CN117384366A - Preparation method of polyester - Google Patents

Preparation method of polyester Download PDF

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Publication number
CN117384366A
CN117384366A CN202311254891.9A CN202311254891A CN117384366A CN 117384366 A CN117384366 A CN 117384366A CN 202311254891 A CN202311254891 A CN 202311254891A CN 117384366 A CN117384366 A CN 117384366A
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Prior art keywords
polyester
catalyst
acid
dicarboxylic acid
mof
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Chinese (zh)
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周光远
李璐
王瑞
刘利鑫
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN202311254891.9A priority Critical patent/CN117384366A/en
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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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

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

Abstract

The application discloses a preparation method of polyester, which comprises the following steps: and (3) carrying out esterification reaction and polycondensation reaction on the mixture containing dihydric alcohol, dibasic acid and catalyst to obtain the polyester. The polyester catalyst has adjustable catalytic active sites, and has the advantages of low esterification temperature, short esterification time, less catalyst consumption and the like compared with the traditional titanium polyester catalyst tetrabutyl titanate; the polyester catalyst is nontoxic, efficient, adjustable and high-temperature resistant.

Description

Preparation method of polyester
Technical Field
The application relates to a preparation method of polyester, belonging to the fields of polymer catalyst technology and polyester materials.
Background
At present, more polyester catalysts are mainly 3 series of catalysts of antimony, germanium and titanium series in industrial production and research, but in recent years, the limited use of antimony by the international society puts new demands, and antimony and compounds thereof are listed as preferential pollutants by the U.S. environmental protection agency and the European Union, and are also closely focused pollutants by the Japanese environmental protection agency, and the maximum allowable mass concentration of antimony in drinking water regulated by the European Union is 5 mug/L. The raw materials of the germanium-based catalyst are difficult and expensive to obtain. The titanium catalyst has no influence on human health and living environment, has higher catalytic activity, no toxicity of antimony, low price and multiple raw material acquisition ways, so the titanium catalyst is the most excellent polyester catalyst from the multiple aspects of national development requirements for environmental protection, and the like, but the titanium catalyst is divided into an organic titanium catalyst and an inorganic titanium catalyst at present, the organic titanium polyester is dark and difficult to control, the surface active site of the inorganic titanium catalyst is difficult to regulate and control and easy to deactivate, most of the inorganic titanium catalyst needs to be compounded with a carrier, the synthesis cost is higher, and based on the problems, the development of a novel environment-friendly titanium polyester catalyst with high catalytic efficiency and easy regulation of the surface active site is vital. The specific surface area and the surface acid sites of the catalyst are key factors influencing the activity of polymerization reaction, and in recent years, the Metal Organic Frameworks (MOFs) of the catalyst are widely studied due to adjustable active sites, high catalytic performance, easy synthesis and low cost.
Disclosure of Invention
The technical problem to be solved by the application is as follows: ti-MOF is used as a catalyst for synthesizing low-color and high-performance polyester for the first time, and the problems of low catalyst activity and yellowing of the prepared polyester in the prior art are solved.
The research shows that the density of the acid sites on the surface of the catalyst has a certain rule with the esterification reaction and the polycondensation reaction kinetics in the polyester polymerization process, so that the stable and efficient catalytic effect of the catalyst can be realized and the color and the viscosity of the polyester can be ensured by regulating and controlling the density of the acid sites on the surface of the Ti-MOF.
According to one aspect of the present application, there is provided a method for producing a polyester, the method comprising:
the polyester is obtained by esterification reaction and polycondensation reaction of a mixture containing dihydric alcohol, dibasic acid and a catalyst; the catalyst is Ti-MOF.
Optionally, the Ti-MOF has oxygen vacancy defects and coordination defects.
Alternatively, the molecular formula of the catalyst is expressed as Ti-MOF-X-Y, wherein X refers to the molar ratio of a titanium source to an organic ligand and Y refers to the amount of Lewis acid (units, mmol/g);
X＝1～20，Y＝0.1～2.6mmol/g。
optionally, the high-efficiency adjustable Ti-MOF polyester catalyst is Ti-MOF-X-Y, wherein X is the molar ratio of a titanium source to an organic ligand, Y is the Lewis acid amount (unit, mmol/g), X=1-20, and Y=0.1-2.6 mmol/g.
