CN108912376B - Surface anti-icing material and preparation method thereof - Google Patents

Surface anti-icing material and preparation method thereof Download PDF

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CN108912376B
CN108912376B CN201810618069.9A CN201810618069A CN108912376B CN 108912376 B CN108912376 B CN 108912376B CN 201810618069 A CN201810618069 A CN 201810618069A CN 108912376 B CN108912376 B CN 108912376B
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CN108912376A (en
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张依帆
尹园
柳美华
斯坦尼斯瓦夫·古托夫斯基 沃伊切赫
邓鹏飏
魏巍
郑春柏
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a preparation method of a surface anti-icing material, which comprises the following steps: a) radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material; b) immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for in-situ growth to obtain an MOF grafted material; c) and c) contacting and adsorbing the MOF grafted material obtained in the step b) with a hydrophilic polymer solution, and drying to obtain the surface anti-icing material. Compared with the prior art, the preparation method provided by the invention combines molecules for inhibiting surface nucleation, water-absorbing polymers and a super-hydrophobic surface containing a micro-nano composite structure, the prepared surface anti-icing material has a hydrophilic/hydrophobic alternate surface, the hydrophobic part of the surface enables water to easily slide off from the surface, and the hydrophilic part can play a role in inhibiting surface water from freezing and forming a water lubricating layer, so that the characteristics of low adhesion, easy sliding and inhibition of water freezing are achieved, and the stability is good.

Description

Surface anti-icing material and preparation method thereof
Technical Field
The invention relates to the technical field of anti-icing materials, in particular to a surface anti-icing material and a preparation method thereof.
Background
Surface anti-icing technology is a worldwide problem and is a hot spot of research in recent years. With the deep understanding of the surface icing mechanism, the surface anti-icing technology is continuously developed. The mechanical deicing method, the solution method, the thermal energy method and other anti-icing methods can effectively remove the surface ice layer, but the methods cannot fundamentally solve the problems and need to provide energy from the outside to realize the anti-icing. Therefore, designing and preparing the surface anti-icing material becomes an ideal way to solve the problem of surface icing.
The surface anti-icing material is designed to reduce the adhesion of the surface to water/ice and delay the freezing of water on the surface. For the design of surface anti-icing materials with the idea of reducing water/ice adhesion, a super-hydrophobic surface and a surface containing lubricating liquid are taken as typical. The super-hydrophobic surface mainly reduces the adhesion to water/ice through the characteristic of low adhesion, the static contact angle with a water drop exceeds 150 degrees, the sliding angle is less than 5 degrees, the water drop is difficult to stay on the super-hydrophobic surface, and the water drop can quickly flow away before releasing the self latent heat; however, the super-hydrophobic surface micro-nano structure is easy to damage, and the hydrophobicity is reduced under the low-temperature and high-humidity environment, so that the anti-icing performance is obviously reduced or even disappears. The surfaces containing lubricating fluids are classified into two categories: firstly, the low surface energy lubricating liquid is attached by utilizing a micro-nano structure, so that the surface is smooth and low in adhesion, the adhesion of the surface to water and ice can be reduced, but the low surface energy lubricating liquid migrates along with the flowing away of the surface liquid, so that the effect of the low surface energy lubricating liquid is continuously reduced in multiple uses; secondly, water-absorbing macromolecules are introduced into the surface, a self-lubricating water layer is formed on the surface, the surface can effectively reduce ice adhesion and has wear resistance, and the surface is hydrophilic, so that supercooled water is gathered on the surface and is not easy to slide. In addition, in the design of the idea of delaying the icing of surface water, a macromolecule capable of inhibiting the nucleation and growth of ice is mainly introduced into the surface, the surface can lower the icing temperature of the surface and delay the icing process of the surface, but once the surface is iced, the ice layer on the surface is difficult to remove.
