Disclosure of Invention
The invention provides a preparation method and application of an environment-friendly titanium composite catalyst for polyester, aiming at the problems of more side reactions and yellow product color phase in the production process of the existing titanium catalytic polyester. The invention regulates and controls the catalytic activity of the titanium composite catalyst by regulating and controlling the size and the aperture of the mesoporous nano-microsphere and the proportion of the mesoporous microsphere, the titanium compound and the metal catalytic auxiliary agent. The catalyst is applied to polyester synthesis, can effectively reduce the occurrence of side reactions, and simultaneously solves the technical problem that the color of a titanium-based catalytic polyester product is yellow.
The specific technical scheme of the invention is as follows:
the preparation method of the environment-friendly titanium composite catalyst for polyester comprises the following steps: dissolving mesoporous nano microspheres, a titanium compound and a metal catalytic assistant in ethylene glycol, performing ultrasonic dispersion, reacting in a solvent, and then removing small molecules in a reaction system to obtain the environment-friendly titanium composite catalyst for polyester; the mass ratio of the mesoporous nano microspheres to the titanium compound is 0.1-20: 1; the molar ratio of the ethylene glycol to the titanium compound is 1-100: 1; the molar ratio of the metal catalytic promoter to the titanium compound is 0.1-10: 1.
In the invention, the added metal catalyst promoter has a certain catalytic effect, so that the dosage of the titanium catalyst can be reduced. While the high catalytic activity of the titanium catalyst causes many side reactions to occur, the side reactions are reduced when the amount of the titanium catalyst is reduced. The titanium catalyst and the metal catalytic auxiliary agent exist in the mesopores of the silicon dioxide, chain growth in the polycondensation process is a chelating coordination reaction in the mesopores, and the size of the mesopores determines the steric hindrance in the reaction process, so that the catalytic activity of the titanium composite catalyst can be regulated and controlled by regulating and controlling the size of the mesopores. The side reaction is reduced and the hue is improved.
Preferably, the mass ratio of the mesoporous nano-microspheres to the titanium compound is 0.5-10: 1; the molar ratio of the ethylene glycol to the titanium compound is 5-50: 1; the molar ratio of the metal catalytic promoter to the titanium compound is 0.5-5: 1.
After a large amount of researches, the team of the invention finds that the proportion of the mesoporous microspheres, the titanium compound and the metal catalytic assistant needs to be strictly controlled, so that the catalytic activity of the titanium composite catalyst can be effectively regulated and controlled. The catalyst is applied to polyester synthesis, can effectively reduce the occurrence of side reactions, and simultaneously solves the technical problem that the color of a titanium-based catalytic polyester product is yellow.
Preferably, the mesoporous nano-microsphere is mesoporous carbon nano-microsphere, mesoporous silica nano-microsphere, mesoporous titania nano-microsphere, mesoporous Al2O3Nano microsphere, mesoporous Fe2O3Nano microsphere, mesoporous Co-SiO2At least one of the nano-microsphere and the mesoporous ZnO nano-microsphere.
Preferably, the titanium compound is at least one of titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, tetramethyl titanate, and diisopropyl titanate, tetraisopropyl titanate.
Preferably, the catalytic assistant is at least one of magnesium acetate, sodium acetate, zinc acetate, calcium acetate, aluminum acetate and potassium acetate.
Preferably, the preparation method of the mesoporous silica nanospheres comprises the following steps: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in deionized water in a molar ratio of 3-5:1 to obtain a solution with a total concentration of 0.02-0.04 mol/L; performing ultrasonic treatment for 20-40min, standing for 20-30h, adding ammonia water and diethyl ether, adding ethyl orthosilicate after vigorous stirring, continuing stirring for 3-5h to complete reaction, performing suction filtration on reaction liquid, repeatedly washing the obtained filter cake with ethanol and water, drying, roasting at 500-600 ℃ for 2-4h, and crushing to obtain the mesoporous silica nano microspheres.
After a great deal of research, the invention finds that the size and the aperture size of the mesoporous nano microspheres need to be strictly controlled, so that the invention strictly limits the preparation method of the mesoporous nano microspheres, and the method is specially designed for the mesoporous nano microspheres needed by the system of the invention, thereby realizing the effective regulation and control of the catalytic activity of the titanium composite catalyst.
