 3—2l0.__ No. Catalyst/100 g. Hours at ° C. 1.0 7.37 ml. BEE-ether... 1 513100-105, 2 at 120-125.... 325 1.5 13.3 rrl. BFgethbr... .....do ___________________ __ 290 5. 0 17.7 ml. Bits-ether.. 1. 73 3.42 rrl. Blkether.. eq. polyene polyene Grams product DD solvent 13.1’. 171-278. . ‘ - . . ._.- do __________________________ .. . 439 Velsieol EL 528, 525 xylene..-254 Velsicol EL 528 ______________ .. .-.-.d0 _ 1,880 phenol __________________ __ ____ do __________________________ _. 2. 5 11.8 ml. B'Fg-ether ._ 5.0 15.75 rrl. BF3-ether._ 10. 0 19.7 Irl. BIB-ether.. 20..-.. 250 resorcinol, 250 dichlorodi~ 250 Velsicol M—144 ______________ -. 21..-.. 250 Panarez 6-210 __________________________ .. 2.0 g. Al __________ -. 262 (N.V.) Penapol 5D __________ .. 9.52 ml. BFa-etller... ethyl ether. 500 p,t-butyl-phenol ___________ .- 22..... 614 biS(4-hydroxyphenyl) di- 1. 36 2.84 4.0 m1. BFa-ether__-. methyl methane, 600 dichloro diethyl ether. 23.._-. 50 phenol, 150 toluene _________ __ 200 0.27 11 g. .4101; ........ .. 0.37 at 10-26, 0.20 at 26-47, ........ . 24..... 188 phenol, 150 toluene ________ __ 50 (N.V.) Pcnapol 3E, 150 toluene. (N.V.) Penapol 313, 150 4.0 266 25....- 188 phenol, 200 toluene ________ .. 63.5 Velsicol EL 528, 100 toluene..- 4.0 209 g. AlClz ....... .. 2.5 at 100-105 ____________ .. 84 26....- 330 resorciuol __________________ _. 212 (N.V.) CTLA polymer ______ .. 3.0 4.5 m1. BFa-etl‘er__._ l at 100-105, 2 at 120-125... 276 27 ........ -_do._.-.. ................... _- 3.0 3.811111. BFs-ether..- ----.<1o ............................. .. toluene. 0.37 at 47~72 261 (N.V.) Penapol 5D .......... -_ Percent by Ex. No. Percent weight Soft pt. phenol vise. added and/or 41. 2 (35. 8) 41. 3 (36. 0) v102 92 36. 6 21.5 30. 4 34. 8 38. 2 32. 8 38.0 43. 7 18.6 17. 2 21.8 22. 1 22. 3 19. 3 24. 4 26. 4 27. 6 12. 0 28. 4 89 80 85 101 106 104 119 121 176 58 141 168 164 113 131 127 122 100 130 Acid value 0. 6 0. 4 0. 6 2. 0 2. 0 0 0.16 0. 2 0. 2 1. 8 3.1 1. 1 1. 5 5. 0 6. 2 0. 9 1.8 3. 1 6. 5 1. 4 0. 7 2. 4 Eq. phenol . Percent Percent weight addition prep/eq. addition as 011 as ——¢OH as ¢0— as —-¢OH phenol in as ¢O-— 3. 9 4.1 4. 9 21.1 3. 66 3. 5 3. 6 2. 76 weight 28. 2 (20.2) 22. 2 (19. 3) 18. 0 19. 1 56. 4 53. 5 3. 4 3. 78 4. 34 5.05 3. 2 3. 1 22. 8 17. 5 21. 7 14.3 19. 3 23.8 28. 2 27.0 12. 8 10. 5 18.9 16. 0 17. 6 18. 7 20.8 23. 9 27. 8 10.3 27. 4 15. 8 4. 0 8. 7 20. 5 21.0 9. 0 9.8 16. 7 5.8 6. 7 2. 9 6. 1 4. 7 0.6 3. 6 2.5 0 1. 7 1. 0 62. 2 81. 5 70.8 41.0 48.0 72.6 74. 2 61. 9 68. 8 61.0 86. 6 72. 3 79.0 96. 7 85.3 90. 5 100. 0 85. 5 96. 5 4.60 30. 8 3. 42 2. 6 3. 51 4. 16 5.09 4. 91 2. 33 1. 9 3. 43 3. 90 3. 19 used in ‘product 18. 8 7. 1 8. 1 11. 3 8.8 19. 7 5.0 5. 1 3.1 5. 1 9. 2 5. 6 6. 7 11.4 19. 3 3. 9 5. 2 83 Percent Percent weight phenol AlCls _______ .. 1 at 70-75, 2.5 at 100-105.-- phenol En. weight Min. Min. weight mol. Incl. OE/ 43. 6 405 1, 090 2.34 46. 5 37. 8 18. 5 29. 2 59. 0 52.0 27. 4 25.8 33. 1 31.2 39. 0 13. 4 27. 7 21.0 3. 3 14.7 9. 5 0 14. 5 3. 5 436 472 616 497 652 485 408 334 346 729 895 495 586 534 500 449 392 336 530 548 1, 092 1, 020 2. 2 2. 13 ..-. _._ 982 1, 035 954 1,033 1,138 849 1. 51 2.1 2. 33 3.1 3. 28 1. 16 423 0.47 448 886 S88 0. 91 1. 51 1. 66 424 463 475 483 392 823 0. 85 1.03 1. 21 1. 44 0.74 1. 5 370 3. 1 1.9 10.6 0.44 1. 34 4.84 3. 87 26.7 21. 4 .............................................. .. 13.1 3.0 67 2 87. 5 8v 5 10. 4 32. 8 12.5 6. 6‘ 6. 66 21.5 1. 8 92. 6 5. 6 7. 4 2. 6 7. 83 25.3 885 351 439 .................. .. 1,065 463 3.0 1. 1 255 .................. . 