Novel Complex and Preparation Method of Poly(Alkylene Carbonate) Using the Same

Patent metadata

Field	Value
Publication number	US-2016376299-A1
Application number	US-201414903453-A
Country	US
Kind code	A1
Filing date	Jul 4, 2014
Priority date	Jul 9, 2013
Publication date	Dec 29, 2016
Grant date	—

Abstract

The present invention is directed to a novel complex synthesized from a Salen-type ligand. The novel complex contains a quaternary ammonium salt. The present invention is also directed to a preparation method of a copolymer of carbon dioxide and epoxide using the complex synthesized from a Salen-type ligand as a catalyst.

First claim

1 . A complex represented by the following Chemical Formula 1:

in Chemical Formula 1,
M is trivalent cobalt or trivalent chromium;
A is oxygen or sulfur;
Q is a diradical connecting two nitrogens;
R 1 to R 10 are each independently hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorus atom; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorus atom; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; a metalloid radical of Group 14 metal substituted with hydrocarbyl; a protonated group of the following Chemical Formula 2; a protonated group of the following Chemical Formula 3; a protonated group of the following Chemical Formula 4; a protonated group of the following Chemical Formula 5; a protonated group of the following Chemical Formula 6; a protonated group of the following Chemical Formula 7; a protonated group of the following Chemical Formula 8; or a protonated group of the following Chemical Formula 9;
wherein at least one or more of R 1 to R 10 are a protonated group selected from a group consisting of the following Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9;

X − is halogen anion; a (C6-C20)aryloxy anion; a (C6-C20)aryloxy anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorus; a (C1-C20)alkylcarboxy anion; a (C1-C20)alkylcarboxy anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C6-C20)arylcarboxy anion; a (C6-C20)arylcarboxy anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C1-C20)alkoxy anion; a (C1-C20)alkoxy anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C1-C20)alkylcarbonate anion; a (C1-C20)alkylcarbonate anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C6-C20)arylcarbonate anion; a (C6-C20)arylcarbonate anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C1-C20)alkylsulfonate anion; a (C1-C20)alkylsulfonate anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C1-C20)alkylamido anion; a (C1-C20)alkylamido anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C6-C20)arylamido anion; a (C6-C20)arylamido anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C1-C20)alkylcarbamate anion; a (C1-C20)alkylcarbamate anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; a (C6-C20)arylcarbamate anion; or a (C6-C20)arylcarbamate anion containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus;
X − may be coordinated to M;
Y 1 − is F − , Cl − , Br − , I − , BF 4 − , ClO 4 − , NO 3 − or PF 6 − ;
*Y 2 2 — is SO 4 2− or CO 3 2− ;
a is an integer obtained by adding 1 to the total number of monovalent cations included in protonated groups of R 1 to R 10 ;
b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and b+c+2d=a is satisfied;
Z 1 to Z 18 are each independently an nitrogen or phosphorusphosphorus;
n is an integer of 1 to 10;
m is an integer of 1 to 10;
R 11 to R 16 , R 21 to R 26 , R 31 to R 36 , R 41 to R 48 , R 51 to R 57 , R 61 to R 66 , R 71 to R 76 and R 81 to R 86 are each independently hydrogen; (C1-C20)alkyl; (C1-C20)alkyl containing one or more selected, from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl containing one or more selected from among halogenhalogen, nitrogennitrogen, oxygenoxygen, siliconsilicon, a sulfur and phosphorusphosphorus; or a metalloid radical of Group 14 metal substituted with hydrocarbyl; two of R 11 to R 16 , two of R 21 to R 26 , two of R 31 to R 36 , two of R 41 to R 48 , two of R 51 to R 57 , two of R 61 to R 66 , two of R 71 to R 76 , and two of R 8′ to R 86 may be linked with each other to thereby form a ring; and
wherein alkyl, alkenyl, alkylaryl, arylalkyl, alkoxy, aryloxy, alkylcarbonyl, and arylcarbonyl of R 1 to R 10 , and alkyl, alkenyl, alkylaryl and arylalkyl of R 11 to R 16 , R 21 to R 26 , R 31 to R 36 , R 43 to R 48 , R 51 to R 57 , R 61 to R 66 , R 71 to R 76 and R 81 to R 86 may be further substituted with any one or more selected from halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C1-C20)alkyl(C6-C20)aryl and (C6-C20)aryl(C1-C20)alkyl.

2 . The complex of claim 1 , wherein Q is (C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene, (C2-C20)alkynylene or (C3-C20)cycloalkylene.

3 . The complex of claim 2 , wherein
M is trivalent cobalt; A is oxygen; and Q is 1,2-cyclohexylene, phenylene or ethylene.

4 . The complex of claim 1 , wherein at least one or more of R 1 , R 2 , R 5 and R 6 are a protonated group selected from a group consisting of Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9 of claim 1 .

5 . The complex of claim 4 , wherein R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are hydrogen.

6 . The complex of claim 5 , which has a structure represented by the following Chemical Formula 11:

in Chemical Formula 11,
M is trivalent cobalt or trivalent chromium;
A is oxygen or sulfur;
R 1 and R 2 are each independently a protonated group selected from a group consisting of hydrogen, (C1-C10)alkyl, Chemical Formulas 2, 3, 4, 5, 6, 7, 8, and 9 of claim 1 ;
R 5 and R 6 identically represent hydrogen, halogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C1-C20)alkoxy, (C1-C20)alkyl(C6-C20)aryl or (C6-C20)aryl(C1-C20)alkyl; alkyl, alkenyl, alkoxy, alkylaryl or arylalkyl of R 5 or R 6 may be further substituted with any one or more selected from halogen

Assignees

• Sk Innovation Co Ltd
• Sk Global Chemical Co Ltd

Inventors

• Kim Jong Chan
• Lee Han Sol
• Park Hyo Seung
• Lee Je Ho
• Noh Jeong Hyun
• Lim Jong Ho
• Lee Jeon Koo

Classifications

• C07F15/065 Primary

  without a metal-carbon linkage · CPC title

• C08G64/34

  and cyclic ethers · CPC title