• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A new process is disclosed for the synthesis of alkylene carbonates having from 2 to 4 carbon atoms in the chain, starting from a corresponding halohydrin having the formula: wherein R., Rb, Rc and Rd are independently hydrogen or alkyl, aryl, alkylaryl or arylalkyl radicals and where X is a halogen, characterized in that said halohydrin is reacted with a bicarbonate of a quaternary -onium compound, where "-onium" means ammonium, phosphonium, arsonium or stibonium, preferably using an organic solvent as diluent and operating in the presence of carbon dioxide.
    公开号:SU812179A3
    申请号:SU792751501
    申请日:1979-04-13
    公开日:1981-03-07
    发明作者:Вентурелло Карло；Д Алоизио Рино
    申请人:Монтэдисон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved use of a toxic phosgene method for producing alkylene and high temperatures limits the carbonates that * find * use this method, some as solvents for - * Closest to the proposed organic polymers, electrochemical. The method is a method for the production of almic solvents in organic synthesis of general formula carbon synthesis.
    There are various methods for producing alkylene carbonates, for example, from θ oxides of the corresponding alkene and carbon dioxide in the presence of lithium bromide at 40-60 ° C in an aprotic solvent with a yield of up to 80% [1]. . .
    The second method of producing alkylene carbonates involves the interaction, for example, of ethylene glycol with phosgene in a molar ratio of 0.5: 1.0 and volumetric phosgene in a mixture with inert gas of 20 eohm of 80-150 volumes per 1 volume of the reaction mixture for 1 h 12].
    The third method for producing alkylene carbonates is that 25 alkylene oxide reacts with carbon dioxide in the presence of a catalyst at a temperature of 100-250 ° C and a pressure of 50-150 atm. The yield of the target product is up to 99%. thirty
    where 1C-th 4 - hydrogen, alkyl, aryl,. arylalkyl, alkylaryl, with up to 10 carbon atoms, 'by the reaction of the corresponding halohydrin, carbon dioxide and amine N (R *) j, where R * 1 is alkyl, in a solvent. The process is conducted mainly under heating (70-130 ° C) and pressure. The alkylene carbonate selectivity is 97.3%. The process takes 2-3 hours [4].
    The aim of the invention is to simplify the process and reduce its duration.
    This goal is achieved by the fact that as a nitrogen-containing
    812179 'or benzyltrimethylammonium can be carried out in a strength layer, the quaternary ammonium bicarbonate or strongly alkaline anion-exchange resin, + k''having NRi groups, where (% - Rg R 3 are the same or different alkyl or oxyalkyl radicals containing from one to two carbon .
    It is most expedient to use tetramethyl ammonium bicarbonate in the process.
    The process of a non-alkaline anion-exchange resin pendant in the reaction liquid.
    As a solvent, acetonitrile can be used.
    This ensures that the process is carried out at room or low (60 ° C) temperature, mainly without pressure in a short time -10-60min. Amberlite-7RA-400-OH or Castel-A-ZOO-OH are predominantly used as a strongly alkaline resin.
    The starting halides may be ethylene chlorohydrin, ethylene bromo or iodohydrin, 2-chloropropanol-1 or 2-bromo or 2-iodopropanol-1, etc.
    As solvents, methanol, butanol, acetone, dioxane, acetonitrile, dimethylformamide, benzene, toluene, xylene, dimethyl sulfoxide can be used.
    From water-organic mixtures, it is advisable to use a mixture of water-dioxane or water-acetonitrile. In special cases, water can be used.
    The amount of ammonium compound, taking into account the groups- + N— 8 -1, should be equivalent to or in excess with respect to the halohydrin.
    Tetraalkylammonium halide or the corresponding resins are readily separated by filtration in almost quantitative yield.
    The target product is isolated from the filter by distillation.
    . In the case of using an anion exchange resin, it is regenerated with an aqueous solution of hydroxide nc ^ gria or ammonium, followed by carbonization. In this case, they work with two or several devices that work alternately, for example, they work in one, and regenerate in the other.
    The synthesis temperature can be changed if necessary, although the best results are obtained at room temperature. An increase in temperature leads to a decrease in the duration of the process, but the temperature should not be higher than the boiling point of a solution with a small amount of exciter or decomposition of an anion-exchange resin. The effect of pressure is two. carbon monoxide is not critical, so it can be in the range from atmospheric to 30 atm.
