Jan. 11, 1944. F. J. SODAY . 2,338,743 SUBSTITUTED STYRENE-POLYPIFERYLENE COPOLYMERS Filed April 1, 1939

PPERYLENE

(cata NST ) RING SUBSTITUTED MONO-METHYL STYRENE CATALYTIGALLY FARTIAL? POYMERIZED PPERYLENE

(HEAT Ayor CAIAEST)

POLYMERIZED RING SUBSTITUTED MONO-METHYL STYRENE - POLYPPERYLENE RES N PRODUCT

77revezz/27 /a e/CQ2%2% /4-67 2sGuwa. 2272, Patented Jan. 11, 1944 2,338,743

UNITED STATES2,338,743. PATENT office subsTITUTED sTyEENE-roLYPIPERYLENE COPOLYMER Frank J. Soday, Upper Darby, Pa., assignor to the United Gas Improvement Company, a corpora tion of Pennsylvanis : Application April 1, 1939, Serial No. 265,514 18 Claims. (C. 260-86.5) This invention relates to new compositions of CsC matter and to a method for their preparation, More particularly, this invention pertains to resins resulting from reacting one or more C monomeric ring substituted mono-methyl sty 5. renes with piperylene which has been partially (m-Methylstyrene) polymerized catalytically. Such material will be referred to herein as partially polymerized gH=CH piperylene. It is an object of this invention to provide a O new type of synthetic resins. It is a further ob ject of this invention to provide, resins having E. ' utility in industrial fields, and particularly in the (p-Methyl styrene) molding and liquid coating composition fields. More particularly, it is an object of this in 15 These ring substituted mono-methyl styrenes vention to provide varnish and lacquer resins may be obtained by the distillation of the light possessing excellent alkali, acid, and Water rea oil from gas, as well as from other sources. sistant properties. It is also a particular Object By partially polymerized piperylene is meant of this invention to provide molding resins which piperylene which has been siected to catalytic may be used with or Without plasticizing agents 20 polymerization conditions sufficient to change its or lubricants. It is a further object of this in chemical constitution from monomeric pipery vention to provide resins adapted to produce a lene, said polymerization conditions, however, be Smooth Surface pleasing in appearance. A further ing insufficient to render the polymerized ma object of the invention is to provide a molding teriai incapable of further reaction. resin with substantially non-shrinking properties. 25 . The properties of the resulting resins vary Still another object of this invention is to pro somewhat with change in polymerization condi vide resins the color of which may be readily con tions, both with respect to the initial partial trolled and varied: polymerization of piperylene and the subsequent A still further object of the invention is to pro- . polymerization of one or more monomeric ring vide resins compatible with a wide variety of 30 Substituted mono-methyl Styrenes and the parti additive agents such as fillers, decorative con ally polymerized piperylene. stituents, pigments, softening agents, plasticizers, For example, the final resins will have increas and the like. ingly higher melting points with increasingly Another object of the invention is to provide greater initial polymerization of piperylene. a process for preparing resins of the above chara 35 Furthermore, the relative proportions of mono acter. meric ring substituted mono-methyl styrene and Still other objects will become apparent to partially polymerized piperylene reflect them those skilled in the art from the following de selves in the properties of the resultant resinous ... scription and illustrative examples. compounds to a large extent, For example, the This invention is based upon the discovery that 40 product obtained by reacting 60 parts of mono new synthetic resins having highly desirable meric para-methylstyrene with 40 parts of parti properties may be prepared by reacting one or ally polymerized piperylene results in a resinous more monomeric ring substituted mono-methyl compound which is particularly suitable for mold styrenes with piperylene which has been previ ing or casting. On the other hand, a resin re ously partially polymerized catalytically. 