CN114316292A - Heavy metal chelating agent with dendritic Dendrimer molecular structure, preparation method and application thereof - Google Patents
Heavy metal chelating agent with dendritic Dendrimer molecular structure, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a heavy metal chelating agent with a dendritic Dendrimer molecular structure, a preparation method and application thereof. The high-efficiency chelation effect of the interior of the molecule and the heavy metal is realized through the space molecular framework and the star-shaped cavity structure of the metal chelating agent, the heavy metal in the waste water and the industrial solid waste is efficiently captured and chelated to form stable flocculation/precipitate, and the heavy metal is not easy to decompose and separate out. Compared with the existing comb-type, linear and small-molecule dithiocarbamate DTC heavy metal chelating agents, the heavy metal chelating agent has the advantages of more excellent molecular space structure, stronger heavy metal chelating capacity and stability, high efficiency, good PH applicability and the like, and can effectively improve the heavy metal chelating efficiency and reduce the risk of secondary pollution.
Description
Technical Field
The invention belongs to the technical field of heavy metal treatment of water, wastewater, sewage, sludge or solid waste, and particularly relates to a heavy metal chelating agent with a dendritic Dendrimer molecular structure, and a preparation method and application thereof.
Background
With the development of economy, the usage amount of metal materials is increased sharply, heavy metal pollution generated in the production processes of industries such as mines, smelting, mechanical manufacturing, chemical industry, electronics, instruments, garbage and solid waste incineration disposal and the like becomes more and more serious, and the health and survival of the environment, people and organisms are seriously influenced. The heavy metal pollution refers to the pollution of mercury, lead, arsenic, cadmium, chromium, copper, cobalt and other heavy metals and compounds thereof with obvious biotoxicity to the environment, the heavy metal pollution cannot be decomposed and degraded by the environment and is difficult to remove, only the position of the heavy metal can be transferred or the form of the heavy metal can be changed, the heavy metal pollution is extremely easy to accumulate and enrich in soil and water environment, long-term poison to the environment and human health is easy to form, and the heavy metal pollution is one of the pollution with the greatest harm to the environment and human, and is also an important difficult problem and research hotspot of the modern world environment. The strengthening of the treatment of heavy metals has very important significance for the development of national economy and the guarantee of the life safety and health of people.
The method for removing and treating heavy metals mainly comprises a chemical chelation precipitation method, an electrolysis method, a membrane method, an ion exchange method and the like. Considering the problems of high investment, high treatment cost, low treatment efficiency and the like of other methods, the chemical chelation precipitation method is widely applied to heavy metal treatment with the advantages of simple process, high efficiency, economy, suitability for large-scale treatment and the like.
Heavy metal chelating agents, also known as complexing agents, are stable water-insoluble complexes having a cyclic structure that can form lone electron pairs and pi-bonded electron vacant orbital ligands with heavy metal ions. It contains two or more electronic groups and can form a stable complex with a cyclic structure with heavy metals, so that the heavy metals are separated from water, precipitated, passivated, and formed into stable compounds or precipitates, thereby inhibiting the pollution of the heavy metals.
The commonly used heavy metal chelating precipitation agents are classified into inorganic and organic types. Although the inorganic medicament has low cost, the problems of needing to add a large amount of alkali to adjust the pH value, poor chelating/complexing stability, low treatment efficiency, poor environmental suitability and the like exist, and the organic chelating agent is mainly commonly used in the current market.
The organic chelating agent has the advantages of small dosage, good stabilizing effect, high efficiency, small risk of secondary pollution, good PH applicability and the like, and is generally applied. Common organic heavy metal chelating agents include mainly Ethylenediaminetetraacetate (EDTA), dithioamino carboxylate (DTC), trimercaptotriazine trisodium salt (TMT). The N-CSS functional group containing the sulfur atom has strong coordination capacity and soft alkali characteristics, and can form a complex, precipitate combination or complexation with almost all transition metals. Meanwhile, most heavy metals belong to acidity and boundary acid, so that the heavy metal chelating agent containing sulfur atoms and soft acid type heavy metal ions are more favorable for forming stable coordination bonds, and the complexing stability of the heavy metal chelating agent avoids secondary pollution of the heavy metals. Heavy metal chelators of the dithioamino carboxylate (DTC) type are most widely used in the market for cost reasons and for the superior coordinating heavy metal chelation advantage of sulfur atoms.
The dithioamino carboxylate (DTC) heavy metal chelating agent used in the market at present is mainly a micromolecule DTC chelating agent (sodium dimethyl carbonate) synthesized by micromolecule amine such as dimethylamine/ethylenediamine and raw materials such as strong base and carbon disulfide, and a linear comb-type high polymer chelating agent synthesized by polymeric polyamine and strong base and carbon disulfide, such as a solid heavy metal treating agent disclosed in Chinese patent application with the publication number of CN102216410A, a manufacturing method and application thereof, a synthetic method of a dithioamino formate diethylenetriamine ethyl polymer disclosed in Chinese patent application with the publication number of CN1831020A, and a chelating agent capable of treating various heavy metal ions simultaneously disclosed in Chinese patent application with the publication number of CN 101081827A. The chemical formulas of the dimethyldithiocarbamate/DTC and the polydimethyldithiocarbamate/DTC are shown as the following formulas I and II.
