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United States Patent Office Patented Dec 3,225,008 United States Patent Office Patented Dec. 21, 1965 2 3,225,008 CEcC-COOC ITACONICESTERS OF 12 ALKANE CARBONATES, POLYMERS, AND COPOLYMERS THEREOF --(CH2)CH-CH Gaetano F. D'Alelio, South Bend, Ind., assignor to Scott Hcoo'". b Paper Company, Philadelphia, Pa., a corporation of Pennsylvania N c^ No Drawing. Filed May 21, 1962, Ser. No. 196,430 O 17 Claims. (C. 260-77.5) This esterification reaction using the anhydride may be performed simply by melting together the two reactants; This invention is concerned with new monomeric esters O but preferably to avoid decarboxylation or other side re of itaconic acid and polymers and copolymers derived actions, the esterification is performed in an inert solvent therefrom. Specifically it relates to itaconic esters of the Such as heptane, hexane, benzene, toluene, dioxane, tetra general formula hydrofurane, etc., and isolating the product. The mono CH=(-COO- R ester thus formed can be used as such for the preparation 5 of polymers and copolymers, or may be used as an inter mediate in the preparation of diesters by conversion to an CHCOO alkali metal salt, such as the sodium, potassium, lithium in which R represents H, a saturated aliphatic hydrocar salt, etc., and reacting the salt with a dialkylsulfate, thus bon radical containing one to eight carbon atoms, and R'; CH=C-COO R represents an alkylene dioxolone radical of the struc 20 --Na. -- R2SO --> ture R E. CHCOO-T -(CH2) --GH, o, o I Oo- R C CHCOO O The new esters of this invention can be prepared also wherein n is an integer having a value of one to four. from itaconic acid, or the lower alkyl esters thereof, and The new monomeric esters of this invention are the ita the cyclic carbonate of the alkane triol desired in accord conic esters of the alpha beta cyclic carbonates of alpha, 30 ance with the general reaction beta, omega alkane triols containing three to six carbon CE=C-COHR -- HO (CH) GH-H, atoms in the alkane chain having the formula CHCOOR O O EO (CH), H-H, Y/ 35 o, -o O C CHC-COO O 2 -R --(CH) CH-CH wherein n is an integer having a value of one to four. C Hi-COO- () () Thus, the new monomers of this invention are the itaconic 40 esters of the 1,2 carbonates of 1,2,3 propane triol; 1,2,4 Ye/ butane triol; 1,2,5 pentane triol, and 1,2,6 hexane triol. Itaconic acid is a dicarboxylic acid, and accordingly, O the itaconic mono- and di-esters of the alcohols, and CeC-C O OR 2HOCH 9HQ, EIO (CEI) (H-H, CHCOOR O www. Y/ O Yo o O O 50 CH=(-COO--(CH2)CH-CH may be prepared and utilized in the practice of this in ECOO vention. O 2 In the monoesters, the remaining carboxylic group may Y/ be left unesterified or may be converted to another ester group containing one to eight carbon atoms as represented 55 O by Rhereinabove. Illustrative examples of the aliphatic The preferred embodiment of R is methyl and ethyl in this hydrocarbon radical R containing one to eight carbon reaction. Alternately, the mono- and di-acid chloride of atoms are methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl itaconic acid can be used in preparing the new monomers, and octyl, which may be linear or branched, such as iso in the presence of a hydrohalide acceptor such as tributyl propyl, secondary butyl, isoamyl, Secondary actyl, etc. 60 amine, sodium carbonate, etc., thus The esters of this invention can be prepared by a num CHiecC-COC pHo(OH). H-B, ber of methods. One convenient method is to use itaconic &HC O Cl O O HAC anhydride and the desired alcohol in accordance with the -- Ye/ mm) reaction I O CatC-CO (CH2) - H-H, Yo - HO(CH2) - E-H, CH=(-COO- o, ) 2 CHCO O &H coo- L s Y/ O O O and 3,225,008 3 4. CH=CC group. The new monomers, in the presence HO(CH2) -H-CH, or absence of other polymerizable >C=C3 containing O O HAC monomers, can be polymerized in bulk, solution, emul Ye/ mm sion, or suspension with or without polymerization initia - s tors and other modifiers. As polymerization initiators there can be used the per-compounds, such as potassium CH=C-COO persulfate, tertiary butyl peracetate, benzoyl peroxide, -R cumene hydroperoxide, tertiary butyl peroxide, tertiary --(CH2)CEI-CI butyl perbenzoate, hydrogen peroxide with or without lood (CH). fill ferrous salts, etc.; the azo catalysts such as alpha, alpha'- o, lo 0. azobis(isobutyronitrile), ultraviolet light in the absence C or presence of ketones, ionizing radiation from X-rays, O electron and particle accelerators, cobalt 60 sources, etc. The specific method used in the preparation of the mon In solution polymerization the medium can be selected omer depends in most cases on the monomer desired; for 5 from solvents which retain the polymer in solution example, when the acid monoester is desired, the method throughout the