Method for producing cyclic carbonate

Patent metadata

Field	Value
Publication number	US-9856229-B2
Application number	US-201414904488-A
Country	US
Kind code	B2
Filing date	Jul 18, 2014
Priority date	Jul 19, 2013
Publication date	Jan 2, 2018
Grant date	Jan 2, 2018

Abstract

Provided is a method for producing a cyclic carbonate obtained by reacting epoxide and carbon dioxide in the presence of a quaternary onium salt as a counter ion or a quaternary phosphonium salt having a halogenated anion as a counter ion, or in the presence of a solid catalyst obtained by immobilizing the quaternary onium salt onto a carrier, wherein an organohalogen compound containing at least one halogen atom in one molecule is added to the reaction system.

First claim

The invention claimed is:

1. A method for producing a cyclic carbonate comprising:
(i) reacting epoxide and carbon dioxide in the presence of a quaternary onium salt selected from the group consisting of a quaternary ammonium salt having a halogenated anion as a counter ion and a quaternary phosphonium salt having a halogenated anion as a counter ion, or
(ii) reacting epoxide and carbon dioxide in the presence of a solid catalyst obtained by immobilizing the quaternary onium salt onto a carrier; and
adding an organohalogen compound to (i) or (ii);
wherein the organohalogen compound is represented by the following formula (2):
RZ  (2),

wherein R represents linear or branched chain alkyl having 1 to 6 of carbon atom, aralkyl having 7 to 20 of carbon atom, alkoxyalkyl having 2 to 12 of carbon atom, alkanoylalkyl having 3 to 12 of carbon atom, formylalkyl having 2 to 6 of carbon atom, or hydroxyalkyl having 1 to 6 of carbon atom, and Z represents a halogen atom,

wherein the organohalogen compound of formula (2) is a different compound compared to the epoxide.

2. The method according to claim 1 , wherein R represents linear or branched chain alkyl having 1 to 6 of carbon atom, or hydroxyalkyl having 1 to 6 of carbon atom.

3. The method according to claim 1 , wherein Z represents a bromine atom.

4. The method according to claim 1 , wherein the carrier is an inorganic oxide carrier.

5. The method according to claim 1 , wherein the epoxide is a compound represented by the following formula (1):

wherein R 1 and R 2 each independently represents a hydrogen atom, alkyl having 1 to 6 of carbon atom, haloalkyl having 1 to 6 of carbon atom, alkenyl having 2 to 6 of carbon atom, haloalkenyl having 2 to 6 of carbon atom, aryl having 6 to 12 of carbon atom or cyano, and R 3 and R 4 each independently represents a hydrogen atom, cyano or aryl having 6 to 12 of carbon atom; or either R 3 or R 4 form cycloalkyl together with either R 1 or R 2 .

6. A method for continuously producing a cyclic carbonate comprising:
filling a catalyst in a fixed bed tubular reactor and continuously supplying carbon dioxide and epoxide to the fixed bed tubular reactor to be brought into contact with the catalyst and, at the same time, continuously extracting the reaction solution contained in the fixed bed tubular reactor, wherein the catalyst comprises a solid catalyst obtained by immobilizing a quaternary onium salt selected from the group consisting of a quaternary ammonium salt having a halogenated anion as a counter ion and a quaternary phosphonium salt having a halogenated anion as a counter ion onto a carrier, and
supplying to the fixed bed tubular reactor an organohalogen compound-represented by the following formula (2):
RZ  (2),

wherein R represents linear or branched chain alkyl having 1 to 6 of carbon atom, aralkyl having 7 to 20 of carbon atom, alkoxyalkyl having 2 to 12 of carbon atom, alkanoylalkyl having 3 to 12 of carbon atom, formylalkyl having 2 to 6 of carbon atom or hydroxyalkyl having 1 to 6 of carbon atom, and Z represents a halogen atom.

7. The method according to claim 6 , wherein R represents linear or branched chain alkyl having 1 to 6 of carbon atom or hydroxyalkyl having 1 to 6 of carbon atom.

8. The method according to claim 6 , wherein Z represents a bromine atom.

9. The method according to claim 6 , wherein the carrier is an inorganic oxide carrier.

10. The method according to claim 6 , wherein the epoxide is a compound represented by the following formula (1):

wherein R 1 and R 2 each independently represents a hydrogen atom, alkyl having 1 to 6 of carbon atom, haloalkyl having 1 to 6 of carbon atom, alkenyl having 2 to 6 of carbon atom, haloalkenyl having 2 to 6 of carbon atom, aryl having 6 to 12 of carbon atom or cyano, R 3 and R 4 each independently represents a hydrogen atom, cyano or aryl having 6 to 12 of carbon atom; or either R 3 or R 4 form cycloalkyl together with either R 1 or R 2 .

11. The method according to claim 6 , wherein a part of the reaction solution obtained by continuously extracting from the fixed bed tubular reactor is supplied to the fixed bed tubular reactor to be circulated.

12. The method according to claim 1 , wherein the amount of the organomonohalogen is 1×10 −5 to 1 mol with respect to 1 mol of the epoxide.

13. The method according to claim 2 , wherein Z represents fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

14. A method for producing a cyclic carbonate comprising:
(i) reacting epoxide and carbon dioxide in the presence of a quaternary onium salt selected from the group consisting of a quaternary ammonium salt having a halogenated anion as a counter ion and a quaternary phosphonium salt having a halogenated anion as a counter ion, or
(ii) reacting epoxide and carbon dioxide in the presence of a solid catalyst obtained by immobilizing the quaternary onium salt onto a carrier; and
adding an organohalogen compound to (i) or (ii), wherein the organomonohalogen compound is a monohalogenated alcohol selected from the group consisting of chloromethanol, chloroethanol, chloropropanol, chlorobutanol, chloropentanol, bromomethanol, bromopropanol, bromobutanol, bromoethanol, bromopentanol, iodomethanol, iodoethanol, and iodopropanol.

15. The method according to claim 14 , wherein the organomonohalogen compound is a monohalogenated alcohol selected from the group consisting of bromoethanol, chloroethanol, bromopropanol, and chloropropanol.

Assignees

• Aist
• Maruzen Petrochem Co Ltd

Inventors

• Takahashi Toshikazu
• Yasuda Hiroyuki
• Yamamoto Shouji
• Naniki Takashi
• Hayashi Yasunori
• Haruna Takeshi
• Furukawa Takuro

Classifications

• B01J31/0239

  Quaternary ammonium compounds · CPC title

• B01J31/0268

  Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous · CPC title

• B01J31/0254

  on mineral substrates · CPC title

• B01J2231/341

  1,2-additions, e.g. aldol or Knoevenagel condensations · CPC title

• C07D317/38 Primary

  Ethylene carbonate · CPC title