WO2023202449A1 - Solid bimetallic titanium-based polyester catalyst, preparation method therefor, and use thereof - Google Patents

Solid bimetallic titanium-based polyester catalyst, preparation method therefor, and use thereof Download PDF

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Publication number
WO2023202449A1
WO2023202449A1 PCT/CN2023/087944 CN2023087944W WO2023202449A1 WO 2023202449 A1 WO2023202449 A1 WO 2023202449A1 CN 2023087944 W CN2023087944 W CN 2023087944W WO 2023202449 A1 WO2023202449 A1 WO 2023202449A1
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titanium
compound
carboxylic acid
reaction
catalyst
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PCT/CN2023/087944
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French (fr)
Chinese (zh)
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陈世昌
谢尚栋
陈文兴
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浙江理工大学
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Publication of WO2023202449A1 publication Critical patent/WO2023202449A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/28—Titanium compounds
    • 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
    • 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
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
    • 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
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof

Definitions

  • the invention relates to the field of polyester synthesis, and in particular to a solid bimetallic titanium polyester catalyst and its preparation method and application.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • PBS polybutylene succinate
  • Germanium-based polyester catalysts are non-toxic to organisms, have high catalytic activity for polyester polycondensation and low catalytic activity for polyester thermal degradation. The dosage is only about 1/10 of that of antimony-based catalysts, and the product has good color and appearance. Excellent, extremely suitable for producing products that require high transparency.
  • the polyether content in the molecular chain is high, resulting in a lower melting point, poorer crystallization properties, and a wider processing and molding window.
  • germanium-based polyester catalysts are expensive and have not been widely used around the world.
  • titanium-based catalysts for polyester is about 40 times that of antimony. It is as harmless to the human body as germanium and has a significant price advantage compared with germanium.
  • titanium-based catalysts also have strong catalytic activity for the degradation reaction of polyester, which causes serious side reactions and is more likely to produce impurity terminal carboxyl groups and acetaldehyde free radicals.
  • the prepared polyester often turns yellow in color, affecting product quality.
  • Common titanium organic ester catalysts, such as tetrabutyl titanate and isopropyl titanate are easily hydrolyzed and lose activity, easily deteriorate during storage, and are inconvenient to add in industrial applications. Therefore, widespread replacement of antimony catalysts has not yet been achieved. use. There is an urgent need for a solid titanium-based catalyst with high forward reaction activity, low side reactions, and stable performance to solve the above technical problems.
  • the present invention proposes a solid bimetallic titanium-based polyester catalyst and a preparation method thereof. ,application.
  • the present invention prepares a highly active solid bimetallic titanium-based polyester catalyst by strictly controlling the types and proportions of organic acids, alcohols and metal compounds coordinated and complexed with titanium compounds. This catalyst can be used in polyester synthesis Effectively suppress side reactions and obtain high-quality polymer products.
  • the present invention provides a solid bimetallic titanium polyester catalyst with a structural formula as shown in formula (II):
  • R 2 and R 3 are respectively selected from an organic structure selected from carboxylic acid compounds and alcohol compounds.
  • M is a metal atom; the metal atom is at least one of magnesium, zinc, aluminum, iron, potassium, silver, and calcium.
  • X is the part other than M in the metal salt containing M
  • the metal salt is at least one of acetate, nitrate, and metal alkoxide.
  • R 2 is selected from the following compounds
  • x is 1 to 5
  • y is 1 to 10
  • n is an integer from 1 to 8;
  • R 3 is a linear alkane with no more than 6 carbon atoms
  • M is selected from one of magnesium, zinc, aluminum, silver and calcium;
  • X is one of acetate, ethoxy, and nitrate.
  • the solid bimetallic titanium-based polyester catalyst is selected from compounds of the following structural formula:
  • the invention provides a preparation method for the above-mentioned solid bimetallic titanium-based polyester catalyst, which includes the following steps:
  • R 1 , R 2 and R 3 are each selected from one of alkyl titanate, carboxylic acid compound and alcohol compound.
  • the titanium compound is an alkyl titanate having no more than 30 carbon atoms.
  • the carboxylic acid compound is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid with no more than three rings.
  • the carboxylic acid derivative is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or no more than three rings. Acid anhydrides formed from four to eight membered cyclic organic acids.
  • the present invention limits the number of carbon atoms or rings to the above preferred range is that we have found that coordination between carboxylic acid and titanate can effectively inhibit the reactivity of the titanium compound.
  • the carboxylic acid compound has too many carbon atoms or ring Too much number can easily lead to too low activity of titanium atoms, resulting in poor catalytic polymerization efficiency.
  • the above-mentioned compounds with carbon or ring numbers have similar structural formulas to polyester raw materials and have high homology. They can not only increase the compatibility and dispersion of the catalyst in the reaction system, but also reduce the concentration of heterogeneous impurities in the product. content, will not excessively affect the performance of the product polyester.
  • the alcohol compound is an aliphatic diol containing at least two hydroxyl groups.
  • the anhydrous alcohol compound is a monohydroxy alcohol or a dihydroxy alcohol with 1 to 10 carbon atoms.
  • step (1) the molar ratio of the titanium compound to the carboxylic acid compound and/or carboxylic acid derivative is 1:1 to 10:1; the molar ratio of the titanium compound to the alcohol compound is 0.5:1 ⁇ 4:1.
  • the reaction conditions are a reaction temperature of 50-120°C and a reaction time of 0.2-2 hours.
  • step (2) the molar ratio of the titanium compound to the anhydrous alcohol compound is 1:1 to 1:10; the molar ratio of the titanium compound to the metal salt is 0.5:1 to 4:1.
  • the reaction conditions are a reaction temperature of 40-150°C and a reaction time of 0.5-4 hours.
  • the present invention provides the application of the above-mentioned solid bimetallic titanium polyester catalyst in polyester synthesis: using diol and dibasic acid as raw materials to perform a polyester synthesis reaction under the action of a solid bimetallic titanium polyester catalyst.
  • the solid bimetallic titanium polyester catalyst is added as a solid or evenly dispersed in the reaction monomer solution before esterification, and the titanium element concentration is calculated based on the mass of the polyester product to be 1 to 30 ppm.
  • the diol includes one or more of aliphatic diols with a linear carbon number of less than 10 and four to eight-membered cyclic diols with no more than three rings; the dibasic acid Including one or more of aliphatic dicarboxylic acids with less than 10 carbon atoms and four to eight-membered cyclic dicarboxylic acids with no more than three rings; the molar ratio of diol to dibasic acid is 1.1: 1 ⁇ 1.8:1.
  • polyester synthesis specifically includes the following steps:
  • reaction conditions are reaction temperature of 180-270°C, reaction time of 0.2-3 hours, pressure of 300-100kPa, and discharge of by-products.
  • the reaction temperature of the prepolymerization stage is higher than that of the esterification stage.
  • reaction conditions are reaction temperature 200 ⁇ 300°C, reaction time 0.5 ⁇ 6 hours, pressure It is 5 ⁇ 500Pa, and the by-products are discharged.
  • the reaction temperature in the final polymerization stage is higher than that in the prepolymerization stage, and the pressure is lower than that in the prepolymerization stage.
  • the present invention has the following technical effects:
  • solid bimetallic titanium-based polyester catalysts are prepared by selecting organic acids, alcohols and metal compounds to coordinate and complex with titanium compounds, and strictly controlling the types, proportions and reaction processes of the coordination compounds. Compared with the currently common single metal liquid titanium system, it has good thermal stability and is not easy to hydrolyze and deteriorate. It can be added as a solid or dissolved and dispersed before being added to the reaction system, which is convenient for use, storage and transportation.
  • the catalyst of the present invention is used in polyester synthesis.
  • the positive reaction activity of chain growth is significantly higher than that of currently used antimony catalysts.
  • the catalyst uses common non-toxic metals and is green and environmentally friendly. However, side reactions during the synthesis process It can be effectively suppressed and high-quality polymer products with lower color value and less impurity content than ordinary titanium catalysts can be obtained.
  • R 2 and R 3 are each selected from carboxylic acid compounds and alcohol compounds.
  • M is a metal atom; the metal atom is at least one of magnesium, zinc, aluminum, iron, potassium, silver, and calcium.
  • X is the part other than M in the metal salt containing M; the metal salt is at least one of acetate, nitrate, and metal alkoxide.
  • R 2 is selected from the following compounds
  • x is 1 to 5
  • y is 1 to 10
  • n is an integer from 1 to 8;
  • R 3 is a linear alkane with no more than 6 carbon atoms
  • M is selected from one of magnesium, zinc, aluminum, silver and calcium;
  • X is one of acetate, ethoxy, and nitrate.
  • the solid bimetallic titanium-based polyester catalyst is selected from compounds of the following structural formula:
  • the preparation of solid bimetallic titanium series polyester catalyst includes the following steps:
  • R 1 , R 2 and R 3 are each selected from one of alkyl titanate, carboxylic acid compound and alcohol compound.
  • the titanium compound is an alkyl titanate having no more than 30 carbon atoms.
  • the carboxylic acid compound is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid with no more than three rings.
  • the carboxylic acid derivative is an anhydride formed from an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid that does not exceed three rings.
  • the alcohol compound is an aliphatic diol containing at least two hydroxyl groups.
  • the molar ratio of the titanium compound to the carboxylic acid compound and/or carboxylic acid derivative is 1:1 to 10:1; the molar ratio of the titanium compound to the alcohol compound is 0.5:1 to 4:1.
