CN102962013A - Preparation and application of clamp type Cu (II) metal organic complex micromolecule gel agent - Google Patents
Preparation and application of clamp type Cu (II) metal organic complex micromolecule gel agent Download PDFInfo
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- CN102962013A CN102962013A CN201210469284XA CN201210469284A CN102962013A CN 102962013 A CN102962013 A CN 102962013A CN 201210469284X A CN201210469284X A CN 201210469284XA CN 201210469284 A CN201210469284 A CN 201210469284A CN 102962013 A CN102962013 A CN 102962013A
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Abstract
The invention belongs to the technical field of oil-water separation and particularly relates to a preparation method of a clamp type Cu (II) metal organic complex micromolecule gel agent and an application of a soft material formed through coagulation of the clamp type Cu (II) metal organic complex micromolecule gel agent and water in oil-water separation. The gel agent can agglomerate water phase in oil bearing sewage in a high selectivity manner and does not agglomerate oily organic matters. After the water phase is agglomerated, the rapid separation of the oil phase and the water phase can be realized in a simple filtration or dumping manner. The expression of the novel water gel agent is NNN-Cu-Cl2, wherein NNN expresses a tridentate nitrogen ligand coordinating with copper. The novel gel gent can quickly form hydrogel in a simple operation (heating or stirring) manner so that the rapid separation of the oil phase and the water phase in an oil-water mixture can be effectively realized in a simple and convenient manner, and the rapid recovery of oil is realized.
Description
Technical field
The invention belongs to the oily water separation technique field, be specifically related to a kind of pincers type Cu(II) preparation of the little molecular gel agent of metallo-organic complex, and with the poly-application of formed soft material in water-oil separating of water-setting.This gel can high selectivity condense water in the sewage of oil-containing, and does not condense the organic phase of oily.Behind the cohesion water, by simple filtration or the method for toppling over, can realize the quick separation of oil, water two-phase.
Background technology
As China's infrastructural industries, petrochemical industry has had development at full speed after reform and opening-up, promoted greatly the growth of national economy.But when oil exploitation, conversion, transportation, because the Oil spills (such as Gulf of Mexico oil spilling, the Bohai Sea Gulf oil spill events) that technical equipment or artificial origin cause is with very serious environment and ecological problem.Effectively reclaiming for the post processing of oil accident and waste oil is to allow at present national governments all feel a very thorny difficult problem, even if often drop into a large amount of manpowers, financial resources, material resources, the effect that obtains neither be obvious.Thereby, seek a kind of fast, the oily water separation technique method has Great significance for petrochemical industry development and oil transport by sea effectively simply and easily.At present for realize the profit component selections from, the gel report that particularly has potential application foreground is few, and mainly concentrate on little molecule and the polymeric gelling agent of the hydrogen bonds functional group that can form organogel, realize that the example of water-oil separating has no report and form hydrogel for selective generation.Because most metallic compound is responsive to empty G﹠W, this has just limited the application of this gellike agent aspect water-oil separating field or oil slick recovery greatly.The introducing of hydrogen bonds functional group tends to hinder coordination and the complexing of metallic element, and this also is the one of the main reasons that this gellike agent is difficult to prepare.With regard to the Low Molecular-Weight Gel agent of having reported at present, mainly be by with the soft material of cohesionization formation glue optionally of organic phase (oil reservoir) in the profit compound, after removing by filter water, just can realize the recovery of oil-containing colloid substance.But this water-oil separating mode major defect is that essential by additive method for further recovered oil, separating of the gel that realization is complicated and oil phase could really realize oily recovery, and this step is very complicated and loaded down with trivial details often.And the pincers type Cu(II that mentions among the present invention) agent of metallo-organic complex micro-molecular hydrogel can selectively condense water by gel and form gluey soft material, is inverted the recovery that decantation just can fast and effeciently realize oil phase through simple again.Therefore the present invention's (metal organic water gel) is as realizing fast that the new technique research that oil water mixture separates has very important realistic meaning and potential prospects for commercial application.
Summary of the invention
The objective of the invention is to propose a kind of pincers type Cu(II) the metallo-organic complex gel, this gel can form hydrogel with the water equal solvent.
Another object of the present invention be propose a kind of quick, easy, effectively realize the new method that oil water mixture separates.Mainly be report and research pincers type Cu(II) preparation method of the little molecular gel agent of metallo-organic complex and the application in oil water mixture separates thereof.
