CN110054765B - Preparation method and application of silicon-titanium composite homogeneous catalyst for polyester synthesis - Google Patents
Preparation method and application of silicon-titanium composite homogeneous catalyst for polyester synthesis Download PDFInfo
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- 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
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- C08G63/82—Preparation processes characterised by the catalyst used
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- 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
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Abstract
The invention relates to the field of polyester synthesis, and discloses a preparation method and application of a silicon-titanium composite homogeneous catalyst for polyester synthesis, wherein the preparation method comprises the following steps: 1) dissolving a titanium compound and a silicon compound in a mixed solvent consisting of ethylene glycol and another alcohol solvent, adding a first cocatalyst and a second cocatalyst, and distilling at 80-120 ℃ under normal pressure; 2) and adding a first complexing agent and a second complexing agent, and continuously distilling at the temperature of 80-120 ℃ under normal pressure to obtain the silicon-titanium composite homogeneous catalyst. In the preparation process of the catalyst, the proportion of titanium and silicon is changed, and sulfonate, organic ligand and phosphoric acid complexing agent are introduced, so that the introduction of the complexing agent does not influence the contents of titanium and silicon, the complexing agent can coordinate titanium atoms, the electronic environment of the catalyst is changed, the activity and stability of the catalyst are improved, the selectivity is also improved, the occurrence of side reactions is effectively reduced, and the yellowing of the hue of a polyester product is prevented.
Description
Technical Field
The invention relates to the field of polyester synthesis, in particular to a preparation method and application of a silicon-titanium composite homogeneous catalyst for polyester synthesis.
Background
PET polyester, which is called polyethylene terephthalate entirely, is widely applied to a plurality of fields such as fibers, films, packaging materials, engineering plastics and the like due to good heat resistance, insulativity, higher rebound resilience and excellent acid resistance and solvent resistance, and especially has the characteristics of washability, stiffness, low price and the like, which occupies the great share of the chemical fiber market. The catalyst is an important link of polyester production, and not only influences the speed of esterification, ester exchange and polycondensation reaction in the polyester production process, but also has obvious influence on side reaction, thermal stability, product color and the like.
At present, the most widely used polyester catalysts in industrial production are mainly antimony and germanium compounds. The antimony catalyst has the advantages of mature preparation process, low production cost, moderate catalytic activity, less side reaction and good hue, but antimony belongs to heavy metal, causes pollution to water and environment, and is not beneficial to green environmental protection and sustainable development. The germanium catalyst has good catalytic activity, and the prepared polyester is pure white in hue, does not contain heavy metal, basically has no pollution, but has rare resources and high price, thereby limiting the development of the polyester. Therefore, the development of a novel catalyst which can replace the traditional antimony catalyst and becomes the development trend of a polyester catalyst is provided, wherein the most important and most promising catalyst is a novel catalyst which takes Ti as a main active component, the catalyst has high catalytic activity and less side reactions and meets the requirements of no toxicity and environmental protection, but at the present stage, the titanium catalyst has the problems of more side reactions, yellowing of hue of polyester products, low stability of the catalyst, easiness in hydrolysis and the like, and thus, the titanium catalyst is not used in a large scale.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a silicon-titanium composite homogeneous catalyst for polyester synthesis, which changes the proportion of titanium and silicon, introduces sulfonate, organic ligand and phosphoric acid complexing agent in the preparation process of the catalyst in a breakthrough manner, does not influence the contents of titanium and silicon, and the complexing agent can coordinate titanium atoms, change the electronic environment of the catalyst, improve the activity and stability of the catalyst, improve the selectivity, effectively reduce the occurrence of side reactions and prevent the yellowing of the hue of polyester products.
