CN112708120B - Titanium polyester catalyst with low content of free hydroxycarboxylic acid and preparation method thereof - Google Patents
Titanium polyester catalyst with low content of free hydroxycarboxylic acid and preparation method thereof Download PDFInfo
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- CN112708120B CN112708120B CN201911015654.0A CN201911015654A CN112708120B CN 112708120 B CN112708120 B CN 112708120B CN 201911015654 A CN201911015654 A CN 201911015654A CN 112708120 B CN112708120 B CN 112708120B
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- 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
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- 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- 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
- C08G63/87—Non-metals or inter-compounds thereof
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Abstract
The invention relates to a titanium series catalyst with low free hydroxycarboxylic acid content and a preparation method thereof, which mainly solve the problems of high free hydroxycarboxylic acid content of the titanium series catalyst in the prior art, and adopts a low free hydroxycarboxylic acid titanium series polyester catalyst which is a composition containing a titanium compound and hydroxycarboxylic acid; wherein, the molar ratio of the hydroxycarboxylic acid to the titanium compound is 0.2-1.5, and the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, so that the problem of high content of the free hydroxycarboxylic acid is solved, and the method can be used for producing polyesters such as polyethylene terephthalate and the like.
Description
Technical Field
The invention relates to a titanium catalyst with low free hydroxycarboxylic acid content for polyester and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is a thermoplastic polyester obtained by polycondensation of Purified Terephthalic Acid (PTA) and Ethylene Glycol (EG). The resin has the characteristics of excellent mechanical properties (high strength, rigidity, toughness, impact resistance and the like), electrical properties, good dimensional stability and the like, so that the resin is widely applied to the fields of various polyester fibers, packaging, electronic and electric appliances, medical sanitation, buildings, automobiles, machinery and the like.
In the polyester preparation process, the catalyst has very important influence on the quality of products such as hue, stability, viscosity and the like. At present, most of the research at home and abroad uses antimony, germanium, titanium and aluminum series catalysts. Wherein, the antimony catalyst is the most common catalyst, which has the characteristics of moderate activity and low cost, and at present, more than 90 percent of the polyester at home and abroad is prepared by antimony catalyst such as antimony acetate, antimony trioxide and ethylene glycol antimony. However, antimony is a heavy metal, and may adversely affect human bodies and the environment in the using process, such as catalyst configuration, polyester processing and recycling, and the use limit of antimony will become stricter with the continuous enhancement of environmental awareness.
In recent years, titanium catalysts, which are the most promising environmentally friendly catalysts to replace antimony catalysts, have the characteristics of high catalytic activity and no harm to human bodies and the environment, and have been the subject of controversial research and application in the polyester industry. With the intensive research on titanium polyester catalysts by domestic and foreign research institutions and various large polyester production enterprises, various catalysts with excellent comprehensive performance are developed in succession, and the defects that the titanium catalysts are easy to hydrolyze, the polyester products are yellow, the stability is poor and the like are overcome. For example, dorf Ketal company (CN 102504226A) adopts citric acid aqueous solution to directly react with titanate, and then sodium hydroxide is added to adjust the pH of the solution to obtain the titanium catalyst, and a polyester product with good performance is obtained based on the titanium catalyst. For example, CN 102382287a, a product of petrochemical corporation, china, reacts a titanium compound, tetraethoxysilane, hydroxycarboxylic acid, etc. in a solvent, and then acetate, a phosphorus compound, etc. are added to obtain a liquid titanium catalyst, which can be dissolved in ethylene glycol, and can prepare polyester and copolyester with good hue and narrow molecular weight distribution. Shanghai Huaming high technology Co., ltd. [ CN101270185A ], adopts titanate to react with glycol and tetraethoxysilane, and then hydroxyl carboxylic acid is added to obtain the liquid titanium catalyst with better performance.
