Carbonates carrying cyclic carbonate groups

United States Patent [19] Burgard et al. [54] CARBONATES CARRYING CYCLIC CARBONATE GROUPS Michel Burgard, Strasbourg; Marc D. Piteau, Itteville; Alain J. Rollat, Strasbourg Neudorf; Jean-Pierre G. Senet, La Chapelle la Reine, all of France Societe Nationale des Poudres et Explosifs, Paris, France [21] Appl. No.: 139,155 [75] Inventors: [73] Assignee: [22] Filed: Apr. 14, 1980 [30] Foreign Application Priority Data Apr. 13, 1979 [FR] France .............................. .. 79 09402 [51] Int. Cl.3 .......................................... .. C07D 317/36 [52] U.S. Cl. .................................... .. 549/229 [58] Field of Search .................... .. 260/340.2; 549/229 [56] References Cited U.S. PATENT DOCUMENTS 2,446,145 7/1948 Strain ................ .; ........... .. 260/340.2 3,072,613 1/1963 Whelan et al. . .. 260/ 340.2 3,542,841 11/1970 Moore et al. 260/463 3,671,563 6/1972 Pfeiffer et al. .. .. 260/ 340.2 3,912,801 10/1975 Stephens et al. ...................... .. 423/8 [11] 4,423,235 [45] Dec. 27, 1983 Primary Examiner—Norma S. Milestone Attorney, Agent, or Firm—Bucknam and Archer [57] ABSTRACT The invention relates to new industrial products of the general formula R—o—fi:—o—cH2—$H——$H2, ‘o o o a process for the manufacture of these products and their application in hydrometallurgy. According to the invention, R is in particular an alkyl, cycloalkyl, aryl, aralkyl, carboxylate, polyoxyethylene, polyester or polycarbonate group. The process consists in reacting an alcohol or a polyol, ROH, with 2,3-diox- ycarbonylpropyl chloroformate, at between — 10° and +20° C., in the presence of an acid acceptor. Application: the compounds according to the invention are extraction agents for hydrometallurgy, which can be used in dilute solution. 9 Claims, No Drawings 4,423,235 1 CARBONATES CARRYING CY CLIC CARBONATE GROUPS The present invention relates to compounds carrying cyclic carbonate groups, to the processes for the manu- facture of these compounds and to their application in- hydrometallurgy. It is known from U.S. Pat. No. 2,446,145 to prepare 2,3-dioxycarbonylpropyl chloroforniate by reacting phosgene with glycerol. It is also known, from the same document, to obtain the carbamate and corresponding urethanes by reacting this chloroformate with ammonia or amines. Furthermore, the value of certain organic substances having the ability wholly or partially to extract metal ions present in aqueous solutions is known. Such ore- leaching solutions, from solutions resulting from attack on recycled scrap metals or, alternatively, from indus- trial effluents which are harmful to the environment. Basically, these organic substances, which are re- ferred to as extraction agents, must be capable not only of more or less selectively extracting metal ions from aqueous solutions, but also of returning them to a new, pure and more concentrated aqueous solution which is then treated in a manner which is in itself known. However, in order to enable all the advantages pecu- liar to hydrometallurgical techniques to be derived from the extraction agents (versatility, production of metals of high purity, automation, continuous operation and, in particular, utilisation of the ores or waste), the said extraction agents must also possess a number of other properties, namely low solubility in the aqueous phases (a cause of loss), low volatility (also a cause of loss), stability (a further cause of loss), good solubility in inexpensive organic media, good reversibility, high extraction rate, selectivity (in the case of complex solu- tions), high extraction capacity, high coefficient of ex- traction, good resistance to recycling, low or zero tox- icity and low or zero corrosive character. In an article appearing in the review HYDRO- METALLURGY in l976, Volume 1, pages 207-240, and entitled “Solvent Extraction of Non-ferrous met- als”, D. S. FLETT and D. R. SPINK focus on the main extraction agents known and give their spectrum of