CN114618450A - Conjugated microporous polymer composite material, preparation method thereof and adsorbent - Google Patents
Conjugated microporous polymer composite material, preparation method thereof and adsorbent Download PDFInfo
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Abstract
The invention relates to the technical field of composite materials, in particular to a conjugated microporous polymer composite material, a preparation method thereof and an adsorbent. The preparation method of the conjugated microporous polymer composite material comprises the steps of providing a base material coated with a first dopamine layer; loading palladium nano particles on the base material coated with the first dopamine layer, then carrying out secondary modification on dopamine to form a second dopamine layer, and heating; mixing the base material with a first monomer, a second monomer and triphenylphosphine, and enabling the first monomer and the second monomer to generate sonogashira-securinega coupling reaction to form a CMP layer on the base material under the catalytic action of palladium nanoparticles and the triphenylphosphine, wherein the first monomer is aromatic hydrocarbon substituted by non-fluorine halogen elements, and the second monomer is aromatic hydrocarbon substituted by alkynyl or boric acid groups. The CMP composite material provided by the invention can be compounded with any matrix material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a conjugated microporous polymer composite material, a preparation method thereof and an adsorbent.
Background
Conjugated Microporous Polymers (CMP) are a random microporous network of high molecular polymers with a pi conjugation effect throughout the entire molecule within the molecular system. It is usually formed by rigid organic monomers through a coupling reaction of carbon-carbon bonds catalyzed by organometallic catalysts to form a rigid conjugated system in which carbon-carbon single bonds and multiple bonds (or conjugated aromatic rings) are alternately connected. The CMP has unique electrical characteristics and excellent porosity, and the good controllability brought by the coupling reaction and the designability brought by various polymerization monomers make the CMP show excellent application potential in various fields, such as adsorption separation, heterogeneous catalysis, photoelectric materials, energy storage materials and the like. However, CMP prepared by a conventional polymerization method is generally in a powder form and is difficult to directly apply as a functional material. The difficulty can be effectively solved by compounding CMP and other matrix materials to form a composite material and endowing the composite material with a corresponding application form.
However, with conventional homogeneous catalysts, CMP forms a powder or flocculent morphology uniformly in the solution. When the matrix material exists, the CMP does not have the space structure condition and the driving force for compounding with the matrix material, and the compounding of the CMP and the matrix material cannot be stably realized. On the other hand, if a conventional heterogeneous palladium catalyst (such as palladium carbon) is adopted, on one hand, the heterogeneous catalytic activity is low, CMP with high polymerization degree is difficult to form, and the formation of a porous structure is not facilitated; on the other hand, heterogeneous catalysts are also difficult to couple with matrix materials, and cannot be made into stable composite materials.
Disclosure of Invention
Based on the conjugated microporous polymer composite material, the preparation method and the adsorbent, the conjugated microporous polymer composite material can improve the compounding capacity of CMP and various base materials, endow the CMP with rich application forms and improve the application effect of the CMP.
In one aspect of the present invention, a method for preparing a conjugated microporous polymer composite material is provided, which comprises the steps of:
providing a base material coated with a first dopamine layer;
loading palladium nanoparticles on the base material coated with the first dopamine layer to prepare a base material loaded with the palladium nanoparticles, wherein the particle size of the palladium nanoparticles is less than or equal to 5 nm;
carrying out secondary dopamine modification on the base material loaded with the palladium nanoparticles to form a second dopamine layer, and then heating to prepare a secondary dopamine modified base material; and
mixing the dopamine secondary modified base material with a first monomer, a second monomer and triphenylphosphine, and under the catalytic action of the palladium nanoparticles and the triphenylphosphine, enabling the first monomer and the second monomer to have sonogashira-suffruticosa coupling reaction to form a conjugated microporous polymer layer on the dopamine secondary modified base material, wherein the first monomer is aromatic hydrocarbon substituted by non-fluorine halogen elements, the second monomer is aromatic hydrocarbon substituted by alkynyl or boric acid groups, and the number of the non-fluorine halogen elements, the alkynyl and the boric acid groups is more than or equal to 2.
In some embodiments, the first dopamine layer in the base material coated with the first dopamine layer is formed by: placing the base material in a first dopamine solution with the pH value of 8-10, and stirring; the mass concentration of the first dopamine solution is 0.5-2 g/L, and the stirring time is 0.5-4 h.
In some embodiments, the method of forming the second dopamine layer comprises: placing the base material loaded with the palladium nanoparticles in a second dopamine solution with the pH value of 8-10, and stirring; the mass concentration of the second dopamine solution is 0.5-2 g/L and is greater than that of the first dopamine solution, and the stirring time is 1-8 hours and is greater than that for forming the first dopamine layer.
In some embodiments, the palladium nanoparticles have a particle size of 1 nm to 3 nm.
