A PET film loaded with amino MOF and its preparation method and application

Abstract

The present invention discloses a PET film loaded with amino MOF, a preparation method and an application thereof, wherein the PET film loaded with amino MOF is a PET film on which amino MOF is grown, and a large number of crystal structures can be observed on the surface of the film by SEM. The present invention grows and fixes amino MOF on the PET film by a hydrothermal method, and can achieve efficient adsorption of formaldehyde.

Description

Technical Field

[0001] The invention belongs to the field of formaldehyde removal and relates to a PET film loaded with amino MOF and a preparation method and application thereof. Background Art

[0002] Formaldehyde is a highly carcinogenic compound. Due to its wide application, there is an urgent need for an effective method to remove formaldehyde. Currently, most methods for removing formaldehyde use adsorption, although adsorption can quickly remove formaldehyde from the air. However, traditional adsorption materials, such as activated carbon, have problems such as poor porosity and low adsorption capacity. Metal-organic framework materials (MOF) have shown broad application prospects in the field of gas adsorption and separation in recent years due to their advantages such as high porosity, large specific surface area, highly adjustable pore size, and diverse structures. However, MOF materials are not easy to form, and the powder properties limit their large-scale use. Therefore, there is an urgent need to develop an effective method to remove formaldehyde. Summary of the invention

[0003] In order to overcome the defects of the prior art, the present invention provides a PET film loaded with amino MOF and a preparation method and application thereof. The present invention grows and fixes amino MOF on the PET film by a hydrothermal method, which can achieve efficient adsorption of formaldehyde.

[0004] The present invention proposes a PET film loaded with amino MOF, wherein the amino MOF is grown on the surface of the PET film, and a large number of crystal structures can be observed on the surface of the film through SEM, which can achieve efficient adsorption of formaldehyde. The specific surface area of ​​the PET film is 60-90 m 2 / g, pore volume is 0.04-0.15cm 3 / g, pore size is 4-5nm.

[0005] The present invention provides a method for preparing a PET film loaded with amino MOF, the method comprising the following steps:

[0006] (1) Soak the PET film in concentrated acid and treat it with ultrasound.

[0007] (2) The ultrasonically treated PET membrane was placed in a buffer solution (pH = 8) containing 1-10 g / L amino acids and subjected to magnetic stirring.

[0008] (3) Dissolve 0.5-5 mol / L of metal salt in DMF, then add 2-aminoterephthalic acid and the PET film treated in step (2) and stir.

[0009] (4) The mixed solution treated in step (3) is poured into a polytetrafluoroethylene autoclave for heating to obtain a PET film loaded with amino MOF.

[0010] In step (1), the concentrated acid includes one or a mixture of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid; preferably, it is concentrated hydrochloric acid.

[0011] In step (1), the liquid-to-solid ratio of the concentrated acid to the PET film is (200-1):(30-1); preferably, it is 100:1.

[0012] In step (1), the ultrasonic treatment time is 0.5-4 h; preferably, 0.5 h.

[0013] The PET film after ultrasonic treatment in step (1) of the present invention further comprises a post-treatment step: washing with pure water.

[0014] In step (2), the amino acid buffer solution is one or a mixture of threonine, tyrosine and serine.

[0015] In step (2), the liquid-to-solid ratio of the PET film to the amino acid buffer solution is (1-60):(1-200); preferably, it is 1:200.

[0016] In step (2), the magnetic stirring time is 4-8 hours; preferably, 6 hours.

[0017] In step (2), the concentration of the amino acid is preferably 1-10 g / L.

[0018] In step (2), after the stirring, a post-processing step is also included: rinsing with ultrapure water three times and drying for later use.

[0019] In step (3), the volume of DMF used is 100-200 mL; preferably, 100 mL.

[0020] In step (3), the metal salt includes one or more of FeCl3, ZrCl2, ZnCl2, CrCl2 and hydrated salts thereof.

[0021] In step (3), the molar ratio of the metal salt to 2-aminoterephthalic acid is 1:1.5-1:10.

[0022] In step (3), the stirring temperature is room temperature.

[0023] In step (3), the stirring time is 30-60 minutes; preferably, 30 minutes.

[0024] In step (4), the heating temperature is 120-200°C.

[0025] In step (4), the heating time is 6-12 hours.

[0026] The present invention further comprises a post-treatment step after heating in step (4): after heating is completed, washing with methanol and drying to obtain a PET film loaded with amino MOF.

[0027] The key technical means of the preparation method of the amino-MOF-loaded PET film of the present invention is to form MOF growth sites after acid hydrolysis on the surface of the PET film. The technical difficulties that need to be overcome by the present invention include: 1. Hydroxyl groups are formed by acid hydrolysis of the PET film, and more hydroxyl groups are supplemented by amino acids to provide more MOF growth sites. 2. Controlling temperature and time, long-term high temperature will accelerate the degradation of PET.

[0028] In a specific embodiment, the method for preparing the amino-MOF-loaded PET film of the present invention comprises the following steps:

[0029] (1) Soak 1-3 g of PET film in 100 mL of concentrated acid, ultrasonically treat for 0.5-4 h, and then rinse with pure water.