    Example 1. 46 g of a methanol solution of 24% tetramethylammonium hydroxide (.0.12 mol) is diluted with 50 ml of methanol and the solution is carbonized with carbon dioxide for 40 minutes, then the methanol is distilled off in vacuo, the residue is diluted with acetonitrile and incubated for 10 minutes in an atmosphere of carbon dioxide to stop gas absorption. 0.1 mol of ethyl bromohydrin was added to the resulting solution, and the suspension was stirred at 20 ° C. under an atmosphere of carbon dioxide for 10 minutes.
    The precipitate is filtered off, washed twice with 40 ml of acetonitrile. The resulting filtrate and washings are distilled in a weak vacuum to separate the solvent; and the residue was washed with methanol to remove traces of salt, filtered, the solvent was evaporated, and 9.63 g of an oil was obtained, which solidified at room temperature. After distillation in vacuo (73-75 C / 0.4-0.5 mm Hg), 8.45 g of solid ethylene carbonate are obtained with an input of 96% bromohydrin.
    Example 2 0.1 mole of 98% propilenyodgidrina added to a solution of tetrabutylammonium bromide in acetonitrile obtained in Example 1. The suspension was stirred at 20 ° C in an atmosphere of carbon dioxide with tetmetilammoniybikarbonatom. Then the precipitate was separated, washed with 50 ml of acetonitrile. The combined solutions together with the filtrate were distilled in vacuo, the remaining liquid was diluted with acetone, and traces of salt (1.5 g) were filtered off. Acetone is distilled off and the resulting oil is distilled in vacuo at 59-60 ° C and 0.5 mm Hg. 9.40 g of propylene carbonate are obtained. The yield of iodohydrin is 91%, and the purity is 98.6%.
    Example 3. To an acetonitrile suspension of tetramethylamionium bicarbonate obtained in example 1, add 0.1 mol of erythro-2-bromobutanol-2. The process is carried out, as in example 1, for 20 minutes at a temperature of 20 ° C. Obtain 11.14 g of oil, cured at room temperature. After distillation in vacuo at 58 ° C and 0.05 mm Hg receive. 10.8 g of trans-1,2-dimethylethylene carbonate with a yield of "· 93%.
    Example 4. The process is conducted, as in example 3 ,. but threo-3-bromobutanol is added, reaction time 60 minutes. After distillation in vacuum at 70-74 ° C and 0.1 mm Hg 11.3 g of cis-1,2-dimethylene carbonate are obtained. Yield .95.3%., Purity 97.85%.
    Example 5. The process is carried out as in example 3, but 2-bromo-1-phenylethanol is used. reaction time 15 minutes 16.57 g of πρίί hardening yellow oil are obtained at room temperature. After distillation at 115 ° C and 0.1. mmHg. get 15.35 g. (93.6%) phenylene carbonate.
    Example 6. The process is carried out as in example 3, but butylene bromohydrin is used, reaction time 15 minutes Upon isolation, 12.5 g of oil is obtained, from which, after distillation in vacuo at 68-70 ° C and 0.4-0.5 mm Hg. 11.2 g of butylene carbonate are obtained as a colorless oil. Yield 96.4%, purity 99%.
    Example 7. Repeat example 2, but apply beneyltrimethylammonium bicarbonate. 8.59 g of propylene carbonate are obtained. Yield 85.48%, purity 98.5%.
    Example 8. 43 g of a wet strongly alkaline anion exchange resin in the OH form (Amberlit-ZKA-400-OH) are suspended in 100 ml of methanol and carbonized with carbon dioxide for 30 minutes. The resin thus treated is filtered off, passed through with acetonitrile to remove methanol and then suspended in 100 ml of acetonitrile with stirring in an atmosphere of carbon dioxide. Then 0.05 mol of propylene iodohydrin is added, stirred for 2 hours at room temperature in an atmosphere of carbon dioxide, filtered, filtered through acetonitrile to separate from methanol and resuspended in 100 ml of acetonitrile. The suspension is then stirred for 10 minutes in an atmosphere of carbon dioxide, 0.05 mol of propylene iodine hydrin is added and stirred for 2 hours at room temperature in an atmosphere of carbon dioxide. After that, the resin is filtered off, passed through with a small amount of acetonitrile. 4.7 g (92.%) of propylene carbonate and 0.46 g of unreacted iodohydrin are obtained from the filtrate.
    Example 9. 0.01 mol of butylene chloride is added to a suspension of 0.01 mol of tetramethylammonium bicarbonate in 25 ml of acetonitrile, then the process is carried out as in Example 6. 1.13 g of butylene carbonate are obtained in 97% yield.
