CN110903576B - Preparation method of polyvinylidene fluoride composite material, polyvinylidene fluoride composite membrane, preparation method and application thereof - Google Patents

Preparation method of polyvinylidene fluoride composite material, polyvinylidene fluoride composite membrane, preparation method and application thereof Download PDF

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CN110903576B
CN110903576B CN201911254086.XA CN201911254086A CN110903576B CN 110903576 B CN110903576 B CN 110903576B CN 201911254086 A CN201911254086 A CN 201911254086A CN 110903576 B CN110903576 B CN 110903576B
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覃慧
陈舒忆
王壹
聂胜强
成刚
罗军
陶泽志
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Guiyang University
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Abstract

The application provides a preparation method of a polyvinylidene fluoride composite material, a polyvinylidene fluoride composite membrane, a preparation method and application thereof, and belongs to the technical field of functional polymer materials. The preparation method of the polyvinylidene fluoride composite material comprises the following steps: dispersing a metal organic framework in a polar organic solvent, then adding polyvinylidene fluoride, and dispersing for 4-10h at the temperature of 50-70 ℃ to obtain a composite material. The preparation method of the polyvinylidene fluoride composite membrane comprises the steps of defoaming, curing and coating the polyvinylidene fluoride composite mixture in sequence. The polyvinylidene fluoride composite membrane prepared by the method has good adsorption capacity and certain blood compatibility, and can be used as a blood contact material.

Description

Preparation method of polyvinylidene fluoride composite material, polyvinylidene fluoride composite membrane, preparation method and application thereof
Technical Field
The application relates to the technical field of functional polymer materials, in particular to a preparation method of a polyvinylidene fluoride composite material, a polyvinylidene fluoride composite membrane, a preparation method and application thereof.
Background
Metal-Organic Frameworks (MOFs) are inorganic-Organic composites formed by self-assembly of Metal ions and Organic ligands with multiple functional groups into crystalline porous materials with periodic network structures. The metal organic framework material is mainly characterized by high porosity and huge specific surface area due to the combination of the properties of a periodic network hole structure and an organic material framework. In recent years, the application field of the metal organic framework material with controllable functional groups in the molecular structure is more and more extensive by designing and synthesizing the metal organic framework material. The catalyst has great application potential in the aspects of hydrogen storage, drug delivery, catalysis, selective separation and the like due to the characteristics of harmonious pore channel shape, size, obvious stability and the like.
The metal organic framework material MIL-100-Fe has good adsorption performance due to the polar functional group and molecular pores in the structure, but has poor film forming property, so the metal organic framework material MIL-100-Fe cannot be directly used for preparing the anti-pollution material.
Disclosure of Invention
The polyvinylidene fluoride composite membrane has good blood compatibility and can be used for preparing blood contact materials.
In a first aspect, an embodiment of the present application provides a preparation method of a polyvinylidene fluoride composite material, including: dispersing a metal organic framework material MIL-100-Fe in a polar organic solvent, then adding polyvinylidene fluoride, and dispersing for 4-10h at the temperature of 50-70 ℃ to obtain a composite material.
Wherein the structural formula of the metal organic framework material MIL-100-Fe is as follows:
Figure BDA0002309347960000021
in a second aspect, embodiments of the present application provide a preparation method of a polyvinylidene fluoride composite film, where the polyvinylidene fluoride composite material is subjected to defoaming, curing, and coating in sequence to obtain the polyvinylidene fluoride composite film.
In a third aspect, an embodiment of the present application provides a polyvinylidene fluoride composite film prepared by the above polyvinylidene fluoride composite film preparation method.
In a fourth aspect, the present application provides an application of a polyvinylidene fluoride composite membrane in preparation of a blood contact material.