45 sulting from reacting 40 parts of monomeric para The ring substituted mono-methyl styrenes . methyl styrene with 60 parts of partially poly may be represented as follows: merized piperlyene is particularly suitable for varnish and lacquer purposes. In other words, larger proportions of nonomeric ring substituted - C=CH s mono-methyl styrere result in resins more par CHs. ticularly suited for molding and casting pur poses whereas larger proportions of partially. polymerized piperylene result in the production of resins more particularly suited for varnish and (o-Methyl styrene) | S5 lacquer purposes, s 2 2,888,748 Other factors which will have a modifying i? a carried out in the liquid state or in the vapor state, fluence are the manner in which the initial and O' both, and in the presence or absence of sol final polymerizations are conducted, the con vents. centration and relative purity of the materialis The partial polymerization of piperylene in a undergoing polymerization, the nature and quaia light oil piperylene fraction is illustrated in the tity of catalyst employed, termperature range, re ifolio Wing example. action time, and the like. For example, drastic conditions with respect to Eacample i temperature, concentration of reactants, propor o A light oil piperylene fraction obtained in the tion of catalyst, and reaction time, may result in Inaufacture of oil gas and containing 78.9% by in Soluble polymers O gels instead of the noire. weight of piperylene was employed. 100 parts desirable soluble resins. iny weight of this piperylene fraction was added the piperylene employed in the preparation of to sufficient toluene to reduce the piperylene Con my new resins may be obtained from any suitable centration to approximately 25%, after which the Source. For instance, piperylene may be obtained S mixture was polymerized by adding to it approxi by a variety of synthetic methods, or it; may ge nately 5 parts by weight of boron trifluoride obtained by the fractionation of condensates Oo diethyl ether complex while maintaining the ten tained in the manufacture of carbureted water perature of the mixture at -20° C., and agitating gas, oil gas, refinery gas, or coke oven gas, or from during a one hour period of addition. Agitation similar sources. Such fractions will be referred was continued at this temperature for a period to herein generally as light oil piperylene fraca of approximately 18 hours after which the reac tions. Fractions obtained in the manufacture of tion mixture Was allowed to come to room ten oil gas are particularly preferred. perature. The catalyst was then hydrolyzed by Hydrocarbon fractions containing from 5 to the addition of a 20% aqueous solution of sodium 100% of piperylene may be successfully used in 25 the production of the herein described partially carbonate. This was followed by approximately polymerized piperylene, although, in general, the 30 minutes of continuous agitation after which use of fractions containing from 5 to 100% the resultant mixture Containing partially poly piperylene is preferred for the production of resins nerized piperylene and unpolymerized constitu of high quality. 30 ents was dried by the addition of a small quantity. Fractions in which piperylene is the only di of lime, with agitation, for a period of approxi olefine present are preferred, although fractions nately 1 hour. All solid extraneous matter was thereafter renoved by filtration. e containing a lesser quantity of butadiene, cycio the fraction containing partially polymerized pentadiene or isoprene, or any combination of piperylene, in addition to unpolymerized mate two or more of these, or similar materials may rial, was employed in the preparation of a methyl he employed without departing from the broad styrene-polypiperylene resin as will be more fully Concept of the invention. Set forth hereinafter in Example 2. - The same applies to olefines, such as olefines On the other hand, the unpolymerized material aving five carbon atons. inay be wholly or partly removed prior to the The accompanying drawing represents a flow final polymerization step. sheet of my invention in its broader aspects. As The ring substituted mono-methyl styrene en shown thereon, an initial step comprises cata ployed in the production of my new resins may lytically partially polymerizing piperylene. The be obtained from any suitable source, and may be esulting product and ring substituted mono in the form of pure or commercially or technically methyl styrene are thereafter subjected to furn pure ring Substituted mono-methyl styrene, or in ther polymerization engioying heat aghd/or a the form of a solution or a fraction such as ob catalyst to obtain a product, which is my novel tained from light oil or a mixture of light oil polymerized ring substituted mono-nnethyl sty hydrocarbons. The source of light oil may be the rene-polypiperylene resin having very desirable Sarine as in the case of the piperylene previously characteristics for use in various arts. Referred to. INITIAL PARTIAL PolyMERIZATION of PIP2RYLENE Mixtures of monomeric ring substituted mono The partial initial polymerization of piperylene methylstyrenes also may be reacted with partially is effected catalytically by means of