Patented Dec. 7, 1948 2,455,873

UNITED STATES PATENT OFFICE 2,455,873 MOD FED WAK-COMPATBLE EYLENE GLYCO, ETRACOROPALA) RESNS Birger W. Nordlander and William E. Cass, Sche nectady, N. Y., assignors to General Electrie Company, a corporation of New York No Drawing. Application July 4, 1945, Serial No. 603288 8 Claims. (C. 260-22) 2 This invention relates to new and useful resin with waxes do not yield honogeneous mixtures. ous compositions and to a method of prepar Also, such reaction products are not perma ing the same. More particularly, the invention nently fusible, but tend to become insoluble and is concerned with compositions comprising the infusible on prolonged heating at an elevated resinous product of reaction of ingredients in temperature, a property that is most undesirable cluding (1) a glycol, e.g., ethylene glycol, diethyl for Our purposes. ene glycol, etc. and (2) a chlorinated compound Reaction products of various glycols and tetra selected from the class consisting of tetre chlorophthaic acid or anhydride show proved chlorophthalic acid and anhydride, said reac flane resistance as compared with similar prods tion product having incorporated therein a mod licts derived from chlorinated phthalic acid or ifying substance selected from the class consist anhydride, but are inited in usefulness by their ing of (a) fatty oils, e. g., castor oil, inseed oil, other inherent physical properties. Thus, the etc., (b) fatty acids having from 10 to 33 care reaction product of ethylene glyco and tetra bon atoms inclusive, e. g., capric acid, Stearic chlorophthalic anhydride is very brittle at room acid, castor oil fatty acids, inseed oil fatty acids, s temperature; the similar reaction product of die nelissic acid, psylic acid, et., and (e) fats and ethylene glycol also is brittle at room tempera waxes containing in free or combined state (e. g., ture or sightly below, and is sticky at slightly as esters) the fatty acids defined in (b), for in above roon temperature; and the similar reac stance tristearin, beeswax, carnauba war, etc. tion product of triethylene glycol is very sticky Compositions having marked flame resistance 20 even at room temperature. are obtained when the chosen glycol and modi When a fatty substance such as a fatty of or a fier and the proportions of the glycol, tetrachlo fatty acid is incorporated into a glycero-tetra rophthalic acid or anhydride and modifier are chlorophthalic reaction product, the resulting such that the composition contains at least 30 materia has increased wax-compatibility as per cent by weight of chlorine. The modifying 25 compared with the unmodified product. Fow substance is incorporated with the glycol and ever, because of the nature of the tri-functional chlorinated compound under heat, and at least alcohol glycerol, a relatively large amount of in part is chemically combined in the final prod mono-functional fatty oil or fatty acid must act. be added to obtain a permanently thermoplastic The resinous compositions of this invention SO or fusible end product, that is, to prevent Cross are non-toxic, permanently fusible, compatible linking under heat. This relatively large amount with waxes and have good electrical properties. of fatty oil or fatty acid results in decreased chlo They are especially suitable for use as a compo rine content of the product and unsatisfactory nent of the compositions disclosed and claimed flane resistance. in the copending application of George J. Bohrer, 35 We have discovered that resinous compositions Serial No. 603,239, fied concurrently herewith which are flame-resistant, permanently fusible, and assigned to the same assignee, as the pres compatible with Waxes so that homogeneous ent invention now Patent No. 2,443,887. mixtures can be obtained, and which have good It was known prior to our invention that tetra electrical and other desirable properties, can be chlorophthalic anhydride forms a resin upon re 40 obtained by effecting reaction under heat between action with glycerol. While such resins have in the ingredients identified in the first paragraph proved properties, specifically improved flame of this specification. Surprisingly it was found resistance, as compared with