CN102060995B - Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin - Google Patents
Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin Download PDFInfo
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Abstract
The invention relates to a method for preparing heavy metal chelating resin, in particular to a method for preparing silica gel supported dithiocarbamate heavy metal chelating resin and adsorption of heavy metals such as lead, cadmium, copper, mercury and the like by the resin. The method comprises the following steps of: reacting carbon disulfide with a polyamine compound to generate a dithiocarbamate compound; and grafting the dithiocarbamate compound onto the surface of silicon dioxide, wherein a halogen group is modified on the surface of the silicon dioxide. By the method, the adsorption capacity of dithiocarbamate chelating resin is effectively improved; and the problem that silica gel is dissolved due to too high alkalinity of a reaction system (pH value is more than 11), or the dithiocarbamate compound cannot be generated through reaction due to too low alkalinity (the pH value is less than 10) when a dithiocarbamate functional group is prepared by reacting the silica gel with the carbon disulfide in the conventional synthetic route is solved, wherein an amino group is modified on the surface of the silica gel.
Description
Technical field
The present invention relates to the preparation method of a heavy metal chelating resin, particularly a kind of silica gel load MGD heavy metal chelate resin preparation method and to the absorption of heavy metals such as lead, cadmium, copper, mercury.
Background technology
Heavy metal is difficult in environment by metabolism because toxicity is big, is prone to by biomagnification and biological amplification is arranged, and is not only serious to water pollution, also serious threat human and animal's existence.To the water body of heavy metal contamination, adoptable treatment technology has chemical precipitation, r-o-, electrowinning, IX and absorption method etc.In these methods, absorption method has the characteristics of high efficiency, easy and simple to handle, environmentally safe and receives widely and paying close attention to.Resin is a kind of as sorbing material, advantage such as have the preparation of being easy to, adsorptive capacity is high, reusable.
The dithiocarbamate(s) organism can form the very high inner complex of stability constant with many heavy metal ion; Extremely strong to the sequestering power of heavy metal ion such as mercury, lead, cadmium, copper especially; And not with basic metal and earth alkali metal chelating, so it is widely used in from environment removing and the enriching heavy metal ion.The MGD resin of bibliographical information adopts SE, PS, polyethers more, contains the hydrophobicity skeletons such as polymkeric substance of polyamines polyene; When can causing sequestrant in the aqueous solution, to use, this is difficult to by the solvent quick humidification; Ion is obstructed in the sequestrant internal divergence; Rate of adsorption and efficient (B.Mathew, V.N.R.Pillai, Divinylhcnzene crosslinkedpolyacrylamide-supported dithocarbamates as metal complexing agents have been reduced; Polymer Bulled.1991,26:603-610A; Denizlia; K.Kesenci; Dithiocarbamate-incorporated monosizepolystyrene microspheres for selective removal of mercury ions, Reactive & FunctionalPolymers.2000,44:235-243).Therefore, the absorption that this resinoid is used for the water body heavy metal has received certain restriction.
Inorganic/the organic materials that with silica gel is matrix is one of focus of current research; This be since silica gel except have excellent mechanical intensity and higher chemicalstability, the thermostability; Also having outstanding characteristics is exactly that its surface is contained abundant silicon hydroxyl and made the silica gel matrix have good hydrophilicity, has improved the absorption property of resin greatly.The compound method of the silica gel load MGD resin of bibliographical information is mainly the grafting method; Promptly earlier at silica gel finishing amino group; Again under alkaline condition; Make amino the reaction generate MGD functional group (K.A.Venkatesan, T.G.Srinivasan, Removal of complexed mercury from aqueous solutionsusing dithiocarbamate grafted on silica gel with dithiocarbonic anhydride; Sep.Sci.Technol.2002,37:1417-1429; K.Dimos; P.Stathi, M.A.Karakassides, Synthesis and characterization of hybrid MCM-41materials for heavy metal adsorption; Microporous Mesoporous.Mater.2009,126:65-71).We discover, adopt this synthetic route that the pH value of reaction system is had strict requirement, and alkalescence too high (the pH value is greater than 11) can make the silica gel dissolving, and alkalescence low excessively (the pH value is lower than 10) almost can not be reacted and generated MGD functional group.Mostly the aminocompound with the dithiocarbonic anhydride reaction of bibliographical information is the polyamine substance of small molecular weight; Like quadrol, diethylenetriamine, triethylene tetramine etc.; Adopt the synthetic MGD number of functional groups that obtains of these materials not high; Cause the low (M.E.Mahmoud of resin adsorptive capacity; Selective solid phase extraction ofmercury (II) by silica gel-immobilized-dithiocarbamate derivatives, Anal.Chim.Acta.1999,398:297-304; S.G.Renaudin, R.Schneiderb, A.Walcarius, Synthesis of newdithiocarbamate-based organosilanes for grafting on silica, Tetrahedron Lett.2007,48:2113-2116).