In some embodiments, the method used to support the palladium nanoparticles comprises:
and (3) placing the substrate material coated with the first dopamine layer in a divalent palladium salt solution with the temperature of 20-60 ℃ and the molar concentration of 5-50 mmol/L for reaction for 0.2-6 h.
In some embodiments, the heating method is a hydrothermal method, and the temperature of the hydrothermal method is 80 ℃ to 180 ℃ and the time is 8 h to 24 h.
In some embodiments, the amount of non-fluorine halogen element is 3 or more.
In some embodiments, the number of alkynyl groups and boronic acid groups is 3 or more.
In some embodiments, the first monomer is selected from the group consisting of p-dibromobenzene, m-dibromobenzene, 1,3, 5-tribromobenzene, 1,2,4, 5-tetrabromobenzene, 1,3, 5-tris (4-bromophenyl) benzene, 2,4, 6-tribromopyridine, 1,3,5, 7-tetrakis (4-bromophenyl) methane, 1,3,5, 7-tetrakis (4-bromophenyl) adamantane, one or more of p-diiodobenzene, m-diiodobenzene, 1,3, 5-triiodobenzene, 1,2,4, 5-tetraiodobenzene, 1,3, 5-tri (4-iodophenyl) benzene, 2,4, 6-triiodopyridine, 1,3,5, 7-tetra (4-iodophenyl) methane and 1,3,5, 7-tetra (4-iodophenyl) adamantane.
In some embodiments, the second monomer is selected from one or more of p-diethynylbenzene, m-diethynylbenzene, 1,3, 5-triethynylbenzene, 2,4, 6-triethynylpyridine, 1,2,4, 5-tetraalkynylbenzene, 1,3,5, 7-tetrakis (4-ethynylphenyl) methane, 1,3,5, 7-tetrakis (4-ethynylphenyl) adamantane, p-diborophenone, 1,3, 5-tribolylbenzene, 1,3,5, 7-tetrakis (4-boronophenyl) methane, and 1,3,5, 7-tetrakis (4-boronophenyl) adamantane.
In some embodiments, the matrix material is an oxide microsphere, elemental carbon, graphene, carbon nanotube, polymer fiber membrane, polymer microporous membrane, sponge, aerogel, or glass sheet.
In one aspect of the present invention, there is also provided a conjugated microporous polymer composite material prepared by the above method.
In another aspect of the present invention, a conjugated microporous polymer composite material is provided, which includes a base material, and a first dopamine layer, a second dopamine layer and a conjugated microporous polymer composite material layer sequentially coated on the surface of the base material.
In another aspect of the present invention, there is further provided an adsorbent, wherein the raw material for preparing the adsorbent comprises the conjugated microporous polymer composite material.
According to the invention, the first dopamine layer and the second dopamine layer are constructed on the base material, so that on one hand, the load of palladium nanoparticles on the base material is realized, on the other hand, the interaction between the CMP layer and the base material is improved, and a load condition is provided for CMP on the surface of the base material, thereby realizing the good combination of CMP and solid base materials (such as microsphere particles, polymer films, sponges and other materials with certain shapes) with any materials and any shapes, having good universality, and further solving the problems of single application form and poor combination operability with the base material of the CMP.
In addition, by regulating and controlling the size and the shape of the palladium nanoparticles, the contradiction between the loss rate and the catalytic efficiency of the palladium nanoparticle catalyst is solved, the catalytic activity of the catalyst is regulated and controlled, and the high-efficiency polymerization rate of the CMP is ensured when the CMP is subjected to heterogeneous catalytic polymerization near the surface of the base material.
Further, a second dopamine layer is constructed through secondary modification of dopamine and is subjected to heating treatment, so that the following effects are achieved: 1. the loss of the catalyst into the solution can be slowed down by utilizing the physical barrier effect of the second dopamine layer and the recapture effect of palladium; 2. the construction of the permeable and loose second dopamine layer provides space for the polymerization and fixation of CMP, and the loading capacity of CMP on the base material is improved.
Drawings
FIG. 1 shows CMP/magnetic Fe particles obtained in example 1 of the present invention3O4TEM images of microsphere composites;
FIG. 2 is an SEM photograph of a CMP/PTFE film composite prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a PTFE film without CMP in example 2 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
The Sonogashira-securinega Coupling reaction (Sonogashira Coupling) refers to a Coupling reaction of a halogenated aromatic hydrocarbon and an alkynyl aromatic hydrocarbon.