The titanium composite catalyst for the environment-friendly polyester is applied to polyester synthesis. Wherein, the environment-friendly polyester titanium composite catalyst is added before or after esterification; based on the yield of the polyester, the addition mass of the environment-friendly titanium composite catalyst for the polyester is 2-50 ppm calculated by titanium element.
Preferably, the polyester synthesis method comprises the following steps: the method comprises the steps of pulping by taking dibasic acid and dihydric alcohol as raw materials, and reacting under the action of an environment-friendly polyester titanium-based composite catalyst to prepare the environment-friendly polyester, wherein the reaction temperature is 220-300 ℃, the reaction pressure is 30-0.5 MPa, and the reaction time is 3.5-11 h.
Preferably, the dibasic acid is one or more of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid and succinic acid; the dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 3-dimethylpropanol, butanediol and pentanediol; the molar ratio of the dihydric alcohol to the dibasic acid is 1.2-2.0: 1.
Preferably, esterification, pre-polycondensation and final polycondensation are sequentially carried out in the polyester synthesis reaction process; wherein the esterification reaction temperature is controlled to be 220-270 ℃, the pressure is normal pressure-0.5 MPa, and the time is 1.5-5.5 h; the temperature of the pre-polycondensation reaction is controlled to be 240-270 ℃, the pressure is 1-101 KPa, and the time is 0.5-2.5 h; the final polycondensation reaction temperature is controlled to be 270-300 ℃, the pressure is 30-300 Pa, and the time is 1-3.5 h.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention regulates and controls the catalytic activity of the titanium composite catalyst by strictly regulating and controlling the size and the aperture of the mesoporous nano-microspheres and the proportion of the mesoporous microspheres, the titanium compound and the metal catalytic auxiliary agent. The catalyst is applied to polyester synthesis, can effectively reduce the occurrence of side reactions, and simultaneously solves the technical problem that the color of a titanium-based catalytic polyester product is yellow.
2. Compared with antimony catalyst, the titanium composite catalyst has the advantages of high catalytic activity, environmental protection; compared with the conventional titanium catalyst, the titanium composite catalyst prepared by the invention has the advantages of adjustable catalytic efficiency, high temperature resistance and hydrolysis resistance; the polyester product prepared by the catalyst has stable quality and good color.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
Preparation of the catalyst:
dissolving mesoporous nano microspheres, a titanium compound and a metal catalytic assistant in ethylene glycol, performing ultrasonic dispersion, reacting in a solvent, and then removing small molecules in a reaction system to obtain the environment-friendly titanium composite catalyst for polyester; the mass ratio of the mesoporous nano microspheres to the titanium compound is 0.1-20: 1; the molar ratio of the ethylene glycol to the titanium compound is 1-100: 1; the molar ratio of the metal catalytic promoter to the titanium compound is 0.1-10: 1.
Wherein the mesoporous nano-microsphere is mesoporous carbon nano-microsphere, mesoporous silica nano-microsphere, mesoporous titanium dioxide nano-microsphere, mesoporous Al2O3Nano microsphere, mesoporous Fe2O3Nano microsphere, mesoporous Co-SiO2At least one of the nano-microsphere and the mesoporous ZnO nano-microsphere.
The titanium compound is at least one of titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, tetramethyl titanate, diisopropyl titanate and tetraisopropyl titanate.
The catalytic auxiliary agent is at least one of magnesium acetate, sodium acetate, zinc acetate, calcium acetate, aluminum acetate and potassium acetate.
Preferably, the mass ratio of the mesoporous nano-microspheres to the titanium compound is 0.5-10: 1; the molar ratio of the ethylene glycol to the titanium compound is 5-50: 1; the molar ratio of the metal catalytic promoter to the titanium compound is 0.5-5: 1.
And (3) synthesis of polyester:
pulping by using dibasic acid and dihydric alcohol as raw materials, and sequentially carrying out esterification, pre-polycondensation and final polycondensation; wherein the esterification reaction temperature is controlled to be 220-270 ℃, the pressure is normal pressure-0.5 MPa, and the time is 1.5-5.5 h; the temperature of the pre-polycondensation reaction is controlled to be 240-270 ℃, the pressure is 1-101 KPa, and the time is 0.5-2.5 h; the final polycondensation reaction temperature is controlled to be 270-300 ℃, the pressure is 30-300 Pa, and the time is 1-3.5 h. Adding the environment-friendly titanium composite catalyst for polyester before or after esterification; based on the yield of the polyester, the addition mass of the environment-friendly titanium composite catalyst for the polyester is 2-50 ppm calculated by titanium element.