[0030] (2) Place the washed PET membrane in a buffer solution (pH = 8) containing 200 mL of 1-10 g / L amino acids and stir it magnetically for 6 hours. Then rinse it three times with ultrapure water and dry it for later use.

[0031] (3) Dissolve 0.5-5 mol / L of metal salt in 100 mL of DMF, add an appropriate amount of 2-aminoterephthalic acid, stir, then add the treated PET film and stir at room temperature for 30 minutes.

[0032] (4) Pour the mixed solution into a polytetrafluoroethylene autoclave and heat it at 120-200°C for 6-12 hours. After heating, wash it with methanol and dry it to obtain a PET film loaded with amino MOF.

[0033] The possible technical principle involved in the method of the present invention is that carboxyl and hydroxyl groups are formed after PET degradation, and more hydroxyl groups are introduced through amino acids to combine with metal ions to help MOF grow and fix.

[0034] The present invention also provides a PET film loaded with amino MOF prepared by the method.

[0035] The present invention also proposes the application of the amino-MOF-loaded PET film in formaldehyde removal.

[0036] The beneficial effects of the present invention are as follows: the present invention fixes and grows MOF on the surface of the PET film, thereby solving the problem that MOF powder is difficult to form; at the same time, the MOF grown in situ on the film retains a high porosity and has a high adsorption capacity for formaldehyde. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1These are photos of a blank PET film and a PET film loaded with MOF according to Examples 1-5 of the present invention;

[0038] Figure 2 This is a SEM photo of the PET film loaded with MOF in Examples 1-5 of the present invention;

[0039] Figure 3 : is the nitrogen adsorption-desorption curve of the MOF-loaded PET film in Examples 1-5 of the present invention;

[0040] Figure 4 It is the formaldehyde removal rate of the blank PET film and the PET film loaded with MOF in Examples 1-5 of the present invention. DETAILED DESCRIPTION

[0041] The present invention is further described in detail with reference to the following specific examples and drawings. The process, conditions, experimental methods, etc. for implementing the present invention, except for the contents specifically mentioned below, are all common knowledge and common common sense in the art and are not particularly limited by the present invention.

[0042] The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0044] Example 1

[0045] (1) Soak 1 g of PET film in 100 mL of concentrated hydrochloric acid, ultrasonically treat for 0.5 h, and then rinse with pure water.

[0046] (2) Place the washed PET membrane in step (1) into 200 mL of 1 g / L threonine buffer solution (pH = 8) and stir magnetically for 6 hours. Then rinse three times with ultrapure water and dry for later use.

[0047] (3) Dissolve 0.5 mol / L ZrCl2 in 100 mL DMF, add 0.75 mol / L 2-aminoterephthalic acid, stir, then add the PET film treated in step (2), and stir at room temperature for 30 minutes.

[0048] (4) The mixed solution was poured into a polytetrafluoroethylene autoclave and heated at 120°C for 6 hours. After heating, it was washed with methanol and dried to obtain a PET film loaded with amino MOF.

[0049] Example 2

[0050] (1) Soak 2 g of PET film in 100 mL of concentrated hydrochloric acid, ultrasonically treat for 0.5 h, and then rinse with pure water.

[0051] (2) Place the washed PET membrane in step (1) into 200 mL of 1 g / L serine buffer solution (pH = 8) and stir magnetically for 6 hours. Then rinse with ultrapure water three times and dry for later use.

[0052] (3) Dissolve 1 mol / L ZnCl2 in 100 mL DMF, then add 2 mol / L 2-aminoterephthalic acid, stir, then add the PET film treated in step (2), and stir at room temperature for 30 minutes.

[0053] (4) The mixed solution was poured into a polytetrafluoroethylene autoclave and heated at 130°C for 8 hours. After heating, it was washed with methanol and dried to obtain a PET film loaded with amino MOF.

[0054] Example 3

[0055] (1) Soak 3 g of PET film in 100 mL of concentrated hydrochloric acid, ultrasonically treat for 0.5 h, and then rinse with pure water.

[0056] (2) Place the washed PET film in step (1) into 200 mL of 2 g / L tyrosine buffer solution (pH = 8) and stir magnetically for 6 hours. Then rinse with ultrapure water three times and dry for later use.

[0057] (3) Dissolve 2 mol / L FeCl3 in 100 mL DMF, add 10 mol / L 2-aminoterephthalic acid, stir, then add the PET film treated in step (2), and stir at room temperature for 30 minutes.

[0058] (4) The mixed solution was poured into a polytetrafluoroethylene autoclave and heated at 150°C for 10 hours. After heating, it was washed with methanol and dried to obtain a PET film loaded with amino MOF.

[0059] Example 4

[0060] (1) Soak 1 g of PET film in 100 mL of concentrated hydrochloric acid, ultrasonically treat for 0.5 h, and then rinse with pure water.

[0061] (2) Place the washed PET film in step (1) into 200 mL of 4 g / L serine buffer solution (pH = 8) and stir magnetically for 6 hours. Then rinse with ultrapure water three times and dry for later use.

