CN110054763B - Titanium-germanium composite catalyst for polyester synthesis and application thereof - Google Patents
Titanium-germanium composite catalyst for polyester synthesis and application thereof Download PDFInfo
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- CN110054763B CN110054763B CN201910278138.0A CN201910278138A CN110054763B CN 110054763 B CN110054763 B CN 110054763B CN 201910278138 A CN201910278138 A CN 201910278138A CN 110054763 B CN110054763 B CN 110054763B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
Abstract
The invention relates to the field of polyester synthesis, and discloses a titanium-germanium composite catalyst for polyester synthesis and application thereof, wherein the titanium dioxide sol and the germanium dioxide sol are mixed firstly, the obtained mixed sol is dropwise added into a complexing agent aqueous solution, and stirring treatment is carried out; and then centrifuging the stirred mixed sol, taking the precipitate, washing to remove chloride ions, and drying to obtain the titanium-germanium composite catalyst. The invention combines titanium and germanium in a special way in a breakthrough way, and the obtained composite catalyst has excellent stability and activity, can effectively inhibit the occurrence of side reactions in polyester synthesis, and effectively prevent the hue of polyester products from yellowing. The invention has low catalytic preparation cost and is beneficial to popularization and application.
Description
Technical Field
The invention relates to the field of polyester synthesis, in particular to a titanium-germanium composite catalyst for polyester synthesis and application thereof.
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.
Currently, the most widely used polyester catalysts in industrial production are mainly antimony-based catalysts. The preparation process is mature, the production cost is low, the catalytic activity is moderate, the side reaction is less, the hue is good, but the antimony belongs to heavy metal, the pollution to water and environment exists, and the preparation method is not beneficial to green environmental protection and sustainable development. Therefore, the development of a catalyst capable of replacing the traditional antimony-based catalyst is a trend of the development of polyester catalysts, and particularly important are novel catalysts which take germanium and titanium as main active components. 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. The titanium catalyst has high catalytic activity and meets the requirements of no toxicity and environmental protection, but the titanium catalyst has the problems of more side reactions, yellow hue of polyester products, low stability of the catalyst, easy hydrolysis and the like at the present stage, so the titanium catalyst is not used on a large scale.
Disclosure of Invention
In order to solve the technical problems, the invention provides a titanium-germanium composite catalyst for polyester synthesis and an application thereof. The invention has low catalytic preparation cost and is beneficial to popularization and application.
The specific technical scheme of the invention is as follows: a titanium germanium composite catalyst for polyester synthesis is prepared by the following steps:
1) mixing titanium dioxide sol and germanium dioxide sol, dropwise adding the obtained mixed sol into a complexing agent aqueous solution, and stirring.
2) And centrifuging the stirred mixed sol, taking the precipitate, washing to remove chloride ions, and drying to obtain the titanium-germanium composite catalyst.
According to the invention, titanium dioxide and germanium dioxide are compounded in a sol mode, and then are subjected to complexing agent and subsequent treatment, compared with a single catalyst or other compound catalysts, the prepared compound catalyst has stronger synergistic effect between titanium and germanium (stronger composite synergistic effect compared with the traditional mode, see the comparative example 2 in detail), germanium has stronger electronegativity compared with titanium, and electron cloud is transferred from titanium to germanium during compounding, so that germanium has stronger coordination capacity and is more easily coordinated with an ester compound, and therefore, compared with a single germanium catalyst, the compound catalyst has higher activity. The complexing agent can play a role in coordinating titanium atoms, the electronic environment of the titanium atoms is changed under the combined action of germanium, the coordination capacity of the titanium is reduced to a certain extent, the titanium has extremely high catalytic activity, and the reduction of the coordination capacity of the titanium can inhibit the occurrence of side reactions to a certain extent, so that the stability is better, and the polyester product prepared by using the catalyst for polyester polymerization has good hue and does not have the problem of heavy metal pollution. In addition, the catalyst has higher catalytic activity, so that the dosage of the catalyst can be reduced, the production cost is almost the same as that of the conventional antimony catalyst, and the catalyst has good industrial application prospect and value.
