CN113461917B - Liquid polyester titanium composite catalyst and preparation method and application thereof - Google Patents

Liquid polyester titanium composite catalyst and preparation method and application thereof Download PDF

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CN113461917B
CN113461917B CN202110945809.1A CN202110945809A CN113461917B CN 113461917 B CN113461917 B CN 113461917B CN 202110945809 A CN202110945809 A CN 202110945809A CN 113461917 B CN113461917 B CN 113461917B
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titanium
composite catalyst
phosphate
polyester
solution
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CN113461917A (en
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陈明
张放
马世魁
康念军
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Zhuhai Huarun Chemical Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a liquid polyester titanium composite catalyst, a preparation method and application thereof. The preparation method of the liquid polyester titanium composite catalyst comprises the following steps: mixing a titanium compound and a first solvent, and then carrying out reflux reaction to obtain a white or light yellow suspension a; dissolving cobalt acetate in a second solvent to obtain a solution b; and mixing the suspension a, the solution b, the phosphate ester and the like, and then carrying out heating reaction, wherein the system is a solution when the heating reaction is finished, and the obtained solution is the liquid polyester titanium composite catalyst. The liquid polyester titanium composite catalyst prepared by the invention has good stability, does not contain heavy metal, has high catalytic activity, can effectively improve the polycondensation reaction efficiency, and the polyester prepared by the catalyst has good color phase, high intrinsic viscosity, narrow molecular weight distribution and excellent performance, and the preparation method of the catalyst is simple and has low requirement on equipment.

Description

Liquid polyester titanium composite catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of polyester catalysts, and relates to a liquid polyester titanium composite catalyst, and a preparation method and application thereof.
Background
The polyester is a general term for a polymer obtained by polycondensation of a polyhydric alcohol and a polybasic acid, and mainly refers to polyethylene terephthalate (PET), and conventionally includes linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate. Polyethylene terephthalate (PET) is prepared by esterification and Polycondensation of Terephthalic Acid (PTA) and Ethylene Glycol (EG), is an important industrial raw material, has wide application, and can be divided into two categories, namely fiber and non-fiber, wherein the latter category comprises films, containers and engineering plastics. The polyester material has excellent comprehensive performance, can maintain excellent physical performance in a wider temperature range, has high impact strength, friction resistance, good rigidity, large hardness, small hygroscopicity, good dimensional stability, excellent electrical performance, stability to most of organic solvents and inorganic acids, and wide application field.
The catalyst is an important raw material in the polyester production process, the research thereof is an important subject of the polyester industry, the polyester catalysts which are mainly applied and researched in the industrial production are mainly three series of catalysts of antimony, germanium and titanium, wherein the most common catalyst used in the polyester industrial device is the antimony series catalystAgents (including Sb) 2 O 3 、SbAc 3 Ethylene glycol antimony and the like), but antimony compounds belong to heavy metals, have the problems of being unfavorable to human health, causing pollution to the environment and the like, and are gradually replaced by other catalysts; the germanium catalyst has good stability, side reactions are less in initiation in the reaction process, the prepared polyester has good color phase, but the catalytic activity is lower than that of an antimony system, the obtained polyester has more ether bonds, the melting point is lower, the germanium resource is rare, the price is high, the economic limit exists in the practical application, and the application is less; the titanium polyester catalyst has high activity, but the polyester prepared by the titanium polyester catalyst has the problems of poor stability, yellowing, turbidity and the like, so that the titanium polyester catalyst is not used on a large scale.
Under the background of increasing global attention on human living environment, the development of polyester catalysts is in the direction of environmental protection, high efficiency and no toxicity, and the production and sale of green products are the development trend of future polyesters. The titanium catalyst does not contain heavy metal, is safe and environment-friendly, has high catalytic activity and moderate price, accords with the development trend of the polyester industry, and is expected to replace antimony catalysts in the future.
Currently, many research works are related to titanium-based catalysts: CN1138339 discloses a titanium polyester catalyst prepared by co-hydrolyzing titanate and silicate, wherein the obtained catalyst has higher activity, but the hue of the prepared polyester is not good, and the hue value is still higher compared with that of the catalyst adopting antimony; CN1259969 discloses a titanium catalyst prepared by coprecipitation of titanate and metal compound, but the problem of yellowing of the prepared polyester is still not solved; CN103539928A discloses a production method of a titanium polyester catalyst, but the preparation process is relatively complicated, the obtained polyester has poor hue, and the method is only applied to the synthesis of PET; CN1962720B provides a method for preparing a titanium catalyst, but the preparation process of the titanium catalyst needs reduced pressure distillation, the requirement on equipment is high, the hue of the obtained polyester is not good, and the viscosity is low.