    Example 10. 43 g of Amber · * lith-ZYA-400-OH resin was charged into a swinging autoclave together with 100 ml of methanol and carbonized at room temperature and a pressure of carbon dioxide of 3 atm for 30 minutes. Then the carbonate resin is filtered off, threaded with a small amount of acetonitrile and again suspended in an autoclave. In 100 ml of acetonitrile, followed by exposure to carbon dioxide and at a pressure of 3 atm. Next, the autoclave is degassed by vacuum and 0.05 mol of propylene chloride is added by suction. Using carbon dioxide, the pressure is brought to 2 atm and heated to 60 ° C (pressure rises to 30 atm). Then the autoclave is cooled, gases are let off, the resin is filtered off and passed through with acetonitrile. 4.12 g of propylene carbonate are obtained from the filtrate, which corresponds to 80% yield, with about 1 g of unreacted chlorohydrin.
    Example 11. Example 10 is repeated, but propylene iodohydrin is used. ' The mixture is kept at 60 ° C for 30 minutes under a pressure of carbon dioxide of 30 atm.
    complete conversion of iodohydrin to propylene carbonate is achieved.
    PRI me R 12. Repeat example 10, but apply a strongly alkaline resin Castel-A-ZOO-OH, in which there are end groups of the formula
    I — Cr-CH3 on a matrix obtained by x CHfCH 2 0H by copolymerization of styrene and divinylbenzene. 3.56 g of propylene carbonate are obtained, yield 70%, the amount of unreacted chlorohydrin is 0.988 g.
    Example '13. Repeat example 12, but apply water as a carbonization solvent for Castel-A-ZOO-OH resin and the reaction is also carried out in a water medium with the mixture kept at 60 ° С for 1.5 hours and at a pressure of 32 atm. 1.64 g of propylene glycol are obtained in a yield of 34%.
    权利要求:
    Claims (3)
    [1]
     ; . ; 1, The invention relates to an improved method for producing alkyl carbonates, which are used as solvents for organic polymers, electrochemical solvents and in organic synthesis. Various methods are known for the production of hykylene carbonates, for example, and the oxides of the corresponding alkene and carbon dioxide in the presence of chromic lithium at 40-b C in an aprotic solvent in a yield of up to 80% fl.l. The second method of producing alkylene carbonates involves reacting, for example, ethylene glycol with phosgene, at a molar ratio of 0.5: 1.0, and a space velocity of phosgene in a mixture with inert gas cm. 80-150 volumes per 1 volume of the reaction mixture at 1 h. 12. The third method of producing alkylene carbonates is that alkylene oxide reacts with carbon dioxide in the presence of a catalyst. at a temperature of 100-250 ° C and a pressure of 50-150 atm. the yield of the target product is up to 99% GZ. The use of toxic phosgene and high temperatures limits the application of this method. The closest to the proposed method is a method for producing alkylene carbonate o ((it of formula b where 1CW is hydrogen, alkyl, aryl, arylalkyl, alkylaryl, with a content of up to 10 carbon atoms, the interaction of the corresponding hydrogen chloride, carbon dioxide and amine N (R) 3 where R is alkyl, in a solvent environment. The process is carried out predominantly with heating (70.) and pressure. The selectivity for alkylene carbonate is 97.3%. The process takes 2-3 hours 4. The aim of the invention is to simplify the process and reduce its duration. The goal is achieved m, that bicarbonate of ammonia or ammonium-based anion-exchange resin is used as a nitrogen-containing compound, having N-BO. groups, where R is Rg identical or different alkyl or oxyalkyl radicals containing from one to two carbon atoms. in the process of using tetramethylammonium bicarbonate or benzyltrimethylammonium ... the process can be carried out in a layer of siltscream anion exchange resin suspended in the reaction liquid. Acetonitrile can be used as a solvent. This ensures that the process is carried out at room or low (60 ° C) temperature mostly without pressure in a short time of 10–60 cm. Ymberlit 7RA-400-OH or Castel-A-300-OH are preferably used as the strongly alkaline resin. Ethylene chlorohydrin, ethyl bromo- or iodohydrin, 2-chloropropanol -1 or 2-bromo- or 2-iodopropanol-1, etc. can serve as the starting halohydrin. Methanol, butanol, acetone, dioxane, acetonitrile, dimethylformamide, benzene can be used as solvents. , toluene, xylene, dimethyl sulfoxide. From water-organic mixtures, it is advisable to use a mixture of water-dioxane or water-acetonitrile. In special cases, it can be used in remote control. The amount of ammonium compound with regard to rpynnio nio g should be equivalent or in small excess