CN112694604B - Preparation method of heterogeneous titanium polyester catalyst - Google Patents

Preparation method of heterogeneous titanium polyester catalyst Download PDF

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CN112694604B
CN112694604B CN202011550603.0A CN202011550603A CN112694604B CN 112694604 B CN112694604 B CN 112694604B CN 202011550603 A CN202011550603 A CN 202011550603A CN 112694604 B CN112694604 B CN 112694604B
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porous carrier
water
polyester
titanate
catalyst
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CN112694604A (en
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刘明明
王松林
王文
杜玮辰
孙妍妍
陈爽
刘雨
张含
易凡丰
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Zhejiang Hengyi Petrochemical Co ltd
Zhejiang Hengyi Petrochemical Research Institute Co Ltd
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Zhejiang Hengyi Petrochemical Co ltd
Zhejiang Hengyi Petrochemical Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Textile Engineering (AREA)
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Abstract

The invention relates to the technical field of polyester catalysts, and discloses a preparation method of a heterogeneous titanium polyester catalyst, which comprises the following steps: (1) after the porous carrier absorbs water, carrying out surface drying to obtain a water-carrying porous carrier; (2) dissolving titanate in an organic solvent to prepare titanate solution; (3) adding a water-carrying porous carrier into a titanate solution to hydrolyze titanate in pore channels of the porous carrier, and then separating out a product to obtain the heterogeneous titanium polyester catalyst. In the catalyst prepared by the method, titanium dioxide is attached in the pore channel of the porous carrier, and when the catalyst is used for catalyzing polyester synthesis, the obtained product has narrow molecular weight distribution range and good polyester spinning performance.

Description

Preparation method of heterogeneous titanium polyester catalyst
Technical Field
The invention relates to the technical field of polyester catalysts, in particular to a preparation method of a heterogeneous titanium polyester catalyst.
Background
Polyester (Polyester) is a general name for a class of high molecular polymers produced by esterification and polycondensation of a polyol and a polyacid. Common polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), Polyarylate (PAR), and the like. According to the application direction, the polyester can be divided into fiber polyester and non-fiber polyester. The fiber polyester is mainly used for manufacturing polyester filament yarns and staple yarns and then is supplied to corresponding fiber processing enterprises as a raw material; the non-fiber polyester is mainly used for manufacturing bottles and film products, and is widely applied to the automobile manufacturing industry, the packaging industry, the electrical appliance industry, the building industry and the like.
In order to increase the reaction rate and improve the production capacity, a catalyst needs to be added in the polyester production process, and antimony-based and titanium-based metal compounds are mainly used in the current production. With the increasing awareness of environmental protection, researchers are gradually turning their research into the preparation of non-heavy metal compounds. The heavy metal antimony has great pollution to the environment, and compared with antimony catalysts, titanium catalysts have the remarkable characteristics of small catalyst dosage and high catalysis rate, and the defect of color difference of polyester synthesized by the titanium catalysts is greatly improved. Therefore, the heavy metal polyester catalysts such as ethylene glycol antimony, antimony trioxide and the like are inevitably replaced, and with the continuous and deep exploration of researchers, more and more titanium catalysts are developed and applied to the catalytic preparation of polyester, and the titanium catalysts have quite excellent effect.
However, the titanium catalysts studied and prepared at present are mainly homogeneous catalysts, and have the defects of low effective concentration of the catalysts, difficult concentration, poor thermal stability and the like compared with heterogeneous catalysts. Therefore, the research on the heterogeneous titanium polyester catalyst has higher application value. Chinese patent document with application number CN201610162126.8 discloses a preparation method of a nano titanium rare earth composite catalyst and application thereof in polyester and copolyester synthesis, wherein the preparation method comprises the steps of reacting a nano carrier with a titanium compound in a solvent, and adding a hydrolytic agent in the reaction process to prepare a titanium dioxide-loaded nano particle solution; then adding chlorides, acetates or stearates selected from Nd, Dy, Sm, Ce, La and Y and from Na, Mg, Zn and Al, removing distillate after reaction, and preparing the product. In the prepared composite catalyst, titanium dioxide is loaded on a nano carrier, so that the defects of low effective concentration, difficult concentration, poor thermal stability and the like of the catalyst in a homogeneous catalyst can be overcome, but the polymerization degree cannot be controlled when the homogeneous catalyst or the composite catalyst prepared by the method is used for catalyzing polyester synthesis, and the polyester molecular weight distribution range in the obtained product is wide, so that the spinning performance is poor.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a heterogeneous titanium polyester catalyst. In the catalyst prepared by the method, titanium dioxide is attached in the pore canal of the porous carrier, and when the catalyst is used for catalyzing polyester synthesis, the obtained product has narrow molecular weight distribution range and good polyester spinning performance.
