CN115624957B - Modified functional silica gel material and preparation method and application thereof - Google Patents

Modified functional silica gel material and preparation method and application thereof Download PDF

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CN115624957B
CN115624957B CN202211553724.XA CN202211553724A CN115624957B CN 115624957 B CN115624957 B CN 115624957B CN 202211553724 A CN202211553724 A CN 202211553724A CN 115624957 B CN115624957 B CN 115624957B
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silica gel
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gel material
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CN115624957A (en
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杨南超
方成跃
杨晓伟
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Suzhou Si Novation New Material Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
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Abstract

The invention discloses a modified functional silica gel material and a preparation method and application thereof; the modified functional silica gel material is obtained by reacting a multifunctional amino functional silica gel material with an aromatic heterocyclic compound or a derivative thereof; the modified functional silica gel material has good chelating capacity with metal ions, good selectivity to polar components, high loading rate, high adsorption capacity and good adsorption effect.

Description

Modified functional silica gel material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a modified functional silica gel material, and a preparation method and application thereof.
Background
The technological development of many different industries and market applications has gradually increased the demand for chemical purity, which is precisely the cornerstone of these technologies. For example, the pharmaceutical and biotechnological industries must control organic and inorganic impurities to lower levels as much as possible, while the metal residues (e.g., ca, zn, mg) common in electronic chemicals must be below 0.1ppm.
The increasing social and legislative pressures for environmental protection have led to a further increasing demand for cleaning processes and efforts to avoid or reduce the production of waste, especially the residual amounts of toxic metals and compounds in the environment.
Precious metals (including platinum, rhodium, palladium, ruthenium, iridium, and gold) are widely used in many different applications in different industries, and are a limited resource. In the smelting and purification processes of the mining industry, very low concentrations of high value metals (e.g., precious metals) often coexist with other metals, which in some cases are very high. To avoid the loss of high value metals in large quantities, a better technique is needed to achieve: a) Reducing the desired metal to very low residual concentrations; b) The high-efficiency action is carried out on the extremely low ppm metal concentration; c) Selectively acting only on high value metals in the presence of higher concentrations of other metals.
The aromatic heterocyclic ring and the derivative thereof are good electron donors, are one of common and important ligands of metal ion complexes, have good adsorption effect on metal ions, particularly divalent metal ions, and can be used for separating noble metals if the aromatic heterocyclic ring and the derivative thereof are loaded on an inorganic carrier. In addition, the nanometer composite material has good selectivity to polar components and strong retention capacity, is loaded on an inorganic carrier, and can be used as a chromatography medium for purification and separation of metals, metal complexes, organic compounds and biological compounds or used for solid phase extraction.
At present, there are few reports about aromatic heterocycles and derivatives thereof loaded on inorganic carriers, and the loading rate is not high due to poor planar structure and poor framework flexibility, if any.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a modified functional silica gel material, and a preparation method and application thereof. The modified functional silica gel material is prepared by introducing aromatic heterocyclic compounds or derivatives thereof into a multifunctional amino functional silica gel material serving as a carrier, has good chelating capacity with metal ions, has good selectivity on polar components, and is high in loading rate, high in adsorption capacity and good in adsorption effect.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a modified functional silica gel material is a compound shown in a structural formula I;
