United States Patent Office 2,918,478 Patented Dec. 22, 1959 2 and non-protonic acids, the vinylene carbonate is poly 2,918,478 merized. The polymerizing agents referred to include: WNYLENE CARBONATE AND METHODS OF Benzoyl peroxide PREPARING T Actyl peroxide Melvin S. Newman, Upper Arlington, Ohio, assignor to Di-t-butyl peroxide corporationThe Ohio Stateof Ohio University Research Foundation, a GN GN Dimethyl azobisisobutyronitrile- CH-i-N-N-(-CH, No Drawing. Original application June 1, 1954, Serial CE CH3 No. 433,795. Divided and this application April 16, O Sulfuric acid 1957, Serial No. 653,053 Hydrochloric acid 6 Claims. (CI. 260-340.2) Hydrofluoric acid Perchloric acid This application is the sole application of Melvin S. Aluminum chloride Newman and is a division of a co-pending joint applica s Zinc chloride tion of Melvin S. Newman and Roger W. Addor, Serial Boron trifluoride No. 433,795, filed June 1, 1954, which itself is in part Hydrogen chloride-aluminum chloride a continuation of copending application Serial No. Hydrogen fluoride-boron trifluoride 338,654, filed February 25, 1953. The invention disclosed in this application relates to 20 On treating with a nitrating agent, an aminating agent, vinylene carbonate; to homo polymers thereof; and to an acetylating agent, an alkylating agent (e.g. an ether derivatives of such vinylene carbonate and of such poly fying agent), a carboxymethylating agent, or with other mers and to processes for the syntheses of such com agents, I react the vinylene carbonate, the polymers, or pounds. the derivatives of such polymers further. One of the objects is therefore the preparation of 25 PREPARATION OF VENYLENE CARBONATE vinylene carbonate. I prepared two amounts of vinylene carbonate Another object is the preparation of derivatives of vinylene carbonate. EC-O Another object is the preparation of homo polymers of vinylene carbonate. 30 Another object is the preparation of derivatives of the in three steps (1) by chlorinating ethylene carbonate to polymers of vinylene carbonate such as, for example, obtain the monochloroethylene carbonate and dichloro reaction products of such polymers. ethylene carbonate followed (2) by dehydrochlorination Further objects and features of my invention should 35 of the monochloroethylene carbonate by the use of a be apparent from a consideration of the following specifi suitable tertiary amine, and (3) by the dechlorination of cation and claims. the dichloroethylene carbonate with zinc dust. Generally my inventions in this connection as disclosed The following equation shows my synthesis of vinylene in this application, the aforesaid prior copending appli carbonate using monochloroethylene carbonate as the cation and in other related applications, include (1) the 40 intermediate: chlorination of ethylene carbonate to form mono and/or H dichloro ethylene carbonate and the subsequent dehydro H2C-O C1C-O HC-O chlorination of the mono chloro ethylene carbonate so N ICl) N -HC N formed and/or the dechlorination of the dichloroethylene / -3 c=o a-H c=o carbonate so formed to obtain vinylene carbonate; (2) H2C-O HC-O C-O the condensation of the vinylene carbonate with certain dienes; (3) the homo polymerization of the vinylene Ethylene Monochloroethylene Vinylene carbonate; (4) the copolymerization of the vinylene car carbonate carbonate carbonate bonate with certain olefins and with acetylene type com The following equation shows my synthesis of vinylene pounds; (5) the hydrolysis of such polymers and copoly carbonate using dichloroethylene carbonate as the inter : mers; (6) the reaction of the hydrolyzed polymers and 50 mediate: copolymers and their derivatives with nitrating agents, H acetylating agents, alkylating agents, carboxy-methylating C-O C-C-O HC-0 agents and other similar reactants. N ICl) N 2C) N More specifically as explained in copending application / =O --> C=o mm) C=O Serial No. 338,654, according to the part of my inven 55 HC-O C--O H –o? tions which is claimed herein, vinylene carbonate is pre H pared (1) by the chlorination of ethylene carbonate to Ethylene Dichloroethylene Winylene obtain monochloroethylene carbonate and/or dichloro carbonate carbonate carbonate ethylene carbonate and thereafter (2) by the dehydro chlorination of the monochloroethylene carbonate and/or 60 Example I.-Chlorination of ethylene carbonate the dechlorination of the dichloroethylene carbonate to CHO obtain vinylene carbonate. On heating the vinylene car bonate so obtained with a polymerizing agent or agents CHO c=o such as organic peroxides and acids of the protonic and 65 In a typical reaction, 103 g (1.17 moles) of ethylene non-protonic types and such as combinations of protonic carbonate was added to a cylindrical container having a 2,918,478 3 4 quartz tube for supplying, ultraviolet light, having an in Example III.