Hydroxycarboxylic acids such as lactic acid, citric acid, malic acid and the like are substances commonly used for modifying the modified titanium catalyst, and have the characteristics of low price, easy obtainment and the like. The chelation of the titanium compound and titanium atoms can effectively inhibit the hydrolysis of titanate, and the hydrolysis-resistant liquid titanium catalyst with good performance is prepared. However, in the processes reported in the prior patents, we have found that the ratio of hydroxycarboxylic acid to titanate is relatively high, for example, in the examples of patents CN102504226a and CN 102382287a, the molar ratio of hydroxycarboxylic acid to titanate is 2.5: 1. 2.0:1, and an unsuitable preparation process such as CN101270185a in the examples, the use of ethylene glycol to react with titanate followed by the addition of hydroxycarboxylic acid results in a lower degree of reaction of hydroxycarboxylic acid with titanate, and the added hydroxycarboxylic acid remains largely free in the catalyst system. Through a large number of experimental studies and observations, the authors found that free hydroxycarboxylic acid in the catalyst system is easy to enter into the polymer, which results in an increase in the color of polyester and a decrease in thermal stability, and meanwhile, free hydroxycarboxylic acid enters into the recycled ethylene glycol along with a vacuum system, thereby reducing the quality of the recycled ethylene glycol, so that in the process of modifying a titanium catalyst with hydroxycarboxylic acid, the reaction degree of hydroxycarboxylic acid and a titanium compound needs to be effectively increased, and the content of free hydroxycarboxylic acid in the titanium catalyst needs to be controlled.
In view of the above, the invention obtains the low free hydroxycarboxylic acid titanium-based polyester catalyst by controlling the ratio of hydroxycarboxylic acid to titanium compound and the content of free hydroxycarboxylic acid, and the polyester prepared by using the catalyst has good hue and thermal stability, and the recycled ethylene glycol has low content of free hydroxycarboxylic acid, thus having good technical effects.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the reaction degree of hydroxycarboxylic acid is low and the content of free hydroxycarboxylic acid is high when the hydroxycarboxylic acid is adopted to modify the titanium polyester catalyst in the prior art. The titanium polyester catalyst with low free carboxyl hydroxy carboxylic acid has the advantages of good product color phase, good thermal stability, low impurity content of recycled ethylene glycol hydroxy carboxylic acid and the like when being used for PET polymerization.
The second technical problem to be solved by the present invention is to provide a method for preparing a low free hydroxyl titanium carboxylate polyester catalyst corresponding to the first technical problem.
The present invention provides the application of the low free hydroxyl titanium carboxylate polyester catalyst corresponding to the first technical problem.
In order to solve one of the above technical problems, the invention adopts the technical scheme that: a low free hydroxy carboxylic acid titanium series polyester catalyst, the catalyst is the composition of titanium compound and hydroxy carboxylic acid, wherein the mole ratio of hydroxy carboxylic acid to titanium compound is 0.2-1.5.
In the above technical scheme, the hydroxycarboxylic acid portion forms a chelate with the titanium compound, and the other portion exists as free hydroxycarboxylic acid.
In the technical proposal, the device comprises a base,the titanium compound preferably has Ti (OR) 4 A compound of the formula, R is selected from linear or branched alkyl of 1 to 10 carbon atoms.
In the above technical solution, the hydroxycarboxylic acid is one or two or more of acids having 1 to 2 hydroxyl groups, and the hydroxycarboxylic acid is more preferably one or two or more of the following general formulae:
in the formula, R 1 Is H or C 1 ～C 4 Alkyl or carboxylic acid groups of R 2 Is C 0 ～C 4 Alkylene or hydroxy-substituted alkylene of (A), R 3 Is C 1 ～C 4 Alkyl or carboxylic acid groups.
In the above technical solutions, R is preferably 1 Is a formate group, R 2 Is methylene, R 3 Is an acetoxy group, then the hydroxycarboxylic acid is citric acid; preferably R 1 Is H, R 2 Is 0, R 3 Is methyl, the hydroxycarboxylic acid is lactic acid; preferably R 1 Is H, R 2 Is methylene, R 3 Is a formate group, the hydroxycarboxylic acid is malic acid; preferably R 1 Is H, R 2 Is hydroxy-substituted methylene, R 3 Is a formate group, the hydroxycarboxylic acid is tartaric acid; preferably R 1 Is H, R 2 Is ethylene, R 3 Is a formate group, the hydroxycarboxylic acid is 2-hydroxyglutaric acid. .