Disclosure of Invention
In view of the above, the present invention provides a surface anti-icing material and a preparation method thereof, and the surface anti-icing material provided by the present invention has a hydrophilic/hydrophobic interphase surface, has the characteristics of low adhesion, easy slipping, and inhibition of water freezing, and has good stability.
The invention provides a preparation method of a surface anti-icing material, which comprises the following steps:
a) radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material;
b) immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for in-situ growth to obtain an MOF grafted material;
c) and c) contacting and adsorbing the MOF grafted material obtained in the step b) with a hydrophilic polymer solution, and drying to obtain the surface anti-icing material.
Preferably, the radiation source for radiating the grafted maleic anhydride in the step a) is a cobalt 60 source or an electron accelerator, the irradiation temperature is 10-50 ℃, the radiation dose rate is 0.3-5 kGy/h, and the radiation dose is 5-100 kGy.
Preferably, the maleic anhydride is grafted by irradiation in step a) by means of pre-irradiation or co-irradiation.
Preferably, the pre-irradiation grafting process specifically comprises the following steps:
pre-radiating a high-molecular solid phase substrate material to obtain an irradiated substrate material, immersing the irradiated substrate material in molten maleic anhydride, performing grafting reaction under the protection of inert gas, filtering out a solid product, and sequentially extracting, washing and drying to obtain a maleic anhydride grafted material;
the temperature of the grafting reaction is 60-150 ℃, and the time is 4-8 h.
Preferably, the process of the co-irradiation grafting is specifically as follows:
immersing a polymer solid phase substrate material in a tetrahydrofuran solution of maleic anhydride, carrying out co-radiation to obtain an irradiated substrate material, and then sequentially extracting, washing and drying the irradiated substrate material to obtain a maleic anhydride grafted material;
the mass fraction of the tetrahydrofuran solution of the maleic anhydride is 10-70%.
Preferably, the organic ligand in step b) has the structure shown in formula (I):
Figure BDA0001697390080000021
in formula (I), -R-is selected from
Figure BDA0001697390080000031
Figure BDA0001697390080000032
Wherein, X is a functional group containing one or more of amino, hydroxyl, carboxyl and sulfhydryl.
Preferably, the step b) is specifically:
immersing the material of the grafted maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for reaction, filtering, and then cleaning, soaking and drying to obtain an MOF grafted material;
the reaction temperature is 100-120 ℃, and the reaction time is 16-24 h.
Preferably, the solution of the hydrophilic polymer in step c) is an aqueous solution of polyvinyl alcohol or an aqueous solution of polyacrylic acid;
the mass concentration of the hydrophilic macromolecule solution is 0.1-5%.
Preferably, the contact adsorption mode in the step c) is circulation filtration or soaking for 1-24 hours.
The invention also provides a surface anti-icing material which is prepared by the preparation method of the technical scheme.
The invention provides a preparation method of a surface anti-icing material, which comprises the following steps: a) radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material; b) immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for in-situ growth to obtain an MOF grafted material; c) and c) contacting and adsorbing the MOF grafted material obtained in the step b) with a hydrophilic polymer solution, and drying to obtain the surface anti-icing material. Compared with the prior art, the preparation method provided by the invention combines molecules for inhibiting surface nucleation, water-absorbing polymers and a super-hydrophobic surface containing a micro-nano composite structure, the prepared surface anti-icing material has a hydrophilic/hydrophobic alternate surface, the hydrophobic part of the surface enables water to easily slide off from the surface, and the hydrophilic part can play a role in inhibiting surface water from freezing and forming a water lubricating layer, so that the characteristics of low adhesion, easy sliding and inhibition of water freezing are achieved, and the stability is good.
In addition, the preparation method provided by the invention has the advantages of clear process route, mild condition, easy control and suitability for large-scale production.
