Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49345—Catalytic device making

Definitions

• the present invention relates to a catalyst used in the production of PBS or its copolyesters and the preparation method thereof.
• Aliphatic polyesters has aroused wide attention and research from domestic and foreign researchers because of their great biodegradable and environmentally non-persistent properties.
• Aliphatic polyesters and in particular poly (butylene succinate) (PBS) even have additional advantage features, such as good mechanical and processing properties. Therefore, PBS, which has enormous application prospect, becomes the focus of attention in industry recently.
• the polycondensation catalyst such as titanium-based catalyst or the mixture of titanium-based catalyst and other metal catalyst
• the polycondensation catalyst is added into the reaction system.
• Chinese Patent application, CN 1424339 discloses a catalyst mixture comprising stannic oxide, antimony trioxide, cadmium acetate and titanium alkoxides.
• Chinese Patent application, CN 1861660A discloses a catalyst mixture comprising tetra-n-butyl titanate, tetra-isopropyl titanate, antimony trioxide and tetra-n-butyl germinate.
• titanate-based catalyst alone can't satisfy production requirements. Therefore, other compounds must be added into titanate catalyst to form a catalyst complex.
• the catalyst system in prior art has following disadvantages such as: (1) The traditional catalyst has low activity and thus the additional amount of catalyst is very high which affects the quality of the products.
• additional amount of active ingredient titanium usually more than 500 ppm (that is, 500 ⁇ 10 ⁇ 6 gTi/gPBS, similarly hereinafter), measured by weight of PBS.
• the additional amount is even higher than 700 ppm.
• Such high catalyst amount could result in many side reactions and it may also increase the melt flow rate of the products, decrease its mechanical properties and turn the products a dark yellow color.
• the catalyst in prior art is not convenient for practical manufacture use because titanium alkoxides would easily cause precipitation while contacting with water.
• the present invention provides a catalyst used in the production of PBS or its copolyesters and the preparation method thereof.
• a manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of:
• step (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., more preferably 85° C. to 160° C., for 0.5 hour to 2.5 hours; (2) removing the unreacted materials and small molecular products in the reaction system obtained in step (1); (3) adding complexing agent into the reaction system obtained in step (2) and conducting the reaction at a temperature of about 80° C. to 180° C., more preferably 85° C. to 160° C., for 0.5 hour to 2.5 hours; (4) removing small molecular products in the reaction system obtained in step (3) and then catalyst could be obtained.
• a manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of:
• step (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., more preferably 85° C. to 160° C., for 0.5 hour to 2.5 hours; (2) removing the unreacted materials and small molecular products in the reaction system obtained in step (1); (3) adding silicon alkoxide and complexing agent into the reaction system obtained in step (2) and conducting the reaction at a temperature of about 80° C. to 180° C., more preferably 85° C. to 160° C., for 0.5 hour to 2.5 hours; (4) removing small molecular products in the reaction system obtained in step (3) and then catalyst could be obtained.
• the method used for removing the unreacted materials or small molecular products in the reaction system could adopt any conventional methods known by those skilled in the art, such as distillation or rectification method, and any other methods which could be adopted by the skilled in the art.
• said titanium alkoxide is selected from the group comprising tetra-n-butyl titanate, tetra-isopropyl titanate and the mixture thereof.
• said silicon alkoxide is selected from the group comprising methyl silicate, ethyl silicate and the mixture thereof.
• the metal co-catalyst and complexing agent both have great influence on catalyst activity and the choices on the catalysts.
• the said metal co-catalyst is selected from the acetates or alkoxides of Group IIA, IIIA, IIB or VIIIB metals, or any mixture thereof. More preferably, the said metal co-catalyst is selected from the group comprising zinc acetate, aluminium isopropoxide, calcium acetate, magnesium acetate, manganese acetate and any mixture thereof.
• the said 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 said complexing agent comprises phosphate ester and hydroxyl carboxylic acids.