the compound shown in the structural formula I is obtained by reacting a compound shown in a structural formula II with an aromatic heterocyclic compound or a derivative thereof;
structural formula II is:
Figure 898428DEST_PATH_IMAGE001
Figure 120462DEST_PATH_IMAGE002
Figure 719940DEST_PATH_IMAGE003
；
wherein Z is
Figure 747938DEST_PATH_IMAGE004
Or>
Figure 867204DEST_PATH_IMAGE005
，
B、B 0 Each is H or another polyamine
Figure 56877DEST_PATH_IMAGE006
But B, B 0 Not both can be H; v is a substituent group and is selected from C 1-22 Alkyl radical, C 2-22 Alkenyl or C 1-22 An alkylaryl group; w is a substituent and is selected from C 1-20 Mercaptoalkyl radical, C 2-20 Alkyl sulfide group, C 1-22 Alkylthiothioalkyl or C 2-20 Alkylene thioether alkyl, C 2-20 Alkyl thioether aryl, C 2-20 Alkylene thioether aryl or C 2-6 Alkyl group SC 2-6 Alkyl NHC (= S) NHR 1 (ii) a By silicon atoms, hydrogen, straight or branched C, of other groups in formula II 1-22 Alkyl, terminal group (R) 2 ) 3 SiO 1/2 Crosslinking agent or chain R 2 q Si(OR 3 ) g O k/2 Or one or more of the silicon atoms of the other groups in formula II saturate the free valences of the silicate oxygen atoms; r 1-3 Are independently selected from straight chain or branched chain C 1-12 Alkyl, aryl and C 1-22 An alkylaryl group; k is an integer from 1 to 3; q is an integer from 1 to 2; g is an integer from 0 to 2, and satisfies g + k + q =4; m is an integer from 2 to 12; p is an integer from 2 to 99; t is an integer from 1 to 49; a. b, c, d, e are integers, and [ a + b ]]C is in the range of 0.00001 to 100000; a. c are all always present; when b, d or e is greater than 0, the ratio of d + e to a + b + c is between 0.00001 and 100000;
the structural formula I is:
Figure 146580DEST_PATH_IMAGE007
Figure 650374DEST_PATH_IMAGE008
Figure 138993DEST_PATH_IMAGE009
，
wherein Z is 1 Is that
Figure 437250DEST_PATH_IMAGE010
Or->
Figure 11320DEST_PATH_IMAGE011
，B 1 、B 2 Is Y or->
Figure 381121DEST_PATH_IMAGE012
But B is 1 、B 2 Not both can be Y; y is one of the following structural formulas:
Figure 209400DEST_PATH_IMAGE013
wherein the variable group on the structural formula is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 (ii) a In the above formula, at least one of the variable groups is-CH 2 -or-CH = CCH 2 -, the other variable groups in the structural formula are respectively and independently selected from H and C 1-3 Alkyl radical, C 2-6 Alkenyl radical, C 3-6 Alkynyl, aryl, C 1-6 Alkylaryl, cl, br, I or-NO 2 。
Further, p is an integer from 2 to 30; the t is an integer of 1 to 14.
The invention further provides a preparation method of the modified functional silica gel material, which comprises the following steps:
1) Will (R) 3 O) 3 Si(CH 2 ) m S(CH 2 ) 3 X 1 With the corresponding amine NH 2 [C 2 H 4 NH] p Reaction of H to silane (R) 3 O) 3 Si(CH 2 ) m S(CH 2 ) 3 NH[C 2 H 4 NH] p H，X 1 Is a halide;
2) Reacting the silane obtained in step 1) with 1, 2-dichloroethane and an amine NH 2 [C 2 H 4 NH] p H, reacting the mixture;
3) Adding silane VSi (OR) to the reactant of the step 1) OR the step 2) as required 3 ) 3 and/OR WSi (OR) 3 ) 3 Then grafted onto silica gel, either in a solvent or with sodium silicate or tetraalkyl [ C ] 1-6 ]Carrying out sol-gel reaction on orthosilicate to obtain a compound shown as a structural formula II; wherein the solvent includes, but is not limited to, hydrocarbons, aromatics, alcohols, or water;
4) Mixing a compound shown in a structural formula II and an aromatic heterocyclic compound or a derivative thereof in a solvent, stirring and reacting for a certain time at a certain temperature, filtering, washing and drying to obtain a compound shown in a structural formula I;
wherein, the aromatic heterocyclic compound or the derivative thereof is YX, X is Cl, br or I, and Y is selected from one of the following structural formulas:
Figure 6455DEST_PATH_IMAGE014
wherein the variable group on the structural formula is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 (ii) a In the above formula, at least one of the variable groups is-CH 2 -or-CH = CCH 2 -, the other variable groups in the structural formula are independently selected from H and C 1-3 Alkyl radical, C 2-6 Alkenyl radical, C 3-6 Alkynyl, aryl, C 1-6 Alkylaryl, cl, br, I or-NO 2 。
In the preparation method, the reaction temperature of the step 1) is 20-160 ℃, the reaction time is 0.5-24h, (R) 3 O) 3 Si(CH 2 ) m S(CH 2 ) 3 X 1 With amines NH 2 [C 2 H 4 NH] p The molar ratio of H is 1:1.5 to 6, X 1 Preferably chlorine or bromine.