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of silica gel load MGD heavy metal chelate resin; Can effectively improve the adsorptive capacity of MGD resin, also overcome state too harsh in the existing process method to a certain extent the pH requirement.
Technical scheme of the present invention is: the present invention adopts and makes polyamine compounds and dithiocarbonic anhydride at OH earlier
-Concentration is to generate MGD under the highly basic condition of 350～500g/L, again the MGD that generates is grafted to the silica gel surface that halogen atom is modified.
Said polyamine compounds comprises a kind of in triethylene tetramine, matter average molecular weight 1000～10000 polymines or matter average molecular weight 1000～10000 polypropylene amines.
What in the silica gel process that halogen atom is modified, adopt is 80～140 ℃ of inert organic solvents, system temperatures with activated silica gel and halogen atom-containing silane coupling agent; Nitrogen atmosphere down reaction obtains, and described inert organic solvents is a kind of in hexanaphthene, heptane, toluene, the YLENE.
Most preferred reaction conditions is that reaction pH value is 8～11 in the process of grafting, and temperature of reaction is 55～65 ℃, and the reaction times is 5～10 hours.
Method of the present invention is with the preparation synthetic route of silica gel load MGD heavy metal chelate resin; Again design through the contriver; Thereby can effectively improve the adsorptive capacity of resin; When having avoided silica gel and the dithiocarbonic anhydride prepared in reaction MGD functional group of finishing amino group in the existing synthetic route simultaneously; Because of reaction system alkalescence too high (the pH value is greater than 11) causes the silica gel dissolving, or alkalescence low excessively (the pH value is lower than 10) can not be reacted generation MGD compound.
The preparation method of a kind of silica gel load MGD heavy metal chelate resin of the present invention, concrete steps are:
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml inert organic solvents that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 80～140 ℃; 80ml inert organic solvents and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 80～140 ℃ of system temperatures, the nitrogen atmosphere 24～48h that refluxes in the entire reaction course.Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml polyamine compounds and 100ml anhydrous methanol and join in the 500ml three-necked bottle mechanical stirring under the ice bath.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 12～24h.Suction filtration obtained the solid-like product after reaction was accomplished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the MGD compound.
(4) get the MGD compound 10g that step (3) obtains and in the 500ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 8～11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 40～60 ℃, mechanical stirring reaction 5～10h.Suction filtration obtained solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load MGD resin.
The said inert organic solvents of step (2) comprises a kind of in hexanaphthene, heptane, toluene, the YLENE.
The said polyamine compounds of step (3) comprises triethylene tetramine, polymine (matter average molecular weight 1000; The 50wt.% aqueous solution; The rich chemical industry ltd of Hubei match) a kind of or in the polypropylene amine (matter average molecular weight 3000, the 50wt.% aqueous solution, the rich chemical industry ltd of Hubei match).