The specific technical scheme of the invention is as follows: a preparation method of a silicon-titanium composite homogeneous catalyst for polyester synthesis comprises the following steps:
1) dissolving a titanium compound and a silicon compound in a mixed solvent consisting of ethylene glycol and another alcohol solvent, adding a first cocatalyst and a second cocatalyst, and distilling at 80-120 ℃ under normal pressure for 2-6 h to remove low-boiling-point components; the first cocatalyst is acetate; the second cocatalyst is an alkylbenzene sulfonate compound;
2) adding a first complexing agent and a second complexing agent, continuously distilling for 2-6 hours at the temperature of 80-120 ℃ under normal pressure, and removing low-boiling-point components to obtain a silicon-titanium composite homogeneous catalyst; the first complexing agent is selected from at least one of hydroxycarboxylic acid, pyrrolidone and lactam; the second complexing agent is at least one selected from the group consisting of phosphoric acid, phosphorous acid, alkylphosphonic acid, phosphonous acid, and esters thereof.
The catalyst prepared by the method of the invention is hydrolysis resistant and has high activity. The catalyst is used for polyester polymerization, no stabilizer is required to be added, the polymerization reaction rate can be improved, the using amount of the catalyst is reduced, and the prepared polyester has good hue, is environment-friendly and has good industrial application prospect and value.
The catalyst of the invention can solve the problems of more side reactions and yellowing of polyester, and is characterized in that:
the invention changes the proportion of titanium and silicon, introduces sulfonate, organic ligand and phosphoric acid complexing agent in the preparation process of the catalyst in a breakthrough way, the introduction of the sulfonate, the organic ligand and the phosphoric acid complexing agent does not influence the content of titanium and silicon, the complexing agent can coordinate titanium atoms to change the electronic environment of the titanium atoms, and under the synergistic cooperation of the substances, the activity and the stability of the catalyst are improved, the selectivity is also improved, the occurrence of side reactions is effectively reduced, and the yellowing of polyester is inhibited.
Preferably, the first cocatalyst is selected from at least one of sodium acetate, potassium acetate, magnesium acetate, calcium acetate, aluminum acetate, zinc acetate, lanthanum acetate and cerium acetate; the molar ratio of the titanium compound to the first cocatalyst is 1: 0.05-20;
the second cocatalyst is selected from at least one of sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; the molar ratio of the titanium compound to the second cocatalyst is 1: 0.05-20.
Preferably, the first cocatalyst is at least one of sodium acetate and magnesium acetate; the molar ratio of the titanium compound to the first cocatalyst is 1: 0.5-10;
the second cocatalyst is sodium dodecyl benzene sulfonate; the molar ratio of the titanium compound to the second cocatalyst is 1: 0.5-10.
Preferably, the first complexing agent is selected from at least one of citric acid, lactic acid, tartaric acid, malic acid, alpha-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, N-ethylcaprolactam, epsilon-caprolactam, 3-amino-2-caprolactam; the molar ratio of the titanium compound to the first complexing agent is 1: 0.05-20;
the second complexing agent is selected from at least one of phenylphosphonic acid, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite and triphenyl phosphite; the molar ratio of the titanium compound to the second complexing agent is 1: 0.05-20.
Preferably, the first complexing agent is at least one selected from lactic acid, citric acid, alpha-pyrrolidone or epsilon-caprolactam, and the molar ratio of the titanium compound to the first complexing agent is 1: 0.5-10;
the second complexing agent is at least one selected from phenylphosphonic acid and triethyl phosphate, and the molar ratio of the titanium compound to the second complexing agent is 1: 0.5-10.
Preferably, the titanium compound is alkoxy titanium and titanium halide; the silicon compound is alkoxy silicon.
Preferably, the titanium compound is at least one selected from tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisooctyl titanate and titanium tetrachloride, and the molar ratio of the titanium compound to the ethylene glycol is 1: 5-100;
the silicon compound is at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate, and the molar ratio of the titanium compound to the silicon compound is 1: 1-20;
the alcohol solvent is at least one selected from ethanol, propanol, isopropanol, butanol, propylene glycol, isopropylene glycol, butanediol, 1-methyl propylene glycol and pentanediol; the molar ratio of the titanium compound to the alcohol solvent is 1: 1-50.
