CN115386074B - Functional nano composite polyester, preparation method and application - Google Patents

Functional nano composite polyester, preparation method and application Download PDF

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CN115386074B
CN115386074B CN202210994355.1A CN202210994355A CN115386074B CN 115386074 B CN115386074 B CN 115386074B CN 202210994355 A CN202210994355 A CN 202210994355A CN 115386074 B CN115386074 B CN 115386074B
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polyester
catalyst
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CN115386074A (en
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周光远
李璐
王瑞
周冠男
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Dalian Institute of Chemical Physics of CAS
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
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    • C08G63/183—Terephthalic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
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    • 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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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/20—Oxides; Hydroxides
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Abstract

The application discloses a functional nano composite polyester, a preparation method and application, wherein the preparation method comprises the following steps: mixing raw materials containing dibasic acid and dihydric alcohol with a catalyst and a modifier, and sequentially carrying out esterification reaction and polycondensation reaction to obtain the functional nano composite polyester; the modifier is nano TiO 2 . The method can efficiently catalyze the synthesis of the functional nano composite polyester, and meanwhile, nano TiO 2 In situ polymerization in functional nanocomposite polyester using nano TiO 2 The structure of the polyester can regulate and control the blue light and ultraviolet light shielding performance of the polyester matrix and endow the polyester with the performance of degrading antibiotics.

Description

Functional nano composite polyester, preparation method and application
Technical Field
The application relates to a functional nano composite polyester, a preparation method and application thereof, belonging to the technical field of high polymer materials.
Background
Pharmacy is a milestone of human science development, which prolongs the service life, cures millions of fatal diseases and improves the quality of life. This success has now led to their emergence as a rapidly growing environmental contaminant. The broad definition of antibiotics is a generic term for antibacterial, antiviral, antifungal and anticancer drugs. Antibiotics have been widely used worldwide in recent years due to their effective role in the treatment of infectious diseases and agricultural production. However, because of the lack of effective degradation methods, large amounts of antibiotic-containing wastewater are discharged directly or indirectly into rivers, and such compounds, although not long-lasting, have resulted in a pseudo-persistence due to long-term and large-scale continuous inflow, causing serious pollution to the environment, and the search for effective methods for degrading antibiotics has been urgent. Inorganic nanometer photocatalyst with high photocatalytic activity is produced, but most of the inorganic nanometer photocatalyst is powder, and the inorganic nanometer photocatalyst is easy to settle and agglomerate in the actual use process, is not easy to recover and recycle, and brings secondary pollution to water quality, and seriously affects actual popularization.
Disclosure of Invention
The application provides a functional nano composite polyester with ultraviolet shielding and antibiotic degradation functions and a preparation method thereof, wherein the functional nano composite polyester comprises tetrabutyl titanate serving as a catalyst and nano TiO 2 The modified polyester is used as a modifier for synthesizing high-performance polyester and improving the blue light and ultraviolet light shielding performance of the polyester.
The application provides a functional composite polyester with ultraviolet shielding and antibiotic degradation functions and a preparation method thereof, and the method realizes the integration of polyester synthesis and nano composite modification.
According to one aspect of the present application, there is provided a method of preparing a functional nanocomposite polyester, the method comprising the steps of:
sequentially carrying out esterification reaction and polycondensation reaction on a mixture containing dibasic acid, dihydric alcohol, a catalyst and a modifier to obtain functional nano composite polyester;
the modifier is nano TiO 2 。
Optionally, the nano TiO 2 The size of (C) is 10-200 nm.
Optionally, the nano TiO 2 The size of (C) is selected from any value of 10nm, 20nm, 50nm, 100nm, 150nm and 200nm or a range value between any two points.
Optionally, the nano TiO 2 Is linear nano TiO 2 。
Optionally, the modifier is used in an amount of 0.1 to 10mol% of the dibasic acid.
Optionally, the modifier is used in an amount selected from any of 0.1mol%, 0.3mol%, 0.5mol%, 0.7mol%, 0.9mol%, 1.0mol%, 5mol%, 10mol%, or any value between any two of the above.
Optionally, the diacid is selected from at least one of furan dicarboxylic acid, terephthalic acid, thiophene dicarboxylic acid, naphthalene dicarboxylic acid.
Alternatively, the glycol is selected from C 2 ～C 8 A glycol.
Optionally, the dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol.