In order to solve the second technical problem, the invention adopts the technical scheme that: a preparation method of a low free hydroxyl carboxylic acid titanium series polyester catalyst comprises the following steps:
1) Dissolving or diluting hydroxycarboxylic acid in a solvent, and stirring to obtain a clear and transparent solution;
2) Dropwise adding a titanium compound into the solution according to the molar ratio of 0.2-1.5 of hydroxycarboxylic acid to the titanium compound; heating for reaction, removing small molecules by vacuum pumping, monitoring the content of free hydroxy acid in the catalyst solution, and stopping the reaction when the content is less than 10% of the addition amount;
3) Adding ethylene glycol into the solution to obtain the low free hydroxyl carboxylic acid titanium series polyester catalyst
In the above technical scheme, the titanium compound is Ti (OR) 4 A compound of formula (I), R is selected from linear or branched alkyl of 1 to 10 carbon atoms;
in the above technical solution, the hydroxycarboxylic acid is one or two or more of acids having 1 to 2 hydroxyl groups, and the hydroxycarboxylic acid is further preferably one or two or more of the following general formulae:
in the formula, R 1 Is H or C 1 ～C 4 Alkyl or carboxylic acid groups of R 2 Is C 0 ～C 4 Alkylene or hydroxy-substituted alkylene of (A), R 3 Is C 1 ～C 4 Alkyl or carboxylic acid groups of (a).
In the above technical solutions, R is preferable 1 Is a formate group, R 2 Is methylene, R 3 Is an acetoxy group, then the hydroxycarboxylic acid is citric acid; preferably R 1 Is H, R 2 Is 0, R 3 Is methyl, the hydroxycarboxylic acid is lactic acid; preferably R 1 Is H, R 2 Is methylene, R 3 Is a formate group, the hydroxycarboxylic acid is malic acid; preferably R 1 Is H, R 2 Is hydroxy-substituted methylene, R 3 Is a formate group, the hydroxycarboxylic acid is tartaric acid; preferably R 1 Is H, R 2 Is ethylene, R 3 Is a formate group, the hydroxycarboxylic acid is 2-hydroxyglutaric acid.
In the above technical scheme, the solvent is one or more of monohydric alcohol with 2-10 carbon atoms such as ethanol and isopropanol and polyhydric alcohol with 2-10 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol and butanediol.
In the technical scheme, the stirring in the step 1) is carried out at the temperature of-20-40 ℃.
In the technical scheme, the reaction conditions in the step 2) are that the reaction temperature is 30-200 ℃, the reaction time is 0.2-24h, and the vacuum degree is 0.1MPa gauge pressure.
In order to solve the third technical problem, the invention adopts the technical scheme that: an application of the titanium carboxylate with low free hydroxyl group polyester catalyst in one of the technical schemes for solving the technical problems.
In the above technical scheme, the application is not particularly limited, and those skilled in the art can apply the catalyst according to the existing technical conditions, for example, but not limited to the application of the catalyst in the preparation of polyester, preferably in the preparation of polyethylene terephthalate.
In the present invention, the intrinsic viscosity, hue, etc. of the polyester are measured by the following methods:
(1) Intrinsic viscosity: the phenol-tetrachloroethane mixture is used as a solvent, and is measured by an Ubbelohde viscometer at the temperature of 25 ℃.
(2) Hue: the pellet samples were treated at 135 ℃ for 1 hour and measured for Hunter L value (lightness), a value (red-green hue) and b value (yellow-blue hue) using a color-view automatic color difference meter from BYK Gardner. Wherein, the higher the L value, the larger the brightness; when the value of b is high, the polyester chip is yellowish. For the present invention, a high L value and a low b value are desired.
(3) Free hydroxycarboxylic acid: HPLC (C18, 95% ACN isocratic elution, detection wavelength 205 nm) was used for the test.
(4) And (3) thermal stability analysis: drying at 150 deg.C under vacuum
A tube furnace is adopted for processing for 30min at 270 ℃ under nitrogen atmosphere.
