CN102276735B - Cellulose multifunctional chelating material, and its preparation method - Google Patents
Cellulose multifunctional chelating material, and its preparation method Download PDFInfo
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- CN102276735B CN102276735B CN2011101244616A CN201110124461A CN102276735B CN 102276735 B CN102276735 B CN 102276735B CN 2011101244616 A CN2011101244616 A CN 2011101244616A CN 201110124461 A CN201110124461 A CN 201110124461A CN 102276735 B CN102276735 B CN 102276735B
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- propyl alcohol
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Abstract
The invention provides a cellulose multifunctional chelating material, the cellulose multifunctional chelating material has fluorescence emitting characteristic, especially presents various phenomena of fluorescence enhancing, fluorescence quenching and coloration differing when being as a complex with different heavy metal ions, and is capable of identifying at an original position, real-time analyzing and separating various heavy metal ions in water system; using a water-soluble sulfide is capable of conveniently eluting the heavy metal ions absorbed by the cellulose multifunctional chelating material, sulfide deposition is generated by the heavy metal ions and negative divalent sulfide ion and centralized to recovery, simultaneously the multifunctional cellulosic material can be regenerated and is safe and effective for circularly using. The cellulose multifunctional chelating material is convenient for usage of the recovery of heavy metal ions in a sewage treating pool of mine enterprises.
Description
Technical field
The present invention relates to a kind of cellulose base functional high molecule material; Be particularly related to the macromolecular material of Mierocrystalline cellulose side chain load Ben Yajiaji rhodanine and quaternary ammonium salt; Can be applicable to detection, analysis, separation, the enrichment of various water system heavy metal ion, belong to field of functional materials.
Technical background
Such as Ag
+, Pd
2+, Hg
2+, Cd
2+, Zn
2+, Ni
2+, Co
2+Or Cu
2+Etc. heavy metal ion all is the important source material of industrial production medical material, communication device and electronic devices and components; But the waste water that contains above-mentioned heavy metal ion also is the essential substance that causes epigeosphere water environment pollution and harm catering industry safety; Therefore, significant in situ detection, content analysis, kind separation, the enriching and recovering of heavy metal ion in industrial and mining enterprises' sewage.
As stated traditional in situ detection of heavy metal ion and analytical procedure trivial operations, working strength is big, the cycle is long, it is wide in variety to expend goods and materials; Fluorescence chemical sensor detection technique and the ion intelligent identification technology of the report original position identification that can realize contents of many kinds of heavy metal ion in recent years and detecting, these technology have trace routine easy, detect sensitive, identification sensitivity, analyzing and testing characteristics such as circulation ratio height as a result.But the chemical structure of heavy metal ion sensor and Intelligent Recognition material is complicated, and synthetic cost is high, and they also only have the analysis recognition function simultaneously, do not have the function or the effect of separation, enrichment, recovery heavy metal ion.
The traditional method of separation, enrichment, recovery heavy metal ion has: evaporation concentration method, chemical precipitation method, film dialysis method, solvent extraction process, electrochemistry precipitation method and solid phase extraction techniques etc.Solid phase extraction techniques is to study the novel method of the more pre-concentration of report, enrichment, recovery heavy metal ion over nearly twenties years; But solid extracting agent only has the function of pre-concentration, enrichment, recovery heavy metal ion; Do not have detection, identification, analytic function, especially can't indicate or in time show the saturated adsorbed state of solid extracting agent heavy metal ion.
Therefore; People eagerly hope to search out a kind of novel material that has heavy metal ion in situ detection, content analysis, kind separation, the enriching and recovering water concurrently; This novel material has the characteristic that manifests the Adsorption of Heavy Metal Ions state of saturation in real time, and the practicality operation that is convenient in the industrial and mining enterprises sanitary sewage disposal pond is disposed.
In view of the problem of current material technology existence and people's expectation; The present invention provides a kind of cellulose base multi-functional chelating material; A kind of Ben Yajiaji rhodanine of load structural unit on the Mierocrystalline cellulose side chain of the multi-functional chelating material of described cellulose base, described Ben Yajiaji rhodanine is qualitative and quantitative analysis Ag
+Or Pa
2+Deng reagent; Ben Yajiaji rhodanine structural unit self has fluorescent characteristic and development properties; The title complex that itself and different metal ion form also presents the totally different phenomenon of fluorescence enhancing, fluorescent quenching, colour developing of various kinds, can original position identification with detect in real time, analysis, separate heavy metal ion in the various water systems.