The preparation method of the polyvinylidene fluoride composite material, the polyvinylidene fluoride composite film, the preparation method and the application of the polyvinylidene fluoride composite material provided by the embodiment of the application have the beneficial effects that:
the polyvinylidene fluoride composite membrane is prepared by defoaming, curing and coating the composite mixture, and the metal organic framework material MIL-100-Fe has good stability, and cannot be decomposed and precipitated from a polyvinylidene fluoride composite membrane matrix in the using process, so that the obtained polyvinylidene fluoride composite membrane has good adsorption performance without adding a pore-forming agent, has blood compatibility, can have the performance of resisting platelet activation and complement activation, and can be used as a blood contact material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method of the polyvinylidene fluoride composite membrane provided by the embodiment of the application comprises the following steps:
s10, preparing a metal organic framework material MIL-100-Fe:
dispersing trimesic acid and ferric ions in a polar organic solvent, and reacting for 16-24h at the temperature of 110-130 ℃ to obtain the metal organic framework material MIL-100-Fe.
Wherein the molar ratio of the trimesic acid to the ferric ions is 1:4-1:6, so that the trimesic acid can be converted into the metal-organic framework material MIL-100-Fe more. For example: the molar ratio of the trimesic acid to the ferric ions is 1:4, 1:5 or 1: 6. Alternatively, the source of ferric ions may be FeCl3Or Fe (NO)3)3。
Optionally, the polar organic solvent is a combination of one or more selected from the group consisting of N-methylpyrrolidone, dimethylacetamide, and N, N' -dimethylformamide. For example: the polar organic solvent is N-methyl pyrrolidone; the polar organic solvent is dimethylacetamide; the polar organic solvent is N, N' -dimethylformamide; the polar organic solvent is a mixture of N-methyl pyrrolidone and dimethylacetamide; the polar organic solvent is a mixture of N-methyl pyrrolidone and N, N' -dimethylformamide; the polar organic solvent is a mixture of N-methylpyrrolidone, dimethylacetamide and N, N' -dimethylformamide.
Mixing trimesic acid and FeCl3Dispersing in a polar organic solvent, and reacting for 16-24h at the temperature of 110-130 ℃ to obtain the metal organic framework material MIL-100-Fe. The reaction temperature is high, so that the metal organic framework material MIL-100-Fe is obtained through reaction. Further, the temperature of the reaction may be 110 ℃, 120 ℃ or 130 ℃; the reaction time may be 16h, 20h or 24 h.
After the reaction is completed, the reaction is stopped, partial impurities (such as trimesic acid) which are not reacted can exist in the product, the reaction liquid is cooled to 20 ℃, the unreacted trimesic acid is washed by ethanol, and then the drying is carried out at the temperature of 80 ℃, and then the grinding is carried out to obtain the metal organic framework material MIL-100-Fe.
Wherein the structural formula of the metal organic framework material MIL-100-Fe is as follows:
Figure BDA0002309347960000041
the obtained metal organic framework material MIL-100-Fe has good stability, polar functional groups and molecular pores, and a good adsorption function.
S20, preparing a polyvinylidene fluoride composite material:
dispersing a metal organic framework material MIL-100-Fe in a polar organic solvent, then adding polyvinylidene fluoride, and dispersing for 4-10h at the temperature of 50-70 ℃ to obtain a composite material.
The reaction is carried out at such a temperature that the two are combined to avoid separation of the metal organic framework material MIL-100-Fe from the polyvinylidene fluoride. Here, the polar organic solvent is the same as the polar organic solvent in step S10, and the description thereof is omitted.
Optionally, the mass ratio of the metal-organic framework material MIL-100-Fe to the polyvinylidene fluoride is 1:1.5-1:4, so that the metal-organic framework material MIL-100-Fe and the polyvinylidene fluoride can be combined more firmly, and the effects of adsorption and blood compatibility are better. For example: the mass ratio of the metal organic framework material MIL-100-Fe to the polyvinylidene fluoride is 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5 or 1: 4.
Further, the mass ratio of the metal organic framework material MIL-100-Fe to the polar organic solvent is 1:7-1:16, so that the raw materials can be fully mixed in the organic solvent for reaction. For example: the mass ratio of the metal organic framework material MIL-100-Fe to the polar organic solvent is 1:7, 1:8, 1:10, 1:12, 1:14 or 1: 16.