Alternatively, the Lewis acid amount of the catalyst is selected from any of 0.1mmol/g, 0.3mmol/g, 0.5mmol/g, 1.6mmol/g, 1.9mmol/g, 2.6mmol/g, or a range of values between any two of the foregoing.
Alternatively, the molar amount of the catalyst is 0.1 to 5 per mill of the molar amount of the dibasic acid.
Optionally, the molar amount of the catalyst is any value of 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or a range between any two of the above molar amounts of the dibasic acid.
Optionally, the molar ratio of the dihydric alcohol to the dibasic acid is (1.1-6): 1.
alternatively, the molar ratio of glycol to diacid is selected from 1.1: 1. 1.5: 1. 2: 1. 3: 1.4: 1.5: 1.6: 1 or a range between any two of the above.
Optionally, the dibasic acid is at least one selected from 2, 5-furandicarboxylic acid, pyrrole dicarboxylic acid, thiophene dicarboxylic acid, terephthalic acid and naphthalene dicarboxylic acid.
Alternatively, the glycol is selected from C 2～6 Is a diol of (3).
Optionally, the dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol and 1, 5-pentanediol.
Optionally, the temperature of the esterification reaction is 180-240 ℃, and the time of the esterification reaction is 0.2-6 h.
Alternatively, the temperature of the esterification reaction is selected from any value or range of values between any two of 180 ℃,190 ℃,200 ℃,210 ℃,220 ℃,230 ℃,240 ℃.
Alternatively, the time of the esterification reaction is selected from any value or range of values between any two of 0.2h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h.
Optionally, the atmosphere of the esterification reaction is an inactive atmosphere.
Optionally, the inert atmosphere is selected from at least one of nitrogen, helium and argon.
Optionally, the temperature of the polycondensation reaction is 200-280 ℃, and the time of the polycondensation reaction is 0.5-6 h.
Alternatively, the temperature of the polycondensation reaction is selected from any value or range of values between any two of 200 ℃,210 ℃,220 ℃,230 ℃,240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃.
Alternatively, the time of the polycondensation reaction is selected from any value of 0.5h, 1h, 2h, 3h, 4h, 5h, 6h or a range of values between any two of the foregoing.
Optionally, the preparation method of the Ti-MOF comprises the following steps:
and (3) reacting and activating the mixture I containing the titanium source, the organic ligand, methanol and N, N-dimethylformamide to obtain the Ti-MOF.
Optionally, the titanium source is selected from tetrabutyl titanate and/or tetraisopropyl titanate.
Optionally, the organic ligand is selected from at least one of terephthalic acid, 2-amino-terephthalic acid, 4-biphenyl dicarboxylic acid, furan dicarboxylic acid, pyrazine dicarboxylic acid, pyrrole dicarboxylic acid, thiophene dicarboxylic acid, naphthalene dicarboxylic acid, trans-cyclohexane dicarboxylic acid.
Optionally, the molar ratio of the titanium source to the organic ligand is (1-20): 1.
optionally, the molar ratio of the titanium source to the organic ligand is selected from 1: 1. 10: 1. 15: 1. 20:1 or a range between any two of the above.
Optionally, the molar volume ratio of the titanium source to methanol is 1: (1-12).
Optionally, the volume ratio of the N, N-dimethylformamide to the methanol is (1-10): 1.
alternatively, the molar ratio of N, N-Dimethylformamide (DMF) to the methanol is selected from 1: 1.5: 1. 10:1 or a range between any two of the above.
Optionally, the reaction temperature is 110-200 ℃ and the reaction time is 4-24 h.
Optionally, the activating temperature is 70-240 ℃, and the activating time is 2-24 h.
According to another aspect of the present application, there is provided a polyester prepared by the above-mentioned preparation method, wherein the chromaticity b of the polyester is less than or equal to 4.0.