Therefore, it is necessary to develop a method for preparing titanium polyester catalyst, which not only has high catalytic activity of the obtained catalyst, but also has good color phase, high intrinsic viscosity, narrow molecular weight distribution, excellent performance, simple preparation method and low requirement for equipment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a liquid polyester titanium composite catalyst, and a preparation method and application thereof.
In order to achieve the above object, in a first aspect, the present invention provides a method for preparing a liquid polyester titanium-based composite catalyst, comprising the following steps:
(1) Mixing a titanium compound and a first solvent, and then carrying out reflux reaction to obtain a white or light yellow suspension a;
(2) Dissolving cobalt acetate in a second solvent to obtain a solution b;
(3) Mixing the suspension a, the solution b and the phosphate, or mixing the suspension a, the solution b, the phosphate and other metal salts, and then carrying out heating reaction, wherein the system is a solution after the heating reaction is finished, and the obtained solution is the liquid polyester titanium composite catalyst;
wherein the other metal salt is at least one metal salt of Mg, al, zn and Mn, and is at least one of acetate and phosphate.
In the preparation method, the sequence of the step (1) and the step (2) is not limited, and the step (1) can be performed first, and then the step (2) can be performed; or the step (2) can be carried out first, and then the step (1) can be carried out; the step (1) and the step (2) may be performed simultaneously.
The liquid polyester titanium composite catalyst prepared by the preparation method has stable property and can be stored for a long time; the heavy metal is not contained, so that the harm to the environment and human can be reduced; the catalyst has high catalytic activity, can effectively improve the reaction efficiency of polyester synthesis, and the polyester prepared by the catalyst has good color phase, high intrinsic viscosity, narrow molecular weight distribution and excellent performance.
Preferably, the molar ratio of titanium in the suspension a to cobalt in the solution b is 1. More preferably, the molar ratio of titanium in the suspension a to cobalt in the solution b is 1.
In the step (3), the molar ratio of titanium in the suspension a to cobalt in the solution b has a great influence on the activity of the catalyst, and when the molar ratio of titanium in the suspension a to cobalt in the solution b is 1.1-10, the activity of the catalyst is high, so that the polyester synthesis reaction rate is accelerated. Considering that the lower amount of cobalt relative to titanium leads to a slight decrease in catalyst activity (but not obvious, P value > 0.05); the molar ratio of the titanium in the suspension a to the cobalt in the solution b is preferably 1.
Preferably, the molar ratio of titanium to the phosphate in the suspension a is 1. More preferably, the molar ratio of titanium to the phosphate in the suspension a is 1.
In the step (3), the addition of phosphate can inhibit the occurrence of side reaction of polyester synthesis, according to production experience, the molar ratio of titanium to phosphate in the suspension a is determined to be 1:0.1-10, and considering that the use amount of phosphate relative to titanium is lower, the effect of inhibiting the side reaction of polyester synthesis is slightly reduced (but not obvious, P value is more than 0.05); the molar ratio of titanium to phosphate in the suspension a is preferably 1.
Preferably, the molar ratio of titanium to the other metal salt in the suspension a is 1.
Preferably, the molar ratio of the titanium-based compound to the first solvent is 1:2-20.
During the reflux reaction, the by-products are distilled off. Preferably, the temperature of the reflux reaction is 50-180 ℃, and the time of the reflux reaction is 0.1-12h. More preferably, the reflux reaction temperature is 90-120 deg.C
The molar ratio of the cobalt acetate to the second solvent is 1:10-30.
The titanium compound is selected from alkyl titanate, such as at least one of n-butyl titanate, tetraethyl titanate, diisopropyl titanate, tetraisopropyl titanate, tetramethyl titanate, and tetraoctyl titanate.
The first solvent can be selected from alcohol solvent, such as at least one of ethanol, propanol, ethylene glycol, butanediol, etc.
The second solvent can be selected from alcohol solvent, such as at least one of ethanol, propanol, ethylene glycol, butanediol, etc.
The phosphate can be at least one selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, triethylene glycol phosphate, hydroxyethylidene diphosphoric acid, aminotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, etc.
In a second aspect, the invention provides the liquid polyester titanium-based composite catalyst prepared by the preparation method.
In a third aspect, the invention also provides an application of the liquid polyester titanium-based composite catalyst in polyester synthesis; the weight of titanium in the liquid polyester titanium composite catalyst is 5-100ppm based on the weight of polyester.