Drawings
FIG. 1 is a flow chart of the preparation of the surface anti-icing material provided by the embodiment of the invention;
FIG. 2 is a schematic illustration of the in situ growth preparation of MOF grafted materials provided by an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of the surface topography of the MOF-grafted non-woven fabric provided in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the surface morphology of the MOF grafted non-woven fabric containing polyvinyl alcohol provided in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the surface morphology of MOF grafted ultra-high molecular weight polyethylene provided in example 2 of the present invention;
FIG. 6 is a scanning electron microscope image of the surface morphology of MOF grafted ultra-high molecular weight polyethylene containing polyacrylic acid provided in example 2 of the present invention;
FIG. 7 is a scanning electron microscope image of the surface morphology of the MOF-grafted PI film provided in example 3 of the present invention;
FIG. 8 is a scanning electron microscope image of the surface morphology of a MOF grafted PI film containing polyvinyl alcohol provided in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a surface anti-icing material, which comprises the following steps:
a) radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material;
b) immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for in-situ growth to obtain an MOF grafted material;
c) and c) contacting and adsorbing the MOF grafted material obtained in the step b) with a hydrophilic polymer solution, and drying to obtain the surface anti-icing material.
Referring to fig. 1, fig. 1 is a flow chart illustrating a process for preparing a surface anti-icing material according to an embodiment of the present invention.
The method comprises the steps of firstly, radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material. In the present invention, the kind of the high molecular solid phase base material is preferably ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polyethylene terephthalate (PET), Polytetrafluoroethylene (PTEF), or Polyimide (PI), and more preferably ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), or Polyimide (PI); the state of the polymer solid phase base material is preferably a nonwoven fabric or a film. In a preferred embodiment of the present invention, the polymeric solid phase substrate material is a non-woven fabric material (PP); in another preferred embodiment of the present invention, the polymeric solid phase base material is ultra-high molecular weight polyethylene (UHMWPE); in another preferred embodiment of the present invention, the polymeric solid phase substrate material is a Polyimide (PI) film material. The source of the polymeric solid phase substrate material is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the radiation source for irradiating the grafted maleic anhydride is preferably a cobalt 60 source or an electron accelerator, and more preferably a cobalt 60 source. In the invention, the irradiation temperature of the radiation grafting maleic anhydride is preferably 10-50 ℃, and more preferably 25-35 ℃; the radiation dose rate of the radiation grafted maleic anhydride is preferably 0.3 kGy/h-5 kGy/h, and more preferably 0.5 kGy/h-3 kGy/h; the radiation dose of the radiation grafted maleic anhydride is preferably 5kGy to 100kGy, and more preferably 20kGy to 50 kGy.
In the present invention, the maleic anhydride is grafted by irradiation preferably by means of pre-irradiation grafting or co-irradiation grafting, more preferably by means of pre-irradiation grafting. In the present invention, the pre-irradiation grafting process is preferably specifically:
pre-radiating a high-molecular solid phase substrate material to obtain an irradiated substrate material, immersing the irradiated substrate material in molten maleic anhydride, performing grafting reaction under the protection of inert gas, filtering out a solid product, and sequentially extracting, washing and drying to obtain the maleic anhydride grafted material.
Before the pre-irradiation of the polymer solid phase substrate material, the invention preferably further comprises:
and cleaning and drying the high-molecular solid-phase substrate material. In the present invention, the cleaning liquid used in the cleaning process is preferably acetone, and the present invention is not particularly limited thereto.
In the present invention, the process of pre-irradiation is preferably carried out in an open container or a closed container, more preferably in a closed container. In a preferred embodiment of the present invention, the polymer solid phase substrate material is placed in a closed container, and then vacuumized and pre-irradiated to obtain an irradiated substrate material.
In the present invention, the radiation source, the irradiation temperature, the radiation dose rate, and the radiation dose of the pre-irradiation are the same as those described in the above technical solution, and are not described herein again.
In the invention, the molten maleic anhydride is liquid maleic anhydride; the melting temperature is preferably 60 ℃ to 100 ℃, more preferably 70 ℃ to 80 ℃. In the present invention, the amount of the maleic anhydride is preferably in excess, and particularly, it is preferable that the irradiated base material can be completely immersed.