  • the anhydrous alcohol compound is a monohydroxy alcohol or a dihydroxy alcohol with 1 to 10 carbon atoms.
  • the molar ratio of the titanium compound to the anhydrous alcohol compound is 1:1 to 1:10; the molar ratio of the titanium compound to the metal salt is 0.5:1 to 4:1.
  • Polyester synthesis reaction is carried out using glycol and dibasic acid as raw materials under the action of solid bimetallic titanium polyester catalyst.
  • the solid bimetallic titanium polyester catalyst is solid or evenly dispersed in Add it to the reaction monomer solution, and calculate the titanium element concentration to be 1 to 30 ppm based on the mass of the polyester product. Specifically, it includes the following steps:
  • the reaction conditions are reaction temperature 140-250°C, reaction time 1-6 hours, pressure 0.1-0.8MPa, and by-products are discharged.
  • the diol includes one or more of aliphatic diols with a linear carbon number of less than 10 and four to eight-membered cyclic diols with no more than three rings;
  • the dibasic acid includes a carbon number of One or more of aliphatic dicarboxylic acids less than 10 and four to eight-membered cyclic dicarboxylic acids not exceeding three rings; the molar ratio of diol to dibasic acid is 1.1:1 ⁇ 1.8 :1.
  • reaction conditions are reaction temperature of 180-270°C, reaction time of 0.2-3 hours, pressure of 300-100kPa, and discharge of by-products.
  • the reaction temperature of the prepolymerization stage is higher than that of the esterification stage.
  • Preparation of the catalyst Put 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol and maintain 80°C for 30 minutes. The reaction product was suction-filtered using a filtration device, and the filtrate was vacuum-dried at 60°C for 12 hours to obtain an intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 71g magnesium acetate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours to obtain Solid titanium magnesium catalyst.
  • PET Polyethylene terephthalate
  • the temperature in the kettle is set to 210°C, the reaction time is 2 hours, and the pressure in the kettle is kept at about 0.4MPa; in the prepolymerization stage, the reaction temperature in the kettle is 235°C, and the reaction time is 20 minutes; in the polycondensation stage, the reaction temperature is 273°C, The reaction time is 4 hours and the pressure is 100Pa.
  • the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
  • Preparation of the catalyst Put 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol, maintain 80°C for 30 minutes, and use a filter device. The reaction product was subjected to suction filtration, and the filtrate was vacuum dried at 60°C for 12 hours to obtain an intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 71g magnesium acetate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours to obtain Solid titanium magnesium catalyst.
  • Polyethylene terephthalate-isosorbide copolyester (PEIT) synthesis use a catalyst with a titanium content of 5 ppm, 342g terephthalic acid, 145 ethylene glycol, 38g isosorbide and catalyst as raw materials and beat them in sequence , esterification, precondensation and polycondensation reaction steps.
  • PEIT Polyethylene terephthalate-isosorbide copolyester
  • the temperature in the kettle reaches 202°C, and the reaction time is 1.2 hours, and the pressure in the kettle is kept between 0.4MPa; in the prepolymerization stage, the reaction temperature in the kettle is 220°C, and the reaction time is 30 minutes; in the polycondensation stage, the reaction temperature is 275°C, and the reaction time The reaction time is 4.2 hours and the pressure is 100Pa.
  • the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
  • Preparation of the catalyst Put 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol, maintain 80°C for 30 minutes, and use a filter device. The reaction product was subjected to suction filtration, and the filtrate was vacuum dried at 60°C for 12 hours to obtain an intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 71g magnesium acetate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours. A solid titanium magnesium catalyst is obtained.
  • PBS polybutylene succinate
  • succinic acid, butylene glycol and catalyst as raw materials to perform beating, esterification, and Precondensation and polycondensation reaction steps.
  • esterification stage the temperature in the kettle reaches 170°C, and the reaction time is 1.5 hours.
  • prepolymerization stage the reaction temperature in the kettle is 190°C, and the reaction time is 4.5 hours.
  • the reaction temperature is 220°C, and the reaction time is 40 minutes.
  • the polycondensation stage and the prepolymerization stage Compared with the reaction temperature, the reaction temperature is high and the pressure is low; by-products need to be continuously discharged during the reaction process.
  • Preparation of the catalyst Put 170g tetrabutyl titanate and 98g gluconic acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 38g propylene glycol, maintain 80°C for 30 minutes, and use a filter device to filter the reaction. The product was subjected to suction filtration, and the filtrate was vacuum dried at 60°C for 12 hours to obtain the intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 95g zinc nitrate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours to obtain Solid titanium zinc catalyst.
  • Polyethylene terephthalate-isosorbide copolyester (PEIT) synthesis use a catalyst with a titanium content of 5 ppm, 342g terephthalic acid, 145 ethylene glycol, 38g isosorbide and catalyst as raw materials and beat them in sequence , esterification, precondensation and polycondensation reaction steps.
  • PEIT Polyethylene terephthalate-isosorbide copolyester
  • the temperature in the kettle reaches 205°C, the reaction time is 1.5 hours, and the pressure in the kettle is kept at 0.42MPa; in the prepolymerization stage, the reaction temperature in the kettle is 220°C, and the reaction time is 40min; in the polycondensation stage, the reaction temperature is 272°C, and the reaction time is 4.6 hour, the pressure is 100Pa.
  • the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
  • Example 2 The same preparation method as in Example 1 was adopted, except that the carboxylic acids used were 69 g of salicylic acid, 98 g of gluconic acid and 29 g of maleic acid.
  • Example 2 The same preparation method as in Example 1 was adopted, except that the metal salts used were 92 g of iron acetate, 49 g of potassium acetate, 82 g of calcium nitrate, 81 g of aluminum ethoxide, and 85 g of silver nitrate.
  • Example 2 The same preparation method as in Example 1 was used, except that 38 g of 1,3-propanediol and 1,4-butanediol were used as diols. Alcohol 45g.
  • Polyethylene terephthalate was synthesized using the steps of Example 1, the catalyst was antimony ethylene glycol, and the antimony element content was 200 ppm (based on the theoretical yield of polyester).
  • Polyethylene terephthalate was synthesized using the steps of Example 1, the catalyst was tetrabutyl titanate, and the titanium element content was 5 ppm (based on the theoretical yield of polyester).
  • Polyethylene terephthalate was synthesized using the steps of Example 1, the catalyst was titanium ethylene glycol, and the element content was 5 ppm (based on the theoretical yield of polyester).
  • Comparative Example 4 (compared with Example 1, the difference is that there is no M-X in the catalyst structural formula, which is a solid single metal titanium catalyst)
  • Preparation of the catalyst Add 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol, maintain 80°C for 30 minutes, and filter. The device performs suction filtration of the reaction product, and the filtrate is vacuum dried at 60°C for 12 hours to obtain a titanium-based single metal catalyst.
  • PET Polyethylene terephthalate
  • the temperature in the kettle is set to 210°C, the reaction time is 2 hours, and the pressure in the kettle is kept at about 0.4MPa; in the prepolymerization stage, the reaction temperature in the kettle is 235°C, and the reaction time is 20 minutes; in the polycondensation stage, the reaction temperature is 273°C, The reaction time is 4 hours and the pressure is 100Pa.
  • the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
  • Example 2 The same preparation method as in Example 1 was adopted, except that 41 g of sodium acetate was used as the metal salt.
  • Example 2 The same preparation method as in Example 1 was adopted, except that 165 g of lead acetate was used as the metal salt.
  • Comparative Example 7 (compared with Example 1, the difference is that the X salt in the catalyst is carbonate)
  • Example 2 The same preparation method as in Example 1 was adopted, except that 42 g of magnesium carbonate was used as the metal salt.
  • Comparative Example 8 (compared with Example 1, the difference is that the X salt in the catalyst is sulfate)
  • Example 2 The same preparation method as in Example 1 was adopted, except that 60 g of magnesium sulfate was used as the metal salt.
  • the polyester product prepared by the bimetallic titanium series catalyst is different from the antimony series catalyst.
  • the intrinsic viscosity of the polymer was increased while reducing the amount of catalyst.
  • the b value was equivalent to the content of diethylene glycol, while the terminal carboxyl group content was greatly reduced, which improved the quality of the polyester product;
  • Ratio the polyester color value dropped significantly, and the diethylene glycol and terminal carboxyl group contents were also lower, indicating that the bimetallic titanium catalyst effectively inhibited the activity of side reactions and could solve the problem of yellowing of polyester products synthesized by current titanium catalysts.
  • the copolyester prepared using a small amount of bimetallic titanium catalyst has similar intrinsic viscosity and color value indicators, but the product diethylene glycol and terminal carboxyl group content are lower, indicating that the use of titanium bimetallic catalysts has fewer side reactions and better product performance.
  • Example 5 and Comparative Example 4 show that the polyester products prepared by the bimetallic titanium catalyst Compared with the titanium-based catalyst without adding the second metal, when using the same catalyst dosage, the intrinsic viscosity of the polymer increased, and the b value, diethylene glycol content and terminal carboxyl group content all decreased, which improved the quality of the polyester product.
  • polyester product test results of Examples 8, 9, 10, 11, 12 and Comparative Examples 5, 6, 7 and 8 show that compared to sodium salt and lead Salt, the intrinsic viscosity of polyesters prepared by several bimetallic catalysts is similar to that of diethylene glycol, but the color value and terminal carboxyl group content are lower.
  • Example 13 and Example 14 Compared with Comparative Example 1, the intrinsic viscosity of Example 13 and Example 14 is significantly increased, and the content of diethylene glycol and terminal carboxyl groups is significantly decreased.
  • raw materials and equipment used in the present invention are all commonly used raw materials and equipment in this field; the methods used in the present invention, unless otherwise specified, are all conventional methods in this field.