217 1 Run in pressure autoclave. The invention generally contemplates mixtures in all quantity of polyepoxide used is su?icient to react with the phenolic hydroxyl groups of the modi?ed petroleum resi relative proportions of phenol addition products of un saturated petroleum resins with all resinous and nonresin 50 due, thus giving a chemically integrated conversion prod uct. In systems using catalysts such as tertiary amines to ous polyepoxides. Conversion systems containing from convert the polyepoxide, the quantity of polyepoxide used about 1 to about 99% by weight of phenol addition prod is su?icient to react with the phenolic hydroxyl groups uct and from about 99 to about 1% by weight of poly of the modi?ed petroleum residue and in addition self epoxide are speci?cally contemplated. Preferred propor tions are from about 5 to about 75 percent by weight of polymerize to give. an infusible, insoluble product. Poly epoxides possess a very wide variation in epoXide equiv phenol addition product and from about 25 to about 95 alent weight ranging from 43 for the simplest diepoxide percent by weight of polyepoxide. (diepoxybutane) to equivalent weights of several thous More speci?cally, the parts by weight of the hydroxy and. As observed from the table entitled “Preparation of phenylated-phenyletherated petroleum residues and parts by weight of polyepoxide may be varied widely depend Hydroxyphenylated Petroleum Residues,” there is con siderable variation in the functionality of these modi?ed ing on the particular modi?ed petroleum residue, on the speci?c polyepoxide, on the type of catalyst or type of petroleum residues. It will, then, be understood, from the Wide variation in functionality of the polyepoxides and active hydrogen coupler used to convert the polyepoxide and the degree of hydrophobic character desired for the also of the modi?ed petroleum residues, that by proper speci?c application. In the case where the polyepoxide choice of the reactive ingredients. to give the desired in conversion system consists of a polyepoxide and an active fusible, insoluble product wide variations in reaction por hydrogen coupler such as an amino or amino-amide com pound, the polyepoxide would be used in suf?cient quan tity to furnish epoxide groups beyond those required to tions are operable. Illustrative of the epoxide compositions which may be . employed in this invention are the complexepoxide resins react with the active hydrogen on the amino or amino~ 70 which are polyether derivatives of polyhydric phenols amide coupling compound so as to furnish free epoxide with such polyfunctional materials as polyhalohydrins, groups to react with the phenolic hydroxyl groups of the polyepoxides, or epihalohydrins to form polymeric, poly modi?ed petroleum residue, thus giving a chemically inte hydric alcohols having alternating aliphatic chains and grated conversion'product. In systems using catalysts aromatic nuclei connected to each other by ether linkages. such as tertiary amines to convert the polyepoxide, the 75 Typical of these complex epoxide resins are the reaction 3,069,373 "13 "products of bis(4-hydroxyphenyl) dimethyl methane (bis 14 A commercial product of this type is Epon 812 having an equivalent Weight to epoxide of approximately 150 and phenol A) with excess ‘molar ,portions of epichlorohydrin. (In; ' (n + 1) marketed by the Shell Ch?l'llillfll Corporation. The prep on aration of a large number of these mixed polyepoxides is described more fully in Zech’s US. Patent 2,581,464._ ‘ ' / Epoxidized polyole?ns such as epoxidized polybutadi a'lkal' 0+ (72 + aoronionxbnz -——1> enes described in 2,826,556; 2,829,131 and 2,829,135 was prise an additional family of aliphatic epoxides useful in the invention. Still other aliphatic polyepoxides which have been found 10 ffCH3' CH3 0 to be valuable in reaction with the resinous polyhydric O F I 0 H2011 H————(l) - (?CH2CHOHCHz_-0 /\ O CHzGHCH: phenols in producing the cured products of this invention include diepoxybutane, diglycidyl ether, limonene diepox ide, and diepoxydicyclopentadiene. Catalysts which are active in inducing the epoxide 15 groups of the polyepoxides to react with the phenolic hy droxyls of the hydroxyphenylated, phenyletherated poly mers include alkaline materials such as