Since CMP is generally a random powder or flocculent material, it is difficult to directly impart an application morphology, and operability is poor during material application. In addition, the traditional synthesis method can not realize good combination of CMP and matrix materials, and is difficult to prepare composite materials. Therefore, how to realize the catalytic synthesis of CMP on the surface of a matrix material; how to ensure the synthesis efficiency of CMP under the condition of using heterogeneous catalysts, namely how to regulate and control the activity of the catalysts; and how to increase the loading of CMP on the substrate and enable CMP to generate a firm and stable interaction with the substrate are problems to be solved. Therefore, the invention provides the following technical scheme:
one aspect of the present invention relates to a method for preparing a conjugated microporous polymer composite material, comprising the steps of:
providing a base material coated with a first dopamine layer;
loading palladium nanoparticles on the substrate material coated with the first dopamine layer to prepare a substrate material loaded with the palladium nanoparticles, wherein the particle size of the palladium nanoparticles is less than or equal to 5 nm;
carrying out secondary dopamine modification on the base material loaded with the palladium nanoparticles to form a second dopamine layer, and then heating to prepare a secondary dopamine modified base material; and
mixing the dopamine secondary modified base material with a first monomer, a second monomer and triphenylphosphine, and under the catalytic action of palladium nanoparticles and the triphenylphosphine, carrying out sonogashira-suffruticosa coupling reaction on the first monomer and the second monomer to form a conjugated microporous polymer layer on the dopamine secondary modified base material, wherein the first monomer is aromatic hydrocarbon substituted by non-fluorine halogen elements, the second monomer is aromatic hydrocarbon substituted by alkynyl or boric acid groups, and the number of the non-fluorine halogen elements, the alkynyl and the boric acid groups is more than or equal to 2.
In some embodiments, the first dopamine layer in the base material coated with the first dopamine layer can be formed by: preparing a dopamine solution by using a trihydroxymethyl aminomethane buffer solution as a solvent and dopamine as a solute, adjusting the pH value to 8-10 by using hydrochloric acid, soaking a base material in the first dopamine solution, and stirring and reacting for 0.5-4 h. After the stirring reaction is finished, deionized water can be used for washing the substrate material to remove the redundant dopamine solution. Preferably, the pH is 8.5.
In some embodiments, the concentration of the tris buffer solution is a concentration commonly used in the art, and may be, for example, 8 mmol/L to 20 mmol/L.
In some embodiments, the dopamine can be added in the form of dopamine hydrochloride, and the mass concentration of the dopamine in the dopamine solution can be any value between 0.5 g/L and 2 g/L.
In some embodiments, the matrix material may be any material, solid matrix material of any morphology, including but not limited to powder, oxide microspheres (e.g., SiO)2Microspheres, Fe3O4Microspheres, Al2O3Microspheres), elemental carbon (e.g., graphene, carbon nanotubes), polymeric membranes (e.g., polymeric fibrous membranes, polymeric microporous membranes), sponges, aerogelsOr a glass sheet. Wherein the polymer membrane can be polytetrafluoroethylene filter membrane, polyvinylidene fluoride fiber membrane, polyethylene glycol fiber membrane, polycaprolactone fiber membrane, polydimethylsiloxane fiber membrane, polyurethane fiber membrane, polyethylene terephthalate fiber membrane, polyimide fiber membrane, polytetrafluoroethylene fiber membrane, polyvinyl chloride fiber membrane, polyvinyl butyral fiber membrane, polyvinylpyrrolidone fiber membrane, polymethyl methacrylate fiber membrane, polyethylene naphthalate fiber membrane, etc.
In some embodiments, the deposition and loading of the palladium nanoparticles on the first dopamine layer can be achieved by utilizing the reducibility of the catechol structure in the dopamine autopolymer in the first dopamine layer. The method for supporting the palladium nano-particles comprises the following steps: and (3) placing the substrate material coated with the first dopamine layer in a divalent palladium salt solution with the temperature of 20-60 ℃ and the molar concentration of 5-50 mmol/L for reaction for 0.2-6 h. Preferably, the molar concentration of the divalent palladium salt solution is 8 mmol/L-15 mmol/L, and the reaction time is 1 h-2 h. The divalent palladium salt is preferably potassium chloropalladite, the temperature can be any value between 20 ℃ and 60 ℃, the temperature can be exemplarily any value between 25 ℃, 30 ℃, 35 ℃, 40 ℃ and 50 ℃, the molar concentration can be any value between 8 mmol/L and 15 mmol/L, for example, 10 mmol/L, 12 mmol/L, 13 mmol/L and 14 mmol/L, and the reaction time can be any value between 1 h and 2 h, and the exemplarily time can be 1.2 h, 1.5 h and 1.8 h. The reaction conditions can be specifically regulated and controlled based on base materials with different materials and forms so as to obtain the optimal size of the palladium nanoparticles.
