Patented Oct. 2, 1945 2,385,931 UNITED STATES PATENT OFFICE 2,385.93 UNSATURATED ESTERS AND POYMERS REO Irving E. Muskat, Akron, and Franki Sahn Norton Center, Ohio, assignors to Pittsbarah Plate Glass Company, Pittsburgh, Pa., a corpor ration of Pennsylvania No Drawing. Appeation December 2, 19, Seria No. 42,665 8 Claims. (C. 26-8) This invention relates to a new class of unsatul or substituted hydrocarbon group which is at rated esters which are capable of polymerization tached to the hydroxy and carboxylic group of to form new and highly valuable resinous con the hydroxy acid. positions and to such compositions. These new The new esters may be prepared by reacting unsaturated compounds are esters of (a) a par a chloroformate with an ester of an hydroxy tial ester of a carbonic acid and (b) an ester of carboxylic acid or by reacting an alcohol with a an hydroxy carboxylic acid. chloroformate of an hydroxy carboxylate. For The new esters are esters of unsaturated alco example, phosgene may be reacted with an un hols, preferably those which contain three to five saturated alcohol ester of an hydroxy acid such carbon atoms and which contain an unsaturated O as ally lactate, allyl glycolate, allyl salicylate, group in an aliphatic chain, such as allyl, meth ally ricinoleate, ally hydroacrylate, trially cl allyl, crotyl, isocrotyl, propargyll, isopropenyl, trate, diallylmalate, ally leucinate, etc., and the methyl propargyl, ethylally, and butadienyl al corresponding methally, vinyl, crotyl, chloroally, cohols, methyl vinyl carbinol, ethyl vinyl carbinol, etc. esters to form corresponding chloroformates and the Corresponding halogen substituted alco s or chlorocarbonates having the structure: hols such as 2-chloroally, chlorocroty, and 2 bromoallyl alcohols. Moreover, the unsaturated alcohol radical attached to the hydroxy acid may be a vinyl group. Esters of alcohols containing This reaction is conducted at low temperatures, six to ten carbon atoms, for example, the esters preferably between O' C. and --10" C. which are of cinnamyl, phenyl propargyl, and propyl ally maintained by means of an ice bath. The ten alcohols, diallyl carbinol, linalool, geraniol, 1 peratures can be more easily regulated by adjust hydroxy hexadiene-2-4, ethyl isobutenyl carbinol, ing the rate of phosgene addition. Since the re 1-hydroxyoctene and the halogen substituted action is exothermic, lower rates of addition favor products of the same such as chlorocinnamyl al lower temperatures. The chloroformates thus cohol and ethyl chlorally carbinol. obtained may be reacted with an equimolar quan The new group of unsaturated compounds are tity of an unsaturated alcohol which may be the esters of a monohydroxy carboxylic acid such as same or different from the unsaturated alcohol glycolic, lactic, hydraacrylic, leucinic, salicylic, used to esterify the hydroxy acid. The reaction hydroxy butyric, phloritic, coumarinic, acetonic, 30 is conducted in the presence of an alkaline re meliotic, valerolactinic, or ricinoleic acids or the agent such as pyridine or other cyclic tertiary monohydroxy polycarboxylic acids such as tar amine, or oxide, hydroxide, or carbonate of a tronic, malic, oxalacetic, citromalic, hydroxy strongly electronegative metal. This second step phthalic, citric, isomalic, and itamalic acids. may be conducted attemperatures of 0 to 10 C., Acids with more than a single hydroxy group in 35 although higher temperatures may also be used which all but one of the hydroxy groups are in certain cases, particularly when calcium car esterified or etherified with a simple monofunc bonate is used as the alkaline reagent. In ac tional group such as methyl, ethyl, ally, etc., or cordance with a further method, an unsaturated with acetate, formate, propionate, etc., groups chloroformate such as ally chloroformate, meth are included within the intended scope of the 40 ally chloroformate, chloroally chloroformate, expression "monohydroxy acid' and accordingly, etc. may be reacted with an hydroxy ester of an esters of such acids may be prepared in accord unsaturated alcohol and an monohydroxy car ance with the present invention. Thus, the boxylic acid in the presence of an alkaline re methyl, ethyl, allyl, etc. mono ethers of tartaric agent. acid, the methyl, ethyl, allyl, etc. monoethers of These new unsaturated esters are true chemical glyceric acid, the methyl, ethyl, ally, etc. ethers compounds having definite boiling and melting of mesoxalic acid and also the monoformate, points. Accordingly, some of thern may be pur monoacetate, monopropionate, etc., of tartaric, fied by distillation at reduced pressures. Bow glyceric, etc. acids are included within the scope ever, some of these esters have such high boiling