CN102962013B - Clamp Cu(II) preparation of metallo-organic complex Small molecular gel and application thereof - Google Patents
Clamp Cu(II) preparation of metallo-organic complex Small molecular gel and application thereof Download PDFInfo
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Abstract
The invention belongs to oily water separation technique field, be specifically related to a kind of clamp Cu(II) preparation of metallo-organic complex Small molecular gel, and gather the formed application of soft material in water-oil separating with water-setting.This gel high selectivity can condense aqueous phase in the sewage of oil-containing, and does not condense oily organic matter phase.After cohesion aqueous phase, by simple filtration or the method for toppling over, the quick separating of oil, water two-phase can be realized.This novel hydrogels agent expression formula NNN-Cu-Cl
2, wherein, NNN represents the three-tooth nitrogen ligand with cupric coordination.This kind of novel hydrogels agent, under shirtsleeve operation (heating or stirring), can form hydrogel fast, effectively realize oil phase in oil water mixture and be separated with the rapid of aqueous phase, realize the quick recovery to oil in easy mode.
Description
Technical field
The invention belongs to oily water separation technique field, be specifically related to a kind of clamp Cu(II) preparation of metallo-organic complex Small molecular gel, and gather the formed application of soft material in water-oil separating with water-setting.This gel high selectivity can condense aqueous phase in the sewage of oil-containing, and does not condense oily organic matter phase.After cohesion aqueous phase, by simple filtration or the method for toppling over, the quick separating of oil, water two-phase can be realized.
Background technology
As China's infrastructural industries, petrochemical industry has had development at full speed after reform and opening-up, facilitates the growth of national economy greatly.But when oil exploitation, conversion, transport, the Oil spills (as Gulf of Mexico oil spilling, Bohai Sea Gulf oil spill events) caused due to technical equipment or artificial origin is with very serious environment and ecological problem.Effectively reclaiming for the post processing of oil accident and waste oil is the difficult problem allowing national governments all feel very thorny at present, even if often drop into a large amount of manpowers, financial resources, material resources, the effect obtained neither be obvious.Thus, find a kind of quick, effective oily water separation technique method simply and easily, for petrochemical industry development and oil transport by sea, there is Great significance.At present for realize oily moisture selective from, the gel report particularly with potential application foreground is few, and mainly concentrate on Small molecular and the polymeric gelling agent of the hydrogen bonds functional group that can form organogel, and report is had no for the example that selective generation formation hydrogel realizes water-oil separating.Due to most metallic compound, be responsive to air and water, this just greatly limit the application of this kind of gel in water-oil separating field or oil slick recovery.The introducing of hydrogen bonds functional group, often hinders coordination and the complexing of metallic element, and this is also the one of the main reasons that this kind of gel is difficult to prepare.With regard to the Low Molecular-Weight Gel agent reported at present, mainly by by the optionally gluey soft material of cohesionization formation of organic phase (oil reservoir) in profit compound, after excessively filtering water, just can realize the recovery of oil-containing colloid substance.But this water-oil separating mode major defect, in order to further recovered oil, must pass through additive method, realize the gel of complexity and being separated of oil phase, real could realize the recovery of oil, and this step is very complicated and loaded down with trivial details often.And the clamp Cu(II mentioned in the present invention) agent of metallo-organic complex micro-molecular hydrogel can form gluey soft material by gel selective cohesion aqueous phase, then warp simple inversion decantation just fast and effeciently can realize the recovery of oil phase.Therefore the present invention (agent of metal organic hydrogels) has very important realistic meaning and potential prospects for commercial application as the new technique research that can realize oil water mixture separation fast.
Summary of the invention
The object of the invention is to propose a kind of clamp Cu(II) metallo-organic complex gel, this gel can form hydrogel with water equal solvent.
Another object of the present invention be propose a kind of quick, easy, effectively realize oil water mixture be separated new method.Mainly report and study clamp Cu(II) preparation method of metallo-organic complex Small molecular gel and the application in oil water mixture is separated thereof.