Abstract

A solid bimetallic titanium-based polyester catalyst, a preparation method therefor, and use thereof. The preparation method for the catalyst comprises: (1) adding a titanium compound to an aqueous solution of a carboxylic acid compound and/or a carboxylic acid derivative, heating, then slowly adding an alcohol compound, and carrying out a reaction to obtain an intermediate product, namely a complex formed by coordination of titanium, alcohol hydroxyl, and carboxylic acid hydroxyl; and (2) adding the intermediate product to an anhydrous alcohol compound, adding a metal salt, and carrying out a reaction to obtain a finished product. The solid bimetallic titanium-based polyester catalyst with high activity is prepared by means of strictly regulating and controlling the types and proportions of the organic acids, alcohols, and metal compounds that coordinate with the titanium compound. When applied to polyester synthesis, the catalyst can effectively inhibit side reactions to obtain a high-quality polymerized product.

Description

一种固态双金属钛系聚酯催化剂及其制备方法、应用A solid bimetallic titanium-based polyester catalyst and its preparation method and application 技术领域Technical field
本发明涉及聚酯合成领域，尤其涉及一种固态双金属钛系聚酯催化剂及其制备方法、应用。The invention relates to the field of polyester synthesis, and in particular to a solid bimetallic titanium polyester catalyst and its preparation method and application.
背景技术Background technique
目前全球包含聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丙二醇酯(PTT)、聚对苯二甲酸丁二醇酯(PBT)、聚丁二酸丁二醇酯(PBS)及其共聚和改性物等品种在内的聚酯产品年产量已超过1亿吨。催化剂是聚酯合成中的一种重要基础材料，每年消耗数十万吨。广受关注的是锑系、锗系、钛系三类催化剂。其中，锑系催化剂具有反应稳定可控、副反应少、产品品质好且价格便宜等优势而成为聚酯合成催化剂市场的主流产品，但锑属于重金属元素，在聚酯织物后整理过程中及聚酯产物使用后会造成环境污染，影响健康。锗系聚酯催化剂对生物体无毒害作用、对聚酯缩聚催化活性高的同时对聚酯热降解催化活性较低，用量仅为锑系催化剂的1/10左右，且产品色泽良好、品相优异，极其适合生产对产品透明度要求较高的产品。但是分子链中聚醚含量较多，导致熔点更低，且结晶性能变差，加工成型窗口变宽，且锗系聚酯催化剂价格昂贵，并未在全球广泛应用。Currently, the world includes polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polybutylene succinate (PBS) ) and its copolymers and modified products, the annual output of polyester products has exceeded 100 million tons. Catalyst is an important basic material in polyester synthesis, with hundreds of thousands of tons consumed every year. The three types of catalysts that have attracted widespread attention are antimony, germanium and titanium catalysts. Among them, antimony-based catalysts have the advantages of stable and controllable reactions, few side reactions, good product quality, and low prices, and have become the mainstream products in the polyester synthesis catalyst market. However, antimony is a heavy metal element and is used in the finishing process of polyester fabrics and polyester fabrics. The use of ester products will cause environmental pollution and affect health. Germanium-based polyester catalysts are non-toxic to organisms, have high catalytic activity for polyester polycondensation and low catalytic activity for polyester thermal degradation. The dosage is only about 1/10 of that of antimony-based catalysts, and the product has good color and appearance. Excellent, extremely suitable for producing products that require high transparency. However, the polyether content in the molecular chain is high, resulting in a lower melting point, poorer crystallization properties, and a wider processing and molding window. Moreover, germanium-based polyester catalysts are expensive and have not been widely used around the world.
钛系催化剂对聚酯的催化活性为锑的40倍左右，与锗一样对人体无害，与锗相比存在显著的价格优势。但钛系催化剂对聚酯的降解反应催化活性同样较强，使得副反应严重，更容易产生杂质端羧基和乙醛自由基，制备出的聚酯往往色泽泛黄，影响产品质量。常见的钛有机酯类催化剂，如钛酸四丁酯、钛酸异丙酯等均易水解而失去活性，储存中容易变质，工业应用中添加不便，因而目前还未实现对锑系催化剂广泛替代使用。迫切需要一种具有高正向反应活性、低副反应、性能稳定的固态钛系催化剂以解决上述技术问题。The catalytic activity of titanium-based catalysts for polyester is about 40 times that of antimony. It is as harmless to the human body as germanium and has a significant price advantage compared with germanium. However, titanium-based catalysts also have strong catalytic activity for the degradation reaction of polyester, which causes serious side reactions and is more likely to produce impurity terminal carboxyl groups and acetaldehyde free radicals. The prepared polyester often turns yellow in color, affecting product quality. Common titanium organic ester catalysts, such as tetrabutyl titanate and isopropyl titanate, are easily hydrolyzed and lose activity, easily deteriorate during storage, and are inconvenient to add in industrial applications. Therefore, widespread replacement of antimony catalysts has not yet been achieved. use. There is an urgent need for a solid titanium-based catalyst with high forward reaction activity, low side reactions, and stable performance to solve the above technical problems.
发明内容Contents of the invention
本发明针对现有钛系聚酯催化剂稳定性不高、易水解，应用于聚酯合成时副反应速率高、产品品质低的难题，提出一种固态双金属钛系聚酯催化剂及其制备方法、应用。本发明通过严格调控与钛化合物配位络合的有机酸、醇和金属化合物的种类及其比例来制备具有高活性的固态双金属钛系聚酯催化剂。该催化剂应用于聚酯合成中可 有效抑制副反应而获得高品质聚合产品。In view of the problems that existing titanium-based polyester catalysts have low stability, are easy to hydrolyze, and are used in polyester synthesis with high side reaction rates and low product quality, the present invention proposes a solid bimetallic titanium-based polyester catalyst and a preparation method thereof. ,application. The present invention prepares a highly active solid bimetallic titanium-based polyester catalyst by strictly controlling the types and proportions of organic acids, alcohols and metal compounds coordinated and complexed with titanium compounds. This catalyst can be used in polyester synthesis Effectively suppress side reactions and obtain high-quality polymer products.
本发明的具体技术方案为：The specific technical solutions of the present invention are:
第一方面，本发明提供了一种固态双金属钛系聚酯催化剂，结构式如式(II)所示：
In a first aspect, the present invention provides a solid bimetallic titanium polyester catalyst with a structural formula as shown in formula (II):
式(II)中，R2，R3分别选自羧酸化合物、醇化合物中的一种有机物结构。In formula (II), R 2 and R 3 are respectively selected from an organic structure selected from carboxylic acid compounds and alcohol compounds.
M为金属原子；所述金属原子为镁、锌、铝、铁、钾、银、钙中的至少一种。M is a metal atom; the metal atom is at least one of magnesium, zinc, aluminum, iron, potassium, silver, and calcium.
X为含M的金属盐中M之外的部分；X is the part other than M in the metal salt containing M;
所述金属盐为醋酸盐、硝酸盐、金属醇盐中的至少一种。The metal salt is at least one of acetate, nitrate, and metal alkoxide.
本发明人通过研究发现，上述三种特定的金属盐类型可有效提高催化剂制备过程中配位组分的溶解能力、均相反应能力，且有利于洗去副产物，提高催化剂纯度。The inventor found through research that the above three specific metal salt types can effectively improve the solubility and homogeneous reaction ability of the coordination components during the catalyst preparation process, and are conducive to washing away by-products and improving the purity of the catalyst.
作为优选，R2选自以下化合物；
Preferably, R 2 is selected from the following compounds;
中，x为1～5、y为1～10、n为1～8中的整数； , x is 1 to 5, y is 1 to 10, n is an integer from 1 to 8;
R3为碳原子数不超过6个碳的直链烷烃；R 3 is a linear alkane with no more than 6 carbon atoms;
M选自镁、锌、铝、银、钙中的一种；M is selected from one of magnesium, zinc, aluminum, silver and calcium;
X为醋酸根、乙氧基、硝酸根中的一种。X is one of acetate, ethoxy, and nitrate.
进一步优选，所述固态双金属钛系聚酯催化剂选自以下结构式的化合物：
Further preferably, the solid bimetallic titanium-based polyester catalyst is selected from compounds of the following structural formula:
第二方面，本发明提供了一种上述固态双金属钛系聚酯催化剂的制备方法，包括以下步骤：In a second aspect, the invention provides a preparation method for the above-mentioned solid bimetallic titanium-based polyester catalyst, which includes the following steps:
(1)将钛化合物加入至羧酸化合物和/或羧酸衍生物的水溶液中，加热后缓慢加入醇化合物，进行反应、抽滤、干燥后获得中间产物，即钛与醇羟基及羧酸羟基配位形成的络合物，结构式如式(I)所示：
(1) Add the titanium compound to the aqueous solution of the carboxylic acid compound and/or carboxylic acid derivative, slowly add the alcohol compound after heating, react, filter, and dry to obtain an intermediate product, that is, titanium and alcohol hydroxyl groups and carboxylic acid hydroxyl groups. The structural formula of the complex formed by coordination is as shown in formula (I):