activity and their conditions of use in each case. A distinction is thus made between solvating, acid, chelat- ing and ionic extraction agents. The solvating extrac- tion agents include phosphates, such as tributyl phos- phate (TBP), ketones, such as methyl isobutyl ketone (or MIBK) or isophorone (U .S. Pat. No. 4,008,308), and ethers, such as glycol dibutyl ether (BUTEX). The acid extraction agents’ include naphthenic and versatic acids and, in particular, di-(2—ethylhexyl)—phosphoric acid (or DZEHPA) (for example U.S. Pat. No. 3,989,607 and French Pat. Nos. 2,342,346 and 2,367,832). The chelat- ing extraction agents essentially include a-hydroxyox- imes (commercially known under the name LIX), which are described in U.S. Pat. Nos. 3,224,873 and 3,449,066. Finally, the ionic extraction agents mainly include amines and quaternary ammonium salts, such as those described in French Pat. No. 1,266,363. The invention itself relates to new chemical com- pounds which, in their application as extraction agents, do not resemble any known type and thereby have a particular spectrum of application, which is suitable for providing solutions to general or specific problems in the field of extraction. 10 15 20 25 30 35 40 45 50 55 60 65 2 The carbonates carrying cyclic carbonate groups, according to the invention, have the general formula: R-0--C--O—CH;_-CH——CH2 (A) II I I 0 in which R is a linear or branched alkyl group which contains from 1 to 20 carbon atoms and is optionally substituted by one to three groups —OCOO-CI-12"‘ CH— CH2, I I o—co——o an alicyclic group which contains 4 to 20 carbon atoms and is optionally substituted by one to three groups ——0—c—o—cH2-—cH—cH2, II I I 0 an aralkyl group which contains from 7 to 20 carbon atoms and is optionally substituted by one to three groups —o—c—o—cH2—cH——'-CH2, II I I o a carboxylate group which contains from 2 to 20 carbon atoms and is optionallysubstituted by a group —O—C-0-CH2—CI-I-—CH2, II — I I o a polyoxyethylene of the formula R'—O—CH7_—CI-12),, in which n is between 1 and 40 and in which R’ is a hydrocarbon group containing from 1 to 10 carbon atoms and optionally carries one or two chains ~—O—CH2——CH2),,', in which n’ is between 1 and 40, which chains are terminated by a group —o—c—o—cH;—cH—cH2, II I I o a polyoxypropylene of the formula R’-(-O-'CH2—?H-)5, CH3 4,423,235 3 in which p is between 1 and 40 and in which R’ is a hydrocarbon group containing from 1 to 10 carbon atoms and optionally carries one or two chains '—('0—CH2-C_—_O (chloroformate) at 1,780 30 cm*1 and v>%O (cyclic carbonate) at 1,800 cm—1 EXAMPLE 2 Preparation of 2,3-Dioxycarbonylpropyl n-Octyl Carbonate 346 g (1.9 mols) of the chloroformate prepared above, 247 g (1.9 mols) of n-octanol and 600 ml of methylene 20 25 35 8 NMR spectrum agrees with the formula. It should be noted that more volatile or less volatile 1 alkyl carbonates can be synthesised with the same ease; under the same conditions and with a comparable suc- cess to that which has just been reported. EXAMPLE 3 Synthesis of trimethylolpropane tri-(-2,3-dioxycar- bonylpropyl carbonate). . 93.8 g (0.7 mol) of trimethylolpropane, 400 cm3 of acetone and 183 g (2.31 mols) of pyridine are introduced into a 2 liter reactor. The temperature is kept at about 0° C. and a solution of 417 g (2.31 mols) of 2,3-dioxycar- bonylpropyl chloroformate in 400 cm3 of acetone is added. After stirring for two hours at ambient tempera- ture, the reaction mixture is filtered, the filtrate is con- centrated under reduced pressure, the residue is taken up in 1.5 liters of methylene chloride and the solution is washed with acidified water and then with pure water. The organic solution is dried, filtered and concentrated under reduced pressure. 