In some embodiments, the reaction temperature to prepare the composite may be 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃. The reaction time for preparing the composite material may be 4h, 6h, 8h or 10 h.
Further, in order to enable the metal organic framework material MIL-100-Fe to be dispersed in the polar organic solvent more uniformly, the metal organic framework material MIL-100-Fe can be dispersed in an ultrasonic dispersion mode (the dispersion is more uniform), polyvinylidene fluoride is added after the dispersion, and then the mixture is stirred for 4-10 hours at the temperature of 60 ℃ to react, so that a composite material is obtained.
S30, preparing a polyvinylidene fluoride composite membrane:
and (3) defoaming, curing and coating the polyvinylidene fluoride composite mixture in sequence to obtain the polyvinylidene fluoride composite membrane.
The polyvinylidene fluoride composite mixed material is defoamed and cured to obtain the modified casting solution. The defoaming may be performed by vacuum defoaming, and the aging treatment is to allow the vacuum defoamed material to stand for a certain period of time to age to obtain a casting solution.
And then, coating on a spin coating machine by adopting a spin coating method, and separating the membrane from the spin coating machine by adopting a liquid-liquid phase separation method to obtain the polyvinylidene fluoride composite membrane. Wherein, the thickness of the polyvinylidene fluoride composite membrane is 50-100 μm, so that the adsorption effect of the composite membrane is better, and the blood compatibility is more obvious. For example: the thickness of the polyvinylidene fluoride composite membrane is 50 μm, 60 μm, 70 μm, 100 μm, 80 μm, 90 μm or 100 μm.
Alternatively, the non-solvent used in the liquid-liquid phase separation method is distilled water, the spin-coating speed is 200r/min, 400r/min, 600r/min, 800r/min or 1000r/min, and the spin-coating time is 20s, 40s, 60s, 80s or 90 s.
The metal organic framework material MIL-100-Fe of the polyvinylidene fluoride composite membrane prepared by the preparation method has good stability, cannot be decomposed and separated out from a polyvinylidene fluoride composite membrane matrix in the using process, can stably exist in the polyvinylidene fluoride composite membrane matrix, and can permanently modify the polyvinylidene fluoride membrane.
The polyvinylidene fluoride composite membrane obtained can have good adsorption performance without adding pore-forming agent, has blood compatibility, and can have the performance of resisting platelet activation and complement activation.
The polyvinylidene fluoride composite membrane can be used for preparing blood contact materials, such as: can be used for preparing artificial blood vessel or blood purification membrane.
The present application is described in detail below with reference to specific examples, but is not limited thereto.
The main reagent information mentioned in the following examples is shown in table 1:
table 1 information on the main reagents used in the examples
Figure BDA0002309347960000061
Example 1
A preparation method of a polyvinylidene fluoride composite membrane comprises the following steps:
(1) 0.21g of trimesic acid and 0.675g of FeCl3Dispersing in 50mL DMF (N, N' -dimethylformamide), reacting at 120 deg.C for 20 hr, stopping reaction, cooling to 20 deg.CWashing unreacted trimesic acid by using ethanol, drying at 80 ℃ to obtain a crystal A, and grinding the crystal A by using a mortar to obtain powder A, wherein the powder A is the metal organic framework material MIL-100-Fe.
(2) Adding 0.5g of metal organic framework material MIL-100-Fe and 8g N-methyl pyrrolidone into a reactor, ultrasonically dispersing for 2h at normal temperature, adding 1.5g of polyvinylidene fluoride into the reactor, and stirring for 4h at 60 ℃ to obtain a composite material.
(3) And (3) carrying out vacuum defoaming and standing curing treatment on the composite mixture to obtain the modified casting solution.
(4) And (3) coating the modified casting solution on a spin coater by adopting a spin coating method (the spin coating speed is 200r/min, and the spin coating time is 20s), and obtaining the polyvinylidene fluoride composite membrane with the thickness of 75 microns by a liquid-liquid phase separation method (non-solvent distilled water is used).