sodium phen oxide and organic amines as well as certain acid-type cata 20 lysts such as the mineral acids, boron tri?uoride, alumi num chloride, and zinc chloride. Preferable catalysts, As used in the above‘ formula, n indicates the degree of however, are the alkaline types such as the tertiary amines polymerization and may have the value of 001' a' whole which tend to favor the reaction of the epoxide group with number. Typical-of‘these complex epoxide resins are phenolic hydroxyl groups as compared to the reaction of those marketed by the Shell Chemical Corporation under epoxide group with alcoholic hydroxyl groups, and the the trade names of Epon 828, Epon 836, Epon 1001, 25 use of these tertiary amines in catalytic quantities induces Epon 1004, Epon 1007, Epon 1009 and Epon 1031. " negligible Weaknesses towards water, alkali, and chemical Another group of resinous polyepoxides useful in re resistance as a result of the presence of the amine. action with the hydroxyphenylated polymers are the gly Generally, it is desirable to employ a conversion tem cidyl ethers'of phenol formaldehyde condensates. perature of between about 100 and 250° C. The epoxide compositions which may be used in pre 30 Table IV, entitled ‘*Polyepoxide Conversion of Hy paring the compositions of this invention also include droxyphenylated Petroleum Residues,” describes the prep aliphatic polyepoxides which may be illustrated by such aration of some protective coating ?lms from reaction mix polyepoxides as the polymerization products obtained by tures containing the hydroxyphenylated petroleum resi polymerizing epoxyalkyl alkenyl ethers such as allyl gly dues, a polyepoxide and an epoxide converting agent of cidyl ether through the unsaturated portions to give the the catalytic or active hydrogen coupling type. Examples so-called polyallyl glycidyl ether (PAGE) having a chemi 2a,'3a, 3b, 6a, 6b, 7a, 100, 16a, 16b, and 21a describe heat cal structure corresponding closely to the following conversion of some hydroxyphenylated petroleum resi formula: v ; dues. Viscosities were measured by the Gardner bubble vis 40 cosimeter. Film hardness was measured with the Sward hardness rocker setting the value for ?at glass plate at 100. ' GL hardness-adhesion readings are in number of grams weight required to scratch the ?lm surface in one case and to completely remove the ?lm from the panel in the other case as read on the Graham-Linton hardness tester. The Graham-Linton instrument provides a means of adjusting various pressures of up to 2,000 grams on a sharp knife These products in which 11:0 to about 7 are available in experimental quantities from the Shell Chemical Corpo edge placed vertical to the ?lm surface and dragged along the surface in this position. ration. Still other aliphatic polyepoxides which may be used are factured by Gardner Laboratories, Inc. Wet ?lms of The bend tests were run using a Mandrel Set manu ‘illustrated by the poly(epoxyalkyl)ethers of polyhydric 0.003" thickness were spread on 30 gauge, bright, dry alcohols. These polyepoxides for instance, may be ob 55 ?nish, coke tin plates cut to 3 x 5 inch dimensions, cured tained by reacting a polyhydric alcohol with an epihalohy by baking as indicated in the tables and bent sharply drin followed by dehydrohalogenation. Illustrative is around a steel rod of the size indicated in the column tab I the reaction, for example, of epichlorohydrin with glycerol , ulating bend test results. in the presence of boron tri?uoride to give an intermediate Other materials and abbreviations used in the tabulated chlorohydrin which is dehydrohalogenated to give a mixed data are described as follows: 60, product represented by the following formula: _ onion 0 \ CHOH+3CH2CHCH2Cl H2011 BF, —-> CHOH | NaAlOq omoomonomol -—s I CH2CHOHCH2C1 /O\ CHgOCHtCHCH: CHOH CHzOCHaC'HCHtCl l Epon X-701: A liquid polymer of allyl glycidyl ether described as polyallyl