acid-acting polymerized piperylene to give these new resins. metallic halides and particularly acid-acting mea. The properties of these resins may be varied con tallic halide-organic solvent complexes. . . Ex siderably by choice of starting materials. amples of such catalysts are given hereinafter. Para-methyl styrene fractions obtained by the Although considerable variation is permissible distillation of light oil and having boiling ranges, when employing an acid-acting metallic halide of between 160 to 180° C. have been satisfactorily an acid-acting metalic halide-organic solvent 8 employed in the preparation of para-methyl sty complex as catalyst, the polymerizing termperature rene-polypiperylene resins. Resins having espe should rarely exceed 300° C., and preferably cially desirable properties have been obtained should not exceed 70° C.; the concentration of . when employing para-methyl styrene fractions piperylene should rarely exceed 80% by weight having boiling ranges between 165 and 175° C. of the total solution, and the concentration of 85 Even more desirable properties are secured in the catalyst, which is preferably uniformly distriba, final resins when the para-methyl styrene frac uted, should rarely exceed 10% by weight of the tions employed have boiling ranges between 167 piperylene present, although these values are noi, and '3' C. to be considered as fixed imits. . . . A comparable degree of purity is preferred when Two or more of the foregoing catalysts might using ring substituted mono-methyl styrenes other than para-methylstyrene in the prepara be era ployed. tion...of these new resins. The use of substantially On the other hand, the initial polymerization pure ring substituted mono-methyl styrene or may be carried out by a combination of heat and anxtures of Substantially pure ring substituted catalyst.The catalytic partial polymerization may be is mono-methylstyrenes is preferred when commer 2,388,743 3 cially feasible, particularly for resins of the mold to any one or more of the reactants, or to the ing type. ) reaction mixture at any stage, but prefsirably prior to complete polymerization...... PoLY ERIZATION or RING SubsTITUTED Mono As a rule, organic dyes and other organic col METHY, STYRENE AND PARTIALLY POYERIZE 5 Oring bodies produce resins with pastel shades. PPERYLENE The coloring compound may, of course, be add Polymerization of monomeric ring substituted led to the unpolymerized piperylene, and may or mono-methyl styrene or styrenes and partially may not be supplemented during the secondary polymerized piperylene is preferably carried out polymerization reaction, as desired. Or the coln by the application of heat, although the reaction 10 oring compound can be added during the secon's may be Carried out through the use of catalysts, phase of the reaction. R With or without the application of heat, without If desired, the coloring material itself may be departing from the broad concept of the inven- . prepared in situ by adding the necessary ma tion, terials to the polymerization reaction. . The polymerization may be carried out in the 5 As an example, a short list of suitable color liquid state or in the vapor state, or both, and in ing materials is given in the following table: the presence or absence of solvents. Table 1 When the polymerization of ring substituted mono-methyl styrene or styrenes and partially polymerized piperylene is effected by the appli 20 Color Dye group cation of heat, a temperature between 50 to 250 Orange------Mono azo. Yellow ---- Do. C. is preferred. Temperatures between 75 and Creen.------. Triphenylmethane. 200 C. are found to be particularly suitable. Heliotrope ---- Triphenylmethanepyronine, The reaction time may be varied over fairly Red------Pyronine. Wide limits, depending upon the extent of the 25 Black.------Diphenylamine, polymerization desired. The following examples illustrate procedure for Mottled effects may be obtained by adding col the preparation of my new resin. oring material to the polymerization mass at a stage in the polymerization reaction after which Eacample, 2 30 thorough stirring is no longer required. A mixture of approximately 170 parts by weight Attention is directed to the fact that certain of monomeric para-methylstyrene in the form of coloring materials may also act as catalysts or a 53.2% light oil fraction and 37 parts by weight as inhibitors to the polymerization reaction. Ac of partially polymerized piperylene prepared as cordingly, coloring 'materials should be selected shown in Example 1 and in the form of a 27.9% 35 as to (1) their inertness, (2) their action as cat Solution in toluene, was placed in a glass bomb