Compared with the prior art, the invention has the beneficial effects that: the liquid polyester titanium composite catalyst prepared by the invention has stable property and can be stored for a long time; the paint does not contain heavy metal, so that the harm to the environment and human can be reduced; the catalyst has high catalytic activity, can effectively improve the reaction efficiency of polyester synthesis, and the polyester prepared by the catalyst has good color phase, high intrinsic viscosity, narrow molecular weight distribution and excellent performance; meanwhile, the preparation method of the catalyst is simple and has low requirements on equipment.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available unless otherwise specified.
Example 1
Embodiment 1 provides a preparation method of a liquid polyester titanium-based composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.1mol of n-butyl titanate and 1mol of ethylene glycol, heating to 90 ℃, and reacting for 4 hours to obtain a white suspension a1;
(2) Stirring and mixing 0.05mol of cobalt acetate and 1mol of ethylene glycol to obtain a purple solution b1;
(3) Mixing the suspension a1 and the solution b1 according to the weight ratio of titanium: cobalt =1:0.5 mol ratio, the content of titanium in the mixed solution is 0.1mol, 0.1mol of trimethyl phosphate and 0.01mol of aluminum acetate are added, the mixture is heated to 140 ℃ to react for 3 hours, and the system becomes homogeneous liquid (namely solution) to obtain the liquid polyester titanium composite catalyst A.
Example 2
Embodiment 2 provides a preparation method of a liquid polyester titanium composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.1mol of n-butyl titanate and 1.5mol of ethylene glycol, heating to 100 ℃, and reacting for 3.5 hours to obtain a white suspension a2;
(2) Stirring and mixing 0.1mol of cobalt acetate and 1.5mol of ethylene glycol to obtain a purple solution b2;
(3) And mixing the suspension a2 and the solution b2 according to the ratio of titanium: cobalt =1:1, adding 0.1mol of trimethyl phosphate and 0.02mol of zinc acetate, heating to 150 ℃, reacting for 3 hours, and obtaining the liquid polyester titanium composite catalyst B.
Example 3
Embodiment 3 provides a preparation method of a liquid polyester titanium-based composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.15mol of tetraethyl titanate and 1.5mol of ethylene glycol, heating to 120 ℃, and reacting for 3.5 hours to obtain a light yellow suspension a3;
(2) Stirring and mixing 0.3mol of cobalt acetate and 4mol of glycol to obtain a purple solution b3;
(3) Mixing the suspension a3 and the solution b3 according to the weight ratio of titanium: cobalt =1:2, the titanium content in the mixed solution is 0.15mol, then 0.1mol of tripropyl phosphate and 0.02mol of magnesium acetate are added, the mixture is heated to 150 ℃ to react for 3 hours, and the system becomes homogeneous liquid (namely solution) to obtain the liquid polyester titanium composite catalyst C.
Example 4
Embodiment 4 provides a preparation method of a liquid polyester titanium-based composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.05mol of tetramethyl titanate and 0.8mol of ethylene glycol, heating to 100 ℃, and reacting for 3 hours to obtain a white suspension a4;
(2) Stirring and mixing 0.2mol of cobalt acetate and 3mol of ethylene glycol to obtain a purple solution b4;
(3) And mixing the suspension a1 and the solution b1 according to the ratio of titanium: cobalt =1:4, the titanium content in the mixed solution is 0.05mol, then 0.1mol of triphenyl phosphate and 0.01mol of aluminum acetate are added, the mixture is heated to 150 ℃ to react for 3 hours, and the system becomes homogeneous liquid (namely solution) to obtain the liquid polyester titanium composite catalyst D.
Example 5
Embodiment 5 provides a preparation method of a liquid polyester titanium-based composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.05mol of tetraisopropyl titanate and 1mol of ethylene glycol, heating to 120 ℃, and reacting for 3 hours to obtain a light yellow suspension a5;
(2) Stirring and mixing 0.2mol of cobalt acetate and 2mol of glycol to obtain a purple solution b5;
(3) Mixing the suspension a1 and the solution b1 according to the weight ratio of titanium: cobalt =1:4, the titanium content in the mixed solution is 0.05mol, then 0.05mol of trimethyl phosphate and 0.05mol of aluminum acetate are added, the mixture is heated to 160 ℃ to react for 3 hours, and the system becomes homogeneous liquid (namely solution) to obtain the liquid polyester titanium composite catalyst E.