The specific technical scheme of the invention is as follows:
a preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) after the porous carrier absorbs water, carrying out surface drying to obtain a water-carrying porous carrier;
(2) dissolving titanate in an organic solvent to prepare titanate solution;
(3) adding a water-carrying porous carrier into a titanate solution to hydrolyze titanate in pore channels of the porous carrier, and then separating out a product to obtain the heterogeneous titanium polyester catalyst.
And (2) drying the surface of the water-carrying porous carrier prepared in the step (1), wherein the pore channels contain water. In step (3), the contact speed between the two phases can be retarded because the mass transfer in the pore channels is relatively slow, the reaction between the two phases will be determined by the diffusion time and the reaction time, and for the hydrolysis reaction of titanate in the aqueous phase, the diffusion time becomes the dominant factor of the reaction because of the short hydrolysis time. Based on the above reasons, after the water-carrying porous carrier is added into the titanate solution, the organic phase and the aqueous phase are mutually diffused in the pore channels to promote the titanate to contact with water on the surface of the pore channels and hydrolyze, and in the obtained composite catalyst, the titanium dioxide is attached in the pore channels of the porous carrier, and the titanium dioxide hardly exists outside the pore channels.
When the heterogeneous titanium polyester catalyst is used for catalyzing polyester synthesis, a polymerization monomer needs to enter a porous carrier pore channel to contact with titanium dioxide for catalysis, although the polycondensation time is prolonged to a certain extent, long-chain polyester cannot continuously enter the pore channel for reaction due to the function of pore channel screening, so that the molecular weight of a polymerization product is more concentrated, namely the polymerization reaction is more uniform, the spinning performance of the polyester is remarkably improved, and yarn breakage and yarn floating are not easy to occur during spinning. And when the polymerization reaction is finished, the polyester with large molecular weight exists in the pore channel of the heterogeneous catalyst, so that titanium dioxide is not easy to contact with other polyester molecular chains, and therefore, the polyester is not easy to degrade and the viscosity is reduced less in the melt conveying process.
Preferably, the specific process of step (1) is as follows: fully dispersing the porous carrier in water, pumping to-100 to-50 kPa at the speed of 10-1000 Pa/s, standing for 1-5 h to ensure that the water is fully immersed into the pore channel, recovering the porous carrier, and drying at the temperature of 60-90 ℃ for 1-4 h to obtain the water-carrying porous carrier.
In the process of water absorption of the porous carrier, because the pore diameter of the pore channel in the porous carrier is small, gas in the pore channel is difficult to discharge under the action of capillary effect, and water is difficult to wet and enter the pore channel, the invention adopts negative pressure water absorption, and destroys the pressure difference inside and outside the pore channel in the form of air exhaust, so that gas escapes to cause low pressure in the pore channel, and further water enters the pore channel.
In the drying process, because the pore channel in the porous carrier is narrow, the saturated vapor pressure of the pure substance in the pore channel is higher, and the boiling point is also higher, therefore, the moisture on the surface of the porous carrier can be removed and the moisture in the pore channel can be reserved by controlling the drying temperature.
Further, in the step (1), after the porous carrier is fully dispersed in the water, the mass fraction of the porous carrier is 1-30 wt%.
Preferably, the specific process of step (2) is as follows: adding titanate into an organic solvent, and continuously stirring for 30-120 min to obtain a titanate solution.
Further, in the step (2), the stirring speed is 50-1000 rpm.
Further, in the step (2), the titanate comprises one or more of tetrabutyl titanate, isopropyl titanate, tetramethyl titanate, tetraethyl titanate, and tetraisopropyl titanate.
Further, in the step (2), the organic solvent includes one or more of ethylene glycol, propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, isopropanol, n-butanol, n-pentanol, isobutanol, and n-hexanol.