In the preparation method, the reaction temperature of the step 2) is 20-160 ℃, and the reaction time is 0.5-24h.
In the preparation method, the silica gel grafting reaction temperature in the step 3) is 20-160 ℃, and the reaction time is 0.5-24h; among them, typical solvents include toluene, xylene, heptane, ethanol and methanol; at the end of the reaction, the composition is separated by filtration or centrifugation, then washed thoroughly to remove any residual reactants, and finally dried. The silica gel grafting reaction process can be widely applied to commercially available silica gel (amorphous or spherical silica gel, preferably spherical silica gel); silica gel particle size ranges from the nanoparticle grade to 5 to 30 millimeters; and the silica gel has a widely distributed known pore size, preferably a pore diameter between 40 and 250 a. The sol-gel reaction is carried out in a solvent under an acidic or basic catalyst, the reaction temperature is 20-160 ℃, the reaction time is 0.5-48 hours, and after the reaction is finished, the solid is ground, washed to remove any residual reactant and dried. Typical acids and bases used in the sol-gel reaction process are hydrochloric acid and aqueous ammonia, respectively, but are not limited thereto, and solvents used include, but are not limited to, methanol, ethanol, and water, and mixtures thereof.
Further, the solvent in step 4) is preferably at least one of methanol, dimethyl sulfoxide, dichloromethane, acetonitrile, chloroform and N, N-dimethylformamide; the organic solvent is preferably at least one of methanol, dimethyl sulfoxide, dichloromethane, acetonitrile, chloroform and N, N-dimethylformamide.
Further, in the step (4), the ratio of the mass gram of the compound represented by the structural formula II to the amount of the substance of the heteroaromatic compound or a derivative thereof is 1.
Further, in the step (4), a certain amount of alkali solution can be added for reaction; the alkali solution is preferably at least one of triethylamine, saturated sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate and sodium hydroxide solution.
Further, the reaction temperature in the step (4) is 30 to 150 ℃, and the reaction time is 0.5 to 12h.
The invention further provides an application of the modified functional silica gel material, and specifically, the compound shown in the structural formula I can be used as an adsorbent for adsorbing metal ions.
Furthermore, the compound shown in the structural formula I is used as an adsorbent for removing impurities of electronic chemicals, removing impurities of medicines and intermediate metals, recovering precious metals and removing heavy metals.
The invention further provides another application of the modified functional silica gel material, and particularly relates to a compound shown in a structural formula I as an adsorbent, which can be used as a chromatography medium or a solid phase extraction material.
Furthermore, the compounds of formula I are useful as adsorbents, as chromatographic media for the purification and separation of metals, metal complexes, organic compounds or biological compounds, or as solid phase extraction materials.