式(I)中，R1，R2和R3分别选自钛酸烷基酯、羧酸化合物、醇化合物中的一种。In formula (I), R 1 , R 2 and R 3 are each selected from one of alkyl titanate, carboxylic acid compound and alcohol compound.
所述钛化合物为碳原子数不超过30的钛酸烷基酯。The titanium compound is an alkyl titanate having no more than 30 carbon atoms.
所述羧酸化合物为羧酸碳之外直链碳数为1～10的脂肪族有机酸或不超过三环的四到八元环状有机酸。The carboxylic acid compound is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid with no more than three rings.
所述羧酸衍生物为羧酸碳之外直链碳数为1～10的脂肪族有机酸或不超过三环的 四到八元环状有机酸形成的酸酐物。The carboxylic acid derivative is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or no more than three rings. Acid anhydrides formed from four to eight membered cyclic organic acids.
本发明将碳数或环数限定在上述优选范围的原因在于，我们发现：利用羧酸与钛酸酯进行配位可有效抑制钛化合物的反应活性，但是若羧酸化合物碳原子过多或环数过多容易导致钛原子活性过低，导致催化聚合反应效率差。另一方面，上述碳数或环数的化合物与聚酯原料的结构式相似，同源性高，不仅可增加催化剂在反应体系中的相容性和分散性，而且可同时降低产物中异性杂质的含量，不会过度影响产物聚酯的性能。The reason why the present invention limits the number of carbon atoms or rings to the above preferred range is that we have found that coordination between carboxylic acid and titanate can effectively inhibit the reactivity of the titanium compound. However, if the carboxylic acid compound has too many carbon atoms or ring Too much number can easily lead to too low activity of titanium atoms, resulting in poor catalytic polymerization efficiency. On the other hand, the above-mentioned compounds with carbon or ring numbers have similar structural formulas to polyester raw materials and have high homology. They can not only increase the compatibility and dispersion of the catalyst in the reaction system, but also reduce the concentration of heterogeneous impurities in the product. content, will not excessively affect the performance of the product polyester.
所述醇化合物为至少含有两个羟基的脂肪族二醇。The alcohol compound is an aliphatic diol containing at least two hydroxyl groups.
(2)将所述中间产物加入至无水醇化合物中，并加入金属盐，再经加热反应、蒸发、洗涤、干燥后，获得固态双金属钛系聚酯催化剂。(2) Add the intermediate product to an anhydrous alcohol compound, add a metal salt, and then undergo heating reaction, evaporation, washing, and drying to obtain a solid bimetallic titanium-based polyester catalyst.
所述无水醇化合物为1～10个碳原子的单羟基醇或双羟基醇。The anhydrous alcohol compound is a monohydroxy alcohol or a dihydroxy alcohol with 1 to 10 carbon atoms.
作为优选，步骤(1)中：所述钛化合物与羧酸化合物和/或羧酸衍生物的摩尔比为1:1～10:1；所述钛化合物与醇化合物的摩尔比为0.5:1～4:1。Preferably, in step (1): the molar ratio of the titanium compound to the carboxylic acid compound and/or carboxylic acid derivative is 1:1 to 10:1; the molar ratio of the titanium compound to the alcohol compound is 0.5:1 ~4:1.
作为优选，步骤(1)中：反应条件为反应温度50～120℃，反应时间为0.2～2小时。Preferably, in step (1): the reaction conditions are a reaction temperature of 50-120°C and a reaction time of 0.2-2 hours.
作为优选，步骤(2)中：所述钛化合物与无水醇化合物的摩尔比为1:1～1:10；所述钛化合物与金属盐的摩尔比为0.5:1～4:1。Preferably, in step (2): the molar ratio of the titanium compound to the anhydrous alcohol compound is 1:1 to 1:10; the molar ratio of the titanium compound to the metal salt is 0.5:1 to 4:1.
作为优选，步骤(2)中：反应条件为反应温度40～150℃，反应时间为0.5～4小时。Preferably, in step (2): the reaction conditions are a reaction temperature of 40-150°C and a reaction time of 0.5-4 hours.
第三方面，本发明提供了上述固态双金属钛系聚酯催化剂在聚酯合成中的应用：以二元醇和二元酸为原料在固态双金属钛系聚酯催化剂作用下进行聚酯合成反应，所述固态双金属钛系聚酯催化剂在酯化前以固体或均匀分散于反应单体溶液中加入，基于聚酯产物质量计算钛元素浓度为1～30ppm。In a third aspect, the present invention provides the application of the above-mentioned solid bimetallic titanium polyester catalyst in polyester synthesis: using diol and dibasic acid as raw materials to perform a polyester synthesis reaction under the action of a solid bimetallic titanium polyester catalyst. , the solid bimetallic titanium polyester catalyst is added as a solid or evenly dispersed in the reaction monomer solution before esterification, and the titanium element concentration is calculated based on the mass of the polyester product to be 1 to 30 ppm.
作为优选，所述二元醇包括直链碳数低于10的脂肪族二元醇、不超过三环的四到八元环状二元醇中的一种或几种；所述二元酸包括碳数低于10的脂肪族二元羧酸、不超过三环的四到八元环状二元羧酸中的一种或几种；二元醇与二元酸的摩尔比为1.1:1～1.8:1。Preferably, the diol includes one or more of aliphatic diols with a linear carbon number of less than 10 and four to eight-membered cyclic diols with no more than three rings; the dibasic acid Including one or more of aliphatic dicarboxylic acids with less than 10 carbon atoms and four to eight-membered cyclic dicarboxylic acids with no more than three rings; the molar ratio of diol to dibasic acid is 1.1: 1～1.8:1.
作为优选，聚酯合成具体包含如下步骤：Preferably, polyester synthesis specifically includes the following steps:
(a)酯化阶段：反应条件为反应温度140～250℃，反应时间为1～6小时，压力为0.1～0.8MPa，排出副产物。(a) Esterification stage: The reaction conditions are reaction temperature 140-250°C, reaction time 1-6 hours, pressure 0.1-0.8MPa, and by-products are discharged.
(b)预聚阶段：反应条件为反应温度180～270℃，反应时间为0.2～3小时，压力为300～100kPa，排出副产物，预聚阶段反应温度高于酯化阶段。(b) Prepolymerization stage: The reaction conditions are reaction temperature of 180-270°C, reaction time of 0.2-3 hours, pressure of 300-100kPa, and discharge of by-products. The reaction temperature of the prepolymerization stage is higher than that of the esterification stage.
(c)终聚阶段：反应条件为反应温度200～300℃，反应时间为0.5～6小时，压力 为5～500Pa，排出副产物，终聚阶段反应温度高于预聚阶段，压力低于预聚阶段。(c) Final polymerization stage: reaction conditions are reaction temperature 200~300℃, reaction time 0.5~6 hours, pressure It is 5~500Pa, and the by-products are discharged. The reaction temperature in the final polymerization stage is higher than that in the prepolymerization stage, and the pressure is lower than that in the prepolymerization stage.
与现有技术相比，本发明具有以下技术效果：Compared with the existing technology, the present invention has the following technical effects:
(1)本发明中通过选用有机酸、醇和金属化合物与钛化合物配位络合，并严格调控配位化合物的种类、比例及反应过程来制备固态双金属钛系聚酯催化剂。与目前常见的单金属液态钛系相比热稳定性好、不易水解与变质，可进行固体添加也可溶解分散后添加入反应体系中，有利于使用、储存与运输。(1) In the present invention, solid bimetallic titanium-based polyester catalysts are prepared by selecting organic acids, alcohols and metal compounds to coordinate and complex with titanium compounds, and strictly controlling the types, proportions and reaction processes of the coordination compounds. Compared with the currently common single metal liquid titanium system, it has good thermal stability and is not easy to hydrolyze and deteriorate. It can be added as a solid or dissolved and dispersed before being added to the reaction system, which is convenient for use, storage and transportation.
(2)本发明催化剂应用于聚酯合成中，链增长的正反应活性显著高于现行使用的锑系催化剂，且该催化剂使用常见无毒金属，具有绿色环保特点，而合成过程中的副反应可得到有效抑制，可获得比普通钛系催化剂色值更低、杂质含量更少的高品质聚合产品。(2) The catalyst of the present invention is used in polyester synthesis. The positive reaction activity of chain growth is significantly higher than that of currently used antimony catalysts. Moreover, the catalyst uses common non-toxic metals and is green and environmentally friendly. However, side reactions during the synthesis process It can be effectively suppressed and high-quality polymer products with lower color value and less impurity content than ordinary titanium catalysts can be obtained.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步的描述。The present invention will be further described below in conjunction with examples.
总实施例General embodiment
一种固态双金属钛系聚酯催化剂，结构式如式(II)所示：
A solid bimetallic titanium polyester catalyst with a structural formula as shown in formula (II):
式(II)中，R2，R3分别选自羧酸化合物、醇化合物中的一种。In formula (II), R 2 and R 3 are each selected from carboxylic acid compounds and alcohol compounds.
M为金属原子；所述金属原子为镁、锌、铝、铁、、钾、银、钙中的至少一种。M is a metal atom; the metal atom is at least one of magnesium, zinc, aluminum, iron, potassium, silver, and calcium.
X为含M的金属盐中M之外的部分；所述金属盐为醋酸盐、硝酸盐、金属醇盐中的至少一种。X is the part other than M in the metal salt containing M; the metal salt is at least one of acetate, nitrate, and metal alkoxide.
作为优选，R2选自以下化合物中；