Alternatively, the intrinsic viscosity of the polyester is from 0.53 to 1.60dL/g.
In the present application, "C 2～6 C in the diol of 2 ～C 6 Refers to the number of carbon atoms.
In the application, the polyester catalyst is Ti-MOF-X-Y, and the surface acid amount of the polyester catalyst has certain rules with the esterification reaction activity and the polycondensation reaction activity in the process of catalyzing the synthesis of the polyester; compared with the traditional titanium polyester catalyst tetrabutyl titanate (TBOT), the polyester catalyst has the advantages of low esterification temperature, short esterification time, less catalyst consumption and the like; the polyester catalyst is nontoxic, efficient, adjustable and high-temperature resistant.
The beneficial effects that this application can produce include:
1) The application develops a novel catalytic system for synthesizing the MOF catalytic polyester, and utilizes the Ti-MOF polyester catalyst to catalyze the synthesis of the polyester in a nontoxic and efficient manner, so that the color and luster of the synthesized polyester can be ensured to be low.
2) The method can greatly regulate the content of Lewis acid sites of the catalyst, obtain quantitative analysis of the density of the surface active sites of the catalyst and the reactivity of the polyester, inhibit the generation of polyether ester by side reaction and realize efficient and controllable polymerization.
3) Compared with the traditional titanium catalyst TBOT, the method has the advantages of less time consumption in esterification reaction, less catalyst consumption and the like, and realizes the reduction of the industrial production cost of the synthetic polyester, the reduction of energy consumption and the cost saving.
Drawings
FIG. 1 is an electron micrograph of Ti-MOF-5-0.3 obtained in preparation example 1 of the present application; the scale was 3. Mu.m.
FIG. 2 is an electron micrograph of Ti-MOF-3-0.6 obtained in preparation example 1 of the present application; the scale was 1. Mu.m.
FIG. 3 is a graph showing the surface acid amount distribution of different Ti-MOF catalysts obtained in preparation example 1 of the present application.
FIG. 4 shows TG/DTA curves of different Ti-MOF catalysts obtained in example 1 of the present application.
FIG. 5 is a thermal weight loss curve of the polyester obtained in example 5 of the present application.
FIG. 6 is a photograph of a polyester film obtained in example 2 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
In the embodiments of the present application:
the color difference meter (CS-826) used for measuring chromaticity,
a medium Wang Ubbelohde viscometer (IVS 100) for measuring the intrinsic viscosity,
the viscosity and chromaticity were measured using the test methods in GB/T14190-2008 standard.
Tetrabutyl titanate (TBOT), isopropyl titanate were purchased from enoKai.
Preparation example 1
Ti-MOF-5-0.3: under the condition of room temperature, injecting terephthalic acid and tetrabutyl titanate into DMF and methanol oil bath for reflux, stirring at room temperature until the mixture is transparent, reacting for 12 hours, naturally cooling, centrifuging after precipitation, washing with methanol for multiple times, and activating for 8 hours to obtain tetrabutyl titanate: terephthalic acid = 1:5 (molar ratio). DMF: methanol=9: 1 (volume ratio).
FIG. 1 is an electron micrograph of Ti-MOF-5-0.3 obtained in preparation example 1 of the present application; the size was 3. Mu.m.
FIG. 3 shows that the prepared Ti-MOF catalysts have different amounts of surface acid and different acid site distributions.
Preparation example 2
Ti-MOF-3-0.6: under the condition of room temperature, injecting terephthalic acid and tetrabutyl titanate into DMF and methanol oil bath for reflux, stirring at room temperature until the mixture is transparent, reacting for 15 hours, naturally cooling, centrifuging after precipitation, washing with methanol for multiple times, and activating for 9 hours to obtain tetrabutyl titanate: terephthalic acid = 1:3 (molar ratio). DMF: methanol=8: 1 (volume ratio).
FIG. 2 is an electron micrograph of Ti-MOF-3-0.6 obtained in preparation example 2 of the present application; the size was 500nm.