The density of the coordination sulfur functional group of the monomer micromolecule and linear macromolecule chelating agent is relatively low, the molecular weight is small, no auxiliary chelating group is provided, the micromolecule presents a comb-shaped and linear molecular structure and a space configuration, a stable chelating coordination structure cannot be formed or is difficult to form, and the mutual chelating effect of the molecules of the chelating agent on heavy metals is easily influenced by factors such as PH and the like to generate the analysis and separation of the heavy metal ions. The chelation of dimethyldithiocarbamate/DTCs with heavy metals is shown in formulas III, IV and V below.
Therefore, the development of the novel heavy metal chelating agent which has a high-density coordination sulfur functional group, a more advantageous chelating molecular structure and three-dimensional coordination space configuration, higher chelating efficiency and an auxiliary chelating group has important practical significance and industrial application value.
The Dendrimer Dendrimer is obtained by introducing reactive and functional groups into molecules by using a molecular design principle, and is shown as the following formula VI. The compound has the advantages of a highly branched structure, a unique monodisperse type, an accurate molecular structure, a large number of functional groups, intramolecular cavities, molecular chain growth controllability and the like, so that the compound has a series of unusual properties and behaviors.
The traditional polymerization is a random reaction process, the polymer is mostly linear and comb-shaped, and the molecular weight has dispersity. The Dendrimer Dendrimer can strictly control and design functional groups, molecular size and shape structure on the molecular level, and meet different performance requirements. PAMAM is the first reported dendrimer with a three-dimensional spherical structure, as shown in formula VII below; compared with linear and comb polymers, the polymer has the characteristics of fixed structure, multifunctional groups and high branching degree radiating from the center to the outside. The structural schematic diagram can be seen, and the multi-arm initiation core consists of three parts, namely a multi-arm initiation core (Initiatorcore), a plurality of internal branching functional groups (Iinteior) and an external surface group (Exterior). The surface groups of the outermost layer of the molecule are linked to the branching functional groups of the outer layer, and each of the concentric branching functional groups becomes a Generation number (Generation) and has a branching point at each Generation.
For example, the Chinese patent application with the publication number of CN106927554A discloses a heavy metal trapping agent of a dendritic polymer with double chelating and flocculating properties and application thereof, and particularly discloses that the heavy metal trapping agent is a PAMAM- (NH) dendritic polymer (the substitution G of which is 1-3)2)8GIndicating that G is algebraic), with carbon disulfide. Said dithiocarbamate-terminated polyamidoamine dendrimers, due to their special trisThe terminal chelating group dithiocarbamate with a dimensional space structure, a proper molecular weight and a high density has strong chelating performance with heavy metal ions, and deposited flocs formed after chelating with heavy metals are large, fast in sedimentation and easy to separate, and have high-efficiency chelating and flocculating heavy metal performances. Although the heavy metal collector is mentioned to be applicable to heavy metal stabilization treatment of industrial and domestic garbage incineration fly ash, in fact, the PAMAM star-shaped macromolecules have low chelating efficiency for heavy metals in the fly ash, and are susceptible to the influence of factors such as PH and the like, so that the problems of analysis and separation of heavy metal ions and the like occur.
At present, the heavy metal chelating agent for sewage treatment is difficult to be simultaneously applied to solid waste treatment, and the heavy metal chelating agent with high chelating efficiency in both waste water treatment and solid waste treatment is not seen. In the prior art, the heavy metal chelating agent with high-efficiency chelating performance in sewage treatment is difficult to achieve the stabilization treatment of heavy metals even if the heavy metal chelating agent is applied to the treatment of solid waste. At present, the heavy metal fly ash chelating agent widely used in the industry has the problems that the density of a coordination sulfur functional group is relatively low, the molecule is small and has a comb-shaped linear molecular structure, the space configuration is not favorable for forming a stable chelating coordination structure, the chelating efficiency is low, and the heavy metal fly ash chelating agent is easily influenced by factors such as PH (potential of hydrogen) to generate the analysis and separation of heavy metal ions.
Disclosure of Invention
Therefore, the heavy metal chelating agent with the dendritic Dendrimer molecular structure and the polythio carbamate functional group and the preparation method thereof solve the problems that the density of the coordination sulfur functional group is relatively low, the micromolecules of the heavy metal fly ash chelating agent are in a comb-shaped linear molecular structure, the space configuration is not favorable for forming a stable chelating coordination structure, the chelating efficiency is low, the heavy metal ions are easy to be analyzed and separated under the influence of factors such as PH and the like in the heavy metal fly ash chelating agent widely used in the prior art, and have efficient chelating effect on heavy metals in sewage and wastewater.
According to the technical scheme provided by the invention, the heavy metal chelating agent with the dendritic Dendrimer molecular structure is applied to sewage and solid waste, and has the advantages that polyamine PA is taken as a molecular structure core, and a plurality of groups of dithiocarbamate functional groups are grafted on a molecular branch chain and the tail end to form a molecular cavity with a six-membered ring structure and a branch chain winding structure.
According to another technical scheme provided by the invention, the heavy metal chelating agent with the dendritic Dendrimer molecular structure is prepared by taking cyanuric chloride and ethylenediamine as raw materials and sequentially and repeatedly performing addition reaction to synthesize the polyamine PA molecular structure core with the dendritic Dendrimer multi-branch structure.
