CN114075330A - Aluminum polyester catalyst and preparation method and application thereof - Google Patents
Aluminum polyester catalyst and preparation method and application thereof Download PDFInfo
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- CN114075330A CN114075330A CN202010809964.6A CN202010809964A CN114075330A CN 114075330 A CN114075330 A CN 114075330A CN 202010809964 A CN202010809964 A CN 202010809964A CN 114075330 A CN114075330 A CN 114075330A
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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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, 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
- C08G63/02—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses an aluminum polyester catalyst and a preparation method and application thereof, wherein the catalyst comprises the following components in parts by weight: a reaction product of an aluminum compound of a diol and an organophosphorus compound, further comprising a diol B; wherein the aluminum compound of the dihydric alcohol is a reaction product of an aluminum compound and dihydric alcohol A. The catalyst of the invention better solves the problems of poor solubility and low activity of the aluminum alcohol compound catalyst in dihydric alcohol. The catalyst has good solubility in dihydric alcohol, high catalytic activity and excellent hue of the produced polyester. The synthesized PET can be used for producing fibers, films, bottle flakes and other fields and can be made into various subsequent PET products.
Description
Technical Field
The invention belongs to the field of polyester catalysts, and particularly relates to an aluminum polyester catalyst, and a preparation method and application thereof.
Background
Thermoplastic polyesters are linear polymers prepared from saturated dibasic acids and dihydric alcohols by polycondensation. Various thermoplastic polyesters can be synthesized according to the difference between dibasic acid and dihydric alcohol. The varieties which are applied to industrial production at present mainly comprise: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polytrimethylene terephthalate (PTT), and the like. Among the several varieties, the most widely used are PET and PBT, especially PET. Because PET has many excellent physical, chemical, and mechanical properties, it is widely used in the fields of containers, packaging materials, films, bottles, films, plastics, and the like.
In the process of synthesizing PET, the catalyst not only has an influence on the reaction rate of esterification and polymerization, but also has an influence on side reactions, reaction selectivity and product performance in the synthesis process. The catalysts used in the polycondensation reaction are of various types, and mainly include antimony-based, germanium-based, titanium-based, and tin-based catalysts. The antimony catalyst is most widely applied, and at present, more than 90 percent of PET factories still use the antimony catalyst. The main variety of the antimony-based catalyst is Sb2O3And Sb (Ac)3Moderate activity and less side reaction. However, the antimony catalyst contains heavy metals which cause environmental pollution, and the polyester product is grey. The germanium catalyst has good stability, causes less side reactions in the reaction process, and the prepared polyester has good color phase, but because of rare resources and high price, the germanium catalyst is only used for synthesizing high-quality polyester generally. The development of novel efficient, nontoxic and pollution-free polyester catalysts is an important part of the technological progress of polyester production, and the research on the polyester catalysts mainly focuses on the development of novel catalysts which are environment-friendly, nontoxic and more efficient. Downstream manufacturers are very interested in using polyester products that do not contain antimony catalysts or heavy metal catalysts. Several companies have developed catalyst systems containing titanium, aluminum, rare earth elements, silicon, zirconium, hafnium metals, and mixtures thereof.
Most of the traditional titanium catalysts are organic compounds of titanium, which are easy to hydrolyze, and have more side reaction products, so that the color of polyester products is poor. Although the titanium catalyst has inherent defects, the titanium catalyst has strong catalytic activity and no harm to biological environment, is an environment-friendly catalyst and is favored by people.
The aluminum catalyst is another novel environment-friendly non-heavy metal PET catalyst, and does not contain heavy metals such as antimony and the like, so that the waste treatment is simple, and the environment is protected; the synthesized polyester has the characteristics of good color phase, less side reaction and the like; meanwhile, the raw materials are easy to obtain and the price is low. The prior polyester polycondensation aluminum catalyst literature only describes that certain aluminum compound or aluminum compound and other metal compounds are used as polyester catalysts, and the catalytic activity and the catalytic speed are still not ideal. For example, patent CN101962437A discloses a method for preparing polyester by using aluminum chelate compound, and the prepared pure aluminum glycol solution has insignificant promoting esterification, and the polycondensation activity and speed are not ideal, so it is not suitable for industrial polyester production equipment. Patent CN102558527A discloses a method for preparing water-soluble polyester by using aluminum compound, which has defects in catalyst performance when preparing conventional PET because a third monomer and a fourth monomer are also used in the synthesis process. Patent CN102234370A discloses a method for preparing polyester by using ethylene glycol aluminum as polycondensation catalyst, the preparation process of the catalyst solution is complicated, the solubility of the compound in glycol is poor, the feeding is inconvenient during polycondensation, and the color of polyester is affected to a certain extent.