And detecting the adsorption capacity of the polyvinylidene fluoride composite membrane. Wherein, the detection mode of the adsorption capacity is as follows: preparing a standard aqueous solution of a dye, and making a concentration-absorbance standard curve by an ultraviolet-visible spectrophotometer under a characteristic wavelength; immersing 5g of polyvinylidene fluoride composite membrane into 100mL of dye aqueous solution with the concentration of 20mg/mL at room temperature, starting timing, taking out the dye solution immersed in the membrane every half hour, and measuring the absorbance of the dye solution by using an ultraviolet visible spectrophotometer until the absorbance is not reduced any more; determining the dye concentration in the final dye solution through a standard curve, comparing the dye concentration with the concentration of the original solution before adsorption, and calculating the adsorption quantity.
The adsorption capacity of the polyvinylidene fluoride membrane to Victoria blue is 50 mg/g; the adsorption capacity to methylene blue is 55 mg/g; the adsorption capacity to methyl orange is 30 mg/g; the adsorption amount of Congo red is 60 mg/g.
And detecting the blood compatibility of the polyvinylidene fluoride composite membrane. The contents of platelet 4 factor (PF4) and complement C3a in plasma after contacting polyvinylidene fluoride composite membrane with plasma for 30 min. PF4 and C3a test methods were carried out according to the methods described in the documents Shengqiang Nie, Hui Qin, Chong Cheng, Weifeng Zhao, Shudong Sun, Baihai Su, Changsheng Zhao, Zhongwei Gu, Blood activity and compatibility on single-molecular-layer biological interface, journal of Materials Chemistry B,2014,2,4911, using ELISA kits such as the human plasma PF4 and C3a test kits produced by the company R & D.
The content of PF4 in the polyvinylidene fluoride composite membrane is 37ng/mL after the polyvinylidene fluoride composite membrane is contacted with plasma for 30min (38 ng/mL of plasma which is not contacted with the composite membrane); PF4 content was 10ng/mL (15 ng/mL for plasma not contacted with the composite membrane), and there was no significant difference before and after contact. Therefore, the polyvinylidene fluoride composite membrane can have the performance of resisting platelet activation and complement activation, and can be used for preparing blood contact materials.
Comparative example 1
The preparation method of the polyvinylidene fluoride composite membrane provided in the comparative example 1 is different from that of the example 1 in that: and (3) adding 5% of vinyl pyrrolidone (PVP-K30) serving as a pore-foaming agent into the step (2). The other steps are consistent in method.
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the polyvinylidene fluoride composite membrane provided by the comparative example 1 has an adsorption capacity of 55mg/g to Victoria blue; the adsorption capacity to methylene blue is 57 mg/g; the adsorption capacity to methyl orange is 42 mg/g; the adsorption amount of Congo red is 60 mg/g. The comparative example 1 shows that although the pore-foaming agent is added in the preparation process, the adsorption capacity of the polyvinylidene fluoride composite membrane on pollutants in wastewater is not improved, and the polyvinylidene fluoride composite membrane can have good adsorption capacity without adding the pore-foaming agent.
Example 2
A preparation method of a polyvinylidene fluoride composite membrane comprises the following steps:
(1) 0.21g of trimesic acid and 0.675g of FeCl3Dispersing the mixture into 50mL of DMF (N, N' -dimethylformamide), reacting at 120 ℃ for 20h, stopping the reaction, cooling to 20 ℃, washing unreacted trimesic acid with ethanol, drying at 80 ℃ to obtain a crystal A, and grinding the crystal A with a mortar to obtain powder A, wherein the powder A is the metal organic framework material MIL-100-Fe.
(2) Adding 1g of metal organic framework material MIL-100-Fe and 7.5g N-methyl pyrrolidone into a reactor, ultrasonically dispersing for 2h at normal temperature, adding 1.5g of polyvinylidene fluoride into the reactor, and stirring for 4h at 60 ℃ to obtain a composite material.