Further, in the step (2), after the titanate is added to the organic solvent, the 2-hydroxycarboxylic acid compound and the phosphorus-containing compound are added thereto.
Further, in the step (2), the 2-hydroxycarboxylic acid compound includes one or more of citric acid, lactic acid and tartaric acid.
Further, in the step (2), the phosphorus-containing compound comprises at least one or more of trimethyl phosphate, triethyl phosphate, triphenyl phosphate and dipropyl phosphite.
In the step (2), the molar ratio of the 2-hydroxycarboxylic acid compound to the titanate is 0.05-20: 1, preferably 0.5-10: 1.
Further, in the step (2), the molar ratio of the phosphorus-containing compound to the titanate is 0.05-20: 1, and preferably 0.5-10: 1.
Preferably, the specific process of step (3) is as follows: under the condition of continuous stirring, adding a water-carrying porous carrier into the titanate solution, condensing and refluxing for 0.5-4 h at the temperature of 60-90 ℃, and then separating out a product to obtain the heterogeneous titanium polyester catalyst.
Further, in the step (3), the stirring speed is 100-2000 rpm.
Preferably, in the step (3), the specific process for separating the product is as follows: and (4) centrifugally separating, and drying the precipitate at 105-115 ℃ for 3-6 hours to obtain the heterogeneous titanium polyester catalyst.
Preferably, in the step (3), after the product is separated, the product is dispersed into ethylene glycol and ground for 1-3 hours to obtain the heterogeneous titanium polyester catalyst.
In the above process, the molecular collision between ethylene glycol and the product (i.e., the titanium dioxide/porous carrier composite) is accelerated by using the grinding effect, so that the ethylene glycol is adsorbed on the surface of the titanium dioxide/porous carrier composite through hydrogen bonds. The heterogeneous titanium polyester catalyst treated by the ethylene glycol can improve the dispersion stability of the catalyst in a polyester monomer, thereby improving the catalytic efficiency, improving the dispersion stability of the catalyst in a polyester melt and preventing the catalyst from precipitating to influence the spinning performance of the polyester.
Preferably, the porous support is one of porous alumina, a porous molecular sieve and porous silica.
Preferably, the porous support is porous alumina.
Compared with other porous materials, the heterogeneous catalyst obtained by using alumina as a porous carrier has higher catalytic activity because: the nano porous alumina has good affinity with water, can adsorb water in a pore channel more easily, has electropositive surface, and can adsorb titanate hydrolysis electronegative intermediates easily, so that the nano porous alumina is adopted as a carrier to be implemented more easily; in addition, the nano porous alumina has good catalytic activity, the electropositive surface is easy to adsorb polyester monomers, the contact between the polyester monomers and a catalyst in a pore channel is promoted, and after the titanium dioxide is coupled with the alumina, the electron transfer can be promoted, the activation energy is reduced, and the reaction rate is improved.
Preferably, the particle size of the porous carrier is 100 to 700 nm.
The reason for controlling the particle size of the porous carrier to be 100-700 nm is as follows: the porous carrier with too small particle size is difficult to prepare and expensive, and the strength after pore forming is greatly influenced; when catalyzing polyester synthesis, the porous carrier with overlarge particle size cannot be stably dispersed and is easy to precipitate, so that the catalysis efficiency is reduced, and the polymerization spinning process is influenced, such as the problems of component hole plugging, poor spinning threading condition and the like are caused.
Preferably, the pore diameter of the porous carrier is 1 to 50 nm.
The reason why the pore diameter of the porous carrier is controlled to be 1-50 nm is as follows: the porous carrier with the too small pore diameter is difficult to prepare, and even if the porous carrier is prepared, when water is absorbed in the step (1) due to the too small pore diameter, gas in a pore channel is difficult to discharge, water is difficult to wet and enter the pore channel, so that the water content in the obtained water-carrying porous carrier is too low, and further, the titanium dioxide content in the heterogeneous titanium polyester catalyst is too low, and the catalytic activity of the catalyst is influenced; if the pore diameter is too large, a large amount of moisture in the pore channel is lost before the surface of the porous carrier is sufficiently dried in the step (1), the moisture content in the water-carrying porous carrier is too low, and the too large pore diameter can cause rapid mass transfer of moisture in the air after the water-carrying porous carrier is added into a titanate solution, the titanate is hydrolyzed outside the pore to form titanium dioxide, and in the prepared catalyst, the molecular weight of polyester is difficult to control due to the titanium dioxide existing outside the pore channel.