In some embodiments, the substrate coated with the first dopamine layer may be subjected to soaking, stirring, filtering or vacuum filtration during the reaction in the divalent palladium salt solution, and may be selected according to the specific substrate, for example, the substrate in a powder, microsphere, two-dimensional or three-dimensional surface state may be subjected to soaking and stirring, and the porous substrate such as a polymer fiber membrane or a polymer filter membrane, a sponge, or the like may be subjected to filtering or vacuum filtration to ensure that the palladium nanoparticles can be supported in the pore structure of the porous substrate.
Generally speaking, the size of the palladium nanoparticles needs to be regulated to be less than or equal to 3 nm, and when the size is too small, the loss of the palladium nanoparticle catalyst is too fast, so that the subsequent CMP polymerization mainly occurs in the solution; the over-sizing can result in a reduction in the catalytic efficiency of the palladium nanoparticle catalyst and a significant reduction in CMP yield. In some embodiments, the palladium nanoparticle size can be any value between 1 nm and 3 nm. Within this range, the palladium nanoparticle catalyst can be supported while approaching a heterogeneous catalyst, improving catalytic performance.
In some embodiments, the method of forming a second dopamine layer comprises: and placing the base material loaded with the palladium nanoparticles into a second dopamine solution with the pH value of 8-10, and stirring, wherein the mass concentration of the second dopamine solution is 0.5-2 g/L and is greater than that of the first dopamine solution, and the stirring time is 1-8 h and is greater than that for forming the first dopamine layer. The thickness of the second dopamine layer can be regulated and controlled by regulating and controlling the mass concentration and the stirring time of the second dopamine solution, so that the loading capacity of subsequent CMP can be ensured. On one hand, the second dopamine layer can be constructed to prevent the palladium nanoparticles from physically falling off; on the other hand, the ionic palladium element can be recaptured in the catalytic process, and the loss of palladium to the solution in the catalytic process is remarkably slowed down. But also to provide space for CMP load.
In some embodiments, the heating method is a hydrothermal method, wherein the temperature of the hydrothermal method can be 80 ℃ to 180 ℃ and the time can be 8 h to 24 h. The second dopamine layer after hydrothermal treatment has good hydrophilicity and water permeability, and has a loose and porous spatial structure, which is beneficial to the transmission of CMP polymerized monomers in the second dopamine layer and the fixation of the generated CMP on the second dopamine layer.
In some embodiments, a specific preparation method for forming the CMP layer is as follows: dissolving and mixing the dopamine secondary modified base material, the first monomer, the second monomer and triphenylphosphine, and carrying out sonogashira-securinega coupling reaction after repeated vacuumizing-backfilling protective gas circulation process. Wherein the temperature of the sonogashira-securinega coupling reaction can be 60-105 ℃, and the reaction time can be 12-60 h. The CMP layer is formed by polymerizing the first monomer and the second monomer under the catalysis of the palladium nanoparticles and the triphenylphosphine, and can provide porosity and other specific functionality, such as adsorbability and the like, for the CMP composite material.
In some embodiments, the solvent used for the sonogashira-securinega coupling reaction is an alkaline organic solvent, i.e., the organic solvent and the alkaline substance are mixed in a volume ratio of 1: (0.1-0.5) by mixing. Wherein the organic solvent is N, N-dimethylformamide, and the alkaline substance can be triethylamine, NaOH aqueous solution with a molar concentration of 2 mol/L and K with a molar concentration of 2 mol/L2CO3One or more of aqueous solutions.
In some embodiments, the sonogashira-securinega coupling reaction may be carried out in the presence of a palladium nanoparticle catalyst, triphenylphosphine, and a copper-containing co-catalyst, wherein the copper-containing co-catalyst may be cuprous chloride and/or cuprous iodide.
In some embodiments, the molar ratio of copper-containing co-catalyst to the total amount of monomer is 1: (10-100), wherein the total amount of the monomers refers to the total amount of the first monomer and the second monomer.
In some embodiments, the amount of non-fluorine halogen element is 3 or more, and the non-fluorine halogen element can be one or more of chlorine, iodine and bromine, preferably iodine or bromine.
In some embodiments, the number of alkynyl and boronic acid groups is 3 or more. The CMP can form a random porous structure by regulating the first monomer and/or the second monomer to be the aromatic hydrocarbon containing at least three substituents, so that the adsorbability of the CMP is further improved.
In some embodiments, the first monomer may be an aromatic hydrocarbon substituted with at least two chlorine and/or iodine, including, but not limited to, one or more of p-dibromobenzene, m-dibromobenzene, 1,3, 5-tribromobenzene, 1,2,4, 5-tetrabromobenzene, 1,3, 5-tris (4-bromophenyl) benzene, 2,4, 6-tribromopyridine, 1,3,5, 7-tetrakis (4-bromophenyl) methane, 1,3,5, 7-tetrakis (4-bromophenyl) adamantane, p-diiodobenzene, m-diiodobenzene, 1,3, 5-triiodobenzene, 1,2,4, 5-tetraiodobenzene, 1,3, 5-tris (4-iodophenyl) benzene, 2,4, 6-triiodopyridine, 1,3,5, 7-tetrakis (4-iodophenyl) methane, and 1,3,5, 7-tetrakis (4-iodophenyl) adamantane.
