A porous polyparalysine material, its preparation method and use

Abstract

This invention provides a porous polypyrrolidine material, its preparation method, and its applications. The material is synthesized using multifunctional aromatic amines and norbornene anhydride as raw materials. After imidization and decarbonylation reactions, polypyrrolidine norbornene monomers are formed. Further ring-opening metathesis polymerization of the polypyrrolidine norbornene monomers completes the synthesis. The preparation method provided by this invention features mild reaction conditions, enabling mass production. The raw materials used are all commercially available, low-cost, and readily available, effectively reducing the cost of preparing adsorbent materials and thus lowering the cost of recovering precious metals from electronic and industrial waste. This material can be applied to the recovery of precious metals (especially gold) from electronic waste. Furthermore, it maintains high adsorption capacity during use and can be recycled after gold desorption, making it an excellent gold adsorbent. 3+ It has extremely high application potential in the field of adsorption.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new chemical materials, in particular to a kind of porous polypyrrolidine material and its preparation method and application. BACKGROUND

[0002] Precious metals (such as gold, palladium, platinum and silver, etc.) are widely used in chemical industry, aerospace, metallurgy, electronics and catalysis, etc. due to their special properties such as un-filled d electron orbit, high stability, excellent electron transport ability and ductility, etc. Especially, the rapid development of electronic industry needs more gold supply. Since most of the precious metals come from mining, continuous mining and overuse cause serious resource crisis, environmental problems and rising mining costs. At the same time, used electronic waste and industrial waste contain a lot of precious metals, such as the gold content of waste printed circuit boards (PCBs) is higher than that of general ore. However, 90% of electronic waste is directly landfilled, causing huge pollution and waste. Therefore, it is urgent to develop efficient and economic strategies for separating and recovering precious metals from secondary resources for environmental protection and resource utilization.

[0003] The existing methods for recovering precious metals from electronic waste and industrial waste include dry method and wet method. The wet method for recovering precious metals from waste materials using only digestive fluid has greater application potential, without the need for excessive energy and the generation of hazardous substances. Further separation and enrichment of precious metals from leaching solution commonly use adsorption method, ion exchange, solvent extraction, membrane separation, etc. Among them, the adsorption method can selectively pick out target metal ions from solution, with the characteristics of low cost, high efficiency, reusability and simple operation, and is considered as a promising technology.

[0004] However, the adsorption method is rarely used at present, mainly because there are still few selective adsorption materials with high adsorption capacity, high selectivity, low cost and easy regeneration that can be used at present, and there are too many different substances in secondary resources, which makes it too difficult to separate and too high in separation cost. SUMMARY

[0005] In view of the above problems existing in the prior art, the present application provides a kind of porous polypyrrolidine material and its preparation method and application. The preparation method provided by the present application has mild reaction conditions and can realize batch production. The raw materials used are low-cost and conventional materials available on the market, which can effectively reduce the cost of preparing adsorption materials and thus reduce the cost of recovering precious metals from electronic waste and industrial waste. The obtained porous polypyrrolidine material has good thermal stability, rich N atom sites, high specific surface area, large total pore volume and small average pore size, can selectively adsorb precious metals in solution, and has high adsorption capacity. The specific invention content is as follows:

[0006] In a first aspect, the present application provides a porous polyparacyclic material, which has a repeating structural unit shown in the following formula I:

[0007]

[0008] In the formula, the structural building block of the porous polyparacyclic material is a multifunctional group containing a phenyl group.

[0009] The porous polyparacyclic material has a polyparacyclic structural unit and a 1,3-divinylcyclopentane connecting structure.

[0010] The porous polyparacyclic material has a micro-mesoporous hierarchical pore structure mainly composed of micropores.

[0011] Optionally, the Linker (structural building block) comprises a benzene ring, a triphenylbenzene, a triphenylamine, a hexahydrotriphenyltricyane, a 1,4,7-triphenyl-1,4,7-triazacyclononane, a bisdispirofluorene, a tetraphenylmethane, a tetraphenylethylene, a porphyrin, (R)-2,2',3,3'-tetrahydro-1,1'-spirobis[indene], or 1,8-dihydroazulene.

[0012] Optionally, the porous polyparacyclic material is connected by the 1,3-divinylcyclopentane connecting structure to form an infinite network structure.

[0013] Optionally, the pore size of the porous polyparacyclic material is 0.5-100 nm.

[0014] The total pore volume of the porous polyparacyclic material is 0.5-50 cm 3 / g.

[0015] The specific surface area of the porous polyparacyclic material is 100-10000 m 2 / g.

[0016] In a second aspect, the present application provides a preparation method of the porous polyparacyclic material obtained by the preparation method of the first aspect, which comprises the following steps:

[0017] S1, dissolving norbornene anhydride in a third organic solvent, adding an appropriate amount of alkaline reagent, mixing uniformly, adding a multifunctional aromatic amine, heating for imidization reaction, and after the reaction is completed, filtering, washing, and drying the product to obtain a multifunctional norbornene imide;

[0018] S2, the reaction liquid composed of the second organic solvent and the reducing agent is placed in an ice water bath; the multi-function norbornene imide is dissolved in the second organic solvent and added dropwise into the reaction liquid, the multi-function norbornene imide undergoes decarbonylation reaction, after the reaction is completed, a quenching agent and an acid-base regulator are added to the reaction system, and the product is filtered, washed and dried to obtain the polypyrrolidine norbornene monomer;

[0019] S3, the polypyrrolidine norbornene monomer is dissolved in the first organic solvent, and a catalyst is added to make the polypyrrolidine norbornene monomer undergo ring-opening metathesis polymerization reaction, after the reaction is completed, a quenching agent is added to the reaction system for quenching, and the product is treated by soaking, washing, filtering and drying to obtain the porous polypyrrolidine material.

[0020] Optionally, in step 1, the functionality of the multi-functional aromatic amine is greater than or equal to 2; the multi-functional aromatic amine includes 1,3,5-triaminobenzene, 1,3,5-tris(4-aminophenyl)benzene, tris(4-amino)aniline, 4,4',4”-(1,3,5-triazinane-1,3,5-triyl)triphenylamine, 4,4',4”-(1,4,7-triazolidine-1,4,7-triyl)triphenylamine, tetraamino-9,9'-bi-spirofluorene, tetra(4-aminophenyl)methane, tetra-(4-aminophenyl)ethylene, 1,2,4,5-benzene tetramine, tetra-p-phenylamino porphyrin, (R)-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-5,5',6,6'-tetraamine or 1,8-dihydrophenanthrene-1,3,6,8-tetramine.

[0021] Optionally, in step 1, the third organic solvent is toluene, xylene, chlorobenzene, N,N-dimethylformamide or N-methyl pyrrolidone, and the concentration of the norbornene anhydride substrate in the third organic solvent is 0.01-1M;

[0022] The basic reagent is triethylamine, diisopropyl ethylamine or pyridine, and the equivalent of the basic reagent is 2-10;

[0023] The reaction time of the imidization reaction is 2-12h, and the reaction temperature is 25-140℃.

[0024] Optionally, in step 2, the second organic solvent is tetrahydrofuran, acetone, ethyl acetate or N,N-dimethylformamide; the concentration of the multi-functional norbornene imide substrate in the second organic solvent is 0.01-1M;

[0025] The reducing agent is lithium aluminum hydride, sodium hydride, sodium borohydride, hydrazine hydrate, sulfonyl hydrazine, silicon hydride, zinc or hydrogen, and the equivalent of the reducing agent is 3-10;

[0026] The quencher is water, ethanol or acetic acid with active hydrogen, and the equivalent of the quencher is 2-10;

[0027] The acid-base regulator is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium methoxide or triethylamine;

[0028] The reaction time of the decarbonylation reaction is 12-24h, and the reaction temperature is 0-60℃.