resinous reaction that, when tested on rats, the resinous composi products of glycerol and phthalic acid or anhy tions of our invention are non-toxic physiologi dride, their field of usefulness is limited due to 45 cally from contact and from ingestion, and also the lack of flexibility of both the soluble, fusible from absorption through the lungs over a pro and insoluble, infusible resins at room tempero longed period, more particularly from 4 to 8 ature. Furthermore, the glycerol-tetrachloro weeks of the vapors resulting from heating these phthalic reaction products have at the most only compositions at an elevated temperature, speci imited Wax compatibility and when compounded SO fically about 325 C. This non-toxic property 2,455,878 S. 4. was entirely unexpected and in no way could the ingredients comprises cooking the mixture for have been predicted, since it is in striking con a relatively short period of time, e. g., about 2 trast to the known toxicity of other chlorinated to 1 hour at a relatively low temperature, e. g., aromatic compounds, more particularly the about 140° to 160° C., and then increasing the chlorinated naphthalenes and chlorinated bi temperature gradually over a period of about 2 phenyls. Since the rat in many of its physiolog to 1 hour to about 200 to 210° C. The reaction ical reactions has been found closely to parallel mass is heated at this higher temperature until man, the practical significance of our discovery a resin of the desired acid number, e. g., about will be immediately apparent to those skilled in 5 to 15 (or higher or lower as may be desired) the art. r O is obtained. This usually requires a total heat We have also discovered that decarboxylation ing period of the order of 9 to 8 hours. occurs when the reaction mass is maintained at In order that those skilled in the art better temperatures of the order of 220 to 250 C. for may understand how the present invention may an appreciable period of time. (More specific in be carried into effect, the following examples are formation on the effect of temperature is given 15 given by way of illustration and not by way of below.) This decarboxylation results in prod limitation. Examples 1 to 4, inclusive, relate to ucts having lower acid numbers and saponifica the unmodified glycol-tetrachlorophthalic resin tion numbers than are obtained when the reac ous materials while the remaining examples are tion is effected by heating for a longer period at directed to the modified glycol-tetrachloro lower temperatures. phthalic reaction products, and show how their From their structures, both tetrachlorophthalic 20 properties differ from the properties of the prod acid and mono esters thereof (produced by reac ucts of Examples 1-4. All parts and percentages tion of the anhydride with an alcohol) belong to are by Weight. the class of 'sterically-hindered' aromatic acids (cf. Meyer and Sudborough, Berichte, 27, 3149 EXAMPLE 1. (1894)). Although we have found that tetra chlorophthalic acid and its mono esters undergo Granas Moles esterification at elevated temperatures (140 to 250° C.), the rate of esterification for these steri Tetrachlorophthalic anhydride------286 cally-hindered acids is much lower than that of Ethylene glycol.------8 1.1 a non-sterically-hindered acid, e. g., unchlorin 8. ated phthalic acid. Hence when low-acid-num were placed in a three-necked, round-bottoned ber alkyd resins derived from tetrachlorophthalic flask fitted with a thermometer, mechanical acid or anhydride are desired in a reasonable pe stirrer and gas-inlet tube and connected to a riod of time, we have found the following pro 3. distillation condenser through a short, insulated cedure to be of practical value: column. While a steady stream of purified Cook the reaction mixtures, examples of Which hydrogen was passed through the flask, the re have been given above, at a moderately high tem - action mixture was heated with constant stir operature, e. g., at about 180 to 210 C., until a ring for 12 hours. During this period of heating product having an acid number of the order of 4) the reaction temperature was gradually raised 25 to 50 is obtained. At this point very little, from 160 to 181° C., and 14 cc. of