The Ben Yajiaji rhodanine structural unit number of load on the Mierocrystalline cellulose side chain of the multi-functional chelating material of cellulose base provided by the invention can quantitatively be introduced according to actual needs; So the multi-functional chelating material of cellulose base provided by the invention can be used as the SPE material of heavy metal ion, it is to the adsorption and enrichment volume-variable of heavy metal ion.
The totally different phenomenon because Ben Yajiaji rhodanine structural unit provided by the invention and different metal ionic title complex develop the color according to the color and luster variation of the multi-functional chelating material of said cellulose base adsorption and enrichment heavy metal ion, can be judged its absorption state of saturation.
Summary of the invention
The present invention provides a kind of cellulose base multi-functional chelating material, has chemical structure shown in the general formula (I):
R in its formula of (I)
1Or R
2Choose C respectively
1～C
4Alkyl, R
3Be selected from H, replacement or unsubstituted C
1～C
4Alkyl or replacement or unsubstituted C
6～C
20A kind of in the aryl, n chooses 500～30000 positive integer.
Ben Yajiaji rhodanine structural unit in general formula of the present invention (I) structure is a kind of chelating ligand with fluorescence developing function; Can form that color and luster is different with multiple metals ion, fluorescent emission or the totally different title complex supramolecular system of fluorescent quenching character; But qualitative detection species of metal ion and valence state in view of the above, concentration of metal ions in the quantitative analysis aqueous solution.
Quaternary ammonium salt in general formula of the present invention (I) structure can improve the wetting ability of said Ben Yajiaji rhodanine chelating ligand, quickens the water parent profit speed of the multi-functional chelating material of said cellulose base, the convenient artificial operation of using.
The multi-functional chelating material of general formula provided by the invention (I) cellulose base presents fiber condition, can carry out the secondary processing moulding, as the material applied range of detection, analysis, separation, enrichment, recovery heavy metal ion.
After the multi-functional chelating material of the cellulose base provided by the invention adsorption and enrichment heavy metal ion; Can use the heavy metal ion of the multi-functional chelating material absorption of inexpensive water-soluble sulfide wash-out cellulose base; Heavy metal ion is able to enriching and recovering with the sulfide precipitation form; The multi-functional chelating material of described cellulose base also is able to regeneration simultaneously, recycles safe and effective.
The preparation raw material of the multi-functional chelating material of general formula provided by the invention (I) cellulose base comprises: Mierocrystalline cellulose, epoxy chloropropane, 5-chloromethyl salicylic aldehyde, n n dimetylaniline, diethylamine, rhodanine and verivate thereof etc. all have supply of commodities, are easy to buy.The technology of preparing of the multi-functional chelating material of general formula (I) cellulose base all belongs to classical chemical synthesis process, and is simple and easy to do, and each step yield is high, and the three wastes are few.
The multi-functional chelating material of general formula provided by the invention (I) cellulose base is to make through following classical synthetic route:
Step 1, receive the effect of BFEE catalyzer, the Mierocrystalline cellulose swelling in organic solvent with the ring-opening reaction of epoxy chloropropane, process chloro propyl alcohol Mierocrystalline cellulose.
Wherein the 1. middle n of reaction formula chooses 500～30000 positive integer; Organic solvent refers to 1 described in the step 1; 4-dioxane, 1,2-ethylene dichloride or ETHYLE ACETATE, described consumption of organic solvent is 2～5 times of Mierocrystalline cellulose quality; The consumption of BFEE is 0.005～10% of a Mierocrystalline cellulose quality, and the consumption of epoxy chloropropane is 0.2～5 times of Mierocrystalline cellulose quality.
Step 2, the prepared chloro propyl alcohol of step 1 Mierocrystalline cellulose is dispersed in mass percent is in 30～45% the secondary amine aqueous solution, and the Soiodin of catalytic amount is as catalyzer, back flow reaction.Again add mass percent and be 10～40% aqueous sodium hydroxide solution, make general formula (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose thereafter.
Wherein reaction formula 2. in R
1Or R
2Choose C respectively
1～C
4Alkyl; Infer described secondary amine thus and refer to a kind of in n n dimetylaniline, diethylamine, dipropyl amine, dibutylamine, methylethyl amine, methyl-propyl amine or the methylbutyl amine; Said mass percent is that the consumption of 30～45% secondary amine aqueous solution is 2～6 times of said chloro hydroxyl propyl alcohol Mierocrystalline cellulose quality; Said mass percent is that the consumption of 10～40% aqueous sodium hydroxide solution is 2～6 times of said chloro hydroxyl propyl alcohol Mierocrystalline cellulose quality, and n chooses 500～30000 positive integer.