The clamp Cu(II that the present invention proposes) metallo-organic complex gel, its expression formula is NNN-Cu-Cl
2, wherein, NNN represents the three-tooth nitrogen ligand with cupric coordination, and its concrete structure is as follows:
，
Wherein, X=O, S.As X=O, i.e. 2-furyl, compound label is 2a; As X=S, i.e. 2-thienyl, compound label is 2b.
The present invention reacts with the Copper dichloride dihydrate of 1.2 times of moles respectively with corresponding three-tooth nitrogen ligand, after filtration, the processing procedure such as washing, vacuumizes drying and obtains corresponding clamp Cu(II) metallo-organic complex hydrogel adhesive.
The clamp Cu(II that the present invention proposes) preparation method of metal organic complex hydrogel adhesive, its process is as follows:
In the round-bottomed flask of 250mL, add three-tooth nitrogen ligand (1-10mmol) respectively, Copper dichloride dihydrate (1-12mmol) and absolute methanol, three-tooth nitrogen ligand is 1:1 ~ 1.2 with the amount of substance ratio of Copper dichloride dihydrate.At room temperature stirring reaction 24 hours, has green solid to be formed, green solid is filtered, wash 3 times, vacuum drying with absolute methanol, obtain corresponding clamp Cu(II in reaction system) metal organic complex hydrogel adhesive.Its reaction equation is as follows:
Wherein, the structural formula of three-tooth nitrogen ligand is shown in above formula reaction equation, as X=O, i.e. and 2-furyl, compound label is 1a; As X=S, i.e. 2-thienyl, compound label is 1b.By research institute synthesis clamp Cu(II) metallo-organic complex finds the experimental result of the cohesion ability of various solvent, compound 2a effectively can realize the gelation to water, and minimum one-tenth gum concentration can reach 0.25wt%, and namely 5.76 × 10
-3mol/mL, can also realize ethylene glycol, the gelation of 1,3-PD and glycerine simultaneously.Compound 2b then can only realize the gelation to glycerine.So in the investigation of water-oil separating below, we only employ clamp Cu(II) metallo-organic complex 2a.
The clamp Cu(II that the present invention is obtained) metallo-organic complex 2 gel is applied to water and other organic alcohols solvent forms gel, and concrete grammar is as follows:
Method 1:
In a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2gel, 0.5mL solvent, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2,dissolve completely, stop heating, sample bottle is left standstill a period of time.Have green gel to be formed in sample bottle, after sample bottle is inverted, gel still remains fixed in bottom sample bottle.
Method 2:
In a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 0.5mL water, finally adds a little magneton, after the sealing of lid of polyvinyl fluoride, is placed on magnetic stirring apparatus and stirs or concussion.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2adissolve completely, stop stirring or concussion, sample bottle is left standstill a period of time.Have Green Water gel-forming in sample bottle, after sample bottle is inverted, hydrogel still remains fixed in bottom sample bottle.
The clamp Cu(II that the present invention is obtained) metallo-organic complex 2a hydrogel adhesive is used for the separation of all kinds of oil water mixture, and concrete steps are as follows:
Method 3:
In a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 1mL water and 1mL oil, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2adissolve completely, stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is oil phase, and lower floor is Green Water gel phase, and after sample bottle is inverted, upper strata oil can be very easy to incline recovery, and hydrogel still remains fixed in bottom sample bottle.
Method 4:
In a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 1mL water and 1mL oil, finally add a little magneton, after the sealing of lid of polyvinyl fluoride, is placed on magnetic stirring apparatus and stirs or concussion.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2adissolve completely, stop stirring or concussion, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is oil phase, lower floor is Green Water gel phase, after sample bottle is inverted, upper oil phase easily can be inclined and recovery, same hydrogel still remains on bottom sample bottle relatively, and these class methods are applicable to oil slick and are not possessing heating condition very much, and the recycling of oil slick under the environment of sea concussion.