[0029] Optionally, in step 3, the first organic solvent is dichloromethane, dichloroethane, acetone, 1,4-dioxane, tetrahydrofuran, ethyl acetate or N,N-dimethylformamide, and the concentration of the polypyrrolidine norbornene monomer in the first organic solvent is 0.01-1M;

[0030] The catalyst is Grubbs catalyst, Hoveyda-Grubbs catalyst, Schrock catalyst, metal salt, metal oxide or metal nitrogen heterocycle, and the equivalent of the catalyst is 0.001-0.1;

[0031] The quencher is an ethylene derivative or a propylene derivative, and the equivalent of the quencher is 2-10;

[0032] The reaction time of the ring-opening metathesis polymerization reaction is 0.5-12h, and the reaction temperature is 0-60℃.

[0033] In a third aspect, the application provides an application of the porous polypyrrolidine material of the first aspect, and the porous polypyrrolidine material is used for adsorbing and reducing noble metal ions; wherein the noble metal is one or more of gold, palladium, ruthenium and silver.

[0034] The ability of the porous polypyrrolidine material to adsorb and reduce the noble metal under light conditions is enhanced.

[0035] Compared with the prior art, the application has the following advantages:

[0036] (1) The application provides a porous polypyrrolidine material, which combines a pyrrolidine functional group with a polynorbornene skeleton structure, forms a micropore-mesopore multi-level pore structure with micropores as the main feature, has rich N atom sites, a high specific surface area, a large total pore volume and a small average pore size, and has photocatalytic potential, and can play an important role in the fields of organic pollutant adsorption, heterogeneous catalysis and gas storage related to the environment and energy.

[0037] (2) The application provides a preparation method of a porous polypyrrolizine material, which comprises the following steps: firstly, carrying out imidization reaction of norbornene anhydride and a multi-functional aromatic amine to obtain a multi-functional norbornene imide; then, carrying out decarbonylation on the multi-functional norbornene imide by means of a reducing agent to obtain a polypyrrolizine norbornene monomer; and finally, carrying out ring-opening metathesis polymerization (ROMP) on the polypyrrolizine norbornene monomer under the action of a catalyst to obtain the porous polypyrrolizine material. The preparation method provided by the application has mild reaction conditions and can realize batch production; the raw materials used are all low-cost and conventional raw materials available on the market, so that the cost of preparing the adsorption material can be effectively reduced, thereby reducing the cost of recovering precious metals from electronic waste and industrial waste.

[0038] (3) The application provides a porous polypyrrolizine material, which has a polynorbornene skeleton and a pyrrolizine structure, so that the adsorption capacity of the polymer to precious metal ions is enhanced; and the material has good thermal stability. Based on the characteristics, the material can be used as a solid adsorbent to extract precious metal (especially gold) ions from a solution. 3+ The material has high adsorption capacity to Au 3+ The adsorption capacity is up to 2320.6 mg·g -1 . And the adsorption capacity is significantly improved to 3063.6 mg·g -1 under light irradiation.

[0039] (4) The application provides an application of the porous polypyrrolizine material, which can be applied to the recovery of precious metals (especially gold) in electronic waste. The material can maintain high adsorption capacity during use, and can still be recycled after gold desorption, so that the material is an excellent gold adsorbent and has high application potential in the field of Au 3+ adsorption. BRIEF DESCRIPTION OF DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort.

[0041] Figure 1 A preparation method flowchart of the porous polypyrrolizine material is shown;

[0042] Figure 2 A preparation method flowchart of the porous polypyrrolizine material is shown; 1H-NMR (CDC13, 400 MHz, 298 K) spectrum;

[0043] Figure 3 APT of the polypyrrolizane norbornene monomer II-a provided by the embodiment 1 of the present application is shown. 13 C-NMR (CDC13, 100 MHz, 298 K) spectrum;

[0044] Figure 4 APT of the polypyrrolizane norbornene monomer II-b provided by the embodiment 2 of the present application is shown. 1 H-NMR (CDC13, 400 MHz, 298 K) spectrum;

[0045] Figure 5 APT of the polypyrrolizane norbornene monomer II-b provided by the embodiment 2 of the present application is shown. 13 C-NMR (CDC13, 100 MHz, 298 K) spectrum;

[0046] Figure 6 APT of the polypyrrolizane norbornene monomer II-c provided by the embodiment 3 of the present application is shown. 1 H-NMR (CDC13, 400 MHz, 298 K) spectrum;

[0047] Figure 7 APT of the polypyrrolizane norbornene monomer II-c provided by the embodiment 3 of the present application is shown. 13 C-NMR (CDC13, 100 MHz, 298 K) spectrum;

[0048] Figure 8 APT of the polypyrrolizane norbornene monomer II-d provided by the embodiment 4 of the present application is shown. 1 H-NMR (CDC13, 400 MHz, 298 K) spectrum;

[0049] Figure 9 APT of the polypyrrolizane norbornene monomer II-d provided by the embodiment 4 of the present application is shown. 13 C-NMR (CDC13, 100 MHz, 298 K) spectrum;

[0050] Figure 10 Infrared spectrum of the porous polypyrrolizane material I-a~I-d provided by the embodiments 1-4 of the present application is shown.

[0051] Figure 11 Solid nuclear magnetic spectrum of the porous polypyrrolizane material I-a~I-d provided by the embodiments 1-4 of the present application is shown.

[0052] Figure 12The nitrogen adsorption-desorption curves and pore size distribution diagrams of the porous polyparalkane materials I-a~I-d provided by the embodiments 1-4 of the present application at 77K are shown;

[0053] Figure 13 The result diagrams (ICP-MS) of the selective adsorption of the noble metal ions by the porous polyparalkane material I-b provided by the embodiments 1-4 of the present application are shown;

[0054] Figure 14 The adsorption result diagrams of the gold ions by the porous polyparalkane material I-b provided by the embodiments 1-4 of the present application at different pH are shown;

[0055] Figure 15 The adsorption efficiency of the noble metals by the porous polyparalkane material I-b provided by the embodiment 2 of the present application is shown;

[0056] Figure 16 The selective effect of the metal ions by the porous polyparalkane material I-b provided by the embodiment 2 of the present application when used in cycles is shown. DETAILED DESCRIPTION

[0057] The following examples are provided to better further understand the present application, and are not limited to the best mode, and do not limit the content and protection scope of the present application, and any person under the inspiration of the present application or the combination of the present application with other prior art features, any product same or similar to the present application falls within the protection scope of the present application.

[0058] The specific experimental steps or conditions are not mentioned in the examples, and can be operated according to the conventional experimental steps described in the prior art in the field. The reagents and other instruments used are not mentioned by the manufacturer, and are conventional reagent products that can be obtained by purchase.

[0059] In the prior art, nanocarbon materials, porous materials, metal organic framework materials and biomass-based materials have been used in the field of recovery of noble metals. Among them, the porous polymer materials connected by covalent bonds have the characteristics of strong function adjustability and high porosity, so that they have the advantages of high adsorption capacity, high selectivity, easy regeneration and the like in the adsorption and enrichment of noble metals, and have attracted much attention in recent years. However, the currently available porous polymer materials with high adsorption capacity, high selectivity and easy regeneration are still few.

[0060] In view of the problems of limited introduction of functional groups in synthesis of porous high polymer selective adsorption material, and low synthesis method and low synthesis efficiency and high synthesis cost, the present application designs and synthesizes a porous material containing a functional group with high adsorption of noble metals, which uses a multi-functionality aromatic amine and a norbornene anhydride as a raw material for synthesis, performs imidization combination and carbonylation reaction to form a polypyrrolidine norbornene monomer, further performs ring-opening metathesis polymerization on the polypyrrolidine norbornene monomer, and connects the monomers with 1,3-divinylcyclopentane to form an infinite network structure containing a polypyrrolidine structural unit (a porous polypyrrolidine material with a micropore-mesopore multi-level pore structure mainly in micropores). The polypyrrolidine structure containing a large number of N atom functional sites as a functional group can selectively adsorb gold, palladium, ruthenium, and silver with positive charges, and can realize high selective and high capacity adsorption and recovery of noble metals (especially gold) from electronic waste and industrial waste. Moreover, the material has good thermal stability, the adsorption capacity is significantly increased under light, the material is simple to desorb and can be recycled multiple times. The specific implementation content is as follows:

[0061] In a first aspect, the present application provides a porous polypyrrolidine material having a repeating structural unit as shown in the following formula I:

[0062]

[0063] The structural building block of the porous polypyrrolidine material is a multi-functionality group containing a phenyl group.