Step 3, with the obtained general formula of step 2 (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose swelling in organic solvent, drop into 5-chloromethyl salicylic aldehyde again, general formula (III) salicylic aldehyde salt cellulose is processed in 20～60 ℃ of reactions.
Wherein reaction formula 3. in R
1Or R
2Choose C respectively
1～C
4Alkyl; N chooses 500～30000 positive integer; Described 5-chloromethyl salicylic aldehyde consumption is 20～500% of general formula (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose quality; Described organic solvent refers to THF, 1, and 4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, ETHYLE ACETATE, acetonitrile, acetone or methylethylketone, the consumption of said organic solvent are 2～6 times of general formula (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose quality.
Step 4, the prepared general formula of step 3 (III) salicylic aldehyde salt cellulose is dispersed in the small molecular alcohol solvent, adds 3-R
3-rhodanine, the hexahydropyridine of catalytic amount or morpholine be as catalyzer, and reflux after reaction finishes, re-uses mass percent and is 10～40% aqueous sodium hydroxide solution and embathe reaction product, makes the multi-functional chelating material of general formula (I) cellulose base.
Wherein reaction formula 4. in R
1Or R
2Choose C respectively
1～C
4Alkyl, R
3Be selected from H, replacement or unsubstituted C
1～C
4Alkyl or replacement or unsubstituted C
6～C
20A kind of in the aryl, n chooses 500～30000 positive integer.Described 3-R
3-rhodanine consumption is 0.02～5 times of general formula (III) salicylic aldehyde salt cellulose quality; Said mass percent is that the consumption of 10～40% aqueous sodium hydroxide solution is 2～6 times of said general formula (III) salicylic aldehyde salt cellulose quality; Described alcoholic solvent refers to methyl alcohol, ethanol, Virahol, n-propyl alcohol, isopropylcarbinol, propyl carbinol or the trimethyl carbinol, and the consumption of described alcoholic solvent is 2～6 times of general formula (III) salicylic aldehyde salt cellulose quality.
Specific embodiment
Following embodiment further specifies multi-functional chelating material of general formula provided by the invention (I) cellulose base and preparation method thereof, and its purpose is to understand better content of the present invention.Therefore, unlisted multi-functional chelating material of general formula (I) cellulose base and preparation method thereof should not be regarded as the restriction to protection domain of the present invention among the embodiment.
Preparation and the characteristic and the application of the plain Quito of embodiment 1I-MC-1 fiber type function chelating material
The cellulosic preparation of step 1 chloro propyl alcohol
Take by weighing short velveteen 100 grams of commercially available oven dry and 250 gram ETHYLE ACETATE, stir together and heat up 80～95 ℃ of swellings after 4 hours, add catalyzer 5 gram boron trifluoride ether solutions again, splash into epoxy chloropropane 45 grams, reacted 2.5 hours.Squeeze and filter takes out, and oven dry makes chloro propyl alcohol Mierocrystalline cellulose 143.5 grams, ultimate analysis: cl content 11.65%.
Step 2 prepares dimethylamino propyl alcohol Mierocrystalline cellulose
It is in 40% dimethylamine agueous solution that 143.5 gram chloro propyl alcohol Mierocrystalline celluloses of step 1 gained are dropped into 400 gram mass percentage concentrations, stirs 60～65 ℃ of reactions 48 hours that heat up.Squeeze and filter takes out filter cake.Filter cake is embathed 3 times with 30% aqueous sodium hydroxide solution, and squeeze and filter takes out to be cleaned, and oven dry makes 161.7 gram dimethylamino propyl alcohol Mierocrystalline celluloses, ultimate analysis: nitrogen content 3.24%.
The preparation of step 3 salicylic aldehyde salt cellulose
Add dimethylamino propyl alcohol Mierocrystalline cellulose 16 gram and 58 milliliters of acetonitrile solvents of step 2 gained in the reaction flask, other takes by weighing 5-chloromethyl salicylic aldehyde 13 grams, and with 22 milliliters of acetonitrile dissolvings, slowly adds in the reaction flask 30～45 ℃ of temperature controls, stirring reaction 2 hours.Squeeze and filter takes out filter cake, and the oven dry filter cake makes salicylic aldehyde first salt cellulose 22.1 grams, ultimate analysis: nitrogen content 2.56%.