Preferably, R 2 is selected from the following compounds;

中，x为1～5，、y为1～10，、n为1～8中的整数；, x is 1 to 5, y is 1 to 10, n is an integer from 1 to 8;
R3为碳原子数不超过6个碳的直链烷烃；R 3 is a linear alkane with no more than 6 carbon atoms;
M选自镁、锌、铝、银、钙中的一种；M is selected from one of magnesium, zinc, aluminum, silver and calcium;
X为醋酸根、乙氧基、硝酸根中的一种。X is one of acetate, ethoxy, and nitrate.
进一步优选，所述固态双金属钛系聚酯催化剂选自以下结构式的化合物：
Further preferably, the solid bimetallic titanium-based polyester catalyst is selected from compounds of the following structural formula:
固态双金属钛系聚酯催化剂的制备，包括以下步骤：The preparation of solid bimetallic titanium series polyester catalyst includes the following steps:
(1)将钛化合物加入至羧酸化合物和/或羧酸衍生物的水溶液中，加热后缓慢加入醇化合物，进行反应(50～120℃，0.2～2小时)、抽滤、干燥后获得中间产物，即钛与醇羟基及羧酸羟基配位形成的络合物，结构式如式(I)所示：
(1) Add the titanium compound to the aqueous solution of the carboxylic acid compound and/or carboxylic acid derivative, slowly add the alcohol compound after heating, react (50-120°C, 0.2-2 hours), filter with suction, and dry to obtain the intermediate The product is a complex formed by titanium coordinated with alcoholic hydroxyl groups and carboxylic acid hydroxyl groups. The structural formula is as shown in formula (I):
式(I)中，R1，R2和R3分别选自钛酸烷基酯、羧酸化合物、醇化合物中的一种。In formula (I), R 1 , R 2 and R 3 are each selected from one of alkyl titanate, carboxylic acid compound and alcohol compound.
所述钛化合物为碳原子数不超过30的钛酸烷基酯。所述羧酸化合物为羧酸碳之外直链碳数为1～10的脂肪族有机酸或不超过三环的四到八元环状有机酸。所述羧酸衍生物为羧酸碳之外直链碳数为1～10的脂肪族有机酸或不超过三环的四到八元环状有机酸形成的酸酐物。所述醇化合物为至少含有两个羟基的脂肪族二醇。The titanium compound is an alkyl titanate having no more than 30 carbon atoms. The carboxylic acid compound is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid with no more than three rings. The carboxylic acid derivative is an anhydride formed from an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid that does not exceed three rings. The alcohol compound is an aliphatic diol containing at least two hydroxyl groups.
所述钛化合物与羧酸化合物和/或羧酸衍生物的摩尔比为1:1～10:1；所述钛化合物与醇化合物的摩尔比为0.5:1～4:1。The molar ratio of the titanium compound to the carboxylic acid compound and/or carboxylic acid derivative is 1:1 to 10:1; the molar ratio of the titanium compound to the alcohol compound is 0.5:1 to 4:1.
(2)将所述中间产物加入至无水醇化合物中，并加入金属盐，再经加热反应(40～150℃，0.5～4小时)、蒸发、洗涤、干燥后，获得固态双金属钛系聚酯催化剂。(2) Add the intermediate product to an anhydrous alcohol compound, add a metal salt, and then undergo a heating reaction (40-150°C, 0.5-4 hours), evaporation, washing, and drying to obtain a solid bimetallic titanium system Polyester catalyst.
所述无水醇化合物为1～10个碳原子的单羟基醇或双羟基醇。所述钛化合物与无水醇化合物的摩尔比为1:1～1:10；所述钛化合物与金属盐的摩尔比为0.5:1～4:1。The anhydrous alcohol compound is a monohydroxy alcohol or a dihydroxy alcohol with 1 to 10 carbon atoms. The molar ratio of the titanium compound to the anhydrous alcohol compound is 1:1 to 1:10; the molar ratio of the titanium compound to the metal salt is 0.5:1 to 4:1.
聚酯合成：以二元醇和二元酸为原料在固态双金属钛系聚酯催化剂作用下进行聚酯合成反应，所述固态双金属钛系聚酯催化剂在酯化前以固体或均匀分散于反应单体溶液中加入，基于聚酯产物质量计算钛元素浓度为1～30ppm。具体包含如下步骤：Polyester synthesis: Polyester synthesis reaction is carried out using glycol and dibasic acid as raw materials under the action of solid bimetallic titanium polyester catalyst. The solid bimetallic titanium polyester catalyst is solid or evenly dispersed in Add it to the reaction monomer solution, and calculate the titanium element concentration to be 1 to 30 ppm based on the mass of the polyester product. Specifically, it includes the following steps:
(a)酯化阶段：反应条件为反应温度140～250℃，反应时间为1～6小时，压力为0.1～0.8MPa，排出副产物。所述二元醇包括直链碳数低于10的脂肪族二元醇、不超过三环的四到八元环状二元醇中的一种或几种；所述二元酸包括碳数低于10的脂肪族二元羧酸、不超过三环的四到八元环状二元羧酸中的一种或几种；二元醇与二元酸的摩尔比为1.1:1～1.8:1。(a) Esterification stage: The reaction conditions are reaction temperature 140-250°C, reaction time 1-6 hours, pressure 0.1-0.8MPa, and by-products are discharged. The diol includes one or more of aliphatic diols with a linear carbon number of less than 10 and four to eight-membered cyclic diols with no more than three rings; the dibasic acid includes a carbon number of One or more of aliphatic dicarboxylic acids less than 10 and four to eight-membered cyclic dicarboxylic acids not exceeding three rings; the molar ratio of diol to dibasic acid is 1.1:1~1.8 :1.
(b)预聚阶段：反应条件为反应温度180～270℃，反应时间为0.2～3小时，压力为300～100kPa，排出副产物，预聚阶段反应温度高于酯化阶段。(b) Prepolymerization stage: The reaction conditions are reaction temperature of 180-270°C, reaction time of 0.2-3 hours, pressure of 300-100kPa, and discharge of by-products. The reaction temperature of the prepolymerization stage is higher than that of the esterification stage.
(c)终聚阶段：反应条件为反应温度200～300℃，反应时间为0.5～6小时，压力为5～500Pa，排出副产物，终聚阶段反应温度高于预聚阶段，压力低于预聚阶段。(c) Final polymerization stage: The reaction conditions are reaction temperature 200~300℃, reaction time 0.5~6 hours, pressure 5~500Pa, and by-products are discharged. The reaction temperature in the final polymerization stage is higher than the prepolymerization stage, and the pressure is lower than the prepolymerization stage. gathering stage.
实施例1Example 1
催化剂的制备：将170g钛酸四丁酯与48g柠檬酸投入到水溶液中，充分搅拌后将混合物加热至80℃，在搅拌的同时缓慢加入32g乙二醇，保持80℃反应30min， 使用过滤装置将反应产物进行抽滤，抽滤物在60℃下真空干燥12小时，得到中间产物。将中间产物放入烧瓶中，加入足量无水乙醇，添加71g醋酸镁，将溶液加热至沸腾反应2小时，反应产物经旋蒸后用乙醇进行洗涤，最后在60℃下真空干燥12小时得到固态钛镁催化剂。Preparation of the catalyst: Put 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol and maintain 80°C for 30 minutes. The reaction product was suction-filtered using a filtration device, and the filtrate was vacuum-dried at 60°C for 12 hours to obtain an intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 71g magnesium acetate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours to obtain Solid titanium magnesium catalyst.
聚对苯二甲酸乙二醇酯(PET)合成：将钛元素含量为5ppm(以聚酯理论产量计)的催化剂添加至20mL乙二醇中均匀分散，以342g对苯二甲酸、170g乙二醇和催化剂为原料依次进行打浆、酯化、预缩聚和缩聚反应步骤。酯化阶段釜内温度设定为210℃，反应时间为2小时，保持釜内压力在0.4MPa左右；预聚阶段釜内反应温度235℃，反应时间为20分钟；缩聚阶段反应温度273℃，反应时间为4小时，压力为100Pa，缩聚阶段与预聚阶段相比反应温度高、压力低；反应过程中需不断排出副产物。Polyethylene terephthalate (PET) synthesis: Add a catalyst with a titanium content of 5ppm (based on the theoretical yield of polyester) to 20mL of ethylene glycol and disperse it evenly, with 342g of terephthalic acid, 170g of ethylene glycol Alcohol and catalyst are used as raw materials to carry out beating, esterification, precondensation and polycondensation reaction steps in sequence. In the esterification stage, the temperature in the kettle is set to 210°C, the reaction time is 2 hours, and the pressure in the kettle is kept at about 0.4MPa; in the prepolymerization stage, the reaction temperature in the kettle is 235°C, and the reaction time is 20 minutes; in the polycondensation stage, the reaction temperature is 273°C, The reaction time is 4 hours and the pressure is 100Pa. Compared with the prepolymerization stage, the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
实施例2Example 2
催化剂的制备：将170g钛酸四丁酯与48g柠檬酸投入到水溶液中，充分搅拌后将混合物加热至80℃，在搅拌的同时缓慢加入32g乙二醇，保持80℃反应30min，使用过滤装置将反应产物进行抽滤，抽滤物在60℃下真空干燥12小时，得到中间产物。将中间产物放入烧瓶中，加入足量无水乙醇，添加71g醋酸镁，将溶液加热至沸腾反应2小时，反应产物经旋蒸后用乙醇进行洗涤，最后在60℃下真空干燥12小时得到固态钛镁催化剂。Preparation of the catalyst: Put 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol, maintain 80°C for 30 minutes, and use a filter device. The reaction product was subjected to suction filtration, and the filtrate was vacuum dried at 60°C for 12 hours to obtain an intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 71g magnesium acetate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours to obtain Solid titanium magnesium catalyst.
聚对苯二甲酸乙二醇-异山梨醇共聚酯(PEIT)合成：以钛元素含量为5ppm的催化剂、342g对苯二甲酸、145乙二醇、38g异山梨醇和催化剂为原料依次进行打浆、酯化、预缩聚和缩聚反应步骤。酯化阶段釜内温度至202℃，反应时间为1.2小时，保持釜内压力在0.4MPa之间；预聚阶段釜内反应温度220℃，反应时间为30min；缩聚阶段反应温度275℃，反应时间为4.2小时，压力为100Pa，缩聚阶段与预聚阶段相比反应温度高、压力低；反应过程中需不断排出副产物。Polyethylene terephthalate-isosorbide copolyester (PEIT) synthesis: use a catalyst with a titanium content of 5 ppm, 342g terephthalic acid, 145 ethylene glycol, 38g isosorbide and catalyst as raw materials and beat them in sequence , esterification, precondensation and polycondensation reaction steps. In the esterification stage, the temperature in the kettle reaches 202°C, and the reaction time is 1.2 hours, and the pressure in the kettle is kept between 0.4MPa; in the prepolymerization stage, the reaction temperature in the kettle is 220°C, and the reaction time is 30 minutes; in the polycondensation stage, the reaction temperature is 275°C, and the reaction time The reaction time is 4.2 hours and the pressure is 100Pa. Compared with the prepolymerization stage, the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