In some embodiments, the second monomer may be an aromatic hydrocarbon substituted with at least two ethynyl groups or at least two boronic acid groups, including but not limited to one or more of p-diethynylbenzene, m-diethynylbenzene, 1,3, 5-triethynylbenzene, 2,4, 6-triethynylpyridine, 1,2,4, 5-tetraalkynylbenzene, 1,3,5, 7-tetrakis (4-ethynylphenyl) methane, 1,3,5, 7-tetrakis (4-ethynylphenyl) adamantane, p-diborophene, 1,3, 5-tribolylbenzene, 1,3,5, 7-tetrakis (4-boronophenyl) methane, and 1,3,5, 7-tetrakis (4-boronophenyl) adamantane.
In some embodiments, the equivalent ratio of the first monomer to the second monomer is 1 (0.5-2). For better porosity, the equivalent ratio of the first monomer to the second monomer is preferably 1 (1.4-1.6).
In some embodiments, the shielding gas may be nitrogen and/or argon.
In one aspect of the present invention, there is also provided a conjugated microporous polymer composite material prepared by the above method for preparing a conjugated microporous polymer composite material.
In another aspect of the present invention, a conjugated microporous polymer composite material is provided, which includes a base material, and a first dopamine layer, a second dopamine layer and a conjugated microporous polymer composite material layer sequentially coated on the surface of the base material.
In another aspect of the present invention, there is further provided an adsorbent, wherein the raw material for preparing the adsorbent comprises the conjugated microporous polymer composite material.
The present invention will be described in further detail with reference to specific examples and comparative examples.
EXAMPLE 1 CMP/magnetic Fe3O4Preparation of microsphere composites
1) Preparing a trihydroxymethyl aminomethane buffer solution with the concentration of 10 mmol/L, and adjusting the pH to 8.5 by using dilute hydrochloric acid. 190 mL of the above buffer solution was taken, and 0.5 g of Fe was added3O4And (4) carrying out microsphere stirring by magnetic force. Another 10 mL of the above buffer was dissolved by adding 0.2 g of dopamine hydrochloride, followed by dissolvingDropwise adding the Fe-containing solution3O4Continuously stirring and reacting for 2 h at room temperature in a reaction system of the microspheres, separating a sample by using a magnet after the reaction is finished, and stirring and washing for three times by using deionized water to prepare dopamine-modified magnetic Fe3O4And storing the microsphere material in deionized water.
2) Preparing 25 mL potassium chloropalladite solution with the concentration of 10 mmol/L, and modifying the dopamine prepared in the step 1) into magnetic Fe3O4The microsphere material is separated from deionized water by a magnet, placed in potassium chloropalladite solution and stirred for reaction for 1 hour at room temperature. Separating a sample by using a magnet after the reaction is finished, stirring and washing the sample by using deionized water for three times, and drying the sample in a vacuum oven at room temperature to prepare the palladium nanoparticle-loaded dopamine modified magnetic Fe3O4A microsphere material, wherein the palladium nanoparticles have a particle size of about 2 nm.
3) 190 mL of the tris buffer solution obtained in step 1) was taken, and the material obtained in step 2) was placed in the buffer solution and kept under stirring. Taking another 10 mL of the tris buffer solution in the step 1), adding 0.5 g of dopamine hydrochloride for dissolution, then dropwise adding the solution into the buffer solution, and stirring and reacting for 4 hours at room temperature. The reaction system was then transferred to an autoclave containing a polytetrafluoroethylene liner and thermally treated at 90 ℃ for 24 h after sealing. Separating a sample by using a magnet after the reaction is finished, washing the sample by using deionized water and methanol in sequence, and drying the sample in a vacuum oven at room temperature to prepare the magnetic Fe which is secondarily modified by dopamine and supports the palladium nanoparticles3O4A microsphere material.
4) Placing the material prepared in the step 3) into a Schlenk tube, adding a mixed solution formed by 20 mL of N, N-dimethylformamide and 6 mL of triethylamine, 1 mmol of 1,3, 5-triethylalkynyl benzene, 1 mmol of p-dibromobenzene, 0.1 mmol of triphenylphosphine and 0.075 mmol of cuprous iodide, sealing and fully mixing. And then vacuumizing the reaction system, backfilling argon, repeatedly circulating for three times, reacting at 80 ℃ for 48 hours, separating a sample by using a magnet after the reaction is finished, and enabling the remaining liquid to be light brown transparent and contain a small amount of flocculent suspended matters. After separationSequentially stirring and cleaning a sample by using N, N-dimethylformamide, methanol and deionized water, and drying in a vacuum oven at 50 ℃ to obtain CMP/magnetic Fe3O4A microsphere composite material. The TEM image of the composite material is shown in FIG. 1, and the related performance test results are shown in Table 1.