The preparation of the plain Quito of step 4 I-MR-1 fiber type function chelating material
Salicylic aldehyde first salt cellulose 20 gram and the 60 milliliters of absolute ethyl alcohols that add the step 3 gained in the reaction flask also add in the reaction flask with 30 milliliters of anhydrous alcohol solutions, 18 gram rhodanines, and make catalyzer with 5 hexahydropyridines, and 65～85 ℃ were reacted 16 hours.Squeeze and filter takes out filter cake, uses the aqueous sodium hydroxide solution of 70 grams 30% to embathe filter cake 3 times, again squeeze and filter; Wash filter cake again 3 times, oven dry makes the plain Quito of safran I-MR-1 fiber type function chelating material 25.3 grams; Ultimate analysis: nitrogen content 3.35%, sulphur content 6.53%.
The multi-functional chelating material of I-MR-1 cellulose base is fluorescent emission characteristic peak wavelength 478nm in DMF solution.Present redness after using the multi-functional chelating material of argentiferous deionized water solution leaching I-MR-1 cellulose base, fluorescence intensity increases by 13 times.After using the multi-functional chelating material of solder(ing)acid leaching I-MR-1 cellulose base, the multi-functional chelating material of I-MR-1 cellulose base presents the brilliant orange look, and fluorescence intensity is compared and strengthened nearly 17 times.Appear behind the multi-functional chelating material of the I-MR-1 cellulose base copper ions aqueous solution blackish green, fluorescent quenching.
The preparation of the plain Quito of embodiment 2I-MR-2 fiber type function chelating material
Get the salicylic aldehyde first salt cellulose of embodiment 1 step 3 gained, make jonquilleous I-MR-2 type multifunctional fibre element with rhodanine-3-acetate condensation.The multi-functional chelating material of I-MR-2 cellulose base fluorescent emission λ max=481nm in DMF solution.Use contains Ag
+Behind the multi-functional chelating material of aqueous solution leaching I-MR-2 cellulose base, present redness, fluorescence intensity obviously strengthens.The multi-functional chelating material absorption of I-MR-2 cellulose base Hg
2+After, present dark reddish purple look, fluorescent quenching.
The preparation of the plain Quito of embodiment 3I-MR-3 fiber type function chelating material
Get the salicylic aldehyde first salt cellulose of embodiment 1 step 3 gained, condensation makes the plain Quito of saffron I-MR-3 fiber type function chelating material to the carboxyl phenyl rhodanine with 3-.The fluorescence emission peak λ max=487nm of the multi-functional chelating material of I-MR-3 cellulose base in the aqueous solution.Use contains Cu
2+, Hg
2+, Cd
2+, Pb
2+Or Cr
3+Fluorescence intensity obviously reduces behind the multi-functional chelating material of leaching I-MR-3 cellulose base.
The preparation of the plain Quito of embodiment 4I-ER-1 fiber type function chelating material
According to the method and the operation steps of embodiment 1 step 2, dimethylamine agueous solution is changed to diethylamine, can make diethylin propyl alcohol Mierocrystalline cellulose.According to the method and the operation steps of embodiment 1 step 3, diethylin propyl alcohol Mierocrystalline cellulose and 5-chloromethyl salicylic aldehyde are reacted in acetone solvent, can make salicylic aldehyde second salt cellulose.
According to the method and the operation steps of embodiment 1 step 4, salicylic aldehyde second salt cellulose and rhodanine are reacted in anhydrous ethanol solvent, can make the multi-functional chelating material of I-ER-1 cellulose base.
The regeneration of the multi-functional chelating material of embodiment 5 cellulose bases and recycling
With the leaching of the multi-functional chelating material of I-MR-1 cellulose base complexing absorption solder(ing)acid zine ion is example, the multi-functional chelating material of cellulose base provided by the invention enriching and recovering zinc is described, autosynthesis and the process that recycles.
After using the multi-functional chelating material of solder(ing)acid leaching I-MR-1 cellulose base, 5. generating polynomial reacts, and generates title complex, and this process is the multi-functional chelating material of I-MR-1 cellulose base complexing absorption Zn
2+Process.
After this, use sodium sulfide solution drip washing to adsorb the multi-functional chelating material of I-MR-1 cellulose base of zine ion, generating polynomial 6. shown in reaction, Zn
2+And S
2-Generate the ZnS deposition, drip washing is concentrated and is obtained white zinc sulfide powder, causes Zn
2+Break away from the multi-functional chelating material of I-MR-1 cellulose base; And Na
+And Cl
-Reaction generates sodium-chlor and gets into water, and after press filtration, the multi-functional chelating material of I-MR-1 cellulose base is isolated from the aqueous solution, and this process is exactly the regenerative process of the multi-functional chelating material of I-MR-1 cellulose base, and I-MR-1 multifunctional fibre element can be recycled.