Preferably, the molecular structure of the dendritic Dendrimer takes polyamine PA as a molecular structure core, and a plurality of groups of dithiocarbamate functional groups are grafted on molecular branched chains and the tail ends; the polyamine PA molecular structure core with the dendritic Dendrimer multi-branch structure is synthesized by taking cyanuric chloride and ethylenediamine as raw materials and sequentially and repeatedly carrying out addition reaction.
Preferably, the polyamine molecular structure core is one of polyamine PA of 1.0 generation and all the above integral generations synthesized by grafting chloramine on the basis of ethylenediamine as an initial molecular architecture, or one of polyamine PA of 0.5 generation and all the above semi-generations synthesized by grafting ethylenediamine on the basis of the initial molecular architecture.
The invention also provides a technical scheme, and the preparation method of the heavy metal chelating agent comprises the following steps:
s1: preparation of dendritic Dendrimer molecular structure core
The polyamine PA molecular structure core is synthesized by adopting a synthesis route I or a synthesis route II, wherein the synthesis route I is to graft chloramine on the basis of taking ethylenediamine as an initial molecular architecture, and the synthesis route II is to graft ethylenediamine on the basis of taking the chloramine as the initial molecular architecture;
s2: preparation of heavy metal chelating agent with dendritic Dendrimer molecular structure and polysulfide carbamate functional group
And (4) adding the polyamine PA prepared in the step S1 into a strong alkali solution, and adding carbon disulfide for reaction to obtain the heavy metal chelating agent with the dendritic Dendrimer molecular structure and the polythiocarbamate functional group.
Preferably, in the synthetic route (i),
synthesis of polyamine PA of 0.5 Generation/Generation dendritic Dendrimer Multi-branched Structure:
adding a solvent and the melamine into a reaction container, stirring until the solvent and the melamine are dissolved, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dropwise adding the mixed solution of ethylenediamine and a solvent into a reaction container, controlling the reaction temperature to be within the range of 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5;
1.0 Generation Synthesis of polyamine PA with dendritic Dendrimer Multi-branched Structure:
adding a solvent and ethylenediamine into a reaction container, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of 0.5 Generation/Generation polyamine PA-0.5 and a solvent into a reaction container, controlling the reaction temperature to be in the range of 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product;
so as to alternately carry out addition reaction of cyanuric chloride and ethylenediamine, and sequentially synthesize 1.5 Generation/Generation, 2.0 Generation/Generation, 2.5 Generation/Generation and 3.0 Generation/Generation polyamine;
in the synthesis reaction of the terminally substituted polyamine, a terminal grafting reaction is carried out with a polyamine.
Preferably, in the synthesis route (II),
synthesis of polyamine PA of 0.5 Generation/Generation dendritic Dendrimer Multi-branched Structure:
adding a solvent and ethylenediamine into a reaction container, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of the melamine and the solvent into a reaction container from a dropping funnel, controlling the reaction temperature to be 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5;
1.0 Generation Synthesis of polyamine PA with dendritic Dendrimer Multi-branched Structure:
adding a solvent and the melamine into a reaction container, stirring until the solvent and the melamine are dissolved, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of 0.5 Generation/Generation polyamine PA-0.5 and a solvent into a reaction container, controlling the reaction temperature to be in the range of 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5;
so as to alternately carry out addition reaction of cyanuric chloride and ethylenediamine, and sequentially synthesize 1.5 Generation/Generation, 2.0 Generation/Generation, 2.5 Generation/Generation and 3.0 Generation/Generation polyamine;
in the synthesis of the most terminal semi-polyamine, a terminal grafting reaction is carried out with a polyamine.
Preferably, the solvent is ethanol and/or isopropanol; the catalytic acid-binding agent is one or two of sodium ethoxide, sodium hydroxide and potassium hydroxide.
Preferably, the side reaction is controlled by regulating and controlling the reaction feeding proportion, the reaction rate, the feeding mode and the solvent proportion.
Preferably, the reaction process of step S2 is: adding water into a reaction kettle, adding strong base under the stirring condition to dissolve the mixture to form alkali liquor, cooling the alkali liquor to the normal temperature, adding a mixed solution of polyamine PA with a dendritic Dendrimer multi-branch structure and a cosolvent according to a certain molar ratio, and stirring and dissolving the mixture uniformly; controlling the temperature to be below 25 ℃, slowly adding/dripping carbon disulfide or a carbon disulfide solution into a mixed mother liquor of alkali and polyamine PA by using compressed air under a closed reaction condition, and controlling the dripping/adding speed to control the reaction temperature; continuously reacting for 30-90 min after the dropwise adding is finished, and keeping the reaction temperature between 25 and 35 ℃ and the pressure between 0.05 and 0.1MPa all the time; and after the reaction is finished, releasing the pressure to obtain a product.
Preferably, the reaction molar ratio of the polyamine PA molecular structure core to the carbon disulfide in the preparation reaction is 1: 1-100.
Has the advantages that:
the heavy metal chelating agent with the dendritic Dendrimer molecular structure provided by the invention is applied to sewage and solid waste, the high-efficiency chelation effect of heavy metals in molecules is realized through the space molecular framework and the star-shaped cavity structure of the metal chelating agent, the heavy metals in the waste water and the industrial solid waste are efficiently captured and chelated to form stable flocculation/precipitates, and the heavy metals are not easy to decompose and separate out.