alysts, and (3) their action as inhibitors in order and Sealed in an atmosphere of nitrogen. The to obtain the desired result. In this connection, bomb was heated for a period of 10 days at a tem. inhibitors may be employed to retard an other perature of approximately 100° C. Unpolymer Wise too hasty reaction. - - - w ized material was removed from the resultant 40 A proper choice of polymerizing conditions will maSS by vaporization at a temperature of ap enable almost any type of coloring material to proximately 100° C. and a pressure of 1.0 mm. of be used. mercury, absolute. Approximately 76 parts by In addition to coloring materials, other ad Weight of a solid thermoplastic resin was secured. ditives may be incorporated, such as fillers, of A portion of the resin was molded at a tem which asbestos, mica, wood flour, cotton linters, perature of approximately 200° C. and a pressure and fabric waste are examples. of 2,000 pounds per square inch. The resulting A decorative filler functioning very much on object resembled ivory in appearance. It had an the order of a coloring material may be added, exceptionally Smooth hard and tough surface and with or without other Coloring matter. Examples took a very high polish. 5 of decorative fillers are pearl essence, faked mer Molding resins made in accordance with m curous chloride, and chitin extracts. invention are characterized not only by hard Furthermore, other agents such as mold lubri ness, toughness, pleasing appearance, ability to cants, softeners, plasticizers, and the like, may take a high polish, good molding properties, and also be added at any stage of the polymerization inert characteristics, but also in imparting a 55 process. warn and pleasing sensation to the touch. The While the use of heat as a polymerizing agent latter is extremeliy important in the trade. is preferred when reacting ring substituted mono My new resins may be prepared in many de methylstyrene or styrenes with catalytically par sirable Color combinations. Color may be ob tially polymerized piperylene, other polymerizing tained either naturally or artificially. Natural agents may be employed if desired, either with or . colors may be secured by varying the source and without the application of heat; quality of either the ring Substituted mono For instance, polymerization catalysts, such as methyl styrene or styrenes, or the piperylene, or metallic halides, metallic halide-organic solvent both. Either plain or mottled color combina complexes, organic peroxides, contact materials, tions may be thus obtained. . ultra violet light, ultra sonics, mineral acids, min Resins which are milk-white in color and which eral acid-organic solvent mixtures, active metals, resemble ivory in appearance may be prepared etc., may be employed. by polymerizing mixtures containing pure mon Examples of catalysts which may be employed omeric ring substituted mono-methyl styrene or in either the initial or final polymerization re styrenes, and partially polymerized piperylene. O action are acid-acting metallic halides such for Artificial colors and color combinations may be example as aluminum chloride, aluminum bro produced through the addition to my new resins mide, stannic chloride, boron trifluoride, boron of suitable chemicil compounds. trichloride, zinc chloride, ferric chloride, organic Coloring materials, such as organic dyes, inor solvent complexes of the foregoing metallic hal ganic dyes, pigments, and lakes, may be added sides. Examples of other catalysts which may ~ 4. 2,838,748 be employed in the final polymerization are merizations, it is preferred to completely remove pinene peroxide, benzoyl peroxide, clay, activated catalyst from the reaction mass after the desired clay, activated carbon, activated alumina, silica polymerization is obtained. gel, fuller's earth, diatomaceous earth, sulfuric Metallic halides, metallic halide-organic sol acid, phosphoric acid, sulfuric acid-diethyl ether vent complexes and organic peroxides may be mixture, sodium and potassium. removed by any suitable means, such as treating Organic Solvent complexes of the metallic hal the reaction mass with an alkaline solution fol ides are formed by adding the halide to the or lowed by thorough washing with water, and fil ganic solvent followed by stirring. Examples of tration. Organic Solvents are benzene, toluene, pentene, O Contact materials may be removed from the decene, diethyl ether, phenyl methyl ether, phenyl reaction mass by settling, filtration, or centri ethyl ether, diisopropyl ether, etc. fuging, or otherwise. Metallic halide catalysts (including complexes While in the foregoing description reference of Such