CN111533917A - High-critical-dissolution-temperature-type temperature-sensitive zirconium-based metal organic framework material and preparation method thereof - Google Patents
High-critical-dissolution-temperature-type temperature-sensitive zirconium-based metal organic framework material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high critical solution temperature type temperature-sensitive zirconium-based metal organic framework material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing a zirconium-based MOF material; (2) reacting with methacrylic anhydride (or acrylic anhydride) such that the zirconium-based MOF material is double bonded; (3) preparing a low-molecular-weight high-critical-dissolution-temperature type temperature-sensitive acrylonitrile-acrylamide copolymer with a mercapto group at the end by a mercapto-alkene click chemistry method; (4) the prepared temperature-sensitive acrylonitrile-acrylamide copolymer is used as a modifier to prepare the temperature-sensitive zirconium-based metal organic framework material with high critical solution temperature by click chemistry. The modified zirconium-based MOF has obvious temperature sensitivity of a high critical solution temperature type, and can be aggregated and settled in water at low temperature and stably dispersed in water at high temperature. The preparation process is simple to operate and easy to implement.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-critical-dissolution-temperature type temperature-sensitive zirconium-based metal organic framework material and a preparation method thereof.
Background
The Metal Organic Framework (MOF) is a crystalline organic-inorganic hybrid material which is formed by self-assembling metal ions or ion clusters and organic connectors through coordination bonds to form a one-dimensional, two-dimensional or three-dimensional framework. The MOF material has the characteristics of both a polymer and a coordination compound as a new generation of a nano material, and has immeasurable development prospect in structural design and functional application. The MOF nano-materials have attracted extensive attention as candidate materials for various potential applications such as gas separation, gas storage, catalysis and sensors due to their advantages such as regular and ordered porous structure, large specific surface area, and adjustability of structure and size. More recently, post-synthesis modification of MOF materials has also taken place. Post-modifications isolated from the synthesis can further functionalize more diverse structures and features.
Currently, stimulus-responsive MOF materials are receiving wide attention for their potential applications in the fields of controlled drug release and environmental detection and management. The stimulus response factors studied at present include pH, temperature, ions, redox, light, pressure, magnetic field, etc., and among numerous environmental stimulus signals, the temperature (T) change widely exists in the nature, and the control is relatively convenient and simple, and the stimulus response factors are relatively easy to apply inside and outside the organism. Therefore, among the numerous types of smart polymers, temperature-sensitive smart polymers have been most widely and intensively studied. Although there have been many studies on temperature stimulus responsive MOF materials, they have focused on modifying modified warm MOF materials with temperature sensitive polymers of the Lower Critical Solution Temperature (LCST) type. By utilizing the conformation transition of the polymer near the LCST, the hydrophilicity and the hydrophobicity of the surface of the MOF material and the pore structure are changed, so that the temperature of the dispersion performance of the MOF material in water is controllable. Namely, the modified MOF can be stably dispersed in water at low temperature, and can be aggregated and settled in water at high temperature, so that the modified MOF has a normal-phase thermal response characteristic. However, in some occasions (drug controlled release, chemical separation, sensors and the like), the temperature-sensitive intelligent MOF material with the dispersibility of the MOF material in water being improved along with the rise of the environmental temperature (reverse thermal response characteristic) is more suitable, so that the preparation of the temperature-responsive temperature-sensitive MOF material has very important significance. Unfortunately, temperature sensitive MOF materials with UCST-type (reversed phase) temperature sensitive behavior have not been reported.
The UCST type temperature-sensitive acrylonitrile-acrylamide copolymer (P (AN-co-AM)) has a temperature-sensitive mechanism just opposite to that of AN LCST type temperature-sensitive polymer, namely low-temperature hydrophobicity and high-temperature hydrophilicity. The method is used for preparing the temperature-sensitive MOF material by modifying the zirconium-based MOF material, so that the reversed-phase UCST type temperature-sensitive zirconium-based MOF material is successfully prepared, and the MOF material has the performance which is completely opposite to that of the normal-phase temperature-sensitive MOF material. The invention provides a method for designing and preparing the reversed phase UCST type temperature-sensitive MOF material.