EXAMPLE 2 preparation of CMP/Polytetrafluoroethylene film composite
1) Preparing a trihydroxymethyl aminomethane buffer solution with the concentration of 10 mmol/L, and adjusting the pH value to 8.5 by using dilute hydrochloric acid. Fixing a polytetrafluoroethylene filter membrane with the diameter of 5 cm on a support, putting the support into a reaction container, keeping the support flat in the reaction process, adding sufficient buffer solution, keeping magnetic stirring, ensuring that the filter membrane does not expose the liquid level in the stirring process, and vacuumizing the reaction system to remove air in a membrane pore channel. And taking a proper amount of the buffer solution, adding dopamine hydrochloride to dissolve, then dropwise adding the buffer solution into the reaction system to ensure that the concentration of the dopamine hydrochloride in the reaction system is 0.5 g/L, stirring and reacting for 2 hours at normal temperature and normal pressure, taking out a membrane sample after the reaction is finished, soaking the membrane sample in deionized water, stirring and washing for three times to prepare the dopamine modified polytetrafluoroethylene filter membrane, and storing the dopamine modified polytetrafluoroethylene filter membrane in the deionized water.
2) Preparing 10 mL of potassium chloropalladite solution with the concentration of 10 mmol/L, taking the dopamine modified polytetrafluoroethylene filter membrane prepared in the step 1) from the bracket, placing the dopamine modified polytetrafluoroethylene filter membrane on a membrane-sandwiched filter, and controlling the suction filtration pressure to ensure that the flow rate of the potassium chloropalladite solution is about 0.2 mL/min. And after the filtration is finished, fixing the membrane sample on the bracket again, soaking the membrane sample in deionized water, stirring and washing the membrane sample for three times to prepare the dopamine modified polytetrafluoroethylene filter membrane loaded with the palladium nano particles, and storing the dopamine modified polytetrafluoroethylene filter membrane in the deionized water, wherein the particle size of the palladium nano particles is about 2 nm.
3) Then taking enough trihydroxymethyl aminomethane buffer solution in the step 1), putting the material prepared in the step 2) into the buffer solution, and keeping stirring. Adding a proper amount of the trihydroxymethyl aminomethane buffer solution obtained in the step 1) into dopamine hydrochloride for dissolving, then dropwise adding the solution into the buffer solution reaction system to ensure that the concentration of the dopamine hydrochloride in the reaction system is 1 g/L, and stirring and reacting for 4 hours at room temperature. The reaction system was then transferred to an autoclave containing a polytetrafluoroethylene liner and thermally treated at 90 ℃ for 24 h after sealing. And taking out a membrane sample after the reaction is finished, soaking the membrane sample in deionized water, stirring and washing the membrane sample for three times, and drying the membrane sample in a vacuum oven at 50 ℃ to obtain the polytetrafluoroethylene filter membrane which is secondarily modified by dopamine and is loaded with the palladium nanoparticles.
4) Placing the membrane sample in the step 3) into a magnetic stirring high-pressure reaction kettle, and adding 40 mL of N, N-dimethylformamide and 10 mL of 2 mol/L K2CO32 mmol of 1,3, 5-triethylynylbenzene, 2 mmol of 2, 5-dibromohydroquinone, 0.4 mmol of triphenylphosphine and 0.3 mmol of cuprous iodide, sealed, reacted and mixed thoroughly. The reaction was then evacuated-back filled with argon and repeated three times before reacting at 80 ℃ for 36 h. And taking out a membrane sample after the reaction is finished, sequentially soaking the membrane sample in N, N-dimethylformamide, methanol and deionized water, stirring and cleaning the membrane sample, and drying the membrane sample in a vacuum oven at 50 ℃ to obtain the CMP/polytetrafluoroethylene membrane composite material. The SEM image of the composite material is shown in fig. 2, and the results of the related performance tests are shown in table 1. FIG. 3 is an SEM image of a PTFE filter without CMP.
Comparative example 1
This comparative example was prepared substantially the same as example 1, except that: step 2) was omitted and 0.05 mmol of palladium acetate was added to the Schlenk tube in step 4).
When the composite material is prepared by the method of the comparative example, it is found that after the reaction of the step 4) is finished, the remaining liquid is filtered, the filtrate is light brown transparent, and the filter residue is a large amount of brown floccules. This result indicates that the polymerization reaction of CMP mainly occurs in the solution and with magnetic Fe3O4No interaction is formed between the microsphere matrix materials. The results of the relevant performance tests of the composite materials obtained are shown in table 1.