glycidyl ether (PAGE) having an crnocmcnonctnot /\ GHnCHCHz epoxide equivalent weight of approximately 135. Epon 828: A bisphenol A-epichlorohydrin type poly vepoxide having a softening point of 8—12‘’ C., and an epoxide equivalent weight of 190-210. Asphalt: An asphalt cement of 120/ 150 penetration ob tained from Socony Mobil Oil Company, Inc. DMP30: Tris(dimethylaminomethyl) phenolmanutac 70 tured by Rohm & Haas Company. Versamid 115: A polyamide prepared by the reaction of polyethylene amines with dimerized vegetable oil acids to give a viscosity of 500—750 poises at 40° C., an amine number of 210-230 and produced by the Chemical Divi' sion of General Mills, Inc. - 3,089,373 ..I 16 Table IV POLYEPOXIDE CONVERSION OF HYDROXYPHENYLATED .P-E'I‘ROLEUMRESIDUES Rocker No. GL GL Viswsitv Composition of con- 0.003” wet hard- suriace ?lm re- verting mixture ?lm baked ness cratch moval > Bond test Color Solvents and chemicals in hours at original and ' after days (d) 1 ' 2a.... 50% in xylene, 5 0.5 hour at parts Example 2, 1 part X-701, 0.06 part DMP30. 100° C. 26 500 1,000 Well converted _____ __ A2, A1 (1d)... H5O, 24+: 50% 150° C. but brittle. H2204, 24+; 10% NaOH, 24+, 100% acet— > io acid, 24+; DMF, 24+. _ 3a____ 1 25° 0. 40% in xvlene, 4 ._.-.d0 ________________________________ __do _______ __ _ parts Example 3, 1 part Epon X-701, 0.025 part DM P80. . 3b____ 42% in xylene, 2 6a____ _.___do_____ 78 500. 900 is” ___________ __ 18 ;A2, E (1d)___ H2O, 27+; 50%. parts Example 3, E2804, 4; 10% 1 part Epon NnOH, 27+; X-701, 1 part Versamid 115. 100% acetic acid, softens. 40% in toluene, 5 ._.__do ___________________________ _. Well converted parts Example 6, 1 part Epon _ A4_ 28% NHE, 24+; acetone, softens; , toluene, softens; 100% acetic acid, softens. ___ but brittle. X-701, 0.03 parts , DMP30. , 6b____ 45% in toluene, 5 _____do_____ 50 450 900 parts Example 6, lé” ......... __.-- " " - 1%} .' A2, R (191)". HzO,~69+; 50% > i ‘I 3 parts Epon X-70], 2 parts ' " - * H2801, ‘27+; ' = ] 7a____ 51%in xvlene,-5 ’ ~ -._-.do.____ parts Example 7, ‘ > " 40 ' 500 > 1,000 ' l/é’?m, ______ -. ' ' r ' > 1 ‘gal (2d); g 1a acid‘,'5;‘ ~ ; ; . .HrO,-24+;50% 7 ~ . - X-701, 2 parts " '- ' ‘ , H2SO|,- 1; 100% 1 acetic acid, 1—; ' DMF, softens, Versamid 115, 0.08 - i part DMP30. ‘ " '7 " “ ’ 1 10a..- 55% in xylene, 3.5 parts Example 10, 0.25 hour 50 at 150° C. . M” _____ __ ' '4 ~ ' 4' ‘ parts Example 16, 1 part Epon 4,; ‘ ; 100% acetic acid, - ‘ 05 hour at 150° C. ______________________ __ but very brittle. . DMP30. , 42 500 1, 100 . , parts Example 16, . - = _A,_Z4 (1d)____ HzO,.27+; 50% ~ ' 111304, ' I l 28% NHa,'24+; -; _ acetone; softens; 10% NaOH, X-701, 2 parts . Versatnid 115, 0.07 100%‘acetic acid, ie acid, soltens. softens. . . , 64 300 1,100 1%" ........... .. 15 A1, B (1d), r E (2d). toluene, softens; 27+; 100% acet- parts DMP30. 21a..- 48% in xylene, 3 _----d0.__-parts Example 21, ‘ -‘ Wellconverted X-TOI, 0.03 parts _____do__..-_ . ' . toluene, ' 16b___ 45% in xylene, 5 ,- Y 10% NaOVH, 1.7 parts Asphaltl. 16a..- 45% in xylene, 5 ' ,HzVQ, 24+; 50% ~ 1.5 parts X-701, 2 Parts Epon 96." ’ _' _DME,-1-. 12 BFQ, (1(1),. ' ~ 3 parts Epon acetone; 120+; , ; 10% NaOH; ' toluene, softens; , 1 69+; 100%;ac,et-. 1 , 100% acetic acid, Versamid115,0.08 parts DMP30. 28%,N-H3,_120+; - _ H2O, 24+; 50+ H1504, ; 2 parts Epon 823, 10% NaOH, 1 part Versaniid M+; 100 0 115, 0.05 part acetic acid, 24+; DMP30. ‘» DMF, softens. 