In order to improve the solubility of the aluminum catalyst and improve the catalytic activity, the key is to control the side reaction in the condensation polymerization process by adjusting the structure of the catalyst.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention starts from the design of the structure of the catalyst, and improves the solubility of the aluminum catalyst in the dihydric alcohol, the polymerization reaction activity and the polyester product performance by optimizing the aluminum compound synthesis method of the dihydric alcohol and introducing the phosphoric acid compound to form the three-component catalyst of the aluminum alkoxide compound, the phosphoric acid compound and the alcohol.
An object of the present invention is to provide an aluminum-based polyester catalyst, which comprises: a reaction product of an aluminum compound of a glycol and an organophosphorus compound.
In a preferred embodiment, the aluminum compound of the diol is the reaction product of an aluminum compound and diol a.
In a further preferred embodiment, the aluminum compound is reacted with the diol A at a temperature of 70 to 150 ℃, preferably 80 to 120 ℃.
In a further preferred embodiment, the aluminium compound of the diol is prepared under a protective atmosphere, preferably under nitrogen and/or argon.
Preferably under high purity argon, with a purity of 99.999%.
In a preferred embodiment, the aluminum compound is an aluminum hydride compound, preferably selected from alkali metal alanates and/or alkaline earth metal alanates.
In a further preferred embodiment:
the alkali metal alanate is selected from lithium aluminum hydride LiAlH4Lithium aluminum hexahydroxide Li3AlH6Sodium aluminum hydride, NaAlH4Sodium aluminum hexahydrogen Na3AlH6Potassium aluminum tetrahydride KAlH4At least one of; and/or
The alkaline earth metal alanates are selected from magnesium tetrahydroaluminate Mg (AlH)4)2Calcium magnesium aluminum tetrahydride Ca (AlH)4)2Strontium aluminum hydride SrAl2H2、Sr2AlH, barium alanate BaAlH5And Ba2AlH7At least one of (1).
In a preferred embodiment, the molar ratio of the aluminum compound to the diol A in the preparation of the aluminum compound of the diol is 1 (5-50), preferably 1 (10-40).
Taking glycol as an example, in the prior art, aluminum oxide, aluminum isopropoxide or aluminum hydroxide is mostly adopted to react with ethylene glycol to prepare aluminum glycol, but the aluminum oxide, aluminum isopropoxide or aluminum hydroxide is difficult to dissolve in ethylene glycol, but the temperature required for treatment is very high, which causes great energy consumption, and the obtained reaction system is inhomogeneous, which can seriously affect the hue of polyester at a later stage. For example, the prior art relates to the use of aluminum isopropoxide or aluminum acetate and ethylene glycol at 90 ℃ mixed solution, the inventor also according to the method of experiment, however, under this condition is not obtained clear transparent solution, although the prior patent describes that the solution, but actually does not obtain a homogeneous solution, but obtain white slurry or aluminum compounds in the form of clusters in ethylene glycol, the heterogeneous catalyst polymerization of polyester, there are a large amount of yellow particles in the polyester product, b value is high, the color difference.
However, the inventors have surprisingly found that (also taking glycol as an example) when the aluminum glycol is prepared by using an aluminum hydride compound and ethylene glycol as raw materials, the aluminum glycol does not need too high temperature (at 70-150 ℃, preferably 80-120 ℃) during preparation, and the aluminum hydride compound can be well dissolved in the ethylene glycol, so as to obtain a uniform reaction system. The method has the characteristics of simplicity and high efficiency, and is characterized in that a uniform reaction system can be obtained, so that the b value of the polyester can be reduced when the method is applied at the later stage.
In a preferred embodiment, the organophosphorus compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, triethyl phosphite, n-butyl phosphate, isopropyl phosphate, triphenyl phosphate, phenylphosphoric acid, ethyldiphenyl phosphate, polysulfonyl phenylphosphonate, 4-hydroxyphenyl phenylphosphonate, 2,4, 6-trimethylbenzoylphenylphosphonic acid, diisopropyl 2-aminophenylphosphonate, dibutyl 2-hydroxyphenyl phosphonate, dioctylphenyl phosphate and pentafluorophenyl diphenyl phosphate.