Preferably, in the step (2), the mass fraction of titanate in the titanate solution is 0.5-5 wt%.
Preferably, in the step (3), the mass ratio of the titanate solution to the porous carrier is 1: 15-300 in terms of titanium.
Preferably, in the step (1), the water content in the water-carrying porous carrier is 0.1-1.5 wt%.
The invention controls the water content in the water-carrying porous carrier to be 0.1-1.5 wt%, because: when the water content in the water-carrying porous carrier is lower, the diffusion mass transfer is slow, the titanate hydrolysis is more uniform and sufficient, the titanium dioxide is more easily synthesized in the pore channel, and the uncontrolled polycondensation reaction caused by the hydrolysis of excessive titanate outside the pore channel can be avoided; however, when the water content is too low, the titanium dioxide loading in the catalyst becomes too low, resulting in low catalytic activity. The water content is controlled within a certain range, and the dosage of the titanate is adjusted based on the water content, so that the polycondensation reaction rate can be improved, and the molecular weight of the product can be well controlled.
Compared with the prior art, the invention has the following advantages:
(1) in the catalyst prepared by the method, titanium dioxide is attached in the pore canal of the porous carrier, and when the catalyst is used for catalyzing polyester synthesis, the obtained product has narrow molecular weight distribution range and good polyester spinning performance;
(2) after the titanium dioxide/porous carrier composite material is obtained, the titanium dioxide/porous carrier composite material is combined with ethylene glycol through grinding and then used for polyester synthesis, and the dispersion stability of the catalyst in a polyester monomer and a melt can be improved, so that the catalytic efficiency and the spinning performance of polyester are improved.
Detailed Description
The present invention will be further described with reference to the following examples.
Water absorption R of the porous Carrier in the following examples1I.e., the water content in the water-laden porous carrier, was tested as follows: before the absorption of water, the porous support is weighed and the mass is recorded as m1(ii) a After water absorption and surface drying, the water-carrying porous support is weighed and the mass is recorded as m2. The water absorption R is calculated according to the following formula1：
Figure BDA0002857814500000051
General examples
A preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) fully dispersing a porous carrier in water to ensure that the mass fraction of the porous carrier in the water is 1-30 wt%, pumping to-100 to-50 kPa at the speed of 10-1000 Pa/s, standing for 1-5 h to ensure that the water is fully immersed into a pore channel, then recovering the porous carrier, and drying at the temperature of 60-90 ℃ for 1-4 h to obtain a water-carrying porous carrier;
the porous carrier is one of porous alumina, a porous molecular sieve and porous silicon dioxide, and is preferably porous alumina; the particle size of the porous carrier is 100-700 nm, and the pore diameter is 1-50 nm;
(2) adding titanate into an organic solvent to ensure that the mass fraction of the titanate in the organic solvent is 0.5-5 wt%, adding a 2-hydroxycarboxylic acid compound and a phosphorus-containing compound, and continuously stirring at the speed of 50-1000 rpm for 30-120 min to obtain a titanate solution;
the titanate comprises one or more of tetrabutyl titanate, isopropyl titanate, tetramethyl titanate, tetraethyl titanate and tetraisopropyl titanate; the organic solvent comprises one or more of ethylene glycol, propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, isopropanol, n-butanol, n-pentanol, isobutanol and n-hexanol; the 2-hydroxycarboxylic acid compounds comprise one or more of citric acid, lactic acid and tartaric acid; the phosphorus-containing compound comprises at least one or more of trimethyl phosphate, triethyl phosphate, triphenyl phosphate and dipropyl phosphite;
the molar ratio of the 2-hydroxycarboxylic acid compound to the titanate is 0.05-20: 1, and the preferable molar ratio is 0.5-10: 1; the molar ratio of the phosphorus-containing compound to the titanate is 0.05-20: 1, and the preferable molar ratio is 0.5-10: 1;
(3) under the condition of continuously stirring at the speed of 100-2000 rpm, adding a water-carrying porous carrier into a titanate solution, wherein the mass ratio of the titanate solution to the porous carrier is 1: 15-300 in terms of titanium, condensing and refluxing for 0.5-4 h at the temperature of 60-90 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 105-115 ℃ for 3-6 h to obtain the heterogeneous titanium polyester catalyst.