1 Asphalt cement of 120/150 penetration obtained from Socony Mobil Oil Company, Inc. It will be noted as illustrated by Examples 2a’ 3a, 6a phalts. Appropriate proportions are [from about 90 to and 16a that conversion products using minor portions about 10 parts by weight of asphalt or coal tar and from of polycpoxidcs of high functionality along with the modi about 10 to about 90 partsby weight of, a conversion ?cd petroleum residues tends to give brittle conversion products. This brittle character is conveniently over 50 ‘It‘will be observed from the data given on resistance come, however, by using ?exibilizing converting agents to chemicals at 100° C. that the converted products pos such as the Versamids which contribute active hydrogen scss unusually high resistance to aqueous systems. The system of the invention. for conversion of the polycpoxidc and at the same time - ' i i “ ‘ ‘Y ' " plus sign following the‘number of hours signi?es that contribute a chemically integrated ?exibilizcr. The brit there was no observable deterioration atthe end of the tlencss of the reaction products of the modi?ed petroleum 55 test, .while a minus sign indicates that the point of de residues with polyepoxidcs may also be overcome by using terioration was inde?nite but below the number given. > the proper quantity of a polyepoxide which tends to give In the formulation of products from mixtures of the ?exible system. modi?ed petroleum residues and polycpoxide conversion Excellent plasticizers for the conversion systems based systems it is often desirable to mix these ingredients with on hydroxyphcnylatcd petroleum residues and polyepox 60 other additives. Such additives may be plasticizers of a ides are asphalt and coal tar materials. An illustration of the use of asphalt is given in Example 100:. The out standing solubility of the hydroxyphcnylatcd petroleum non-reactive type or those of an active type which com bine into the system through reaction of active hydrogen groups contained therein withthe epoxidcs. The additives may also be pigments and ?llers added to give desired residues and their conversion products with asphalt is surprisingly unique and very advantageous from their 165 variations in physical properties and performance. Other economy and outstanding chemical resistance. It is gen organic resin forming materials may also be incorporated erally known that asphaltic materials have outstanding along with the mixture of modi?ed petroleum residues and polyepoxides. Typical resinous materials useful in water and aqueous chemical resistance, however, their use is normally limited to applications where soft, solvent this respect include the formaldehyde condensates of soluble, thermoplastic materials will function. As illus 70 phenols, melamine and urea, polyester resins, alkyd trated in Example 10a, such materials may now be used to give formulations capable of thcrmosctting to water and solvent resistant products. In general the invention resins, and epoxy resin esters. I claim: contemplates mixtures of the conversion systems of the , reacting a phenol selected from the group consisting of invention in varying proportions with coal tars and as 1. A hydroxyphenylated petroleum resin prepared by 175 monohydric phenols and dihydric phenols having at least 3,069,378 17 one of the ortho or para position carbon atoms unsubsti tuted on an aromatic nucleus to which a phenolic hydroxyl group is attached, with an unsaturated petroleum resin having an iodine value of from about 100 to about 500, an average molecular weight of from about 250 to about 2500 and containing an average of at least two double 18 11. A curable, resinous conversion system comprising a polyepoxide and a hydroxyphenylated petroleum resin prepared by reacting a phenol selected from the group consisting of monohydric phenols and dihydric phenols having at least one of the ortho or para position carbon atoms unsubstituted on an aromatic nucleus to which a bonds per molecule, said material containing at least about phenolic hydroxyl group is attached, with an unsaturated 2.5% phenolic hydroxyl by weight, an average of at least petroleum resin having an iodine value of from about 0.75 phenolic hydroxyl groups per molecule and a total 100 to about 500, an average molecular weight of from phenol addition of at least about 8% by weight. 