In a further preferred embodiment, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphite, and triphenyl phosphate.
In a preferred embodiment, the aluminum compound of the dihydric alcohol is reacted with the organic phosphorus compound at 70 to 150 ℃.
In a further preferred embodiment, the aluminum compound of the diol is reacted with the organic phosphorus compound at 80 to 120 ℃.
Through a large number of experiments, the inventor finds that if the aluminum compound of the dihydric alcohol and the organophosphorus compound are reacted for a period of time at a high temperature (at 70-150 ℃, preferably 80-120 ℃) (not directly mixed at room temperature), a homogeneous solution is obtained, and compared with direct mixing, the catalyst obtained by the method provided by the invention is used for preparing polyester, the obtained polyester has more excellent hue, and the specific value is lower b value.
In a preferred embodiment, the molar ratio of the aluminum compound to the organic phosphorus compound in the diol is 1 (0.01 to 10), preferably 1 (0.1 to 4), and more preferably 1 (1 to 4).
In a preferred embodiment, the aluminum-based polyester catalyst further comprises a diol B.
In a further preferred embodiment, the molar ratio of the aluminum compound of the diol to the diol B in the catalyst is 1 (10 to 300).
In a further preferred embodiment, the molar ratio of the aluminum compound of the diol to the diol B in the catalyst is 1 (20 to 200), preferably 1 (30 to 100).
In a preferred embodiment, the diols a and B are selected from at least one of ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol.
In a further preferred embodiment, the diol a is the same as the diol B.
In a still further preferred embodiment, both glycol a and glycol B are selected from ethylene glycol.
Wherein, the selection of the dihydric alcohol can be determined according to the polyester reaction which needs to be applied subsequently, such as: if the subsequent polyester is made from glycol, the glycol A and the glycol B are more suitable to be selected from glycol; for example: if the subsequent polyester is made from propylene glycol, the diol A and the diol B are preferably selected from propylene glycol, and so on.
The second purpose of the present invention is to provide a method for preparing the aluminum-based polyester catalyst, which comprises the following steps:
step 1, mixing an aluminum compound with dihydric alcohol A for reaction, and carrying out post-treatment to obtain the aluminum compound of the dihydric alcohol;
and 2, mixing the aluminum compound of the dihydric alcohol, the organic phosphorus compound and the dihydric alcohol B obtained in the step 1, and reacting to obtain the aluminum polyester catalyst.
In a preferred embodiment, in the step 1, the molar ratio of the aluminum compound to the diol A is 1 (5-50), preferably 1 (10-40).
In a preferred embodiment, in step 1, the aluminum compound and the diol A are reacted at 70-150 ℃ for 1 hour or more, preferably 80-120 ℃ for 1-5 hours.
In a further preferred embodiment, step 1 is carried out under a protective atmosphere, preferably under nitrogen and/or argon.
In a preferred embodiment, the aluminum compound is an aluminum hydride compound, preferably selected from alkali metal alanates and/or alkaline earth metal alanates.
In a further preferred embodiment:
the alkali metal alanate is selected from lithium aluminum hydride LiAlH4Lithium aluminum hexahydroxide Li3AlH6Sodium aluminum hydride, NaAlH4Sodium aluminum hexahydrogen Na3AlH6Potassium aluminum tetrahydride KAlH4At least one of; and/or
The alkaline earth metal alanates are selected from magnesium tetrahydroaluminate Mg (AlH)4)2Calcium magnesium aluminum tetrahydride Ca (AlH)4)2Strontium aluminum hydride SrAl2H2、Sr2AlH, barium alanate BaAlH5And Ba2AlH7At least one of (1).
In a preferred embodiment, the organophosphorus compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, triethyl phosphite, n-butyl phosphate, isopropyl phosphate, triphenyl phosphate, phenylphosphoric acid, ethyldiphenyl phosphate, polysulfonyl phenylphosphonate, 4-hydroxyphenyl phenylphosphonate, 2,4, 6-trimethylbenzoylphenylphosphonic acid, diisopropyl 2-aminophenylphosphonate, dibutyl 2-hydroxyphenyl phosphonate, dioctylphenyl phosphate and pentafluorophenyl diphenyl phosphate.
In a further preferred embodiment, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphite, and triphenyl phosphate.
In a preferred embodiment, in the step 2, the molar ratio of the aluminum compound and the organophosphorus compound of the diol is 1 (0.01-10), preferably 1 (0.1-4), and more preferably 1 (1-4).