As can be seen from the above, the present invention is not limited to any catalyst obtained by arbitrarily combining titanium and germanium, but is characterized by a specific combination method of titanium and germanium.
Preferably, in the step 1), the molar ratio of the titanium element to the germanium element is 1-10: 1.
The ratio of titanium to germanium needs to be strictly controlled in consideration of the overall performance of the catalyst. If the titanium content is too high, side reactions are severe in the polymerization process, and the color phase of the sliced product is poor; if the content of titanium is too low, although the color of the slice is good, the overall activity of the catalyst is relatively low, and the increase of the content of germanium increases the preparation cost of the catalyst. The molar ratio of the titanium element to the germanium element is selected to be 1-10: 1 in comprehensive consideration.
Preferably, the step 1) is carried out at room temperature, and the stirring treatment is carried out for 0.5-5 h.
Preferably, the preparation method of the titanium dioxide sol comprises the following steps: and (2) dropwise adding the titanium compound into the hydrochloric acid aqueous solution at room temperature, and continuously stirring for 1-6 hours after dropwise adding to obtain the titanium dioxide sol.
Preferably, the preparation method of the germanium dioxide sol comprises the following steps: and (3) dropwise adding germanium chloride into deionized water at room temperature, and continuously stirring for 12-24 hours after dropwise adding to obtain the germanium dioxide sol.
Preferably, the titanium compound is at least one of alkoxy titanium, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisooctyl titanate.
Preferably, the concentration of the hydrochloric acid aqueous solution is 0.05-1 mol/L.
Preferably, the molar ratio of the titanium compound to the hydrochloric acid is 1-10: 1.
Hydrochloric acid is mainly used as a precipitator, the concentration of the hydrochloric acid is too high, the use amount of the hydrochloric acid is too large, the tetrabutyl titanate is hydrolyzed too violently, the catalytic activity of a hydrolysis product is reduced, if the use amount is too small, the hydrolysis of the tetrabutyl titanate is incomplete, the activity of a catalyst is uncontrollable, and the hue of a polyester product is influenced. The molar ratio of the titanium compound to the hydrochloric acid is selected to be 1-10: 1 in comprehensive consideration.
Preferably, the molar ratio of the germanium chloride to the deionized water is 0.01-0.5: 1.
The reaction of the high-purity germanium chloride and water is violent after mixing, the hydrated germanium oxide and hydrogen chloride with low solubility can be generated, a large amount of heat is released, the reaction system cannot be effectively cooled due to too low water consumption, the hydrolysis process is influenced, and the separation of the hydrated germanium oxide is difficult due to too high water consumption. The molar ratio of germanium chloride to deionized water is selected to be 0.01-0.5: 1 in comprehensive consideration.
Preferably, the complexing agent is at least one of citric acid, lactic acid, tartaric acid, malic acid, alpha-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, N-ethylcaprolactam, -caprolactam, and 3-amino-2-caprolactam.
Preferably, the concentration of the complexing agent aqueous solution is 0.05-1 mol/L.
Preferably, the molar ratio of the titanium element to the complexing agent is 0.05-1: 1.
The ratio of the titanium element to the complexing agent is based on experimental results, and the selection ratio is 0.05-1: 1, so that the controllability of the activity of the titanium element is ensured and the occurrence of side reactions is reduced while the catalytic activity of the titanium is kept to the maximum extent under the ratio.
Preferably, in the step 2), the drying is vacuum drying, and the temperature is 60-100 ℃.
In the present invention, in order to further improve the catalyst performance, the above process parameters and reagent selection need to be strictly controlled.