The invention has the beneficial effects that:
the invention takes a multifunctional amino-functional silica gel material shown in a structural formula II as a carrier, and utilizes a plurality of amino groups contained in the carrier and-CH contained in an aromatic heterocyclic compound or a derivative thereof 2 X or-CH = CCH 2 The X group reacts, so that a plurality of aromatic heterocyclic compounds or derivatives thereof are introduced, and the load rate of the aromatic heterocyclic compounds or the derivatives thereof is greatly improved. Moreover, the aromatic heterocyclic ring or the derivative thereof has very good chelating capacity for metal ions, especially divalent metal ions due to the plane structure and steric hindrance; the modified functional silica gel material loaded with the aromatic heterocyclic compound or the derivative thereof can effectively and selectively adsorb metal ions. In addition, the modified functional silica gel material loaded with the aromatic heterocyclic compound or the derivative thereof has good selectivity on polar components and strong retention capacity, and can be used as a chromatography medium for purification and separation of metals, metal complexes, organic compounds or biological compounds or a solid phase extraction material.
The modified functional silica gel material greatly improves the loading rate of the aromatic heterocyclic compound or the derivative thereof, improves the adsorption capacity and the adsorption effect, and can solve the problems that the aromatic heterocyclic compound and the derivative thereof are difficult to load on an inorganic carrier and the loading rate is low in the prior art.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a multifunctional amino-functionalized silica gel represented by structural formula II: adding polyethylene polyamine (0.4 mol) and 3- (3-chloropropyl) thiopropyl trimethoxy silane (0.4 mol) into a 500mL three-neck flask provided with a glass plug and a condensation reflux device, refluxing for 2.5h at 150 ℃, cooling to 70 ℃, adding methanol (40 mL), refluxing for 1h, cooling, adding the reacted substance and 3-mercaptopropyl trimethoxy silane (0.2 mol) into a mixed solution of xylene (125 mL) and spherical silica gel (90g, 200-500 mu m), refluxing for 7h at 150 ℃, cooling, filtering, washing with ethanol for 5 times and drying to obtain the compound shown in the structural formula II, wherein m is 3, p is 9, W is 3-mercaptopropyl, a, c and e exist, and b and d are all zero.
Example 1-1
10g of the compound represented by the structural formula II in example 1 was accurately weighed, 100ml of methanol solution was added, then 2-chloromethylimidazole (3.5 g, 0.03mol) and 5.5ml of triethylamine were added, stirred and refluxed at 120 ℃ for 4 hours, cooled, filtered, washed with deionized water for 5 times, and dried to obtain the compound represented by the structural formula I.
Wherein Y is
Figure 802241DEST_PATH_IMAGE015
，R 1 is-CH 2 -，R 2、 R 3 Is H, A is NH.
Examples 1 to 2
10g of the compound of the formula II prepared in example 1 were weighed out accurately, 90ml of dichloromethane solution were added, followed by 2-chloromethylpyridine (10.2 g, 0.08mol) and 10ml of triethylamine, stirred at 30 ℃ for 1.5h, filtered and diluted with saturated NaHCO 3 The solution is washed, and then the solution is washed,and washing the mixture for 5 times by using deionized water, and drying the mixture to obtain the compound shown in the structural formula I.
Wherein Y is
Figure 913417DEST_PATH_IMAGE016
，R 1 is-CH 2 -，R 2、 R 3、 R 4、 R 5 Is H.
Examples 1 to 3
10g of the compound of formula II of example 1 was weighed accurately, 50ml of acetonitrile solution was added, then 6-chloromethyl-imidazo [2,1-B ] thiazole (3.5g, 0.02mol) was added and stirred at 30 ℃ for 1h, filtered, washed with 0.001M NaOH solution, washed with deionized water for 5 times and dried to give the compound of formula I.
Wherein Y is
Figure 108119DEST_PATH_IMAGE017
，R 3 is-CH 2 -，R 1、 R 2、 R 4 Is H.
