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UNITED STATES PATENT OFFICE 2,385.93 UNSATURATED ESTERS and POYMERS REO Irving E

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UNITED STATES PATENT OFFICE 2,385.93 UNSATURATED ESTERS and POYMERS REO Irving E 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.
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