Wherein the dibasic acid is one or more of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid and succinic acid; the dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 3-dimethylpropanol, butanediol and pentanediol; the molar ratio of the dihydric alcohol to the dibasic acid is 1.2-2.0: 1.
Example 1
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water, 25ml of ethanol and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica nano microspheres. Then, adding ethylene glycol, magnesium acetate and titanium tetrachloride into a three-neck flask in sequence, adding the mixture according to the molar ratio of 20: 4: 1, then adding mesoporous silica nano microspheres according to the mass ratio of 5:1 to titanium tetrachloride, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 160 ℃, and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst A.
Preparation of polyester: 396.8g of ethylene glycol and 664g of purified terephthalic acid and catalyst A (5 ppm by mass of titanium atom, based on the theoretical yield of polyester) were charged into a 2-liter reactor and slurried. Controlling the esterification temperature at 240 ℃, the pressure at 0.3MPa, the time at 2.5h and the esterification rate at 93 percent; adding flatting agent titanium dioxide after esterification, wherein the addition amount is 0.25 percent (calculated by the theoretical yield of polyester); the temperature of the pre-polycondensation is controlled to be 260 ℃, and the reaction pressure is 50 KPa; and the final polycondensation is controlled at 280 ℃, the pressure is 50Pa, and the polycondensation time is 2.5h to obtain the polyester product.
The test results are shown in Table 1.
Example 2
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica microspheres. Then, adding ethylene glycol, magnesium acetate and titanium tetrachloride into a three-neck flask in sequence, adding the mixture according to the molar ratio of 20: 4: 1, then adding mesoporous silica according to the mass ratio of 5:1 to titanium tetrachloride, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 160 ℃, and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst B.
Preparation of polyester: the preparation method of the polyester is the same as that of the example 1, and the adopted catalyst is a titanium composite catalyst B.
The test results are shown in Table 1.
Example 3
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water, 25ml of ethanol and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica microspheres. Then, adding ethylene glycol, zinc acetate and titanium tetrachloride into a three-neck flask in sequence, adding the mixture according to the molar ratio of 20: 4: 1, then adding mesoporous silica according to the mass ratio of 5:1 to titanium tetrachloride, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 160 ℃, and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst C.
Preparation of polyester: the preparation method of the polyester is the same as that of the example 1, and the adopted catalyst is a titanium composite catalyst C.
The test results are shown in Table 1.
Example 4
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica nano microspheres. Then, adding ethylene glycol, zinc acetate and titanium tetrachloride into a three-neck flask in sequence, adding the mixture according to the molar ratio of 20: 4: 1, then adding mesoporous silica nano particles according to the mass ratio of 5:1 to titanium tetrachloride, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 160 ℃, and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst D.
Preparation of polyester: the preparation method of the polyester is the same as that of the example 1, and the adopted catalyst is a titanium composite catalyst D.
The test results are shown in Table 1.
Example 5
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water, 25ml of ethanol and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica microspheres. Then, adding ethylene glycol, magnesium acetate and tetraethyl titanate into a three-neck flask in sequence, adding the mixture according to the molar ratio of 15: 5:1, then adding mesoporous silica according to the mass ratio of 8: 1 to the tetraethyl titanate, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 165 ℃ and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst E.
Preparation of polyester: the polyester was prepared in the same manner as in example 1, using a titanium-based composite catalyst E.
The test results are shown in Table 1.
Example 6
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica microspheres. Then, adding ethylene glycol, zinc acetate and tetraethyl titanate into a three-neck flask in sequence, adding the mixture according to the molar ratio of 15: 5:1, then adding mesoporous silica according to the mass ratio of 8: 1 to the tetraethyl titanate, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 165 ℃ and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst F.
Preparation of polyester: the polyester was prepared in the same manner as in example 1, using a titanium-based composite catalyst F as the catalyst.
The test results are shown in Table 1.
Example 7
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water, 25ml of ethanol and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica microspheres. Then, adding ethylene glycol, zinc acetate and tetraethyl titanate into a three-neck flask in sequence, adding the mixture according to the molar ratio of 15: 5:1, then adding mesoporous silica according to the mass ratio of 5:1 to the tetraethyl titanate, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 165 ℃ and the stirring speed is 120 r/min. And standing for 24h after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst G.