The present invention is not particularly limited in kind of the inert gas, and nitrogen known to those skilled in the art may be used.
In the present invention, the temperature of the grafting reaction is preferably 60 to 150 ℃, more preferably 100 to 105 ℃; the time of the grafting reaction is preferably 4 to 8 hours, more preferably 6 to 7 hours.
The process of filtering, extracting, washing and drying is not particularly limited by the invention, and the technical scheme familiar to the technical personnel in the field can be adopted, so as to obtain the material of the grafted maleic anhydride; the material of the grafted maleic anhydride is a macromolecular solid phase substrate grafted with maleic anhydride.
In the present invention, the co-irradiation grafting process is preferably specifically:
immersing a polymer solid phase substrate material in a tetrahydrofuran solution of maleic anhydride, carrying out co-radiation to obtain an irradiated substrate material, and then sequentially extracting, washing and drying the irradiated substrate material to obtain the maleic anhydride grafted material.
Before co-irradiation of the polymer solid phase substrate material, the invention preferably further comprises:
and cleaning and drying the high-molecular solid-phase substrate material. In the present invention, the cleaning liquid used in the cleaning process is preferably acetone, and the present invention is not particularly limited thereto.
In the present invention, the co-irradiation process is preferably carried out in an open container or a closed container, more preferably in a closed container.
In the present invention, the mass fraction of the tetrahydrofuran solution of maleic anhydride is preferably 10% to 70%, and more preferably 40% to 60%. In the present invention, the amount of the tetrahydrofuran solution of maleic anhydride is preferably used in excess in order to ensure that the polymeric solid phase substrate material is completely immersed in the tetrahydrofuran solution of maleic anhydride.
In the present invention, the radiation source, the irradiation temperature, the radiation dose rate, and the radiation dose of the co-radiation are the same as those described in the above technical solution, and are not described herein again.
The process of the extraction, washing and drying is not particularly limited by the invention, and the technical scheme familiar to the technical personnel in the field can be adopted, so as to obtain the material of the grafted maleic anhydride; the material of the grafted maleic anhydride is a macromolecular solid phase substrate grafted with maleic anhydride.
After the material of the grafted maleic anhydride is obtained, the obtained material of the grafted maleic anhydride is immersed in a mixed solution of metal salt and an organic ligand for in-situ growth, and the MOF grafted material is obtained.
Referring to fig. 2, fig. 2 is a schematic diagram of the in-situ growth process for preparing MOF grafted materials according to an embodiment of the present invention.
In the present invention, the metal salt provides a metal cation Mn+(ii) a The metal cation Mn+Is selected from Zr4+、Fe3+、Al3+、Cr3+、Cu2+And Zn2+More preferably Fe3+. The source of the metal salt is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the organic ligand preferably has a structure represented by formula (I):
Figure BDA0001697390080000071
in formula (I), -R-is preferably selected from
Figure BDA0001697390080000081
Figure BDA0001697390080000082
The structures of the corresponding organic ligands are respectively:
Figure BDA0001697390080000091
Figure BDA0001697390080000092
all of the organic ligands of the above structure are at leastA conjugated rigid structure with benzene ring, both ends of which contain carboxyl.
Wherein X preferably comprises an amino group (-NH)2) And one or more of hydroxyl (-OH), carboxyl (-COOH) and mercapto (-SH). In the invention, the X is a group with a side end modified, and the in-situ growth of the MOF on the surface of the material is not influenced.
In a preferred embodiment of the invention, the organic ligand is terephthalic acid.
In the invention, the mass ratio of the metal salt to the organic ligand is preferably (2-4): 1, more preferably 3: 1.
in the present invention, the mixed solution of the metal salt and the organic ligand is preferably an N, N-Dimethylformamide (DMF) solution of the metal salt and the organic ligand. In the present invention, the metal salt and organic ligand are in excess relative to the material of the grafted maleic anhydride; although the mixing proportion and the concentration of different metal salts and different organic ligands are different, the MOF on the surface of the material can be formed by immersing the material of the grafted maleic anhydride in a reaction kettle after mixing.
