CN110614089A - Preparation method of functionalized polyamide-amine dendrimer adsorbent - Google Patents
Preparation method of functionalized polyamide-amine dendrimer adsorbent Download PDFInfo
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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Abstract
The invention relates to a preparation method of a functionalized polyamide-amine dendrimer adsorbent, which comprises the following steps: firstly, modifying the 1.0 or 2.0 generation triethoxy silicon-based polyamide-amine dendrimer by adopting methyl isothiocyanate to obtain a functionalized triethoxy silicon-based polyamide-amine dendrimer, and then carrying out sol-gel reaction with tetraethoxysilane according to a specific proportion to obtain the functionalized polyamide-amine dendrimer adsorbent. The adsorbent prepared by the invention contains rich nitrogen, oxygen and sulfur functional groups, has good adsorption performance and adsorption selectivity to Hg (II), and can be used for adsorption separation, selective removal and the like of Hg (II) in water.
Description
Technical Field
The invention relates to a preparation method of a functionalized polyamide-amine dendrimer adsorbent, belonging to the field of environment functional materials.
Background
With the development of industrialization, the discharge amount of industrial wastewater increases, wherein water pollution caused by metal ions has become a serious environmental problem. The metal ions are difficult to degrade and toxic, and cause serious harm to the ecological environment and human bodies, so that the method has important significance on how to effectively remove the metal ions in the water body.
Adsorption methods are widely used for the separation and removal of metal ions due to their advantages such as simplicity and high efficiency. The polyamide-amine dendrimer contains a large number of nitrogen and oxygen functional groups and intramolecular cavities, and is easy to realize the adsorption and separation of metal ions. And the polyamide-amine dendrimer is easy to functionalize and can be modified according to specific requirements so as to realize selective adsorption and separation of specific metal ions. However, the polyamide-amine dendrimer and the metal ion complex are easily dissolved in aqueous solution and most organic solvents, which greatly limits the application of the polyamide-amine dendrimer and the metal ion complex as adsorbents. Immobilization of polyamidoamine dendrimers onto specific groups is an effective approach to solve this problem. The silica gel has the advantages of good mechanical strength, good thermal stability and chemical stability, rich pore structure, large specific surface area, rich silicon hydroxyl on the surface, easy modification and the like, and is often used as a matrix for immobilizing the polyamide-amine dendrimer. At present, there are two methods for immobilizing the polyamidoamine dendrimer on the silica gel, one is to introduce reactive sites on the surface of the silica gel and then gradually synthesize the polyamidoamine dendrimer by a dispersion method; the other is to connect the synthesized polyamide-amine dendrimer to the surface of the silica gel through the coupling reaction among the functional groups. The first synthesis method is convenient for separation and purification of products in the synthesis process, but can cause the polyamide-amine dendrimer to form intramolecular and intermolecular cross-linked structures in the growth process of the silica gel surface, and reduce silica gel pore channels. The second method can effectively avoid the structural defect in the polyamide-amine dendrimer, but the loading of the polyamide-amine dendrimer on the surface of the silica gel is easily reduced due to the existence of the steric hindrance effect. The problems can cause that the adsorption quantity of the adsorbent for immobilizing the higher-generation polyamide-amine dendrimer to the metal ions is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a functionalized polyamide-amine dendrimer metal ion adsorbent. The adsorbent prepared by the invention takes sulfur-containing polyamide-amine dendrimer as a functional group, has good binding capacity to Hg (II), and can realize effective adsorption and selective separation of Hg (II) in a water body.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a functionalized polyamide-amine dendrimer adsorbent comprises the following steps:
adding 1.0 or 2.0 substituted triethoxysilyl polyamide-amine dendrimer into methyl isothiocyanate, heating and stirring to react by taking 150-300 ml of absolute ethanol as a solvent to prepare 1.0 or 2.0 substituted triethoxysilyl sulfur-containing polyamide-amine dendrimer, and then cooling to 25 ℃; adding tetraethoxysilane, water and ammonium fluoride, continuing stirring for reaction, aging a sample at 50 ℃ for 48 hours after the reaction is finished, filtering a product, extracting the product for at least 12 hours by using absolute ethyl alcohol, and drying to obtain the 1.0 or 2.0 generation functionalized polyamide-amine dendrimer adsorbent.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the whole preparation process is carried out under the protection of nitrogen;
further, the molar ratio of the amino group to the methyl isothiocyanate in the 1.0 or 2.0 generation triethoxysilylpolyamidoamine dendrimer is 1: (1.2-6), the reaction temperature is 50-70 ℃, and the reaction time is 24-36 hours;
further, the molar ratio of the 1.0 or 2.0-substituted triethoxysilyl sulfur-containing polyamidoamine dendrimer to the tetraethoxysilane, the water and the ammonium fluoride is 1: (2-10): (1-12): (0.01-0.05), the reaction temperature is 25 ℃, and the reaction time is 24-36 hours.