Preferably, the titanium compound is tetrabutyl titanate, and the molar ratio of the titanium compound to the ethylene glycol is 1: 10-50; the silicon compound is tetraethyl silicate, and the molar ratio of the titanium compound to the silicon compound is 1: 2-10; the alcohol solvent is ethanol, and the molar ratio of the titanium compound to the alcohol solvent is 1: 5-30.
The application of the silicon-titanium composite homogeneous catalyst prepared by the method in polyester synthesis comprises the following steps: firstly, dicarboxylic acid or an ester forming derivative thereof and dihydric alcohol are subjected to esterification reaction at 230-260 ℃, the pressure is not more than 0.3MPa, and the reaction lasts for 1-3 h to obtain a prepolymer; then carrying out polycondensation reaction under the vacuum condition, wherein the reaction temperature is 270-290 ℃, the pressure is lower than 100Pa, and the reaction is carried out for 1-4 h to prepare polyester; the silicon-titanium composite homogeneous catalyst is added before and after the esterification reaction, and the dosage is 0.5-10 ppm calculated by polyester.
The catalyst prepared by the method has good hydrolysis resistance, so that the catalyst can be added before esterification reaction, and provides convenience for polyester synthesis.
Preferably, the dicarboxylic acid or ester-forming derivative thereof is at least one of terephthalic acid, phthalic acid, isophthalic acid, diphenic acid, oxalic acid, succinic acid, adipic acid, dimethyl terephthalate or diethyl terephthalate; the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol or hexanediol; the dosage of the silicon-titanium composite homogeneous catalyst is 1-6 ppm calculated by polyester.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention changes the proportion of titanium and silicon, introduces sulfonate, organic ligand and phosphoric acid complexing agent in the preparation process of the catalyst in a breakthrough way, the introduction of the sulfonate, the organic ligand and the phosphoric acid complexing agent does not influence the content of titanium and silicon, the complexing agent can coordinate titanium atoms to change the electronic environment of the titanium atoms, and under the synergistic cooperation of the substances, the activity and the stability of the catalyst are improved, the selectivity is also improved, and the occurrence of side reactions is effectively reduced.
2. The catalyst prepared by the method of the invention is hydrolysis resistant and has high activity. The catalyst is used for polyester polymerization, no stabilizer is needed to be added, the polymerization reaction rate can be improved, the dosage of the catalyst is reduced, and the prepared polyester has good hue.
3. The titanium homogeneous catalyst does not contain heavy metal elements, the solvent used in the preparation process is non-toxic and harmless, the preparation process is simple, the titanium homogeneous catalyst can be mixed with glycol, the long-term storage is facilitated, the titanium homogeneous catalyst is a novel environment-friendly polyester catalyst, and the titanium homogeneous catalyst has good industrial application prospect and value.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
Preparing a silicon-titanium composite homogeneous catalyst:
1) dissolving a titanium compound and a silicon compound in a mixed solvent consisting of ethylene glycol and another alcohol solvent, adding a first cocatalyst and a second cocatalyst, and distilling at 80-120 ℃ under normal pressure for 2-6 h to remove low-boiling-point components; the first cocatalyst is acetate; the second cocatalyst is an alkylbenzene sulfonate compound;
2) adding a first complexing agent and a second complexing agent, continuously distilling for 2-6 hours at the temperature of 80-120 ℃ under normal pressure, and removing low-boiling-point components to obtain a silicon-titanium composite homogeneous catalyst; the first complexing agent is selected from at least one of hydroxycarboxylic acid, pyrrolidone and lactam; the second complexing agent is at least one selected from the group consisting of phosphoric acid, phosphorous acid, alkylphosphonic acid, phosphonous acid, and esters thereof.