Optionally, the catalyst is at least one selected from tetrabutyl titanate, isopropyl titanate, aluminum acetylacetonate, scandium triflate, antimony oxide, germanium oxide, tin oxide and zinc acetate.
Optionally, the molar ratio of the dihydric alcohol to the dibasic acid is 1.5-4.0: 1.
optionally, the catalyst is used in an amount of 0.1 to 0.5mol% of the dibasic acid.
Optionally, the molar ratio of the dihydric alcohol to the dibasic acid is selected from any value of 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or a range of values between any two points.
Alternatively, the catalyst is used in an amount selected from any of 0.1mol%, 0.2mol%, 0.3mol%, 0.4mol%, 0.5mol% or a range between any two of the above.
Alternatively, the esterification reaction occurs under inert atmosphere conditions.
Optionally, the inactive atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, argon atmosphere.
Optionally, the temperature of the esterification reaction is 180-230 ℃.
Optionally, the esterification reaction time is 0.2-4 h.
Alternatively, the temperature of the esterification reaction is selected from any value or range of values between any two points of 180 ℃, 190 ℃,200 ℃, 210 ℃, 220 ℃,230 ℃.
Optionally, the time of the esterification reaction is selected from any value of 0.2h, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or a range value between any two points.
Optionally, the temperature of the polycondensation reaction is 200-275 ℃.
Alternatively, the polycondensation reaction time is 0.2 to 5 hours.
Alternatively, the temperature of the polycondensation reaction is selected from any value or range of values between any two points of 200 ℃, 210 ℃, 220 ℃,230 ℃, 245 ℃, 250 ℃,275 ℃.
Optionally, the time of the polycondensation reaction is selected from any value of 0.2h, 0.5h, 1h, 1.5h, 2h, 3h, 4h, 5h or a range of values between any two points.
According to another aspect of the present application, there is provided a functional nanocomposite polyester prepared by the above-described preparation method.
Optionally, the functional nanocomposite polyester has a visible light transmittance of >70% at 800 nm.
Optionally, the functional nanocomposite polyester has an ultraviolet light transmittance of <10% at 400 nm.
Optionally, the functional nanocomposite polyester has an intrinsic viscosity of 0.60-1.25 dL/g, a tensile strength of 50-105 MPa, and an elongation at break of 35-550%.
According to yet another aspect of the present application, there is provided a method of antibiotic degradation comprising: adding polyester into an aqueous solution containing antibiotics for degradation reaction, and detecting the content of the antibiotics;
wherein the polyester is at least one of the functional nano-composite polyester prepared by the preparation method and the functional nano-composite polyester;
the antibiotic is at least one selected from moxifloxacin, norfloxacin, sulfadiazine, sulfamethoxazole, metronidazole, trimethoprim and isoniazid.
Optionally, the antibiotic is selected from moxifloxacin and/or norfloxacin.
Alternatively, the time required for complete degradation of the antibiotic is between 30 and 200 minutes.
Alternatively, the time required for complete degradation of the antibiotic is selected from any value of 30 minutes, 50 minutes, 100 minutes, 150 minutes, 200 minutes or a range of values between any two of the above.
The beneficial effects that this application can produce include:
(1) The application develops the functional nano composite polyester with ultraviolet shielding and antibiotic degradation functions and the preparation method thereof, can improve the added value of polyester industry and utilizes nano TiO 2 Under the excitation of ultraviolet light or sunlight, the generation of conduction band electrons can be stimulated, and corresponding holes are generated at the same time. The photo-generated electrons in this excited state can recombine with holes, during which process the light energy can be converted into thermal or other forms of energy, thereby indirectly or directly decomposing organic contaminants into non-toxic substances such as water, carbon dioxide and phosphate. Can effectively endow ultraviolet shielding and antibiotic degradation performance to polyester.
(2) Nanometer TiO 2 The catalyst itself has catalytic activity and can become a catalyst promoter of tetrabutyl titanate, thereby improving the synthesis rate of polyester and the molecular weight of polyester.
Drawings
FIG. 1 is an optical photograph of a polyester prepared in example 1 of the present application.
FIG. 2 is an optical photograph of the polyester prepared in example 2 of the present application.
FIG. 3 is an optical photograph of the polyester prepared in example 3 of the present application.
FIG. 4 is an optical photograph of the polyester prepared in example 4 of the present application.
FIG. 5 is an optical photograph of the polyester prepared in example 5 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, both the starting materials and the catalysts in the examples of the present application were purchased commercially.