In a preferred embodiment, in step 2, the aluminum compound of the diol and the organic phosphorus compound are reacted at 70 to 150 ℃ for 1 hour or more, preferably 80 to 120 ℃ for 2 to 6 hours.
In a preferred embodiment, in the step 2, the molar ratio of the aluminum compound of the diol to the diol B is 1 (10-300), preferably 1 (20-200), and more preferably 1 (30-100).
In a preferred embodiment, in step 2, the diol a and the diol B are selected from at least one of ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; preferably, diol a is the same as diol B; more preferably, the diols a and B are both selected from ethylene glycol.
In a preferred embodiment, in step 1, the post-treatment comprises distillation, filtration, washing and drying.
In a further preferred embodiment, the distillation is a vacuum distillation, and the drying is performed at 80 to 200 ℃ for 8 to 24 hours.
Among them, grinding is preferably performed after drying.
The third object of the present invention is to provide the use of the aluminum-based polyester catalyst of the first object of the present invention or the aluminum-based polyester catalyst obtained by the second preparation method of the first object of the present invention in the preparation of polyester, especially in the preparation of PET polyester.
The fourth purpose of the invention is to provide a preparation method of polyester, which comprises the following steps: in the presence of the aluminum polyester catalyst of the first purpose or the aluminum polyester catalyst obtained by the preparation method of the second purpose, dibasic acid and dihydric alcohol C are used as raw materials to react to obtain the polyester; preferably, the dihydric alcohol C is the same as the dihydric alcohol A and the dihydric alcohol B; and/or the dibasic acid is selected from terephthalic acid and/or naphthalene dicarboxylic acid.
Most preferably, the dihydric alcohol C, the dihydric alcohol A and the dihydric alcohol B are all ethylene glycol, and the dibasic acid is terephthalic acid, so as to prepare the PET polyester.
The synthesized PET can be used for producing fibers, films, bottle flakes and other fields and can be made into various subsequent PET products.
In a preferred embodiment, the esterification reaction is carried out at 210 to 270 ℃ and 0.1 to 0.3MPa, and the polymerization reaction is carried out at a reduced pressure and a temperature of 275 to 285 ℃ and a pressure of less than 100 Pa.
In a preferred embodiment, the catalyst is used in an amount of 10 to 300ppm based on the weight of the polyester, wherein the catalyst is used in an amount of Al element.
Wherein the weight of the polyester is theoretical polyester weight calculated based on raw materials before reaction, and is obtained as follows: the diacid is reacted with the diol 1:1 and the weight of water removed is removed.
In the above technical scheme, the application is not particularly limited, and those skilled in the art can apply the catalyst composition according to the existing technical conditions, for example, but not limited to, the application of the catalyst composition in the preparation of polyester.
Compared with the prior art, the invention has the following beneficial effects:
(1) the aluminum polyester catalyst does not contain antimony compounds or germanium compounds, so that the environmental pollution can be reduced, and the environment is protected;
(2) the invention preferably adopts the reaction of the aluminum hydride and the dihydric alcohol to prepare the aluminum alkoxide, the reaction temperature is lower, the reaction time is short, and the preparation is convenient;
(3) the liquid polyester polycondensation catalyst is prepared through the three-component reaction of the aluminum alkoxide compound, the phosphoric acid compound and the dihydric alcohol, so that the feeding operation of the catalyst in the esterification or polycondensation stage is facilitated;
(4) the catalyst of the invention better solves the problems of poor solubility and low activity of the aluminum alcohol compound catalyst in dihydric alcohol;
(5) the catalyst of the invention has good solubility in dihydric alcohol and high catalytic activity, can obviously reduce the byproducts of the reaction, and the produced polyester has good hue.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
In the present invention, the intrinsic viscosity, hue, etc. of the polyester are measured by the following methods:
(1) intrinsic viscosity: the phenol-tetrachloroethane mixture is used as a solvent, and is measured by an Ubbelohde viscometer at the temperature of 25 ℃.
(2) Hue: the pellet samples were treated at 135 ℃ for 1 hour and measured for Hunter L value (lightness), a value (red-green hue) and b value (yellow-blue hue) using a color-view automatic color difference meter from BYK Gardner. Wherein, the higher the L value, the larger the brightness; when the value of b is high, the polyester chip is yellowish. For the present invention, a high L value and a low b value are desired.