实施例3Example 3
催化剂的制备：将170g钛酸四丁酯与48g柠檬酸投入到水溶液中，充分搅拌后将混合物加热至80℃，在搅拌的同时缓慢加入32g乙二醇，保持80℃反应30min，使用过滤装置将反应产物进行抽滤，抽滤物在60℃下真空干燥12小时，得到中间产物。将中间产物放入烧瓶中，加入足量无水乙醇，添加71g醋酸镁，将溶液加热至沸腾反应2小时，反应产物经旋蒸后用乙醇进行洗涤，最后在60℃下真空干燥12小 时得到固态钛镁催化剂。Preparation of the catalyst: Put 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol, maintain 80°C for 30 minutes, and use a filter device. The reaction product was subjected to suction filtration, and the filtrate was vacuum dried at 60°C for 12 hours to obtain an intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 71g magnesium acetate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours. A solid titanium magnesium catalyst is obtained.
聚丁二酸丁二醇酯(PBS)合成：将钛元素含量为5ppm的催化剂添加至一定量丁二醇中均匀分散，以丁二酸、丁二醇和催化剂为原料依次进行打浆、酯化、预缩聚和缩聚反应步骤。酯化阶段釜内温度至170℃，反应时间为1.5小时，预聚阶段釜内反应温度190℃，反应时间为4.5小时；缩聚阶段反应温度220℃，反应时间为40min，缩聚阶段与预聚阶段相比反应温度高、压力低；反应过程中需不断排出副产物。Synthesis of polybutylene succinate (PBS): Add a catalyst with a titanium content of 5ppm to a certain amount of butylene glycol and disperse it evenly. Use succinic acid, butylene glycol and catalyst as raw materials to perform beating, esterification, and Precondensation and polycondensation reaction steps. In the esterification stage, the temperature in the kettle reaches 170°C, and the reaction time is 1.5 hours. In the prepolymerization stage, the reaction temperature in the kettle is 190°C, and the reaction time is 4.5 hours. In the polycondensation stage, the reaction temperature is 220°C, and the reaction time is 40 minutes. The polycondensation stage and the prepolymerization stage Compared with the reaction temperature, the reaction temperature is high and the pressure is low; by-products need to be continuously discharged during the reaction process.
实施例4Example 4
催化剂的制备：将170g钛酸四丁酯与98g葡萄糖酸投入到水溶液中，充分搅拌后将混合物加热至80℃，在搅拌的同时缓慢加入38g丙二醇，保持80℃反应30min，使用过滤装置将反应产物进行抽滤，抽滤物在60℃下真空干燥12小时，得到中间产物。将中间产物放入烧瓶中，加入足量无水乙醇，添加95g硝酸锌，将溶液加热至沸腾反应2小时，反应产物经旋蒸后用乙醇进行洗涤，最后在60℃下真空干燥12小时得到固态钛锌催化剂。Preparation of the catalyst: Put 170g tetrabutyl titanate and 98g gluconic acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 38g propylene glycol, maintain 80°C for 30 minutes, and use a filter device to filter the reaction. The product was subjected to suction filtration, and the filtrate was vacuum dried at 60°C for 12 hours to obtain the intermediate product. Put the intermediate product into a flask, add enough absolute ethanol, add 95g zinc nitrate, heat the solution to boiling and react for 2 hours. The reaction product is washed with ethanol after rotary evaporation, and finally vacuum dried at 60°C for 12 hours to obtain Solid titanium zinc catalyst.
聚对苯二甲酸乙二醇-异山梨醇共聚酯(PEIT)合成：以钛元素含量为5ppm的催化剂、342g对苯二甲酸、145乙二醇、38g异山梨醇和催化剂为原料依次进行打浆、酯化、预缩聚和缩聚反应步骤。酯化阶段釜内温度至205℃，反应时间为1.5小时，保持釜内压力在0.42MPa；预聚阶段釜内反应温度220℃，反应时间为40min；缩聚阶段反应温度272℃，反应时间为4.6小时，压力为100Pa，缩聚阶段与预聚阶段相比反应温度高、压力低；反应过程中需不断排出副产物。Polyethylene terephthalate-isosorbide copolyester (PEIT) synthesis: use a catalyst with a titanium content of 5 ppm, 342g terephthalic acid, 145 ethylene glycol, 38g isosorbide and catalyst as raw materials and beat them in sequence , esterification, precondensation and polycondensation reaction steps. In the esterification stage, the temperature in the kettle reaches 205℃, the reaction time is 1.5 hours, and the pressure in the kettle is kept at 0.42MPa; in the prepolymerization stage, the reaction temperature in the kettle is 220℃, and the reaction time is 40min; in the polycondensation stage, the reaction temperature is 272℃, and the reaction time is 4.6 hour, the pressure is 100Pa. Compared with the prepolymerization stage, the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
实施例5-7Example 5-7
采用与实施例1相同制备方法，区别在于羧酸分别使用水杨酸69g、葡萄糖酸98g和马来酸29g。The same preparation method as in Example 1 was adopted, except that the carboxylic acids used were 69 g of salicylic acid, 98 g of gluconic acid and 29 g of maleic acid.
实施例8-12Examples 8-12
采用与实施例1相同制备方法，区别在于金属盐分别使用醋酸铁92g、醋酸钾49g、硝酸钙82g、乙氧基铝81g和硝酸银85g。The same preparation method as in Example 1 was adopted, except that the metal salts used were 92 g of iron acetate, 49 g of potassium acetate, 82 g of calcium nitrate, 81 g of aluminum ethoxide, and 85 g of silver nitrate.
实施例13-14Example 13-14
采用与实施例1相同制备方法，区别在于二醇分别使用1,3-丙二醇38g和1,4-丁二 醇45g。The same preparation method as in Example 1 was used, except that 38 g of 1,3-propanediol and 1,4-butanediol were used as diols. Alcohol 45g.
对照例1Comparative example 1
采用实施例1的步骤合成聚对苯二甲酸乙二醇酯，催化剂为乙二醇锑，锑元素含量为200ppm(以聚酯理论产量计)。Polyethylene terephthalate was synthesized using the steps of Example 1, the catalyst was antimony ethylene glycol, and the antimony element content was 200 ppm (based on the theoretical yield of polyester).
对照例2Comparative example 2
采用实施例1的步骤合成聚对苯二甲酸乙二醇酯，催化剂为钛酸四丁酯，钛元素含量为5ppm(以聚酯理论产量计)。Polyethylene terephthalate was synthesized using the steps of Example 1, the catalyst was tetrabutyl titanate, and the titanium element content was 5 ppm (based on the theoretical yield of polyester).
对照例3Comparative example 3
采用实施例1的步骤合成聚对苯二甲酸乙二醇酯，催化剂为乙二醇钛，元素含量为5ppm(以聚酯理论产量计)。Polyethylene terephthalate was synthesized using the steps of Example 1, the catalyst was titanium ethylene glycol, and the element content was 5 ppm (based on the theoretical yield of polyester).
对照例4(与实施例1相比区别在于，催化剂结构式中没有M-X，即为固态单金属钛催化剂)Comparative Example 4 (compared with Example 1, the difference is that there is no M-X in the catalyst structural formula, which is a solid single metal titanium catalyst)
催化剂的制备：将170g钛酸四丁酯与48g柠檬酸按投入到水溶液中，充分搅拌后将混合物加热至80℃，在搅拌的同时缓慢加入32g乙二醇，保持80℃反应30min，使用过滤装置将反应产物进行抽滤，抽滤物在60℃下真空干燥12小时，得到钛系单金属催化剂。Preparation of the catalyst: Add 170g tetrabutyl titanate and 48g citric acid into the aqueous solution, stir thoroughly and heat the mixture to 80°C. While stirring, slowly add 32g ethylene glycol, maintain 80°C for 30 minutes, and filter. The device performs suction filtration of the reaction product, and the filtrate is vacuum dried at 60°C for 12 hours to obtain a titanium-based single metal catalyst.
聚对苯二甲酸乙二醇酯(PET)合成：将钛元素含量为5ppm(以聚酯理论产量计)的钛系单金属催化剂添加至20mL乙二醇中均匀分散，以342g对苯二甲酸、170g乙二醇和催化剂为原料依次进行打浆、酯化、预缩聚和缩聚反应步骤。酯化阶段釜内温度设定为210℃，反应时间为2小时，保持釜内压力在0.4MPa左右；预聚阶段釜内反应温度235℃，反应时间为20分钟；缩聚阶段反应温度273℃，反应时间为4小时，压力为100Pa，缩聚阶段与预聚阶段相比反应温度高、压力低；反应过程中需不断排出副产物。Polyethylene terephthalate (PET) synthesis: Add a titanium-based single metal catalyst with a titanium content of 5ppm (based on the theoretical yield of polyester) into 20mL ethylene glycol and disperse it evenly, and add 342g terephthalic acid to , 170g of ethylene glycol and catalyst are used as raw materials to carry out beating, esterification, pre-polycondensation and polycondensation reaction steps in sequence. In the esterification stage, the temperature in the kettle is set to 210°C, the reaction time is 2 hours, and the pressure in the kettle is kept at about 0.4MPa; in the prepolymerization stage, the reaction temperature in the kettle is 235°C, and the reaction time is 20 minutes; in the polycondensation stage, the reaction temperature is 273°C, The reaction time is 4 hours and the pressure is 100Pa. Compared with the prepolymerization stage, the reaction temperature is higher and the pressure is lower in the polycondensation stage; by-products need to be continuously discharged during the reaction process.
对照例5(与实施例1相比区别在于，催化剂中的M金属为钠)Comparative Example 5 (compared with Example 1, the difference is that the M metal in the catalyst is sodium)
采用实施例1相同制备方法，区别在于金属盐使用醋酸钠41g。 The same preparation method as in Example 1 was adopted, except that 41 g of sodium acetate was used as the metal salt.
对照例6(与实施例1相比区别在于，催化剂中的M金属为铅)Comparative Example 6 (compared with Example 1, the difference is that the M metal in the catalyst is lead)
采用实施例1相同制备方法，区别在于金属盐使用醋酸铅165g。The same preparation method as in Example 1 was adopted, except that 165 g of lead acetate was used as the metal salt.
对照例7(与实施例1相比区别在于，催化剂中的X盐为碳酸盐)Comparative Example 7 (compared with Example 1, the difference is that the X salt in the catalyst is carbonate)
采用实施例1相同制备方法，区别在于金属盐使用碳酸镁42g。The same preparation method as in Example 1 was adopted, except that 42 g of magnesium carbonate was used as the metal salt.
对照例8(与实施例1相比区别在于，催化剂中的X盐为硫酸盐)Comparative Example 8 (compared with Example 1, the difference is that the X salt in the catalyst is sulfate)
采用实施例1相同制备方法，区别在于金属盐使用硫酸镁60g。The same preparation method as in Example 1 was adopted, except that 60 g of magnesium sulfate was used as the metal salt.
性能测试Performance Testing
各实施例和对照例所制得的聚酯产品数据对比如下表所示：