Disclosure of Invention
Aiming at the problems that in the existing temperature-sensitive MOF material, modifier temperature-sensitive polymers are LCST type temperature-sensitive polymers, so that all MOF materials have normal-phase thermal response characteristics, the invention adopts UCST type temperature-sensitive acrylonitrile-acrylamide copolymer P (AN-co-AM) to perform UIO-66-NH treatment on zirconium-based MOF materials2Modified to graft to UIO-66-NH2The UCST type temperature-sensitive zirconium-based MOF material with the reversed phase thermal response characteristic is obtained on the surface or in the nano-pores.
One of the technical schemes of the invention is as follows: a high critical solution temperature type temperature-sensitive zirconium-based metal organic framework material is prepared by grafting and modifying a double-bonded zirconium-based metal organic framework material and a high critical solution temperature type temperature-sensitive acrylonitrile-acrylamide copolymer with a sulfydryl at the tail end. The high critical solution temperature type temperature-sensitive zirconium-based metal organic framework material is insoluble in water at a temperature lower than the UCST and cannot be stably dispersed in water, and is soluble in water at a temperature higher than the UCST and can be uniformly and stably dispersed in water, so that the material shows obvious UCST type temperature sensitivity.
The second technical scheme of the invention is as follows: the preparation method of the high-critical-dissolution-temperature-type temperature-sensitive zirconium-based metal organic framework material comprises the following steps of:
(1) preparation of zirconium-based Metal-organic framework Material (UIO-66-NH)2)；
(2) Zirconium-based metal organic framework material (UIO-66-NH)2) Reacting with methacrylic anhydride or acrylic anhydride to double bond the zirconium-based metal organic framework material;
(3) preparing a low-molecular-weight high-critical-dissolution-temperature type temperature-sensitive acrylonitrile-acrylamide copolymer P (AN-co-AM) with a mercapto group at the tail end;
(4) and (3) taking the temperature-sensitive acrylonitrile-acrylamide copolymer P (AN-co-AM) prepared in the step (3) as a modifier, and carrying out graft modification on the double-bond zirconium-based metal organic framework material prepared in the step (2) through click chemistry to prepare the high-critical solution temperature type temperature-sensitive zirconium-based metal organic framework material.
Preferably, the zirconium-based metal organic framework material (UIO-66-NH) is prepared by a solvothermal method in step (1)2) The method specifically comprises the following steps: reacting ZrCl4Adding acetic acid into dry N, N-Dimethylformamide (DMF) for dissolving, adding 2-amino terephthalic acid into the solution for dissolving, adding ultrapure water to prepare a mixed solution, placing the mixed solution into a reaction kettle for solvothermal reaction to obtain the zirconium-based metal organic framework material (UIO-66-NH)2)。
Preferably, said ZrCl4The mass percentage of the mixed solution is 0.5 to 1.2 percent of the total weight of the mixed solution, and the mass of the 2-amino terephthalic acid is ZrCl477.33% -90.0%; the adding amount of the acetic acid is 4.0 to 8.0 percent of the total weight of the mixed solution; the ultrapure water accounts for 0.2-0.4% of the total weight of the mixed liquid; the solvothermal reaction temperature is 120 ℃, and the reaction time is 24 hours.
Preferably, step (2) comprises the steps of: mixing zirconium-based metal organic framework material (UIO-66-NH)2) Dispersing in dry Dichloromethane (DMF), adding methacrylic anhydride or acrylic anhydride, reacting for a certain time, centrifuging after the reaction is finished, washing and drying.
Preferably, the mass fraction of the zirconium-based metal organic framework material is 3-10%; the mass of the methacrylic anhydride or the acrylic anhydride is 1-6 times of that of the zirconium-based metal organic framework material; the reaction condition is room temperature, and the reaction time is 24-96 h.
Preferably, step (3) comprises the steps of: dissolving Acrylonitrile (AN) and Acrylamide (AM) in dimethyl sulfoxide (DMSO), adding mercaptoethylamine hydrochloride (AES) and Azobisisobutyronitrile (AIBN), introducing nitrogen to remove air, sealing, reacting under heating, cooling after reaction, precipitating in methanol, and drying to obtain the product.