The pincers type 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, its concrete structure is as follows:
Wherein, X=O, S.When X=O, i.e. 2-furyl, compound is labeled as 2a; When X=S, i.e. 2-thienyl, compound is labeled as 2b.
The present invention be with corresponding three-tooth nitrogen ligand respectively with the reaction of the Copper dichloride dihydrate of 1.2 times of moles, after filtration, the processing procedure such as washing, vacuumize drying and clamped accordingly type Cu(II) the metallo-organic complex hydrogel adhesive.
The pincers type 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 250 mL, add respectively three-tooth nitrogen ligand (1-10 mmol), Copper dichloride dihydrate (1-12 mmol) and absolute methanol, the molar ratio of three-tooth nitrogen ligand and Copper dichloride dihydrate is 1:1～1.2.At room temperature stirring reaction is 24 hours, has green solid to form in the reaction system, and green solid is filtered, and with absolute methanol washing 3 times, vacuum drying is clamped type Cu(II accordingly) metal organic complex hydrogel adhesive.Its reaction equation is as follows:
Wherein, the structural formula of three-tooth nitrogen ligand is seen the following formula reaction equation, when X=O, i.e. and 2-furyl, compound is labeled as 1a; When X=S, i.e. 2-thienyl, compound is labeled as 1b.By the synthetic pincers type Cu(II of research institute) metallo-organic complex finds that to the experimental result of the cohesion ability of various solvents compound 2a can effectively realize the gelation to water, minimum one-tenth gum concentration can reach 0.25 wt%, and namely 5.76 * 10
-3Mol/mL can also realize to 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 the water-oil separating of back, we have only used pincers type Cu(II) metallo-organic complex 2a.
With the resulting pincers type of the present invention Cu(II) metallo-organic complex 2 gels are applied to water and other organic alcohols solvent forms gel, and concrete grammar is as follows:
Method 1:
In 5 a mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2Gel, 0.5 mL solvent is with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2,Fully dissolving, stopped heating leaves standstill a period of time to sample bottle.Have green gel to form in the sample bottle, after sample bottle was inverted, gel still remained fixed in the sample bottle bottom.
Method 2:
In 5 a mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 0.5 mL water adds a little magneton at last, with behind the sealing of lid of polyvinyl fluoride, is placed on and stirs on the magnetic stirring apparatus or concussion.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2aFully dissolving stops to stir or concussion, and sample bottle is left standstill a period of time.The Green Water gel-forming is arranged in the sample bottle, and after sample bottle was inverted, hydrogel still remained fixed in the sample bottle bottom.
With the resulting pincers type of the present invention Cu(II) metallo-organic complex 2a hydrogel adhesive is used for the separation of all kinds of oil water mixtures, and concrete steps are as follows:
Method 3:
In 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 1 mL water and 1 mL oil are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2aFully dissolving, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is oil phase, and lower floor is the Green Water gel phase, and after sample bottle was inverted, upper strata oil can be very easy to incline to recovery, and hydrogel still remains fixed in the sample bottle bottom.
Method 4:
In 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 1 mL water and 1 mL oil add a little magneton at last, with behind the sealing of lid of polyvinyl fluoride, are placed on and stir on the magnetic stirring apparatus or concussion.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2aFully dissolving stops to stir or concussion, and sample bottle is left standstill a period of time.Minute have two-layer in the sample bottle, the upper strata is oil phase, lower floor is the Green Water gel phase, after sample bottle is inverted, upper oil phase can be inclined easily and recovery, same hydrogel still remains on the sample bottle bottom relatively, and these class methods are fit to oil slick and are not possessing heating condition very much, and the recycling of oil slick under the environment of sea concussion.
The pincers type Cu(II of the present invention's preparation) metal organic complex hydrogel adhesive under shirtsleeve operation (heating or stirring, concussion condition), can easily and effectively by the selective hydrogel that forms, be realized the quick separation of oil in the oil water mixture.
Description of drawings
Fig. 1 is the pincers type Cu(II of embodiment 1 gained) the metallo-organic complex hydrogel adhesive
2aCrystal structure figure.Main bond distance's [] and bond angle data [°] be:
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 pincers type Cu(II of embodiment 8 gained) the metallo-organic complex hydrogel adhesive
2aThe separating resulting figure that is used for water and n-hexane mixed liquor.
Fig. 3 is the pincers type Cu(II of embodiment 9 gained) the metallo-organic complex hydrogel adhesive
2aThe separating resulting figure that is used for water and normal octane mixed liquor.