Example 2
Preparing a multifunctional amino-functionalized silica gel represented by structural formula II: a solution of 3-chloropropylthiopropyltrimethoxysilane (0.3 mol) and diethylenetriamine (0.6 mol) was heated to 70 ℃ with stirring for 2 hours, a 1, 2-dichloroethane solution (0.3 mol) was added, the solution was heated with stirring at 100 to 110 ℃ for 3 hours, methanol (150 mL) was added and the solution was heated with stirring for 1 hour, and then cooled. This solution was added to a stirred mixture of silica gel (200g, 60-200 μm, 100-140) and toluene (400 mL), the mixture was stirred and refluxed for 6 hours, the solid was cooled and filtered, washed centrifugally with ethanol (3 × 400 mL) and dried to give the compound of formula II, where m is 3, p is 2,a, b and c are all present, and d and e are both zero.
Example 2-1
20g of the compound of the formula II prepared in example 2 were weighed out accurately, 120ml of methanol were added, and 5-bromo-2 (chloromethyl) -imidazo [2,1-A ] was added]Pyridine (9.2g, 0.04mol) was stirred at 65 ℃ for 8h, filtered and diluted with saturated NaKCO 3 Washing the solution, washing the solution with deionized water for 5 times, and drying the solution to obtain the compound shown in the structural formula I.
Wherein Y is
Figure 76075DEST_PATH_IMAGE018
，R 1 is-CH 2 -，R 2、 R 4、 R 5、 R 6 Is H, R 3 Is Br.
Examples 2 to 2
Accurately weigh 20g of the compound of formula II prepared in example 2, add 150ml N, N-dimethylformamide, then 2-chloro-5-chloromethylthiazole (16.8g, 0.1mol) and 10ml triethylamine, stir at 120 ℃ for 0.5h, filter, and add 1M Na 2 CO 3 Washing the solution, washing the solution for 5 times by using deionized water, and drying the solution to obtain the compound shown in the structural formula I.
Wherein Y is
Figure 109890DEST_PATH_IMAGE019
A is S, R 1 Is Cl, R 2 Is H, R 3 is-CH 2 -。
Examples 2 to 3
20g of the compound of formula II prepared in example 2 were weighed accurately, added to 200 ml of dimethylsulfoxide solution, then added with 3- (chloromethyl) pyrazole hydrochloride (18.5 g, 0.12mol) and 15ml of triethylamine, stirred at 90 ℃ for 1.5h, filtered, washed with 0.02M NaOH solution, washed with deionized water for 5 times and dried to give the compound of formula I.
Y is
Figure 821494DEST_PATH_IMAGE020
，R 3 is-CH 2 -，R 1、 R 2 Is H.
Application example 1
5g of the compound represented by the structural formula I obtained in example 1-1 was added to 100ml of a 1M hydrochloric acid system having concentrations of 200 ppm each of Pd (II), rh (III) and Ir (III), and the mixture was stirred at room temperature for 30 minutes, and the filtrate was analyzed by ICP-MS, whereby the removal rate of Pd was 99% and the removal rate of Rh and Ir was less than 5%. The same experiment was performed using the compounds represented by the formula I obtained in examples 1 to 2,1 to 3,2 to 1,2 to 2,2 to 3, and the results were the same. The material has very good adsorption rate to divalent palladium, and can selectively adsorb palladium from rhodium and iridium.
Application example 2
An electronic grade reagent methanol containing 1.05 pmm Ni, 0.73ppm Cu, 0.5ppm Zn, 0.48ppm Ca, 0.22 ppm Mg was added to 100ml of this methanol reagent, 2g of the compound represented by the formula I obtained in example 1-2 was added thereto, and the mixture was stirred at room temperature for 1 hour to analyze the concentration of the filtrate, whereby it was found that the concentrations of Ni, cu, zn, ca and Mg were all less than 0.001ppm.
Application example 3
A certain zinc gluconate solution contains 1.28ppm Cd and 0.5ppm Pb, 100ml of the solution is taken, added with the compound shown in the structural formula I obtained in the example 2-3, stirred at normal temperature for 2 hours, and the concentration of the filtrate is analyzed, so that neither Cd nor Pb is detected.