• the said phosphate ester is selected from the group comprising trimethyl phosphate, trimethyl phosphite, triethyl phosphate, triethyl phosphite and any mixture thereof.
• the said hydroxyl carboxylic acids is selected from the group comprising citric acid, tartaric acid, lactic acid and any mixture thereof.
• the said solvent is selected from the group comprising ethanol, n-butanol, isopropanol and any mixture thereof.
• the molar ratio of titanium atom and dihydric alcohol is ranging from 1:5 to 1:30, more preferably ranging from 1:20 to 1:30.
• the molar ratio of titanium atom and the metal co-catalyst is ranging from 1:0.05 to 1:2, more preferably ranging from 1:0.05 to 1:0.5.
• the molar ratio of titanium atom and hydroxyl carboxylic acids is ranging from 1:0.5 to 1:2, more preferably ranging from 1:0.5 to 1:1.5.
• the molar ratio of titanium atom and silicon atom is ranging from 1:0.01 to 1:2, more preferably ranging from 1:0.05 to 1:1.
• the molar ratio of titanium atom and phosphorus atoms is ranging from 1:0.01 to 1:2, more preferably ranging from 1:0.01 to 1:1.5.
• the molar ratio of titanium atom and the solvent is ranging from 1:5 to 1:50, more preferably ranging from 1:5 to 1:30.
• the catalyst prepared according to the above methods could be used in the production of PBS or its copolyester.
• the above-mentioned catalyst could be added directly into the reaction system or be added into the reaction system after being diluted with 1,4-butanediol.
• the catalyst also could be added into the reaction system before the esterification reaction, or be added into the reaction system after the esterification reaction and before the start of the prepolycondensation.
• the amount of catalyst added could be determined by the weight of titanium atoms it contains, and the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is ranging from 80 ⁇ 10 ⁇ 6: 1 ⁇ 200 ⁇ 10 ⁇ 6 :1.
• the amount of catalyst could be determined by the weight of titanium atoms it contained, and the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is ranging from 100 ⁇ 10 ⁇ 6 :1 ⁇ 150 ⁇ 10 ⁇ 6 :1.
• the catalyst containing metal co-catalyst in the present invention which is prepared using complexation technology, has the following advantages. Firstly, 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. Secondly, the catalyst in the present invention could be used alone in the production of PBS or its copolyester without the need for other materials. Therefore, there is no need for additional preparation step as in the traditional preparation method. Thirdly, the catalyst in the present invention will not react with water and it thus could be added into the reaction system before the esterification reaction, or after the esterification reaction and before the start of the prepolycondensation. In addition, the catalyst in the present invention could be stored for a long time. In sum, the catalyst in the present invention has a broad prospect in industrial application.
• the melt mass-flow rate of PBS is measured according to the determination method in “GB/T 3682-2000 Determination of the melt mass-flow rate (MFR) and the melt volume-flow rate (MVR) of thermoplastics”.
• the color of PBS is estimated using L, a, b-color system as assessment baseline.
• L means luminance factor
• a and “b” mean color measurement numbers.