Example 6
Embodiment 6 provides a preparation method of a liquid polyester titanium composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.02mol of n-butyl titanate and 0.3mol of ethylene glycol, heating to 100 ℃ and reacting for 2.5 hours to obtain a white suspension a6;
(2) Stirring and mixing 0.16mol of cobalt acetate and 2mol of ethylene glycol to obtain a purple solution b6;
(3) And mixing the suspension a1 and the solution b1 according to the ratio of titanium: cobalt =1:8, adding 0.02mol of triethyl phosphate and 0.01mol of zinc acetate, heating to 160 ℃ for reacting for 2.5 hours, and obtaining the liquid polyester titanium composite catalyst F.
Example 7
Embodiment 7 provides a preparation method of a liquid polyester titanium-based composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.02mol of n-butyl titanate and 0.3mol of ethylene glycol, heating to 100 ℃, and reacting for 2.5 hours to obtain a white suspension a7;
(2) Stirring and mixing 0.2mol of cobalt acetate and 2mol of ethylene glycol to obtain a solution b7;
(3) Mixing the suspension a1 and the solution b1 according to the weight ratio of titanium: cobalt =1:10, the titanium content in the mixed solution is 0.02mol, then 0.02mol of tributyl phosphate and 0.01mol of magnesium acetate are added, the mixture is heated to 160 ℃ to react for 2.5 hours, and the system becomes homogeneous liquid (namely solution), thus obtaining the liquid polyester titanium composite catalyst G.
Example 8
Embodiment 8 provides a preparation method of a liquid polyester titanium composite catalyst, which comprises the following steps:
(1) Stirring and mixing 0.02mol of tetramethyl titanate and 0.3mol of ethylene glycol, heating to 110 ℃, and reacting for 2.5 hours to obtain a light yellow suspension a8;
(2) Stirring and mixing 0.02mol of cobalt acetate and 0.4mol of ethylene glycol to obtain a purple solution b8;
(3) Mixing the suspension a1 and the solution b1 according to the weight ratio of titanium: cobalt =1:1, the titanium content in the mixed solution is 0.02mol, then 0.02mol of trimethyl phosphate is added, the mixture is heated to 150 ℃ to react for 3 hours, and the system becomes homogeneous liquid (namely solution) to obtain the liquid polyester titanium composite catalyst H.
Example 9
Example 9 provides a method of making a PET polyester, comprising the steps of: weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly mixing and stirring, adding into a reaction kettle, starting esterification reaction at the temperature of 250 ℃ for 2.5 hours, adding 10ppm (mass ratio of titanium to a polyester finished product) of a polyester-titanium composite catalyst A after the esterification reaction is finished, vacuumizing and reducing pressure until the system pressure is less than 100Pa, starting polycondensation reaction at the temperature of 275 ℃ for 2 hours, extruding, cooling and granulating a product through a casting belt opening, and sampling for performance test.
Example 10
Example 10 provides a process for producing a PET polyester, which is the same as in example 9 except that the titanium-containing polyester composite catalyst a is replaced with a titanium-containing polyester composite catalyst B in the same amount as in example 9.
Example 11
Example 11 provides a process for producing a PET polyester, which is similar to example 9 except that the polyester titanium composite catalyst a is replaced with a polyester titanium composite catalyst C and the like in terms of the amount of titanium.
Example 12
Example 12 provides a process for producing a PET polyester, which is the same as in example 9 except that the titanium composite catalyst a is replaced with a titanium composite catalyst D having a titanium content equal to that of example D.
Example 13
Example 13 provides a method for producing a PET polyester, which is the same as in example 9 except that the titanium composite catalyst a is replaced with a titanium composite catalyst E having a titanium content such as a polyester titanium composite catalyst E.
Example 14
Example 14 provides a process for producing a PET polyester, which comprises the same procedure as in example 9 except that the titanium-containing polyester composite catalyst a is replaced with a titanium-containing polyester composite catalyst F in an amount of titanium.
Example 15
Example 15 provides a process for producing a PET polyester, which is similar to example 9 except that the polyester titanium composite catalyst a is replaced with a polyester titanium composite catalyst G and the like in terms of the amount of titanium.
Example 16
Example 16 provides a process for producing a PET polyester, which is similar to example 9 except that the polyester titanium composite catalyst a is replaced with a titanium such as a polyester titanium composite catalyst H.