[0062] (3) Dissolve 5 mol / L CrCl2 in 100 mL DMF, add 15 mol / L 2-aminoterephthalic acid, stir, then add the PET film treated in step (2), and stir at room temperature for 30 minutes.

[0063] (4) The mixed solution was poured into a polytetrafluoroethylene autoclave and heated at 180°C for 12 hours. After heating, it was washed with methanol and dried to obtain a PET film loaded with amino MOF.

[0064] Example 5

[0065] (1) Soak 1 g of PET film in 100 mL of concentrated hydrochloric acid, ultrasonically treat for 0.5 h, and then rinse with pure water.

[0066] (2) Place the washed PET film in step (1) into 200 mL of 5 g / L threonine buffer solution (pH = 8) and stir magnetically for 6 hours. Then rinse with ultrapure water three times and dry for later use.

[0067] (3) Dissolve 4 mol / L FeCl3 in 100 mL DMF, add 40 mol / L 2-aminoterephthalic acid, stir, then add the PET film treated in step (2), and stir at room temperature for 30 minutes.

[0068] (4) The mixed solution was poured into a polytetrafluoroethylene autoclave and heated at 200°C for 12 hours. After heating, it was washed with methanol and dried to obtain a PET film loaded with amino MOF.

[0069] Experimental results of Examples 1-5:

[0070] Photograph: The color change of the amino-MOF-loaded PET film after treatment in Examples 1-5 of the present invention is as follows: Figure 1 As shown, compared with the untreated blank PET film, the surface color of the treated film becomes darker.

[0071] SEM characterization: SEM can be used to observe the formation of MOF structure on the surface of PET film ( Figure 2 ), pore volume and pore diameter are shown in Table 1.

[0072]

[0073] Example 6

[0074] N2 adsorption and desorption test:

[0075] The adsorption-desorption isotherm of N2 at 298 K was tested using the adsorption instrument ASAP 2460, and the Brunauer-Emmett-Teller (BET) specific surface area was calculated from the relative pressure of 0.05 ~ 0.3 bar. Finally, the pore size of the membrane was deduced from the N2 isotherm according to the micropore (HK) model. The specific experimental results are shown in Figure 3 .

[0076] Example 7

[0077] Formaldehyde adsorption experiment: The formaldehyde removal experiment was carried out in a 200L sealed cabin. The heating table was preheated to 80°C, 150ul of formaldehyde solution was dropped into a glass culture dish and placed on the heating table for 30 minutes to completely volatilize the formaldehyde, then 10g of membrane sample was placed in it, and the atmospheric sampler was used to sample at different time points and record the values. The results are as follows Figure 4 As shown, compared with the untreated PET film, Examples 1-5 of the present invention can effectively remove formaldehyde, among which Example 3 of the present invention can remove 85% of formaldehyde within 24 hours.

[0078] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0079] As used in the present invention, the term "comprising" is an open expression, that is, including the contents specified in the present invention but not excluding other contents.

[0080] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0081] Although the embodiments of the present description have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present description, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a PET film loaded with amino MOF, characterized in that: The method comprises the following steps: (1) Soak the PET film in concentrated hydrochloric acid and treat it with ultrasound; (2) placing the ultrasonically treated PET membrane in a buffer solution containing 1-10 g / L amino acids, pH = 8, and performing magnetic stirring; (3) dissolving 0.5-5 mol / L of a metal salt in DMF, adding 2-aminoterephthalic acid and the PET film treated in step (2) and stirring; the metal salt is selected from one or more of FeCl3, ZrCl2, ZnCl2, CrCl2 and their hydrated salts; (4) The mixed solution treated in step (3) is poured into a polytetrafluoroethylene autoclave for heating to obtain a PET film loaded with amino MOF.

2. The method according to claim 1, characterized in that In step (1), the liquid-to-solid ratio of concentrated hydrochloric acid to PET film is (1-200) mL: (1-30) g; and the ultrasonic treatment time is 0.5-4 h.

3. The method according to claim 1, characterized in that In step (2), the amino acid buffer solution is one or a mixture of threonine, tyrosine and serine; and / or the liquid-to-solid ratio of the PET film to the amino acid buffer solution is (1-60) g: (1-200) mL.

4. The method according to claim 1, characterized in that In step (2), the magnetic stirring time is 4-8 hours.

5. The method according to claim 1, characterized in that In step (3), the molar ratio of the metal salt to 2-aminoterephthalic acid is 1:1.5-1:10; the stirring temperature is room temperature; and the stirring time is 30-60 minutes.

6. The method according to claim 1, characterized in that In step (4), the heating temperature is 120-200° C. and the heating time is 6-12 hours.

7. A PET film loaded with amino MOF prepared by the method according to any one of claims 1 to 6, characterized in that: The amino-MOF-loaded PET film is a PET film on which amino-MOF is grown. The specific surface area of ​​the PET film is 60-90 m 2 / g, pore volume is 0.04-0.15cm 3 / g, pore size is 4-5nm.

8. Use of the amino-MOF-loaded PET film as claimed in claim 7 in formaldehyde removal.

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