In the present invention, the process for preparing the MOF grafted material by in-situ growth is preferably specifically:
immersing the material of the grafted maleic anhydride obtained in the step a) in a mixed solution of metal salt and organic ligand for reaction, filtering, and then cleaning, soaking and drying to obtain the MOF grafted material.
In the present invention, the temperature of the reaction is preferably 100 to 120 ℃, more preferably 110 ℃; the reaction time is preferably 16 to 24 hours, more preferably 20 hours.
In the present invention, the washing and soaking processes are preferably performed with ethanol. In the invention, the soaking temperature is preferably 50-70 ℃, and more preferably 60 ℃; the soaking time is preferably 2 to 4 hours, and more preferably 3 hours. In a preferred embodiment of the present invention, the soaking process is repeated.
The invention adopts in-situ growth to prepare the MOF grafting material which has a porous MOFs (metal-organic framework) structure and can be used as an absorbing materialA hydrophobic material attached with a polymer. MOFs are a new type of nanoporous materials formed by metal ions and organic ligands, with controllable pore size and modifiable pore surface, ultra-low density, ultra-high specific surface area (up to 7000 m)2In terms of/g) and good thermal and chemical stability. In the invention, the MOF grafting material has a better grafting rate, and the MOF material grafted on the surface of the polymer film has a compact micro-nano composite structure and has good flexibility and stability.
After the MOF grafted material is obtained, the obtained MOF grafted material is contacted with a hydrophilic polymer solution for adsorption, and the surface anti-icing material is obtained after drying. In the present invention, the solution of the hydrophilic polymer is preferably an aqueous solution of polyvinyl alcohol or an aqueous solution of polyacrylic acid. The source of the hydrophilic polymer solution is not particularly limited in the present invention.
In the present invention, the mass concentration of the hydrophilic polymer solution is preferably 0.1% to 5%, more preferably 0.5% to 2%.
In the invention, the contact adsorption mode is preferably circulating filtration or soaking; the time for the contact adsorption is preferably 1 to 24 hours. In a preferred embodiment of the present invention, the contact adsorption mode is a cyclic filtration, and the time of the cyclic filtration is preferably 1h to 5h, and more preferably 2 h; in another preferred embodiment of the present invention, the contact adsorption manner is soaking, and the soaking time is preferably 2h to 24h, and more preferably 12 h.
In the present invention, the purpose of the drying is to remove the solvent; the drying temperature is preferably 50-70 ℃, and more preferably 60 ℃; the drying time is preferably 2 to 6 hours, and more preferably 3 to 5 hours.
According to the invention, the hydrophobic MOFs membrane containing the micro-nano composite structure is prepared through radiation grafting and in-situ growth, and hydrophilic polymers are introduced to the surface of the MOFs membrane through contact adsorption, so that the surface waterproof material is prepared.
The invention also provides a surface anti-icing material which is prepared by the preparation method of the technical scheme. According to the preparation method provided by the invention, the molecules for inhibiting surface nucleation, the water-absorbing polymer and the super-hydrophobic surface containing the micro-nano composite structure are combined, the prepared surface anti-icing material has a surface with alternate hydrophilic and hydrophobic properties, the hydrophobic part on the surface enables water to easily slide off from the surface, and the hydrophilic part can play a role in inhibiting the freezing of the surface water and forming a water lubricating layer, so that the characteristics of low adhesion, easy sliding and inhibition of the freezing of the water are achieved, and the stability is good.