Fig. 4 is the pincers type Cu(II of embodiment 10 gained) the metallo-organic complex hydrogel adhesive
2aThe separating resulting figure that is used for water and dimethicone mixed liquor.
Fig. 5 is the pincers type Cu(II of embodiment 11 gained) the metallo-organic complex hydrogel adhesive
2aThe separating resulting figure that is used for water and paraffin oil mixed liquor.
Fig. 6 is the pincers type Cu(II of embodiment 12 gained) the metallo-organic complex hydrogel adhesive
2aThe separating resulting figure that is used for water and pump oil mixed liquor.
Fig. 7 is the pincers type Cu(II of embodiment 13 gained) the metallo-organic complex hydrogel adhesive
2aThe separating resulting figure that is used for water and soya-bean oil mixed liquor.
The specific embodiment
Further specifically describe the present invention below by embodiment, the present invention is not limited to following embodiment.
Embodiment 1:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aPreparation:
In the round-bottomed flask of 250 mL, add respectively three-tooth nitrogen ligand
1a(2.993 g, 10 mmol), Copper dichloride dihydrate (2.05 g, 12 mmol) and 200 mL absolute methanols.At room temperature stirring reaction is 24 hours, has green solid to form in the reaction system, green solid is filtered, with absolute methanol washing 3 times, vacuum drying, the tong type Cu(II that obtains) the organic network thing of metal Heshui gel
2aProductive rate 99%.
Mass spectral analysis:
1H NMR (D
2O, 400 MHz, 353 K): δ=10.68 (bs, 6H), 10.24 (bs, 2H), 10.06 (bs, 3H), 6.91 (bs, 3H); HR-MS (ESI): m/z 397.0043 (Calcd. [M-Cl]
+), 397.0078 (Found. [M-Cl]
+).
Embodiment 2:Pincers type Cu(II) metal organic complex hydrogel adhesive
2bPreparation:
In the round-bottomed flask of 250 mL, add respectively three-tooth nitrogen ligand
1b(0.315 g, 1.0 mmol), Copper dichloride dihydrate (0.205 g, 1.2 mmol) and 20 mL absolute methanols.At room temperature stirring reaction is 24 hours, has green solid to form in the reaction system, green solid is filtered, with absolute methanol washing 3 times, vacuum drying, the pincers type Cu(II that obtains) the metallo-organic complex hydrogel adhesive
2bProductive rate 91%.
Mass spectral analysis: HR-MS (ESI): m/z 412.9815 (Calcd. [M-Cl]
+), 412.9827 (Found. [M-Cl]
+).
Because the paramagnetic properties of copper metal, in addition compound 2b solubility property extreme difference in organic solvent, so From Spectral Signal are difficult to ownership a little less than extremely.
Embodiment 3:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for water and form hydrogel:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 1: in 5 mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 0.5 mL water is with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2a, fully dissolving, stopped heating leaves standstill a period of time to sample bottle.The Green Water gel-forming is arranged in the sample bottle, and after sample bottle was inverted, hydrogel still remained fixed in the sample bottle bottom.
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 2: in 5 mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 0.5 mL water adds a little magneton at last, with behind the sealing of lid of polyvinyl fluoride, is placed on and stirs on the magnetic stirring apparatus or concussion.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2aFully dissolving stops to stir or concussion, and sample bottle is left standstill a period of time.The Green Water gel-forming is arranged in the sample bottle, and after sample bottle was inverted, hydrogel still remained fixed in the sample bottle bottom.
Embodiment 4:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for ethylene glycol and form organogel:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 1: in 5 mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 0.5 mL ethylene glycol is with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2a, fully dissolving, stopped heating leaves standstill a period of time to sample bottle.Have green organogel to form in the sample bottle, after sample bottle was inverted, organogel still remained fixed in the sample bottle bottom.
Embodiment 5:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for 1,3-PD and form organogel:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 1: in 5 mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 0.5 mL 1,3-PD is with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2a, fully dissolving, stopped heating leaves standstill a period of time to sample bottle.Have green organogel to form in the sample bottle, after sample bottle was inverted, organogel still remained fixed in the sample bottle bottom.
Embodiment 6:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for glycerine and form organogel:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 1: in 5 mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2aHydrogel adhesive, 0.5 mL glycerine is with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2a, fully dissolving, stopped heating leaves standstill a period of time to sample bottle.Have green organogel to form in the sample bottle, after sample bottle was inverted, organogel still remained fixed in the sample bottle bottom.
