Catalyst for producing polybutylene succinate or copolyester thereof, and preparing mehtods of the catalyst

Abstract

The present invention provides a catalyst used in the production of PBS or its copolyesters and the preparation method thereof. The method comprises the following steps: (1) adding titanium alkoxide, silicon alkoxide, dihydric alcohol and metal co-catalyst into the solvent and conducting the reaction at a temperature of about 80° C. to 180° C., then removing the unreacted materials and small molecular products in the reaction system; (2) adding complexing agent into the reaction system, then collecting catalyst from the products obtained in this step. Moreover, the method may comprises steps of: (1) adding titanium alkoxide, dihydric alcohol and metal co-catalyst into the solvent and conducting the reaction at a temperature of about 80° C. to 180° C., then removing the unreacted materials and small molecular products in the reaction system; (2) adding silicon alkoxide and complexing agent into the reaction system, then collecting catalyst from the products obtained in this step. The catalyst in the present invention has higher activity and thus the catalyst additional amount is reduced which will improve the quality of the products. Moreover, the catalyst in the present invention could be used alone in the production of PBS or its copolyester without the need for other materials and it won't react with water and thus could be stored for a long time. In sum, the catalyst in the present invention has a broad prospect in industrial application.

1 . A manufacturing method of the catalyst used in the production of PBS or its copolyesters comprising steps of:
 (1) adding titanium alkoxide, silicon alkoxide, dihydric alcohol and metal co-catalyst into the solvent and conducting the reaction at a temperature of about 80° C. to 180° C., then removing the unreacted materials and small molecular products in the reaction system;   (2) adding complexing agent into the reaction system obtained in step (1) and conducting the reaction at a temperature of about 80° C. to 180° C., then collecting catalyst from the products obtained in this step.   
     
     
         2 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 1 , wherein the reaction time in step (1) is ranging from 0.5 hour to 2.5 hours and the reaction temperature in step (1) is ranging from 85° C. to 160° C. 
     
     
         3 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 1 , wherein the reaction time in step (2) is ranging from 0.5 hour to 2.5 hours and the reaction temperature in step (2) is ranging from 85° C. to 160° C. 
     
     
         4 . A manufacturing method of the catalyst used in the production of PBS or its copolyesters comprising steps of:
 (1) adding titanium alkoxide, dihydric alcohol and metal co-catalyst into the solvent and conducting the reaction at a temperature of about 80° C. to 180° C., then removing the unreacted materials and small molecular products in the reaction system;   (2) adding silicon alkoxide and complexing agent into the reaction system obtained in step (1) and conducting the reaction at a temperature of about 80° C. to 180° C., then collecting catalyst from the products obtained in this step.   
     
     
         5 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 4 , wherein the reaction time in step (1) is ranging from 0.5 hour to 2.5 hours and the reaction temperature in step (1) is ranging from 85° C. to 160° C. 
     
     
         6 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 4 , wherein the reaction time in step (2) is ranging from 0.5 hour to 2.5 hours and the reaction temperature in step (2) is ranging from 85° C. to 160° C. 
     
     
         7 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 1 , wherein the titanium alkoxide is selected from the group comprising tetra-n-butyl titanate, tetra-isopropyl titanate and the mixture thereof, and the silicon alkoxide is selected from the group comprising methyl silicate, ethyl silicate and the mixture thereof. 
     
     
         8 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 1 , wherein the metal co-catalyst is selected from the group comprising acetates or alkoxides of Group IIA, IIIA, IIB or VIIIB metals, or any mixture thereof;
 the dihydric alcohol is selected from the group comprising 1,4-butanediol, ethanediol, 1,3-propanediol, 2-methyl-2,4-pentadiol, 1,5-pentanediol, 1,6-hexanediol and any mixture thereof;   the solvent is selected from the group comprising ethanol, n-butanol, isopropanol and any mixture thereof;   the complexing agent comprises phosphate ester and hydroxyl carboxylic acid.   
     
     
         9 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 8 , wherein the metal co-catalyst is selected from the group comprising zinc acetate, aluminium isopropoxide, calcium acetate, magnesium acetate, manganese acetate and any mixture thereof;
 the phosphate ester is selected from the group comprising trimethyl phosphate, trimethyl phosphite, triethyl phosphate, triethyl phosphite and any mixture thereof;   the hydroxyl carboxylic acids is selected from the group comprising citric acid, tartaric acid, lactic acid and any mixture thereof;   the molar ratio of titanium atom and dihydric alcohol is ranging from 1:5 to 1:30;   the molar ratio of titanium atom and metal co-catalyst is ranging from 1:0.05 to 1:2;   the molar ratio of titanium atom and hydroxyl carboxylic acids is ranging from 1:0.5 to 1:2;   the molar ratio of titanium atom and silicon atom is ranging from 1:0.01 to 1:2;   the molar ratio of titanium atom and phosphorus atoms is ranging from 1:0.01 to 1:2;   the molar ratio of titanium atom and solvent is ranging from 1:5 to 1:50.   
     
     
         10 . The catalyst used in the production of PBS or its copolyesters obtained by the method of  claim 1 . 
     
     
         11 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 4 , wherein the titanium alkoxide is selected from the group comprising tetra-n-butyl titanate, tetra-isopropyl titanate and the mixture thereof, and the silicon alkoxide is selected from the group comprising methyl silicate, ethyl silicate and the mixture thereof. 
     
     
         12 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 4 , wherein the metal co-catalyst is selected from the group comprising acetates or alkoxides of Group IIA, IIIA, IIB or VIIIB metals, or any mixture thereof;
 the dihydric alcohol is selected from the group comprising 1,4-butanediol, ethanediol, 1,3-propanediol, 2-methyl-2,4-pentadiol, 1,5-pentanediol, 1,6-hexanediol and any mixture thereof;   the solvent is selected from the group comprising ethanol, n-butanol, isopropanol and any mixture thereof;   the complexing agent comprises phosphate ester and hydroxyl carboxylic acid.   
     
     
         13 . The manufacturing method of the catalyst used in the production of PBS or its copolyesters, as recited in  claim 12 , wherein the metal co-catalyst is selected from the group comprising zinc acetate, aluminium isopropoxide, calcium acetate, magnesium acetate, manganese acetate and any mixture thereof;
 the phosphate ester is selected from the group comprising trimethyl phosphate, trimethyl phosphite, triethyl phosphate, triethyl phosphite and any mixture thereof;   the hydroxyl carboxylic acids is selected from the group comprising citric acid, tartaric acid, lactic acid and any mixture thereof;   the molar ratio of titanium atom and dihydric alcohol is ranging from 1:5 to 1:30;   the molar ratio of titanium atom and metal co-catalyst is ranging from 1:0.05 to 1:2;   the molar ratio of titanium atom and hydroxyl carboxylic acids is ranging from 1:0.5 to 1:2;   the molar ratio of titanium atom and silicon atom is ranging from 1:0.01 to 1:2;   the molar ratio of titanium atom and phosphorus atoms is ranging from 1:0.01 to 1:2;   the molar ratio of titanium atom and solvent is ranging from 1:5 to 1:50.   
     
     
         14 . The catalyst used in the production of PBS or its copolyesters obtained by the method of  claim 4 .