By adopting the technical scheme of the invention, the obtained titanium polyester catalyst is used for preparing polyethylene terephthalate resin, the catalyst has the advantages of low content of free hydroxycarboxylic acid, good color phase and good thermal stability of the prepared PET, and simultaneously, the content of free hydroxycarboxylic acid impurities in recycled ethylene glycol is low, so that better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ] A method for producing a polycarbonate
1.0mol of citric acid and a proper amount of isopropanol are added into a reactor provided with a stirrer, a condenser and a thermometer, and stirred for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating until reflux reaction is carried out for 2 hours, removing small molecules by adopting vacuum, simultaneously sampling, testing the content of free hydroxycarboxylic acid in a system by adopting liquid chromatography, stopping the reaction when the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
[ example 2 ]
0.5mol of citric acid and a proper amount of isopropanol are added into a reactor provided with a stirrer, a condenser and a thermometer, and stirred for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating until reflux reaction is carried out for 2 hours, removing small molecules by adopting vacuum, simultaneously sampling, testing the content of free hydroxycarboxylic acid in a system by adopting liquid chromatography, stopping the reaction when the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
[ example 3 ]
0.3mol of citric acid and a proper amount of isopropanol are added into a reactor provided with a stirrer, a condenser and a thermometer, and stirred for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating to reflux reaction for 2 hours, removing small molecules by vacuum, simultaneously sampling and testing the content of free hydroxycarboxylic acid in a system by adopting liquid chromatography, stopping the reaction when the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
[ example 4 ]
1.5mol of citric acid and a proper amount of isopropanol are added into a reactor provided with a stirrer, a condenser and a thermometer, and stirred for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating to reflux reaction for 2 hours, removing small molecules by vacuum, simultaneously sampling and testing the content of free hydroxycarboxylic acid in a system by adopting liquid chromatography, stopping the reaction when the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
[ example 5 ]
Adding 1.0mol of citric acid and a proper amount of ethanol into a reactor provided with a stirrer, a condenser and a thermometer, and stirring for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating to reflux reaction for 2 hours, removing small molecules by vacuum, simultaneously sampling and testing the content of free hydroxycarboxylic acid in a system by adopting liquid chromatography, stopping the reaction when the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
[ example 6 ] A method for producing a polycarbonate
1.0mol of citric acid is added into a reactor provided with a stirrer, a condenser and a thermometer, then a proper amount of diethylene glycol is added, and the mixture is stirred for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating to reflux reaction for 2 hours, removing small molecules by vacuum, simultaneously sampling and testing the content of free hydroxycarboxylic acid in a system by adopting liquid chromatography, stopping the reaction when the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
Comparative example 1
2.0mol of citric acid and a proper amount of isopropanol are added into a reactor provided with a stirrer, a condenser and a thermometer, and stirred for 2 hours at room temperature to obtain a clear and transparent citric acid solution. Slowly dropwise adding 1.0mol of tetraisopropyl titanate into the solution, after dropwise adding, heating to reflux reaction for 2 hours, removing small molecules by vacuum, stopping the reaction after about 1 hour, and adding a certain amount of glycol for dilution to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
Comparative example 2
Adding 1.0mol of tetraisopropyl titanate into a reactor provided with a stirrer, a condenser and a thermometer, slowly dropwise adding 2.5mol of aqueous solution of citric acid into the solution, heating the solution until reflux reaction is carried out for 2 hours after dropwise adding to obtain turbid solution, removing micromolecules in vacuum, and adding a certain amount of glycol for dilution to obtain slightly turbid catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
Comparative example 3
Adding 1.0mol of tetraisopropyl titanate into a reactor provided with a stirrer, a condenser and a thermometer, slowly dropwise adding an ethylene glycol solution (200 g) into the solution, heating to 80 ℃ after dropwise adding, reacting for 2 hours to obtain a turbid solution, removing small molecules in vacuum, adding an ethylene glycol citrate solution (the citric acid content is 1 mol) to obtain a clear transparent solution, and then adding ethylene glycol to dilute to obtain a catalyst solution with the titanium content of 3.0 wt%. The free acid content is listed in table 1.
[ example 7 ]
500 g of terephthalic acid, 316 g of ethylene glycol and the catalyst of example 1 (based on the amount of polyester produced, the weight of titanium atoms is 5 ppm) were mixed to prepare a slurry, which was added to a polymerizer to conduct esterification at 230-250 ℃ under a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, extruding the reaction product from the bottom of the polymerization kettle, cooling, and granulating for performance test.