Claims (3)
1. multi-functional chelating material of cellulose base, the chemical structure shown in (I) that it is characterized in that having general formula:
R in its formula of (I)
1And R
2Choose C respectively
1～C
4Alkyl; R
3Be selected from H, replacement or unsubstituted C
1～C
4Alkyl or replacement or unsubstituted C
6～C
20A kind of in the aryl, n chooses 500～30000 positive integer.
2. according to the multi-functional chelating preparation methods of the described cellulose base of claim 1, it is characterized in that may further comprise the steps:
Step 1, receive the effect of BFEE catalyzer, the Mierocrystalline cellulose swelling in organic solvent with the ring-opening reaction of epoxy chloropropane, process chloro propyl alcohol Mierocrystalline cellulose;
Wherein the 1. middle n of reaction formula chooses 500～30000 positive integer; The said organic solvent of step 1 refers to 1; 4-dioxane, 1,2-ethylene dichloride or ETHYLE ACETATE, described consumption of organic solvent is 2～5 times of Mierocrystalline cellulose quality; The consumption of BFEE is 0.005～10% of a Mierocrystalline cellulose quality, and the consumption of epoxy chloropropane is 0.2～5 times of Mierocrystalline cellulose quality;
Step 2, the prepared chloro propyl alcohol of step 1 Mierocrystalline cellulose is dispersed in mass percent is in 30～45% the secondary amine aqueous solution; Back flow reaction; Again add mass percent and be 10～40% aqueous sodium hydroxide solution, make general formula (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose thereafter;
Wherein reaction formula 2. in R
1And R
2Choose C respectively
1～C
4Alkyl is inferred the described secondary amine of step 2 thus and is referred to R
1And R
2Choose C respectively
1～C
4The secondary amine of alkyl; Said mass percent is that the consumption of 30～45% secondary amine aqueous solution is 1～3 times of said chloro propyl alcohol Mierocrystalline cellulose quality; Said mass percent is that the consumption of 10～40% aqueous sodium hydroxide solution is 2～6 times of said chloro propyl alcohol Mierocrystalline cellulose quality, and n chooses 500～30000 positive integer;
Step 3, with the obtained general formula of step 2 (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose swelling in organic solvent, drop into 5-chloromethyl salicylic aldehyde again, general formula (III) salicylic aldehyde salt cellulose is processed in 20～60 ℃ of reactions;
Wherein reaction formula 3. in R
1And R
2Choose C respectively
1～C
4Alkyl; N chooses 500～30000 positive integer; Described 5-chloromethyl salicylic aldehyde consumption is 20～500% of general formula (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose quality; Described organic solvent refers to THF, 1, and 4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, ETHYLE ACETATE, acetonitrile, acetone or methylethylketone, the consumption of said organic solvent are 2～6 times of general formula (II) tertiary amine groups propyl alcohol Mierocrystalline cellulose quality;
Step 4, the prepared general formula of step 3 (III) salicylic aldehyde salt cellulose is dispersed in the small molecular alcohol solvent, adds 3-R
3-rhodanine, the hexahydropyridine of catalytic amount or morpholine be as catalyzer, and reflux after reaction finishes, adds mass percent and be 10～40% aqueous sodium hydroxide solution again, makes the multi-functional chelating material of general formula (I) cellulose base;
Wherein reaction formula 4. in R
1And R
2Choose C respectively
1～C
4Alkyl, R
3Be selected from H, replacement or unsubstituted C
1～C
4Alkyl or replacement or unsubstituted C
6～C
20A kind of in the aryl, n chooses 500～30000 positive integer, described 3-R
3-rhodanine consumption is 0.02～5 times of general formula (III) salicylic aldehyde salt cellulose quality; Said mass percent is that the consumption of 10～40% aqueous sodium hydroxide solution is 2～6 times of said general formula (III) salicylic aldehyde salt cellulose quality; Described alcoholic solvent refers to methyl alcohol, ethanol, Virahol, n-propyl alcohol, isopropylcarbinol, propyl carbinol or the trimethyl carbinol, and the consumption of described alcoholic solvent is 2～6 times of general formula (III) salicylic aldehyde salt cellulose quality.
3. according to the multi-functional chelating preparation methods of the described cellulose base of claim 2, it is characterized in that described 3-R
3-rhodanine is selected from chemical structure shown in the general formula (IV):
R wherein
3Be selected from H, replacement or unsubstituted C
1～C
4Alkyl or replacement or unsubstituted C
6～C
20A kind of in the aryl.
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