[0064] The porous polypyrrolidine material has a polypyrrolidine structural unit and a 1,3-divinylcyclopentane connecting structure.

[0065] The porous polypyrrolidine material has a micropore-mesopore multi-level pore structure mainly in micropores.

[0066] In specific implementation, the polypyrrolidine structural unit and the 1,3-divinylcyclopentane connecting structure are formed by ring-opening of a norbornene pyrrolidine. The polypyrrolidine structural unit as a functional building block provides a large number of N atom functional sites, which can interact with metal ions with positive charges to achieve high adsorption selectivity.

[0067] From the outside, the material has a micropore-mesopore multi-level pore structure mainly in micropores. The pore size distribution is 0.5-100 nm, most of the pore size distribution is 0.6-2.8 nm, and the total pore volume is 0.5-50 cm 3 / g. Moreover, the material has good thermal stability and a high specific surface area, and the specific surface area is 300-10000 m 2 / g.

[0068] The multifunctional group containing phenyl can be specifically: benzene ring, triphenylbenzene, triphenylamine, hexahydrotriphenyltricyano, 1,4,7-triphenyl-1,4,7-triazacyclononane, bis-spirofluorene, tetraphenylmethane, tetraphenyl ethylene, porphyrin, (R)-2,2',3,3'-tetrahydro-1,1'-spirobis[indene], or 1,8-dihydroazulene.

[0069] In a second aspect, the present application provides a preparation method of the porous polyparalkylamine material of the first aspect, Figure 1 A flow chart of the preparation method of the porous polyparalkylamine material provided by the embodiment of the present application is shown in Figure 2. Figure 1 As shown in the figure, the preparation method comprises the following steps:

[0070] S1, dissolving norbornene anhydride in a third organic solvent, adding an appropriate amount of alkaline reagent, mixing uniformly, then adding a multifunctional aromatic amine, heating for imidization reaction, after the reaction is completed, the product is filtered, washed and dried to obtain a multifunctional norbornene imide;

[0071] In specific implementation, the functionality of the multifunctional aromatic amine is greater than or equal to 2. As an example, the following reaction formula (a) and reaction formula (b) show the reaction process of obtaining the porous polyparalkylamine material by taking norbornene anhydride and a three / four-functionality aromatic amine as the reaction raw materials in the embodiment of the present application:

[0072]

[0073]

[0074] The reaction formula (a) shows the reaction process of obtaining the porous polyparalkylamine material by taking norbornene anhydride and a three-functionality aromatic amine as the reaction raw materials in the embodiment of the present application, and the reaction formula (b) shows the reaction process of obtaining the porous polyparalkylamine material by taking norbornene anhydride and a four-functionality aromatic amine as the reaction raw materials in the embodiment of the present application. The specific reactions and operation processes involved include: adding a third organic solvent to dissolve the norbornene anhydride shown in the structural formula V, slowly adding an alkaline reagent after dissolution, then adding the aromatic amine shown in the structural formula IV, and heating for imidization reaction; after the raw materials are completely converted, filtering, washing and drying are performed to obtain the multifunctional norbornene imide shown in the structural formula III, the reaction time is 2-12h, and the reaction temperature is 25-140℃.

[0075] In the present embodiment, the tri-functional aromatic amine can be selected from 1,3,5-triaminobenzene, 1,3,5-tris(4-aminophenyl)benzene, tris(4-amino)aniline, 4,4',4”-(1,3,5-triazinane-1,3,5-triyl)triphenylamine, 4,4',4”-(1,4,7-triazinane-1,4,7-triyl)triphenylamine, as shown in structural formula IV-1 to IV-5; the tetra-functional aromatic amine can be selected from tetraamino-9,9'-bifluorene, tetra(4-aminophenyl)methane, tetra-(4-aminophenyl)ethylene, 1,2,4,5-benzenetetramine, tetra-p-phenylamino porphyrin, (R)-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-5,5',6,6'-tetramine, or 1,8-dihydrophenalene-1,3,6,8-tetramine, as shown in structural formula IV-6 to IV-12.

[0076] In the present embodiment, the third organic solvent is selected from toluene, xylene, chlorobenzene, N,N-dimethylformamide, or N-methylpyrrolidone, so that the concentration of the norbornene anhydride substrate is 0.01-1M; as the dehydrating agent of the reaction system, the basic reagent is selected from triethylamine, diisopropylethylamine, or pyridine, and the equivalent of the basic reagent is 2-10.

[0077] S2, the reaction liquid composed of the second organic solvent and the reducing agent is placed in an ice water bath; the multi-functional norbornene imide is dissolved in the second organic solvent and added dropwise into the reaction liquid, the multi-functional norbornene imide undergoes decarbonylation reaction, after the reaction is completed, a quenching agent and an acid-base regulator are added to the reaction system, and the product is filtered, washed, and dried to obtain a multi-pyrrolidine norbornene monomer;

[0078] Continuing to refer to the above reaction formula (a) and reaction formula (b); in the specific implementation of S2, the second organic solvent is added to the reaction device, and then placed in an ice water bath, the reducing agent is slowly added, and the mixture is fully stirred and mixed; the tri-functional / tetra-functional norbornene imide shown in structural formula III is dissolved in the first organic solvent, and after dissolution, it is added dropwise into the reaction liquid in the ice water bath through a dropping funnel, and the decarbonylation reaction is continuously stirred; after the raw material is completely converted, a quenching agent is added, and then an acid-base regulator is added to remove the unreacted raw material, and the product is purified. The product is filtered, washed, and dried to obtain a multi-pyrrolidine norbornene monomer shown in structural formula II. The reaction time of the decarbonylation reaction is 12-24h, and the reaction temperature is 0-60℃.

[0079] In the present embodiment, the second organic solvent is selected from tetrahydrofuran, acetone, ethyl acetate or N,N-dimethylformamide, so that the concentration of the multi-function norbornene imide substrate is 0.01-1M; the reducing agent is selected from lithium aluminum hydride, sodium hydride, sodium borohydride, hydrazine hydrate, sulfonyl hydrazine, silicon hydride, zinc or hydrogen, and the equivalent is 3-10; the quenching agent is selected from water, ethanol or acetic acid with active hydrogen, so as to consume the excess reducing agent in the reaction system, and the equivalent is 2-10; and the acid-base regulator is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium methoxide or triethylamine.

[0080] S3, dissolving the polypyrrolidine norbornene monomer in a first organic solvent and adding a catalyst to cause ring-opening metathesis polymerization of the polypyrrolidine norbornene monomer; after the reaction is completed, a quenching agent is added to the reaction system for quenching; and the product is subjected to soaking, washing, filtering and drying treatment to obtain the porous polypyrrolidine material.

[0081] Continuing to refer to the above reaction formula (a) and reaction formula (b); in the specific implementation of the S3 step, first, the trifunctional / tetrafunctional pyrrolidine norbornene monomer shown in the structural formula II is dissolved in a first organic solvent, then a catalyst is added after dissolution, and the reaction device is heated after being fully mixed by continuous stirring; the trifunctional / tetrafunctional pyrrolidine norbornene monomer shown in the structural formula II undergoes ring-opening metathesis polymerization (ROMP) under the action of the catalyst; after the conversion of the raw material is completed, a quenching agent is added to the reaction system for quenching; and after soaking, washing, filtering and drying treatment, the porous polypyrrolidine material shown in the structural formula I can be obtained; the reaction time of the ring-opening metathesis polymerization is 0.5-12h, and the reaction temperature is 0-60℃.

[0082] In the present embodiment, the first organic solvent is selected from dichloromethane, dichloroethane, acetone, 1,4-dioxane, tetrahydrofuran, ethyl acetate or N,N-dimethylformamide, so that the concentration of the polypyrrolidine norbornene monomer is 0.01-1M; the catalyst is selected from Grubbs catalyst, Hoveyda-Grubbs catalyst, Schrock catalyst, metal salt, metal oxide or metal nitrogen heterocycle carbine, and the equivalent is 0.001-0.1; and the pyrrolidine norbornene monomer quenching agent shown in the structural formula II is selected from ethylene derivative or propylene derivative during the ring-opening metathesis polymerization, and the equivalent is 2-10.