Comparative example 2
This comparative example was prepared substantially the same as example 1, except that: the stirring reaction time in the step 2) is shortened from 1 h to 40 min. Magnetic Fe of prepared load palladium nano particle3O4In the microsphere matrix materialThe particle size of the palladium nano-particles is less than 1 nm.
When the composite material is prepared by the method of the comparative example, the fact that after the reaction in the step 4) is finished, the residual liquid is filtered, the filtrate is light brown transparent, and the filter residue is brown floccule is found. The result shows that the reaction time is too short, the size of the formed palladium nano particles is too small, the catalytic CMP polymerization efficiency is high, but the palladium element is easy to be lost into the solution along with the reaction, so that part of CMP is generated in the solution, and the CMP is performed in magnetic Fe3O4The loading rate on the microsphere matrix material decreases. The results of the relevant performance tests of the composite materials obtained are shown in table 1.
Comparative example 3
This comparative example was prepared substantially the same as example 1, except that: increasing the concentration of the potassium chloropalladite solution in the step 2) to 20 mmol/L, and increasing the stirring reaction time from 1 h to 4 h. Magnetic Fe of prepared load palladium nano particle3O4The particle size of the palladium nanoparticles in the microsphere matrix material is about 10 nm.
When the composite material was prepared by the method of this comparative example, it was found that after the reaction of step 4) was completed, the remaining liquid was filtered, the filtrate was dark brown transparent, and the residue was a small amount of brown powder. The results show that the reaction time is too long, the palladium nano particles are too large in size, the heterogeneous catalysis property is more, the catalysis efficiency is lower, and the monomer can form more oligomers to be deposited on the magnetic Fe3O4On the microsphere matrix material or lost into solution. The results of the relevant performance tests of the composite materials obtained are shown in table 1.
Comparative example 4
This comparative example was prepared substantially the same as example 1, except that: step 3) is omitted.
When the composite material is prepared by the method of the comparative example, it is found that after the reaction of the step 4) is finished, the remaining liquid is filtered, the filtrate is light brown transparent, and the filter residue is a large amount of brown floccules. The results show that the catalytic CMP cannot react with magnetic Fe without secondary modification of dopamine3O4The microsphere matrix material generates enough interaction and is difficult to be fixed on the magnetismFe3O4On the microsphere matrix material, but is present primarily in solution. The results of the relevant property tests of the materials obtained are shown in table 1.
Comparative example 5
This comparative example was prepared substantially identically to example 1, except that: omitting step 3) "the reaction system was then transferred to an autoclave containing a polytetrafluoroethylene liner and subjected to hydrothermal treatment at 90 ℃ for 24 hours after sealing.
When the composite material was prepared by the method of this comparative example, it was found that after the reaction of step 4) was completed, the remaining liquid was filtered, the filtrate was dark brown transparent, and the residue was a small amount of brown powder. The result shows that the dopamine interface layer which is not subjected to hydrothermal treatment is not favorable for the transmission of substances in the interface layer due to relatively poor permeability, the palladium nano particles are difficult to contact with enough polymerized monomers, the polymerization efficiency is poor, and the magnetic Fe in CMP is small3O4The loading on the microsphere matrix material is low. The results of the relevant performance tests of the materials obtained are shown in table 1.
And (3) performance testing:
1) specific surface areas of the composite materials in examples 1 and 2 and comparative examples 1-5 are tested by adopting a nitrogen adsorption and desorption experiment;
2) preparing 5 mg/L methylene blue solution, putting 50 mg of the composite material in the embodiment 1 and the comparative examples 1-5 into 20 mL of 5 mg/L methylene blue solution, stirring and reacting for 10 min, separating the composite material from the methylene blue solution by using a magnet, measuring the absorbance of the methylene blue solution at the wavelength of 664 nm by using a spectrophotometer, converting the absorbance into the concentration of the methylene blue, and calculating the removal rate to represent the adsorbability of the composite material;
3) preparing 5 mg/L methylene blue solution, performing suction filtration on 10 mL of the methylene blue solution by using the composite material in the example 2, measuring the absorbance of the filtrate at the wavelength of 664 nm by using a spectrophotometer, converting the absorbance into the concentration of the methylene blue, and calculating the removal rate of the methylene blue to characterize the adsorbability of the composite material.