Advantage of the present invention and positively effect are; The inventive method provides a kind of loading capacity big (metal ions M (II) adsorptive capacity can reach 0.4mmol/g, has improved 2～3 times than the adsorptive capacity of the MGD resin of existing silica gel load), physical strength is good, dynamic performance is good silica gel load MGD heavy metal chelate resin and preparation method thereof.The product for preparing through present method; Not only effectively improved the adsorptive capacity of MGD resin; When also having overcome silica gel and the dithiocarbonic anhydride prepared in reaction MGD functional group of finishing amino group in the existing synthetic route; Because of reaction system alkalescence too high (the pH value is greater than 11) causes the silica gel dissolving, or alkalescence low excessively (the pH value is lower than 10) can not be reacted generation MGD compound.
Embodiment
Following embodiment is intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1 adopts the different inert organic solvent to prepare silica gel load MGD resin
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, 150ml hexanaphthene, heptane, toluene or the YLENE that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 80～140 ℃; 80ml hexanaphthene, heptane, toluene or YLENE and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keep 80～140 ℃ of system temperatures, the nitrogen atmosphere 24～48h that refluxes in the entire reaction course.Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml polymine (matter average molecular weight 1000, the 50wt.% aqueous solution) and join in the 500ml three-necked bottle mechanical stirring under the ice bath with the 100ml anhydrous methanol.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 24h.Suction filtration obtained the solid-like product after reaction was accomplished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the MGD compound.
(4) get the MGD compound 10g that step (3) obtains and in the 500ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH=11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 60 ℃, mechanical stirring reaction 10h.Suction filtration obtained solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load MGD resin.
Table 1 adopts the silica gel load MGD resin of different inert organic solvent preparation and the relation of heavy metal ion adsorbed amount
Embodiment 2 adopts different polyamine compounds to prepare silica gel load MGD resin
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml triethylene tetramine, polymine (matter average molecular weight 1000, the 50wt.% aqueous solution) or polypropylene amine (matter average molecular weight 3000, the 50wt.% aqueous solution) and join in the 500ml three-necked bottle mechanical stirring under the ice bath with the 100ml anhydrous methanol.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 12～24h.Suction filtration obtained the solid-like product after reaction was accomplished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the MGD compound.
(4) get the MGD compound 10g that step (3) obtains and in the 250ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH=11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 60 ℃, mechanical stirring reaction 10h.Suction filtration obtained solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load MGD resin.
Table 2 adopts the silica gel load MGD resin of polyamine compounds preparation and the relation of heavy metal ion adsorbed amount
The different pH value preparation of embodiment 3 control reaction systems silica gel load MGD resin
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml polymine (matter average molecular weight 1000, the 50wt.% aqueous solution) and join in the 500ml three-necked bottle mechanical stirring under the ice bath with the 100ml anhydrous methanol.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 24h.Suction filtration obtained the solid-like product after reaction was accomplished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the MGD compound.
(4) get the MGD compound 10g that step (3) obtains and in the 250ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 8～11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 60 ℃, mechanical stirring reaction 5～10h.Suction filtration obtained solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load MGD resin.
The silica gel load MGD resin of the different pH value preparations of table 3 control reaction system and the relation of heavy metal ion adsorbed amount
Comparative Examples 1
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/LHNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get silanized silica gel and the 100ml anhydrous methanol that 10g step (2) obtains and join in the 250ml three-necked bottle, heat temperature raising to 60 ℃.Add the 20ml triethylene tetramine, react 24h under the mechanical stirring.Suction filtration obtains solid product, and this product is used deionized water, 1mol/L sulfuric acid, 1mol/L ammoniacal liquor, methanol wash successively, in 50 ℃ of vacuum-drying 12h, obtains amido modified silica gel.
(4) get amido modified silica gel 10g and the 100ml deionized water that step (3) obtains and place the 500ml three-necked bottle, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 9～12 under the mechanical stirring.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol, dropwise drips under the ice bath to three-necked bottle, continues to stir, and treats that dithiocarbonic anhydride-methanol solution dropwises, and is warming up to 60 ℃ of reaction 24h.Use 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution regulation system pH value 9～12 in the reaction process.Suction filtration got solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this solid product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load MGD resin.