Comparative example 1
Comparative example 1 provides a method for preparing a PET polyester, comprising the steps of: weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly mixing and stirring, adding into a reaction kettle, starting esterification reaction at 250 ℃ for 2.5 hours, adding 10ppm (mass ratio of titanium to a polyester finished product) of titanium glycol and 1.25g of phosphoric acid after the esterification reaction is finished, vacuumizing and reducing pressure until the system pressure is less than 100Pa, starting polycondensation reaction at 275 ℃ for 2 hours, extruding, cooling and granulating a product through a casting belt opening, and sampling for performance test.
The PET polyester products obtained in examples 9 to 16 and comparative example 1 were sampled respectively for intrinsic viscosity and color value tests, and the relevant parameters were determined by the following methods:
intrinsic Viscosity (IV): the molecular weight of the polyester is measured, and according to GB/T14190-2008, the solvent is a mixed solvent of phenol and tetrachloroethane with a weight ratio of 60/40, the test temperature is 25 ℃, and the polymer concentration is 5mg/mL.
Polyester color number: polyester chip color values were measured using a Konica Minolta CM-2300d spectrophotometer. The sections were dried before measurement.
TABLE 1
Figure BDA0003215243370000091
As can be seen from Table 1, when the titanium-based composite catalyst is used, the viscosity of the product is higher than that of the common titanium catalyst within the same reaction time, which indicates that the catalytic activity of the composite catalyst is higher, and the b value of the product is lower than that of the common titanium catalyst, so that the hue is better.
In addition, when the catalysts obtained in examples 1 to 8 were stored at room temperature (e.g., 25 ℃ C.) for one year, no abnormality was observed in appearance, and the catalytic activity was stable and not lowered.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (6)

1. The preparation method of the liquid polyester titanium composite catalyst is characterized by comprising the following steps of:
(1) Mixing a titanium compound and a first solvent, and then carrying out reflux reaction to obtain a white or light yellow suspension a;
(2) Dissolving cobalt acetate in a second solvent to obtain a solution b;
(3) Mixing the suspension a, the solution b and the phosphate, or mixing the suspension a, the solution b, the phosphate and other metal salts, and then carrying out heating reaction, wherein the system is a solution after the heating reaction is finished, and the obtained solution is the liquid polyester titanium composite catalyst; the molar ratio of the titanium in the suspension a to the cobalt in the solution b is 1.5-4;
wherein the other metal salt is at least one metal salt of Mg, al, zn and Mn, and is at least one of acetate and phosphate;
in the step (3), the molar ratio of titanium to phosphate in the suspension a is 1;
the molar ratio of the titanium compound to the first solvent is 1-20, the temperature of the reflux reaction is 50-180 ℃, and the time of the reflux reaction is 0.1-12h; the molar ratio of the cobalt acetate to the second solvent is 1; the heating reaction temperature in the step (3) is 50-180 ℃, and the heating reaction time is 0.1-12h;
the titanium compound is at least one of n-butyl titanate, tetraethyl titanate, diisopropyl titanate, tetraisopropyl titanate, tetramethyl titanate and tetraoctyl titanate; the first solvent and the second solvent are at least one of ethanol, propanol, ethylene glycol and butanediol.
2. The method according to claim 1, wherein in the step (3), the molar ratio of titanium to phosphate in the suspension a is 1.
3. The method according to claim 1, wherein in the step (3), the molar ratio of titanium to other metal salts in the suspension a is 1.
4. The method according to claim 1, wherein the phosphoric acid ester is at least one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, triethylene glycol phosphate, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, and ethylenediamine tetramethylene phosphonic acid.
5. The liquid polyester titanium composite catalyst prepared by the preparation method of any one of claims 1 to 4.
6. The use of the liquid polyester titanium composite catalyst in polyester synthesis according to claim 5, wherein the weight of titanium in the liquid polyester titanium composite catalyst is 5-100ppm based on the weight of polyester.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270185A (en) * 2007-03-20 2008-09-24 上海华明高技术（集团）有限公司 Process for preparing liquid condition titanium catalyst for preparing polyester and copolyester
CN104558574A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Titanium polyester catalyst
CN107513154A (en) * 2017-09-14 2017-12-26 江苏景宏新材料科技有限公司 A kind of titanium series polyester catalyst and its method for producing copolyesters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270185A (en) * 2007-03-20 2008-09-24 上海华明高技术（集团）有限公司 Process for preparing liquid condition titanium catalyst for preparing polyester and copolyester
CN104558574A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Titanium polyester catalyst
CN107513154A (en) * 2017-09-14 2017-12-26 江苏景宏新材料科技有限公司 A kind of titanium series polyester catalyst and its method for producing copolyesters

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