[0083] The preparation method of the porous polypyrrolidine material provided by the embodiment of the present application can prepare a large amount of organic porous polymeric material with polypyrrolidine and poly-norbornene structure under mild conditions through the reduction of a multi-functional imide monomer to prepare a norbornene pyrrolidine monomer and then performing a high-efficiency ring-opening metathesis polymerization reaction under the action of a catalyst. The preparation method provided by the present application has mild reaction conditions and can realize batch production. The raw materials used are all commercially available low-cost and conventional raw materials, which can effectively reduce the cost of preparing the adsorption material and thus reduce the cost of recovering precious metals from electronic waste and industrial waste.

[0084] In a third aspect, the present application provides an application of the porous polypyrrolidine material of the second aspect, the porous polypyrrolidine material is used for adsorbing and reducing noble metal ions; wherein the noble metal is one or more of gold, palladium, ruthenium and silver.

[0085] In specific implementation, the porous polypyrrolidine material provided by the embodiment of the present application can be applied to the recovery of noble metals (especially gold) in electronic waste. Moreover, the material can maintain high adsorption capacity during use and can continue to be recycled after desorption of gold, and is an excellent gold adsorbent, which has extremely high application potential in the adsorption field. 3+ In specific implementation, the porous polypyrrolidine material provided by the embodiment of the present application can be applied to the recovery of noble metals (especially gold) in electronic waste. Moreover, the material can maintain high adsorption capacity during use and can continue to be recycled after desorption of gold, and is an excellent gold adsorbent, which has extremely high application potential in the adsorption field.

[0086] As a preferred, the porous polypyrrolidine material provided by the embodiment of the present application adsorbs and reduces noble metals under the condition of pH≤7, and the removal efficiency of the porous polypyrrolidine material to Au 3+ is higher than 99.9% within 30 minutes under the condition of pH 2-7, which shows a rapid and efficient adsorption effect. This indicates that the material has a wide pH tolerance range and can work under strong acidic conditions or can not depend on an acidic environment.

[0087] Further, the adsorption and reduction capacity of the porous polypyrrolidine material to the noble metal is enhanced under light conditions.

[0088] In specific implementation, the adsorption capacity of the porous polypyrrolidine material to the noble metal is significantly increased under light conditions. Experimental results show that the material of this type shows a high adsorption capacity to Au 3+ under the condition of 298K, and the adsorption capacity to Au 3+ is as high as 2320.6mg·g -1 . Moreover, the adsorption capacity is significantly increased to 3063.6mg·g -1 under light irradiation.

[0089] In order for those skilled in the art to more clearly understand the present application, the porous polypyrrolidine material, the preparation method and the application thereof are described in detail through the following examples.

[0090] Example 1 Preparation of Exo-phenyl-1,3,5-tricyclohexene pyrrolidine I-a

[0091] Step 1: Preparation of Exo-configured norbornene imide monomer III-a

[0092]

[0093] Into a 250 mL single necked flask, 1,3,5-triaminobenzene hydrochloride (1.23 g, 10.0 mmol, 1.0 equiv.) and Exo-norbornene anhydride (5.4 g, 33.0 mmol, 1.1 equiv.) were weighed, toluene (100 mL) and triethylamine (3 mL) were added respectively, and heated to 135 °C. The reaction solution changed from turbid to clear, and precipitate gradually separated out as the reaction proceeded. After 5 h, the reaction solution was cooled to room temperature, and filtered under reduced pressure. The filter cake was washed with water and ethanol for 2-3 times, and dried to give off-white solid (5.41 g, 96% yield).

[0094] 1 H NMR (400 MHz, CDC13) δ (ppm): 7.48 (s, 3H), 6.35 (s, 6H), 3.40 (s, 6H), 2.85 (s, 6H), 1.62 (d, J = 10.0 Hz, 3H), 1.47 (d, J = 10.0 Hz, 3H); 13 C NMR (100 MHz, CDC13) δ (ppm): 176.14, 138.02, 132.53, 122.73, 47.83, 45.85, 43.29. HRMS (ESI): m / z calcd for C 33 H 28 N3O6 + [M+H] + 562.1973, found 562.1967. FIT-IR (cm -1 ): 2971, 2938, 2871, 1786, 1707, 1612, 1466, 1359, 1278, 1178, 1017, 890, 783, 723, 669.

[0095] Step 2: Preparation of Exo-configured polypyrrolidine norbornene monomer II-a

[0096]

[0097] THF (30 mL) was measured and placed in a 250 mL flask, the apparatus was cooled in an ice water bath, lithium aluminum hydride (2.0 g) was weighed and slowly added to the flask. Exo-norbornene imide monomer III-a (3.0 mmol) dissolved in dichloromethane (60 mL) was added dropwise through a dropping funnel, and stirred at room temperature overnight. After the raw material was completely converted, the reaction system was cooled using an ice water bath, and pure water (2.5 mL) and 10 wt% NaOH aqueous solution (2.5 mL) were slowly added dropwise. Filtration was performed under reduced pressure, the filter cake was washed with dichloromethane 3 times, the filtrate was collected and dried with anhydrous magnesium sulfate. After filtration again, the obtained filtrate was concentrated to obtain the target crude product. It was washed with methanol, ethanol and water 3 times respectively, and white solid was obtained after drying under heating (1.3 g, 91% yield). Figure 2 APT spectra of the poly pyrrolizane norbornene monomer II-a provided by Example 1 of the present application are shown in 1 H-NMR(CDCl3, 400MHz, 298K) spectra; Figure 3 APT spectra of the poly pyrrolizane norbornene monomer II-a provided by Example 1 of the present application are shown in 13 C-NMR(CDCl3, 100MHz, 298K) spectra.

[0098] 1 H NMR (400 MHz, CDCl3) δ (ppm): 6.17 (s, 6H), 5.28 (s, 3H), 3.53-3.33 (m, 6H), 3.08 (dd, J = 9.6, 2.6 Hz, 6H), 2.73 (t, J = 1.8 Hz, 6H), 2.41-2.28 (m, 6H), 1.68 (d, J = 8.8 Hz, 3H), 1.39-1.28 (m, 3H); 13 C NMR (101 MHz, CDCl3) δ (ppm): 150.0, 137.7, 87.5, 52.9, 47.6, 44.3, 42.5

[0099] Step 3: Preparation of Exo-configured poly norborn pyrrolizane material I-a

[0100]

[0101] Trifunctional norbornene pyrrolidine monomer II-a (2.0 mmol, 1.0 equiv.) and Grubbs-II (85 mg, 5 mol%) were weighed into a 250 mL single neck flask, dichloromethane (120 mL) was added, and the addition was completed. The reflux condenser was installed, and the reaction solution was transferred to the stirrer for stirring and mixing. The reaction system was allowed to stand, and heating was performed to gradually increase the temperature from room temperature to 45 °C. After about 5 minutes, a gel was formed. To ensure complete conversion of the monomer, the gel was stirred for 30 minutes, and the reaction system was cooled to room temperature. The insoluble gel product was soaked, washed and filtered with an appropriate amount (50-100 mL / time) of dichloromethane, dimethyl sulfoxide, methanol, ethanol and water. The above purification operation was repeated 2-3 times, and the sample was freeze-dried for 24 hours to obtain a light green powder I-a (0.74 g, 98% yield).

[0102] 13 FT-IR (cm-1): 2938, 2864, 2821, 1592, 1472, 1359, 1284, 1185, 1051, 970, 790, 676. Elemental Analysis: C (78.54%), N (7.84%), H (8.57%). -1

[0103] Example 2 Preparation of Exo-configured porous polypyrrolidine material I-b

[0104] Step 1: Preparation of Exo-configured norbornene imide monomer III-b

[0105]

[0106] Tris(4-aminophenyl)benzene (3.51 g, 10.0 mmol, 1.0 equiv.) and Exo-norbornene anhydride (5.4 g, 33 mmol, 1.1 equiv.) were weighed into a 250 mL single neck flask, and toluene (100 mL) and triethylamine (3 mL) were added, respectively. The reaction liquid was heated to 130 °C. At the beginning, the reaction liquid became clear from turbidity, and precipitates gradually separated out as the reaction proceeded. After 6 h of reaction, the temperature was cooled to room temperature, and vacuum filtration was performed. The filter cake was washed with water and ethanol 2-3 times, and then dried to obtain a light white solid (7.1 g, 91% yield).