aqueous distil if any, decarboxylation will have occurred. Then late was collected. On cooling to room tempera increase the temperature, completing the reaction ture a hard, glassy, brittle resin was obtained. within the temperature range of about 210 to This resin had an acid number of 48.5 and a 250° C. At the higher temperatures decarboxyla Saponification number of 325 (calculated 330). tion of the remaining carboxyl groups with the Petroleum waxes were not compatible with the evolution of carbon dioxide takes place rapidly, molten resin. Asbestos impregnated with this yielding a resin having a very low acid num resin yielded a product having adequate flame ber, more particularly from 0 to about 10. A resistance, which was determined by holding the correlation of the rate of decarboxylation with 50 sample vertically in a hot flame from a Bunsen temperature is given below: burner for 10 to 15 seconds, and noting that the sample did not continue to burn after the removal Rate of Decarb of the Bunsen flame. However, the resin-im Temperature, C. oxylation pregnated asbestos was very brittle, showing that 55 the resin would not be suitable for use as an im Insignificant. Very slow. pregnant in the construction of for example - Slow. asbestos-type cables. - Moderate. Rapid. A compound was prepared by mixing 84 parts of the above resin with 16 parts tricresyl phos 60 phate. The cold flexibility of asbestos impreg This discovery with regard to the effect of heat nated with this compound was poor, and the Sam on the decarboxylation of tetrachlorophthalic ple was slightly tacky. (Cold flexibility was de acid (or anhydride) during esterification to form termined by cooling the sample to 0 C. in a re a polyester thereof is general, and is not limited frigerator and observing its behavior when bent to modified glycol-tetrachlorophthalic reaction around its own diameter. If the sample did not products of the kind described in the first para crack during this treatment, its flexibility was graph of this specification. Thus it is equally considered "excellent,' a slight cracking of the applicable in the production of glycerol- and impregnated sample was considered "good,' pro pentaerythritol - tetrachlorophthalic reaction nounced cracking was considered 'poor.' The products, unmodified and modified with other 0. tack of the sample was evaluated by its feel at substances, e. g., fatty oils, fatty acids, fats and room temperature.) Waxes such as hereinbefore mentioned, as well as A mixture was prepared by compounding 80 in the preparation of unmodified glycol-tetra parts.of the above resin, 10 parts tricresyl phos chlorophthalic reaction products. phate and 0 parts beeswax. The cold flexibility Another method of effecting reaction between 5 Of asbestOS impregnated with this compound was 2,455,878 5 poor. Such a compound, like the compound de were heated together for 4 hours at 173° to 240 scribed in the preceding paragraph, would be C. as described, more fully under Example 1. unsatisfactory for use as an impregnant in mak The resulting flame-resisting resin, which was ing, for instance, asbestos-type cables. hard and cloudy at room temperature, had a slightly waxy feeling. It possessed considerably EXAMPLE 2 more inherent flexibility and wax compatibility Same as Example 1 with the exception that than the resinous product of Example i. Its 117 grams (1.1 moles) of diethylene glycol were acid number was 39.8 and its saponification num used in place of 68 grams of ethylene glycol, and ber 279 (calculated 284). A composition formed the heating period was 7 hours within the tem O of 78 parts of this resin, 9 parts tricresyl phos perature. range of 160 to 215° C. The resulting phate, 8 parts beeswax and 5 parts ceresin wax resin was hard and glassy at room temperature was applied in molten state to asbestos-covered but was tacky at slightly above room tempera Copper wire. The resulting impregnated asbestos ture. It had an acid number of 75 and a saponi insulation had good flame resistance, was free fication number of 288 (calculated 286). Petro 5 from tack at room temperature and was flexible leum waxes were not compatible with the molten at 0° C. resin. When asbestos impregnated with