of this invention. points that the use of distillation methods for The esters which contain two or more radicals purification is impracticable. Accordingly, the derived from unsaturated alcohols are of especial compounds maybe purified by Washing with dilute importance. Many of these esters may be rep acids, water, or salt solutions to remove water resented by the general formula: soluble impurities and by heating under normal 55 or reduced pressures to vaporize the more volate inapurities. When the unsaturated esters being R-0--R-0--0-R,O O prepared or any of the reactants or intermediate products are solids it may be desirable to conduct in which R1 and R3 are radicals derived from the synthesis in the presence of a suitable solvent unsaturated alcohols and R2 is the hydrocarbon 60 such as benzene, toluene, ether, xylene, chloro 2 2,885,931 formate, etc., to enable the reaction to proceed thereby relieving the polymerization strains. The in liquid phase. Most of the liquid esters are gel may thereafter be shaped, if desired, and poly. clear, colorless, and miscible with numerous or merized to the final infusible state. Smooth, opti ganic solvents such as acetone, alcohol, chloro cally perfect sheets may be made by this method. formate, dioxane, benzene, xylene, toluene, ethyl 5 Preferably, the initial polymerization is conducted ether paraffin hydrocarbons, etc. at a temperature sufficiently low to prevent the The monomeric esters are valuable as plasti decomposition of the peroxide catalyst. This tem cizers for various resin materials such as styrene, perature is dependent upon the catalyst used. cellulose, vinyl, urea, protein, phenolic or acrylic For benzoyl peroxide temperatures of 65 to 80° C. resins. Other uses such as solvents, insecticides, 10 are suitable while for acetone peroxide tempera and liquid coating compositions are noteworthy. tures of 140-150° C. may be used. The soft sheet The new compounds polymerize in the presence of gel is then freed of the mold and in accordance of heat or light and polymerizable catalysts to with one modification the gel may be coated on yield solid or liquid compositions of widely differ both sides with monomer or the syrupy polymer. ent physical properties. The polymerization is 15 The coated article is then polymerized between preferably conducted in the presence of catalysts Smooth heated plates to the final insoluble state. such as Oxygen, O2One, or Organic peroxides such In order to inhibit formation of cracks dur as lauryl, benzoyl, and acetone peroxides. ing the initial polymerization, it is frequently de The products of polymerization vary greatly in sirable to minimize the polymerization on one their physical properties, depending upon the 20 side of the sheet. This is done by conducting molecular structure of the monomer as well as the polymerization with one side exposed to the upon the extent of polymerization. In general, air which inhibits polymerization in the presence the polymers are clear and transparent and upon of a peroxide catalyst such as benzoyl peroxide. polymerizption, a range of resins from hard, By this means a sheet is produced which is hard brittle products to soft, flexible materials may be 25 and Smooth on one side while being soft and secured. tacky on the other. The sheet may then be fin Compounds having only a single polymerizable ished by coating the tacky side with monomer group may be polymerized to form thermoplastic Or Syrupy polymer and polymerizing it in con resins which are capable of fusion at elevated tact with a smooth plate to the insoluble infusible temperatures. On the other hand, when the poly 30 state. Often it is found desirable to release the unsaturated compounds are polymerized come polymer from the plate one or more times dur pletely, an infusible insoluble resin is produced. ing the polymerization of the coating in order to Intermediate polymers of the polyunsaturated minimize formation of cracks or other surface compounds having a wide range of properties may defects. be secured. Upon the initial polymerization of 35 Other methods have been developed for poly liquid monomers or solutions of the monomers in merization of the polyunsaturated compounds suitable solvents, an increase in the viscosity of herein contemplated while avoiding formation of the liquids occurs due to the formation of a simple cracks and fractures. By one of the methods polymer which is soluble in the monomer and in the polymerization may be suspended while the solvents such as acetone. benzene, xylene, dioxane, 40 monomer-polymer mixture is in the liquid state toluene, or carbon tetrachloride. Upon further and before the polymer is converted to the gel by polymerization, the liquid sets up to form a soft