Embodiment 7:Pincers type Cu(II) metallo-organic complex gel
2bBe used for glycerine and form organogel:
Adopt the pincers type Cu(II of embodiment 2 preparations) the metallo-organic complex gel
2bWith method 1: in 5 mL white sample bottle, add successively 5 mg pincers type Cu(II) metallo-organic complex
2bGel, 0.5 mL glycerine is with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metallo-organic complex
2b, fully dissolving, stopped heating leaves standstill a period of time to sample bottle.Have green organogel to form in the sample bottle, after sample bottle was inverted, organogel still remained fixed in the sample bottle bottom.
Embodiment 8:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for separating of water and n-hexane mixed liquor:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 3: in 5 mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL n-hexane are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) the metallo-organic complex hydrogel adhesive dissolves fully, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is n-hexane, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata n-hexane can very easily flow to incline and, and hydrogel still remains fixed in bottom the sample bottle.This separating resulting is seen accompanying drawing 2.
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 4: in 5 mL white sample bottle, add successively 10 mg pincers type Cu(II) metal organic complex hydrogel adhesive, 1 mL water and 1 mL n-hexane add a little magneton at last, behind the sealing of lid with polyvinyl fluoride, be placed on the magnetic stirring apparatus and stir.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metal organic complex hydrogel adhesive dissolves fully, stops to stir, and sample bottle is left standstill a period of time.Minute have two-layerly in the sample bottle, the upper strata is n-hexane, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata n-hexane can very easily flow to incline and, and hydrogel still remains on bottom the sample bottle relatively.
Embodiment 9:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for separating of water and normal octane mixed liquor:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 3, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL normal octane are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metal organic complex hydrogel adhesive dissolves fully, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is normal octane, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata normal octane can very easily flow to incline and, and hydrogel still remains fixed in bottom the sample bottle.This separating resulting is seen accompanying drawing 3.
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 4, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL normal octane, add at last a little magneton, with behind the sealing of lid of polyvinyl fluoride, be placed on the magnetic stirring apparatus and stir.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) the metallo-organic complex hydrogel adhesive dissolves fully, stops to stir, and sample bottle is left standstill a period of time.Minute have two-layerly in the sample bottle, the upper strata is normal octane, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata normal octane can very easily flow to incline and, and hydrogel still remains on bottom the sample bottle relatively.
Embodiment 10:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for separating of water and dimethyl-silicon oil mixture:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 3, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL dimethicone are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metal organic complex hydrogel adhesive dissolves fully, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is dimethicone, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata dimethicone can very easily flow to incline and, and hydrogel still remains fixed in bottom the sample bottle.This separating resulting is seen accompanying drawing 4.
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 4, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL dimethicone, add at last a little magneton, with behind the sealing of lid of polyvinyl fluoride, be placed on the magnetic stirring apparatus and stir.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metal organic complex hydrogel adhesive dissolves fully, stops to stir, and sample bottle is left standstill a period of time.Minute have two-layerly in the sample bottle, the upper strata is dimethicone, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata dimethicone can very easily flow to incline and, and hydrogel still remains on bottom the sample bottle relatively.
Embodiment 11:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for separating of water and paraffin oil mixture:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 3, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL paraffin oil are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) the metallo-organic complex hydrogel adhesive dissolves fully, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is paraffin oil, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata paraffin oil can very easily flow to incline and, and hydrogel still remains fixed in bottom the sample bottle.This separating resulting is seen accompanying drawing 5.
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 4, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL paraffin oil, add at last a little magneton, with behind the sealing of lid of polyvinyl fluoride, be placed on the magnetic stirring apparatus and stir.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) metal organic complex hydrogel adhesive dissolves fully, stops to stir, and sample bottle is left standstill a period of time.Minute have two-layerly in the sample bottle, the upper strata is paraffin oil, and lower floor is the Green Water gel, and after sample bottle was inverted, the upper strata paraffin oil can very easily flow to incline and, and hydrogel still remains on bottom the sample bottle relatively.
Embodiment 12:Pincers type Cu(II) metal organic complex hydrogel adhesive
2aBe used for separating of water and pump oil mixture:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 3, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL pump oil are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) the metallo-organic complex hydrogel adhesive dissolves fully, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is pump oil, and lower floor is the Green Water gel, and after sample bottle was inverted, upper strata pump oil can very easily flow to incline and, and hydrogel still remains fixed in bottom the sample bottle.This separating resulting is seen accompanying drawing 6.