metallic halides) are well-known to be has not been expressly made to a change in poly distinguished as a class by their tendency to s merization agent during any single polymeriza hydrolyze in the presence of water, giving an acid tion step, it is to be understood that a change reaction. They are therefore frequently desig in polymerization agent during any single poly nated as "acid-acting metallic halides.' This merization step might be resorted to if desired. term includes the boron halides and boron halide For instance, the initial partial polymerization complexes. ------20 of piperylene might be carried out in part by The catalyst employed in the initial reaction the use of a catalyst, the catalyst removed and may be used as such or in admixture such as the partial polymerization completed by the ap With a suitable solvent to form a suspension, plication of heat. On the other hand, heat might Solution or emulsion. A catalyst when employed be applied initially followed by the use of a cata in the final reaction may be used in similar 25 lyst. The use of both heat and catalyst has lane. already been referred to. Likewise, the reactants may be employed as Likewise, the polymerization of monomeric Such or in admixture such as with a suitable ring substituted mono-methylstyrene or styrenes Solvent, or with additives such as coloring mate with partially polymerized piperylene might be rials etc. referred to above. 30 effected in part by the use of heat and completed In order to control more closely the speed and by the use of a catalyst, or the polymerization uniformity of the reaction, I may slowly add, might be started by use of a catalyst, the catalyst with thorough agitation, a solution of the re removed and the polymerization completed by actant or reactants to a suspension, or solution the use of heat. The use of heat and/or catalyst of the catalyst in an organic solvent. Or, the 3. has already been referred to. ' catalyst may be added to the reactant or react I prefer to carry out both the initial and the ants, or to a Solution containing the same. final polymerizations in the presences of an inert Examples of suitable solvents or diluents for and preferably non-catalytic gas, such as carbon both catalysts and reactants are benzene, toluene, - dioxide, or nitrogen, or in the presence of solvent Xylene, solvent naphtha, petroleum naphtha and 4. vapors, or vapors of the reaction mass, or in a carbon tetrachloride. - vacuum. In general, the exclusion of air or oxy. . In any event, the addition of one material to gen from the material during the polymerization the other is preferably accompanied by thorough process will prevent any possible formation of stirring which is preferably rapid to insure uni undesirable compounds, although this step is by no means, essential. form distribution of both materials and tem 45 Furthermore, while it is preferred to carry out perature. the initial catalytic partial polymerization and In addition, the reaction is preferably carried the final polymerization with the reactants at out in apparatus capable of temperature control least for the most part in the liquid phase, it is Such as a jacketed vessel provided with an agi to be understood that the reactants might be in tator. 50 the gaseous phase or partly in the gaseous phase The quantity of catalyst may be varied over and partly in the liquid phase. a rather wide range in both the initial and the While any proportion of partially polymerized final polymerization reactions, although it is piperylene to ring substituted mono-methyl sty found preferable to employ limited quantities rene or styrenes may be employed in making my such as from 0.1% to 10% by weight of reactants 5 new resin, I prefer in the case of coating com present. positions to employ between 50 and 99% partially In general, when employing catalysts to poly polymerized piperylene on the undiluted basis to merize ring substituted mono-methyl styrene or between 1 and 50% nonomeric ring substituted styrenes and partially polymerized piperylene, mono-methylstyrene or styrenes on the undiluted temperatures between -60 and 145° C. are suit 60 basis. 