The heavy metal chelating agent with the dendritic Dendrimer molecular structure and the multi-sulfur carbamate functional group provided by the invention has a high-density coordination sulfur functional group, a more advantageous chelating molecular structure and a three-dimensional coordination space configuration, an auxiliary chelating group, low dripping during use, a better heavy metal chelating effect, a high-efficiency chelating effect between the interior of a molecule and heavy metals by utilizing the space molecular framework and the star-shaped cavity structure, and higher chelating efficiency, so that the heavy metal chelating agent has important practical significance and industrial application value.
The metal chelating agent is prepared by using cyanuric chloride and ethylenediamine as initial raw materials and sequentially and repeatedly performing nucleophilic substitution and quaternary ammonium salinization reaction, and compared with the prior art, the obtained metal chelating agent has the following advantages: 1) a multi-branch star structure is formed, and the number of functional groups is more and the density is higher; 2) the chelation of heavy metal can not only utilize the adjacent groups on a single branched chain to carry out the joint chelation of heavy metal, but also utilize the functional groups on different branched chains to carry out the chelation; 3) the chelation mode has higher density of functional units and greatly improves the stability and the action efficiency of heavy metal capture and chelation due to the free activity of molecular branched chains; 4) the molecular cavity or the branched chain winding structure formed by the coordination chelation of the multiple branched chains and the six-membered ring structure in the molecular structure is more favorable for the stability of heavy metals and difficult decomposition and precipitation.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The reagents used in this specification are commercially available products unless otherwise specified.
The heavy metal chelating agent has a dendritic Dendrimer molecular structure, polyamine PA is taken as a molecular structure core, and a plurality of groups of dithiocarbamate functional groups are grafted on a molecular branch chain and the tail end to form a molecular cavity with a six-membered ring structure and a branch chain winding structure. Is favorable for the stability of heavy metal after chelation and is not easy to decompose and separate out.
The polyamine molecular structure core is one of polyamine PA of 1.0 generation and above all integral generations synthesized by grafting chloramine on the basis of taking ethylenediamine as an initial molecular architecture, or one of polyamine PA of 0.5 generation and above all semi-integral generations synthesized by grafting ethylenediamine on the basis of taking the chloramine as the initial molecular architecture.
The preparation method of the heavy metal chelating agent comprises the following steps:
s1 preparation of dendritic Dendrimer multi-branched molecular structure core
Cyanuric chloride and ethylenediamine are used as raw materials, and polyamine PA with a dendritic Dendrimer multi-branch structure is synthesized as a molecular structure core by adopting a mode of sequentially and repeatedly carrying out addition reaction.
The synthetic route is: grafting melamine based on ethylene diamine as initial molecular architecture
Synthesis of polyamine PA of 0.5 Generation/Generation dendritic Dendrimer Multi-branched Structure:
placing a reaction container provided with a stirrer, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an ice-water bath, adding a certain amount of solvent and a certain amount of melamine into the reaction container, stirring until the solvent and the melamine are dissolved, adding a certain amount of catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of ethylenediamine and the solvent into a reaction container from a dropping funnel, controlling the reaction temperature to be within the range of 0-25 ℃, and reacting for 60-90 min; and adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5, shown as a reaction formula I.
1.0 Generation Synthesis of polyamine PA with dendritic Dendrimer Multi-branched Structure:
placing a reaction container provided with a stirrer, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an ice-water bath, adding a certain amount of solvent and a certain amount of ethylenediamine into the reaction container, adding a certain amount of catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping a set amount of 0.5 Generation/Generation polyamine PA-0.5 and a solvent mixed solution into a reaction container from a dropping funnel, controlling the reaction temperature to be within the range of 0-25 ℃, and reacting for 60-90 min; and (3) adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely polyamine PA with a 1.0 Generation/Generation dendritic Dendrimer multi-branch structure, shown in a reaction formula II.
Thus, addition reaction was performed alternately with cyanuric chloride and ethylenediamine to synthesize 1.5 Generation/Generation, 2.0 Generation/Generation, 2.5 Generation/Generation, and 3.0 Generation/Generation polyamines in this order.
In the synthesis of the terminally substituted polyamines, a terminal grafting reaction may be carried out with the polyamines.
The side reaction control is realized by regulating and controlling the reaction feeding proportion, the reaction rate, the feeding mode, the solvent proportion and the like.
A synthesis route II: grafting ethylenediamine based on initial molecular architecture of melamine
Synthesis of polyamine PA of 0.5 Generation/Generation dendritic Dendrimer Multi-branched Structure: placing a reaction vessel equipped with a stirrer, a condenser tube, a thermometer and a constant pressure dropping funnel in ice water
In a bath, adding a certain amount of solvent and a certain amount of ethylenediamine into a reaction container, adding a certain amount of catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping a mixed solution of trimeric chloramine and a solvent with a set amount into a reaction container from a dropping funnel, controlling the reaction temperature to be within the range of 0-25 ℃, and reacting for 60-90 min; and adding a catalytic acid-binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5, shown as a reaction formula III.