The invention provides a preparation method of a surface anti-icing material, which comprises the following steps: a) radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material; b) immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for in-situ growth to obtain an MOF grafted material; c) and c) contacting and adsorbing the MOF grafted material obtained in the step b) with a hydrophilic polymer solution, and drying to obtain the surface anti-icing material. Compared with the prior art, the preparation method provided by the invention combines molecules for inhibiting surface nucleation, water-absorbing polymers and a super-hydrophobic surface containing a micro-nano composite structure, the prepared surface anti-icing material has a hydrophilic/hydrophobic alternate surface, the hydrophobic part of the surface enables water to easily slide off from the surface, and the hydrophilic part can play a role in inhibiting surface water from freezing and forming a water lubricating layer, so that the characteristics of low adhesion, easy sliding and inhibition of water freezing are achieved, and the stability is good.
In addition, the preparation method provided by the invention has the advantages of clear process route, mild condition, easy control and suitability for large-scale production.
To further illustrate the present invention, the following examples are provided for illustration. The radiation source described in the following examples of the invention is a cobalt 60 source.
Example 1
(1) Taking 10g of non-woven fabric material (PP), cleaning with acetone, drying, putting into a closed container, vacuumizing, putting into a radiation source, and irradiating at the irradiation temperature of 30 ℃, the radiation dose rate of 3kGy/h and the radiation dose of 30kGy to obtain an irradiated substrate material; then adding maleic anhydride into a three-neck flask connected with a stirring paddle, and heating at 80 ℃ to melt the maleic anhydride to obtain a reaction solution; and introducing nitrogen below the liquid level of the reaction liquid by using a glass tube, after 15min, adding the irradiated substrate material into a flask to be completely immersed in the reaction liquid, reacting at 105 ℃ for 6h, stopping, filtering out a solid product, extracting, washing and drying the product to obtain the maleic anhydride grafted material.
(2) Dissolving 3 parts by weight of ferric chloride and 1 part by weight of terephthalic acid in DMF, uniformly mixing, adding into a reaction kettle, adding the material of the grafted maleic anhydride obtained in the step (1) into the reaction kettle for immersion, heating to 110 ℃ for reaction for 20h, filtering, adding ethanol into a crude product, treating for 3h at 60 ℃, and performing vacuum overnight drying at room temperature after twice to obtain an MOF grafted material (MOF grafted non-woven fabric); the scanning electron micrograph of the surface topography is shown in FIG. 3.
(3) And (3) performing circulating filtration on the MOF grafted material obtained in the step (2) in a polyvinyl alcohol solution with the concentration of 1%, wherein the filtration time is 2h, and then placing the MOF grafted material in an oven at 60 ℃ for drying for 5h to obtain a surface anti-icing material (MOF grafted non-woven fabric containing polyvinyl alcohol), wherein a scanning electron microscope image of the surface morphology of the surface anti-icing material is shown in fig. 4.
The MOF grafting rate of the MOF grafted material provided in example 1 of the present invention was determined by the following test method: weighing the MOF graft Material Mass MMOF(g) Mass of material before grafting of MOF is M0Thus the MOF graft ratio is (M)MOF-M0)/M0X 100%. The results show that the MOF grafting ratio of the MOF grafted material provided in example 1 of the present invention is 7.23%.
The surface condensed water icing temperature of the MOF grafted material provided in embodiment 1 of the present invention is detected by the following test method: introducing saturated steam into a closed environment with controllable temperature, and placing a sample on a cooling table in the closed environment; cooling the surface of the sample through a cooling table at a constant cooling speed (5 ℃/min); recording the process of condensing-icing water drops on the surface of the sample and the icing temperature of all condensed water drops on the surface by using a microscope, and calculating the average icing temperature of the condensed water drops on the surface to be the surface condensed water icing temperature; the number of measurements is not less than 5, and the average value is taken. The result shows that the surface condensed water freezing temperature of the surface anti-icing material provided by the embodiment 1 of the invention is-27.6 ℃, and the surface condensed water freezing temperature of the non-woven fabric material containing polyvinyl alcohol is-20.6 ℃, so that the anti-icing effect of the surface anti-icing material provided by the invention is better.