And (3) placing the obtained slices in a vacuum oven, drying at 150 ℃ for 12 hours, then placing the slices in a tube furnace with nitrogen atmosphere, carrying out heat treatment at 270 ℃ for 30min, and testing the intrinsic viscosity of the samples before and after the heat treatment.
The recycle glycol collected during the polycondensation was subjected to liquid chromatography testing to determine the free hydroxycarboxylic acid content.
The test results are shown in Table 2
[ example 8 ]
500 g of terephthalic acid, 316 g of ethylene glycol and the catalyst of example 2 (based on the amount of polyester produced, the weight of titanium atoms is 5 ppm) were mixed to prepare a slurry, which was added to a polymerizer to conduct esterification at 230-250 ℃ under a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, extruding the reaction product from the bottom of the polymerization kettle, cooling, and granulating for performance test.
And placing the obtained slices in a vacuum oven, drying at 150 ℃ for 12 hours, then placing the slices in a tube furnace equipped with nitrogen atmosphere, carrying out heat treatment at 270 ℃ for 30min, and carrying out intrinsic viscosity test on samples before and after the heat treatment.
The test results are shown in Table 2
Comparative example 4
500 g of terephthalic acid, 316 g of ethylene glycol and the catalyst of comparative example 1 (based on the amount of polyester produced, the weight of titanium atom is 5 ppm) were mixed to prepare a slurry, which was added to a polymerizer to conduct esterification at 230 to 250 ℃ and under 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually raising the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, then extruding the reaction product from the bottom of the polymerization kettle, cooling, and pelletizing for performance test.
And placing the obtained slices in a vacuum oven, drying at 150 ℃ for 12 hours, then placing the slices in a tube furnace equipped with nitrogen atmosphere, carrying out heat treatment at 270 ℃ for 30min, and carrying out intrinsic viscosity test on samples before and after the heat treatment.
The test results are shown in Table 2
Comparative example 5
500 g of terephthalic acid, 316 g of ethylene glycol and the catalyst of comparative example 2 (based on the amount of polyester produced, the weight of titanium atom is 5 ppm) were mixed to prepare a slurry, which was added to a polymerizer to conduct esterification at 230 to 250 ℃ and under 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, extruding the reaction product from the bottom of the polymerization kettle, cooling, and granulating for performance test.
And placing the obtained slices in a vacuum oven, drying at 150 ℃ for 12 hours, then placing the slices in a tube furnace equipped with nitrogen atmosphere, carrying out heat treatment at 270 ℃ for 30min, and carrying out intrinsic viscosity test on samples before and after the heat treatment.
The test results are shown in Table 2
Comparative example 6
500 g of terephthalic acid, 316 g of ethylene glycol and the catalyst of comparative example 3 (based on the amount of polyester produced, the weight of titanium atom is 5 ppm) were mixed to prepare a slurry, which was added to a polymerizer to conduct esterification at 230 to 250 ℃ and under 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, extruding the reaction product from the bottom of the polymerization kettle, cooling, and granulating for performance test.
And (3) placing the obtained slices in a vacuum oven, drying at 150 ℃ for 12 hours, then placing the slices in a tube furnace with nitrogen atmosphere, carrying out heat treatment at 270 ℃ for 30min, and testing the intrinsic viscosity of the samples before and after the heat treatment.
The recycle glycol collected during the polycondensation was subjected to liquid chromatography testing to determine the free hydroxycarboxylic acid content.
The test results are shown in Table 2.
TABLE 1
TABLE 2
Claims (13)
1. A preparation method of a low free hydroxyl carboxylic acid titanium series polyester catalyst comprises the following steps:
1) Dissolving or diluting hydroxycarboxylic acid in a solvent, and stirring to obtain a clear and transparent solution;
2) Dropping a titanium compound into the solution according to the molar ratio of the hydroxycarboxylic acid to the titanium compound being 0.2-1.5; heating for reaction, removing small molecules by vacuum pumping, monitoring the content of free hydroxy acid in the catalyst solution, and stopping the reaction when the content is less than 10% of the addition amount;
3) And adding ethylene glycol into the solution to obtain the low free hydroxyl carboxylic acid titanium polyester catalyst.