the resin was tested for flame resistance as described under EXAMPLE 6 Example 1, the sample continued to burn for Grams Moles some time after removal of the Bunsen flame, 20 but eventually extinguished its own flame. The Ethylene glycol------130 2. cold flexibility of the sample was poor, and it Tetrachlorophthalic anhydride 572 2 was slightly tacky at room temperature. A mix Bayberry wax------40 1 0,144 ture of 87 parts of this resin with 13 parts tri cresyl phosphate had better flame resistance and 1 Estimated. cold flexibility but was excessively tacky. The above ingredients were heated together for EXAMPLE 3 5 hours at 154 to 237 C. in a manner similar to that described under Example 1 with the excep Grams Moles tion that carbon dioxide was used in place of 30 purified hydrogen as the inert atmosphere. The Tetrachlorophthalic anhydride:------388 1.35 resulting resin was hard and slightly cloudy (at Diethylene glycol------157 1.48 room temperature). It was flame-resistant, compatible With Waxes and had better inherent were heated together for 6 hours with constant flexibility than the resin of Example 1. A com stirring under an atmosphere of purified hydro 35 pound formed of 82 parts of the resin of this gen as described in Example 1. The tempera example, 10 parts tricresyl phosphate and 8 parts ture of heating was 160° to 248 C. The resultant Ceresin wax was applied in molten state to as resin was tacky at room temperature and was bestos-covered copper wire. The impregnated much less viscous when melted than the resin asbestos covering had good flame resistance and of Example 2. This difference in physical prop 40 was free from tack at room temperature. erties is believed to be the result of decarboxyla tion that occurred during heating at the elevated temperature (above 210° C.). Evidence that de EXAMPLE 7 carboxylation took place is given by the fact that the saponification number of the resin was found 45 Grams Moles to be 244, although the calculated value is 296. Ethylene glycol------130 2. This difference corresponds to 17.5% decarbox Tetrachlorophthalic anhydride------572 2. ' Vegetable stearin, specifically completely hydro ylation of all carboxyl groups originally present. genated catton Seed oil------140 10,157 The resin had an acid number of 10.3 and it was 50 incompatible with petroleum Waxes. 1 Estimated. EXAMPLE 4 were heated together for 44 hours at 153 to 240° C. as described under Example 1, but using Grams Moles 55 carbon dioxide as the inert atmosphere as in Tetrachlorophthalic anhydride------572 2 Example 6. The resulting flame-resisting resin, Triethylenoglycol------230 22 which had an acid number of 30, had properties quite similar to those of the resin of Example 6. Asbestos-covered copper Wire was impregnated were heated together to form a resin in a manner with a molten composition formed of 76 parts of similar to that described under Example 1. 80 the resin of this example and 8 parts of tricresyl Heating was continued for 31 hours at 150° to phosphate, beeswax and Ceresin wax. The im 208° C. (mostly at 175° to 200° C.). The result pregnated asbestos showed good flexibility at 0° ing resin had an acid number of 43 and was a C. and was free from tackiness at room, tem viscous fluid at room temperature. It was too perature. tacky for practical use as an impregnant in pro 65 ducing, for example, asbestos-type cables. EXAMPLE 8 EXAMPLE 5 Grams Moles

Grams Moles 70 Ethylene glycol...... ------118 1.9 Tetrachlorophthalic anhydride..... 572 2 Ethylene glycol...... 35, 6 E 0.55 Castor oil------...I.I.I.I.I. 140 1 0,132 Tetrachlorophthalic anhydride------.... 