Preparation example 3
Ti-MOF-9-0.7: under the condition of room temperature, the furandicarboxylic acid and the tetrabutyl titanate are injected into DMF and methanol oil bath for reflux, stirred at room temperature until the mixture is transparent, then reacted for 13 hours, naturally cooled, centrifuged after precipitation, washed by methanol for more times, activated for more than 10 hours, and tetrabutyl titanate: furandicarboxylic acid = 1:9 (molar ratio). DMF: methanol=1: 1 to 10:1 (volume ratio).
Preparation example 4
Ti-MOF-11-0.8: under the condition of room temperature, thiophene dicarboxylic acid and tetrabutyl titanate are injected into DMF and methanol oil bath for reflux, stirred at room temperature until the mixture is transparent, then reacted for 16 hours, naturally cooled, centrifuged after precipitation, washed by methanol for more than 9 hours, and activated for tetrabutyl titanate: thiophene dicarboxylic acid=1: 11 (molar ratio). DMF: methanol=1: 10 (volume ratio).
Preparation example 5
Ti-MOF-15-1.4: under the condition of room temperature, the pyrazine dicarboxylic acid and the tetraisopropyl titanate are injected into DMF and methanol oil bath for reflux, stirred at room temperature until the mixture is transparent, then reacted for 18 hours, naturally cooled, precipitated, centrifuged, washed by methanol for more times, activated for more than 8 hours, and TBOT: pyrazine dicarboxylic acid = 1:15 (molar ratio). DMF: methanol=1: 8 (volume ratio).
Preparation example 6
Ti-MOF-16-1.6: under the condition of room temperature, injecting terephthalic acid and tetrabutyl titanate into DMF and methanol oil bath for reflux, stirring at room temperature until the mixture is transparent, reacting for 19 hours, naturally cooling, centrifuging after precipitation, washing with methanol for more times, and activating for more than 8 hours, wherein the reaction time is TBOT: terephthalic acid = 1:16 (molar ratio). DMF: methanol=1: 1 to 10:1 (volume ratio).
Example 1
0.1mol of 2, 5-furandicarboxylic acid and 0.15mol of glycol are used as raw materials (the molar ratio of alkyd is 1.5), ti-MOF-5-0.3 is used as a catalyst, the dosage of Ti-MOF-5-0.3 is 0.1 per mill of the molar amount of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out for 2.5 hours at 200 ℃, the polycondensation is carried out for 3.5 hours at 230 ℃, the reaction is stopped, and the obtained product poly (ethylene 2, 5-furandicarboxylic acid) PEF is subjected to chromaticity and viscosity test, and the results are shown in Table 1. As can be seen from FIG. 4, the Ti-MOF catalyst prepared in any ratio has high thermal stability of 300 ℃, and this condition meets the requirements for polyester catalysts.
Example 2
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of glycol are used as raw materials (the molar ratio of alkyd is 2.5), ti-MOF-9-0.7 is used as a catalyst, the dosage of Ti-MOF-9-0.7 is 0.3 per mill of the molar quantity of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out for 2.5 hours at 190 ℃, the polycondensation reaction is stopped for 3.5 hours at 225 ℃, and the chromaticity and viscosity test are carried out on the obtained product polyethylene glycol 2, 5-furandicarboxylate PEF, wherein the result is shown in Table 1. It can be seen from fig. 6 that the PEF film synthesized by the Ti-MOF catalyst has the advantage of low color.
Example 3
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of glycol are used as raw materials (the molar ratio of alkyd is 2.5), ti-MOF-11-0.8 is used as a catalyst, the dosage of Ti-MOF-11-0.8 is 0.3 per mill of the molar amount of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out for 3 hours at 200 ℃, the polycondensation is carried out for 3.5 hours at 230 ℃, the reaction is stopped, and the obtained product polyethylene 2, 5-furandicarboxylic acid PEF is subjected to chromaticity and viscosity test, and the results are shown in Table 1.