Preferably, the first cocatalyst is selected from at least one of sodium acetate, potassium acetate, magnesium acetate, calcium acetate, aluminum acetate, zinc acetate, lanthanum acetate and cerium acetate; the molar ratio of the titanium compound to the first cocatalyst is 1: 0.05-20;
the second cocatalyst is selected from at least one of sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; the molar ratio of the titanium compound to the second cocatalyst is 1: 0.05-20.
As a further preference, the first cocatalyst is at least one of sodium acetate and magnesium acetate; the molar ratio of the titanium compound to the first cocatalyst is 1: 0.5-10; the second cocatalyst is sodium dodecyl benzene sulfonate; the molar ratio of the titanium compound to the second cocatalyst is 1: 0.5-10.
Further preferably, the first complexing agent is at least one selected from the group consisting of citric acid, lactic acid, tartaric acid, malic acid, α -pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, N-ethylcaprolactam, e-caprolactam, 3-amino-2-caprolactam; the molar ratio of the titanium compound to the first complexing agent is 1: 0.05-20;
the second complexing agent is selected from at least one of phenylphosphonic acid, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite and triphenyl phosphite; the molar ratio of the titanium compound to the second complexing agent is 1: 0.05-20.
As a further preference, the first complexing agent is selected from at least one of lactic acid, citric acid, α -pyrrolidone or ∈ -caprolactam, and the molar ratio of the titanium compound to the first complexing agent is 1:0.5 to 10;
the second complexing agent is at least one selected from phenylphosphonic acid and triethyl phosphate, and the molar ratio of the titanium compound to the second complexing agent is 1: 0.5-10.
As further preferred, the titanium compound is an alkoxy titanium and a titanium halide; the silicon compound is alkoxy silicon.
More preferably, the titanium compound is at least one selected from tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisooctyl titanate and titanium tetrachloride, and the molar ratio of the titanium compound to the ethylene glycol is 1: 5-100;
the silicon compound is at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate, and the molar ratio of the titanium compound to the silicon compound is 1: 1-20;
the alcohol solvent is at least one selected from ethanol, propanol, isopropanol, butanol, propylene glycol, isopropylene glycol, butanediol, 1-methyl propylene glycol and pentanediol; the molar ratio of the titanium compound to the alcohol solvent is 1: 1-50.
Preferably, the titanium compound is tetrabutyl titanate, and the molar ratio of the titanium compound to the ethylene glycol is 1: 10-50; the silicon compound is tetraethyl silicate, and the molar ratio of the titanium compound to the silicon compound is 1: 2-10; the alcohol solvent is ethanol, and the molar ratio of the titanium compound to the alcohol solvent is 1: 5-30.
Preparation of polyester: firstly, dicarboxylic acid or an ester forming derivative thereof and dihydric alcohol are subjected to esterification reaction at 230-260 ℃, the pressure is not more than 0.3MPa, and the reaction lasts for 1-3 h to obtain a prepolymer; then carrying out polycondensation reaction under the vacuum condition, wherein the reaction temperature is 270-290 ℃, the pressure is lower than 100Pa, and the reaction is carried out for 1-4 h to prepare polyester; the silicon-titanium composite homogeneous catalyst is added before and after the esterification reaction, and the dosage is 0.5-10 ppm calculated by polyester.
Wherein the dicarboxylic acid or the ester-forming derivative thereof is at least one of terephthalic acid, phthalic acid, isophthalic acid, diphenic acid, oxalic acid, succinic acid, adipic acid, dimethyl terephthalate or diethyl terephthalate; the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol or hexanediol; preferably, the dosage of the silicon-titanium composite homogeneous catalyst is 1-6 ppm calculated by polyester.