Example 2
(1) Taking 10g of ultrahigh molecular weight polyethylene (UHMWPE), cleaning with acetone, drying, placing into a closed container, vacuumizing, placing into a radiation source for irradiation, wherein the irradiation temperature is 30 ℃, the radiation dose rate is 0.5kGy/h, and the radiation dose is 20kGy, so as to obtain an irradiated substrate material; then adding maleic anhydride into a three-neck flask connected with a stirring paddle, and heating at 70 ℃ to melt the maleic anhydride to obtain a reaction solution; and introducing nitrogen into the flask below the liquid level of the reaction liquid, after 15min, adding the irradiated substrate material into the flask to be completely immersed in the reaction liquid, reacting at 100 ℃ for 7h, filtering out a solid product, extracting, washing and drying the product to obtain the maleic anhydride grafted material.
(2) Dissolving 3 parts by weight of ferric chloride and 1 part by weight of terephthalic acid in DMF, uniformly mixing, adding into a reaction kettle, immersing the grafted maleic anhydride material obtained in the step (1), and heating to 110 ℃ for reaction for 20 hours. Adding ethanol into the filtered crude product, treating for 3h at 60 ℃, and performing vacuum overnight drying at room temperature after twice to obtain an MOF (metal organic framework) grafted material (MOF grafted ultra-high molecular weight polyethylene); a scanning electron micrograph of its surface topography is shown in FIG. 5.
(3) And (3) performing circulating filtration on the MOF grafted material obtained in the step (2) in a polyacrylic acid solution with the concentration of 0.5%, wherein the filtration time is 2h, and then placing the material in a 60 ℃ drying oven for drying for 5h to obtain a surface anti-icing material (MOF grafted ultra-high molecular weight polyethylene containing polyacrylic acid), wherein a scanning electron microscope image of the surface morphology of the material is shown in FIG. 6.
The test method provided in example 1 was used to test the MOF grafting rate of the MOF grafted material provided in example 2 of the present invention. The results show that the MOF grafting ratio of the MOF grafted material provided in example 2 of the present invention is 8.51%.
The test method provided in embodiment 1 is adopted to detect the freezing temperature of the surface condensed water of the surface anti-icing material provided in embodiment 2 of the invention. The results show that the surface condensed water freezing temperature of the surface anti-icing material provided by the embodiment 2 of the invention is-29.3 ℃,
example 3
(1) Taking a Polyimide (PI) film material with the area of 10mm multiplied by 10mm as a substrate material, washing and drying the Polyimide (PI) film material with acetone, putting the cleaned Polyimide (PI) film material into a closed container, adding a maleic anhydride tetrahydrofuran solution with the mass fraction of 50% into the container and enabling the maleic anhydride tetrahydrofuran solution to submerge the substrate material, sealing the container, putting the sealed container into a radiation source, and irradiating the sealed container at the irradiation temperature of 30 ℃, the radiation dose rate of 2kGy/h and the radiation dose of 50kGy to obtain the irradiated substrate material; and then extracting, washing and drying the irradiated substrate material to obtain the maleic anhydride grafted material.
(2) Dissolving 3 parts by weight of ferric chloride and 1 part by weight of terephthalic acid in DMF, uniformly mixing, adding into a reaction kettle, adding the material of the grafted maleic anhydride obtained in the step (1) into the reaction kettle for immersion, heating to 110 ℃ for reaction for 20h, filtering, adding ethanol into a crude product, treating for 3h at 60 ℃, and performing vacuum overnight drying at room temperature after twice to obtain an MOF grafted material (MOF grafted PI membrane); a scanning electron micrograph of its surface topography is shown in FIG. 7.
(3) Soaking the MOF grafted material obtained in the step (2) in a polyvinyl alcohol solution with the concentration of 2% for 12h, and then drying in an oven at 60 ℃ for 3h to obtain a surface anti-icing material (the MOF grafted PI film containing polyvinyl alcohol), wherein a scanning electron microscope image of the surface morphology of the surface anti-icing material is shown in FIG. 8.