[ example 1 ]
Preparation of the catalyst:
62 g (1 mol) of ethylene glycol was added to a reactor equipped with a stirrer, a condenser and a thermometer, and after introducing argon gas into the reactor, 100 ml of 1 mol/l lithium aluminum hydride was slowly droppedLiAlH4Toluene solution, at 100 ℃ for 2 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance was placed in a reactor equipped with a stirrer, a condenser and a thermometer, 14 g (0.1 mol) of trimethyl phosphate and 200 g of ethylene glycol were added, and reacted at a reaction temperature of 100 ℃ for 3 hours until the system became a homogeneous liquid, to obtain catalyst a.
Preparation of polyester:
600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst A (based on the amount of the polyester produced, the weight of titanium atoms is 30ppm) are mixed into slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the reaction pressure is 0.25MPa, and water produced by the reaction is discharged through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The intrinsic viscosity of the polyester chip was 0.83, and the hue was L89.6 and b 4.7.
[ example 2 ]
Preparation of the catalyst:
62 g (1 mol) of ethylene glycol was added to a reactor equipped with a stirrer, a condenser and a thermometer, and after introducing argon gas into the reactor, 100 ml of 1 mol/l lithium aluminum hydride LiAlH was slowly dropped4Toluene solution, at 100 ℃ for 2 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance is placed in a reactor with a stirrer, a condenser and a thermometer, 32.6 g (0.1 mol) of triphenyl phosphate and 200 g of ethylene glycol are added, and the mixture reacts for 3.5 hours at the reaction temperature of 120 ℃ until the system becomes homogeneous liquid, thus obtaining the catalystB。
Preparation of polyester:
600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst B (based on the amount of the polyester produced, the weight of titanium atoms is 30ppm) are mixed into slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the reaction pressure is 0.25MPa, and water produced by the reaction is discharged through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The intrinsic viscosity of the polyester chip was 0.85, and the hue L88.7 and b4.3 were obtained.
[ example 3 ]
Preparation of the catalyst:
62 g (1 mol) of ethylene glycol was added to a reactor equipped with a stirrer, a condenser and a thermometer, and after introducing argon gas into the reactor, 100 ml of 1 mol/l sodium aluminum hydride NaAlH as a tetrahydrofuran was slowly added dropwise4Toluene solution, at 110 ℃ for 2 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance was put into a reactor equipped with a stirrer, a condenser and a thermometer, and 32.6 g (0.1 mol) of triphenyl phosphate and 200 g of ethylene glycol were added, and reacted at a reaction temperature of 120 ℃ for 3.5 hours until the system became a homogeneous liquid, to obtain catalyst C.
Preparation of polyester:
600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst C (based on the amount of the polyester produced, the weight of titanium atoms is 30ppm) are mixed into slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the reaction pressure is 0.25MPa, and water produced by the reaction is discharged through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The intrinsic viscosity of the polyester chip was 0.82, and the hue was L88.7 and b 4.4.
[ example 4 ]
Preparation of the catalyst:
62 g (1 mol) of ethylene glycol was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and after introducing argon gas into the reactor, 100 ml of 1 mol/l potassium aluminum hydride KAlH (tetrahydroaluminum potassium) was slowly dropped4Toluene solution, at 120 ℃ for 2 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance was put into a reactor equipped with a stirrer, a condenser and a thermometer, and 32.6 g (0.1 mol) of triphenyl phosphate and 200 g of ethylene glycol were added, and reacted at a reaction temperature of 100 ℃ for 4 hours until the system became a homogeneous liquid, to obtain catalyst D.
Preparation of polyester:
600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst D (based on the amount of the polyester produced, the weight of titanium atoms is 30ppm) are mixed into slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the reaction pressure is 0.25MPa, and water produced by the reaction is discharged through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The intrinsic viscosity of the polyester chip was 0.85, and the hue L87.9 and b5.1 were obtained.
[ example 5 ]
Preparation of the catalyst:
62 g (1 mol) of ethylene glycol was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and after introducing argon gas into the reactor, 50 ml of 1 mol/l magnesium aluminum tetrahydride Mg (AlH) was slowly added dropwise4)2Toluene solution, at 120 ℃ for 4 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance was placed in a reactor equipped with a stirrer, a condenser and a thermometer, 28 g (0.2 mol) of trimethyl phosphate and 200 g of ethylene glycol were added, and reacted at a reaction temperature of 120 ℃ for 3 hours until the system became a homogeneous liquid, to obtain catalyst E.
