Metal catalysts for selective formation of cyclic carbonates, process for preparing cyclic carbonate using the same and use of cyclic carbonate

Patent metadata

Field	Value
Publication number	US-9850223-B2
Application number	US-201615207906-A
Country	US
Kind code	B2
Filing date	Jul 12, 2016
Priority date	Sep 18, 2015
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

Provided are a novel metal catalyst for preparing cyclic carbonate, and a method for preparing cyclic carbonate using the same, and more particularly, a method for selectively preparing cyclic carbonate in a high yield and at a higher conversion rate as compared to the existing catalysts, using the metal complex including a ligand represented by Chemical Formula 1 below and a trivalent metal in Group 8 or Group 13 as a catalyst and using various structures of epoxide compounds and carbon dioxide as raw materials. In addition, provided are the prepared cyclic carbonate, and an electrolyte including the same:

in Chemical Formula 1, R 1 is hydrogen, (C1-C20)alkyl or halogen; R 2 is hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halogen or nitro.

First claim

What is claimed is:

1. A metal complex comprising a ligand represented by Chemical Formula 1 below and a trivalent metal in Group 8 or Group 13:

in Chemical Formula 1, R 1 is hydrogen, (C1-C20)alkyl or halogen; R 2 is hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halogen or nitro.

2. The metal complex of claim 1 , wherein the metal complex is represented by Chemical Formula 2 below:

in Chemical Formula 2, M is Fe or Al; R 1 is hydrogen, (C1-C20)alkyl or halogen; R 2 is hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halogen or nitro.

3. The metal complex of claim 2 , wherein the metal complex is selected from the following structures:

4. A method for preparing cyclic carbonate by reacting carbon dioxide with alkylene oxide using the metal complex of claim 1 , as a catalyst.

5. The method of claim 4 , wherein the alkylene oxide is represented by Chemical Formula 3 below, and the cyclic carbonate is represented by Chemical Formula 4 below:

in Chemical Formulas 3 and 4,
R 3a and R 4a are each independently hydrogen, (C1-C10)alkyl, halo(C1-C10)alkyl or (C6-C12)aryl, and R 3a and R 4a may be linked via (C3-C5)alkylene with or without a fused ring to form a ring, wherein the formed ring may be further substituted with vinyl, —(CH 2 ) a SiR 11 R 12 R 13 , oxiranyl or (7-oxa-bicyclo[4.1.0]heptane-3-yl)acetyl;
R 3b and R 4b are each independently hydrogen, (C1-C10)alkyl, halo(C1-C10)alkyl or (C6-C12)aryl, and R 3b and R 4b may be linked via (C3-C5)alkylene with or without a fused ring to form a ring, wherein the formed ring may be further substituted with vinyl, —(CH 2 ) a SiR 11 R 12 R 13 , 1,3-dioxolan-2-one-4-yl or (hexahydrobenzo[d][1,3]dioxol-2-one-5-yl)acetyl;
R 11 to R 13 are each independently (C1-C10)alkyl or (C1-C10)alkoxy; and
a is an integer of 1 to 5.

6. The method of claim 4 , wherein the metal complex catalyst has an amount of 0.1 to 2.0 mol % relative to the alkylene oxide.

7. The method of claim 4 , wherein an ammonium co-catalyst or an amine-based co-catalyst is further included.

8. The method of claim 7 , wherein the ammonium co-catalyst or the amine-based co-catalyst has an amount of 0.1 to 10.0 mol % relative to the alkylene oxide.

9. The method of claim 8 , wherein the ammonium co-catalyst is selected from the group consisting of tetrabutylammonium bromide (NBu 4 Br), tetramethylammonium bromide (NMe 4 Br), tetraethylammonium tetrafluoroborate (NEt 4 BF 4 ), tetrapropylammonium bromide (NPr 4 Br), tetrahexylammonium chloride (N[(CH 2 ) 5 CH 3 ] 4 Cl), tetrapentylammonium bromide (N[(CH 2 ) 4 CH 3 ] 4 Br), tetraheptylammonium bromide (N[(CH 2 ) 6 CH 3 ] 4 Br), tetraoctylammonium bromide (N[CH 2 ) 7 CH 3 ] 4 Br), trimethyldodecylammonium chloride (CH 3 (CH 2 ) 11 N(CH 3 ) 3 Cl), trimethyltetradecylammonium bromide (CH 3 (CH 2 ) 13 N(CH 3 ) 3 Br), trimethylhexadecylammonium chloride (CH 3 (CH 2 ) 15 N(CH 3 ) 3 Cl), methyltrioctylammonium chloride (CH 3 N[(CH 2 ) 7 CH 3 ] 3 Cl), tetrabutylammonium fluoride (NBu 4 F), tetrabutylammonium chloride (NBu 4 Cl), tetrabutylammonium iodide (NBu 4 I), 1-butyl-3-methylimidazolium bromide ([bmim]Br), 1-butyl-3-methylimidazolium chloride ([bmim]Cl), and bis(triphenylphosphine)iminium chloride ([((C 6 H 5 ) 3 P) 2 N]Cl, PPNCl), and the amine-based co-catalyst is selected from the group consisting of triethylamine (Et 3 N), 1,8-diazabicycloundec-7-ene (DBU), pyridine (C 5 H 5 N), and 4-dimethylaminopyridine (C 7 H 10 N 2 , DMAP).

10. The method of claim 4 , wherein a reaction temperature is 25 to 120° C., and a reaction pressure is 1 to 10 bar.

11. The method of claim 4 , wherein the reaction is a neat reaction.

Assignees

• Korea Advanced Inst Sci & Tech

Inventors

• Kim Hyunwoo
• Lee Yuseop

Classifications

• B01J2531/842

  Iron · CPC title

• B01J2231/49

  Esterification or transesterification · CPC title

• C07D317/70

  condensed with ring systems containing two or more relevant rings · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• C07D317/46

  condensed with one six-membered ring · CPC title