Preferably, the mass ratio of the Acrylonitrile (AN) to the Acrylamide (AM) is 1 (2.5-6), and the total mass concentration of the Acrylonitrile (AN) and the Acrylamide (AM) is 1.0-3.0 mol/L; the ratio of the total mass of Acrylonitrile (AN) and Acrylamide (AM) to the mass of mercaptoethylamine hydrochloride material is (10-100) to 1; the mass ratio of mercaptoethylamine hydrochloride (AES) to Azobisisobutyronitrile (AIBN) is (3-8) to 1; and (3) filling nitrogen for 20-30min, heating at 60 ℃, reacting for 6-8h, and cooling in an ice water bath after the reaction is finished.
Preferably, step (4) comprises the steps of: dispersing the double-bond zirconium-based metal organic framework material prepared in the step (2) in dimethyl sulfoxide (DMSO), adding the high-critical-dissolution-temperature type temperature-sensitive acrylonitrile-acrylamide copolymer prepared in the step (3) and Azobisisobutyronitrile (AIBN), filling nitrogen, reacting under a heating condition, centrifuging after the reaction is finished, washing the precipitate with distilled water, and drying to obtain a product.
Preferably, the mass fraction of the double-bonded zirconium-based metal organic framework material is 0.5-5%; the mass of the added high critical solution temperature type temperature-sensitive acrylonitrile-acrylamide copolymer is 0.75-10 times that of the double-bond zirconium-based metal organic framework material; the addition amount of the azodiisobutyronitrile is 1 to 20 percent of the mass of the high critical solution temperature type temperature-sensitive acrylonitrile-acrylamide copolymer; and (3) filling nitrogen for 20-30min, heating at 80 ℃, and reacting for 8-24 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the UCST type temperature-sensitive zirconium-based MOF material by modifying the zirconium-based MOF material by using the UCST type temperature-sensitive polymer P (AN-co-AM) for the first time. The product of the invention has the characteristics of simple process, lower cost, easy industrial implementation and the like. The UCST type temperature-sensitive zirconium-based MOF material UIO-66-NH prepared by the invention2Has obvious inverse UCST type temperature responsiveness: i.e. low temperature (T)<UCST) type temperature-sensitive zirconium-based MOF material UIO-66-NH2Insoluble in water and high in temperature (T)>UCST) type temperature-sensitive zirconium-based MOF material UIO-66-NH2Uniformly dispersed in water.
According to the invention, the grafting rate of the prepared modified MOF material is controlled to be between 1 and 24 percent by controlling the adding amount of the high critical solution temperature type temperature-sensitive acrylonitrile-acrylamide copolymer and the double-bonded zirconium-based metal organic framework material, and the UCST temperature of the modified MOF material is controlled to be between 5 and 55 ℃.
Drawings
FIG. 1 is a UIO-66-NH zirconium-based MOF material prepared in example 1 of the present invention2(U0), double-bonded UIO-66-NH2(U1), UCST type UIO-66-NH2(U2) an X-ray view;
FIG. 2 is a UIO-66-NH zirconium-based MOF material prepared in example 1 of the present invention2(U0) scanning electron micrographs;
FIG. 3 is a diagram of a doubly-bonded UIO-66-NH prepared in example 1 of the present invention2(U1) scanning electron micrographs;
FIG. 4 is a UCST type UIO-66-NH prepared in example 1 of the present invention2(U2) scanning electron micrographs;
FIG. 5 is UIO-66-NH before and after modification prepared in example 1 of the present invention and comparative example 12Thermogravimetry of (a);
FIG. 6 is a UIO-66-NH zirconium-based MOF material prepared in example 1 of the present invention2(U0) schematic dispersion in water;
FIG. 7 is a diagram of a doubly-bonded UIO-66-NH prepared in example 1 of the present invention2(U1) schematic dispersion in water;
FIG. 8 is a UCST type UIO-66-NH prepared in example 1 of the present invention2(U2) schematic diagram for dispersion in water.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
Example 1
(1) Zirconium-based MOF material UIO-66-NH2Preparation of (U0): a250 ml round bottom flask was charged with 0.756g ZrCl4And 5.5ml of acetic acid and 115ml of dried DMF, 0.6525g of 2-aminoterephthalic acid is added after the solid is completely dissolved by ultrasonic waves, 0.27ml of ultrapure water is added after the solid is completely dissolved by ultrasonic waves, and the mixed solution is placed in a reaction kettle to react for 24 hours at 120 ℃. After the reaction is finished, washing and centrifuging by using a large amount of DMF, and drying in vacuum for later use.