Application example 4
1g of the product of formula I obtained in examples 1-3 was added to 100mL of a waste solution containing 50ppm of ferrous and ferric iron. The mixture was stirred at 30 ℃ for 6h and then filtered. Analysis of the filtrate showed that ferrous iron had been removed. The products from examples 1-1,1-2,2-1,2-2,2-3 have the same effect in this test.
Application example 5
The product of formula I from example 2-1 (10 g) was loaded into a 20mL adsorption column, a waste stream of pH 6 containing 6ppm copper, 2 pmm nickel and 5ppm cobalt was passed through the column at a flow rate of 1mL/min, and after 2h the filtrate was analyzed for copper, nickel and cobalt adsorption rates of > 99%. Eluting the adsorption column with 10ml of nitric acid solution with pH of 5, analyzing to completely elute cobalt, retaining copper and nickel in the adsorption column, eluting the adsorption column with 10ml of nitric acid solution with pH of 3, analyzing to completely elute nickel and copper, eluting the adsorption column with nitric acid solution with pH of 0, analyzing to completely elute copper. The products from examples 1-1,1-2,1-3,2-2,2-3 have the same effect in this test. The material is shown to be capable of separating copper, nickel and cobalt very well through chromatographic separation.
Application example 6
A sample containing uracil, uridine, adenosine, and adenosine was packed into a 4.6 × 250mM column using the product of formula I obtained in example 1-1, and the column was purified using acetonitrile/10 mM ammonium acetate =10:90 as mobile phase, with flow rate of 0.5ml/min, separating by chromatography, uracil at retention time of 5.6min, uridine at retention time of 9.4min, adenosine at retention time of 11.2min, and adenosine at retention time of 22.5 min. It is thus understood that the material of the present invention is effective for chromatographic separation of a biological compound.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (10)

1. A modified functionalized silica gel material is characterized in that: is a compound shown in a structural formula I;
the compound shown in the structural formula I is obtained by reacting a compound shown in a structural formula II with an aromatic heterocyclic compound or a derivative thereof;
structural formula II is:
Figure QLYQS_1
Figure QLYQS_4
(ii) a Wherein Z is->
Figure QLYQS_6
Or
Figure QLYQS_3
，B、B 0 Each is H or another polyamine
Figure QLYQS_5
But B, B 0 Not both can be H; v is a substituent group and is selected from C 1-22 Alkyl radical, C 2-22 Alkenyl or C 1-22 An alkylaryl group; w is a substituent and is selected from C 1-20 Mercaptoalkyl radical, C 2-20 Alkyl sulfide group, C 1-22 Alkylthiothioalkyl or C 2-20 Alkylene thioether alkyl, C 2-20 Alkyl thioether aryl, C 2-20 Alkylene thioether aryl or C 2-6 Alkyl group SC 2-6 Alkyl radicals or alkyl radicals>
Figure QLYQS_7
(ii) a By silicon atoms, hydrogen, straight or branched C, of other groups in formula II 1-22 Alkyl, terminal group (R) 2 ) 3 SiO 1/2 Crosslinking agents or chains>
Figure QLYQS_8
Or one or more of the silicon atoms of the other groups in formula II saturate the free valences of the silicate oxygen atoms; r is 1-3 Are independently selected from straight chain or branched chain C 1-12 Alkyl, aryl and C 1-22 An alkylaryl group; k is an integer from 1 to 3; q is an integer from 1 to 2; g is an integer from 0 to 2 and satisfies->
Figure QLYQS_2
(ii) a m is an integer from 2 to 12; p is an integer from 2 to 99; t is an integer from 1 to 49; a. b, c, d, e are integers and [ a + b]C is in the range of 0.00001 to 100000; a. c are all always present; when b, d or e is greater than 0, the ratio of d + e to a + b + c is between 0.00001 and 100000;
the structural formula I is:
Figure QLYQS_9
Figure QLYQS_10
wherein Z is 1 Is->
Figure QLYQS_11
Or
Figure QLYQS_12
Are Y or->
Figure QLYQS_13
But B is 1 、B 2 Not both can be Y; y is one of the following structural formulas: />
Figure QLYQS_14
；
Wherein the variable group on the structural formula is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 (ii) a In the above formula, at least one of the variable groups is
Figure QLYQS_15
The other variable groups in the structural formula are respectively and independently selected from H and C 1-3 Alkyl radical, C 2-6 Alkenyl radical, C 3-6 Alkynyl, aryl, C 1-6 Alkylaryl, cl, br, I or-NO 2 。
2. The modified functionalized silica gel material of claim 1, wherein p is an integer from 2 to 30; the t is an integer of 1 to 14.