The 1.0 or 2.0 generation triethoxy silicon based polyamide-amine dendrimer used in the invention is obtained by a divergent synthesis method, and the specific preparation method is described in the references Rongjun Qu, Xilu Ma, Minghua Wang, et al, Journal of Industrial and Engineering Chemistry, 2014, 20: 4382-4392。
the synthesis steps of the 1.0 th generation triethoxysilylamide-amine dendrimer are as follows:
160 ml of methyl acrylate solution in methanol (volume ratio of 1:1) was added dropwise to 150 ml of 3-aminopropyltriethoxysilane solution in methanol (volume ratio of 1:1) under nitrogen protection, and the reaction mixture was stirred at 0 ℃ for 0.5 hour and then raised to 25 ℃ for further 24 hours. After the reaction is finished, methanol and excessive methyl acrylate are evaporated by a rotary evaporator at 40 ℃ to obtain 0.5 th generation triethoxysilylpolyamide-amine dendrimer. Then, a methanol solution (25 g is dissolved in 30 ml of methanol) of the 0.5 th generation triethoxysilylpolyamidoamine dendrimer is dropwise added into 240 ml of a methanol solution of ethylenediamine (the volume ratio is 1:1) at 0 ℃, and after 0.5 hour of reaction, the temperature is raised to 25 ℃ for 96 hours. After the reaction is finished, methanol and excessive ethylenediamine are evaporated by a rotary evaporator at 70 ℃ to prepare the 1.0 th generation triethoxysilylamide-amine dendrimer.
The synthesis of the 2.0 th generation triethoxysilylamide-amine dendrimer comprises the following steps:
under the protection of nitrogen, 40 ml of methyl acrylate methanol solution (volume ratio is 1:1) is dropwise added into the 1.0 generation triethoxysilylpolyamidoamine dendrimer methanol solution (20 g in 30 ml of methanol), the mixture is stirred and reacted at 0 ℃ for 0.5 hour, and then the reaction is continued for 24 hours at 25 ℃. After the reaction is finished, methanol and excessive methyl acrylate are evaporated by a rotary evaporator at 40 ℃ to obtain the 1.5 th generation triethoxysilylpolyamidoamine dendrimer. Then, a methanol solution (12 g is dissolved in 15 ml of methanol) of the 1.5 th generation triethoxysilylpolyamidoamine dendrimer is dropwise added into 100 ml of methanol solution of ethylenediamine (the volume ratio is 1:1) at 0 ℃, and after 0.5 hour of reaction, the temperature is raised to 25 ℃ for 96 hours. After the reaction is finished, methanol and excessive ethylenediamine are evaporated by a rotary evaporator at 70 ℃ to prepare the 2.0 th generation triethoxysilylamide-amine dendrimer.