cooling, by removal from exposure to ultra-violet gel containing a substantial portion of a polymer light, by adding inhibiting materials such as which is substantially insoluble in the monomer pyrogallol, hydroquinone, aniline, phenylene and organic solvents and containing as well, a diamine, or sulphur, or by destruction of the poly substantial portion of soluble material which may merization catalyst. The fusible polymer may be monomer and/or soluble fusible polymer. be separated from all or part of the monomer These gels are soft and bend readily. However, by any of several methods. It may be precipi they are fragile and crumble or tear under low tated by the addition of nonsolvents for the stresses. They may be further polymerized in the 50 fusible polymer such as water, ethyl alcohol, presence of catalysts to the final infusible insolu methyl alcohol, or glycol. Alternatively, it may ble state in which the polymer is substantially in also be separated from the monomer by distilia fusible and substantially insoluble in organic sol tion in the presence of an inhibitor for polymeri vents, acids, and alkalies. 2ation, and preferably, at reduced pressures. The monomeric polyunsaturated compounds 55 The fusible polymer is thus obtained in stable may be cast polymerized directly to the insoluble, solid form and as such may be used as a molding infusible state. This procedure is subject to cer powder or may be redissolved in suitable solvent tain inherent difficulties due to the reduction in for use in liquid form. It is soluble in organic volume during the polymerization. The loss of solvents which are normally capable of dissolving volume or shrinkage causes strains to be estab 60 methyl methacrylate polymer or similar vinyl lished in the hardening gel which frequently re type polymer. Preferably, the polymers are pro sults in fractures as the final hard form is at duced by heating the monomer or a solution tained. It has been discovered that these dif thereof in the presence of 2 to 5 percent of ben culties may be avoided by releasing the strains Zoyl peroxide until the viscosity of the solution established in the gel. This may be done by inter. 65 has increased about 100 to 500 percent. This rupting the polymerization at an intermediate may require Several hours While heating at stage and permitting the strains to be relieved 65-85 C. in the presence of benzoyl peroxide. or by conducting polymerization under conditions The resulting viscous solution is poured into an which permit gradual release of these strains. equal volume of water, methyl or ethyl alcohol, For example, the polymerization may be con 70 glycol or other nonsolvent for the fusible poly ducted in a simple mold until a soft firm gel has mer. A polymer usually in the form of a powder formed. At this point the polymerization may be or a gummy precipitate is thus formed which interrupted and the shaped polymer freed from may be filtered and dried. This permits sub the mold to which it adheres strongly. When stantially complete separation of a soluble fusible released the polymer contracts substantially, 75 polymer from unpolymerized monomer. Often, 2,885,981 3 however, such complete separation may not be The fusible polymers may be dissolved in suit desirable since hazy products may be secured able solvents and used as coating and impregnat upon further polymerization. Accordingly, it is ing compositions. For example, the solution or often desirable to produce compositions compris dispersion of fusible polymer in monomer or other, ing the fusible polymer and the monomer. This is Organic solvent such as benzene, toluene, chloro may be effected by partial distillation or extrac form, acetone, dioxane, carbon tetrachloride, tion of monomer from the polymer or by re phenyl Cellosolve, dichlorethyl ether, dibuty blending a portion of the fusible polymer with phthalate, or mixtures thereof is useful as a liq the same or a different polymerizable monomer. luid coating composition. Objects of paper, metal, In such applications the composition should O Wood, cloth, leather, or synthetic resins may be contain at least 40 percent and preferably in ex coated with the solution of polymer in solvent cess of 50 percent fusible polymer and from about and Subsequently polymerized to yield attractive 5 percent to 50 or 60 percent monomer. Prefer ly finished coatings. Similarly, porous objects ably, the production of these fusible polymers of felt, cloth, leather, paper, etc., either in single is conducted by treatment of a solution of the 5 layers or laminated may be impregnated with the monomer in a solvent for monomer and polymer dissolved fusible polymer and subjected to the such as benzene, xylene, toluene, carbon tetra polymerization