Wherein furandicarboxylic acid was prepared as in example 1 of patent CN201810442696.1, terephthalic acid and various antibiotics were purchased from enokay, and other raw materials were purchased from the national drug group.
In the embodiments of the present application:
a medium Wang Ubbelohde viscometer (IVS 100) for measuring the intrinsic viscosity;
the viscosity is measured by a testing method in GB/T14190-2008 standard;
an Instron electronic universal material tester (Instron-1121) used for measuring tensile strength and elongation at break was used to conduct a tensile test at 25℃using an Instron-1121 tester according to ASTM D638, at a tensile speed of 5mm/min, and a dumbbell-shaped specimen 3.18mm wide and 3.2mm thick was prepared by injection molding using an injection molding machine, to obtain the tensile strength and elongation at break of the specimen.
The spectrum of the film is detected by a Nicolet 5700 spectrometer, and the spectrum range is 4000-200 cm -1 Resolution of 0.4cm -1 。
The method for measuring the visible light transmittance comprises the following steps: a film with a thickness of 150um is tested by an ultraviolet-visible tester, and the transmittance of visible light at 800nm is tested.
The method for measuring the ultraviolet transmittance comprises the following steps: a film with a thickness of 150um is tested by an ultraviolet-visible tester, and the transmittance of ultraviolet light at 400nm is tested.
The method for testing the content and degradation rate of antibiotics comprises the following steps: and (3) testing the antibiotic aqueous solution with deionized water as a blank by using an ultraviolet-visible tester, and testing the ultraviolet absorbance of the antibiotic. The degradation rate is calculated from the characteristic peak heights by determining whether the antibiotic is completely degraded by the characteristic peak of ultraviolet absorption of the antibiotic.
In the examples of the present application, in the test of degrading antibiotics with polyesters, the antibiotics used were: moxifloxacin, norfloxacin, sulfadiazine, sulfamethoxazole, metronidazole, trimethoprim, isoniazid. The antibiotic was prepared as an aqueous solution at a concentration of 1 mg/ml.
Preparation example 1
nano-TiO employed in the examples of the present application 2 The modifier is prepared according to the following preparation method:
nanometer TiO 2 The preparation method comprises the following steps: by hydrothermal method with TiCl 4 Is prepared from Ti source, aqueous solution of strong alkali as solvent through heating, stirring, adding hydrochloric acid to prepare nano-wire titanate, centrifugal separation, washing with absolute alcohol, high-temp calcining, and regulating the variety of strong alkali and reaction time to obtain 10-200 nm linear nano-TiO 2 。
Wherein:
10nm linear nano TiO 2 The process parameters of (a) are as follows: 99.9% TiCl 4 The reaction is carried out for 24 hours by taking a titanium source and a potassium hydroxide aqueous solution as a solvent.
20nm linear nano TiO 2 The process parameters of (a) are as follows: 99.9% TiCl 4 The reaction is carried out for 36h by taking titanium source and potassium hydroxide aqueous solution as solvent.
50nm linear nano TiO 2 The process parameters of (a) are as follows: 99.9% TiCl 4 The reaction is carried out for 12h by taking a titanium source and a sodium hydroxide aqueous solution as a solvent.
100nm linear nano TiO 2 The process parameters of (a) are as follows: 99.9% TiCl 4 The reaction is carried out for 24h by taking a titanium source and a sodium hydroxide aqueous solution as a solvent.
200nm linear nano TiO 2 The process parameters of (a) are as follows: 99.9% TiCl 4 The reaction is carried out for 48h by taking a titanium source and a sodium hydroxide aqueous solution as a solvent.
Example 1
0.1mol of furandicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 10nm of linear nano TiO obtained in preparation example 1 2 The catalyst is tetrabutyl titanate, the catalyst is 0.05 mol percent of furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 200 ℃ for 1.5h, the polycondensation is carried out at 230 ℃ for 2h, the reaction is stopped, the obtained product poly (ethylene 2, 5-furandicarboxylic acid) (PEF) is subjected to viscosity and test, the obtained sample is crushed, and then injection molding and mechanical and optical property tests are carried out, the degradation antibiotic is norfloxacin, and the result is shown in table 1.
