Supported catalysts for the fixation of carbon dioxide into aliphatic polycarbonates and a process for preparing the same

• US 20030134740A1
• Filed: 12/13/2002
• Published: 07/17/2003
• Est. Priority Date: 12/18/2001
• Status: Active Grant

• Current Assignee: Guangzhou Institute of Chemistry Chinese Academy of Sciences
• Original Assignee: Guangzhou Institute of Chemistry Chinese Academy of Sciences
• Inventors: Zhu, Quan, Li, Xiuhua, Zhang, Shizhen, Du, Longchao, Meng, Yuezhong
• Granted Patent: US 6,844,287 B2
• Time in Patent Office: Days
• US Class Current: 502/170
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 31/04 containing carboxylic acids or their salts B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226
• CPC Class Codes: B01J 31/1616 Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts catalysts comprising molecular sieves B01J29/00
• CPC Class Codes: B01J 31/1691 Coordination polymers, e.g. metal-organic frameworks [MOF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 31/223 At least two oxygen atoms present in one at least bidentate or bridging ligand
• CPC Class Codes: B01J 37/0036 Grinding
• CPC Class Codes: C07C 51/418 Preparation of metal complexes containing carboxylic acid moieties
• CPC Class Codes: C07C 55/02 Dicarboxylic acids
• CPC Class Codes: C07C 55/10 Succinic acid
• CPC Class Codes: C07C 55/12 Glutaric acid
• CPC Class Codes: C07C 55/14 Adipic acid
• CPC Class Codes: C07C 55/16 Pimelic acid
• CPC Class Codes: C08G 64/34 and cyclic ethers

Abstract

The present invention provides a process for preparing supported zinc dicarboxylate catalysts with high activity for the copolymerization of carbon dioxide and epoxides by supporting zinc dicarboxylate on silica support. The zinc dicarboxylate may be synthesized from zinc oxide and dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid. The silica support can be selected from the group consisting of aerosil, silica gel for chromatography or reagent grade silicon dioxide. The supporting process is performed in a planetary ball grinder under vacuum.

Claims

1. A process for preparing supported catalysts for the copolymerization of carbon dioxide and epoxides to form poly(alkylene carbonate)s, comprising the step of supporting a zinc dicarboxylate on the silica, wherein the zinc dicarboxylate is selected from the group consisting of zinc succinate, zinc glutarate, zinc adipate, zinc pimelate and zinc suberate, and the mixture thereof, and the weight ratio of zinc dicarboxylate to silica support varies from 1/1 to 1/15.

2. The process of claim 1, wherein said zinc dicarboxylate is selected from the group consisting of zinc glutarate, zinc adipate and zinc pimelate.

3. The process of claim 1, wherein the silica support is selected from the group consisting of aerosil, silica gel for chromatography and reagent grade silicon dioxide.

4. The process of claim 3, wherein said silica support is aerosil or silica gel.

5. The process of claim 1, wherein weight ratio of zinc dicarboxylate to silica support varies from 1/2 to 1/5.

6. The process of claim 1, wherein said supporting process is carried out in a planetary ball grinder under vacuum, and the silica support may be activated prior to usage.

7. The process of claim 6, wherein said supporting process is performed at the revolutions ranging from 200 to 600 per minute for 30 to 120 minutes.

8. A supported catalyst for the copolymerization of carbon dioxide and epoxides to form poly(alkylene carbonate)s obtained by a process claimed in claim 1.