[0107] 1 ​H NMR (400 MHz, CDC13) δ (ppm): 7.77 (d, J = 8.4 Hz, 9H), 7.43 (d, J = 8.4 Hz, 6H), 6.38 (t, J = 1.9 Hz, 6H), 3.46 (t, J = 1.9 Hz, 6H), 2.92 (d, J = 1.3 Hz, 6H), 1.72-1.63 (m, 3H), 1.55 (d, J = 9.9 Hz, 3H); 13 C NMR (100 MHz, CDC13) δ (ppm): 177.07, 141.65, 141.20, 138.05, 131.38, 128.13, 126.84, 125.65, 47.97, 45.90, 43.06. HRMS (ESI): m / z calcd for C 51 H 40 N3O6 + [M+H] + 790.2912, found 790.2917. FIT-IR (cm -1 ): 3071, 2984, 2871, 1774, 1699, 1600, 1519, 1452, 1371, 1291, 1171, 1017, 950, 877, 830, 790, 716, 622.

[0108] Step 2: Preparation of Exo-configured polypyrrolidine norbornene monomer II-b

[0109]

[0110] THF (30 mL) was measured and placed in a 250 mL flask, the device was cooled in an ice water bath, lithium aluminum hydride (2.0 g) was weighed and slowly added to the flask. Exo-norbornene imide monomer (3.0 mmol) dissolved in dichloromethane (60 mL) was added dropwise into the flask through a dropping funnel, stirred at room temperature overnight. When the raw material was completely converted, the reaction system was cooled in an ice water bath, pure water (2.5 mL) and 10 wt% NaOH aqueous solution (2.5 mL) were slowly added dropwise. Filtration under reduced pressure, the filter cake was washed with dichloromethane for 3 times, the filtrate was collected and dried with anhydrous magnesium sulfate. After filtration again, the obtained filtrate was concentrated to obtain the target crude product. It was washed with methanol, ethanol and water for 3 times respectively, and white solid was obtained after drying under heating (1.72 g, 89% yield).

[0111] Figure 4 The H-NMR (CDC13, 400 MHz, 298 K) spectrum of the polypyrrolidine norbornene monomer II-b provided by Example 2 of the present application is shown. 1 H-NMR (CDC13, 400 MHz, 298 K) spectrum; Figure 5APT of the polypyrrolizane norbornene monomer II-b provided by the embodiment 2 of the present application is shown 13 C-NMR(CDCl3, 100 MHz, 298 K) spectrum.

[0112] 1 H NMR (400 MHz, CDC13) δ 6.17 (s, 6H), 5.28 (s, 3H), 3.53-3.33 (m, 6H), 3.08 (dd, J = 9.6, 2.6 Hz, 6H), 2.73 (t, J = 1.8 Hz, 6H), 2.41-2.28 (m, 6H), 1.68 (d, J = 8.8 Hz, 3H), 1.39-1.28 (m, 3H); 13 C NMR (101 MHz, CDC13) δ 150.0, 137.7, 87.5, 52.9, 47.6, 44.3, 42.5.

[0113] Step 3: Preparation of Exo-form polynorbornenepyrrolizane material I-a

[0114]

[0115] The trifunctional norbornene pyrrolizane monomer II-a (2.0 mmol, 1.0 equiv.) and Grubbs-II (85 mg, 5 mol%) were weighed into a 250 mL single neck flask, dichloromethane (120 mL) was added, and after the addition was complete, the reaction solution was transferred to a stirrer for stirring and mixing. The reaction system was allowed to stand, and heating was performed to gradually increase the temperature from room temperature to 45 °C. After about 5 minutes, a gel was formed; to ensure complete conversion of the monomer, the gel was stirred for 30 minutes, and then the reaction system was cooled to room temperature. The insoluble gel product was soaked, washed and filtered with an appropriate amount (50-100 mL / time) of dichloromethane, dimethyl sulfoxide, methanol, ethanol and water, and the above purification operation was repeated 2-3 times. After the sample was freeze-dried for 24 hours, a blue powder I-b (1.26 g, 99% yield) was obtained.

[0116] 13 C CP / MS NMR, δ (ppm): 143.8, 134.5, 131.4, 128.1, 109.9, 52.8, 49.3, 45.8, 42.3. FT-IR (cm -1 ): 3011, 2938, 2851, 2810, 1620, 1566, 1479, 1326, 1185, 1124, 964, 810, 736. Elemental Analysis: C (83.08%), N (7.55%), H (6.52%).

[0117] Example 3 Preparation of Exo-configured porous polypyrrolidine material I-c

[0118] Step 1: Preparation of Exo-configured norbornene imide monomer III-c

[0119]

[0120] Exo-norbornene anhydride (7.4 g, 44 mmol, 1.1 equiv.) and 2,2',7,7'- tetraamino-9,9'-spirobifluorene (3.72 g, 10.0 mmol, 1.0 equiv.) were weighed into a 250 mL single neck flask, toluene (60 mL) and triethylamine (2 mL) were added respectively, and heated to 135 °C. The reaction solution became clear at the beginning, and precipitates gradually appeared as the reaction proceeded. After 6 h of reaction, the reaction solution was cooled to room temperature, and filtered under reduced pressure. The filter cake was washed with water and ethanol for 2-3 times, and dried to obtain a yellow solid (9.02 g, 94% yield).

[0121] 1 H NMR (400 MHz, CDC13) δ (ppm): 7.90 (d, J = 8.1 Hz, 4H), 7.33 (dd, J = 8.2, 1.9 Hz, 4H), 6.73 (d, J = 1.9 Hz, 4H), 6.29 (t, J = 1.9 Hz, 8H), 3.34 (s, 8H), 2.75 (s, 8H), 1.55 (d, J = 9.8 Hz, 4H), 1.42 (d, J = 9.9 Hz, 4H); 13 C NMR (100 MHz, CDC13) δ (ppm): 176.57, 148.36, 140.84, 137.97, 131.89, 126.65, 122.63, 120.77, 65.94, 47.79, 45.62, 43.24. HRMS (ESI): m / z calcd for C 61 H 48 N5O8 + [M+NH4] + 978.3497, found 978.3498. FIT-IR (cm -1 ): 2911, 2877, 1774, 1707, 1606, 1472, 1371, 1284, 1171, 1147, 1017, 870, 716, 616.

[0122] Step 2: Preparation of Exo-configured polypyrrolidine norbornene monomer II-c

[0123]

[0124] THF (30 mL) was measured and placed in a 250 mL flask, cooled in an ice water bath, lithium aluminum hydride (2.0 g) was weighed and added slowly into the flask. Exo-norbornene imide monomer III-c (3.0 mmol) dissolved in dichloromethane (60 mL) was added dropwise into the reaction system through a dropping funnel, stirred at room temperature overnight. After the complete conversion of the raw material, the reaction system was cooled in an ice water bath, pure water (2.5 mL) and 10 wt% NaOH aqueous solution (2.5 mL) were added slowly dropwise. Filtration under reduced pressure, the filter cake was washed with dichloromethane for 3 times, the filtrate was collected and dried with anhydrous magnesium sulfate. After filtration again, the obtained filtrate was concentrated to obtain the target crude product. It was washed with methanol, ethanol and water for 3 times respectively, and dried after heating to obtain an orange solid (2.34 g, 92% yield).

[0125] Figure 6 APT spectra of the polypyrrolidine norbornene monomer II-c provided in Example 3 of the present application are shown in FIG. 3. 1 H-NMR (CDC13, 400 MHz, 298 K) spectra; Figure 7 APT spectra of the polypyrrolidine norbornene monomer II-c provided in Example 3 of the present application are shown in FIG. 3. 13 C-NMR (CDC13, 100 MHz, 298 K) spectra.