157 0.548 Beeswax------40 0.064 1 Estimated. Estimated, 75 were heated together for 4% hours at 160° to 225° 2,455,878 7 C. The procedure was in general the same as that phere at 140°-160° C. for a hour, after which the described in Example 1 with the exception that temperature was raised to 200 to 210°C. The re carbon dioxide instead of purifled hydrogen was action was continued at this higher temperature used as the inert atmosphere. The resulting until a resinous product having an acid value flame-resisting resin had an acid number of 45 of 10 was obtained. The total reaction period and was brittle and slightly tacky at room tem was 17 hours. perature. A compound formed of 82 parts of this It will be understood of course by those skilled resin, 6 parts tricresyl phosphate, 6 parts beeswax in the art that our invention is not limited to the and 6 parts ceresin wax was applied in molten specific ingredients and proportions thereof that state to an asbestos-covered copper wire. The 10 are given in the above examples. Thus, instead of impregnated asbestos had good flame resistance. tetrachlorophthalic anhydride we may use an EXAMPLE 9 equivalent amount of tetrachlorophthalic acid. Resinous compositions made as described in the Granus Moles examples but using an equivalent amount of a s less highly chlorinated phthalic acid or anhydride Ethylene glycol.------860 3.85 instead of tetrachlorophthalic acid or anhydride Tetrachlorophthalic anhydride------3,438 12 are less flame-resistant than the resins of the ex Stearic acid------341 1.2 amples. Instead of the particular glycols named in the The above ingredients were heated together for 20 examples, other glycols may be employed, e. g., 84 hours at 140° to 230° C. as described more fully tetraethylene glycol, dipropylene glycol, 13 bu under Example 1, but using carbon dioxide as the tylene glycol, etc. The ease of effecting reaction inert atmosphere instead of purified hydrogen. between, for instance, tetrachlorophthalic anhy At temperatures above 220° C. the evolution of dride and the various glycols is a function of the carbon dioxide from the reaction mass was noted. 25 glycol employed, as shown by the fact that eth During the reaction period 266 cc. of aqueous dis ylene glycol reacts more readily than diethylene tillate was collected. The acid number of the glycol, and diethylene glycol more rapidly than resulting hard, flame-resisting resin was only 1. triethylene glycol. We prefer to use ethylene and the saponification number was 299. The cal glycol. culated saponification number for this resin was 30 Warious other fats, waxes, fatty oils and fatty 323, the difference between these two values in acids may be used in place of the particular rod dicating that approximately 7.5% decarboxyla fying substance mentioned in the individual ex tion had occurred. A composition formed of 70 amples, for instance tung oil, soya bean oil, olti parts of this resin, 10 parts tricresyl phosphate cica, oil, COConut oil, fish oils, perilla oil, cotton and 20 parts of ethylene distearamide was applied Seed oii, Sunflower oil, etc., the fatty acids of such in molten state to asbestos-covered copper wire. fatty oils, undecylic acid, myristic acid, palmitic The impregnated asbestos insulation had good acid, margaric acid, arachidic acid, carnaubic fame resistance, good flexibility at 0° C. and a acid, Cerotic acid, lacceroic acid, montanic acid, waxy, non-tacky feeling. Ethylene distearamide linoieic acid, linolinic acid, etc., tallow and other is a synthetic wax (melting point 37-39 C.) 40 animal fats, Japan wax, candelilla wax, palm produced and sold by Glyco Products Company, wax, flax wax, Cottonseed wax, spermaceti, etc. New York, N.Y. The proportions of reactants may be varied con EXAMPLE 10 siderably depending, for instance, upon the para ticular reactants employed and the particular Approximate 45 properties desired in the final product. Ordi per cent narily the glycol is used in a slight molar excess, Tetrachlorophthalic anhyride------63.4 e.g., a 10 or 15% molar excess, of that required Propylene glycol------22.0 for reaction with the tetrachlorophthalic acid or Oleic acid------14.3 anhydride, but lower or higher amounts. (e. g., as Triphenyl phosphite ------0.3 50 little as about 5% molar excess or as much as The triphenyl phosphite is an oxidation inhibitor and about 25% molar excess) may be employed de aids in preventing discoloration of the resin. pending, for example, upon the kind and amount The above ingredients were heated together of modifying agent employed. Stated alter under a nitrogen atmosphere for 9% hours at 200 natively, for each mol of the chlorinated com to 210° C. The resulting flame-resisting resin had 55 pound, from about 1.05 to 1.25 mols of the glycol an acid number of 16 and a penetration value may be employed. The amount of modifier may (200 gram weight, 5 seconds, 25 C.; method: be varied considerably, but usually will constitute A. S. T. M. Designation D5-25) of 68. from about 5 to 25% by weight of the total start ing ingredients. When the resinous product is EXAMPLE 1. 