Optionally, in the step (3), the precipitate is dried at 105-115 ℃ for 3-6 hours, dispersed into ethylene glycol, and ground for 1-3 hours to obtain the heterogeneous titanium polyester catalyst.
Example 1
A preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) fully dispersing 30g of porous alumina nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 2 hours to enable the water to be fully immersed in pore channels, centrifuging to recover a porous carrier, and drying at 80 ℃ for 2 hours to obtain a water-carrying porous carrier;
(2) adding tetrabutyl titanate with titanium-containing mass of 2g (0.0313mol) into 696g of ethylene glycol, adding 60g of citric acid and 44g of triethyl phosphate, and continuously stirring at 300rpm for 60min to obtain titanate solution;
(3) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 2 hours at the temperature of 80 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 110 ℃ for 4 hours to obtain a titanium dioxide/porous carrier composite material;
(4) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 30g of ethylene glycol, and grinding for 3 hours to obtain the heterogeneous titanium polyester catalyst.
Example 2
A preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) fully dispersing 30g of porous alumina nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 1h to enable the water to be fully immersed in a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 4h to obtain a water-carrying porous carrier;
(2) tetrabutyl titanate with the titanium-containing mass of 0.15g (0.001566mol) is added into 212g of ethylene glycol, 6g of citric acid and 4.4g of triethyl phosphate are added into the ethylene glycol, and the mixture is continuously stirred at the speed of 300rpm for 60min to obtain titanate solution;
(3) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 2 hours at the temperature of 80 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 110 ℃ for 4 hours to obtain a titanium dioxide/porous carrier composite material;
(4) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 380g of ethylene glycol, and grinding for 3 hours to obtain the heterogeneous titanium polyester catalyst.
Examples 3 to 8
The heterogeneous titanium based polyester catalysts of examples 3 to 8 were prepared according to the method of example 1 except that the corresponding data in table 1 were used instead of the preparation parameters of example 1.
TABLE 1
Figure BDA0002857814500000061
Figure BDA0002857814500000071
Example 9
A preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) fully dispersing 30g of porous alumina nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 2h to enable the water to be fully immersed in a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 2h to obtain a water-carrying porous carrier;
(2) adding tetrabutyl titanate with the titanium-containing mass of 2g (0.0313mol) into 696g of ethylene glycol, adding 60g of citric acid and 44g of triethyl phosphate, and continuously stirring at 300rpm for 60min to obtain a titanate solution;
(3) the water-loaded porous carrier was added to the titanate solution with constant stirring at 1000rpm and was condensed under reflux at 80 ℃ for 2h, followed by centrifugation, and the precipitate was dried at 110 ℃ for 4h to obtain a heterogeneous titanium-based polyester catalyst.
Example 10
A preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) fully dispersing 30g of porous molecular sieve nanospheres with the pore diameter of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 2h to enable the water to be fully immersed into a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 2h to obtain a water-carrying porous carrier;
(2) adding tetrabutyl titanate with titanium-containing mass of 2g (0.0313mol) into 696g of ethylene glycol, adding 60g of citric acid and 44g of triethyl phosphate, and continuously stirring at 300rpm for 60min to obtain titanate solution;
(3) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 2 hours at the temperature of 80 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 110 ℃ for 4 hours to obtain a titanium dioxide/porous carrier composite material;
(4) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 30g of ethylene glycol, and grinding for 3 hours to obtain the heterogeneous titanium polyester catalyst.
Example 11
A preparation method of a heterogeneous titanium polyester catalyst comprises the following steps:
(1) fully dispersing 30g of porous silicon dioxide nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 2h to enable the water to be fully immersed in a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 2h to obtain a water-carrying porous carrier;
(2) adding tetrabutyl titanate with titanium-containing mass of 2g (0.0313mol) into 696g of ethylene glycol, adding 60g of citric acid and 44g of triethyl phosphate, and continuously stirring at 300rpm for 60min to obtain titanate solution;
(3) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 2 hours at the temperature of 80 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 110 ℃ for 4 hours to obtain a titanium dioxide/porous carrier composite material;
(4) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 30g of ethylene glycol, and grinding for 3 hours to obtain the heterogeneous titanium polyester catalyst.