Clamp Cu(II prepared by the present invention) metal organic complex hydrogel adhesive, under shirtsleeve operation (heating or stir, concussion condition), can easily and effectively by selective formation hydrogel, realize quick separating oily in oil water mixture.
Accompanying drawing explanation
Fig. 1 is the clamp Cu(II of embodiment 1 gained) metallo-organic complex hydrogel adhesive
2acrystal structure figure.Main bond distance's [] and bond angle data [°] are:
Cu(1)-N(2)=1.947(3)，Cu(1)-N(3)=2.043(3)，Cu(1)-N(1)=2.052(3)，Cu(1)-Cl(2)=2.2192(11)，Cu(1)-Cl(1)=2.6006(11)，N(1)-C(1)=1.326(4)，N(1)-C(5)=1.362(4)，N(2)-C(14)=1.336(4)，N(2)-C(6)=1.339(4)，N(3)-C(19)=1.343(4)，N(3)-C(15)=1.363(4)，C(8)-C(9)=1.432(5)，C(9)-C(10)=1.340(5)，C(9)-O(1)=1.362(4)，C(10)-C(11)=1.409(5)，C(11)-C(12)=1.329(6)，C(12)-O(1)=1.369(5)，C(5)-C(6)=1.483(5)，C(14)-C(15)=1.473(4)，N(2)-Cu(1)-N(3)=79.38(11)，N(2)-Cu(1)-N(1)=79.37(12)，N(3)-Cu(1)-N(1)=156.70(11)，N(2)-Cu(1)-Cl(2)=164.37(9)，N(3)-Cu(1)-Cl(2)=99.04(8)，N(1)-Cu(1)-Cl(2)=98.84(9)，N(2)-Cu(1)-Cl(1)=93.90(9)，N(3)-Cu(1)-Cl(1)=94.74(9)，N(1)-Cu(1)-Cl(1)=96.12(9)，Cl(2)-Cu(1)-Cl(1)=101.73(4)，C(1)-N(1)-C(5)=117.7(3)，C(1)-N(1)-Cu(1)=127.6(3)，C(5)-N(1)-Cu(1)=114.6(2)，C(14)-N(2)-C(6)=121.6(3)，C(14)-N(2)-Cu(1)=119.4(2)，C(6)-N(2)-Cu(1)=119.0(2)，C(19)-N(3)-C(15)=118.9(3)，C(19)-N(3)-Cu(1)=127.2(3)，C(15)-N(3)-Cu(1)=113.9(2).
Fig. 2 is the clamp Cu(II of embodiment 8 gained) metallo-organic complex hydrogel adhesive
2athe separating resulting figure for water and n-hexane mixed liquor.
Fig. 3 is the clamp Cu(II of embodiment 9 gained) metallo-organic complex hydrogel adhesive
2athe separating resulting figure for water and normal octane mixed liquor.
Fig. 4 is the clamp Cu(II of embodiment 10 gained) metallo-organic complex hydrogel adhesive
2athe separating resulting figure for water and dimethicone mixed liquor.
Fig. 5 is the clamp Cu(II of embodiment 11 gained) metallo-organic complex hydrogel adhesive
2athe separating resulting figure for water and paraffin oil mixed liquor.
Fig. 6 is the clamp Cu(II of embodiment 12 gained) metallo-organic complex hydrogel adhesive
2afor water and pump oil mixed liquor separating resulting figure.
Fig. 7 is the clamp Cu(II of embodiment 13 gained) metallo-organic complex hydrogel adhesive
2athe separating resulting figure for water and soya-bean oil mixed liquor.
Detailed description of the invention
Specifically describe the present invention further below by embodiment, the present invention is not limited to following embodiment.
embodiment 1:clamp Cu(II) metallo-organic complex hydrogel adhesive
2apreparation:
In the round-bottomed flask of 250mL, add three-tooth nitrogen ligand respectively
1a(2.993g, 10mmol), Copper dichloride dihydrate (2.05g, 12mmol) and 200mL absolute methanol.At room temperature stirring reaction 24 hours, has green solid to be formed, green solid is filtered, wash 3 times, vacuum drying with absolute methanol in reaction system, the novel clamp Cu(II obtained) metal organic network thing Heshui gel
2a.Productive rate 99%.