TABLE 1
From the above test results, the CMP composite material provided by the present invention has excellent composite ability between CMP and various matrix materials (e.g., microspheres, films, particles, other two-dimensional or three-dimensional solid materials, etc.), thereby enabling CMP to have various application forms. And the CMP composite material has excellent specific surface area and adsorbability.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. A preparation method of a conjugated microporous polymer composite material is characterized by comprising the following steps:
providing a substrate material coated with a first dopamine layer;
loading palladium nanoparticles on the base material coated with the first dopamine layer to prepare a base material loaded with the palladium nanoparticles, wherein the particle size of the palladium nanoparticles is less than or equal to 5 nm;
carrying out secondary dopamine modification on the base material loaded with the palladium nanoparticles to form a second dopamine layer, and then heating to prepare a secondary dopamine modified base material; and
mixing the dopamine secondary modified base material with a first monomer, a second monomer and triphenylphosphine, and under the catalytic action of the palladium nanoparticles and the triphenylphosphine, enabling the first monomer and the second monomer to have sonogashira-suffruticosa coupling reaction to form a conjugated microporous polymer layer on the dopamine secondary modified base material, wherein the first monomer is aromatic hydrocarbon substituted by non-fluorine halogen elements, the second monomer is aromatic hydrocarbon substituted by alkynyl or boric acid groups, and the number of the non-fluorine halogen elements, the alkynyl and the boric acid groups is more than or equal to 2.
2. The method of claim 1, wherein the first dopamine layer of the base material coated with the first dopamine layer is formed by: placing the base material in a first dopamine solution with the pH value of 8-10, and stirring; the mass concentration of the first dopamine solution is 0.5-2 g/L, and the stirring time is 0.5-4 h.
3. The method of preparing a conjugated microporous polymer composite according to claim 2, wherein the method of forming the second dopamine layer comprises: placing the base material loaded with the palladium nanoparticles in a second dopamine solution with the pH value of 8-10, and stirring; the mass concentration of the second dopamine solution is 0.5-2 g/L and is greater than that of the first dopamine solution, and the stirring time is 1-8 hours and is greater than that for forming the first dopamine layer.
4. The method of claim 1, wherein the palladium nanoparticles have a particle size of 1 nm to 3 nm.
5. The method of claim 4, wherein the supported palladium nanoparticles are prepared by a method comprising:
and (3) placing the substrate material coated with the first dopamine layer in a divalent palladium salt solution with the temperature of 20-60 ℃ and the molar concentration of 5-50 mmol/L for reaction for 0.2-6 h.
6. The method for preparing the conjugated microporous polymer composite material according to any one of claims 1 to 5, wherein the heating method is a hydrothermal method, and the temperature of the hydrothermal method is 80 ℃ to 180 ℃ and the time is 8 h to 24 h.
7. The method for preparing a conjugated microporous polymer composite according to any one of claims 1 to 5, wherein the amount of the non-fluorine halogen element is not less than 3.
8. The method of any one of claims 1 to 5, wherein the number of alkynyl groups and boronic acid groups is 3 or more.
9. The method of any one of claims 1 to 5, wherein the first monomer is selected from the group consisting of p-dibromobenzene, m-dibromobenzene, 1,3, 5-tribromobenzene, 1,2,4, 5-tetrabromobenzene, 1,3, 5-tris (4-bromophenyl) benzene, 2,4, 6-tribromopyridine, 1,3,5, 7-tetrakis (4-bromophenyl) methane, 1,3,5, 7-tetrakis (4-bromophenyl) adamantane, p-diiodobenzene, m-diiodobenzene, 1,3, 5-triiodobenzene, 1,2,4, 5-tetraiodobenzene, 1,3, 5-tris (4-iodophenyl) benzene, 2,4, 6-triiodopyridine, 1,3,5, 7-tetrakis (4-iodophenyl) methane, and 1, one or more of 3,5, 7-tetra (4-iodophenyl) adamantane.
10. The method of any one of claims 1-5, wherein the second monomer is selected from one or more of p-diethynylbenzene, m-diethynylbenzene, 1,3, 5-triethynylbenzene, 2,4, 6-triethynylpyridine, 1,2,4, 5-tetraenylbenzene, 1,3,5, 7-tetrakis (4-ethynylphenyl) methane, 1,3,5, 7-tetrakis (4-ethynylphenyl) adamantane, p-diborophenone, 1,3, 5-tribolylbenzene, 1,3,5, 7-tetrakis (4-boronophenyl) methane, and 1,3,5, 7-tetrakis (4-boronophenyl) adamantane.
11. The method for preparing the conjugated microporous polymer composite material according to any one of claims 1 to 5, wherein the matrix material is oxide microspheres, carbon simple substance, polymer fiber membrane, polymer microporous filter membrane, sponge, aerogel or glass sheet.
12. A conjugated microporous polymer composite material prepared by the method of claim 1 to 11.
13. The conjugated microporous polymer composite material is characterized by comprising a base material, and a first dopamine layer, a second dopamine layer and a conjugated microporous polymer composite material layer which are sequentially coated on the surface of the base material.
14. An adsorbent, wherein a starting material for the preparation comprises the conjugated microporous polymer composite of claim 12 or 13.
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