60 to 90% partially polymerized piperylene able. I prefer, however, to use temperatures to 40 to 10% monomeric ring substituted mono betweenThe upper -40 limitand 60° of C.permissible temperature is methyl styrene or styrenes is very suitable, largely determined by (1) the concentration of The resin obtained by the polymerization of a reactants, (2) the concentration of catalyst, and 8. mixture containing 80 parts of partially poly (3) the reaction time employed. Therefore, if it merized piperylene to 20 parts of monomeric ring is found that polymerization conditions are suff substituted mono-methyl styrene or styrenes is ciently drastic to produce an insoluble polyme: excellent. y On the other hand, in the case of casting or or gel when a soluble polymer is desired, one or molding compositions, I prefer to employ between more of the four conditions, namely (1) temperae go 50 to 99% monomeric ring substituted mono ture, (2) concentration of reactants, (3) propora methyl styrene or styrenes to between 50 to 1% tion of catalyst, and (4) reaction time should pastially polymerized piperylene on the undiluted be reduced until the desired soluble polymer is basis. 70 to 95% monomeric ring Substituted obtained.In general, in both the initial and final polya is nono-methyl styrene or styrenes to 30 to 5% 2,888,748 5 partially polymerized piperylene is very suitable. good yield by employing drastic conditions as to The resin obtained by the polymerization of a (1) concentration of reactants, (2) concentra mixture containing 90 parts of monomeric ring tion of catalyst, (3) temperature, and (4) reac substituted mono-methyl styrene or styrenes to tion time. 10 parts of partially polymerized piperylene It is to be understood that while it is preferred usually possesses excellent molding properties. to change all or substantially all of the mono In the event of the removal of extraneous mate meric piperylene to partially polymerized pipery rials, such as unpolymerized material from the lene during the initial polymerization reaction, partially polymerized piperylene and hydrocar is such initial polymerization may be conducted in . bons of similar boiling point from the monomeric 10 such a manner as to polymerize only a part of ring substituted mono-methylstyrene or styrenes the piperylene present without departing from before their polymerization, a highly superior the spirit of the invention. product is obtained. If desired, a polymerization While in the examples listed, the initial partial diluent such as benzene, toluene, etc., may be polymerization of the piperylene or piperylene employed, 5 fraction is terminated prior to the addition of While when partially polymerized piperylene the monomeric ring substituted mono-methyl is present in greater proportion in the reaction styrene or styrenes, the reaction can also be car mass, the resulting resin is ideally suited to the ried out by the partial polymerization of the pi coating of surfaces in general, such as of metal, perylene, the addition of the monomeric ring wood, glass, ceramic substances, etc., and par 20 substituted mono-methylstyrene or styrenes dur ticularly to the coating of metal surfaces, it may ing the course of this reaction, and the comple be used for any other purposes, for instance, for tion of the reaction in any desired manner. lacquers generally, for varnishes either alone or Furthermore, while as above particularly de in admixture with other resins, for enamels, for scribed, the catalyst was removed from the par paints, for coating compositions generally, or 25 tially polymerized piperylene before its co-poly perhaps, if desired, for casting and molding par merization with monomeric ring Substituted ticularly when the spread in proportion of re mono-methylstyrene or styrenes, it is to be un actants is not too great. derstood that the co-polymerization may, if de While when monomeric ring substituted mono sired, be carried forward without first removing methyl styrene or styrenes are present in larger 30 such catalyst. proportion in the reaction mass, the resulting The term 'ring substituted mono-methyl sty resin is ideally suited for casting or molding pur rene' as used in the claims, and unless otherwise poses in which it may be employed alone, or in modified, is intended to embrace pure and Sub admixture with other plastics or resins, either stantially pure monomeric ring substituted mono with or without the addition of coloring agents, 5 methyl styrene or a mixture of such substituted fillers, etc., it is conceivable...that, if desired, the styrenes, commercial and technical grades there resin might be used for coating purposes, particus of, and any mixture or fraction in which One or larly if the spread in proportion of reactants is more monomeric ring substituted mono-methyl not too great. styrenes is the predominating active material of Furthermore, while in the case of the catalyst said mixture or fraction in the polymerization employed in the initial catalytic partial poly reaction with partially polymerized piperylene. merization step and when a catalyst is employed The term "piperylene' as used in the claims, in the final polymerization step, it is preferred