(3) And (3) carrying out vacuum defoaming and standing curing treatment on the composite mixture to obtain the modified casting solution.
(4) And (3) coating the modified casting solution on a spin coater by adopting a spin coating method (the spin coating speed is 1000r/min, and the spin coating time is 30s), and obtaining the polyvinylidene fluoride composite membrane with the thickness of 50 mu m by a liquid-liquid phase separation method (non-solvent distilled water used).
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the adsorption capacity of the polyvinylidene fluoride composite membrane to Victoria blue is 100 mg/g; the adsorption capacity to methylene blue is 103 mg/g; the adsorption capacity to methyl orange is 65 mg/g; the adsorption amount of Congo red was 105 mg/g.
The method for detecting the blood compatibility of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the content of PF4 in the polyvinylidene fluoride composite membrane is 35ng/mL (38 ng/mL in the plasma which is not contacted with the composite membrane) after 30min of contact between the polyvinylidene fluoride composite membrane and the plasma; the PF4 content was 15ng/mL (15 ng/mL for plasma not contacted with the composite membrane), and there was no significant difference before and after contact. Therefore, the polyvinylidene fluoride composite membrane can have the performance of resisting platelet activation and complement activation, and can be used for preparing blood contact materials.
Comparative example 2
The preparation method of the polyvinylidene fluoride composite membrane provided by the comparative example 2 is different from that of the example 2 in that: and (3) adding 5% of vinyl pyrrolidone (PVP-K30) serving as a pore-foaming agent into the step (2). The other steps are consistent in method.
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the polyvinylidene fluoride composite membrane provided by the comparative example 2 has the adsorption capacity of 110mg/g to Victoria blue; the adsorption capacity to methylene blue is 100 mg/g; the adsorption capacity to methyl orange is 70 mg/g; the adsorption amount of Congo red is 116 mg/g. The comparative example 2 shows that although the pore-foaming agent is added in the preparation process, the adsorption capacity of the pore-foaming agent on pollutants in wastewater is not improved, and the polyvinylidene fluoride composite membrane can have good adsorption capacity without adding the pore-foaming agent.
Example 3
A preparation method of a polyvinylidene fluoride composite membrane comprises the following steps:
(1) 0.21g of trimesic acid and 0.675g of FeCl3Dispersing the mixture into 50mL of DMF (N, N' -dimethylformamide), reacting at 120 ℃ for 20h, stopping the reaction, cooling to 20 ℃, washing unreacted trimesic acid with ethanol, drying at 80 ℃ to obtain a crystal A, and grinding the crystal A with a mortar to obtain powder A, wherein the powder A is the metal organic framework material MIL-100-Fe.
(2) Adding 1g of metal organic framework material MIL-100-Fe and 7g N-methyl pyrrolidone into a reactor, performing ultrasonic dispersion for 2 hours at normal temperature, adding 2g of polyvinylidene fluoride into the reactor, and stirring for 4 hours at 60 ℃ to obtain a composite material.
(3) And (3) carrying out vacuum defoaming and standing curing treatment on the composite mixture to obtain the modified casting solution.
(4) And (3) coating the modified casting solution on a spin coater by adopting a spin coating method (the spin coating speed is 300r/min, and the spin coating time is 90s), and obtaining the polyvinylidene fluoride composite membrane with the thickness of 100 mu m by a liquid-liquid phase separation method (non-solvent distilled water used).
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the absorption capacity of the polyvinylidene fluoride composite membrane to Victoria blue is 70 mg/g; the adsorption capacity to methylene blue is 80 mg/g; the adsorption capacity to methyl orange is 40 mg/g; the adsorption capacity to Congo red was 80 mg/g.