Comparative example 1
Commercial titanium C-94 catalyst of Acordis, Germany is adopted as the titanium polyester catalyst.
Comparative example 2
The difference between the comparative example and the example 5 is that in the step (1), porous alumina nanospheres with the pore diameter of 50-100 nm and the particle diameter of 300-1000 nm are adopted.
According to the detection, in the comparative example, after water absorption and surface drying, the water absorption rate R of the porous carrier1It was 0.07%.
Comparative example 3
The difference between the comparative example and the example 5 is that in the step (1), porous alumina nanospheres with the pore diameter of 50-100 nm and the particle diameter of 300-1000 nm are adopted, after the porous carrier is centrifugally recovered, the water absorption rate is controlled to be 0.29% by controlling the temperature and time of surface drying (drying at 80 ℃ for 60 min).
In the preparation process of the catalyst, white flocculent precipitate is found to be generated in the comparative example, which is probably that the titanate is hydrolyzed outside the pores due to the rapid mass transfer of water in the pores.
Comparative example 4
The difference between the comparative example and the example 5 is that in the step (1), porous alumina nanospheres with no pores and the particle size of 100-700 nm are adopted.
According to the detection, in the comparative example, after water absorption and surface drying, the water absorption rate R of the porous carrier1Is 0%.
Comparative examples 5 to 10
The heterogeneous titanium based polyester catalysts of comparative examples 5 to 10 were prepared according to the method of example 5, except that the corresponding data in table 2 were used instead of the preparation parameters of example 5.
TABLE 2
Figure BDA0002857814500000081
Figure BDA0002857814500000091
Application example 1
800g of purified terephthalic acid and 505.6g of ethylene glycol are uniformly mixed in a reaction kettle, and then the catalysts of examples 1-11 and comparative examples 1-9 are respectively added into the reaction kettle, wherein the adding amount of the catalyst is 5ppm based on the mass of Ti atoms to the theoretical generation amount of polyester. Carrying out esterification reaction at the temperature of 230-255 ℃, and slowly discharging water generated by esterification through a rectifying device under the reaction pressure of 0.200-0.250 MPa. And (3) after the water is completely discharged, the pressure in the reaction kettle is normal pressure, a vacuum pump is started to enable the pressure of the system to be less than 100Pa, the temperature of a heating medium is increased to gradually increase the temperature of the reaction kettle to 280 ℃, the reaction is stopped when the current reading of a stirrer for the system reaction reaches 0.67, then a product is pressurized and extruded from the bottom of the reaction kettle, and the water phase is cooled and formed and then is cut into granules to obtain the polyester chips.
Application example 2
And pouring the polyester chips prepared in the application example 1 into a chip spinning hopper, and spinning for 24 hours by selecting the specification of 75D/144f to obtain the polyester POY yarn.
Test example
The water absorption rate R of the porous carrier in the process of preparing the catalysts of examples 1 to 11 and comparative examples 2 to 9 was detected and recorded1The polycondensation time and hue of the polyester chips obtained in application example 1, and the viscosity drop during melt transportation and the full-package percentage, breaking strength and boiling water shrinkage of the polyester POY filaments obtained in application example 2 were as shown in Table 3.
TABLE 3
Figure BDA0002857814500000092
Figure BDA0002857814500000101
From table 3 the following conclusions can be drawn:
(1) comparative example 1 is a commercial titanium polyester catalyst, and examples 1 to 11 are heterogeneous titanium polyester catalysts prepared by the method of the present invention; as can be seen from Table 3, compared with comparative example 1, when the catalysts of examples 1-11 are used for preparing polyester, although the polycondensation time is prolonged, the hue of the prepared polyester chip is better, the viscosity reduction during melt conveying is lower, the full-package rate and the breaking strength of the prepared polyester POY are higher, and the boiling water shrinkage rate is lower. In addition, the non-porous alumina nanosphere is adopted in the comparative example 4, and the rest of the process is the same as that of the example 5; as can be seen from Table 3, the polyester prepared by using the catalyst of example 5 has better properties in both the polyester chip and the POY yarn, although the polycondensation time is prolonged, as compared with comparative example 4. The above results show that the present invention can improve the polyester properties by attaching titania inside the channels of the porous support (almost no titania outside the channels) because: in the catalyst prepared by the invention, titanium dioxide is attached in the pore channel of the porous carrier, and the polyester monomer needs a certain time to contact the titanium dioxide, so the polycondensation time is prolonged; meanwhile, due to the function of pore channel screening, long-chain polyester cannot continuously enter the pore channels for reaction, so that the molecular weight of a polymerization product is more concentrated, namely the polymerization reaction is more uniform, and the obtained polyester is not easy to break and fly during spinning; in addition, when the polymerization reaction is finished, the polyester with large molecular weight exists in the pore channels, so that titanium dioxide is not easy to contact with other polyester molecular chains, and therefore, the polyester is not easy to degrade and the viscosity is reduced less in the melt conveying process.