and unless otherwise modified, is intended to em to have, both the catalyst and the reactants in brace pure and substantially pure monomeric diluted form, it is to be understood that any 45 piperylene, commercial and technical grades other procedure might be followed without des thereof, and any mixture or fraction in which parting from the broad concept of the invention. monomeric piperylene is the predominating active. For instance, all of the diluent may be first mixed material of said mixture or fraction in the partial with either the catalyst or the reactant, or react polymerization thereof. ants, leaving the other in concentrated form. 50 The term "partially polymerized piperylene' as Or the larger part of the diluent may be added used in the claims, and unless otherwise modi to one, thus leaving the other relatively concene fied, is intended to embrace piperylene, as de trated. On the other hand, both the catalyst fined in the preceding paragraph, which has been and the reactant or reactants might be employed subjected to polymerization conditions sufficient - in concentrated form, particularly if the observa 55 to change the chemical constitution of at least tions herein with respect to (1) proportion of a part of the monomeric piperylene, said poly catalyst, (2) temperature, and (3) reaction time merization conditions, however, being insufficient are followed. m to render the polymerized piperylene incapable of It will be understood that any other suitable further reaction. m alkali, such as sodium hydroxide, sodium carbor 60 The term 'acid-acting metallic halide cata ate, sodium bicarbonate, magnesium hydroxide, lyst as used in the claims is intended to include an amine or other basic substance might be sub within its scope not only acid-acting metallic stituted for lime in the removal of catalyst, pref halides per se but also complexes thereof such as erably followed by a non-acidic drying agent such organic solvent complexes as fully described in as sodium sulphate or soda lime. Both neutral 65 the foregoing specification. The term "acid izing and drying is effected by lime. Neutraliza acting metallic halide" is likewise intended to in tion is preferably followed by filtration, centri clude within its scope boron halides as well as fuging or settling to remove extraneous solids. . complexes thereof...... While I have spoken rather disparagingly of When percentages of ring-substituted mono the insoluble type of resin, this is because it is 70 methyl styrene and partially polymerized pipery also generally infusible and, therefore, has few, lene are expressly recited in the claims, these are if any, important uses at the present time. intended to express the proportions of these spe Should an important use develop for resin which cific compounds on the undiluted basis, that is is insoluble and infusible, before use my process irrespective of the presence of other material. may likewise be used to obtain this material in 5 It is to be understood that the above particular 6 2,838,78. ing compositions comprising the product of the description is by way of illustration and that polymerization of from 70% to 95% of ring sub changes, Omissions, additions, substitutions, stituted mono-methyl styrene with from 30% to and/or modifications might be made within the 5% piperylene which has been previously par scope of the claims without departing from the tially polymerized catalytically with the aid of spirit of the invention which is intended to be an acid-acting metallic halide catalyst. limited only as required by the prior art. i0. A molding composition comprising the I claim: product resulting from the polymerization of 1. A process comprising polymerizing a light from 50% to 99% highly concentrated ring sub oil ring substituted methyl styrene fraction ob stituted mono-methyl styrene with from 1% to tained in the manufacture of oil gas with a light O 50% piperylene which has been previously par oil piperylene fraction which has been previously tially polymerized catalytically with the aid of an partially polymerized catalytically with the aid acid-acting metallic halide catalyst. of an acid-acting metallic halide catalyst; said 11. A molding composition comprising the light oil piperylene fraction having been obtained product resulting from the polymerization of in the manufacture of oil gas. 5 from 50% to 99% highly concentrated ring sub 2. A synthetic resin comprising the product re stituted mono-methyl styrene with from 1% to Sulting from the polymerization of ring substi 50% highly concentrated piperylene which has tuted mono-methylstyrene with piperylene which been previously partially polymerized catalyt has been previously partially polymerized cata ically with the aid of an acid-acting metallic lytically with the aid of an acid-acting metallic 20 halide catalyst. halide catalyst. 