2. The method for preparing the titanium polyester catalyst with low free hydroxy carboxylic acid according to claim 1, wherein the titanium compound is Ti (OR) 4 A compound of the formula, R is selected from linear or branched alkyl of 1 to 10 carbon atoms.
3. The method for preparing the titanium polyester catalyst with low free hydroxy carboxylic acid as claimed in claim 1, wherein the hydroxy carboxylic acid is an acid containing 1-2 hydroxy groups.
4. The method for preparing the titanium polyester catalyst with low free hydroxycarboxylic acid according to claim 1, wherein the hydroxycarboxylic acid is one or more of citric acid, lactic acid, malic acid, tartaric acid, and 2-hydroxyglutaric acid.
5. The method for preparing the titanium carboxylate with low free radical content as claimed in claim 1, wherein the solvent is one or more of monohydric alcohol with 2-10 carbon atoms and polyhydric alcohol with 2-10 carbon atoms.
6. The method for preparing the titanium polyester catalyst with low free hydroxyl carboxylic acid content as claimed in claim 5, wherein the monohydric alcohol is ethanol or isopropanol, and the polyhydric alcohol is ethylene glycol, diethylene glycol, propylene glycol or butylene glycol.
7. The method for preparing the titanium carboxylate with low free hydroxyl group as claimed in claim 1, wherein the stirring in the step 1) is performed at room temperature; the reaction conditions in the step 2) are that the reaction temperature is 30-200 ℃, the reaction time is 0.2-24h, and the vacuum degree is 0.1MPa gauge pressure.
8. A low free hydroxy carboxylic acid titanium series polyester catalyst, which is a composition containing titanium compound and hydroxy carboxylic acid; wherein the molar ratio of the hydroxycarboxylic acid to the titanium compound is 0.2-1.5, the content of the free hydroxycarboxylic acid is less than or equal to 10% of the amount of the added hydroxycarboxylic acid, and is more than or equal to 5.4% of the amount of the added hydroxycarboxylic acid;
the titanium carboxylate with low free hydroxyl group series polyester catalyst is prepared by the preparation method of one of claims 1 to 7.
9. The titanium polyester catalyst with low free hydroxy carboxylic acid content as claimed in claim 8, wherein the titanium compound is Ti (OR) 4 A compound of formula (I), R is selected from linear or branched alkyl of 1 to 10 carbon atoms.
10. The titanium carboxylate with low free radical content as claimed in claim 8, wherein the hydroxy carboxylic acid is an acid containing 1-2 hydroxyl groups.
11. The titanium polyester catalyst with low free hydroxycarboxylic acid content as claimed in claim 8, wherein the hydroxycarboxylic acid is one or more selected from the group consisting of citric acid, lactic acid, malic acid, tartaric acid, and 2-hydroxyglutaric acid.
12. Use of the titanium carboxylate with low free hydroxyl group as defined in any one of claims 8 to 11 as a catalyst.
13. The use according to claim 12, wherein said use is the use of said titanium low free hydroxy carboxylate polyester catalyst in the preparation of polyesters.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005126449A (en) * | 2003-10-21 | 2005-05-19 | Toyobo Co Ltd | Polymerization catalyst for polyester, polyester manufactured using the same and manufacturing method of polyester |
| CN105121500A (en) * | 2013-02-06 | 2015-12-02 | 乌德伊万塔-费希尔有限公司 | Method for the production of a titanium containing catalyst, titanium containing catalyst, method for the production of polyester and polyester |
| CN107964092A (en) * | 2016-10-18 | 2018-04-27 | 中国石油化工股份有限公司 | Produce catalyst of polypropylene terephthalate and its preparation method and application |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005126449A (en) * | 2003-10-21 | 2005-05-19 | Toyobo Co Ltd | Polymerization catalyst for polyester, polyester manufactured using the same and manufacturing method of polyester |
| CN105121500A (en) * | 2013-02-06 | 2015-12-02 | 乌德伊万塔-费希尔有限公司 | Method for the production of a titanium containing catalyst, titanium containing catalyst, method for the production of polyester and polyester |
| CN107964092A (en) * | 2016-10-18 | 2018-04-27 | 中国石油化工股份有限公司 | Produce catalyst of polypropylene terephthalate and its preparation method and application |
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