Example 2
0.1mol of furfureStarting with furandicarboxylic acid and 0.4mol of ethylene glycol (molar ratio of alkyd: 4) to prepare 20nm of linear nano TiO from example 1 2 The catalyst is isopropyl titanate, the catalyst is esterified under the protection of nitrogen, the esterification is carried out for 1.5h at 200 ℃, the polycondensation is carried out for 2h at 230 ℃, the reaction is stopped, the obtained product polyethylene 2, 5-furandicarboxylic acid glycol (PEF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, the type of the degraded antibiotic is moxifloxacin, and the result is shown in table 1.
Example 3
0.1mol of furandicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 10nm of linear nano TiO obtained in preparation example 1 2 The modifier is 5mol% of furandicarboxylic acid, the catalyst is tetrabutyl titanate, the catalyst is 0.05 mol% of furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 200 ℃ for 1.5h, the polycondensation is carried out at 230 ℃ for 2h, the reaction is stopped, the obtained product poly (ethylene-2, 5-furandicarboxylic acid) (PEF) is subjected to viscosity and test, the obtained sample is crushed, and then injection molding, mechanical and optical property test is carried out, the degradation antibiotic is norfloxacin, and the result is shown in Table 1.
Example 4
0.1mol of furandicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 10nm of linear nano TiO obtained in preparation example 1 2 The catalyst is tin oxide, the catalyst is 0.05 mol percent of furandicarboxylic acid, esterification is carried out under the protection of nitrogen, esterification is carried out at 200 ℃ for 1.5h, polycondensation is carried out at 230 ℃ for 2h, the reaction is stopped, the obtained product polyethylene 2, 5-furandicarboxylic acid glycol (PEF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical performance test are carried out, the type of degradation antibiotic is moxifloxacin, and the result is shown in table 1.
Example 5
0.1mol of furandicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 100nm linear nano TiO obtained in example 1 2 The catalyst is scandium triflate, the catalyst is in esterification reaction under the protection of nitrogen, the esterification reaction is carried out for 2h at 180 ℃ and the polycondensation reaction is carried out for 2h at 230 ℃ to stop the reaction, the obtained product polyethylene 2, 5-furandicarboxylate (PEF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, the type of the degradation antibiotic is sulfadiazine, and the result is shown in Table 1.
Example 6
0.1mol of furandicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 100nm linear nano TiO obtained in example 1 2 The catalyst is aluminum acetylacetonate, the catalyst is 0.05 mol percent of furandicarboxylic acid, esterification is carried out under the protection of nitrogen, esterification is carried out at 180 ℃ for 2 hours, polycondensation is carried out at 230 ℃ for 2 hours, the reaction is stopped, the obtained product poly (2, 5-furandicarboxylic acid) glycol ester (PEF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical performance test are carried out, the type of degradation antibiotic is sulfamethoxazole, and the results are shown in Table 1.
Example 7
0.1mol of furandicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 100nm linear nano TiO obtained in example 1 2 The catalyst is tetrabutyl titanate, the catalyst is 0.05 mol percent of furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out for 2 hours at 180 ℃ and the polycondensation is carried out for 2 hours at 230 ℃ to stop the reaction, the obtained product poly (ethylene-2, 5-furandicarboxylic acid) (PEF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical performance test are carried out, the type of degradation antibiotic is metronidazole, and the results are shown in Table 1.
Example 8
0.1mol of furandicarboxylic acid and 0.3mol of 1, 4-butanediol (molar ratio of alkyd: 3) were used as raw materials to prepare 10nm of linear nano TiO obtained in example 1 2 The modifier is 1mol percent of furandicarboxylic acid, the catalyst is germanium oxide, and the dosage is 0.05 mol percent of furandicarboxylic acidThe reaction is stopped by esterification reaction for 3h at 200 ℃ and polycondensation reaction for 2.5h at 230 ℃ under the protection of nitrogen, the obtained product poly (butylene-2, 5-furandicarboxylate) (PBF) is subjected to viscosity and test, and the obtained sample is crushed and then subjected to injection molding and mechanical and optical performance test, and the degraded antibiotic is trimethoprim, and the result is shown in Table 1.
Example 9
0.1mol of furandicarboxylic acid and 0.3mol of 1, 4-butanediol (molar ratio of alkyd: 3) were used as raw materials to prepare 10nm of linear nano TiO obtained in example 1 2 The catalyst is tetrabutyl titanate, the catalyst is 0.05 mol percent of furandicarboxylic acid, esterification is carried out under the protection of nitrogen, esterification is carried out for 3h at 200 ℃, polycondensation is carried out for 2.5h at 230 ℃, the reaction is stopped, the obtained product poly (2, 5-furandicarboxylic acid) butanediol (PBF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, and the degradation antibiotic is norfloxacin, and the result is shown in Table 1.