Compared with the prior art, the invention has the following advantages:
the functional polyamide-amine dendrimer adsorbent prepared by the synthesis method has the advantages of regular polyamide-amine dendrimer structure, high functional group content, uniform distribution of adsorption sites, good binding capacity for Hg (II), and capability of realizing effective adsorption and selective separation of Hg (II) in a water body.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Under the protection of nitrogen, 8 mmol of 1.0 th generation triethoxysilyl polyamide-amine dendrimer and 24 mmol of methyl isothiocyanate are added into a 500 ml three-neck flask, then 150 ml of absolute ethyl alcohol is added as a solvent, the reaction mixture reacts for 36 hours at 50 ℃, and then the reaction mixture is cooled to 25 ℃ to obtain the 1.0 th generation triethoxysilyl sulfur-containing polyamide-amine dendrimer; then 16 millimole of ethyl orthosilicate, 8 millimole of water and 0.08 millimole of ammonium fluoride are added, the reaction mixture reacts for 24 hours at 25 ℃, a sample is aged for 48 hours at 50 ℃ after the reaction is finished, a product is filtered and extracted by absolute ethyl alcohol for 12 hours, and the product is dried to obtain the 1.0 th functionalized polyamide-amine dendrimer adsorbent.
Example 2
Under the protection of nitrogen, 8 mmol of 1.0 generation triethoxysilyl polyamide-amine dendrimer and 48 mmol of methyl isothiocyanate are added into a 500 ml three-neck flask, 250 ml of absolute ethyl alcohol is added as a solvent, the reaction mixture reacts for 24 hours at 70 ℃, and then the reaction mixture is cooled to 25 ℃ to obtain the 1.0 generation triethoxysilyl sulfur-containing polyamide-amine dendrimer; then 32 millimole of ethyl orthosilicate, 16 millimole of water and 0.16 millimole of ammonium fluoride are added, the reaction mixture reacts for 36 hours at 25 ℃, a sample is aged for 48 hours at 50 ℃ after the reaction is finished, a product is filtered and extracted by absolute ethyl alcohol for 12 hours, and the product is dried to obtain the 1.0 functionalized polyamide-amine dendrimer adsorbent.
Example 3
Under the protection of nitrogen, 8 mmol of 2.0 generation triethoxysilyl polyamide-amine dendrimer and 48 mmol of methyl isothiocyanate are added into a 500 ml three-neck flask, 250 ml of absolute ethyl alcohol is added as a solvent, the reaction mixture reacts for 30 hours at 60 ℃, and then is cooled to 25 ℃ to obtain the 2.0 generation triethoxysilyl sulfur-containing polyamide-amine dendrimer; then adding 32 millimole of ethyl orthosilicate, 24 millimole of water and 0.16 millimole of ammonium fluoride, reacting the reaction mixture at 25 ℃ for 32 hours, ageing the sample at 50 ℃ for 48 hours after the reaction is finished, filtering the product, extracting the product with absolute ethyl alcohol for 12 hours, and drying to obtain the 2.0-th functionalized polyamide-amine dendrimer adsorbent.
Example 4
Under the protection of nitrogen, 8 mmol of 2.0 generation triethoxysilyl polyamide-amine dendrimer and 80 mmol of methyl isothiocyanate are added into a 500 ml three-neck flask, then 300 ml of absolute ethyl alcohol is added as a solvent, the reaction mixture reacts for 24 hours at 70 ℃, and then is cooled to 25 ℃ to obtain the 2.0 generation triethoxysilyl sulfur-containing polyamide-amine dendrimer; then 24 millimole of ethyl orthosilicate, 16 millimole of water and 0.24 millimole of ammonium fluoride are added, the reaction mixture reacts for 24 hours at 25 ℃, a sample is aged for 48 hours at 50 ℃ after the reaction is finished, a product is filtered and extracted by absolute ethyl alcohol for 12 hours, and the product is dried to obtain the 2.0 th functionalized polyamide-amine dendrimer adsorbent.