(2) Double-bonded UIO-66-NH2Preparation of (U1): u0(1g) was dispersed by sonication in 15ml of dry dichloromethane, 2.5g of methacrylic anhydride was added and the reaction was carried out at room temperature for 72 h. After the reaction is finished, washing the reaction product by using a large amount of dichloromethane, centrifuging the reaction product, and drying the reaction product in vacuum for later use.
(3) Preparing a UCST type temperature-sensitive copolymer P (AN-co-AM): dissolving 6.5g of Acrylamide (AM) and 1.6g of Acrylonitrile (AN) in 70ml of dimethyl sulfoxide (DMSO), adding 0.354g of mercaptoethylamine hydrochloride and 0.1g of Azobisisobutyronitrile (AIBN), introducing nitrogen for 20-30min, and reacting for 6-8h under the heating condition of 60 ℃. After the reaction is finished, the mixture is cooled in an ice-water bath, methanol is precipitated for three times, and the mixture is dried in vacuum, so that the yield is 48 percent.
(4) UCST type temperature-sensitiveZirconium-based MOF material UIO-66-NH2Preparation of (U2): adding 0.2g of double-bond modified MOF material U1 into 30ml of DMSO, then oscillating for about 15 minutes by ultrasonic waves, dissolving 0.6g of UCST type temperature-sensitive copolymer P (AN-co-AM) and 10mg of AIBN in the system, filling nitrogen for 20-30min, and reacting for 24 hours under the heating condition of 80 ℃. After the reaction is finished, cooling, centrifuging, washing by a large amount of distilled water, washing by methanol, centrifuging and then drying in vacuum, wherein the grafting rate is 2.6%.
The zirconium-based MOF material UIO-66-NH prepared in the step (1)2(U0) and the double-bonded UIO-66-NH prepared in step (2)2(U1) and the UCST type temperature-sensitive zirconium-based MOF material UIO-66-NH prepared in the step (4)2(U2) X-ray diagram FIG. 1, the structure of the modified MOF material (U1, U2) was unchanged compared to that before modification (U0); the scanning electron micrographs are shown in FIGS. 2-4, and the morphology of the modified MOF material (U1, U2) is similar to that before modification (U0), except that the surface of the U2 particle is smoother and the dispersibility is better after the polymer is grafted and modified; the thermal weight loss graph is shown in figure 5, the thermal weight loss result shows that after 730 ℃, all substances are kept stable (no weight loss is caused) through thermal weight loss, the modifier UCST type copolymer P (AN-co-AM) is completely decomposed (weight loss is 100 percent), and the double-bond modified UIO-66-NH is2(U1) weight loss on heating was 69.3%, whereas UIO-66-NH of UCST-type copolymer P (AN-co-AM)2(U2) the weight loss on heating was 71.9%. The polymer grafting rate can be calculated by comparing the weight loss mass fraction after weight loss stabilization before and after graft modification of the copolymer (for example, U2 grafting rate is U2 weight loss mass fraction-U1 weight loss mass fraction is 71.9% -69.3% -2.6%); MOF Material before and after modification (5mg ml)-1) The dispersion in water after 10 minutes incubation at different temperatures is schematically shown in FIGS. 6-8. As can be seen from FIG. 6, UIO-66-NH2(U0) was dispersed in water at both low temperature (25 ℃) and high temperature (45 ℃), probably because U0 had a large number of carboxyl and amino groups, making U0 more hydrophilic; double-bonded UIO-66-NH in FIG. 72(U1) could not be stably dispersed in water at either low temperature (25 ℃) or high temperature (45 ℃), probably because the introduction of methacryloyl groups when U0 reacts with methacrylic anhydride to form U1 decreased the hydrophilicity of U1, enhanced the hydrophobicity of U1; in FIG. 8, a UCST-type temperature sensitive zirconium-based MOF material UIO-66-NH2(U2) is low at a temperature (e.g., 25 ℃ C.)The UCST (29.2 ℃) can not be stably dispersed in water, and the UCST can be stably dispersed in water at the temperature (for example, 45 ℃) higher than the UCST (29.2 ℃), and obvious UCST type temperature sensitivity is presented, which shows that the temperature-sensitive polymer modification can improve the hydrophilicity of the zirconium-based MOF material and endow the zirconium-based MOF material with obvious reversed phase UCST type temperature-sensitive performance.