[0126] 1 H NMR (400 MHz, CDC13) δ (ppm): 7.56 (d, J = 8.3 Hz, 4H), 6.56 (dd, J = 8.3, 2.3 Hz, 4H), 6.12 (t, J = 1.8 Hz, 8H), 5.99 (d, J = 2.2 Hz, 4H), 3.43-3.15 (m, 8H), 2.92 (dd, J = 9.7, 2.8 Hz, 8H), 2.66 (d, J = 1.8 Hz, 8H), 2.34-2.19 (m, 8H), 1.58 (d, J = 8.8 Hz, 4H), 1.35-1.25 (m, 4H); 13 C NMR (101 MHz, CDC13) δ (ppm): 151.3, 147.3, 137.6, 131.5, 118.6, 111.5, 108.8, 66.6, 53.2, 47.4, 44.4, 42.6.

[0127] Step 3: Preparation of Exo-configured poly-norbornenopyrrolidine material I-c

[0128]

[0129] A three-functional norbornene pyrrolidine monomer II-c (2.0 mmol, 1.0 equiv.) and Grubbs-II (85 mg, 5 mol%) were weighed into a 250 mL single neck flask, dichloromethane (120 mL) was added, and the addition was followed by the installation of a reflux condenser. The reaction solution was stirred and mixed on a stirrer. The reaction system was allowed to stand and was heated to gradually increase the temperature from room temperature to 45 °C. A gel was formed after about 5 minutes; to ensure complete conversion of the monomer, the gel was stirred for 30 minutes, and the reaction system was cooled to room temperature. The insoluble gel product was soaked, washed, and filtered with an appropriate amount (50-100 mL / time) of dichloromethane, dimethyl sulfoxide, methanol, ethanol, and water. The above purification operation was repeated 2-3 times, and the sample was freeze-dried for 24 hours to obtain an orange powder I-a (1.26 g, 99% yield).

[0130] 13 C CP / MS NMR, δ (ppm): 149.6, 146.3, 134.5, 134.4, 130.5, 116.8, 109.7, 106.3, 64.8, 48.7, 46.4, 42.6. FT-IR (cm -1 ): 3058, 2938, 2851, 2804, 1673, 1572, 1466, 1446, 1359, 1291, 1218, 1131, 1023, 970, 803, 696.

[0131] Elemental Analysis: C (83.37%), N (7.39%), H (6.53%).

[0132] Example 4 Preparation of Exo-configured porous polypyrrolidine material I-d

[0133] Step 1: Preparation of Exo-configured norbornene imide monomer III-d

[0134]

[0135] A four (4-aminophenyl) methane (3.8 g, 10.0 mmol, 1.0 equiv.) and Exo-norbornene anhydride (7.4 g, 44 mmol, 1.1 equiv.) were weighed into a 250 mL single neck flask, and toluene (100 mL) and triethylamine (3 mL) were added, respectively, and heated to 135 °C. The reaction solution was initially turbid and then became clear, and precipitates gradually separated out as the reaction proceeded. After 6 h of reaction, it was cooled to room temperature, and vacuum filtration was performed. The filter cake was washed with water and ethanol 2-3 times, and then dried to obtain an off-white solid (8.9 g, 93% yield).

[0136] 1 H NMR (400 MHz, CDC13) δ (ppm): 7.33 (d, J = 7.5 Hz, 8H), 7.24 (d, J = 1.5 Hz, 8H), 6.36 (t, J = 1.8 Hz, 8H), 3.41 (q, J = 1.7 Hz, 8H), 2.86 (s, 8H), 1.62 (d, J = 9.9 Hz, 4H), 1.47 (d, J = 9.9 Hz, 4H); 13 C NMR (100 MHz, CDC13) δ (ppm): 176.92, 145.74, 138.02, 131.55, 130.14, 125.44, 63.39, 47.83, 45.91, 43.01. 1 H NMR (400 MHz, DMSO-d6) δ (ppm): 7.36 (d, J = 8.7 Hz, 8H), 7.24 (d, J = 8.8 Hz, 8H), 6.32 (t, J = 1.8 Hz, 8H), 3.19-3.13 (m, 8H), 2.81 (s, 1H), 1.39 (q, J = 9.7 Hz, 8H); 13 C NMR (100 MHz, DMSO-d6) δ (ppm): 177.17, 146.22, 138.26, 130.94, 130.51, 126.91, 64.57, 47.91, 45.47, 43.11. HRMS (ESI): m / z calcd for C 61 H 52 N5O8 + [M+NH4] + 982.3810, found 982.3795. FIT-IR (cm -1 ): 3078, 2971, 2877, 1774, 1713, 1599, 1499, 1452, 1365, 1318, 1291, 1024, 937, 877, 837, 750, 723, 629.

[0137] Step 2: Preparation of Exo-configured polypyrrolidine norbornene monomer II-d

[0138]

[0139] THF (30 mL) was measured and placed in a 250 mL flask, cooled in an ice water bath, lithium aluminum hydride (2.0 g) was weighed and added slowly into the flask. Exo-norbornene imide monomer III-d (3.0 mmol) dissolved in dichloromethane (60 mL) was added dropwise into the flask through a dropping funnel, stirred at room temperature overnight. After the starting material was completely converted, the reaction system was cooled in an ice water bath, pure water (2.5 mL) and 10 wt% NaOH aqueous solution (2.5 mL) were added slowly dropwise. Filtration under reduced pressure, the filter cake was washed with dichloromethane for 3 times, the filtrate was collected and dried with anhydrous magnesium sulfate. After filtration again, the obtained filtrate was concentrated to obtain the target crude product. It was washed with methanol, ethanol and water for 3 times respectively, and dried after heating to obtain a light blue solid (2.35 g, 93% yield).

[0140] Figure 8 APT spectra of the poly pyrrolizane norbornene monomer II-d provided by Example 4 of the present application are shown in FIG. 2. 1 H-NMR (CDC13, 400 MHz, 298 K) spectra; Figure 9 APT spectra of the poly pyrrolizane norbornene monomer II-d provided by Example 4 of the present application are shown in FIG. 2. 13 C-NMR (CDC13, 100 MHz, 298 K) spectra.

[0141] 1 H NMR (400 MHz, CDC13) δ (ppm): 7.06 (d, J = 8.1 Hz, 8H), 6.43 (d, J = 8.3 Hz, 8H), 6.16 (s, 8H), 3.39 (d, J = 8.2 Hz, 8H), 3.03 (d, J = 9.8 Hz, 8H), 2.72 (s, 8H), 2.37 (d, J = 6.5 Hz, 8H), 1.65 (d, J = 8.9 Hz, 4H), 1.34 (d, J = 8.9 Hz, 4H); 13 C NMR (101 MHz, CDC13) δ (ppm): 146.5, 137.7, 133.3, 130.0, 112.2, 60.2, 54.2, 52.9, 47.3, 44.5, 42.5.

[0142] Step 3: Preparation of Exo-configured poly norborn pyrrolizane material I-d

[0143]

[0144] A 250 mL single neck flask was charged with trifuunctional norbornene pyrrolidine monomer II-d (2.0 mmol, 1.0 equiv.) and Grubbs-II (85 mg, 5 mol%), then dichloromethane (120 mL) was added, after the addition was completed, the reflux condenser was installed, and the reaction solution was stirred and mixed on the stirrer. The reaction system was allowed to stand, and heating was performed to gradually increase the temperature from room temperature to 45℃. After about 5 minutes, a gel was formed; in order to ensure complete conversion of the monomer, the gel was stirred, and after 30 minutes, the reaction system was cooled to room temperature. The insoluble gel product was soaked, washed and filtered with appropriate amount (50-100 mL / time) of dichloromethane, dimethyl sulfoxide, methanol, ethanol and water, and the above purification operation was repeated 2-3 times. After the sample was freeze-dried for 24 hours, a light blue powder I-d (1.7 g, 98% yield) was obtained.