to the final infusible insoluble chloride, acetone or other solvent which normally state. - dissolves vinyl polymers. Other polymerization The following examples are illustrative: methods may involve the interruption of the 20 polymerization while the polymer is a ge. For Eacample I example, a soft solid gel containing a substantial - portion of fusible polymer may be digested with 365 parts by weight of allyl chloroformate was a quantity of solvent for the fusible polymer to added over a period of 24 hours to 357 parts by extract the fusible gel from the infusible. The 25 weight of ally lactate dispersed in 268 pts. by solution may be then treated as above described wt. of pyridine with stirring at a temperature to separate the fusible polymer from the solvent. maintained between 2 and 18°C. The reaction , These polymers may be used as molding or coat mixture was acidified to the methyl orange end ing compositions. Due to their solubility they point, washed with water, dilute HCI, dilute are particularly desirable for use in paint com 30 Na2CO3 solution, and finally again with water. positions. The new compound was dried over anhydrous so Other fusible polymers may be prepared by dium carbonate and purified by distillation. The carrying the initial polymerization to the point product, an ester of allyl acid carbonate and ally where the polymer is in the form of a gel which lactate, was a colorless liquid of low viscosity generally contains at least 20 percent and pref 35 which boiled at 112 C. at 2 mm. of pressure and erably about 45 to 80 percent by weight of sub had an index of refraction (n) of 1.438 and a stantially insoluble polymer, but at which point density (d) of 1,064. The formula of this com the gel is still fusible. This solid resin composi pound probably is as follows: tion may be disintegrated to a pulverulent form Ho and used as a molding powder. Alternatively, a O desirable polymer may be prepared by emulsify CB- --ochsch-CH, ing the monomer Or a syrupy polymer in an aqueous medium with or without a suitable emulsification agent such as polyvinyl alcohol, polyallyl alcohol, polymethallyl alcohol, etc., and then polymerizing to the point where the gel &B,CH=CH, precipitates. This polymer may be separated A quantity of the ester of ally acid carbonate and used as molding powder. and ally lactate was heated over an oil bath at The solid forms of the fusible polymers may a temperature of 150° C., while bubbling a stream be used as molding compositions to form desir of air through the monomer. After about three able molded products which may be polymerized hours the viscosity of the polymerizing ester had to a thermohardened state. Preferably, the increased noticeably. The fusible polymer was molding is conducted in a manner such that the then precipitated by adding methanol and re polymer fuses or blends together to form a sub stantially homogeneous product before the com 55 covered. The fusible polymer was mixed with position is polymerized to a substantially in one percent benzoyl peroxide and molded in a fusible state. This may be effected by conduct press under a pressure of 2000 pounds per square ing polymerization at an elevated temperature inch for 30 minutes at a temperature of 145 C. and/or pressure in the presence of to 5 per The resulting product was a colorless solid resin. cent of benzoyl peroxide, generally in a heated 60 Eacample II mold. The polymers may be mixed with filers such as alpha cellulose, wood pulp, and other 453 gms. of methally lactate was mixed with fibrous substances, mineral fillers, or pigments 298 gms. of pyridine in a reaction vessel equipped such as zinc oxide or calcium carbonate, lead with a stirring device. 464 gns. Of methally chromate, magnesium carbonate, calcium silicate, 65 chloroformate was slowly added thereto while etc., plasticizers such as the saturated alcohol the reaction mixture was maintained between 10 esters of maleic, fumaric, succinic, and adipic and 20° C. The product was washed with water acids or di- or triethylene glycol bis (butyl car and heated at 95-100°C. in the presence of acti bonate). The polymeric molding powder may be vated charcoal at a total pressure of 15-20 mm., copolymerized with phenolic, cellulose acetate, O whereby most of the impurities were removed. urea, vinylic, protein, or acrylic resins. It is After the carbon was removed by filtration the thus possible to produce transparent or opaque methaly acid carbonate ester of methally forms of a wide variety of colors and hardnesses, lactate was dried over anhydrous Sodium Sul depending upon the proper selection of the modi phate. The product is a clear colorless liquid fying agents, 75 having a density (do) of 1.058 and an index of 4. 