in relation to the amount of halohydrin. The tetraalkylammonium halide, or the corresponding resin, is easily separated by filtration in almost quantity yield. The desired product is recovered from the filtrate by distillation. In the case of using an anion exchange resin, it is regenerated with an aqueous solution of Hch-ri or C1MMONIUM hydroxide followed by carbonization. In this case, they work with two devices or several devices, working alternately, for example, one works, and the other is regenerated. The synthesis temperature can be varied as needed, although better results are obtained at room temperature. An increase in temperature leads to a decrease in the process time, but the temperature should not be higher than the boiling point of the solvent or decomposition of the anion exchange resin. The effect of carbon dioxide, carbon dioxide is not decisive, so it can be in the range from atmospheric to 30 atm. -Example 1. 46 g of a methanol solution of 24% tetramethylammoxy hydroxide (.0, .12 mol) is diluted with 50 ml of methanol and carbonized with carbon dioxide for 40 minutes, then methanol is distilled off in vacuum, the residue is diluted with acetonitrile and incubated for 10 minutes in carbon dioxide atmosphere until gas uptake ceases. To the resulting solution, 0.1 mol of ethyl bromohydrin was added and the suspension was stirred at 20 ° C under carbon dioxide for 10 minutes. The precipitate is filtered off, washed twice with 40 ml of acetonitrile. The resulting filtrate and washings were distilled under low vacuum to separate the solvent; and the residue is washed with methanol to remove traces of salt, the solvent is filtered and evaporated to give 9.63 g of oil, which solidifies at room temperature. After distillation in vacuum (73-75 C / 0.4-0.5 mm Hg), 8.45 g of solid ethylene carbonate are obtained with an inlet of 96% hydrobromine. Example 2. 0.1 mol of 98% propylene iodohydrin was added to a solution of tetramethylammonium bromide in the sconitrile prepared in Example 1. The suspension was stirred under carbon dioxide in an atmosphere of carbon dioxide with tetmethylammonium bicarbonate. The precipitate is then separated, washed with 50 ml of acetonitrile. The combined solutions together with the filtrate are distilled in vacuo, the remaining liquid is diluted with acetone, the traces of salt are filtered out (1.5 g). Acetone is distilled off and the resulting oil is distilled under vacuum at 59-60 ° C and 0.5 mm Hg. 9.40 g of propylene carbonate are obtained. The yield on iodhydrin 91%, the degree of purity of 98.6%. Example 3. To the acetonitrile suspension of tetramethylamhunium dicarbonate prepared in Example 1 was added 0.1 mol of erythro-2-bromobutanol-2. The process is conducted as in example 1 for 20 minutes at a temperature of 20 ° C. This gives 11.14 g of oil, which is cured at all temperatures at room temperature. After distillation in vacuum at and 0.05 mm Hg. receive. 10.8 g of trans-1,2-dimethylethylene carbonate with a yield of 93%. Example 4. The process is conducted as in example 3 ,. but added threo-3-bromobutanol, reaction time 60 minutes. After distillation in vacuum at 70-74 0 and 0.1 mm Hg. 11.3 g of cis-1,2-dimethylene carbonate are obtained. Yield 95.3%., Purity 97.85%. Example 5. The process is carried out as in Example 3, but 2-bro-1-phenylethanol is used. reaction time 15 mi. 16.57 g of a yellow oil hardening at room temperature is obtained. After distillation at 115 s and 0.1 mm Hg. get 15.35 g. (93.6%) phenylene ethyl carbonate. Example 6 The process is carried out as in Example 3, but butylene bromohydrin is used, the reaction time is 15 minutes. At installation, 12.5 g of oil are obtained from which, after distillation in vacuum at 68–70 s and 0.4–0.5 mm Hg, 11.2 g of butyl carbonate are obtained as a colorless oil. Output 96.4%, purity 99%. Example 7. Example 2 is repeated, but benzyltrimethylammonium dicarbopath is used. 8.59 g of propylene carbonate are obtained. Yield 85.48%, purity 98.5%. Example 8. 43g of the wet forces of the alkali anion exchange resin in the OH form (Amberlite-SKA-00-OH) are suspended in 100 ml of methanol and carbonated with carbon dioxide for 30 minutes. The resin thus treated is filtered off, shed with acetonitrile to remove the methanol and then suspended in 100 m acetonitrile with stirring under carbon dioxide. Then, 0.05 mol of propylene iodohydride is added, stirred for 2 hours at room temperature under a carbon dioxide atmosphere, filtered, washed with acetone with nitrile to be separated from methanol again suspended in 100 ml of acetonitrile. Next, the suspension is stirred for 10 minutes under carbon dioxide atmosphere, 0.05 mol of propylene-iodohydrin is added and stirred for 2 hours at room temperature in an atmosphere of carbon dioxide. After that, the resin is filtered off, washed with a small amount of acetonitrile. From the filtrate, 4.7 g (92.