Example 4
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of glycol are used as raw materials (the molar ratio of alkyd is 2.5), ti-MOF-15-1.4 is used as a catalyst, the dosage of Ti-MOF-15-1.4 is 0.4 per mill of the molar amount of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out for 3 hours at 200 ℃, the polycondensation is carried out at 230 ℃ for 3.5 hours, the reaction is stopped, and the obtained product polyethylene 2, 5-furandicarboxylic acid PEF is subjected to chromaticity and viscosity test, and the results are shown in Table 1.
Example 5
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of glycol are used as raw materials (the molar ratio of alkyd is 2.5), ti-MOF-16-1.6 is used as a catalyst, the dosage of Ti-MOF-16-1.6 is 0.5 per mill of the molar amount of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 200 ℃ until the reaction is transparent, the polycondensation reaction is carried out at 235 ℃ for 3.5 hours, the reaction is stopped, and the obtained product polyethylene 2, 5-furandicarboxylic acid PEF is subjected to chromaticity and viscosity test, and the results are shown in Table 1. It can be seen from fig. 5 that the PEF film synthesized by the Ti-MOF catalyst has high thermal stability.
Example 6
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of propylene glycol are used as raw materials (the molar ratio of alkyd is 2.5), ti-MOF-16-1.6 is used as a catalyst, the dosage of Ti-MOF-16-1.6 is 1 permillage mol of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out for 3h at 190 ℃ and the polycondensation is carried out for 3.5h at 230 ℃, the chromaticity and viscosity test are carried out on the obtained product poly (propylene glycol 2, 5-furandicarboxylic acid) PTF, and the result is shown in Table 1
Example 7
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of butanediol are used as raw materials (the molar ratio of alkyd is 2.5), ti-MOF-11-0.8 is used as a catalyst, the dosage of Ti-MOF-11-0.8 is 2 per mill mol of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 190 ℃ for 3 hours, the polycondensation is carried out at 230 ℃ for 3.5 hours, the reaction is stopped, and the obtained product poly (2, 5-furandicarboxylic acid) butanediol PBF is subjected to chromaticity and viscosity test, and the result is shown in Table 1
Example 8
0.1mol of terephthalic acid and 0.25mol of glycol are used as raw materials (molar ratio of alkyd is 2.5), ti-MOF-9-0.7 is used as a catalyst, the dosage of Ti-MOF-9-0.7 is 2.2 per mill mol of terephthalic acid, esterification is carried out under the protection of nitrogen, esterification is carried out at 205 ℃ for 3h, polycondensation is carried out at 230 ℃ for 3.5h, the reaction is stopped, and the obtained product polyethylene terephthalate PET is subjected to chromaticity and viscosity test, and the result is shown in Table 1
Example 9
0.1mol of naphthalene dicarboxylic acid and 0.15mol of glycol are used as raw materials (molar ratio of alkyd is 1.5), ti-MOF-5-0.3 is used as a catalyst, the dosage of Ti-MOF-5-0.3 is 4 permillage mol of 2, 5-furandicarboxylic acid, esterification reaction is carried out under the protection of nitrogen, esterification is carried out at 210 ℃ for 3h, polycondensation is carried out at 225 ℃ for 3.5h, the reaction is stopped, and the obtained product polyethylene naphthalate PEN is subjected to chromaticity and viscosity test, and the result is shown in Table 1
Example 10
0.1mol of thiophene dicarboxylic acid and 0.25mol of glycol are used as raw materials (molar ratio of alkyd is 2.5), ti-MOF-16-1.6 is used as a catalyst, the dosage of Ti-MOF-16-1.6 is 2.3 per mill mol of thiophene dicarboxylic acid, esterification is carried out under the protection of nitrogen, esterification is carried out for 3h at 180 ℃, polycondensation is carried out for 3.5h at 220 ℃, the reaction is stopped, and the obtained product polyethylene thiophene dicarboxylic acid glycol ester PETF is subjected to chromaticity and viscosity test, and the results are shown in Table 1
Comparative example 1
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of glycol are used as raw materials (the molar ratio of alkyd is 2.5), tetrabutyl titanate (TBOT) is used as a catalyst, the dosage of tetrabutyl titanate (TBOT) is 0.1 per mill mol of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 220 ℃ for 3 hours, the polycondensation reaction at 225 ℃ is carried out for 3.5 hours, the reaction is stopped, and the obtained product polyethylene 2, 5-furandicarboxylic acid glycol PEF is subjected to chromaticity and viscosity test, and the results are shown in table 1.
