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United States Patent Office Patented Dec 3,069,391 United States Patent Office Patented Dec. 18, 1962 2 polymeric structure comprising no more than about 25% 3,069,391 POLYHYEOROXYMETHYLENE POLYMERS of a repeating unit of the formula John Raymond Schaefgeia, Wilmington, Del, assignor to E. E. du Peret de Nenagers and Company, Wilmington, O O Del, a corporation of Delaware 5 N / No Drawing. Fied Feb. 5, 1960, Ser. No. 6,838 4 Claims. (C. 260-77.5) O This invention relates to shaped structures of polymeric and at least about 75% of a repeating structural unit of materials derived from polyvinylene carbonate. More the formula particularly, it relates to a process for producing shaped -C-CH articles of predominantly polyhydroxymethylene or deriva or R tives thereof. wherein -R represents the same or different members of OBJECTS the class consisting of a hydrogen atom and a monovalent It is an object of this invention to produce shaped arti radical, is formed by a process which comprises immers cles comprising high molecular weight polymeric mate ing a useful shaped structure of polyvinylene carbonate rials derived from polyvinylene carbonate. in a hydrolyzing reagent. In a preferred method a shaped Another object is to produce shaped articles compris structure of polyvinylene carbonate is immersed in a ing polyhydroxymethylene. dilute alkaline methanol solution for periods ranging up A still further object is to produce shaped articles from 20 to several days. It is found that the hydrolysis may be derivatives of polyhydroxymethylene. effected quantitatively in about 1 or 2 days if the immersed These and other objects will become apparent in the structure is maintained at a temperature of between about course of the following specification and claims. 50 C. and 60 C. About 3 to 5 days are necessary where the immersed structure stands at room temperature. The STATE OF THE ART hydrolysis may be accelerated by the addition of small Polyhydroxymethylene has been prepared by the hy amounts of water to the methanolic solution. Metal drolysis of the homopolymer of vinylene carbonate. alkoxides in alcohols, alcoholic ammonia, concentrated Newman and Addor (J. Am. Chem. Soc. 75, 1263 aqueous ammonia and other similar basic media may be (1953)), described the preparation of vinylene carbonate 30 employed in the hydrolysis. Fibers and films formed in by bubbling chlorine through ethylene carbonate, the this manner may be oriented by drawing to structures hav reaction being activated by ultraviolet radiation, follow ing good properties. In a preferred embodiment, at least ing which the resulting chloroethylene carbonate is de about 99% of the polyvinylene carbonate is hydrolyzed hydrochlorinated in the presence of an acid acceptor as, to form essentially a homopolymer of polyhydroxymeth e.g., a tertiary amine. A second method of preparation 3 5 ylene. By a “useful shaped structure' is meant one in employs an initial chlorination activated by ultraviolet which no more than two dimensions are minor with refer radiation in a refluxing solution of ethylene carbonate in ence to the third dimension. carbon tetrachloride, followed by dehydrochlorination as The shaped polyhydroxymethylene structures may be described above. The polymerization of the pure mono treated to form derivatives such as polyacetoxymethylene, mer may be initiated by benzoyl peroxide, and polyvi 40 copolymers of hydroxymethylene and acetoxymethylene nylene carbonate is describedf as a clear, colorless solid. and in general derivatives wherein -R, as defined above, The shaping of the polyvinylene carbonate may be accom may be any structure of the class consisting of plished by generally recognized procedures. After prepa O ration by bulk polymerization, solution polymerization, -C-R emulsion polymerization, or other applicable processes, the reaction being initiated by any suitable free-radical-liberat O ing material, the polymer is shaped into film by casting -(-NH-R from solution from one of several solvents, including di -SO-R' and -A wherein -R" is a member of the methylformamide and dimethyl sulfoxide or formed into class consisting of -H and a monovalent organic radi fibers by wet- or dry-spinning techniques, by plasticized 50 cal of the class consisting of aliphatic, aromatic and ali melt-spinning, or by other methods. Wet-spinning may phatic-aromatic types, and -A represents a monovalent be accomplished, for example, by extruding a solution radical derived from an oxygen-containing inorganic of the polymer in dimethylformamide into methanol-wa acid such as -NO2 and -SO3H. Since polyhydroxy ter mixtures. Polyvinylene carbonate may be dry-spun methylene becomes swollen in molten urea, reactions to from a solution in dimethylformamide or from solution form its derivatives are conveniently carried out in that in dimethyl sulfoxide. medium. Since the esterified polymer is soluble in the re Newman and Addor further suggest the hydrolysis of action medium, following isolation it may be shaped by. the polymer to form polyhydroxymethylene, which