[0145] 13 FT-IR (cm-1): 2938, 2857, 2810, 1612, 1566, 1485, 1365, 1191, 1078, 970, 803, 743. Elemental Analysis: C (82.37%), N (7.39%), H (6.53%). -1

[0146] The preparation method of the porous polypyrrrolidine material for selectively adsorbing noble metal ions provided by the embodiment of the present application can prepare a large amount of organic porous polymer material with pyrrolidine and polynorbornene structure under mild conditions by reducing a multifunctional imide monomer to prepare a polypyrrrolidine norbornene monomer and then performing a high-efficiency ring-opening metathesis polymerization reaction under the action of a catalyst. The organic porous polymer material with pyrrolidine functionalized polynorbornene structure prepared by the present application can interact with noble metal ions at the functional sites of N atoms in the material structure, and can obtain adsorption beyond the theoretical adsorption limit under light, is an excellent photosensitizer, and shows great application potential in the adsorption application of Au 3+ .

[0147] Example 5: Infrared spectroscopic characterization of pyrrolidine functionalized polynorbornene porous material I

[0148] First, the prepared polymers I-a to I-d were characterized by infrared spectroscopy respectively to explore the connection mode of the polymers and the functional group structure in the material. Figure 10 ​The infrared spectra of the porous polypyrrolidine materials I-a~I-d provided by the embodiments 1-4 of the present application are shown. Compared with the infrared spectrum of the monomer, the infrared spectrum of the polymer shows that the absorption peak intensity in the range of 1600-1400 cm -1 and 900-600 cm -1 is obviously weakened, indicating that the stretching vibration of the chemical bond is limited after the polymerization of the monomer; in addition, a new group of medium-intensity absorption peaks appears near 978 cm -1 , which is attributed to the stretching vibration peak of the trans C=C double bond, i.e., the ring-opening metathesis polymerization between the monomer molecules successfully occurs.

[0149] Solid-state nuclear magnetic characterization of the pyrrolidine-functionalized polynorbornene porous material I of Example 6

[0150] The carbon atoms of I-a~I-d are characterized and attributed by using 13 C solid-state nuclear magnetic spectrum. Figure 11 The solid-state nuclear magnetic spectrum of the porous polypyrrolidine material I-a~I-d provided by the embodiments 1-4 of the present application is shown. As shown in Figure 11 , the chemical shift at 145 ppm is observed to be attributed to the signal of C on the benzene ring directly connected with the N atom of pyrrolidine, and the chemical shifts in the range of 109-146 ppm are attributed to the signals of the remaining C atoms in the benzene ring. The three chemical shifts near 42, 45 and 49 ppm are attributed to the C atoms on the norbornene ring. In addition, the chemical shifts at 59 ppm and 65 ppm in the C solid-state nuclear magnetic spectrum can clearly identify the quaternary carbon in the skeleton node (tetraphenylmethane and spirofluorene). 13

[0151] Porous structure test of the pyrrolidine-functionalized polynorbornene porous material I of Example 7

[0152] The porous structure of I-a~I-d is explored by nitrogen adsorption isotherm test (under the condition of 77 K). Figure 12 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the porous polypyrrolidine material I-a~I-d provided by the embodiments 1-4 of the present application under 77 K are shown, in which Figure 12 (a) is the nitrogen adsorption-desorption curve, Figure 12 (b) is the pore size distribution diagram, as shown in Figure 12 (a), the adsorption curve of I-a~I-d shows a large N2 adsorption amount in the low pressure region, and then the adsorption amount slowly increases with the increase of the pressure, indicating that the gas has multi-layer adsorption behavior in addition to the single-layer adsorption in I-a~I-d, which is consistent with the Type I and Type IV adsorption isotherm model. It is preliminarily judged that I-a~I-d has microporous and mesoporous structures.

[0153] ​The specific surface area and pore volume of I-a~I-d were calculated by Brunauer-Emmett-Teller (BET) equation, that is, the specific surface area of I-a~I-d was 654, 852, 889 and 805 m 2 / g, respectively, and the total pore volume was 1.051, 1.763, 0.924 and 1.552 cm 3 / g, respectively. Figure 12 As shown in (b), the pore size distribution of I-a and I-c was mainly 0.60, 1.45 and 2.80 nm calculated by non-local density functional theory (NLDFT); and the pore size distribution of I-b and I-d was similar to that of I-a and I-c, and additionally had pore sizes of 25.3 nm and 26.2 nm, indicating that the pore sizes of the four materials were microporous and mesoporous.

[0154] Example 10 Selective adsorption test of gold ions on pyrrolidine-functionalized polynorbornene porous material I

[0155] I-b with the highest specific surface area and the largest pore volume was used as the adsorption material to explore the potential application of recovering noble metals. Figure 13 The results of selective adsorption of the porous polypyrrolidine material I-b provided by the embodiments 1-4 to noble metal ions are shown in the result graph (ICP-MS), as shown in Figure 13 The I-b was used for selective adsorption test in an aqueous solution containing 29 kinds of metal ions compatible, and the I-b showed excellent adsorption efficiency (removal efficiency was greater than 99.8%) to Au 3+ , Pd 2+ and Pt 2+ , and showed moderate adsorption effect (removal efficiency was 46%) to Ag + , and had no good adsorption response to most metal ions. The results showed that the I-b had high adsorption selectivity to noble metal ions (Au 3+ , Pd 2+ and Pt 2+ ), and could be used as a candidate material for metal recovery.

[0156] Example 11 Selective gold adsorption of pyrrolidine-functionalized polynorbornene porous material I under different pH, temperature and light

[0157] I-b with the highest specific surface area and the largest pore volume was used as the adsorption material to explore the adsorption capacity of gold ions under different conditions. First, since the existing form of metal ions in the solution changes with the pH value, the pH value most favorable to the adsorption effect was first selected. Figure 14 The adsorption results of the porous polypyrrolidine material I-b provided by the embodiments 1-4 to gold ions under different pH values are shown in the result graph, as shown inFigure 14 As shown, under pH conditions of 2, 4, and 7, I-b affects Au 3+ It exhibits rapid and efficient adsorption (ICP-MS detection). Within 30 minutes, Au... 3+ The removal efficiency was higher than 99.9%, indicating that our material has a wide pH tolerance range, can operate under strong acidic conditions, and can also operate independently of acidic environments. Meanwhile, Au... 3+ The adsorption capacity reached 2160 mg·g -1 2320 mg·g -1 and 2180 mg·g -1 However, under alkaline conditions (pH 9), I-b affects Au. 3+ The adsorption effect is significantly reduced. Therefore, the optimal pH range for the adsorption of gold ions by I-b is pH ≤ 7.

[0158] Furthermore, through Au 3+ Adsorption control experiments revealed that factors such as temperature and light influence the levels of Au. 3+ The adsorption capacity is significantly affected by Au. 3+ Adsorption curves and the Langmuir isotherm adsorption model were used to obtain Au values ​​under different adsorption conditions. 3+ Adsorption capacity, at temperatures of 308 K and 293 K, I-b for Au 3+ The adsorption capacities were 2418.7 mg·g⁻¹. -1 and 2147.4 mg·g -1 The adsorption capacity increases with increasing temperature, indicating that the adsorption process absorbs heat. Furthermore, under LED (30W) lighting and in the dark, I-b adsorbs Au... 3+ The adsorption capacities were 3063.3 mg·g⁻¹. -1 and 1880.7 mg·g -1 The above experimental results show that: Au 3+ The adsorption process is regulated by factors such as light and heat. Among them, the adsorption of Au by the material under light conditions... 3+ The adsorption capacity increase was most significant for Au. Under 298K and light conditions, different concentrations of Au showed varying adsorption capacities. 3+ After the aqueous solution was adsorbed by I-b, its color changed significantly; at the same time, the filter residue obtained after simple filtration showed a solid with a metallic luster, which contrasted sharply with the light blue I-b; indicating that Au3+ had been successfully captured by I-b and "gold" was obtained directly.