The data comparison of the polyester products produced in each embodiment and the comparative example is as shown in the following table:

通过对比表1中的实施例和对照例可看出，以本发明的钛系复合催化剂制备的聚酯品质总体高于普通钛系催化剂和锑系催化剂。具体地：By comparing the examples and comparative examples in Table 1, it can be seen that the quality of polyester prepared with the titanium-based composite catalyst of the present invention is generally higher than that of ordinary titanium-based catalysts and antimony-based catalysts. specifically:
根据实施例1、实施例4、实施例5、实施例6、实施例7和对照例1、对照例2的聚酯产品测试结果显示，双金属钛系催化剂制得的聚酯产品与锑系催化剂相比，在减少催化剂用量下实现了聚合物特性黏度上升，b值与二甘醇含量相当，而端羧基含量大幅降低，提升了聚酯产品品质；与单金属钛系催化剂制得的相比，聚酯色值显著下降，二甘醇和端羧基含量也较低，表明双金属钛系催化剂有效抑制了副反应的活性，可解决现行钛系催化剂合成聚酯产品泛黄的问题。According to the polyester product test results of Example 1, Example 4, Example 5, Example 6, Example 7 and Comparative Example 1 and Comparative Example 2, the polyester product prepared by the bimetallic titanium series catalyst is different from the antimony series catalyst. Compared with the catalyst, the intrinsic viscosity of the polymer was increased while reducing the amount of catalyst. The b value was equivalent to the content of diethylene glycol, while the terminal carboxyl group content was greatly reduced, which improved the quality of the polyester product; Ratio, the polyester color value dropped significantly, and the diethylene glycol and terminal carboxyl group contents were also lower, indicating that the bimetallic titanium catalyst effectively inhibited the activity of side reactions and could solve the problem of yellowing of polyester products synthesized by current titanium catalysts.
根据实施例2和对照例3的共聚酯产品测试结果显示，采用少量双金属钛系催化剂制得的共聚酯，在特性黏度和色值指标相近的情况下，产品二甘醇和端羧基含量均更低，表明采用钛系双金属催化剂的副反应少，产品性能更好。According to the copolyester product test results of Example 2 and Comparative Example 3, the copolyester prepared using a small amount of bimetallic titanium catalyst has similar intrinsic viscosity and color value indicators, but the product diethylene glycol and terminal carboxyl group content are lower, indicating that the use of titanium bimetallic catalysts has fewer side reactions and better product performance.
实施例5与对照例4的聚酯产品测试结果显示，双金属钛系催化剂制得的聚酯产 品与未添加第二金属的钛系催化剂相比，在使用相同催化剂用量时，聚合物特性黏度上升，b值、二甘醇含量和端羧基含量均有所下降，提升了聚酯产品品质。The test results of the polyester products of Example 5 and Comparative Example 4 show that the polyester products prepared by the bimetallic titanium catalyst Compared with the titanium-based catalyst without adding the second metal, when using the same catalyst dosage, the intrinsic viscosity of the polymer increased, and the b value, diethylene glycol content and terminal carboxyl group content all decreased, which improved the quality of the polyester product.
实施例8、实施例9、实施例10、实施例11、实施例12和对照例5、对照例6、对照例7、对照例8的聚酯产品测试结果显示，相比于钠盐和铅盐，几种双金属催化剂制得的聚酯特性黏度和二甘醇含量相当，但是在色值、端羧基含量方面更低。The polyester product test results of Examples 8, 9, 10, 11, 12 and Comparative Examples 5, 6, 7 and 8 show that compared to sodium salt and lead Salt, the intrinsic viscosity of polyesters prepared by several bimetallic catalysts is similar to that of diethylene glycol, but the color value and terminal carboxyl group content are lower.
实施例13、实施例14和对照例1相比，特性黏度明显提高，二甘醇和端羧基含量明显下降。Compared with Comparative Example 1, the intrinsic viscosity of Example 13 and Example 14 is significantly increased, and the content of diethylene glycol and terminal carboxyl groups is significantly decreased.
本发明中所用原料、设备，若无特别说明，均为本领域的常用原料、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。The raw materials and equipment used in the present invention, unless otherwise specified, are all commonly used raw materials and equipment in this field; the methods used in the present invention, unless otherwise specified, are all conventional methods in this field.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换，均仍属于本发明技术方案的保护范围。 The above are only preferred embodiments of the present invention and do not limit the present invention in any way. Any simple modifications, changes and equivalent transformations made to the above embodiments based on the technical essence of the present invention still belong to the technical solution of the present invention. scope of protection.