Experiments prove that the UCST temperature of the UCST type temperature-sensitive copolymer P (AN-co-AM) is influenced by the dosage ratio of acrylamide and acrylonitrile. 5mg ml prepared in example 1-1The UCST temperature of the UCST type temperature-sensitive copolymer P (AN-co-AM) is 39.5 ℃, the temperature is lower than 39.5 ℃, the UCST is insoluble in water, and the UCST is soluble in water at the temperature of more than 39.5 ℃;
the UCST temperature of the modified MOF material was 29.2 ℃, i.e. it was not stably dispersible in water below 29.2 ℃ and was uniformly dispersible in water above 29.2 ℃, the above experimental temperatures of 25 ℃ and 45 ℃ being only two exemplary temperatures below and above 29.2 ℃.
Example 2
(1) Zirconium-based MOF material UIO-66-NH2The preparation of (1): same as example 1, step (1).
(2) Double-bonded UIO-66-NH2The preparation of (1): same as example 1, step (2).
(3) Preparing a UCST type temperature-sensitive copolymer P (AN-co-AM): same as example 1, step (3).
(4) UCST type temperature-sensitive zirconium-based MOF material UIO-66-NH2Preparation of (U3): adding 0.2g of double-bond modified MOF material U1 into 30ml of DMSO, then oscillating for about 15 minutes by ultrasonic waves, dissolving 1.0g of UCST type temperature-sensitive copolymer P (AN-co-AM) and 10mg of AIBN in the system, filling nitrogen for 20-30min, and reacting for 24 hours under the heating condition of 80 ℃. After the reaction is finished, cooling, centrifuging, washing with a large amount of distilled water, washing with methanol, centrifuging, and then carrying out vacuum drying, wherein the polymer grafting rate is 7.6% (the calculation method is the same as U2), the modified MOF material can not be stably dispersed in water when the temperature is lower than UCST (33.8 ℃) of the modified MOF material, and can be stably dispersed in water when the temperature is higher than UCST (33.8 ℃), and obvious UCST-type temperature sensitivity is presented, which indicates that the temperature-sensitive polymer grafting modification endows the zirconium-based MOF material with obvious reversed-phase UCST-type temperature-sensitive performance.
Example 3
(1) Zirconium-based MOF material UIO-66-NH2The preparation of (1): same as example 1, step (1).
(2) Double-bonded UIO-66-NH2The preparation of (1): same as example 1, step (2).
(3) Preparing a UCST type temperature-sensitive copolymer P (AN-co-AM): same as example 1, step (3).
(4) UCST type temperature-sensitive zirconium-based MOF material UIO-66-NH2The preparation of (1): adding 0.2g of double-bond modified MOF material U1 into 30ml of DMSO, then oscillating for about 15 minutes by ultrasonic waves, dissolving 0.15g of UCST type temperature-sensitive copolymer P (AN-co-AM) and 10mg of AIBN in the system, filling nitrogen for 20-30min, and reacting for 24 hours under the heating condition of 80 ℃. After the reaction is finished, cooling, centrifuging, washing by a large amount of distilled water, washing by methanol, centrifuging and then drying in vacuum, wherein the grafting rate is 1%. The modified MOF material can not be stably dispersed in water at a temperature lower than UCST (5 ℃) of the modified MOF material, and can be stably dispersed in water at a temperature higher than UCST (5 ℃), and obvious UCST type temperature sensitivity is presented, which indicates that the temperature-sensitive polymer graft modification endows the zirconium-based MOF material with obvious reversed phase UCST type temperature-sensitive performance.