Preparation of polyester:
600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst E (based on the amount of the polyester produced, the weight of titanium atoms is 30ppm) are mixed into slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the reaction pressure is 0.25MPa, and water produced by the reaction is discharged through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The intrinsic viscosity of the polyester chip was 0.81, and the hue was L88.9 and b 4.0.
[ example 6 ]
Preparation of the catalyst:
adding 4 mol of ethylene glycol into a reactor provided with a stirrer, a condenser and a thermometer, introducing argon into the reactor, and slowly dripping 100 ml of 1 mol/L strontium aluminum hydride SrAl2H2Toluene solution, at 80 ℃ for 5 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. Grinding the white powderPlacing the powder into a reactor with a stirrer, a condenser and a thermometer, adding 1 mol of n-butyl phosphate and 10mol of ethylene glycol, and reacting at the reaction temperature of 80 ℃ for 6 hours until the system becomes homogeneous liquid to obtain the catalyst.
Preparation of polyester:
mixing 600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst (based on the amount of the generated polyester, the weight of titanium atoms is 10ppm) to form slurry, adding the slurry into a polymerization kettle, carrying out esterification reaction at the esterification temperature of 240-265 ℃ and the reaction pressure of 0.3MPa, and discharging water generated in the reaction through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 285 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing. The products obtained likewise have a good hue and a high intrinsic viscosity.
[ example 7 ]
Preparation of the catalyst:
0.5 mol of ethylene glycol is added into a reactor provided with a stirrer, a condenser and a thermometer, 100 ml of 1 mol/L magnesium calcium tetrahydroaluminate Ca (AlH) is slowly dropped into the reactor after argon is introduced into the reactor4)2Toluene solution, at 70 ℃ for 1 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. And (3) placing the ground white powdery substance into a reactor with a stirrer, a condenser and a thermometer, adding 0.3 mol of triethyl phosphite and 20mol of ethylene glycol, and reacting at the reaction temperature of 70 ℃ for 2 hours until the system becomes homogeneous liquid to obtain the catalyst.
Preparation of polyester:
mixing 600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst (based on the amount of the generated polyester, the weight of titanium atoms is 50ppm) to form slurry, adding the slurry into a polymerization kettle, carrying out esterification reaction at the esterification temperature of 220-245 ℃ and the reaction pressure of 0.1MPa, and discharging water generated in the reaction through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 275 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The products obtained likewise have a good hue and a high intrinsic viscosity.
[ example 8 ]
Preparation of the catalyst:
5 mol of ethylene glycol is added into a reactor provided with a stirrer, a condenser and a thermometer, 100 ml of 1 mol/L sodium hexahydroaluminum Na is slowly dropped into the reactor after argon is introduced into the reactor3AlH6Toluene solution, at 150 ℃ for 1 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. Putting the ground white powdery substance into a reactor with a stirrer, a condenser and a thermometer, adding 0.2 mol of ethyl diphenyl phosphate and 2mol of ethylene glycol, and reacting at the reaction temperature of 150 ℃ for 2 hours until the system becomes homogeneous liquid to obtain the catalyst.
Preparation of polyester:
mixing 600 g of terephthalic acid, 300 g of ethylene glycol and a catalyst (based on the amount of the generated polyester, the weight of titanium atoms is 80ppm) to form slurry, adding the slurry into a polymerization kettle, carrying out esterification reaction at the esterification temperature of 210-235 ℃ and the reaction pressure of 0.2MPa, and discharging water generated in the reaction through a rectifying device. And finishing the esterification when the water yield of the esterification reaches 95 percent of theoretical water yield. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the pressure of a reaction system is lower than 100Pa, gradually increasing the reaction temperature to 275 ℃, stopping the reaction when the reaction of the system reaches 150 minutes, continuously extruding a reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing. The products obtained likewise have a good hue and a high intrinsic viscosity.
[ COMPARATIVE EXAMPLE 1 ]
Aluminum ethylene glycol as a catalyst (30 ppm by weight of aluminum atom based on the amount of polyester produced) was prepared by the same method as in example 1. A polyester was produced in the same manner as in example 1, and the intrinsic viscosity of the polyester chip thus produced was 0.74, and the hues L87.9 and b 6.6.
[ COMPARATIVE EXAMPLE 2 ]
Aluminum glycolate was prepared by the same method as in example 1, and a room-temperature mixture (molar ratio 1:1:10) of the prepared aluminum glycolate with trimethyl phosphate and ethylene glycol was used as a catalyst (weight of aluminum atom was 30ppm based on the amount of polyester produced). A polyester was produced in the same manner as in example 1, and the intrinsic viscosity of the polyester chip thus produced was 0.73, and the color thereof was 88.49, b 5.8.