The method for detecting the blood compatibility of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the content of PF4 in the polyvinylidene fluoride composite membrane is 38ng/mL (38 ng/mL in the plasma which is not contacted with the composite membrane) after 30min of contact between the polyvinylidene fluoride composite membrane and the plasma; PF4 level was 14ng/mL (15 ng/mL for plasma not contacted with the composite membrane), and there was no significant difference before and after contact. Therefore, the polyvinylidene fluoride composite membrane can have the performance of resisting platelet activation and complement activation, and can be used for preparing blood contact materials.
Comparative example 3
The preparation method of the polyvinylidene fluoride composite membrane provided by the comparative example 3 is different from that of the example 3 in that: and (3) adding 5% of vinyl pyrrolidone (PVP-K30) serving as a pore-foaming agent into the step (2). The other steps are consistent in method.
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the polyvinylidene fluoride composite membrane provided by the comparative example 3 has an adsorption capacity of 75mg/g to victoria blue; the adsorption capacity to methylene blue is 79 mg/g; the adsorption capacity to methyl orange is 50 mg/g; the adsorption amount of Congo red is 85 mg/g. The comparative example 3 shows that although the pore-foaming agent is added in the preparation process, the adsorption capacity of the composite polyvinylidene fluoride membrane on pollutants in wastewater is not improved, and the polyvinylidene fluoride composite membrane can have good adsorption capacity without adding the pore-foaming agent.
Example 4
The difference between the preparation method of the polyvinylidene fluoride composite membrane provided in the embodiment 4 and the embodiment 3 is that: and (3) replacing the polar organic solvent in the step (2) with N, N' -dimethylformamide. The other steps are consistent in method.
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the adsorption capacity of the polyvinylidene fluoride composite membrane to Victoria blue is 65 mg/g; the adsorption capacity to methylene blue is 87 mg/g; the adsorption capacity to methyl orange is 38 mg/g; the adsorption amount of Congo red is 75 mg/g.
The method for detecting the blood compatibility of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the content of PF4 in the polyvinylidene fluoride composite membrane is 47ng/mL (44 ng/mL in the plasma which is not contacted with the composite membrane) after 30min of contact between the polyvinylidene fluoride composite membrane and the plasma; PF4 level was 17ng/mL (18 ng/mL for plasma not contacted with composite membrane), with no significant difference before and after contact. Therefore, the polyvinylidene fluoride composite membrane can have the performance of resisting platelet activation and complement activation, and can be used for preparing blood contact materials.
Example 5
The difference between the preparation method of the polyvinylidene fluoride composite membrane provided in the embodiment 5 and the embodiment 3 is that: the step (2) is as follows: adding 1g of metal organic framework material MIL-100-Fe and 7g N-methyl pyrrolidone into a reactor, performing ultrasonic dispersion for 2h at normal temperature, adding 2g of polyvinylidene fluoride into the reactor, and stirring for 10h at 50 ℃ to obtain a composite material. The polar organic solvent in (1) is replaced by N, N' -dimethylformamide. The other steps are consistent in method.
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the absorption capacity of the polyvinylidene fluoride composite membrane to Victoria blue is 60 mg/g; the adsorption capacity to methylene blue is 85 mg/g; the adsorption capacity to methyl orange is 40 mg/g; the adsorption amount of Congo red was 76 mg/g.
The method for detecting the blood compatibility of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the content of PF4 in the polyvinylidene fluoride composite membrane is 45ng/mL (44 ng/mL in the plasma which is not contacted with the composite membrane) after 30min of contact between the polyvinylidene fluoride composite membrane and the plasma; PF4 level was 20ng/mL (18 ng/mL for plasma not contacted with composite membrane), and there was no significant difference before and after contact. Therefore, the polyvinylidene fluoride composite membrane can have the performance of resisting platelet activation and complement activation, and can be used for preparing blood contact materials.
Example 6
The difference between the preparation method of the polyvinylidene fluoride composite membrane provided in the embodiment 6 and the embodiment 3 is that: the step (2) is as follows: adding 1g of metal organic framework material MIL-100-Fe and 7g N-methyl pyrrolidone into a reactor, performing ultrasonic dispersion for 2h at normal temperature, adding 2g of polyvinylidene fluoride into the reactor, and stirring for 4.5h at 70 ℃ to obtain a composite material. The polar organic solvent in (1) is replaced by N, N' -dimethylformamide. The other steps are consistent in method.