(2) Example 1 after the titanium dioxide/porous carrier composite material was prepared, it was dispersed in ethylene glycol to form a heterogeneous titanium-based polyester catalyst, and example 9 used the titanium dioxide/porous carrier composite material as a heterogeneous titanium-based polyester catalyst without being dispersed in ethylene glycol. As can be seen from Table 3, the polymerization time was shorter and the full-package yield and breaking strength of the polyester POY yarn were higher when the polyester was prepared by using the catalyst of example 1, as compared with example 9. The reason is that: the ethylene glycol treatment can improve the dispersion stability of the catalyst in the polyester monomer, thereby improving the catalytic efficiency, and simultaneously improving the dispersion stability of the catalyst in the polyester melt, and preventing the catalyst from precipitating to influence the spinning performance of the polyester.
(3) Example 1, example 10 and example 11 use porous alumina nanospheres, porous molecular sieve nanospheres and porous silica nanospheres, respectively, as porous supports. As can be seen from Table 3, the porous alumina is used as the carrier to obtain better catalytic performance, and various indexes of the polyester product are better. The reason is that: the nano porous alumina has good catalytic activity, the electropositive surface is easy to adsorb polyester monomers, the contact of the polyester monomers and a catalyst in a pore channel is promoted, and after the titanium dioxide is coupled with the alumina, the electron transfer can be promoted, the activation energy is reduced, and the reaction rate is improved.
(4) In the embodiment 5, porous alumina nanospheres with the pore diameter of 1-50 nm are adopted, in the comparative example 2, porous alumina nanospheres with the pore diameter of 50-100 nm are adopted, and the surface drying temperature and time are the same. As seen from Table 3, the water absorption of comparative example 2 was significantly reduced as compared to example 5, and the polycondensation time was extended when used for polyester synthesis, and the obtained polyester chip and POY yarn were inferior in properties. The reason is that: too large pore diameter of the porous carrier can cause great loss of water in pore channels when the surface is dry, so that the water content in the water-carrying porous carrier is too low, the loading capacity of titanium dioxide in the prepared catalyst is too low, and the polycondensation time is prolonged; in addition, the hydrolysis speed of titanate is high, and the mass transfer speed of two phases in the macropores is high, so that the titanate is easy to hydrolyze, the process cannot be controlled, the titanate is partially hydrolyzed outside the pore channel and is not uniformly distributed, the polymerization catalytic reaction is not uniform, and finally the performance of polyester chips and POY (polyester oriented yarn) yarns is poor.
(5) The example 5 adopts porous alumina nanospheres with the pore diameter of 1-50 nm, the comparative example 3 adopts porous alumina nanospheres with the pore diameter of 50-100 nm, and the water absorption rate is the same as that of the example 5 by controlling the temperature and time of surface drying. It was found during the catalyst preparation that comparative example 3 had white flocculation; also, as can be seen from table 3, when the polyester was prepared using the catalyst of comparative example 3, the polycondensation time was extended and the properties of the prepared polyester chip and POY yarn were inferior as compared to example 5. The reason is that: the excessive pore diameter of the porous carrier can cause the rapid mass transfer of water in pores, so that titanate is hydrolyzed outside the pores to generate white flocculent precipitate, and the molecular weight of polyester is difficult to control due to the fact that part of titanium dioxide exists outside pore channels in the prepared catalyst, thereby affecting the spinning performance; in addition, in the process of preparing the titanium dioxide catalyst by titanate hydrolysis, the hydrolysis process is not uniform, and the catalyst obtained by hydrolysis outside the pores has low catalytic efficiency, so that the polycondensation time is prolonged.