[ COMPARATIVE EXAMPLE 3 ]
62 g (1 mol) of ethylene glycol was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and 20.4 g (0.1 mol) of aluminum isopropoxide was charged into the reactor and reacted at 100 ℃ for 2 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 14 g (0.1 mol) of trimethyl phosphate and 200 g of ethylene glycol were added to react at a reaction temperature of 100 ℃ for 3 hours to obtain catalyst F.
A polyester was produced in the same manner as in example 1, using a catalyst F catalyst (30 ppm by weight of aluminum atom based on the amount of the polyester produced). The intrinsic viscosity of the polyester chip was 0.76, and the hue was L88.1 and b 6.2.
[ COMPARATIVE EXAMPLE 4 ]
The procedure of example 1 was repeated except that: replacement of lithium aluminum tetrahydride LiAlH with equal amounts of aluminum isopropoxide4Other conditions were unchanged.
62 g (1 mol) of ethylene glycol was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and 7.8 g (0.1 mol) of aluminum isopropoxide was charged into the reactor and reacted at 100 ℃ for 2 hours. The solution was distilled off under reduced pressure, filtered, and the residue was washed 3 times with distilled water. Vacuum drying the product at 80 deg.C, grinding the dried block solid to powder of less than or equal to 120 meshes. The ground white powdery substance was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 14G (0.1 mol) of trimethyl phosphate and 200G of ethylene glycol were added to react at a reaction temperature of 100 ℃ for 3 hours to obtain catalyst G.
A polyester was produced in the same manner as in example 1, using a catalyst G (30 ppm by weight of aluminum atom based on the amount of the polyester produced). The intrinsic viscosity of the polyester chip was 0.67, and the hue was L87.8 and b 7.3.
Claims (16)
1. An aluminum-based polyester catalyst comprising: a reaction product of an aluminum compound of a glycol and an organophosphorus compound.
2. The aluminum-based polyester catalyst according to claim 1, wherein the aluminum compound of the diol is a reaction product of an aluminum compound and a diol a; preferably, the aluminum compound is reacted with the diol A at 70 to 150 ℃, preferably at 80 to 120 ℃.
3. The aluminum-based polyester catalyst according to claim 2, wherein the aluminum compound of the diol is prepared under a protective atmosphere, preferably under nitrogen and/or argon.
4. The aluminum-based polyester catalyst of claim 2, wherein the aluminum compound is an aluminum hydride compound, preferably selected from alkali metal alanates and/or alkaline earth metal alanates; preferably, the first and second electrodes are formed of a metal,
the alkali metal alanate is selected from LiAlH4、Li3AlH6、NaAlH4、Na3AlH6、KAlH4At least one of; and/or
The alkaline earth metal alanates are selected from Mg (AlH)4)2、Ca(AlH4)2、SrAl2H2、Sr2AlH、BaAlH5And Ba2AlH7At least one of (1).
5. The aluminum-based polyester catalyst according to claim 2, wherein the molar ratio of the aluminum compound to the diol A is 1 (5-50), preferably 1 (10-40), when the aluminum compound of the diol is prepared.
6. The aluminum-based polyester catalyst according to claim 1, wherein the organic phosphorus compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, triethyl phosphite, n-butyl phosphate, isopropyl phosphate, triphenyl phosphate, phenylphosphoric acid, ethyldiphenyl phosphate, polyphenylphosphonic acid disulfone ester, phenylphosphonic acid 4-hydroxyphenyl ester, 2,4, 6-trimethylbenzoylphenylphosphonic acid, 2-aminophenylphosphonic acid diisopropyl ester, dibutyl 2-hydroxyphenyl phosphonate, dioctylphenyl phosphate and pentafluorophenyl diphenyl phosphate.
7. The aluminum-based polyester catalyst according to claim 1, wherein the aluminum compound of the diol is reacted with the organic phosphorus compound at 70 to 150 ℃, preferably 80 to 120 ℃.
8. The aluminum-based polyester catalyst according to any one of claims 1 to 7, wherein the molar ratio of the aluminum compound to the organic phosphorus compound in the diol is 1 (0.01 to 10), preferably 1 (0.1 to 4).
9. The aluminum polyester catalyst according to claim 8, further comprising a diol B, preferably, the molar ratio of the aluminum compound of the diol to the diol B in the catalyst is 1 (10-300), preferably 1 (20-200).