polymerization, or can be chosen So that using itaconic anhydride is preferred; when a symmetri the polymer precipitates when formed and can be selected cal diester is desired then either itaconyl dichloride, di from the class of aliphatic, cycloaliphatic and aromatic - methyl or diethyl itaconate is reacted with the cyclic hydrocarbons, esters, ethers, ketones, halogenated hydro carbonate of the alkane triol, and when a mixed ester, 20 carbons, etc., or mixtures thereof depending on the form that is, an itaconic ester containing a lower alkyl group in which the polymer is desired. When halogenated hy together with the cyclic carbonate ester group is desired, drocarbons are used, they also act as modifiers of the then the itaconyl chloride lower alkyl monoester, or a polymerizations. In emulsion polymerization, the emul lower alkyl diester is reacted with the cyclic carbonate sifying agent to be used in the aqueous system is selected of the triol as indicated in the reactions hereinabove. 25 from the class of fatty acid soaps, salts of sulfonated The esters of this invention are polymerizable mon alkyl benzenes, polyvinyl alcohol, gelatin, polyacrylic omers possessing a polymerizable CH2=CC structure acid, salts of styrene-maleic acid polymers, gelatin and and may be polymerized to form homopolymers, or co the like, which can be used alone or with buffering agents polymers from a mixture of two or more of these esters, such as sodium acetate, borax, trisodium phosphate and or copolymers from one or more of these new esters with 30 the like. In suspension polymerization, the dispersion other monomers containing a vinyl, CH2=CH-; a vinyl agent can be selected from the class of insoluble inor idene, CH2=C-3 or a vinylene group, ganic carbonates, phosphates and silicates to be used alone or in the presence of minor amounts of defloccu gil-gir lating agents such as sodium dodecylbenzene sulfonate 35 or potassium stearate. illustrative examples of monomers containing such The following examples illustrate the synthesis of the groups are the acrylic esters such as methyl acrylate, ethyl monomers, polymers, and copolymers of this invention acrylate, hexylacrylate, allylacrylate, phenylacrylate, and are not given by way of limitation but by way of illus benzylacrylate, methyl-alpha-chloroacrylate, etc.; the tration. The parts and percentages given are parts and methacrylic esters such as methyl methacrylate, ethyl 40 percentages by weight unless otherwise specified. methacrylate, propyl methacrylate, methallyl methacry late, ethylene dimethacrylate, etc.; the vinyl esters such as EXAMPLE vinyl chloride, vinyl acetate, vinyl stearate, vinyl benzo There were combined in 500 parts of benzene, 84.0 ate, vinyl chloroacetate, divinyl phthalate, divinyl suc parts of itaconic anhydride and 88.5 parts of glyceryl car cinate, etc.; the polymerizable amides and nitriles such bonate, as acrylamide, hydroxymethylacrylamide, methacrylam 45 ide, itaconic monoamides, itaconic diamide, acrylonitrile, O CH, H-H, methacrylonitrile, etc.; the alkenyl aryl compounds such o, o as styrene, o-methyl styrene, p-methyl styrene, alpha C methyl styrene, the chloro-styrenes, divinyl benzene, di 50 O allyl benzene, etc.; the mono- and polyally esters such as in a reaction vessel equipped with stirrer, condenser, and allyl acetate, diallyl succinate, diallyl phthalate, diallyl heating means, and the mixture refluxed at 60° C. for maleate, diallyl fumarate; the vinylidene compounds such 48 hours. Upon standing at room temperature, crystals as vinylidene chloride, vinylidene cyanide, methylene of the ester product are formed and when separated from malonic esters, etc.; vinylene compounds such as vinyl 55 the benzene by filtration will be in an almost quantita ene carbonates, maleic anhydride, maleic monoesters and tive yield. The crude can be used as such or may be maleic diesters; the itaconic compounds such as itaconic purified by recrystallization from water. The ester prod anhydride, the itaconic mono- and the itaconic diesters uct has a melting point of 132-134 C. of the lower and higher aliphatic alcohols; the dienes such Elemental analysis for C and H gives values of 46.85% as butadiene, isoprene, 2-chlorobutadiene 1,3, and the 60 like. The proportion of the new monomers in copoly and 4.57% respectively, which is in excellent agreement mers with other monomer will depend, in accordance with with the calculated values of 47.0% and 4.35% respec the accepted principles of copolymerization, on the reac tively, for the compound, 4-(1,3 dioxolone-2) methyl hy tivity and selectivity constants, r1 and r2 of the comon drogen itaconate, represented by the formula omers used in preparing the copolymer, the ratio of the 65 monomers used and the extent of conversion.
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