Preparation of polyester: the polyester was prepared in the same manner as in example 1, using titanium composite catalyst G as the catalyst.
The test results are shown in Table 1.
Example 8
Preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate in 100ml deionized water in the molar ratio of 4 to 1 to prepare a solution with the total concentration of 0.03mol/L, and standing for 24 hours after 0.5 hour of ultrasonic treatment. Then adding 1ml of ammonia water and 25ml of diethyl ether, stirring vigorously for 0.5h, then adding 3g of ethyl orthosilicate, and continuing to stir for 4h to complete the reaction. And (3) carrying out suction filtration on the reaction liquid, repeatedly washing a filter cake for 5 times by using ethanol and water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, then placing a product in a muffle furnace at 550 ℃ for roasting for 3 hours, and crushing to obtain the mesoporous silica microspheres. Then, adding ethylene glycol, magnesium acetate and tetraethyl titanate into a three-neck flask in sequence, adding the mixture according to the molar ratio of 15: 5:1, then adding mesoporous silica according to the mass ratio of 5:1 to the tetraethyl titanate, and carrying out ultrasonic reaction for 4 hours under the protection of nitrogen, wherein the reaction temperature is controlled at 165 ℃ and the stirring speed is 120 r/min. And standing for 24H after the reaction is finished, filtering to obtain a solid, repeatedly washing with ethanol and deionized water for 3 times, and drying to obtain the titanium composite catalyst H.
Preparation of polyester: the preparation method of the polyester is the same as that of the example 1, and the adopted catalyst is a titanium composite catalyst H.
The test results are shown in Table 1.
Example 9
Preparation of the catalyst: the catalyst was prepared as in example 1.
Preparation of polyester: 396.8g of ethylene glycol and 664g of purified terephthalic acid were charged into a 2L reactor and slurried. Controlling the esterification temperature at 245 ℃, the pressure at 0.3MPa and the time at 2.5h, adding a catalyst A (the mass of titanium atoms is 5ppm calculated by the theoretical yield of polyester) after the esterification, and adding a delustering agent titanium dioxide with the addition amount of 0.25% (calculated by the theoretical yield of polyester); the temperature of the pre-polycondensation is controlled to be 265 ℃, and the reaction pressure is 60 KPa; and the final polycondensation is controlled at 280 ℃, the pressure is 50Pa, and the polycondensation time is 2.5h to obtain the polyester product.
The test results are shown in Table 1.
Comparative example 1
Preparation of the catalyst: the catalyst was prepared according to the method of example 1 of chinese patent application 201210239821.1. 28.4 g (0.1 mol) of tetraisopropyl titanate was charged into a reactor equipped with a stirrer, a condenser and a thermometer, 12.4 g (0.2 mol) of ethylene glycol was slowly dropped into the reactor, and reacted at 70 ℃ for 2 hours to give a white emulsion, 107 g (0.5 mol) of magnesium acetate tetrahydrate, 36g (0.4 mol) of lactic acid and 45.5 g (0.25 mol) of triethyl phosphate were added to give a pH of 5.5, and reacted for 2 hours to give a homogeneous clear liquid as catalyst I.
Preparation of polyester: the preparation method of the polyester is the same as that of the example 1, and the adopted catalyst is a titanium composite catalyst I.
Comparative example 2
A polyester was prepared as described in example 1, using ethylene glycol antimony as catalyst (mass of antimony atoms 200ppm, calculated on the theoretical yield of polyester).
Table 1: the polyester product data obtained in examples 1-9 and comparative examples 1-2 are compared as follows:
as can be seen by comparing comparative example 1 and the examples in Table 1, the L value, the a value and the b value of the polyester prepared by the titanium composite catalyst of the invention are improved to different degrees compared with the polyester prepared by the conventional titanium catalyst, the hue of the prepared polyester is improved, particularly the b value is improved remarkably, the problem of yellowing of the color is solved, and the side reaction is reduced. Further, it can be also explained that the occurrence of side reactions is reduced by the titanium-based composite catalyst of the present invention from the viewpoint of the reduction of the content of diethylene glycol. As can be seen from the comparison of comparative example 2 and the example, the quality of the polyester prepared by the titanium composite catalyst of the invention is equivalent to that of the antimony catalyst (but the antimony is more expensive), and the effect of the antimony catalyst is basically achieved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.