-Preparation of vinylene carbonate from let tube serving as an inlet for chlorine and having also monochloro ethylene carbonate an outlet tube and a heating bath. The apparatus was C-CEO CEO tared and set up so that the ethylene carbonate was N heated to 70-80° C. with glycerine bath. The ultra 5 violet light source was activated by applying a high po tential current and chlorine was passed in at a moderate Monochloro ethylene carbonate (25.9 g; 0.211 mole) rate. After passage of chlorine for 25 hours, the total was mixed with 150 ml. of dry ether in a 500 ml. three gain in weight was 39 g. neck flask equipped with stirrer, condenser, and sepa The reaction mixture was rectified through a small O ratory funnel. Freshly fractionated triethylamine (22.4 g.; 5% excess) in 50 ml. of dry ether was added drop packed column. The following fractions were taken: wise over a 10 hour period at room temperature. Stirring was continued overnight and for the following day. The Fraction B.P., C. in mm. Weightin i. 724 amber colored liquid was decanted from the dark semi 5 crystalline triethylamine hydrochloride which lined the 87-91. 32-33 7.7 46S 91-93-- 33-34 6.2. 460 flask and the ether was stripped off until a total of 50 ml. 93-129 34-35 10.2 ---------- remained. 29-32 34-35 3.7 1. 4562 132-134 34-35 57.3 1.4534 The flask was stoppered with a calcium chloride tube. 24-125 23-24 24,7 14538 and set aside for one week. During that time a large 125-125- 23-24 11.2 4526 20 amount of triethylamine hydrochloride mixed with some 13.0. dark amorphous material precipitated out. After de cantation, the remaining ether was removed under vacu Fractions 1 and 2 (sharp smelling, lacrymatory, color um and the residue distilled to yield 10.3 g. (0.12 mole; less liquid) consisted mainly of 1,2-dichloroethylene car 56.6%) of a colorless liquid, B.P. 74-77/30-31 mm. 25 which solidified when cooled by ice. A purer sample of bonate. A pure refractionated sample formed a colorless vinylene carbonate was obtained by fractionation and liquid. This was dichloroethylene carbonate: had the following properties: B.P. 73-74/31-32 mm.; C-CEO M.P.-20-21; n25=1.4190. Yo-o Found: percent C=42.14; percent H-2.41. Theor. / 30 for C3H2O3 percent C=41.87; percent H=2.33. C-CEO Infrared analysis showed distinctive carbon hydrogen B.P.s 78-79/19-20 mm.; n25=1.4605. absorption at 3.12a and strained ring carbonyl absorp Analysis.--Found percent C-22.95; percent H=1.21; tion at 5.48u, as well as characteristic maxima at 7.40, percent Cl=45.34. Theor. for CH2O3Cl2 percent 8.60, 9.45 and 11.15u. The compound decolorized chlo C=22.94; percent H= 1.28; percent Cl=45.18. 35 rine in chloroform readily. It decolorized neutral per Infrared analysis of the pure liquid shows its most manganate solution instantaneously as contrasted to the prominent absorption at 5.40u indicating the continued inertness of ethylene carbonate and slowness of reaction presence of a strained ring carbonyl function as is present of monochloro ethylene carbonate with this reagent. A in ethylene carbonate itself. In this paragraph and else freshly distilled sample absorbed 95% of the theoretical where herein, temperatures should be understood at C. 40 quantity of hydrogen on catalytic hydrogenation over a even though not so specifically designated as centigrade. platinum oxide catalyst to yield ethylene carbonate. The Fractions 5, 6 and 7 were nearly pure monochloro hydrogenation product was identified as ethylene car ethylene carbonate: bonate by melting point, mixed melting point, and Cl-CEO infrared analysis. Yo-o 45 CEO / H-0, N CHO c=o - H -- Cseo A pure refractionated sample formed a colorless liquid. H-O B.P. 106-107/10-11 mm.; no.25-1.4530. Analysis.--Found percent C=29.58; percent H=2.54; The infrared absorption maxima were identical at 5.52, percent Cl=29.15. Theor. for CH3OCl percent 50 10.38, 12.98 and 14.02u, (in ether). The melting point C=29.41; percent H=2.47; percent Cls=28.95. data were: Infrared analysis showed sharp strained ring carbonyl Hydrogenation product ----- M.P. 35.8-36.0°; 1°/min. absorption at 5.45p. (uncorr.) Ethylene carbonate -------- M.P. 36.0-36.2; 1/min. Example II.-Chlorination of ethylene carbonate (uncorr.) A stream of chlorine was passed through 303 g. (3.44 Mixed melt---------------- M.P. 36.0-36.2; 1/min. moles) of freshly distilled ethylene carbonate at 63-70 (uncorr.) in the presence of the ultraviolet light. After 24 hours the gain in weight was 119 g. (3.44 moles for mono Recrystallized from ether at low temperature.