12. A process comprising polymerizing ring 3. A snythetic resin comprising the product re substituted mono-methyl styrene with piperylene sulting from the polymerization of a light oil which has been previously partially polymerized ring substituted methyl styrene fraction in which catalytically with the aid of an acid-acting ring-substituted methyl styrene is the predomi 25 metallic halide catalyst. nating active compound with piperylene which 13. A process comprising heat polymerizing has been previously partially polymerized cata ring Substituted mono-methyl styrene with pi lytically with the aid of an acid-acting metallic perylene which has been previously partially poly halide catalyst. merized catalytically with the aid of an acid 4. A snythetic resin comprising the product re 30 acting metallic halide catalyst, sulting from the polymerization of ring substi 14. A Synthetic resin comprising the product tuted mono-methyl styrene with a light oil resulting from the heat polymerization of mono piperylene fraction which has been previously meric ring substituted mono-methylstyrene with partially polymerized catalytically with the aid piperylene which has been previously partially of an acid-acting metallic halide catalyst, said 35 polymerized catalytically with the aid of an acid light oil piperylene fraction prior to said partial acting metallic halide catalyst. polymerization containing more piperylene than 15. A new resinous composition comprising the any other diolefine, thermoplastic product resulting from the heat 5. A synthetic resin comprising the product re polymerization of from 60% to 90% piperylene sulting from the polymerization of a light oil ring 40 which has been previously partially polymerized substituted methyl styrene fraction in which catalytically with the aid of an acid-acting me ring-substituted methyl styrene is the predomi tallic haide catalyst with from 40% to 10% nating active compound with a light oil pipery monomeric ring substituted mono-methylstyrene. lene fraction which has been previously partially 6. A new resinous composition comprising the polymerized catalytically with the aid of an acid thermoplastic product resulting from the heat acting metallic halide catalyst, said light oil polymerization of from 70% to 95% monomeric piperylene fraction prior to said partial polymer ring Substituted mono-methyl styrene with from ization containing more piperylene than any 30% to 5% piperylene which has been pre other diolefine. viously partially polymerized catalytically with 6. A new resinous composition for use in liquid 50 the aid of an acid-acting metallic halide catalyst. coating compositions comprising the product of 17. A process for the copolymerization of ring the polymerization of from 50% to 99% pipery substituted mono-methyl styrene and a light oil lene which has been previously partially polymer piperylene fraction at least 50% in piperylene ized catalytically with the aid of an acid-acting concentration, comprising subjecting said light metallic halide catalyst with from 1% to 50% oil piperylene fraction to polymerizing conditions ring substituted mono-methyl styrene. in the presence of an acid-acting metallic haide 7. A new resinous composition for use in liquid catalyst and maintaining the temperature coating compositions comprising the product of throughout the reaction mass not in excess of the polymerization of from 60% to 90% pipery 100° C., the concentration of piperylene not in lene which has been previously partially polymer. BC excess of 80% by weight, and the proportion of ized catalytically with the aid of an acid-acting catalyst to piperylene not in excess of 10% by metallic halide catalyst with from 40% to 10% of Weight, stopping the foregoing reaction while ring substituted mono-methyl styrene. said piperylere is still in partially polymerized 8. A new resinous composition for use in mold state, admixing resulting partially polymerized ing compositions comprising the product of the 65 piperylene and monomeric ring substituted polymerization of from 50% to 99% ring substi In oro-methyl styrene, and subjecting the result tuted mono-methylstyrene with from 50% to 1% ing admixture to polymerizing conditions to pro piperylene which has been previously partially duce a synthetic resin. polymerized catalytically with the aid of an acid 28. The product of the process of claim 17. acting metallic halide catalyst. FRANK. J. SODAY, 9. A new resinous composition for use in mold.