latter spinning or casting from solution by standard procedures. compound has been more fully described in later publica Among suitable reagents for treating polyhydroxymeth tions: Smets and Hayashi, J. Polymer Sci. 27, 281 (1958); 60 ylene are acetic anhydride, trifluoroacetic acid, trifluoro Haas and Schuler, J. Polymer Sci. 31, 237 (1958); and acetic anhydride, and other similar simple monobasic Unruh and Smith, J. Org. Chem. 23, 625 (1958). Each carboxylic acids or their anhydrides, chlorides, or other of these publications describes the hydrolysis in aqueous reactive derivatives. Sulfonic acids, as benzenesulfonic solution. The polymer is initially solubilized, but as the acid and other simple compounds of the type, may be hydrolysis proceeds, polyhydroxymethylene precipitates. 65 utilized in the formation of suitable derivatives. Iso The latter is found to be insoluble in water and in or cyanates, by reaction with polyhydroxymethylene, form ganic solvents, and thus cannot be formed directly into urethane derivatives, Inorganic orygen-containing acids, shaped articles. as sulfuric acid and nitric acid, may be reacted with poly STATEMENT OF INVENTION 70 hydroxymethylene, and ethers may be prepared by treat ment with simple alcohols under recognized ether-form In accordance with the present invention a useful shaped ing conditions. Ammonia and primary or secondary 3,069,391 A. amines react with the non-hydrolyzed polyvinylene car 5 days at room temperature. The fiber of polyhydroxy bonate to yield a polymer having both hydroxyl and methylene, which has retained the shape imparted to the urethane units. polyvinylene carbonate, is drawn 3.5x in water at 60° C., The following examples are cited to illustrate the in and is then heat-set while taut at a temperature of 200 C. vention. They are not intended to limit it in any way. for two minutes. The product exhibits a tenacity/elon Inherent viscosities have been determined in accordance gation/modulus ratio of 5/10/120. with the following equation: Example 3 A 3 mg. sample of polyhydroxymethylene film is 0. swollen in 0.1 gram of urea containing about 5% anhy The relative viscosity (mei) may be determined by divid drous sodium acetate as a catalyst at a temperature of ing the flow time in a capillary viscometer of a dilute 140° C. Acetic anhydride, in the amount of 0.3 cc., is solution of the polymer by the flow time for the pure sol added. The swollen film is quickly esterified, acetic acid vent. The concentration (c) is in accordance with the is distilled from the reaction mixture, and a clear, color usual practice 0.5 gram of polymer per 100 ml. of solu 5 less, viscous solution results. After 10 minutes, the re tion, and the measurements are made at a temperature action mixture is poured into water, heated to a tempera of 30 C. ture of 70 C. to dissolve the by-product, N-acetylurea, Example 1 and filtered. The resulting polyacetoxymethylene is thylene carbonate, in the amount of 500 grams, is soluble in acetone and dimethylformamide and swollen placed in a reaction vessel with 1000 cc. of carbon tetra 20 by water. Infrared analysis confirms the absence of chloride. An ultra-violet lamp in a quartz jacket is in characteristic hydroxyl absorption and the presence of mersed in the solution, and the mixture is heated to the the expected carbonyl band. An oriented product may point of reflux. Chlorine gas is added rapidly to the be produced by drawing the film to 4.8 times its original refluxing reaction mixture. The course of the reaction length, at a temperature of 200 C. on a hot pin, may be followed by the observation of two “clear" points, 25 Example 4 the first occurring when the refractive indices of the two . A small sample of a film of polyhydroxymethylene is phases are the same, and the second when the mixture placed in a tube with urea, as in Example 2, and an ex becomes homogeneous. Following the appearance of the cess of trifluoroacetic anhydride is added. The tube is second "clear' point, the addition of chlorine is con alternately flushed with nitrogen and evacuated to re tinued until a total of about 600 grams has been removed move traces of air, and is finally evacuated and sealed. from the chlorine tank. The solvent is removed by dis After heating to a temperature of 140 C. for one hour, tillation, and the product distilled under vacuum. The the tube is cooled and opened, and the contents removed. resulting chloroethylene carbonate may be dehydro The product is a partially esterified polyhydroxymethyl chlorinated by treatment with a refluxing solution of tri 35 ene, 50% of the hydroxyl groups having been converted ethylamine in diethyl ether. Following overnight reac to trifluoroacetoxy groups, tion, the solids are removed and washed with ether, and the combined Solutions are evaporated to remove ether. Example 5 Distillation of the residue yields vinylene carbonate, A 3 milligram sample of polyvinylene carbonate film which is purified by reduced pressure reflux treatment with is placed in a solution of ammonia in methanol.
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