347 g (yield 88%) of trimethyl- olpropane tri-(2,3-dioxycarbonylpropyl carbonate) are thus obtained. Melting point: 120° C. Residual OH level: 0% Infra-red spectrum: v E (linear carbonate): 1,750 cm'‘1 0 v OIIIJ (cyclic carbonate): 1,800 cm‘1 0 This spectrum is in total agreement with theory. EXAMPLE 4 Synthesis of tetraethylene glycol di-(2,3-dioxycar- bonylpropyl carbonate). CH2-— CH— CH2'—O-C’-O-('CH2'— CH2--O')2;-C-0-' CH2-' CH——CH2 ! I o chloride are introduced into a reactor equipped with a reflux condenser, a thermometer, a stirrer and a drop- ping funnel. 152 g (2.2 mols) of pyridine (that is to say a molar excess of 15%) are run in over a period of about 1 hour, whilst keeping the temperature between —5° and 5° C. The mixture is stirred for 1 hour at 0° C. and is then left to return to ambient temperature in the course of about 2 hours. The pyridine hydrochloride is removed by filtration 55 and the organic phase is washed with twice 500 ml of water. ‘ ' After drying over magnesium sulphate and removing the solvent by evaporation under reduced pressure, the product is topped at 100° C. under a pressure of 1 mm Hg for 30 minutes. 460 g of a colourless oil, which crystallises at ambient temperature, are thus obtained. The yield is 88% rela- tive to the chloroformate. Analyses: Infra-red spectrum: absorption bands vC-:0 (linear carbonate) at 1,740 cm—1 and vC=O (cyclic carbonate) at 1,800 cm-1 50 60 65 O\ /O C II 0 II II 0 0 2.888 kg (16 mols) of 2,3-dioxycarbonylpropyl chlo- roformate and 5 liters of anhydrous methylene chloride are introduced into a 20 liter glass reactor. The temperature is kept between -4“ and +2° C. and a mixture of 1.552 kg (8 mols) of tetraethylene glycol, 1.430 kg (18.1 mols) of pyridine (that is to say an excess of 13% relative to stoichiometry) and 1 liter of anhydrous methylene chloride is run in slowly, whilst stirring. After the introduction, which takes 1 hour 45 min- utes, the reaction mixture is heated to between +15° and + 18° C. and this temperature is maintained for one hour. 7 liters of salt water are added and the organic phase is separated off. The latter is washed three times with a mixture of 7 liters of salt water and 500 ml of concen- trated hydrochloric acid, twice with 7 liters of salt water and once with 7 liters of demineralised water. The organic phase is dried over anhydrous sodium sulphate and the solvent is removed by evaporation under reduced pressure at 50° C. ' 4,423,235 9 10 3.225 kg (yield 83.6%) of a very viscous product are thus collected, the main characteristics of this product EXAMPLE 6 being as follows: Synthesis of poly—[(diethy1ene glycol) carbonate] water content: 0.040% di-(2,3-dioxycarbonylpropyl carbonate) cH2—CH-cH;o—c—o—(-CH2-—CH2-o—cH1—cH2—o-c—oa-,;—cH2——cH———cH2 I I II II I I o 0 o o 0 o \ C / \C./ ‘ II II 0 O m = 10 content of residual OH groups §10—2 eq/kg The procedure used is strictly identical to the above Tetraethylene glycol di—(2,3-dioxycarbonylpropyl procedure (Example 5), using 410 g (0.33 mol) of poly- carbonate) 15 (diethylene glycol carbonate), 58 g (0.73 mol) of pyri- Cill-lz—-'CH"'CH2— O—C—O'f'CH2— CI-12- O‘)trC-" 0- CH2—(|3HjC|IH2 II II o\ /o 0 o o\ /o C II ' II 0 Viscous liquid, slightly amber—coloured, possessing a dine (that is to say an excess of 10% relative to stoichi- slight odour: 25 ometry), 600 ml of anhydrous methylene chloride and Melting point: 14° C. (transition point) 132 g (0.73 mol) of 2,3-dioxycarbonylpropyl chlorofor- Vapour pressure mate. at 20° C.: 5 mm Hg . 435 g of product are thus collected, the infra-red at 100° C.: 22 mm Hg spectrum of this product agrees with the formula given Density d2525: 1.41 30 above and its number—average molecular weight is Viscosity at 25° C.: 60,000 cP about 1,500, its content of OH groups is less than or Refractive index at 25° C., nD25: 1.4750 equal to 0.02 eq/kg and the total chlorine level is 0.06%. Solubility: insoluble in water, good solubility in or- ganic solvents (60 g in 100 g of CH2C12 at 20° c.) EXAMPLE 7 Synthesis of 2,3-dioxycarbonylpropyl (ethyl 35 EXAMPLE 5 methacrylate) carbonate Synthesis of poly-(ethy1eneglycol)di-(2,3-dioxycar- bonylpropyl carbonate) 11.4 g (0.1 mol) of 2-hydroxyethyl methacrylate, 9 g (0.11 mol) of pyridine and 50 ml of 2,3-dioxycarbonyyl-