60 to be used in applications where flame resistance Same as Example 10 with the exception that is a property of considerable importance, then the 14.3% commercial stearic acid (about 95% acid) amount of modifier preferably is such that the was used in place of oleic acid. The resinous re amount of chlorine in the final resin is not below action product was flame-resisting and had an 30%, and preferably is from about 35 to 40%, by acid value of 15. Its penetration number was 32 65 weight of the resin. when determined in the manner described in Ex A requirement of an impregnating resin is ample 10. that it be relatively non-volatile and thermally EXAMPLE 12 stable. Table I lists data obtained in testing Approximate the rate of evaporation at 150 C. of (1) a stearic per cent 70 acid-modified glycol-tetrachlorophthalic resin Ethylene glycol ------7.0 ous reaction product similar to that described Tetrachlorophthalic anhydride------723 under Example 9 and (2) commercial hexa Coconut oil fatty acids------10.7 chloronaphthalene, which is a toxic compound formerly used as a base material in preparing were cooked together under a nitrogen atmos- 75 flame-proof impregnants. 9488,878 10 9 of (a) ethylene glycol, (b) tetrachlorophthalic TABLE anhydride, the ethylene glycol being present in Euaporation rates at 150 C. an amount equal to from 1.05 to 1.25 mols per mol A. Commercial hexachloronaphthalene (weight, 44.2970 grams; of tetrachlorophthalic anhydride, and (c) from area, 72.5 cm.) 5 to 25 per cent, by weight, stearic acid, based on the total weight of ingredients (a), (b), and (c), Time, Loss Rate of Oss, the said stearic acid being at least in part chemi Hours Gransm. Grams/cnn.hour cally combined in the resinous composition. 3. The method of producing a permanently 0.077 0.0026 O fusible, flame-resistant, wax-compatible, resinous 0,0468 0.020 0, O656 0.00204 composition containing from 30 to 40 per cent, by 0,086 0.00200 weight, chlorine, which method comprises heat ing together simultaneously to form a resin at B. Modified tetrachlorophthalie resin (weight, 28.0075 a temperature within the range of 140° to 250 grams; area, 91.7 cm.) - 5 C., a mixture of ingredients consisting of (a)

ethylene glycol, (b) tetrachlorophthalic anhy dride, the ethylene glycol being present in an Time, Rate of loss, hours grain. grans?en.hour amount equal to from 1.05 to 1.25 mols per mol of tetrachlorophthalic anhydride and (c) from 5 2 0.0017 0.000385 to 25 percent, by weight, based on the total weight 7 0.00356 0,00050 25 0.00899 0.000359 of (a), (b) and (c) of a modifying substance be A9 0.01520 0.00030 ing at least in part chemically combined in the 73 0.02160 0,000298 resinous composition and being selected from the 88 0.02680 0.00030 class consisting of (1) fatty oils, (2) fatty acids having from 10 to 33 carbon atoms, inclusive, and From the data in Table I it will be apparent (3) fats and waxes containing esters of the fatty that the modified tetrachlorophthalic resin has acids defined in (2). a lower volatility at 150 C. than commercial 4. The process of preparing a permanently hexachloronaphthalene. Furthermore, unlike fusible, flame-resistant, wax-compatible, resin the latter compound, which is toxic, the modified 30 Olus composition Containing from 30 to 40 per tetrachlorophthalic resin is non-toxic. cent, by weight, chlorine, which method com The resinous compositions of this invention prises (1) heating together simultaneously to may be used alone or with other ingredients, e.g., form a resin at a temperature of from 180° to 210° a volatile solvent, in coating or coating and im C. a mixture of ingredients consisting of (a) pregnating fabric and other textile materials, 35 ethylene glycol, (b) tetrachlorophthalic anhy e.g., materials comprising natural or synthetic dride, the ethylene glycol being present in an fibers. They may be employed as modifiers of amount equal to from 1.05 