(6) Comparative example 5 and comparative example 6 increase and decrease the water absorption rate by controlling the surface drying conditions, respectively, compared to example 5. As seen from Table 3, when the catalysts of comparative examples 5 and 6 were used for polyester synthesis, the polycondensation time was prolonged and the obtained polyester chips and POY yarns were inferior in properties, as compared to example 5. The reason is that: when the water content in the water-carrying porous carrier is lower, the diffusion mass transfer is slow, the titanate hydrolysis is more uniform and sufficient, the titanium dioxide is more easily synthesized in the pore channel, and the excessive titanate hydrolysis outside the pore channel can be avoided; however, when the water content is too low, the titanium dioxide loading in the catalyst becomes too low, resulting in low catalytic activity.
(7) Comparative example 7 and comparative example 11 reduced the hydrolysis time and the hydrolysis temperature, respectively, and comparative example 8 reduced the hydrolysis time and the hydrolysis temperature, respectively, compared to example 5. As seen from Table 3, when the catalysts of comparative examples 7 and 11 were used for polyester synthesis, the polycondensation time was prolonged and the obtained polyester chips and POY yarns were inferior in properties, as compared to example 5, while the polyester could not be synthesized using the catalyst of comparative example 8. The reason is that: the short hydrolysis time or the low temperature can lead to insufficient and uneven hydrolysis of titanate, the content of titanium dioxide in the prepared catalyst is too low, and the titanium dioxide is unevenly distributed in the porous carrier, so that the catalytic activity of the catalyst is low.
(8) Comparative example 9 had no citric acid added and comparative example 10 had no triethyl phosphate added, compared to example 5. As seen from Table 3, when the catalysts of comparative examples 9 and 10 were used for polyester synthesis, the polycondensation time was prolonged and the obtained polyester chips and POY yarns were inferior in properties, as compared to example 5. The reason is that: the citric acid and the triethyl phosphate help to improve the stability of the titanate and promote the uniform hydrolysis of the titanate, so that the hydrolysis process of the titanate is more uniform and complete.
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. The preparation method of the heterogeneous titanium polyester catalyst is characterized by comprising the following steps:
(1) after the porous carrier absorbs water, carrying out surface drying at the temperature of 60-90 ℃ for 1-4 h to obtain a water-carrying porous carrier with the water content of 0.1-1.5 wt%; the porous carrier is one of porous alumina, porous molecular sieve and porous silicon dioxide, the particle size is 100-700 nm, and the pore diameter is 1-50 nm;
(2) dissolving titanate in an organic solvent, and adding a 2-hydroxycarboxylic acid compound and a phosphorus-containing compound into the organic solvent to prepare a titanate solution;
(3) adding a water-carrying porous carrier into a titanate solution to hydrolyze titanate in a pore channel of the porous carrier, wherein the hydrolysis temperature is 60-90 ℃ and the hydrolysis time is 0.5-4 h, and then separating out a product to obtain the heterogeneous titanium polyester catalyst.
2. The method according to claim 1, wherein the specific process of step (1) is as follows: fully dispersing the porous carrier in water, pumping to-100 to-50 kPa at the speed of 10-1000 Pa/s, standing for 1-5 h to fully immerse the water into the pore channel, recovering the porous carrier, and drying at the temperature of 60-90 ℃ for 1-4 h to obtain the water-carrying porous carrier.
3. The method according to claim 1, wherein the specific process of step (2) is as follows: adding titanate into an organic solvent, adding a 2-hydroxycarboxylic acid compound and a phosphorus-containing compound, and continuously stirring for 30-120 min to obtain a titanate solution.
4. The method according to claim 1, wherein the specific process of step (3) is as follows: under the condition of continuous stirring, adding a water-carrying porous carrier into the titanate solution, condensing and refluxing for 0.5-4 h at the temperature of 60-90 ℃, and then separating out a product to obtain the heterogeneous titanium polyester catalyst.
5. The preparation method according to claim 1 or 4, wherein in the step (3), after separating the product, the product is dispersed in ethylene glycol and ground for 1-3 hours to obtain the heterogeneous titanium polyester catalyst.
6. The method of claim 1, wherein the porous support is porous alumina.
7. A heterogeneous titanium based polyester catalyst prepared by the preparation method according to any one of claims 1 to 6.
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