The application of the titanium-germanium composite catalyst in polyester synthesis comprises the following steps: carrying out esterification reaction on dicarboxylic acid and/or ester-forming derivatives thereof and dihydric alcohol at 230-260 ℃, wherein the pressure is not more than 0.3MPa, and the reaction time is 1-3 h to obtain a prepolymer; and 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 obtain the polyester.
Preferably, the titanium-germanium composite catalyst is added before esterification or before polycondensation after esterification, 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 and the ester-forming derivative of the dicarboxylic acid are at least one of terephthalic acid, phthalic acid, isophthalic acid, diphenic acid, oxalic acid, succinic acid, adipic acid, dimethyl terephthalate, and diethyl terephthalate.
Preferably, the dihydric alcohol is at least one of ethylene glycol, propylene glycol, and butylene glycol and hexylene glycol.
More preferably, the amount of the titanium germanium composite catalyst is 1 to 6ppm based on the polyester.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention combines the titanium and germanium catalyst systems in a special way, reduces the preparation cost of the catalyst, has a coordination function on titanium atoms by a complexing agent, changes the electronic environment, has better synergistic effect on the titanium and the germanium, improves the stability and the activity of the catalyst, inhibits the occurrence of side reaction, and effectively prevents the yellowing of the hue of polyester products.
2. The catalyst prepared by the method is hydrolysis-resistant, high in activity, simple in preparation process and capable of being stored for a long time, the polymerization reaction rate can be improved and the dosage of the catalyst can be reduced by using the catalyst for polyester polymerization, and the catalyst does not contain heavy metals, is very environment-friendly and has good industrial application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
Preparation of the catalyst:
1) and (2) dropwise adding the titanium compound into the hydrochloric acid aqueous solution at room temperature, and continuously stirring for 1-6 hours after dropwise adding to obtain the titanium dioxide sol. Preferably, the titanium compound is at least one of alkoxy titanium, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisooctyl titanate. The concentration of the hydrochloric acid aqueous solution is 0.05-1 mol/L, and the molar ratio of the titanium compound to the hydrochloric acid is 1-10: 1.
2) And (3) dropwise adding germanium tetrachloride into deionized water at room temperature, and continuously stirring for 12-24 hours after dropwise adding to obtain the germanium dioxide sol. Preferably, the molar ratio of the germanium chloride to the deionized water is 0.01-0.5: 1.
3) And mixing the titanium dioxide sol and the germanium dioxide sol at room temperature, dropwise adding the mixed sol into an aqueous solution containing a complexing agent, and continuously stirring for 0.5-5 hours. The molar ratio of the titanium compound to the germanium chloride is 1-10: 1. The complexing agent is at least one of citric acid, lactic acid, tartaric acid, malic acid, alpha-pyrrolidone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-methyl caprolactam, N-ethyl caprolactam, -caprolactam and 3-amino-2-caprolactam. More preferably, the concentration of the complexing agent aqueous solution is 0.05-1 mol/L, and the molar ratio of the titanium compound to the complexing agent is 0.05-1: 1.
4) Centrifuging to obtain a precipitate, washing with deionized water to remove chloride ions, and drying at 60-100 ℃ in vacuum to constant weight to obtain the titanium-germanium composite catalyst.
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 titanium germanium composite 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 titanium germanium composite catalyst is 1-6 ppm calculated by polyester.