[0159] Example 12: Application of pyrrolidine-functionalized polynorbornene porous material I in gold recovery from waste printed circuit boards (PCBs)

[0160] To verify the practicability of the material in recycling gold in PCBs, we used the reported method of N-bromosuccinimide / pyridine and 1M HNO3 / HCl aqueous solution to dissolve PCBs to obtain extract solutions containing 5.6 ppm and 8.5 ppm of Au, respectively 3+ The two PCB extract solutions obtained above were passed through the adsorption column filled with I-b at a flow rate of 0.2 mL / min, respectively Figure 15 The adsorption efficiency of the porous polypyrrolane material I-b provided by the embodiment 2 of the present application to noble metals is shown. The experimental results show that the adsorption efficiency of I-b to Au 3+ is as high as more than 95% after 84 hours of continuous use, and the adsorption efficiency is still higher than 82% after 156 hours of continuous use, and the removal rate of common metal ions is less than 10%. The I-b enriched with Au 3+ is washed and eluted by 0.1M thiourea in 1M hydrochloric acid aqueous solution, neutralized by sodium carbonate aqueous solution, and activated, and can still be used repeatedly. The yellow solution enriched with Au 3+ is obtained after elution by thiourea / hydrochloric acid solution, and the removal efficiency of Au 3+ is 98.2% measured by ICP-MS. This shows that the material has high adsorption capacity and high selectivity to Au 3+ , and the metal ions are easy to be eluted from the material, which shows practicability in recycling gold in PCBs.

[0161] The isothermal adsorption experiment of I-b after elution of metal ions and activation on PCB(NBS / Py) soaking solution is used to investigate the selection effect of the material on metal ions when used repeatedly. Figure 16 The selection effect of the porous polypyrrolane material I-b provided by the embodiment 2 of the present application on metal ions when used repeatedly is shown. As shown in the figure, Figure 16 the adsorption efficiency of the material to Au 3+ in the Au 3+ adsorption experiment of extracting PCB(NBS / Py) soaking solution is still as high as 99.3%, and the removal rate of common metal ions (such as Cu, Ni, Zn and Al, etc.) is less than 5%. In addition, the tests by infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) confirm that the functional groups and structure of the material remain stable, which shows that the material has good recycling potential in gold recycling applications.

[0162] The above describes in detail the porous polyparalkane material, the preparation method and the application thereof. The principles and the implementation manners of the present application are described by using specific examples. The above examples are only used to help understand the method and the core idea of the present application. Meanwhile, for the general skilled in the art, the specific implementation manners and the application range can be changed according to the idea of the present application. In conclusion, the content of the present application should not be understood as the limitation of the present application.

Claims

1. Use of a porous polypyrrolizine material, characterized in that The porous polypyrrolizane material is used for adsorbing and reducing noble metal ions; wherein the noble metal is one or more of gold, palladium, ruthenium and silver; The ability of the porous polypyrrolizane material to adsorb and reduce the noble metal under light conditions is enhanced; The porous polypyrrolizane material has a repeating structural unit as shown in formula I; The structural building block of the porous polypyrrolizane material is a multifunctional group containing a phenyl group; The porous polypyrrolizane material has a pyrrolizane functional structural unit and a 1,3-divinylcyclopentane connecting structure; The porous polypyrrolizane material has a micropore-based micropore-mesopore multi-level pore structure; The structural building block includes a benzene ring, a triphenylbenzene, a triphenylamine, a hexahydrotriphenyltricyano, a 1,4,7-triphenyl-1,4,7-triazacyclononane, a bis-spirofluorene, a tetraphenylmethane, a tetraphenylethylene, a porphyrin, (R)-2,2',3,3'-tetrahydro-1,1'-spirobis[indene], or 1,8-dihydrogen pyrene.

2. Use of a porous polypyrrolalkane material according to claim 1, characterized in that The porous polypyrrolizane material is connected by the 1,3-divinylcyclopentane connecting structure to form an infinite network structure.

3. Use of a porous polypyrrolalkane material according to claim 1, characterized in that The pore size of the porous polypyrrolizane material is 0.5-100 nm; The total pore volume of the porous polyparalkyls material is in the range of 0.5-50 cm 3 / g; The porous polyparalkyls material has a specific surface area of 100-10000 m 2 / g.

4. Use of a porous polypyrrolalkane material according to any one of claims 1 to 3, characterized in that The preparation method of the porous polypyrrolizane material includes the following steps: S1, dissolving norbornene anhydride in a third organic solvent, adding an appropriate amount of alkaline reagent, mixing uniformly, then adding a multifunctional aromatic amine, heating for imidization reaction, after the reaction is completed, the product is filtered, washed and dried to obtain a multifunctional norbornene imide; S2, placing a reaction liquid composed of a second organic solvent and a reducing agent in an ice water bath; dissolving the multifunctional norbornene imide in the second organic solvent and adding it dropwise into the reaction liquid, the multifunctional norbornene imide undergoes decarbonylation reaction, after the reaction is completed, a quenching agent and an acid-base regulator are added to the reaction system, the product is filtered, washed and dried to obtain a polypyrrolizane norbornene monomer; S3, dissolving the polypyrrolizane norbornene monomer in a first organic solvent and adding a catalyst to make the polypyrrolizane norbornene monomer undergo ring-opening metathesis polymerization reaction, after the reaction is completed, a quenching agent is added to the reaction system for quenching, the product is treated by soaking, washing, filtering and drying to obtain the porous polypyrrolizane material.

5. Use of a porous polypyrrolalkane material according to claim 4, characterized in that The functionality of the multifunctional aromatic amine in step S1 is greater than or equal to 2; the multifunctional aromatic amine includes 1,3,5-triaminobenzene, 1,3,5-tris(4-aminophenyl)benzene, tris(4-amino)aniline, 4,4',4''-(1,3,5-triazinane-1,3,5-triyl)triphenylamine, 4,4',4''-(1,4,7-triazinane-1,4,7-triyl)triphenylamine, tetraamino-9,9'-bifluorene, tetra(4-aminophenyl)methane, tetra-(4-aminophenyl)ethylene, 1,2,4,5-benzene tetramine, tetra-p-phenylamino porphyrin, (R)-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-5,5',6,6'-tetramine, or 1,8-dihydropyrane-1,3,6,8-tetramine.

6. Use of a porous polypyrrolalkane material according to claim 4, characterized in that The third organic solvent in step S1 is toluene, xylene, chlorobenzene, N,N-dimethylformamide, or N-methylpyrrolidone, and the concentration of the norbornene anhydride substrate in the third organic solvent is 0.01-1M; The basic reagent is triethylamine, diisopropylethylamine, or pyridine, and the equivalent of the basic reagent is 2-10; the reaction time of the imidization reaction is 2-12h, and the reaction temperature is 25-140℃.

7. Use of a porous polypyrrolalkane material according to claim 4, characterized in that The second organic solvent in step S2 is tetrahydrofuran, acetone, ethyl acetate, or N,N-dimethylformamide; the concentration of the multifunctional norbornene imide substrate in the second organic solvent is 0.01-1M; The reducing agent is lithium aluminum hydride, sodium hydride, sodium borohydride, hydrazine hydrate, sulfonyl hydrazine, silicon hydride, zinc, or hydrogen, and the equivalent of the reducing agent is 3-10; The quenching agent is water, ethanol, or acetic acid with active hydrogen, and the equivalent of the quenching agent is 2-10; the acid-base regulator is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium methoxide, or triethylamine; The reaction time of the decarbonylation reaction is 12-24h, and the reaction temperature is 0-60℃.

8. Use of a porous polypyrrolalkane material according to claim 4, characterized in that The first organic solvent in step S3 is dichloromethane, dichloroethane, acetone, 1,4-dioxane, tetrahydrofuran, ethyl acetate, or N,N-dimethylformamide, and the concentration of the polypyrrolidine norbornene monomer in the first organic solvent is 0.01-1M; The catalyst is Grubbs catalyst, Hoveyda-Grubbs catalyst, Schrock catalyst, metal salt, metal oxide, or metal nitrogen heterocycle, and the equivalent of the catalyst is 0.001-0.1; The quenching agent is an ethylene derivative or a propylene derivative, and the equivalent of the quenching agent is 2-10; the reaction time of the ring-opening metathesis polymerization reaction is 0.5-12h, and the reaction temperature is 0-60℃.

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