2,385,981 refraction (N) of 1.445. This compound has pyrogallol were heated at 85-95 C. for 4 hours. the following probable structure: The evolution of water vapor had apparently ceased and the reaction was then cooled to 0° C. and mixed with 500 cc. benzene and 100 gms. of 5 pyridine. Allyl chloroformate was then dropped 6 h, in slowly at a rate which permitted the reaction (=o CH temperature to remain below --10° C. The mix (-CH-C-CH, ture was permitted to stand for 15 hours after the The compound was polymerized by heating in the addition was completed. The ester prepared was presence of 5 percent of benzoyl peroxide at a 0. a high boiling, substantially colorless liquid which temperature of 70 to 80 C. to form a hard, trans is believed to have the following structure: parent, and colorless resin. Eacample III CH=CH-0----0--0-CH-CH=CH,bH, A mixture of 100 gms. of pyridine and 116 gms. 5 -CH of allyl glycolate was prepared and 130 gms, of The ester was separated from its impurities by methallyl chloroformate was added slowly, while heating at 2-10 mm. until all of the benzene was the temperature was maintained between --5 and evolved and was then washed with water and --18 C. The resulting ester was believed to have dried Over anhydrous sodium sulphate. The ester the molecular constitution: polymerized upon heating with 2 percent benzoyl C-C-C-O-C-O-CH-C-O-CH-CHsCH peroxide at 85 C. for one and one-half hours. bH, s Eacample VII It was freed of impurities by washing with water 60 gms. of allyl alcohol, 1% gms. of hydro and dilute HCl and separating from the benzene 25 quinone, and 100 gms, of valerolactinic acid were by distillation at reduced pressures. A five-gram heated at 80-90° C. for 6 hours. After the ester sample was polymerized readily by heating to 75 ification had taken place to a substantial extent, C. for one hour in the presence of 5 percent ben the excess allyl alcohol was distilled off by heat Zoyl peroxide. ing to 95 C. for one-half hour. One-half liter Eacample IV 30 of benzene was added and the mixture was cooled 150 gms. Of allyl leucinate made by the direct to 0 C. on an ice bath. Phosgene was passed esterification of leucinic acid with allyl alcohol in at a rate of about 20 millimeters per minute was mixed with 500 cc. of benzene. The solu for 10 minutes and then at a rate of 25-30 mil tion was cooled to about 0° C. in a mixture of ice limeters per minute for a hour. The temper and salt. Phosgene was bubbled into the cold so 35 ature was maintained between 5° C. and 12° C. lution at a rate of about 20-30 millimoles per min throughout the entire reaction. The benzene ute while the reaction mass was stirred. The Solution of the chloroformate of the allyl temperature of the reaction vessel remained be Valerolactinate was washed with dilute hydro tween --2 and --12 C. throughout the reaction. chloric acid and water water. The solution The reaction was substantially complete in about 40 was then mixed with 40 gms, of allyl alcohol 2 hours. A mixture of 50 gms. Of allyl alcohol and and 80 gms, of pyridine were added slowly at 80 gms. of pyridine was prepared and the chloro such a rate that the temperature was maintained formate solution slowly added while cooling to below 15 C. at all times, keep the reaction mass at a temperature below The crude benzene solution was washed with --10 C. at all times. The resulting benzene solu 45 dilute hydrochloric acid, Na2CO3 solution and tion was washed with dilute HCl and with water finally with water. The benzene was removed and finally dried Over anhydrous sodium sulphate. by evaporation. The ester was mixed with 2 The ester was separated from the benzene solvent percent acetone peroxide and heated at 150° C. by heating at a total pressure of between 2 mm. for one hour. A hard polymerized material was . and 10 mm. until the benzene was evaporated. 50 formed. The ester was believed to have the structure: Eacample VIII A Solution of 178 gms. of allyl salicylate in CH=CH-CH-O--H-0--0-CH-CH=CH, 1000 cc. of benzene was cooled on an ice bath O ch, O to +2' C. 100 gms. of pyridine was added to CH-CH-CH, 5 5 the mixture. Allyl chloroformate (120 gms.) was Eacample V added slowly at a rate of about 2-3 grams per A quantity of the ester prepared as in Example minute while maintaining the reaction vessel sub IV was dissolved in benzene to form a 15 percent merged in the ice-salt mixture. The temperature solution thereof. This solution was mixed with 60 rose to 12 C. but through most of the reaction 5 percent benzoyl peroxide (based upon the ester) it remained below --5° C. When the addition and heated at 50 C. for two hours. A pronounced of the chloroformate was completed the reaction increase in viscosity was noted. The viscous so mass