The MOF grafting rate of the MOF grafted material provided in example 3 of the present invention was tested using the test method provided in example 1. The results show that the MOF grafting ratio of the MOF grafted material provided in example 3 of the present invention is 2.75%.
The test method provided in embodiment 1 is used to detect the freezing temperature of the surface condensed water of the surface anti-icing material provided in embodiment 3 of the present invention. The results show that the surface condensed water freezing temperature of the surface anti-icing material provided by the embodiment 3 of the invention is-23.7 ℃,
in summary, in the surface anti-icing material provided in embodiments 1 to 3 of the present invention, hydrophilic polymers are introduced into the micro-nano structure of the hydrophobic MOF film material, so that a micro-nano level hydrophilic region and a hydrophobic region are formed on the surface, but the surface hydrophobicity is not significantly changed, and thus, water drops are easy to roll off on the surface of the material, and the freezing of surface condensed water is delayed.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A preparation method of a surface anti-icing material comprises the following steps:
a) radiating and grafting maleic anhydride on the surface of a high-molecular solid-phase substrate material to obtain a maleic anhydride grafted material;
b) immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for in-situ growth to obtain an MOF grafted material;
the organic ligand has a structure shown in formula (I):
Figure FDA0002625376480000011
in formula (I), -R-is selected from
Figure FDA0002625376480000012
Figure FDA0002625376480000013
Wherein, X is independently selected from amino, hydroxyl, carboxyl or sulfhydryl;
c) and c) contacting and adsorbing the MOF grafted material obtained in the step b) with a hydrophilic polymer solution, and drying to obtain the surface anti-icing material.
2. The preparation method according to claim 1, wherein the radiation source for irradiating the grafted maleic anhydride in the step a) is a cobalt 60 source or an electron accelerator, the irradiation temperature is 10 ℃ to 50 ℃, the radiation dose rate is 0.3kGy/h to 5kGy/h, and the radiation dose is 5kGy to 100 kGy.
3. The method according to claim 1, wherein the maleic anhydride is grafted by irradiation in step a) by pre-irradiation or co-irradiation.
4. The method according to claim 3, wherein the pre-irradiation grafting comprises the following steps:
pre-radiating a high-molecular solid phase substrate material to obtain an irradiated substrate material, immersing the irradiated substrate material in molten maleic anhydride, performing grafting reaction under the protection of inert gas, filtering out a solid product, and sequentially extracting, washing and drying to obtain a maleic anhydride grafted material;
the temperature of the grafting reaction is 60-150 ℃, and the time is 4-8 h.
5. The preparation method according to claim 3, wherein the co-irradiation grafting process is specifically:
immersing a polymer solid phase substrate material in a tetrahydrofuran solution of maleic anhydride, carrying out co-radiation to obtain an irradiated substrate material, and then sequentially extracting, washing and drying the irradiated substrate material to obtain a maleic anhydride grafted material;
the mass fraction of the tetrahydrofuran solution of the maleic anhydride is 10-70%.
6. The preparation method according to claim 1, wherein the step b) is specifically:
immersing the material grafted with maleic anhydride obtained in the step a) in a mixed solution of metal salt and an organic ligand for reaction, filtering, and then cleaning, soaking and drying to obtain an MOF grafted material;
the reaction temperature is 100-120 ℃, and the reaction time is 16-24 h.
7. The method according to claim 1, wherein the solution of the hydrophilic polymer in step c) is an aqueous solution of polyvinyl alcohol or an aqueous solution of polyacrylic acid;
the mass concentration of the hydrophilic macromolecule solution is 0.1-5%.
8. The preparation method according to claim 1, wherein the contact adsorption in step c) is performed by cyclic filtration or soaking for 1-24 h.
9. A surface anti-icing material characterized by being produced by the production method according to any one of claims 1 to 8.
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