Claims (10)

  1. 一种固态双金属钛系聚酯催化剂，其特征在于：结构式如式(II)所示：
    A solid bimetallic titanium polyester catalyst, characterized by: the structural formula is as shown in formula (II):
    式(II)中，R2，R3分别选自羧酸化合物、醇化合物中的一种有机物结构；In formula (II), R 2 and R 3 are respectively selected from an organic structure selected from carboxylic acid compounds and alcohol compounds;
    M为金属原子；所述金属原子为镁、锌、铝、铁、钾、银、钙中的至少一种；M is a metal atom; the metal atom is at least one of magnesium, zinc, aluminum, iron, potassium, silver, and calcium;
    X为含M的金属盐中M之外的部分；所述金属盐为醋酸盐、硝酸盐、金属醇盐中的至少一种。X is the part other than M in the metal salt containing M; the metal salt is at least one of acetate, nitrate, and metal alkoxide.
  2. 如权利要求1所述的固态双金属钛系聚酯催化剂，其特征在于：The solid bimetallic titanium polyester catalyst as claimed in claim 1, characterized in that:
    R2选自以下化合物；
    R 2 is selected from the following compounds;
    其中，x为1～5、y为1～10、n为1～8中的整数；Among them, x is 1 to 5, y is 1 to 10, and n is an integer from 1 to 8;
    R3为碳原子数不超过6个碳的直链烷烃；R 3 is a linear alkane with no more than 6 carbon atoms;
    M选自镁、锌、铝、银、钙中的一种；M is selected from one of magnesium, zinc, aluminum, silver and calcium;
    X为醋酸根、乙氧基、硝酸根中的一种。X is one of acetate, ethoxy, and nitrate.
  3. 如权利要求2所述的固态双金属钛系聚酯催化剂，其特征在于：选自以下结构式的化合物：
    The solid bimetallic titanium-based polyester catalyst as claimed in claim 2, characterized in that: it is selected from compounds of the following structural formulas:
  4. 一种如权利要求1所述固态双金属钛系聚酯催化剂的制备方法，其特征在于包括以下步骤：A method for preparing a solid bimetallic titanium-based polyester catalyst as claimed in claim 1, characterized by comprising the following steps:
    (1)将钛化合物加入至羧酸化合物和/或羧酸衍生物的水溶液中，加热后缓慢加入醇化合物，进行反应、抽滤、干燥后获得中间产物，即钛与醇羟基及羧酸羟基配位形成的络合物，结构式如式(I)所示：
    (1) Add the titanium compound to the aqueous solution of the carboxylic acid compound and/or carboxylic acid derivative, slowly add the alcohol compound after heating, react, filter, and dry to obtain an intermediate product, that is, titanium and alcohol hydroxyl groups and carboxylic acid hydroxyl groups. The structural formula of the complex formed by coordination is as shown in formula (I):
    式(I)中，R1，R2和R3分别选自钛酸烷基酯、羧酸化合物、醇化合物中的一种有机物结构；In formula (I), R 1 , R 2 and R 3 are respectively selected from an organic structure selected from alkyl titanate, carboxylic acid compounds and alcohol compounds;
    所述钛化合物为碳原子数不超过30的钛酸烷基酯；The titanium compound is an alkyl titanate with a carbon number of not more than 30;
    所述羧酸化合物为羧酸碳之外直链碳数为1～10的脂肪族有机酸或不超过三环的四到八元环状有机酸；The carboxylic acid compound is an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid with no more than three rings;
    所述羧酸衍生物为羧酸碳之外直链碳数为1～10的脂肪族有机酸或不超过三环的四到八元环状有机酸形成的酸酐物；The carboxylic acid derivative is an anhydride formed from an aliphatic organic acid with a linear carbon number of 1 to 10 other than the carboxylic acid carbon or a four- to eight-membered cyclic organic acid that does not exceed three rings;
    所述醇化合物为至少含有两个羟基的脂肪族二醇；The alcohol compound is an aliphatic diol containing at least two hydroxyl groups;
    (2)将所述中间产物加入至无水醇化合物中，并加入金属盐，再经加热反应、蒸 发、洗涤、干燥后，获得固态双金属钛系聚酯催化剂；(2) Add the intermediate product to the anhydrous alcohol compound, add the metal salt, and then react by heating and steaming After hair growth, washing and drying, a solid bimetallic titanium polyester catalyst is obtained;
    所述无水醇化合物为1～10个碳原子的单羟基醇或双羟基醇。The anhydrous alcohol compound is a monohydroxy alcohol or a dihydroxy alcohol with 1 to 10 carbon atoms.
  5. 如权利要求4所述的制备方法，其特征在于：步骤(1)中：The preparation method according to claim 4, characterized in that: in step (1):
    所述钛化合物与羧酸化合物和/或羧酸衍生物的摩尔比为1:1～10:1；The molar ratio of the titanium compound to the carboxylic acid compound and/or carboxylic acid derivative is 1:1 to 10:1;
    所述钛化合物与醇化合物的摩尔比为0.5:1～4:1；The molar ratio of the titanium compound to the alcohol compound is 0.5:1 to 4:1;
    反应条件为反应温度50～120℃，反应时间为0.2～2小时。The reaction conditions are reaction temperature 50-120°C and reaction time 0.2-2 hours.
  6. 如权利要求5所述的制备方法，其特征在于：步骤(2)中：The preparation method according to claim 5, characterized in that: in step (2):
    所述钛化合物与无水醇化合物的摩尔比为1:1～1:10；The molar ratio of the titanium compound to the anhydrous alcohol compound is 1:1 to 1:10;
    所述钛化合物与金属盐的摩尔比为0.5:1～4:1。The molar ratio of the titanium compound to the metal salt is 0.5:1 to 4:1.
  7. 如权利要求4或6所述的制备方法，其特征在于：步骤(2)中：反应条件为反应温度40～150℃，反应时间为0.5～4小时。The preparation method according to claim 4 or 6, characterized in that in step (2): the reaction conditions are a reaction temperature of 40-150°C and a reaction time of 0.5-4 hours.
  8. 如权利要求1-3之一所述固态双金属钛系聚酯催化剂或权利要求4-7之一所述制备方法获得的固态双金属钛系聚酯催化剂在聚酯合成中的应用，其特征在于：The application of the solid bimetallic titanium polyester catalyst according to one of claims 1 to 3 or the solid bimetallic titanium polyester catalyst obtained by the preparation method according to one of claims 4 to 7 in polyester synthesis has the characteristics lies in:
    以二元醇和二元酸为原料在固态双金属钛系聚酯催化剂作用下进行聚酯合成反应，所述固态双金属钛系聚酯催化剂在酯化前以固体或均匀分散于反应单体溶液中加入，基于聚酯产物质量计算钛元素浓度为1～30ppm。A polyester synthesis reaction is carried out using diols and dibasic acids as raw materials under the action of a solid bimetallic titanium polyester catalyst. The solid bimetallic titanium polyester catalyst is solid or evenly dispersed in the reaction monomer solution before esterification. When added, the titanium element concentration is calculated to be 1 to 30 ppm based on the mass of the polyester product.
  9. 如权利要求8所述的应用，其特征在于：The application as claimed in claim 8, characterized in that:
    所述二元醇包括直链碳数低于10的脂肪族二元醇、不超过三环的四到八元环状二元醇中的一种或几种；The diols include one or more of aliphatic diols with a linear carbon number of less than 10, and four to eight-membered cyclic diols with no more than three rings;
    所述二元酸包括直链碳数低于10的脂肪族二元羧酸、不超过三环的四到八元环状二元羧酸中的一种或几种；The dibasic acid includes one or more of aliphatic dicarboxylic acids with a linear carbon number of less than 10, and four to eight-membered cyclic dicarboxylic acids with no more than three rings;
    二元醇与二元酸的摩尔比为1.1:1～1.8:1。The molar ratio of diol to dibasic acid is 1.1:1 to 1.8:1.
  10. 如权利要求8所述的应用，其特征在于：聚酯合成具体包含如下步骤：The application as claimed in claim 8, characterized in that polyester synthesis specifically includes the following steps:
    (a)酯化阶段：反应条件为反应温度140～250℃，反应时间为1～6小时，压力为0.1～0.8MPa，排出副产物；(a) Esterification stage: reaction conditions are reaction temperature 140~250°C, reaction time 1~6 hours, pressure 0.1~0.8MPa, and by-products are discharged;
    (b)预聚阶段：反应条件为反应温度180～270℃，反应时间为0.2～3小时，压力为300～100kPa，排出副产物，预聚阶段反应温度高于酯化阶段；(b) Prepolymerization stage: The reaction conditions are reaction temperature 180~270℃, reaction time 0.2~3 hours, pressure 300~100kPa, and by-products are discharged. The reaction temperature in the prepolymerization stage is higher than the esterification stage;
    (c)终聚阶段：反应条件为反应温度200～300℃，反应时间为0.5～6小时，压力为5～500Pa，排出副产物，终聚阶段反应温度高于预聚阶段，压力低于预聚阶段。 (c) Final polymerization stage: The reaction conditions are reaction temperature 200~300℃, reaction time 0.5~6 hours, pressure 5~500Pa, and by-products are discharged. The reaction temperature in the final polymerization stage is higher than the prepolymerization stage, and the pressure is lower than the prepolymerization stage. gathering stage.
PCT/CN2023/087944 2022-04-19 2023-04-13 Solid bimetallic titanium-based polyester catalyst, preparation method therefor, and use thereof WO2023202449A1 (en)

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