10 about 250 to about 2500 and containing an average of at 2. The hydroxyphenylated petroleum resin of claim 1 least two double bonds per molecule, said material con containing at least about 3.5% by weight of phenolic taining at least about 0.75 phenolic hydroxyl groups per hydroxyl groups. molecule and a total phenol addition of at least 8% by 3. The hydroxyphenylated petroleum resin of claim 1 weight. claiming on the average about 1.5 phenolic hydroxyl 15 12. The conversion system of claim 11 containing from groups per molecule. about 5 to about 75% by weight of hydroxyphenylated 4. The hydroxyphenylated petroleum resin of claim 1 petroleum resin and from about 25 to about 95% by characterized by a phenolic hydroxyl content of from weight of polyepoxide. about 3.5 to about 10% by weight, and characterized by 13. The conversion system of claim 11 containing a a content of from about 1.5 to about 10 phenolic hydroxyl 20 material selected from the group consisting of asphalts groups per molecule. 5. A process for preparing a hydroxyphenylated pe troleum resin which comprises reacting of a phenol se and coal tars. 14. The mixture of claim 13 containing from about 10 to about 90 parts by weight of the conversion system lected from the group consisting of monohydric phenols of claim 11 and from about 90 to about 10 parts by and dihydric phenols having at least one of the ortho 25 weight or" a material selected from the group consisting or para position carbon atoms unsubstituted on an aro of asphalts and coal tars. matic nucleus to which a phenolic hydroxyl group is 15. A cured resinous material formed by the reaction attached with an unsaturated petroleum resin having an of a polyepoxide and a hydroxyphenylated petroleum iodine value of from about 100 to about 500, an average resin prepared by reacting a phenol selected from the molecular Weight of from about 250 to about 2500 and 30 group consisting of monohydric phenols and dihydric containing an average of at least two double bonds per phenols having at least one of the ortho or para position molecule, said material containing at least about 2.5% carbon atoms unsubstituted on an aromatic nucleus to phenolic hydroxyl by weight, an average of at least about which a phenolic hydroxyl group is attached, with an 0.75 phenolic hydroxyl groups per molecule and a total unsaturated petroleum resin having an iodine value of phenol addition of at least about 8% by weight. 35 from about 100 to about 500, an average- molecular 6. The process of claim 5 wherein the product is char weight of from about 250 to about 2500 and containing acterized by a phenolic hydroxyl content of from about an average of at least two double bonds per molecule, 3.5 to about 10% by weight and characterized by a con said material containing at least about 0.75 phenolic hy tent of from about 1.5 to about 10 phenolic hydroxyl droxyl groups per molecule and a total phenol addition groups per molecule. 40 of at least about 8% by weight. 7. The process of claim 5 in which the reaction is 16. The cured material of claim 15 containing a mate carired out in the presence of an acid type catalyst. rial selected from the group consisting of asphalts and 8. The process of claim 5 in which the reaction is car ried out in the presence of boron tri?uoride at a tempera coal tars. 17. The cured mixture of claim 16 containing from ture of between about 25° C. and about 300° C. 45 about 10 to about 90 parts by weight of the material 9'. The process of claim 5 carried out in the presence selected ‘from the group consisting of asphalts and coal of an aluminum phenoxide catalyst at a temperature of tars and about 90 to about 10% by weight of the poly between about 50° C. and 300 C. epoxide hydroxyphenylated petroleum resin mixture. 10. The process of claim 5 in which the phenol is pres ent in an amount at least about twice that amount theo 50 No references cited. retically required by the alkylation equivalent of the pe troleum resin.