%) of propylene carbonate is obtained, and 0.46 g of unreacted iodohydrin. Example 9. 0.01 mol of butylene chlorohydrin is added to a suspension of 0.01 mol of tetramethylammonium bicarbonate in 25 ml of acetonitrile, then the process is carried out as in Example 6. 1.13 g of butylene carbonate is obtained with a yield of 97%. Example 10. 43g of Amboit-ZKA-400-OH resin is loaded into an autoclave rocking with an autoclave together with 100 mp of methanol and carbonized at room temperature and carbon dioxide pressure of 3 atm for 30 minutes. Then the carbonate resin is filtered off, washed with a small amount of acetonitrile and again suspended in an autoclave in 100 ml of acetonitrile, followed by keeping in an atmosphere of carbon dioxide and at a pressure of 3 atm. Next, the autoclave is degassed by vacuum and 0.05 mol of propylene chlorohydrin is added by suction. With carbon dioxide, the pressure is adjusted to 2 atm and heated to (the pressure rises to 30 atm). Then the autoclave is cooled, the gases are lowered, the resin is filtered off and washed with acetonitrile. From the filtrate, 4.12 g of propylene carbonate is obtained, which corresponds to 80% vyrdu, with about 1 g of unreacted chlorohydrin. Example 11. Example 10 is repeated, but propyleniodohydrin is used. The mixture is maintained for 30 minutes under a carbon dioxide pressure of 30 atm. A complete conversion of iodohydrin to propylene carbonate is achieved. EXAMPLE 12 Example 10 is repeated, but the highly alkaline Castel-A-300-OH resin, in which there are end groups of the formula, is applied on a matrix, obtained by the CH2O2 copolymerization of styrene and divinylbenzene. About 3.56 g of propylene carbonate is obtained, yield 70%, the amount of unreacted chlorohydrin is 0.988 g. Example 13. Example 12 is repeated, but using: water as carbonation solvent for Castel-A-300-OH and the reaction is also carried out in water with keeping the mixture at 60 ° C for 1.5 h and at a pressure of 32 atm. 1.64 g of propylene glycol is obtained with a yield of 34%. Claims 1. A method for producing alkylene carbonates of the general formula: where f (is hydrogen. Skyl, aryl, arylalkyl, alkylaryl, with up to 10 carbon atoms, by reacting. Corresponding to loggenhydrin with a nitrogen-containing compound in a solvent medium in the presence of carbon dioxide, characterized in that , in order to simplify the process and shorten its duration, bicarbonate of quaternary substituted ammonium 7.88 or a strongly alkaline arion exchange resin having the groups; -K-1) 2 is used as a nitrogen-containing compound; h - the same or different alkyl or oxyalkyl radicals containing from one to two carbon atoms. . 2. The method according to claim 1, of which is that with the use of tetramethyl and onium or benzyltrimethylammonium in the process. . 3. A method according to PP, 1 and 2, of which is carried out in that the process is carried out in a layer of a strong anion exchange resin suspended in a reactive liquid. . 8 4. Way popp. 1-3, characterized in that acetoiitrile is used as a solvent. . sources of information taken into account in the examination i. French patent 1538576, cl. From 07 s, publish. 1968.
    [2]
    2. Patent of Germany 1226117, cl. C 07 d, pub. 1966.
    [3]
    3. US patent 3535341, cl. From 07 d 13/06, published 1970. 4. U.S. Patent 3,923,842, cl. 260-348, pub. 1975 (prototype).
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    同族专利:
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    引用文献:
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    US1907891A|1928-11-14|1933-05-09|Ig Farbenindustrie Ag|Production of carbonic acid esters of the glycols|
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    IT1022442B|1974-09-30|1978-03-20|Montedison Spa|PROCEDURE FOR THE PREPARATION OF ALKYLENCARBONATES|US4325874A|1981-05-26|1982-04-20|The Halcon Sd Group, Inc.|Process for producing alkylene carbonates|
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    DE3529263A1|1985-08-16|1987-02-19|Hoechst Ag|METHOD FOR PRODUCING 2-OXO-1,3-DIOXOLANES|
    DE3723782C2|1987-07-16|1989-10-19|Dai Nippon Ink And Chemicals, Inc., Tokio/Tokyo, Jp|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT2232378A|IT1095606B|1978-04-14|1978-04-14|PROCESS FOR THE SYNTHESIS OF ALCHILENCARBONATES|
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