Example 10
0.1mol of furandicarboxylic acid and 0.3mol of 1, 4-butanediol (molar ratio of alkyd: 3) were used as raw materials to prepare 50nm of linear nano TiO obtained in example 1 2 The catalyst is tetrabutyl titanate, the catalyst is 0.05 mol percent of furandicarboxylic acid, esterification is carried out under the protection of nitrogen, esterification is carried out for 3h at 200 ℃, polycondensation is carried out for 2.5h at 230 ℃, the reaction is stopped, the obtained product poly (2, 5-furandicarboxylic acid) butanediol (PBF) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, and the degradation antibiotic is sulfadiazine, and the result is shown in Table 1.
Example 11
0.1mol of furandicarboxylic acid and 0.3mol of 1, 4-butanediol (molar ratio of alkyd: 3) were used as raw materials to prepare 100nm of linear nano TiO obtained in example 1 2 The catalyst is tetrabutyl titanate, the catalyst is 0.05 mol percent of furandicarboxylic acid, the esterification is carried out under the protection of nitrogen, the esterification is carried out for 3h at 200 ℃ and the polycondensation is carried out for 2.5h at 230 ℃, and the obtained product is polymerizedThe viscosity and test of 2, 5-furandicarboxylic acid butanediol (PBF) are carried out, and the obtained samples are crushed and then are subjected to injection molding and mechanical and optical property test, and the type of the degradation antibiotic is moxifloxacin, and the result is shown in Table 1.
Example 12
0.1mol of furandicarboxylic acid and 0.2mol of 1, 3-propanediol (molar ratio of alkyd: 2) to prepare 100nm of linear nano TiO obtained in example 1 2 The catalyst is germanium oxide and zinc acetate (molar ratio 1:1), the catalyst is furan dicarboxylic acid, the catalyst is esterified under the protection of nitrogen, the esterification is carried out for 1.5h at 200 ℃, the polycondensation is carried out for 2h at 230 ℃, the reaction is stopped, the obtained product poly (propylene glycol) (PTF) 2, 5-furan dicarboxylic acid is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical property tests are carried out, the type of degraded antibiotic is isoniazid, and the result is shown in Table 1.
Example 13
0.1mol of furandicarboxylic acid and 0.2mol of 1, 3-propanediol (molar ratio of alkyd: 2) were used as raw materials to prepare 200nm of linear nano TiO obtained in example 1 2 The catalyst is germanium oxide and zinc acetate (molar ratio 1:1), the catalyst is germanium oxide and zinc acetate (molar ratio) accounting for 5% of furandicarboxylic acid, the catalyst is used for esterification reaction under nitrogen protection, esterification is carried out for 1.5h at 200 ℃ and polycondensation is carried out for 2h at 230 ℃ to stop the reaction, the obtained product poly (propylene glycol) (PTF) is subjected to viscosity and test, and after the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, the type of degraded antibiotic is sulfamethoxazole, and the result is shown in Table 1.
Example 14
0.1mol of terephthalic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 100nm linear nano TiO obtained in example 1 2 The catalyst is germanium oxide and zinc acetate (molar ratio 1:1), the catalyst is furan dicarboxylic acid 0.05 mol%, esterification is carried out under nitrogen protection, esterification is carried out at 230 ℃ for 2h, polycondensation is carried out at 260 ℃ for 2h, the reaction is stopped, and the obtained product polyethylene terephthalate (PET) is fed inViscosity and test, and injection molding and mechanical and optical performance test are carried out after the obtained sample is crushed, the type of the degradation antibiotic is norfloxacin, and the results are shown in table 1.
Example 15
0.1mol of thiophene dicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 100nm linear nano TiO obtained in example 1 2 The catalyst is germanium oxide and zinc acetate (molar ratio 1:1), the catalyst is 0.05 mol percent of furandicarboxylic acid, the esterification reaction is carried out under the protection of nitrogen, the esterification is carried out at 200 ℃ for 1.5h, the polycondensation reaction is carried out at 230 ℃ for 2h, the reaction is stopped, the obtained product, namely, the polythiophene dicarboxylic acid glycol ester (PETF), is subjected to viscosity and test, and the obtained sample is crushed, is subjected to injection molding and mechanical and optical property test, and the type of degradation antibiotic is moxifloxacin, and the result is shown in Table 1.