Mass spectral analysis:
1hNMR (D
2o, 400MHz, 353K): δ=10.68 (bs, 6H), 10.24 (bs, 2H), 10.06 (bs, 3H), 6.91 (bs, 3H); HR-MS (ESI): m/z397.0043 (Calcd. [M-Cl]
+), 397.0078 (Found. [M-Cl]
+).
embodiment 2:clamp Cu(II) metal organic complex hydrogel adhesive
2bpreparation:
In the round-bottomed flask of 250mL, add three-tooth nitrogen ligand respectively
1b(0.315g, 1.0mmol), Copper dichloride dihydrate (0.205g, 1.2mmol) and 20mL absolute methanol.At room temperature stirring reaction 24 hours, has green solid to be formed, green solid is filtered, wash 3 times, vacuum drying with absolute methanol, the clamp Cu(II obtained in reaction system) metallo-organic complex hydrogel adhesive
2b.Productive rate 91%.
Mass spectral analysis: HR-MS (ESI): m/z412.9815 (Calcd. [M-Cl]
+), 412.9827 (Found. [M-Cl]
+).
Due to the paramagnetic properties of copper metal, compound 2b solubility property extreme difference in organic solvent in addition, therefore From Spectral Signal is extremely weak is difficult to ownership.
embodiment 3:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor forming hydrogel in water:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 1: in a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 0.5mL water, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2a, dissolve completely, stop heating, sample bottle is left standstill a period of time.Have Green Water gel-forming in sample bottle, after sample bottle is inverted, hydrogel still remains fixed in bottom sample bottle.
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 2: in a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 0.5mL water, finally adds a little magneton, after the sealing of lid of polyvinyl fluoride, is placed on magnetic stirring apparatus and stirs or concussion.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2adissolve completely, stop stirring or concussion, sample bottle is left standstill a period of time.Have Green Water gel-forming in sample bottle, after sample bottle is inverted, hydrogel still remains fixed in bottom sample bottle.
embodiment 4:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor forming organogel in ethylene glycol:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 1: in a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 0.5mL ethylene glycol, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2a, dissolve completely, stop heating, sample bottle is left standstill a period of time.Have green organogel to be formed in sample bottle, after sample bottle is inverted, organogel still remains fixed in bottom sample bottle.
embodiment 5:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor forming organogel in 1,3-PD:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 1: in a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 0.5mL1, ammediol, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2a, dissolve completely, stop heating, sample bottle is left standstill a period of time.Have green organogel to be formed in sample bottle, after sample bottle is inverted, organogel still remains fixed in bottom sample bottle.
embodiment 6:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor forming organogel in glycerine:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 1: in a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2ahydrogel adhesive, 0.5mL glycerine, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2a, dissolve completely, stop heating, sample bottle is left standstill a period of time.Have green organogel to be formed in sample bottle, after sample bottle is inverted, organogel still remains fixed in bottom sample bottle.
embodiment 7:clamp Cu(II) metallo-organic complex gel
2bfor forming organogel in glycerine:
Adopt clamp Cu(II prepared by embodiment 2) metallo-organic complex gel
2bwith method 1: in a 5mL white pigmented samples bottle, add 5mg clamp Cu(II successively) metallo-organic complex
2bgel, 0.5mL glycerine, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex
2b, dissolve completely, stop heating, sample bottle is left standstill a period of time.Have green organogel to be formed in sample bottle, after sample bottle is inverted, organogel still remains fixed in bottom sample bottle.
embodiment 8:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor being separated of water and n-hexane mixed liquor:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 3: in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL n-hexane, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex hydrogel adhesive dissolves completely, and stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is n-hexane, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata n-hexane can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle.This separating resulting is shown in accompanying drawing 2.