• the “b”, which is used to estimate yellow-blue balance, is a significant evaluation number for the color of polyesters. A lower “b” value is a sign of a better color.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 50 g of 1,4-butanediol (0.55 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 1.73 g of calcium acetate (0.0098 mol) into the flask, (2) after that, add 29 g of tetra-n-butyl titanate (0.0852 mol) and 31.51 g of ethanol (0.685 mol) into the flask, then conduct the reaction at a temperature of 80° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 2.04 g of tetraethoxysilane (0.0098 mol) and 8.22 g of tartaric acid (0.0548 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 80° C. for 2.5 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in liquid state which contains 5.12% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 50 g of 1,4-butanediol (0.55 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 2.4 g of manganese acetate (0.0098 mol) into the flask, (2) after that, add 19.44 g of tetra-isopropyl titanate (0.0685 mol) and 31.51 g of ethanol (0.685 mol) into the flask, then conduct the reaction at a temperature of 110° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 1.02 g of tetraethoxysilane (0.0049 mol) and 12.76 g of trimethyl phosphite (0.1028 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 110° C. for 0.5 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 4.14% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 50 g of 1,4-butanediol (0.55 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 2.2 g of zinc acetate (0.01 mol) into the flask, (2) after that, add 22.80 g of tetra-n-butyl titanate (0.067 mol) and 92.46 g of ethanol (2.01 mol) into the flask, then conduct the reaction at a temperature of 180° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 8.41 g of citric acid (0.04 mol), 5.10 g of tartaric acid (0.034 mol), 2.08 g of tetraethoxysilane (0.01 mol) and 6.74 g of triethyl phosphate (0.037 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 180° C. for 1 hour; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 4.02% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 100 g of 1,4-butanediol (1.11 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 3.29 g of zinc acetate (0.015 mol) into the flask, (2) after that, add 10.21 g of tetra-n-butyl titanate (0.03 mol), 8.517 g of tetra-isopropyl titanate (0.03 mol), 3.12 g of tetraethoxysilane (0.015 mol) and 46 g of ethanol (1 mol) into the flask, then conduct the reaction at a temperature of 100° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 9.05 g of lactic acid (0.105 mol) and 14.22 g of trimethyl phosphate (0.1 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 150° C. for 1.2 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 2.01% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 50 g of 1,4-butanediol (0.55 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 3.22 g of magnesium acetate (0.015 mol) and 1.02 g of aluminium isopropoxide (0.005 mol) into the flask, (2) after that, add 22.80 g of tetra-n-butyl titanate (0.067 mol), 3.12 g of tetraethoxysilane (0.015 mol) and 46 g of ethanol (1 mol) into the flask, then conduct the reaction at a temperature of 80° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 10.06 g of tartaric acid (0.067 mol) and 18.22 g of triethyl phosphate (0.1 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 80° C. for 1.2 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 3.24% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 50 g of 1,4-butanediol (0.55 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 3.29 g of zinc acetate (0.015 mol) and 1.76 g of calcium acetate (0.01 mol) into the flask, (2) after that, add 22.80 g of tetra-n-butyl titanate (0.067 mol) and 46 g of ethanol (1 mol) into the flask, then conduct the reaction at a temperature of 180° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 7.04 g of citric acid (0.034 mol), 2.28 g of methyl silicate (0.015 mol) and 14.22 g of triethyl phosphate (0.1 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 120° C. for 2 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 3.49% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 50 g of 1,4-butanediol (0.55 mol), 2.04 g of aluminium isopropoxide (0.01 mol) and 2.45 g of manganese acetate (0.01 mol) into a 250 ml flask which is equipped with propeller and condensing unit, (2) after that, add then add 22.80 g of tetra-n-butyl titanate (0.067 mol) and 46 g of ethanol (1 mol) into the flask, then conduct the reaction at a temperature of 80° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 10.55 g of citric acid (0.050 mol), 3.12 g of tetraethoxysilane (0.015 mol) and 12.41 g of trimethyl phosphite (0.1 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 80° C. for 2.5 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 3.42% of titanium by weight could be obtained.
• the manufacturing method of the catalyst used in the production of PBS or its copolyesters comprises steps of: (1) add 31 g of ethanediol (0.5 mol) and 45.45 g of 1,4-butanediol (0.5 mol) into a 250 ml flask which is equipped with propeller and condensing unit, then add 2.04 g of aluminium isopropoxide (0.01 mol) and 1.73 g of calcium acetate (0.0098 mol) into the flask, (2) after that, add 22.80 g of tetra-n-butyl titanate (0.067 mol) and 31 g of ethanol (0.67 mol) into the flask, then conduct the reaction at a temperature of 80° C.