1.0 Generation Synthesis of polyamine PA with dendritic Dendrimer Multi-branched Structure:
placing a reaction container provided with a stirrer, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an ice-water bath, adding a certain amount of solvent and a certain amount of melamine into the reaction container, stirring until the solvent and the melamine are dissolved, adding a certain amount of catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of 0.5 Generation/Generation polyamine PA-0.5 and a solvent into a reaction container from a dropping funnel, controlling the reaction temperature to be in the range of 0-25 ℃, and reacting for 60-90 min; and adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 1.0 Generation/Generation polyamine PA-1.0, shown as a reaction formula IV.
Thus, the addition reaction of cyanuric chloride and ethylenediamine was alternated to synthesize 1.5 Generation/Generation (see reaction formula V), 2.0 Generation/Generation, 2.5 Generation/Generation, and 3.0 Generation/Generation polyamines, in that order.
In the synthesis of the terminally substituted polyamines, a terminal grafting reaction may be carried out with the polyamines.
The side reaction control is realized by regulating and controlling the reaction feeding proportion, the reaction rate, the feeding mode, the solvent proportion and the like. The addition reaction of the melamine and the ethylenediamine, wherein the two raw materials are symmetrical structures with a plurality of graftable reaction sites. The main side reaction is that the grafting reaction is carried out at the molecular position which is not designed according to the patent in the reaction process, but the grafting position of the addition reaction can be controlled by controlling the material molar ratio, the material adding mode and the adding speed by considering the factors such as the steric hindrance of the reaction and the like. For example: in the technical scheme 1, the molar ratio of ethylenediamine to cyanuric chloride is 1:4, and the feeding mode is that ethylenediamine is slowly dripped into cyanuric chloride to ensure that ethylene diamine tetra-homosite hydrogen atoms are subjected to saturated grafting; in the technical scheme 2, the molar ratio of the ethylenediamine to the cyanuric chloride is 3:1, and the cyanuric chloride is slowly dripped into the ethylenediamine, so that the saturated grafting of three chlorine atoms of the cyanuric chloride is ensured. The side reaction is avoided while the reaction is fully carried out.
2) Preparation of heavy metal chelating agent with dendritic Dendrimer molecular structure and polysulfide carbamate functional group
Adding water into a reaction kettle, adding a certain amount of strong base under the stirring condition to dissolve the mixture to form an alkali liquor, cooling to normal temperature, adding a certain amount of polyamine PA and cosolvent mixed liquor with a dendritic Dendrimer multi-branch structure according to a certain molar ratio, and uniformly stirring and dissolving; controlling the temperature below 25 ℃, slowly adding/dripping carbon disulfide or a carbon disulfide solution into a mixed mother liquor of alkali and polyamine PA by using compressed air under a closed reaction condition, and controlling the dripping/adding speed to control the reaction temperature. And after the dropwise addition is finished, continuing the reaction for 30-90 min, and keeping the reaction temperature between 25 and 35 ℃ and the pressure between 0.05 and 0.1MPa all the time. And after the reaction is finished, releasing the pressure to obtain a product.
The synthetic route is: the heavy metal chelating agent synthesized by using the whole generation polyamine PA formed by grafting the melamine on the basis of the initial molecular architecture as a molecular structure core is shown in a reaction formula VI.
A synthesis route II: the heavy metal chelating agent synthesized by taking semi-generation polyamine PA formed by grafting ethylenediamine on the basis of the original molecular architecture as a molecular structure core is shown in a reaction formula VII and a reaction formula VIII.
The preferable molecular structure core of the polyamine PA with the Dendrimer molecular structure is polyamine PA with 1.0 generation and all the integral generations in the synthesis route I and polyamine PA with 0.5 generation and all the semi-generations in the synthesis route II.
The preferable solvent of the invention is one or two compounds of ethanol and isopropanol, and the compounding proportion is arbitrary.
The preferable cosolvent of the invention is one or two compounds of ethanol and isopropanol, and the compounding proportion is arbitrary.
The preferable catalytic acid-binding agent is one or two compounds of sodium ethoxide, sodium hydroxide and potassium hydroxide, and the compound proportion is arbitrary.
According to the invention, the reaction molar ratio of the core PA of the preferable preparation reaction molecular structure to the carbon disulfide is within the range of 1: 1-100, preferably 1: 1-64, and more preferably 1: 12-48 according to different reaction generations; further preferably, the reaction molar ratio of the molecular structure core PA, the carbon disulfide and the sodium hydroxide is in the range of 1: 1-100.
The preferred strong base in the invention is one of sodium hydroxide and potassium hydroxide.
The preferable polyamine which can be used for synthesizing the molecular structure core polyamine PA molecule and grafted at the tail end is one or more compounds of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine and polyethylene polyamine, and the compound proportion is arbitrary.
The heavy metal chelating agent synthesized by taking the whole generation (1.0G) PA as a molecular structure core and the chelating action of the heavy metal are shown in the following formula IX.
The chelating action of the heavy metal chelating agent synthesized by the molecular structure core synthesized by half-generation PA and the heavy metal is shown in formula X for the chelating action of the metal chelating agent prepared by using 0.5 generation GenerationPA as the molecular structure core and formula XI for the chelating action of the metal chelating agent prepared by using 1.5 generation GenerationPA as the molecular structure core through the synthesis route (II).