3. The method for preparing a modified functionalized silica gel material according to claim 1 or 2,
a process for the preparation of a compound of formula I comprising the steps of:
1) Will be provided with
Figure QLYQS_16
Is associated with the corresponding amine->
Figure QLYQS_17
Reaction to form silane
Figure QLYQS_18
Is a halide;
2) Reacting the silane obtained in step 1) with 1, 2-dichloroethane and an amine
Figure QLYQS_19
Reacting the mixture of (a);
3) Adding silane to the reaction of step 1) or 2) as required
Figure QLYQS_20
Then, grafting on silica gel in a solvent, or carrying out sol-gel reaction with sodium silicate or tetraalkyl orthosilicate to obtain a compound shown in a structural formula II; wherein the solvent comprises hydrocarbons, aromatics, alcohols or water; wherein the alkyl group in the tetraalkylorthosilicate is selected from C 1-6 An alkyl group;
4) Mixing a compound shown as a structural formula II and an aromatic heterocyclic compound or a derivative thereof in a solvent, stirring and reacting for a certain time at a certain temperature, filtering, washing and drying to obtain a compound shown as a structural formula I;
wherein, the aromatic heterocyclic compound or the derivative thereof is YX, X is Cl, br or I, and Y is selected from one of the following structural formulas:
Figure QLYQS_21
；
wherein the variable group on the structural formula is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 (ii) a In the above formula, at least one of the variable groups is
Figure QLYQS_22
The other variable groups in the structural formula are respectively and independently selected from H and C 1-3 Alkyl radical, C 2-6 Alkenyl radical, C 3-6 Alkynyl, aryl, C 1-6 Alkylaryl, cl, br, I or-NO 2 。
4. The method for preparing a modified functionalized silica gel material according to claim 3,
the solvent in the step 4) is at least one of methanol, dimethyl sulfoxide, dichloromethane, acetonitrile, chloroform and N, N-dimethylformamide.
5. The method for preparing the modified functionalized silica gel material according to claim 3,
the ratio of the gram mass of the compound shown in the structural formula II to the mass of the substance of the aromatic heterocyclic compound or the derivative thereof is 1g (0.001 to 10) mol.
6. The preparation method of the modified functional silica gel material as claimed in claim 3, wherein the reaction temperature in the step (4) is 30 to 150 ℃ and the reaction time is 0.5 to 12h.
7. The use of the modified functionalized silica gel material according to claim 1 or 2, wherein the compound of formula I is used as an adsorbent for adsorbing metal ions.
8. The use of the modified functionalized silica gel material according to claim 7, wherein the compound represented by the structural formula I is used as an adsorbent for electronic chemical metal impurity removal, medical and intermediate metal impurity removal, and precious metal recovery.
9. The use of the modified functionalized silica gel material according to claim 1 or 2, wherein the compound of formula I is used as an adsorbent as a chromatography medium.
10. The use of the modified functionalized silica gel material according to claim 9, characterized in that the compound of formula I is used as an adsorbent as a chromatography medium for the purification and separation of metals, metal complexes, organic compounds or biological compounds.
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