10. The aluminum-based polyester catalyst according to claim 9, wherein the diol a and the diol B are selected from at least one of ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; preferably, diol a is the same as diol B; more preferably, the diols a and B are both selected from ethylene glycol.
11. A method for preparing the aluminum-based polyester catalyst according to any one of claims 1 to 10, comprising the steps of:
step 1, mixing an aluminum compound with dihydric alcohol A for reaction, and carrying out post-treatment to obtain the aluminum compound of the dihydric alcohol;
and 2, mixing the aluminum compound of the dihydric alcohol, the organic phosphorus compound and the dihydric alcohol B obtained in the step 1, and reacting to obtain the aluminum polyester catalyst.
12. The production method according to claim 11, wherein, in step 1,
the molar ratio of the aluminum compound to the dihydric alcohol A is 1 (5-50), preferably 1 (10-40); and/or
Reacting the aluminum compound with the dihydric alcohol A at 70-150 ℃ for more than 1h, preferably at 80-120 ℃ for 1-5 h; and/or
Step 1 is carried out under a protective atmosphere, preferably under nitrogen and/or argon; and/or
The post-treatment in step 1 comprises distillation, filtration, washing and drying.
13. The production method according to claim 11 or 12, wherein, in step 2,
the molar ratio of the aluminum compound to the organic phosphorus compound of the dihydric alcohol is 1 (0.01-10), preferably 1 (0.1-4); and/or
Reacting an aluminum compound of dihydric alcohol with an organic phosphorus compound at 70-150 ℃ for more than 1h, preferably at 80-120 ℃ for 2-6 h; and/or
The molar ratio of the aluminum compound of the dihydric alcohol to the dihydric alcohol B is 1 (10-300), preferably 1 (20-200).
14. Use of the aluminum-based polyester catalyst according to any one of claims 1 to 10 or the aluminum-based polyester catalyst obtained by the production method according to any one of claims 11 to 13 for producing polyester, particularly for producing PET polyester.
15. A method of making a polyester comprising: reacting dibasic acid and dihydric alcohol C as raw materials in the presence of the aluminum polyester catalyst of any one of claims 1 to 10 or the aluminum polyester catalyst obtained by the preparation method of any one of claims 11 to 13 to obtain the polyester; preferably, the dihydric alcohol C is the same as the dihydric alcohol A and the dihydric alcohol B; and/or the dibasic acid is selected from terephthalic acid and/or naphthalene dicarboxylic acid.
16. The method for producing a polyester according to claim 15,
carrying out esterification reaction at the temperature of 210-270 ℃ and under the pressure of 0.1-0.3 MPa, and then gradually reducing the pressure and heating to 275-285 ℃ and carrying out polymerization reaction under the pressure of less than 100 Pa; and/or
The amount of the catalyst is 10-300 ppm based on the weight of the polyester, wherein the amount of the catalyst is calculated by the amount of Al element.
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| CN115521634A (en) * | 2022-10-15 | 2022-12-27 | 温州市和沐环保科技有限公司 | Regenerated flame-retardant plastic particle and processing technology thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005325163A (en) * | 2004-05-12 | 2005-11-24 | Toyobo Co Ltd | Polyester polymerization catalyst and polyester manufactured using the same, and manufacturing method of polyester |
| JP2006176572A (en) * | 2004-12-21 | 2006-07-06 | Toyobo Co Ltd | Polyester polymerization catalyst, polyester prepared by using the same and preparation method of the polyester |
| US20070106055A1 (en) * | 2004-02-10 | 2007-05-10 | Katsuhiko Kageyama | Polyester polymerization catalyst, polyester produced therewith and process for producing the polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070106055A1 (en) * | 2004-02-10 | 2007-05-10 | Katsuhiko Kageyama | Polyester polymerization catalyst, polyester produced therewith and process for producing the polyester |
| JP2005325163A (en) * | 2004-05-12 | 2005-11-24 | Toyobo Co Ltd | Polyester polymerization catalyst and polyester manufactured using the same, and manufacturing method of polyester |
| JP2006176572A (en) * | 2004-12-21 | 2006-07-06 | Toyobo Co Ltd | Polyester polymerization catalyst, polyester prepared by using the same and preparation method of the polyester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521634A (en) * | 2022-10-15 | 2022-12-27 | 温州市和沐环保科技有限公司 | Regenerated flame-retardant plastic particle and processing technology thereof |
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