The different pH values of table 4 are triethylene tetramine modified silica-gel and the silica gel load MGD resin of dithiocarbonic anhydride prepared in reaction and the relation of heavy metal ion adsorbed amount down
Comparative Examples 2
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get silanized silica gel and the 100ml anhydrous methanol that 10g step (2) obtains and join in the 250ml three-necked bottle, heat temperature raising to 60 ℃.Add 20ml polymine (matter average molecular weight 1000, the 50wt.% aqueous solution), react 24h under the mechanical stirring.Suction filtration obtains solid product, and this product is used deionized water, 1mol/L sulfuric acid, 1mol/L ammoniacal liquor, methanol wash successively, in 50 ℃ of vacuum-drying 12h, obtains amido modified silica gel.
(4) get amido modified silica gel 10g and the 100ml deionized water that step (3) obtains and place the 500ml three-necked bottle, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 9～12 under the mechanical stirring.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol, dropwise drips under the ice bath to three-necked bottle, continues to stir, and treats that dithiocarbonic anhydride-methanol solution dropwises, and is warming up to 60 ℃ of reaction 24h.Use 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution regulation system pH value 9～12 in the reaction process.Suction filtration got solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this solid product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load MGD resin.
The different pH values of table 5 are polyethylene imine beautify silica gel and the silica gel load MGD resin of dithiocarbonic anhydride prepared in reaction and the relation of heavy metal ion adsorbed amount down
Claims (1)
1. the preparation method of a silica gel load MGD heavy metal chelate resin may further comprise the steps:
(1) gets 30 g chromatograms and fill out post silica gel in 500 ml three-necked bottles, add 1 mol/L HNO
3Solution 200 ml, at 50 ℃ of following mechanical stirring 6 h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12 h obtain activated silica gel;
(2) get activated silica gel, the 150 ml inert organic solvents that 20 g steps (1) obtain and be added to 500 ml three-necked bottles, mechanical stirring, the oil bath heating makes reaction system be warming up to 80 ~ 140 ℃; 80 ml inert organic solvents and dropwise splash into three-necked bottle after 20 ml γ-the chloropropyl triethyl silicane mixes keep 80 ~ 140 ℃ of system temperatures, nitrogen atmosphere 24 ~ 48 h that reflux in the entire reaction course; Suction filtration obtained solid product after reaction was accomplished, and it is extracted 6 h with methyl alcohol Suo Shi, and the suction filtration solid product in 50 ℃ of vacuum-drying 12 h, obtains silanized silica gel;
(3) get 20 ml polyamine compounds and 100 ml anhydrous methanols and join in the 500 ml three-necked bottles mechanical stirring under the ice bath; Get sodium hydroxide 30 g and be dissolved in 100 ml deionized waters, the stirring and dissolving postcooling is to room temperature; Other gets 50 ml dithiocarbonic anhydride and is dissolved in 100 ml methyl alcohol; Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃; Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 12 ~ 24 h; Suction filtration obtained the solid-like product after reaction was accomplished, and this product is washed the back in 50 ℃ of vacuum-drying 12 h with anhydrous methanol, obtained the MGD compound;
(4) get MGD compound 10 g that step (3) obtains and in 500 ml three-necked bottles, be dissolved in 200 ml deionized waters, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 8 ~ 11; Add the silanized silica gel that 10 g steps (2) obtain, be warming up to 40 ~ 60 ℃, mechanical stirring reaction 5 ~ 10h; Suction filtration obtained solid product after reaction was accomplished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12 h, obtained silica gel load MGD resin;
The said inert organic solvents of step (2) comprises a kind of in hexanaphthene, heptane, toluene, the YLENE;
The said polyamine compounds of step (3) comprises a kind of in triethylene tetramine, polymine or the polypropylene amine; What described polymine adopted is to be matter average molecular weight 1000, the 50 wt.% aqueous solution, and what described polypropylene amine adopted is matter average molecular weight 3000, the 50 wt.% aqueous solution.
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| CN101215250A (en) * | 2007-12-28 | 2008-07-09 | 上海电力学院 | Chelating agent containing double DTC group and preparation method thereof |
| CN101759809A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing dithiocarbamate-based modified porous starch |
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