to 1.25 mols per mol other materials, e. g., waxes, natural and syn tetrachlorophthalic anhydride, and (c) from 5 thetic resins, etc., to impart improved properties to 25 percent, by weight, stearic acid, based on thereto, as a component of varnishes, enamels, the total weight of (a), (b) and (c), said heat lacquers, paints and other liquid coating compo ing being continued until an acid number of the sitions, etc. Because of their wax compatibility . order of 25 to 50 is obtained, and (2) thereafter they are especially suitable for use as a modifier further heating the resulting mixture within the of natural and synthetic waxes to form impreg temperature range of 220' to 250° C. until an acid nating compositions that are particularly valu 45 value of from 0 to 10 is obtained. able as an impregnant of asbestos, mineral wool, 5. The process of preparing a permanently glass fibers in yarn, felted, fabric or other form, fusible, flame-resistant, wax-compatible, resinous paper, etc. composition containing from 30 to 40 per cent, What we claim as new and desire to secure by by weight, chlorine, which method comprises (1) Letters Patent of the United States, is: 50 heating together simultaneously to form a resin 1. A flame-resistant, wax-compatible, perma a mixture of ingredients consisting of (a) ethyl nently fusible, resinous composition, containing ene glycol, (b) tetrachlorophthalic anhydride, the from 30 to 40 percent, by weight, of chlorine, said ethylene glycol being present in an amount equal composition being the resinous product of si to from 1.05 to 1.25 mols per mol of the tetra multaneous reaction of ingredients consisting of 55 chlorophthalic anhydride, and (c) from 5 to 25 (a) ethylene glycol, (b) tetrachlorophthalic an per cent, by weight, based on the total weight of hydride, the ethylene glycol being present in an (a), (b) and (c), of a modifying substance se amount equal to from 1.05 to 1.25 mols per mol lected from the class consisting of (A) fatty oils, of tetrachlorophthalic anhydride, and (c) a (B) fatty acids having from 10 to 33 carbon modifying substance being at least in part chem 60 atoms, inclusive, and (C) fats and waxes con ically combined in the resinous composition and taining esters of the fatty acids defined in (B), being selected from the class consisting of (1) said heating being conducted for a period of fatty oils, (2) fatty acids having from 10 to 33 from A to 1 hour within the temperature range carbon atoms, inclusive, and (3) fats and waxes of 140 to 160° C. and (2) thereafter further heat containing esters of the fatty acids defined in 65 ing the resulting mass by increasing the tem (2), the modifying substance being present, by perature gradually from 200 to 210° C. and main weight, in an amount corresponding to from 5 taining this temperature until a resin having an to 25 per cent of the total weight of the starting acid number of about 5 to 15 is obtained. ingredients. 6. The process of preparing a permanently 2. A permanently fusible, wax-compatible, 70 fusible, flame-resistant, wax-compatible, resin flame-resistant, resinous composition containing Ous composition containing from 35 to 40 per from 30 to 40 per cent, by weight, chlorine and cent chlorine, which process consists in heating which forms a homogeneous mixture with waxes, to an acid number of 1.7 a mixture consisting, by said composition being the resinous product of weight, of 860 parts ethylene glycol, 3438 parts simultaneous reaction of ingredients consisting 75 tetrachlorophthalic anhydride, and 341 parts 2,455,878 11 12 stearic acid for 8% hours at a gradually rising temperature of from 140° to 230° C., using carbon UNITED STATES PATENTS dioxide as an inert atmosphere, the said heating Number Nane bate being conducted while the water of esterification 1864,909 Jaeger ------June 28, 1932 resulting from the reaction is removed from the 5 1992,249 Snyder ------Feb. 26, 1935 reaction naaSS. 2,106,523 Ellis ------Jan. 25, 1938 WAME,BRGER. W. NORDANDER.CASS. v - - - - OTHER REFERENCEs Kienle et al., Ind. Eng. Chem., April, 1929 vol REFERENCES CTE) 10 ume 21, pages 349-352. fileThe of followingthis patent: references are of record in the v6: Esit. Simical Review,