According to the dendritic Dendrimer molecular structure, the molecular branched chain and the multi-thio carbamate functional group grafted on the tail end of the molecular branched chain greatly improve the density of the coordination sulfur functional group.
The dendritic Dendrimer molecular structure provided by the invention has a molecular structure and a spatial configuration which are more beneficial to heavy metal chelation, widely used micromolecules or chelating agents with comb-shaped and linear molecular structures, and the heavy metal chelation efficiency and stability realized in the space star-shaped structure molecule are improved.
The dendritic Dendrimer molecular structure provided by the invention has a molecular cavity, and has excellent electron coordination and auxiliary chelation stabilization effects on heavy metals.
The invention has the advantages of better adaptability to PH value and low risk of secondary pollution by analysis and separation due to the monomolecular chelation mode and the cavity coordination-assisted chelation stabilization.
The chelating agent has higher chelating efficiency, low dripping during use and better chelating effect on heavy metals.
Example 1
Referring to the preparation method, the synthesis route is as follows: the method takes ethylenediamine as an initial molecular architecture to graft the chloramine for Generation-by-Generation addition reaction, and synthesizes 1.0 Generation of Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is as follows: the molar ratio of the initial ethylenediamine to the melamine reaction is 1: 4; the reaction molar ratio of 0.5 Generation polyamine PA to ethylene diamine is 1: 8.
The whole Generation 1.0 Generation polyamine PA is used as a molecular structure core, and reacts with strong alkali liquor and carbon disulfide to prepare the multi-branched dithiocarbamate heavy metal chelating agent. According to the weight ratio of PAG-1.0, carbon disulfide and sodium hydroxide 1:24:24, carrying out synthetic reaction to prepare the heavy metal chelating agent.
Example 2
Referring to the preparation method, the synthesis route is as follows: the method takes ethylenediamine as an initial molecular architecture to graft the chloramine for Generation-by-Generation addition reaction, and synthesizes 1.0 Generation of Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the reaction molar ratio of the initial ethylenediamine to the melamine is 1: 4; the reaction molar ratio of 0.5 Generation polyamine PA to ethylene diamine is 1: 8.
The whole Generation 1.0 Generation polyamine PA is used as a molecular structure core, and reacts with strong alkali liquor and carbon disulfide to prepare the multi-branched dithiocarbamate heavy metal chelating agent. According to the weight ratio of PAG-1.0, carbon disulfide and sodium hydroxide 1:12:12, carrying out synthetic reaction to prepare the heavy metal chelating agent.
Example 3
Referring to the preparation method, according to a synthesis route II: the method takes melamine as an initial molecular architecture and is used for grafting ethylenediamine addition reaction to synthesize 0.5 Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the initial reaction molar ratio of the melamine to the ethylenediamine is 1: 3.
Taking 0.5 Generation polyamine PA as a molecular structure core, and reacting with strong alkali liquor and carbon disulfide to prepare the dithiocarbamate heavy metal chelating agent with a multi-branch structure. According to the weight ratio of PAG-0.5, carbon disulfide and sodium hydroxide 1: 9: 9, the synthesis reaction is carried out.
Example 4
Referring to the preparation method, according to a synthesis route II: the method takes melamine as an initial molecular architecture and grafts ethylenediamine to carry out successive addition reaction to synthesize 1.5 Generation of Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the initial reaction molar ratio of the melamine to the ethylenediamine is 1: 3; the reaction molar ratio of 0.5 Generation polyamine PA to the melamine is 1: 3; the reaction molar ratio of the 1.0 Generation polyamine PA to the ethylene diamine is 1: 6.
Taking 1.5 Generation polyamine PA as a molecular structure core, and reacting with strong alkali liquor and carbon disulfide to prepare the dithiocarbamate heavy metal chelating agent with a multi-branch structure. According to the molar ratio of PAG-1.5, carbon disulfide and sodium hydroxide of 1:24:24, the preparation of the catalyst is carried out by synthetic reaction.
Example 5
Referring to the preparation method, according to a synthesis route II: the method takes melamine as an initial molecular architecture and grafts ethylenediamine to carry out successive addition reaction to synthesize 1.5 Generation of Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the initial reaction molar ratio of the melamine to the ethylenediamine is 1: 3; the reaction molar ratio of 0.5 Generation polyamine PA to the melamine is 1: 3; the reaction molar ratio of the 1.0 Generation polyamine PA to the ethylene diamine is 1: 6.
Taking 1.5 Generation polyamine PA as a molecular structure core, and reacting with strong alkali liquor and carbon disulfide to prepare the dithiocarbamate heavy metal chelating agent with a multi-branch structure. According to the mole ratio of PAG-1.5, carbon disulfide and sodium hydroxide of 1:12:12, carrying out synthetic reaction.
Example 6
Referring to the preparation method, the synthesis route is as follows: the method takes ethylenediamine as an initial molecular architecture to graft the chloramine for Generation-by-Generation addition reaction, and synthesizes 2.0 Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the reaction molar ratio of the initial ethylenediamine to the melamine is 1: 4; the reaction molar ratio of 0.5 Generation polyamine PA to ethylene diamine is 1: 8; 1.0 Generation polyamine PA and melamine reaction molar ratio is 1: 8; the reaction molar ratio of 1.5 Generation polyamine PA to ethylene diamine is 1: 8.