Example 4
(1) Zirconium-based MOF material UIO-66-NH2The preparation of (1): same as example 1, step (1).
(2) Double-bonded UIO-66-NH2The preparation of (1): same as example 1, step (2).
(3) Preparing a UCST type temperature-sensitive copolymer P (AN-co-AM): same as example 1, step (3).
(4) UCST type temperature-sensitive zirconium-based MOF material UIO-66-NH2The preparation of (1): adding 0.2g of double-bond modified MOF material U1 into 30ml of DMSO, then oscillating for about 15 minutes by ultrasonic waves, dissolving 1.8g of UCST type temperature-sensitive copolymer P (AN-co-AM) and 20mg of AIBN in the system, filling nitrogen for 20-30min, and reacting for 24 hours under the heating condition of 80 ℃. After the reaction is finished, cooling, centrifuging, washing by a large amount of distilled water, washing by methanol, centrifuging and then drying in vacuum, wherein the grafting rate is 24%. The modified MOF material is not stably dispersible in water at temperatures below its UCST (55 deg.C) and is stably dispersible in water at temperatures above its UCST (55 deg.C)The zirconium-based MOF material has obvious inverse UCST-type temperature sensitivity, and the temperature-sensitive polymer graft modification is shown to endow the zirconium-based MOF material with obvious inverse UCST-type temperature-sensitive performance.
Comparative example 1
(1) Zirconium-based MOF material UIO-66-NH2The preparation of (1): same as example 1, step (1).
(2) Double-bonded UIO-66-NH2The preparation of (1): in the same manner as in step (2) of example 1, as shown in FIG. 7, double bond-modified UIO-66-NH2Has no temperature sensitivity.
(3) Preparing a UCST type temperature-sensitive copolymer P (AN-co-AM): same as example 1, step (3).
(4) UCST type temperature-sensitive zirconium-based MOF material UIO-66-NH2Preparation of (U4): adding 0.2g of double-bond modified MOF material U1 into 30ml of DMSO, then oscillating for about 15 minutes by ultrasonic waves, dissolving 0.1g of UCST type temperature-sensitive copolymer P (AN-co-AM) and 10mg of AIBN in the system for about 10mg, filling nitrogen for 20-30min, and reacting for 24 hours under the heating condition of 80 ℃. After the reaction is finished, cooling, centrifuging, washing by a large amount of distilled water, washing by methanol, centrifuging and then drying in vacuum, wherein the polymer grafting rate is 0.8% (the calculation method is the same as U2), and the modified MOF material cannot be dispersed in water and has no temperature sensitivity because the polymer grafting rate is low.
The results of the above examples and the results of the comparative examples show that a certain amount of UCST type temperature-sensitive copolymer P (AN-co-AM) grafted by a thiol-ene click chemistry method obviously endows the zirconium-based MOF material with temperature-sensitive performance, and meanwhile, the grafting rate of the modified MOF also has a certain influence on the UCST of the zirconium-based MOF material.
Claims (10)
1. The high critical solution temperature type temperature sensitive zirconium-based metal organic framework material is characterized by being prepared by grafting and modifying a double-bonded zirconium-based metal organic framework material and a high critical solution temperature type temperature sensitive acrylonitrile-acrylamide copolymer with a sulfydryl at the tail end.
2. The preparation method of the high critical solution temperature type temperature sensitive zirconium-based metal organic framework material as claimed in claim 1, characterized by comprising the following steps:
(1) preparing a zirconium-based metal organic framework material;
(2) reacting the zirconium-based metal organic framework material with methacrylic anhydride or acrylic anhydride to double bond the zirconium-based metal organic framework material;
(3) preparing a low-molecular-weight high-critical-dissolution-temperature type temperature-sensitive acrylonitrile-acrylamide copolymer with a mercapto group at the tail end;
(4) and (3) taking the temperature-sensitive acrylonitrile-acrylamide copolymer prepared in the step (3) as a modifier, and carrying out graft modification on the double-bond zirconium-based metal organic framework material prepared in the step (2) through click chemistry to prepare the high-critical solution temperature type temperature-sensitive zirconium-based metal organic framework material.