Example 1
Under the condition of room temperature, 4.5mmol of tetrabutyl titanate is dropwise added into 20mL of 0.1mol/L hydrochloric acid solution, and stirring is continued for 3h after the dropwise addition is finished to obtain the titanium dioxide sol. And (3) dropwise adding 1.5mmol of germanium tetrachloride into 2.5mL of deionized water, and continuously stirring for 15 hours after dropwise adding to obtain the germanium dioxide sol. Mixing titanium dioxide sol and germanium dioxide sol, dropwise adding the mixed sol into 150 mL-caprolactam water solution with the concentration of 0.14mol/L, and continuously stirring for 1 h. Centrifuging to obtain a precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 100 ℃ to constant weight to obtain the titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Example 2
At room temperature, 10mmol of tetraisopropyl titanate is added dropwise into 20mL of 0.2mol/L hydrochloric acid solution, and stirring is continued for 4h after the dropwise addition is finished to obtain the titanium dioxide sol. 5mmol of germanium tetrachloride is added into 8mL of deionized water drop by drop, and stirring is continued for 20h after the addition is finished to obtain germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, dropwise adding the mixed sol into 300mL of citric acid aqueous solution with the concentration of 0.1mol/L, and continuously stirring for 2 h. Centrifuging to obtain precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 80 deg.C to constant weight to obtain titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Example 3
Under the condition of room temperature, 24mmol tetraethyl titanate is added dropwise into 30mL hydrochloric acid solution with the concentration of 0.1mol/L, and stirring is continued for 3h after the dropwise addition is finished to obtain the titanium dioxide sol. 4mmol of germanium tetrachloride is added into 5mL of deionized water drop by drop, and stirring is continued for 20h after the addition is finished to obtain germanium dioxide sol. Titanium dioxide and germanium dioxide sol are mixed, and the mixed sol is dropwise added into 200mL of lactic acid aqueous solution with the concentration of 0.36 mol/L. Stirring was continued for 4 h. Centrifuging to obtain a precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 100 ℃ to constant weight to obtain the titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Example 4
And (3) dropwise adding 30mmol tetrapropyl titanate into 30mL 0.2mol/L hydrochloric acid solution at room temperature, and continuously stirring for 6h after dropwise adding to obtain the titanium dioxide sol. And (3) dropwise adding 3mmol of germanium tetrachloride into 5mL of deionized water, and continuously stirring for 12h after dropwise adding to obtain the germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, and dropwise adding the mixed sol into 30mL of tartaric acid aqueous solution with the concentration of 1 mol/L. Stirring was continued for 4 h. Centrifuging to obtain precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 80 deg.C to constant weight to obtain titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Example 5
Under the condition of room temperature, 10mmol of tetraisooctyl titanate is dropwise added into 10mL of 1mol/L hydrochloric acid solution, and stirring is continued for 2 hours after the dropwise addition is finished to obtain titanium dioxide sol. And (3) dropwise adding 10mmol of germanium tetrachloride into 18mL of deionized water, and continuously stirring for 20h after dropwise adding to obtain the germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, and dropwise adding the mixed sol into 50mL of malic acid aqueous solution with the concentration of 0.8 mol/L. Stirring was continued for 3 h. Centrifuging to obtain a precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 60 ℃ to constant weight to obtain the titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Example 6
Under the condition of room temperature, 25mmol of tetrabutyl titanate is dropwise added into 50mL of 0.05mol/L hydrochloric acid solution, and stirring is continued for 6 hours after the dropwise addition is finished to obtain the titanium dioxide sol. 5mmol of germanium tetrachloride is added into 4.5mL of deionized water drop by drop, and stirring is continued for 16h after the addition is finished to obtain germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, and dropwise adding the mixed sol into 100mL of alpha-pyrrolidone aqueous solution with the concentration of 0.5 mol/L. Stirring was continued for 2 h. Centrifuging to obtain precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 80 deg.C to constant weight to obtain titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Example 7
And (3) dropwise adding 30mmol of tetraethyl titanate into 20mL of 0.5mol/L hydrochloric acid solution at room temperature, and continuously stirring for 5 hours after dropwise adding to obtain the titanium dioxide sol. And (3) dropwise adding 15mmol of germanium tetrachloride into 21.6mL of deionized water, and continuously stirring for 24 hours after dropwise adding to obtain the germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, and dropwise adding the mixed sol into 200mL of N-methylpyrrolidone aqueous solution with the concentration of 0.2 mol/L. Stirring was continued for 5 h. Centrifuging to obtain a precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 100 ℃ to constant weight to obtain the titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Comparative example 1
Catalyst preparation was carried out in the same manner as in example 1 except that no germanium component was added. The product performance results of polyester chips prepared by the polyester synthesis process (same as example 1) using this catalyst are shown in Table 1.