was permitted to warm to room tempera lution was then poured into an equal volume of ture. The solution was washed with dilute HC methyl alcohol. A fine pulverulent polymer was 65 and with water and then dried over anhydrous precipitated and separated by filtration. After Sodium sulphate. The benzene was evaporated washing and drying a light yellow granular solid by boiling at 2-10 mm. total pressure. The ester was obtained. A five-gram sample was mixed thus obtained had the following structure: with 3 percent benzoyl peroxide and pressed in C=CH-C-O-C-O C-O-CH-CH=CH a mold at 2000 pounds per square inch at 135 C. 70 A brittle, transparent, and nearly colorless resin of NO was formed. Eacample VI A five-gram sample was mixed with 4 percent A quantity of 60 gms. of methallyl alcohol, 95 acetone peroxide and heated for one hour. A gms. Of alpha hydroxybutyric acid and 1 gm of 75 tough polymerized material was produced. s 2,885,981 5 Eacample IX Eacamplex Ricinoleic acid (150 gms.) was esterified by heating with 72 gms. of methallyl alcohol and The procedure of Example VIII was duplicated one gram of phenolsulphonic acid for about 3 except that chlorallyl alcohol was used in place 5 of allyl alcohol. An ester having the following hours. The ester Was Washed with a Small quan molecular constitution was believed to have been tity of water and dried over Sodium sulphate. Synthesized: The methally ricinoleate thereby produced was dissolved in 1000 cc. of benzene and 50 gms, of O pyridine. The mixture was cooled to 0° C. and CH-C-CH-O- 65 gms. of methallyl chloroformate were added O b slowly at a rate which permitted the maintenance of the temperature below 0° C. throughout the reaction. The reaction vessel was immersed in an ice salt mixture during the reaction. The on-onl benzene solution of the unsaturated ester was 15 Although the invention has been described with washed with HCl and water and then dried. The respect to certain specific details, it is not in ester was separated from the benzene and other tended that these details shall constitute limita impurities by distillation. It has a structure tions upon the invention except as they are in believed to be as follows: Corporated in the following claims. CH-(CH2)-CH-CH-CH=CH-(CH), 20 This application is a continuation-in-part of Os applications Serial No. 392,103, filed May 6, 1941, o- CH-C-CH-) and Serial No. 361,280, filed October 15, 1940, both CH-C-CH-) by Irving E. Muskat and Franklin Strain, &B, 25 We claim: H 1. An ester of triallyl citrate and allyl acid Eacample X Carbonate. 2. An ester of chlorally salicylate and chlor A solution of 165 gms. of triallyl citrate in 1000 allyl acid carbonate. cc. of benzene was treated with an excess of phos 3. An ester of methally ricinoleate and meth gene at temperatures between 0° C. and 10° C. SO allyl acid carbonate. maintained by immersing the reaction vessel in an ice salt mixture. The solution was warmed 4. A polymer of an ester of triallyl citrate and to 50° C. to evolve the excess phosgene. The ally acid carbonate. benzene Solution was Washed with Water and 5. A polymer of an ester of chlorallyl salicylate dried with sodium sulphate. A mixture of 30 is and chlorallyl acid carbonate. gms, of allyl alcohol and 50 gms. Of pyridine was 6. A polymer of an ester of methally ricinoleate prepared in a 1500 cc. flask and placed in an and methallyl acid carbonate. ice bath. The benzene solution of the chloro 7. A compound having the structural formula: formate was added slowly at the rate of 20-30 cC. per minute. The temperature of the reac O R-0--0-R, --O-R, tion mass varied from -2° C. to --12 C, during io-lo the addition. The ester in benzene Solution was wherein R is a radical equivalent to the radical R. washed in HCl and Water. The benzene was in the alcohol ROH, said alcohol being an un removed by heating in a vacuum. An ester of saturated monohydric alcohol having from 3 to the following composition was thereby produced: d's 10 carbon atoms and having a carbon to carbon unsaturated linkage between the beta and gamma O carbon atoms therein, R1 is a hydrocarbon radical CH-i-o-CH-CH=CH, having a valence of (X-1), R2 is a radical equiv O O alent to the radical Ra in the alcohol RaOH, said 0 alcohol being an unsaturated monohydric alcohol -o- --O-CH-CH=CH, having from 2 to 10 carbon atoms and having a carbon to carbon unsaturated linkage adjacent . bi-o-o-on-on-on, the beta carbon atom therein, and X is a small le, s whole number from One to three. SS 8. A polymer of the compound defined in claim A ten-gram sample was mixed with five percent 7. benzoyl peroxide and heated at 75 C. for one hour. A brittle, transparent, resinous compou RVNG. E. MUSKAT. sition was produced. FRANKLN STRAN.