3. The preparation method of the temperature-sensitive zirconium-based metal organic framework material with the high critical solution temperature according to claim 2, wherein the zirconium-based metal organic framework material is prepared by a solvothermal method in the step (1), and the method specifically comprises the following steps: reacting ZrCl4And acetic acid is added into dry N, N-dimethylformamide for dissolution, 2-amino terephthalic acid is added into the solution for dissolution, ultrapure water is added into the solution for preparation of mixed solution, and the mixed solution is placed into a reaction kettle for solvothermal reaction to obtain the zirconium-based metal organic framework material.
4. The method for preparing a temperature-sensitive zirconium-based metal organic framework material of high critical solution temperature type according to claim 3, wherein ZrCl is added4The mass percentage of the mixed solution is 0.5 to 1.2 percent of the total weight of the mixed solution, and the mass of the 2-amino terephthalic acid is ZrCl477.33% -90%; the adding amount of the acetic acid is 4 to 8 percent of the total weight of the mixed solution; the ultrapure water accounts for 0.2-0.4% of the total weight of the mixed liquid; the solvothermal reaction temperature is 120 ℃, and the reaction time is 24 hours.
5. The method for preparing the temperature-sensitive zirconium-based metal organic framework material of the high critical solution temperature type according to claim 2, wherein the step (2) comprises the steps of: dispersing the zirconium-based metal organic framework material in dry dichloromethane, adding methacrylic anhydride or acrylic anhydride for reaction, centrifugally separating after the reaction is finished, washing and drying.
6. The preparation method of the high critical solution temperature type temperature-sensitive zirconium-based metal organic framework material as claimed in claim 5, wherein the mass fraction of the zirconium-based metal organic framework material is 3-10%; the mass of the methacrylic anhydride or the acrylic anhydride is 1-6 times of that of the zirconium-based metal organic framework material; the reaction condition is room temperature, and the reaction time is 24-96 h.
7. The preparation method of the temperature-sensitive zirconium-based metal organic framework material of the high critical solution temperature type according to claim 2, wherein the step (3) comprises the steps of: dissolving acrylonitrile and acrylamide in dimethyl sulfoxide, adding mercaptoethylamine hydrochloride and azobisisobutyronitrile, charging nitrogen, reacting under heating condition, cooling after the reaction is finished, precipitating in methanol, and drying to obtain the product.
8. The preparation method of the temperature-sensitive zirconium-based metal organic framework material with the high critical solution temperature according to claim 7, wherein the mass ratio of the acrylonitrile to the acrylamide is 1 (2.5-6), and the mass concentration of the total mass of the acrylonitrile and the acrylamide is 1.0-3.0 mol/L; the ratio of the total mass of the acrylonitrile and the acrylamide to the mass of the mercaptoethylamine hydrochloride material is (10-100) to 1; the mass ratio of the mercaptoethylamine hydrochloride to the azodiisobutyronitrile is (3-8) to 1; and (3) filling nitrogen for 20-30min, heating at 60 ℃, reacting for 6-8h, and cooling in an ice water bath after the reaction is finished.
9. The preparation method of the temperature-sensitive zirconium-based metal organic framework material of the high critical solution temperature type according to claim 2, wherein the step (4) comprises the steps of: dispersing the double-bond zirconium-based metal organic framework material prepared in the step (2) in dimethyl sulfoxide, adding the high-critical-dissolution-temperature type temperature-sensitive acrylonitrile-acrylamide copolymer prepared in the step (3) and azobisisobutyronitrile, charging nitrogen, reacting under a heating condition, centrifuging after the reaction is finished, washing the precipitate with distilled water, and drying to obtain the product.