Performance evaluation 1: the adsorption performance of the functionalized polyamide-amine dendrimer adsorbent prepared in example 2 and example 3 on Hg (II)
20 mg of the generation 1.0 and 2.0 functionalized polyamidoamine dendrimer adsorbents prepared in example 2 and example 3 were weighed out, respectively, and placed in 100 ml conical flasks, 20 ml of 0.001 mol/l Hg (II) solution was added, respectively, and placed in a gas bath shaker and shaken at 25 ℃ for 12 hours. The concentration of the residual Hg (II) in the solution is measured by an atomic absorption spectrophotometer, and the adsorption amounts of the Hg (II) ions of the 1.0 generation-functionalized polyamide-amine dendrimer adsorbent and the 2.0 generation-functionalized polyamide-amine dendrimer adsorbent to the Hg (II) ions are respectively calculated to be 1.55 mmol/g and 1.68 mmol/g according to the change of the Hg (II) ion concentration before and after adsorption.
Performance evaluation 2: selective adsorption of functionalized polyamidoamine dendrimer adsorbents prepared in examples 2 and 3 to Hg (II)
A series of preparations, each weighing approximately 20 mg, of example 2 and example 3 were preparedThe generation 1.0 and generation 2.0 functionalized polyamide-amine dendrimer adsorbents are placed in a 100 ml conical flask with a plug, and then 20 ml of the conical flask with a plug are respectively added with 0.001 mol/L Hg (Hg) (in each case))-Co()、Hg()-Pb()、Hg()-Mn()、Hg()-Ni()、Hg()-Fe(III)、Hg()-Cu()、Hg()-Cd() The mixed ion solution of (4) was placed in a gas bath shaker and shaken at 25 ℃ for 12 hours. By atomsThe absorption spectrophotometer measured the concentration of the remaining Hg (ii) and the concentration of other metal ions in the solution, and the amount of adsorption and selectivity coefficient to Hg (ii) and coexisting ions were calculated from the change in the metal ion concentration before and after adsorption, and the results are shown in tables 1 and 2. It can be seen that the functionalized polyamide-amine dendrimer adsorbent shows good adsorption selectivity to Hg (II) when Hg (II)) And Co ()、Pb()、Mn()、Ni() And Fe (III) plasma can selectively adsorb Hg (II) by 100%.
TABLE 1 Selective adsorption of Hg (II) by the generation 1.0 functionalized polyamidoamine dendrimer adsorbent
TABLE 2 Selective adsorption of 2.0 generation functionalized polyamidoamine dendrimer adsorbent to Hg (II)
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a functionalized polyamide-amine dendrimer adsorbent is characterized by comprising the following steps:
adding 1.0 or 2.0 substituted triethoxysilyl polyamide-amine dendrimer into methyl isothiocyanate, heating and stirring to react by taking 150-300 ml of absolute ethanol as a solvent to prepare 1.0 or 2.0 substituted triethoxysilyl sulfur-containing polyamide-amine dendrimer, and then cooling to 25 ℃; adding tetraethoxysilane, water and ammonium fluoride, continuing stirring for reaction, aging a sample at 50 ℃ for 48 hours after the reaction is finished, filtering a product, extracting the product for at least 12 hours by using absolute ethyl alcohol, and drying to obtain the 1.0 or 2.0 generation functionalized polyamide-amine dendrimer adsorbent.
2. The preparation method according to claim 1, wherein the whole preparation process is carried out under the protection of nitrogen.
3. The method according to claim 1 or 2, wherein the molar ratio of amino group to methyl isothiocyanate in the 1.0 or 2.0 generation triethoxysilylpolyamidoamine dendrimer is 1: (1.2-6), the reaction temperature is 50-70 ℃, and the reaction time is 12-24 hours; the molar ratio of the triethoxysilyl sulfur-containing polyamide-amine dendrimer to the tetraethoxysilane, the water and the ammonium fluoride is 1: (2-10): (1-12): (0.01-0.05), the reaction temperature is 25 ℃, and the reaction time is 24-36 hours.
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