The whole Generation 2.0 Generation polyamine PA is used as a molecular structure core, and reacts with strong alkali liquor and carbon disulfide to prepare the multi-branched dithiocarbamate heavy metal chelating agent. According to the weight ratio of PAG-2.0, carbon disulfide and sodium hydroxide 1:36:36, and carrying out synthetic reaction to obtain the heavy metal chelating agent.
Example 7
Referring to the preparation method, the synthesis route is as follows: the method takes ethylenediamine as an initial molecular architecture to graft the chloramine for Generation-by-Generation addition reaction, and synthesizes 3.0 Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the reaction molar ratio of the initial ethylenediamine to the melamine is 1: 4; the reaction molar ratio of 0.5 Generation polyamine PA to ethylene diamine is 1: 8; 1.0 Generation polyamine PA and melamine reaction molar ratio is 1: 8; 1.5 Generation polyamine PA and ethylene diamine reaction molar ratio is 1: 8; 2.0 Generation polyamine PA and melamine reaction molar ratio is 1: 8; the reaction molar ratio of 2.5 Generation polyamine PA to ethylene diamine is 1: 8.
The whole Generation 3.0 Generation polyamine PA is used as a molecular structure core, and reacts with strong alkali liquor and carbon disulfide to prepare the multi-branched dithiocarbamate heavy metal chelating agent. According to the weight ratio of PAG-3.0, carbon disulfide and sodium hydroxide 1: 48: 48, and carrying out synthetic reaction to obtain the heavy metal chelating agent.
Example 8
Referring to the preparation method, according to a synthesis route II: the method takes melamine as an initial molecular architecture and grafts ethylenediamine to carry out successive addition reaction, so as to synthesize 2.5-Generation polyamine PA with a dendritic Dendrimer multi-branch structure as a molecular structure core. The reaction route is that the initial reaction molar ratio of the melamine to the ethylenediamine is 1: 3; the reaction molar ratio of 0.5 Generation polyamine PA to the melamine is 1: 3; 1.0 Generation polyamine PA and ethylenediamine reaction molar ratio is 1: 6; 1.5 Generation polyamine PA and melamine reaction molar ratio is 1: 6; the reaction molar ratio of 2.0 Generation polyamine PA to ethylene diamine is 1: 6.
Taking 2.5 Generation polyamine PA as a molecular structure core, and reacting with strong alkali liquor and carbon disulfide to prepare the multi-branched dithiocarbamate heavy metal chelating agent. According to the molar ratio of PAG-2.5, carbon disulfide and sodium hydroxide of 1:36:36, the preparation method is carried out by synthetic reaction.
Detection test
Taking fly ash of a certain waste incineration fly ash disposal project in river of Cangzhou city of Hebei province as an example, 1-5 of the invention embodiment/product and common DTC heavy metal chelating agent sodium thiram are respectively added into the original fly ash according to the proportion of fly ash: heavy metal chelating agent: water = 1: 0.025 to 0.03: adding the mixture in the range of 0.15-0.25, uniformly stirring, and standing for 24 hours in a natural state. Then, the performance is verified according to HJ/T300-2007 'solid waste heavy metal leaching toxic acetic acid buffer leaching method', GB16889-2008 'pollution control standard of domestic waste landfill', and the data conditions are shown in the following tables 1 and 2:
table 1 examples 1-8 chelator molecular design structures
TABLE 2 post-treatment leaching toxicity test of stabilization/chelation treatment of fly ash from incineration of garbage in Hebei province, Cangzhou city, Hezhou city
As can be seen from the data in tables 1 and 2, the molecular DTC heavy metal chelating agent sodium ferforth has very obvious stabilizing effect and action efficiency, the lower limit concentration of chelation is low, and multiple parameter indexes are 1-2 orders of magnitude lower than the limit of GB16889-2008 'pollution control Standard for municipal solid waste landfill'.
And (3) taking the simulated heavy metal water sample as experimental water, and respectively preparing 10-100 mg/L heavy metal water samples containing mercury, copper, zinc, lead, cadmium, chromium and nickel for detection. The heavy metal chelating agent of the embodiment/product 1-5 of the invention is added into a heavy metal water sample respectively, the heavy metal chelating agent is added according to the range of 50-1000 mg/L, the mixture is stirred uniformly and then stands for 30 min-2 h in a natural state, and performance verification is carried out, wherein the data conditions are shown in the following table 3.
TABLE 3 results of treatment of simulated heavy metal water samples (unit: mg/L) with inventive examples/products 1-5
As is clear from the results in Table 3, the metal chelate agent of the present invention can achieve excellent treatment effects even when used for treating heavy metal water samples.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The heavy metal chelating agent with the dendritic Dendrimer molecular structure is characterized in that cyanuric chloride and ethylenediamine are used as raw materials, and addition reaction is sequentially repeated to synthesize a polyamine PA molecular structure core with the dendritic Dendrimer multi-branch structure.
2. The heavy metal chelator of claim 1, wherein said polyamine PA molecular structure core is one of 1.0 and all the above total polyamine PA synthesized by grafting chloramine on ethylenediamine as a base of an initial molecular architecture, or one of 0.5 and all the above half-total polyamine PA synthesized by grafting ethylenediamine on the base of an initial molecular architecture.