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 4: in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metal organic complex hydrogel adhesive, 1mL water and 1mL n-hexane, finally add a little magneton, after the sealing of lid of polyvinyl fluoride, is placed on magnetic stirring apparatus and stirs.Solution when the inside becomes transparent, i.e. clamp Cu(II) metal organic complex hydrogel adhesive dissolves completely, stops stirring, and sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is n-hexane, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata n-hexane can very easily flow to incline and, and hydrogel still remains on bottom sample bottle relatively.
embodiment 9:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor being separated of water and normal octane mixed liquor:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 3, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL normal octane, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metal organic complex hydrogel adhesive dissolves completely, and stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is normal octane, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata normal octane can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle.This separating resulting is shown in accompanying drawing 3.
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 4, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL normal octane, finally add a little magneton, after the sealing of lid of polyvinyl fluoride, is placed on magnetic stirring apparatus and stirs.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex hydrogel adhesive dissolves completely, stops stirring, and sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is normal octane, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata normal octane can very easily flow to incline and, and hydrogel still remains on bottom sample bottle relatively.
embodiment 10:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor being separated of water and simethicone mixture:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 3, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL dimethicone, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metal organic complex hydrogel adhesive dissolves completely, and stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is dimethicone, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata dimethicone can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle.This separating resulting is shown in accompanying drawing 4.
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 4, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL dimethicone, finally add a little magneton, after the sealing of lid of polyvinyl fluoride, be placed on magnetic stirring apparatus and stir.Solution when the inside becomes transparent, i.e. clamp Cu(II) metal organic complex hydrogel adhesive dissolves completely, stops stirring, and sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is dimethicone, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata dimethicone can very easily flow to incline and, and hydrogel still remains on bottom sample bottle relatively.
embodiment 11:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor being separated of water and paraffin oil mixture:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 3, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL paraffin oil, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex hydrogel adhesive dissolves completely, and stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is paraffin oil, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata paraffin oil can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle.This separating resulting is shown in accompanying drawing 5.
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 4, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL paraffin oil, finally add a little magneton, after the sealing of lid of polyvinyl fluoride, is placed on magnetic stirring apparatus and stirs.Solution when the inside becomes transparent, i.e. clamp Cu(II) metal organic complex hydrogel adhesive dissolves completely, stops stirring, and sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is paraffin oil, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata paraffin oil can very easily flow to incline and, and hydrogel still remains on bottom sample bottle relatively.
embodiment 12:clamp Cu(II) metal organic complex hydrogel adhesive
2afor being separated of water and pump oil mixture:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 3, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL pump oil, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex hydrogel adhesive dissolves completely, and stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is pump oil, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata pump oil can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle.This separating resulting is shown in accompanying drawing 6.
embodiment 13:clamp Cu(II) metallo-organic complex hydrogel adhesive
2afor being separated of water and soya-bean oil:
Adopt clamp Cu(II prepared by embodiment 1) metallo-organic complex hydrogel adhesive
2awith method 3, in a 5mL white pigmented samples bottle, add 10mg clamp Cu(II successively) metallo-organic complex hydrogel adhesive, 1mL water and 1mL soya-bean oil, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex hydrogel adhesive dissolves completely, and stop heating, sample bottle is left standstill a period of time.Point to have two-layer in sample bottle, upper strata is soya-bean oil, and lower floor is Green Water gel, and after sample bottle is inverted, upper strata soya-bean oil can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle.This separating resulting is shown in accompanying drawing 7.
Claims (6)
1. clamp Cu(II) a metallo-organic complex Small molecular gel, its expression formula is NNN-Cu-Cl
2, NNN represents the three-tooth nitrogen ligand with cupric coordination, and concrete structure is as follows:
,
Wherein, X=O, or S,
As X=O, this clamp Cu(II) metallo-organic complex and water, ethylene glycol, 1,3-PD or glycerine forms gel;
As X=S, this clamp Cu(II) metallo-organic complex and glycerine forms gel.