The method for detecting the adsorption capacity of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the adsorption capacity of the polyvinylidene fluoride composite membrane to Victoria blue is 65 mg/g; the adsorption capacity to methylene blue is 88 mg/g; the adsorption capacity to methyl orange is 36 mg/g; the adsorption amount of Congo red is 72 mg/g.
The method for detecting the blood compatibility of the polyvinylidene fluoride composite membrane is consistent with the method provided by the embodiment 1, and the obtained result is as follows: the content of PF4 in the polyvinylidene fluoride composite membrane is 42ng/mL (44 ng/mL in the plasma which is not contacted with the composite membrane) after 30min of contact between the polyvinylidene fluoride composite membrane and the plasma; PF4 content was 15ng/mL (18 ng/mL for plasma not contacted with the composite membrane), and there was no significant difference before and after contact. Therefore, the polyvinylidene fluoride composite membrane can have the performance of resisting platelet activation and complement activation, and can be used for preparing blood contact materials.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. 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 application.

Claims (8)

1. A preparation method of a polyvinylidene fluoride composite film is characterized by comprising the following steps: dispersing a metal organic framework material MIL-100-Fe in a polar organic solvent, then adding polyvinylidene fluoride, and dispersing for 4-10h at the temperature of 50-70 ℃ to obtain a polyvinylidene fluoride composite material;
wherein the structural formula of the metal organic framework is as follows:
Figure 207302DEST_PATH_IMAGE001
；
wherein no pore-forming agent is added into the polyvinylidene fluoride composite material;
the mass ratio of the metal organic framework material MIL-100-Fe to the polyvinylidene fluoride is 1:1.5-1: 4; the mass ratio of the metal organic framework material MIL-100-Fe to the polar organic solvent is 1:7-1: 16;
and (3) defoaming, curing and coating the polyvinylidene fluoride compound mixture in sequence.
2. The method according to claim 1, wherein the polar organic solvent is one or more selected from the group consisting of N-methylpyrrolidone, dimethylacetamide, and N, N' -dimethylformamide.
3. The method of claim 1 or 2, wherein the method of preparing the metal-organic framework material MIL-100-Fe comprises: dispersing trimesic acid and ferric ions in a polar organic solvent, and reacting for 16-24h at the temperature of 110-130 ℃.
4. The method according to claim 3, wherein the molar ratio of the trimesic acid to the ferric ions is 1:4 to 1: 6.
5. A polyvinylidene fluoride composite film produced by the production method according to any one of claims 1 to 4.
6. The polyvinylidene fluoride composite film according to claim 5, wherein the thickness of the polyvinylidene fluoride composite film is 50 to 100 μm.
7. Use of the polyvinylidene fluoride composite membrane of claim 5 or 6 in the preparation of a blood contact material.
8. Use of a polyvinylidene fluoride composite membrane according to claim 7, wherein the blood contact material is an artificial blood vessel or a blood purification membrane.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498553A (en) * 2015-12-11 2016-04-20 华南理工大学 Polyvinylidene fluoride and metal-organic framework composite ultra-filtration membrane and preparation and application
CN108893873A (en) * 2018-07-05 2018-11-27 贵阳学院 A kind of anticoagulation tunica fibrosa and its preparation method and application

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US20180043656A1 (en) * 2017-09-18 2018-02-15 LiSo Plastics, L.L.C. Oriented Multilayer Porous Film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498553A (en) * 2015-12-11 2016-04-20 华南理工大学 Polyvinylidene fluoride and metal-organic framework composite ultra-filtration membrane and preparation and application
CN108893873A (en) * 2018-07-05 2018-11-27 贵阳学院 A kind of anticoagulation tunica fibrosa and its preparation method and application

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