10. The preparation method of the high critical solution temperature type temperature-sensitive zirconium-based metal organic framework material according to claim 9, wherein the mass fraction of the double-bonded zirconium-based metal organic framework material is 0.5-5%; the mass of the added high critical solution temperature type temperature-sensitive acrylonitrile-acrylamide copolymer is 0.75-10 times that of the double-bond zirconium-based metal organic framework material; the addition amount of the azodiisobutyronitrile is 1 to 20 percent of the mass of the high critical solution temperature type temperature-sensitive acrylonitrile-acrylamide copolymer; and (3) filling nitrogen for 20-30min, heating at 80 ℃, and reacting for 8-24 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354952A (en) * | 2021-05-26 | 2021-09-07 | 浙江中财管道科技股份有限公司 | Polypropylene pipeline material with ultra-silent effect |
| CN114539498A (en) * | 2022-01-28 | 2022-05-27 | 浙江大学 | Water-phase dispersible composite material based on covalent organic framework and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899250A (en) * | 2010-07-20 | 2010-12-01 | 长春理工大学 | Temperature-sensitive paint for measuring large-area solid field temperature distribution and preparation method thereof |
| CN103407992A (en) * | 2013-07-17 | 2013-11-27 | 同济大学 | Method for preparing hydrophilic temperature and pH dual-sensitive graphene through thiol-ene click chemistry method |
| CN105498694A (en) * | 2015-11-30 | 2016-04-20 | 山东省分析测试中心 | Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof |
| CN107596367A (en) * | 2017-08-23 | 2018-01-19 | 西安交通大学 | The preparation method and application of double response type " synergistic treatment of the chemotherapy photo-thermal " nano-particles of high critical inversion temperature and pH |
| CN109021246A (en) * | 2018-08-17 | 2018-12-18 | 山东师范大学 | A kind of temperature-responsive metal organic frame nanocrystal and preparation method and application |
| CN110652890A (en) * | 2019-10-14 | 2020-01-07 | 曲靖师范学院 | Surface hydrophilic modification method for polyacrylonitrile separation membrane |
| CN110961156A (en) * | 2019-11-06 | 2020-04-07 | 西安交通大学 | Dye solvent thermal-sensitized MOFs photocatalyst and preparation method and application thereof |
-
2020
- 2020-04-30 CN CN202010363353.3A patent/CN111533917A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899250A (en) * | 2010-07-20 | 2010-12-01 | 长春理工大学 | Temperature-sensitive paint for measuring large-area solid field temperature distribution and preparation method thereof |
| CN103407992A (en) * | 2013-07-17 | 2013-11-27 | 同济大学 | Method for preparing hydrophilic temperature and pH dual-sensitive graphene through thiol-ene click chemistry method |
| CN105498694A (en) * | 2015-11-30 | 2016-04-20 | 山东省分析测试中心 | Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof |
| CN107596367A (en) * | 2017-08-23 | 2018-01-19 | 西安交通大学 | The preparation method and application of double response type " synergistic treatment of the chemotherapy photo-thermal " nano-particles of high critical inversion temperature and pH |
| CN109021246A (en) * | 2018-08-17 | 2018-12-18 | 山东师范大学 | A kind of temperature-responsive metal organic frame nanocrystal and preparation method and application |
| CN110652890A (en) * | 2019-10-14 | 2020-01-07 | 曲靖师范学院 | Surface hydrophilic modification method for polyacrylonitrile separation membrane |
| CN110961156A (en) * | 2019-11-06 | 2020-04-07 | 西安交通大学 | Dye solvent thermal-sensitized MOFs photocatalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| S NAGATA等: "Metal–organic framework tethering PNIPAM for ON–OFF controlled release in solution", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
| 冯新德: "《高分子辞典》", 30 June 1998, 中国石化出版社 * |
| 柴春鹏等: "《高分子合成材料学》", 31 January 2019, 北京理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354952A (en) * | 2021-05-26 | 2021-09-07 | 浙江中财管道科技股份有限公司 | Polypropylene pipeline material with ultra-silent effect |
| CN114539498A (en) * | 2022-01-28 | 2022-05-27 | 浙江大学 | Water-phase dispersible composite material based on covalent organic framework and application thereof |
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