3. The preparation method of the heavy metal chelating agent with the dendritic Dendrimer molecular structure is characterized by comprising the following steps:
s1: preparation of dendritic Dendrimer molecular structure core
The polyamine PA molecular structure core is synthesized by adopting a synthesis route I or a synthesis route II, wherein the synthesis route I is to graft chloramine on the basis of taking ethylenediamine as an initial molecular architecture, and the synthesis route II is to graft ethylenediamine on the basis of taking the chloramine as the initial molecular architecture;
s2: preparation of heavy metal chelating agent with dendritic Dendrimer molecular structure and polysulfide carbamate functional group
And (4) adding the polyamine PA prepared in the step S1 into a strong alkali solution, and adding carbon disulfide for reaction to obtain the heavy metal chelating agent with the dendritic Dendrimer molecular structure and the polythiocarbamate functional group.
4. The method for preparing a heavy metal chelator according to claim 3, wherein in scheme I,
synthesis of polyamine PA of 0.5 Generation/Generation dendritic Dendrimer Multi-branched Structure:
adding a solvent and the melamine into a reaction container, stirring until the solvent and the melamine are dissolved, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dropwise adding the mixed solution of ethylenediamine and a solvent into a reaction container, controlling the reaction temperature to be within the range of 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5;
1.0 Generation Synthesis of polyamine PA with dendritic Dendrimer Multi-branched Structure:
adding a solvent and ethylenediamine into a reaction container, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of 0.5 Generation/Generation polyamine PA-0.5 and a solvent into a reaction container, controlling the reaction temperature to be in the range of 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product;
so as to alternately carry out addition reaction of cyanuric chloride and ethylenediamine, and sequentially synthesize 1.5 Generation/Generation, 2.0 Generation/Generation, 2.5 Generation/Generation and 3.0 Generation/Generation polyamine;
in the synthesis reaction of the terminally substituted polyamine, a terminal grafting reaction is carried out with a polyamine.
5. The method for preparing a heavy metal chelator according to claim 3, wherein in scheme (II),
synthesis of polyamine PA of 0.5 Generation/Generation dendritic Dendrimer Multi-branched Structure:
adding a solvent and ethylenediamine into a reaction container, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of the melamine and the solvent into a reaction container from a dropping funnel, controlling the reaction temperature to be 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5;
1.0 Generation Synthesis of polyamine PA with dendritic Dendrimer Multi-branched Structure:
adding a solvent and the melamine into a reaction container, stirring until the solvent and the melamine are dissolved, adding a catalytic acid-binding agent, and uniformly mixing until the pH value is 9-9.5; slowly dripping the mixed solution of 0.5 Generation/Generation polyamine PA-0.5 and a solvent into a reaction container, controlling the reaction temperature to be in the range of 0-25 ℃, and reacting for 60-90 min; adding a catalytic acid binding agent for the second time, uniformly mixing, raising the pH to 9-9.5, carrying out reflux reaction for 1-4 hours at the temperature of 60-90 ℃, and carrying out suction filtration to remove the solvent to obtain a product, namely 0.5 Generation/Generation polyamine PA-0.5;
so as to alternately carry out addition reaction of cyanuric chloride and ethylenediamine, and sequentially synthesize 1.5 Generation/Generation, 2.0 Generation/Generation, 2.5 Generation/Generation and 3.0 Generation/Generation polyamine;
in the synthesis of the most terminal semi-polyamine, a terminal grafting reaction is carried out with a polyamine.
6. The method for preparing a heavy metal chelator according to claim 4 or 5, wherein the solvent is ethanol and/or isopropanol; the catalytic acid-binding agent is one or two of sodium ethoxide, sodium hydroxide and potassium hydroxide.
7. The method for preparing a heavy metal chelating agent according to claim 4 or 5, wherein the side reaction is controlled by controlling the reaction feeding proportion, the reaction rate, the feeding mode and the solvent proportion.
8. The method for producing a heavy metal chelate agent according to claim 3,
the reaction process of step S2 is: adding water into a reaction kettle, adding strong base under the stirring condition to dissolve the mixture to form alkali liquor, cooling the alkali liquor to the normal temperature, adding a mixed solution of polyamine PA with a dendritic Dendrimer multi-branch structure and a cosolvent according to a certain molar ratio, and stirring and dissolving the mixture uniformly; controlling the temperature to be below 25 ℃, slowly adding/dripping carbon disulfide or a carbon disulfide solution into a mixed mother liquor of alkali and polyamine PA by using compressed air under a closed reaction condition, and controlling the dripping/adding speed to control the reaction temperature; continuously reacting for 30-90 min after the dropwise adding is finished, and keeping the reaction temperature between 25 and 35 ℃ and the pressure between 0.05 and 0.1MPa all the time; and after the reaction is finished, releasing the pressure to obtain a product.
9. The method for preparing a heavy metal chelating agent according to claim 3, wherein the reaction molar ratio of the polyamine PA molecular structure core to the carbon disulfide in the preparation reaction is 1: 1-100.
10. The application of the heavy metal chelating agent with the dendritic Dendrimer molecular structure in sewage and solid waste is characterized in that the heavy metal chelating agent is the heavy metal chelating agent in claim 1 or 2.
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