Example 16
0.1mol of naphthalene dicarboxylic acid and 0.15mol of ethylene glycol (molar ratio of alkyd: 1.5) were used as raw materials to prepare 10nm of linear nano TiO obtained in example 1 2 The catalyst is tetrabutyl titanate, the catalyst is 0.05 mol percent of furandicarboxylic acid, esterification is carried out under the protection of nitrogen, esterification is carried out at 200 ℃ for 1.5h, polycondensation is carried out at 275 ℃ for 2h, the reaction is stopped, the obtained product polyethylene naphthalate (PEN) is subjected to viscosity and test, the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, the type of degradation antibiotic is sulfamethoxazole, and the result is shown in Table 1.
Comparative example 1
0.1mol of furandicarboxylic acid and 0.15mol of glycol are used as raw materials (molar ratio of alkyd is 1.5), tetrabutyl titanate is used as a catalyst, the dosage is 1% of the molar amount of furandicarboxylic acid, esterification is carried out under the protection of nitrogen, each esterification is carried out for 1.5h at 200 ℃, polycondensation is carried out at 230 ℃ for 2h, the reaction is stopped, the obtained product poly (2, 5-furandicarboxylic acid) glycol ester (PEF) is subjected to viscosity and test, and after the obtained sample is crushed, injection molding and mechanical and optical property tests are carried out, the type of degraded antibiotic is norfloxacin, and the result is shown in table 1.
Comparative example 2
0.1mol of terephthalic acid and 0.15mol of ethylene glycol are used as raw materials (the molar ratio of alkyd is 1.5), tetrabutyl titanate is used as a catalyst, the dosage is 1% of the molar amount of terephthalic acid, esterification is carried out under the protection of nitrogen, esterification is carried out at 200 ℃ for 1.5h, polycondensation is carried out at 230 ℃ for 2h, the reaction is stopped, the obtained product polyethylene terephthalate (PET) is subjected to viscosity and test, and after the obtained sample is crushed, injection molding and mechanical and optical property test are carried out, the type of degradation antibiotic is moxifloxacin, and the result is shown in Table 1.
Table 1 shows the viscosity, mechanical and optical properties of the polyesters prepared (optical test: film thickness 150 μm)
Nanocomposite is an effective method for modifying polymers, and the structure of the polymers can be influenced by introducing a very small amount of nano materials, so that in-situ nanocomposite is more beneficial to uniform dispersion of the nano materials in a polymer matrix. Simultaneous nano TiO 2 Has good ultraviolet absorption effect and can bring about the improvement of the self-ultraviolet shielding performance of the polyester. As can be seen from examples 1 to 4, 14 and comparative examples 1 and 2, the viscosity of the polyesters obtained in comparative examples 1 and 2 was lower than that obtained in examples 1 to 14 by nano TiO under the same polyester synthesis temperature 2 Can be used as a catalyst promoter of tetrabutyl titanate when being used as a modifier, thereby improving the viscosity of the obtained polyester, namely the nano TiO adopted by the invention 2 In order to improve the catalytic activity of the catalyst, the polyester can be prepared at the same synthesis temperature to obtain the polyester with higher viscosity and better viscosity. And the tensile strength and the elongation at break of the PEF and the PET obtained in the examples 1 to 4 and 14 are superior to those of the PEF and the PET prepared in the comparative examples 1 and 2 by using tetrabutyl titanate as a catalyst, namely, the PEF and the PET are prepared by adopting nano TiO 2 As a modifier, the strength and toughness of the obtained polyester are better.
As can be seen from examples 1 to 16, the visible light transmittance of the obtained polyester was 70% or more and the ultraviolet transmittance was 10% or less. To demonstrate the UV shielding and blue light protection effects of the polyesters prepared in accordance with the invention, examples 1 to 16 incorporate nano TiO 2 Compared with comparative examples 1 and 2, no nano TiO was added 2 It can be seen that nano TiO is added 2 When used as a modifier, the ultraviolet transmittance of the obtained polyester is below 10%, which is obviously lower than that of the polyester in the case of comparative examples 1 and 2 by using tetrabutyl titanate as a catalyst. Namely, the invention adopts nano TiO 2 The ultraviolet light absorption effect of the polyester prepared by the modifier is good.