• step (3) remove small molecular products in the reaction system obtained in step (2) by dilution, (4) add 14.14 g of citric acid (0.067 mol), 13.96 g of tetraethoxysilane (0.067 mol) and 12.41 g of trimethyl phosphite (0.1 mol) into the reaction system in step (3) and conduct the reaction at a temperature at a temperature of 80° C. for 2.5 hours; (5) remove small molecular products in the reaction system obtained in step (4) by dilution and then catalyst in fluid state which contains 2.34% of titanium by weight could be obtained.
• the production of PBS using the catalyst obtained in the previous embodiment comprises steps of:
• the production of PBS using the catalyst obtained in the previous embodiment comprises steps of:
• the production process of PBS using the catalyst obtained in the previous embodiment comprises almost the same steps with the tenth embodiment, however, the catalyst added is different.
• the catalyst obtained in the third embodiment is added (the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is 100 ppm), after the final polycondensation which is proceeded for 140 minutes, PBS products are obtained.
• the melt flow rate of the PBS product is 16 g/10 min and the “b” value of the PBS product is 5.6.
• the production process of PBS using the catalyst obtained in the previous embodiment comprises almost the same steps with the tenth embodiment, however, the catalyst added is different.
• the catalyst obtained in the fourth embodiment is added (the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is 140 ppm), after the final polycondensation which is proceeded for 105 minutes, PBS products are obtained.
• the melt flow rate of the PBS product is 20 g/10 min and the “b” value of the PBS product is 4.5.
• the production process of PBS using the catalyst obtained in the previous embodiment comprises almost the same steps with the ninth embodiment, however, the catalyst added is different.
• There is 4 g of the catalyst obtained in the fifth embodiment is added (the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is 130 ppm), after the final polycondensation which is proceeded for 108 minutes, PBS products are obtained.
• the melt flow rate of the PBS product is 18 g/10 min and the “b” value of the PBS product is 4.9.
• the production process of PBS using the catalyst obtained in the previous embodiment comprises almost the same steps with the tenth embodiment, however, the catalyst added is different.
• the catalyst obtained in the sixth embodiment is added (the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is 105 ppm), after the final polycondensation which is proceeded for 134 minutes, PBS products are obtained.
• the melt flow rate of the PBS product is 16 g/10 min and the “b” value of the PBS product is 5.3.
• the production process of PBS using the catalyst obtained in the previous embodiment comprises almost the same steps with the tenth embodiment.
• the catalyst added is different.
• There are 3.5 g of the catalyst obtained in the seventh embodiment is added (the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is 120 ppm), after the final polycondensation which is proceeded for 125 minutes, PBS products are obtained.
• the melt flow rate of the PBS product is 19 g/10 min and the “b” value of the PBS product is 3.9.
• the production of PBS using the catalyst obtained in the previous embodiment comprises steps of:
• copolyester products containing PBS and polyethylene terephthalate(PET) are obtained.
• the melt flow rate of the products is 8 g/10 min and the “b” value of the PBS product is 6.2.
• the production process of PBS using the catalyst obtained in the previous embodiment comprises almost the same steps with the tenth embodiment.
• the catalyst added is different.
• There is 4 g of tetrabutyl titanate is added (the weight ratio of titanium atoms contained in the catalyst and total weight of PBS or its copolyester is 560 ppm), after the final polycondensation which is proceeded for 125 minutes, PBS products are obtained.
• the melt flow rate of the PBS product is 25g/10 min and the “b” value of the PBS product is 15.7.

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• Geology (AREA)
• Inorganic Chemistry (AREA)
• Polyesters Or Polycarbonates (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2008
  • 2008-09-08 CN CN200810042621.0A patent/CN101671435B/zh active Active
  • 2008-12-29 WO PCT/CN2008/002110 patent/WO2010025590A1/fr active Application Filing
  • 2008-12-29 US US13/062,695 patent/US20110162205A1/en not_active Abandoned

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