Comparative example 2
The product performance results of polyester chips prepared by the polyester synthesis process using tetrabutyl titanate and germanium oxide as catalysts (the ratio of titanium to germanium is the same as that in example 1, and the respective addition molar amounts are the same as those in example 1) are shown in Table 1.
COMPARATIVE EXAMPLE 3 (high ratio of Ti to Ge)
And (3) dropwise adding 30mmol tetrapropyl titanate into 30mL 0.2mol/L hydrochloric acid solution at room temperature, and continuously stirring for 6h after dropwise adding to obtain the titanium dioxide sol. Dropwise adding 1mmol of germanium tetrachloride into 1.5mL of deionized water, and continuously stirring for 12h after dropwise adding to obtain germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, and dropwise adding the mixed sol into 30mL of tartaric acid aqueous solution with the concentration of 1 mol/L. Stirring was continued for 4 h. Centrifuging to obtain precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 80 deg.C to constant weight to obtain titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
COMPARATIVE EXAMPLE 4 (Low titanium germanium ratio)
Under the condition of room temperature, 10mmol of tetraisooctyl titanate is dropwise added into 10mL of 1mol/L hydrochloric acid solution, and stirring is continued for 2 hours after the dropwise addition is finished to obtain titanium dioxide sol. And (3) dropwise adding 15mmol of germanium tetrachloride into 27mL of deionized water, and continuously stirring for 24h after dropwise adding to obtain the germanium dioxide sol. Mixing titanium dioxide and germanium dioxide sol, and dropwise adding the mixed sol into 50mL of malic acid aqueous solution with the concentration of 0.8 mol/L. Stirring was continued for 3 h. Centrifuging to obtain a precipitate, washing with deionized water to remove chloride ions, and vacuum drying at 60 ℃ to constant weight to obtain the titanium-germanium composite catalyst. The product performance results of the polyester chip prepared by the catalyst are shown in the table 1.
Comparative example 5
Catalyst preparation was carried out in the same manner as in example 1 except that the concentration of the aqueous caprolactam solution was changed to 0.05mol/L and the amount was changed to 50 mL. The product performance results of polyester chips prepared by the polyester synthesis process (same as example 1) using this catalyst are shown in Table 1.
The catalysts prepared in the embodiments and the comparative examples are used for evaluating the catalytic performance after being used for producing environment-friendly polyester, and the preparation method comprises the following steps: 664.0g (4.0mol) of terephthalic acid (PTA), 396.8g (6.4mol) of Ethylene Glycol (EG) and the catalyst solution prepared in each example (the amount of the catalyst is 1-6 ppm based on the weight of PET) are uniformly mixed, added into a reaction kettle and subjected to esterification reaction for 2 hours at 250 ℃ and under the pressure of not more than 0.3 MPa. After the esterification reaction is finished, vacuumizing until the pressure is lower than 100Pa, and reacting for a certain time at 280 ℃ to obtain the polyester chip. The corresponding product performance index is shown in table 1.
TABLE 1
As is clear from the data in the table, the viscosity, melting point and diethylene glycol index of examples 7 are all normal, L value is 85 or more, and b value is within 6. Comparative examples 1 to 5 viscosity, melting point and diethylene glycol content, several examples other than comparative example 4 were significantly different from the examples. In comparative example 1, in the case of no germanium, the activity of the titanium catalyst alone is higher, the reaction rate is faster, although the side reaction is inhibited under the coordination of the complexing agent, the side reaction is still more obvious, so the value L is lower, and the value b is higher, in the same case, we can also find in comparative examples 2 and 3, in comparative example 2, because the homogeneous tetrabutyl titanate is added, the synergistic effect with the heterogeneous germanium oxide can not be generated, and no complexing agent is added, the value b is higher, in contrast, in comparative example 3, the hue is slightly better, but the ratio of germanium is too low, and the values L and b are still different compared with the examples. Comparative example 4 the germanium content is higher than the ratio of titanium and germanium in the patent, the overall hue is better, but the catalyst activity is lower, the reaction time is longer, and the preparation cost is higher. In comparative example 5, the titanium activity was suppressed slightly by adding a small amount of the complexing agent, and the side reaction was still slightly more severe than in the examples, although the synergistic effect between titanium and germanium existed, so that the hue was not good.