Example 1
A250 ml flask equipped with a magnetic stirring and condensing device was charged with 37.2g (0.6mol) of ethylene glycol, 2.4608g (0.03mol) of sodium acetate and 1.0454g (0.003mol) of sodium dodecylbenzenesulfonate were dissolved therein, then 10.2g (0.03mol) of n-butyl titanate, 25.0g (0.12mol) of ethyl orthosilicate and 13.8g (0.3mol) of ethanol were added to the solution, reacted at 85 ℃ for 2.5 hours, after small molecules were distilled off, 6.3028g (0.03mol) of citric acid monohydrate and 4.7676g (0.03mol) of phenylphosphonic acid were added to the reaction system, reacted at 85 ℃ for 2.5 hours, and after small molecules were distilled off, a 1.4001% titanium-containing liquid catalyst was obtained. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
Example 2
A250 ml flask equipped with a magnetic stirring and condensing device was charged with 37.2g (0.6mol) of ethylene glycol, 6.4342g (0.03mol) of magnesium acetate tetrahydrate and 0.5227g (0.0015mol) of sodium dodecylbenzenesulfonate were dissolved therein, then 10.2g (0.03mol) of n-butyl titanate, 25.0g (0.12mol) of ethyl orthosilicate and 13.8g (0.3mol) of ethanol were added to the solution, reacted at 85 ℃ for 2.5 hours, after small molecules were removed by distillation, 2.7042g (0.03mol) of lactic acid and 4.7676g (0.03mol) of phenylphosphoric acid were added to the reaction system, reacted at 85 ℃ for 2.5 hours, and after small molecules were removed by distillation, a 1.4526% titanium-containing liquid catalyst was obtained. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
Example 3
A250 ml flask equipped with a magnetic stirring and condensing device was charged with 37.2g (0.6mol) of ethylene glycol, 6.4342g (0.03mol) of magnesium acetate tetrahydrate and 2.1875g (0.006mol) of potassium dodecylbenzenesulfonate were dissolved therein, then 10.2g (0.03mol) of n-butyl titanate, 25.0g (0.12mol) of ethyl orthosilicate and 13.8g (0.3mol) of ethanol were added to the solution, reacted at 85 ℃ for 2.5 hours, after small molecules were distilled off, 2.7042g (0.03mol) of lactic acid and 5.4670g (0.03mol) of triethyl phosphate were added to the reaction system, reacted at 85 ℃ for 2.5 hours, and after small molecules were distilled off, a liquid catalyst containing 1.4322% titanium was obtained. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
Example 4
A250 ml flask equipped with a magnetic stirring and condensing device was charged with 37.2g (0.6m0l) of ethylene glycol, 2.4608g (0.03m0l) of sodium acetate and 2.0909g (0.006m0l) of sodium dodecylbenzenesulfonate were dissolved therein, then 10.2g (0.03mol) of n-butyl titanate, 25.0g (0.12mol) of ethyl orthosilicate and 13.8g (0.3mol) of ethanol were added to the solution, reacted at 85 ℃ for 2.5 hours, after small molecules were removed by distillation, 2.5533g (0.03mol) of α -pyrrolidone and 4.7676g (0.03mol) of phenylphosphoric acid were added to the reaction system, reacted at 85 ℃ for 2.5 hours, and after small molecules were removed by distillation, a liquid catalyst containing 1.4721% of titanium was obtained. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
Example 5
A250 ml flask equipped with a magnetic stirrer and a condenser was charged with 37.2g (0.6mol) of ethylene glycol, 6.4342g (0.03mol) of magnesium acetate tetrahydrate and 0.5469g (0.0015mol) of potassium dodecylbenzenesulfonate were dissolved therein, then 10.2g (0.03mol) of n-butyl titanate, 25.0g (0.12mol) of ethyl orthosilicate and 13.8g (0.3mol) of ethanol were added to the solution, reacted at 85 ℃ for 2.5 hours, after small molecules were distilled off, 3.3948g (0.03mol) of epsilon-caprolactam and 10.9340g (0.06mol) of triethyl phosphate were added to the reaction system, reacted at 85 ℃ for 2.5 hours, and after small molecules were distilled off, a 1.4469% titanium-containing liquid catalyst was obtained. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
Comparative example 1 (conventional titanium-based catalyst)
The product performance results of polyester chips prepared by the conventional polyester process using n-butyl titanate as a catalyst are shown in Table 1.