From examples 1 to 16 it can be seen that the polyester is obtained using nano TiO 2 As a modifier, the polyester is given the ability to degrade antibiotics. To demonstrate the antibiotic degrading effect of the polyester prepared in the present invention, examples 1 to 16 incorporate nano TiO 2 Compared with comparative examples 1 and 2, no nano TiO was added 2 It can be seen that nano TiO is added 2 When used as a modifier, all kinds of antibiotics can be degraded in a short time without adding nano TiO 2 The polyester prepared by the modifier does not have the capability of degrading antibiotics, and obvious change cannot be observed after 500 minutes of reaction. Namely, the invention adopts nano TiO 2 The preparation of the polyester for the modifier imparts the ability of the polyester to degrade antibiotics.
FIGS. 1 to 5 are photomicrographs of the polyesters prepared in examples 1 to 5, and it can be seen that nano TiO 2 The polyester matrix has no obvious agglomeration phenomenon, so that the nano modifier is in-situ dispersed in the polyester matrix, and has good dispersibility and light transmittance.
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 (9)

1. A method of antibiotic degradation, the method comprising:
adding polyester into an aqueous solution containing antibiotics for degradation reaction, and detecting the content of the antibiotics;
wherein the polyester is a functional nanocomposite polyester;
the antibiotics are selected from at least one of sulfadiazine, sulfamethoxazole and trimethoprim;
the time required for complete degradation of the antibiotics is 30-150 minutes;
the preparation method of the functional nano composite polyester comprises the following steps:
sequentially carrying out esterification reaction and polycondensation reaction on a mixture containing dibasic acid, dihydric alcohol, a catalyst and a modifier to obtain functional nano composite polyester;
the dibasic acid is at least one selected from furan dicarboxylic acid and naphthalene dicarboxylic acid;
the modifier is nano TiO 2 ；
The nano TiO 2 The size of (2) is 10-200 nm;
the nano TiO 2 Is linear nano TiO 2 ；
The modifier is used in an amount of 0.1-1 mol% of dibasic acid;
the catalyst is at least one selected from tetrabutyl titanate, isopropyl titanate, aluminum acetylacetonate, scandium trifluoromethane sulfonate, antimony oxide, germanium oxide, tin oxide and zinc acetate;
the visible light transmittance at the functional nanocomposite polyester 800nm is >70%;
the ultraviolet light transmittance of the functional nano composite polyester 400 and nm is less than 10 percent.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the dihydric alcohol is selected from C 2 ~C 8 A glycol.
3. The method of claim 1, wherein the glycol is selected from at least one of ethylene glycol, 1, 3-propanediol, and 1, 4-butanediol.
4. The method of claim 1, wherein the molar ratio of glycol to diacid is 1.5-4.0: 1, a step of;
the dosage of the catalyst is 0.1-0.5 mol% of the dibasic acid.
5. The method of claim 1, wherein the esterification reaction occurs under inert atmosphere conditions.
6. The method of claim 5, wherein the inert atmosphere is selected from at least one of a nitrogen atmosphere, a helium atmosphere, and an argon atmosphere.
7. The method of claim 1, wherein the temperature of the esterification reaction is 180-230 ℃;
the esterification reaction time is 0.2-4 h.
8. The method of claim 1, wherein the temperature of the polycondensation reaction is 200-275 ℃;
the time of the polycondensation reaction is 0.2-5 h.
9. The method of claim 1, wherein the functional nanocomposite polyester has an intrinsic viscosity of 0.60 to 1.25dl/g, a tensile strength of 50 to 105mpa, and an elongation at break of 35 to 550%.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN106311195A (en) * 2015-07-06 2017-01-11 新加坡国立大学 Catalyst for photocatalytic degradation of antibiotic as well as preparation method and application thereof
CN110606941A (en) * 2018-05-29 2019-12-24 中国科学院化学研究所 Low-end carboxyl hydrolysis-resistant polyester and preparation method and application thereof
CN113336927A (en) * 2021-06-21 2021-09-03 中国科学院大连化学物理研究所 Preparation method of polyester

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311195A (en) * 2015-07-06 2017-01-11 新加坡国立大学 Catalyst for photocatalytic degradation of antibiotic as well as preparation method and application thereof
CN110606941A (en) * 2018-05-29 2019-12-24 中国科学院化学研究所 Low-end carboxyl hydrolysis-resistant polyester and preparation method and application thereof
CN113336927A (en) * 2021-06-21 2021-09-03 中国科学院大连化学物理研究所 Preparation method of polyester

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