Comparative example 2
0.1mol of 2, 5-furandicarboxylic acid and 0.25mol of glycol are used as raw materials (molar ratio of alkyd is 2.5), tetrabutyl titanate (TBOT) is used as a catalyst, the dosage of tetrabutyl titanate (TBOT) is 3 per mill molar weight of 2, 5-furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 220 ℃ for 3h, the polycondensation reaction is carried out at 240 ℃ for 3.5h, the reaction is stopped, and the obtained product polyethylene 2, 5-furandicarboxylic acid glycol PEF is subjected to chromaticity and viscosity test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the Ti-MOF polyester catalyst is applied to a catalytic polymerization system of polyester, and the catalytic effect of the Ti-MOF polyester catalyst is obviously better than that of the traditional catalyst no matter the color and the viscosity, so that the Ti-MOF catalyst is high-efficiency, nontoxic, stable, simple and easy to prepare, and is an environment-friendly catalyst.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (10)

1. A process for the preparation of a polyester, comprising:
the polyester is obtained by esterification reaction and polycondensation reaction of a mixture containing dihydric alcohol, dibasic acid and a catalyst;
the catalyst is Ti-MOF.
2. The preparation method according to claim 1, wherein the molar amount of the catalyst is 0.1 to 5%o of the molar amount of the dibasic acid;
preferably, the molar ratio of the dihydric alcohol to the dibasic acid is (1.1-6): 1.
3. the method according to claim 1, wherein the dibasic acid is at least one selected from the group consisting of 2, 5-furandicarboxylic acid, pyrrole dicarboxylic acid, thiophene dicarboxylic acid, terephthalic acid, naphthalene dicarboxylic acid;
preferably, the glycol is selected from C 2～6 Is a diol of (2);
preferably, the dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol and 1, 5-pentanediol.
4. The preparation method according to claim 1, wherein the temperature of the esterification reaction is 180-240 ℃, and the time of the esterification reaction is 0.2-6 h;
preferably, the atmosphere of the esterification reaction is an inactive atmosphere;
preferably, the inactive atmosphere is selected from at least one of nitrogen, helium, argon.
5. The method according to claim 1, wherein the polycondensation reaction is carried out at a temperature of 200 to 280℃for a period of 0.5 to 6 hours.
6. The method of claim 1, wherein the Ti-MOF preparation method comprises:
and (3) reacting and activating the mixture I containing the titanium source, the organic ligand, methanol and N, N-dimethylformamide to obtain the Ti-MOF.
7. The method of claim 6, wherein the titanium source is selected from tetrabutyl titanate and/or tetraisopropyl titanate;
preferably, the organic ligand is at least one selected from terephthalic acid, 2-amino-terephthalic acid, 4-biphenyl dicarboxylic acid, furan dicarboxylic acid, pyrazine dicarboxylic acid, pyrrole dicarboxylic acid, thiophene dicarboxylic acid, naphthalene dicarboxylic acid, and trans-cyclohexane dicarboxylic acid.
8. The method according to claim 6, wherein the molar ratio of the titanium source to the organic ligand is (1 to 20): 1, a step of;
preferably, the molar volume ratio of the titanium source to methanol is 1: (1-12);
preferably, the volume ratio of the N, N-dimethylformamide to the methanol is (1 to 10): 1.
9. the preparation method according to claim 6, wherein the reaction temperature is 110-200 ℃ and the reaction time is 4-24 hours;
preferably, the activation temperature is 70-240 ℃ and the activation time is 2-24 h.
10. The polyester prepared by the process according to any one of claims 1 to 9, wherein the polyester has a color b of 4.0 or less;
preferably, the intrinsic viscosity of the polyester is from 0.53 to 1.60dL/g.
CN202311254891.9A 2023-09-25 2023-09-25 Preparation method of polyester Pending CN117384366A (en)

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