Comparative example 2 (only one complexing agent was used)
Catalyst preparation was carried out in the same manner as in example 1, except that citric acid monohydrate was not added. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
Comparative example 3 (only one catalytic assistant is used)
Catalyst preparation was carried out in the same manner as in example 1, except that phenylphosphonic acid was not added. The product performance results of polyester chips prepared by the conventional polyester process using the catalyst are shown in Table 1.
The catalyst prepared in each example is used for evaluating the catalytic performance after being used for producing environment-friendly polyester, and the preparation method can adopt a known polyester preparation process, wherein the polyester preparation method specifically comprises the following steps: 664.0g (4.0mol) of terephthalic acid (PTA), 396.8g (6.4mol) of Ethylene Glycol (EG) and the catalyst solution (Ti content is 1-6 ppm based on the weight of PET) prepared in each example are uniformly mixed, added into a reaction kettle and subjected to esterification reaction at 250 ℃ and under the pressure of not more than 0.3 MPa. And after the esterification reaction is finished, vacuumizing until the pressure is lower than 100MPa, and reacting for 1-3 h at 280 ℃ to obtain the polyester chip. The corresponding product performance index is shown in table 1.
TABLE 1
From the results of polymerization experiments, the conventional tetrabutyl titanate is adopted as a catalyst in the comparative example 1, the polycondensation time is long in the polymerization process, the viscosity rises very slowly along with the reaction time, the viscosity of the finally obtained product cannot meet the conventional requirements, and the tetrabutyl titanate is supposed to be partially hydrolyzed in the esterification process to influence the catalytic activity of the tetrabutyl titanate and have poor stability; the viscosity index of the products obtained in comparative examples 2 and 3 is normal, but the L value is lower, the b value is higher, and the color phase is yellowish, and the two complexing agents citric acid monohydrate and phenylphosphonic acid are supposed to have a certain synergistic effect, so that the stability of the catalyst is improved, the occurrence of side reactions is inhibited, and the color phase is improved, so that the color phase is deteriorated if any one of the two complexing agents is not used, particularly if the phenylphosphonic acid is not used. Each index in examples 1 to 5 was normal and the hue was good.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a silicon-titanium composite homogeneous catalyst for polyester synthesis is characterized by comprising the following steps:
1) dissolving a titanium compound and a silicon compound in a mixed solvent consisting of ethylene glycol and another alcohol solvent, adding a first cocatalyst and a second cocatalyst, and distilling at 80-120 ℃ under normal pressure for 2-6 h to remove low-boiling-point components;
the molar ratio of the titanium compound to the silicon compound is 1: 2-10;
the first cocatalyst is sodium acetate; the molar ratio of the titanium compound to the first cocatalyst is 1: 0.5-10;
the second cocatalyst is selected from at least one of sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; the molar ratio of the titanium compound to the second cocatalyst is 1: 0.05-20;
2) adding a first complexing agent and a second complexing agent, continuously distilling for 2-6 hours at the temperature of 80-120 ℃ under normal pressure, and removing low-boiling-point components to obtain a silicon-titanium composite homogeneous catalyst;
the first complexing agent is at least one selected from alpha-pyrrolidone or epsilon-caprolactam, and the molar ratio of the titanium compound to the first complexing agent is 1: 0.5-10;
the second complexing agent is phenylphosphonic acid, and the molar ratio of the titanium compound to the second complexing agent is 1: 0.5-10.
2. The method for preparing the silicon-titanium composite homogeneous catalyst for polyester synthesis according to claim 1, wherein the second cocatalyst is sodium dodecylbenzenesulfonate; the molar ratio of the titanium compound to the second cocatalyst is 1: 0.5-10.
3. The method for preparing the silicon-titanium composite homogeneous catalyst for polyester synthesis according to claim 1, wherein the titanium compound is alkoxy titanium and titanium halide; the silicon compound is alkoxy silicon.