From the above, the invention has strict limitations on the compounding method of the titanium germanium element and various process parameters, and better effects can be obtained by not compounding arbitrarily, selecting reagents and selecting process parameters.
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 (8)
1. A titanium germanium composite catalyst for polyester synthesis is characterized in that the preparation method comprises the following steps:
1) mixing titanium dioxide sol and germanium dioxide sol, dropwise adding the obtained mixed sol into a complexing agent aqueous solution, and stirring; the molar ratio of the titanium element to the germanium element is 1-10: 1; the concentration of the complexing agent aqueous solution is 0.05-1 mol/L, and the molar ratio of the titanium element to the complexing agent is 0.05-1: 1;
2) centrifuging the stirred mixed sol, taking the precipitate, washing to remove chloride ions, and drying to obtain the titanium-germanium composite catalyst;
wherein the content of the first and second substances,
the preparation method of the titanium dioxide sol comprises the following steps: dropwise adding a titanium compound into a hydrochloric acid aqueous solution at room temperature, and continuously stirring for 1-6 hours after dropwise adding to obtain titanium dioxide sol; the molar ratio of the titanium compound to the hydrochloric acid is 1-10: 1;
the preparation method of the germanium dioxide sol comprises the following steps: under the condition of room temperature, dropwise adding germanium chloride into deionized water, and continuously stirring for 12-24 hours after dropwise adding to obtain germanium dioxide sol; the molar ratio of the germanium chloride to the deionized water is 0.01-0.5: 1.
2. The titanium-germanium composite catalyst for polyester synthesis according to claim 1, wherein the step 1) is performed at room temperature, and the stirring treatment is performed for 0.5-5 hours.
3. The titanium germanium composite catalyst for polyester synthesis according to claim 1, wherein said titanium compound is at least one of alkoxy titanium, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate and tetraisooctyl titanate.
4. The titanium-germanium composite catalyst for polyester synthesis according to claim 1, wherein the concentration of the hydrochloric acid aqueous solution is 0.05-1 mol/L.
5. The titanium germanium composite catalyst for polyester synthesis according to claim 1, wherein the complexing agent is at least one of citric acid, lactic acid, tartaric acid, malic acid, α -pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylhexalactam, N-ethylcaprolactam, -caprolactam and 3-amino-2-caprolactam.
6. The titanium-germanium composite catalyst for polyester synthesis according to claim 1, wherein in the step 2), the drying is vacuum drying at a temperature of 60-100 ℃.
7. Use of a titanium germanium composite catalyst according to any one of claims 1 to 6 in polyester synthesis, characterized in that it comprises the following steps: carrying out esterification reaction on dicarboxylic acid and/or ester-forming derivatives thereof and dihydric alcohol at 230-260 ℃, wherein the pressure is not more than 0.3MPa, and the reaction time is 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 titanium germanium composite catalyst is added before esterification or before polycondensation after esterification, and the dosage is 0.5-10 ppm calculated by polyester.
8. The use of claim 7, wherein: the dicarboxylic acid and the ester-forming derivative of the dicarboxylic acid are at least one of terephthalic acid, phthalic acid, isophthalic acid, diphenic acid, oxalic acid, succinic acid, adipic acid, dimethyl terephthalate and diethyl terephthalate; the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol and hexanediol; the dosage of the titanium germanium composite catalyst is 1-6 ppm calculated by polyester.
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