2. clamp Cu(II as claimed in claim 1) preparation method of metallo-organic complex Small molecular gel, it is characterized in that concrete steps are as follows:
In round-bottomed flask, add three-tooth nitrogen ligand respectively, Copper dichloride dihydrate and absolute methanol, three-tooth nitrogen ligand is 1:1 ~ 1.2, at room temperature stirring reaction 24 hours with the amount of substance ratio of Copper dichloride dihydrate, has green solid to be formed in reaction system, green solid is filtered, with absolute methanol washing, vacuum drying, obtains corresponding clamp Cu(II) metallo-organic complex hydrogel adhesive.
3. a clamp Cu(II as claimed in claim 1) metallo-organic complex Small molecular gel be applied to water, ethylene glycol, 1,3-PD or glycerine formed gel.
4. clamp Cu(II as claimed in claim 1) metallo-organic complex Small molecular gel is used for the separation of oil water mixture, it is characterized in that concrete steps are as follows:
Method 1:
In a 5mL white pigmented samples bottle, add the clamp Cu(II of 10mgX=O successively) metallo-organic complex Small molecular gel, 1mL water and 1mL oil, after the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle; Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic compound hydrogel adhesive dissolves completely, stop heating, sample bottle is left standstill a period of time, point to have two-layer in sample bottle, upper strata is oil, lower floor is Green Water gel, after sample bottle is inverted, upper strata oil can very easily flow to incline and, and hydrogel still remains fixed in bottom sample bottle;
Method 2:
In a 5mL white pigmented samples bottle, add 10mgX=O clamp Cu(II successively) metallo-organic complex Small molecular gel, 1mL water and 1mL oil, finally add a little magneton, after the sealing of lid of polyvinyl fluoride, be placed on magnetic stirring apparatus and stir; Solution when the inside becomes transparent, i.e. clamp Cu(II) metallo-organic complex Small molecular gel dissolves completely, stop stirring, sample bottle is left standstill a period of time, point to have two-layer in sample bottle, upper strata is oil, lower floor is Green Water gel, after sample bottle is inverted, upper strata oil can very easily flow to incline and, and hydrogel still remains on bottom sample bottle relatively.
5. clamp Cu(II according to claim 4) metallo-organic complex Small molecular gel is used for the separation of oil water mixture, and it is characterized in that, described oil is the liquid grease immiscible with water.
6. clamp Cu(II according to claim 5) metallo-organic complex Small molecular gel is used for the separation of oil water mixture, and it is characterized in that, described oil is normal hexane, normal octane, dimethicone, paraffin oil, one or more in pump oil or soya-bean oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210469284.XA CN102962013B (en) | 2012-11-20 | 2012-11-20 | Clamp Cu(II) preparation of metallo-organic complex Small molecular gel and application thereof |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN201210469284.XA CN102962013B (en) | 2012-11-20 | 2012-11-20 | Clamp Cu(II) preparation of metallo-organic complex Small molecular gel and application thereof |
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| Publication Number | Publication Date |
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| CN1974576A (en) * | 2006-12-01 | 2007-06-06 | 周成勇 | N1,N8-disubstituent-triethyl tetramine copper (II) complex and its prepn process |
| CN101084262A (en) * | 2004-12-21 | 2007-12-05 | 陶氏环球技术公司 | Vulcanizable halogenated elastomer compositions |
| CN101733158A (en) * | 2009-12-09 | 2010-06-16 | 湖北兴发化工集团股份有限公司 | Tridentate copper chelate catalyst and method for synthesizing dimethyl carbonate thereby |
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| CN101084262A (en) * | 2004-12-21 | 2007-12-05 | 陶氏环球技术公司 | Vulcanizable halogenated elastomer compositions |
| CN1974576A (en) * | 2006-12-01 | 2007-06-06 | 周成勇 | N1,N8-disubstituent-triethyl tetramine copper (II) complex and its prepn process |
| CN101733158A (en) * | 2009-12-09 | 2010-06-16 | 湖北兴发化工集团股份有限公司 | Tridentate copper chelate catalyst and method for synthesizing dimethyl carbonate thereby |
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