4. The method for preparing the silicon-titanium composite homogeneous catalyst for polyester synthesis according to claim 3, wherein the titanium compound is at least one selected from the group consisting of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisooctyl titanate, and titanium tetrachloride, and the molar ratio of the titanium compound to the ethylene glycol is 1: 5-100;
the silicon compound is selected from at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate;
the alcohol solvent is at least one selected from ethanol, propanol, isopropanol, butanol, propylene glycol, isopropylene glycol, butanediol, 1-methyl propylene glycol and pentanediol; the molar ratio of the titanium compound to the alcohol solvent is 1: 1-50.
5. The preparation method of the silicon-titanium composite homogeneous catalyst for polyester synthesis according to claim 4, wherein the titanium compound is tetrabutyl titanate, and the molar ratio of the titanium compound to the ethylene glycol is 1: 10-50; the silicon compound is tetraethyl silicate; the alcohol solvent is ethanol, and the molar ratio of the titanium compound to the alcohol solvent is 1: 5-30.
6. Use of a silicon-titanium composite homogeneous catalyst prepared according to the method of any one of claims 1 to 5 in polyester synthesis, characterized by comprising the steps of: firstly, dicarboxylic acid or an ester forming derivative thereof and dihydric alcohol are subjected to esterification reaction at 230-260 ℃, the pressure is not more than 0.3MPa, and the reaction lasts for 1-3 h to obtain a prepolymer; then carrying out polycondensation reaction under the vacuum condition, wherein the reaction temperature is 270-290 ℃, the pressure is lower than 100Pa, and the reaction is carried out for 1-4 h to prepare polyester; the silicon-titanium composite homogeneous catalyst is added before and after the esterification reaction, and the dosage is 0.5-10 ppm calculated by polyester.
7. The use according to claim 6, wherein the dicarboxylic acid or ester-forming derivative thereof is at least one of terephthalic acid, phthalic acid, isophthalic acid, diphenyldicarboxylic acid, oxalic acid, succinic acid, adipic acid, dimethyl terephthalate, or diethyl terephthalate; the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol or hexanediol; the dosage of the silicon-titanium composite homogeneous catalyst is 1-6 ppm calculated by polyester.
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| CN2018110346536 | 2018-09-05 |
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| CN112048059B (en) * | 2020-08-19 | 2023-02-14 | 海宁澜钛新材料有限公司 | Method for catalytically synthesizing polyester by using titanium catalyst |
| CN112280012B (en) * | 2020-11-13 | 2021-09-07 | 康辉新材料科技有限公司 | Preparation method of poly (butylene succinate) |
| CN115466378B (en) * | 2021-10-19 | 2023-12-15 | 源创核新(北京)新材料科技有限公司 | Application of titanium-aluminum composite catalyst in polyoxalate synthesis |
| CN113999379B (en) * | 2021-12-31 | 2022-03-15 | 江苏新视界先进功能纤维创新中心有限公司 | Titanium composite catalyst for polyester synthesis and preparation and application thereof |
| CN114621426B (en) * | 2022-04-11 | 2023-06-30 | 山东瑞丰高分子材料股份有限公司 | Catalyst for synthesizing degradable polyester, preparation method and application thereof |
| CN117624573B (en) * | 2024-01-25 | 2024-04-30 | 江苏恒力化纤股份有限公司 | Flame-retardant polyester with homogeneously dispersed silicon dioxide, and preparation method and application thereof |
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Address after: 310000 Yaqian town Chenghu Road, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: ZHEJIANG HENGYI PETROCHEMICAL Co.,Ltd. Patentee after: Zhejiang Hengyi Petrochemical Research Institute Co., Ltd Address before: 310000 Yaqian town Chenghu Road, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: ZHEJIANG HENGYI PETROCHEMICAL Co.,Ltd. Patentee before: Zhejiang Henglan Technology Co., Ltd |