Embodiment 13:Pincers type Cu(II) metallo-organic complex hydrogel adhesive
2aBe used for separating of water and soya-bean oil:
Adopt the pincers type Cu(II of embodiment 1 preparation) the metallo-organic complex hydrogel adhesive
2aWith method 3, in 5 a mL white sample bottle, add successively 10 mg pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL soya-bean oil are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle.When the solution becomes of the inside get transparent, i.e. pincers type Cu(II) the metallo-organic complex hydrogel adhesive dissolves fully, stopped heating leaves standstill a period of time to sample bottle.Minute have two-layerly in the sample bottle, the upper strata is soya-bean oil, and lower floor is the Green Water gel, and after sample bottle was inverted, upper strata soya-bean oil can very easily flow to incline and, and hydrogel still remains fixed in bottom the sample bottle.This separating resulting is seen accompanying drawing 7.
Claims (6)
1. pincers type Cu(II) the little molecular gel agent of metallo-organic complex, its expression formula is NNN-Cu-Cl
2, NNN represents and the three-tooth nitrogen ligand of cupric coordination that concrete structure is as follows:
Wherein, X=O, or S,
When X=O, this pincers type Cu(II) metallo-organic complex and water, ethylene glycol, 1,3-PD or glycerine formation gel;
When X=S, this pincers type Cu(II) metallo-organic complex and glycerine formation gel.
2. the pincers type Cu(II as claimed in claim 1) preparation method of metallo-organic complex gel is characterized in that concrete steps are as follows:
In round-bottomed flask, add respectively three-tooth nitrogen ligand, Copper dichloride dihydrate and absolute methanol, the molar ratio of three-tooth nitrogen ligand and Copper dichloride dihydrate is 1:1～1.2, and at room temperature stirring reaction is 24 hours, has green solid to form in the reaction system, green solid is filtered, with the absolute methanol washing, vacuum drying is clamped type Cu(II accordingly) the metallo-organic complex hydrogel adhesive.
3. pincers type Cu(II as claimed in claim 1) the metallo-organic compound gel is applied to water, ethylene glycol, 1,3-PD or glycerine and forms gel.
4. pincers type Cu(II as claimed in claim 1) the metallo-organic compound gel is used for the separation of oil water mixture, it is characterized in that concrete steps are as follows:
Method 1:
In 5 a mL white sample bottle, add successively the pincers type Cu(II of 10 mg X=O) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL oil are with behind the sealing of lid of polyvinyl fluoride, with heat gun heated sample bottle; Solution becomes when the inside gets transparent, i.e. pincers type Cu(II) the metallo-organic compound hydrogel adhesive dissolves fully, stopped heating, sample bottle is left standstill a period of time, minute have two-layerly in the sample bottle, the upper strata is oil, lower floor is the Green Water gel, after sample bottle was inverted, upper strata oil can very easily flow to incline and, and hydrogel still remains fixed in the sample bottle bottom;
Method 2:
In 5 a mL white sample bottle, add successively 10 mg X=O pincers type Cu(II) the metallo-organic complex hydrogel adhesive, 1 mL water and 1 mL oil add a little magneton at last, with behind the sealing of lid of polyvinyl fluoride, are placed on the magnetic stirring apparatus and stir; Solution becomes when the inside gets transparent, i.e. pincers type Cu(II) the metallo-organic complex hydrogel adhesive dissolves fully, stop to stir, sample bottle is left standstill a period of time, minute have two-layerly in the sample bottle, the upper strata is oil, lower floor is the Green Water gel, after sample bottle was inverted, upper strata oil can very easily flow to incline and, and hydrogel still remains on the sample bottle bottom relatively.
5. pincers type Cu(II according to claim 4) the metallo-organic compound hydrogel adhesive is used for the separation of oil water mixture, it is characterized in that described oil is the liquid grease immiscible with water.
6. pincers type Cu(II according to claim 5) the metallo-organic compound hydrogel adhesive is used for the separation of oil water mixture, it is characterized in that described oil is normal hexane, normal octane, dimethicone, paraffin oil, one or more in pump oil or the soya-bean oil.
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| CN108148078A (en) * | 2018-01-23 | 2018-06-12 | 南华大学 | A kind of copper（II）Complex, hydrogel and its preparation method and application |
| CN110354699A (en) * | 2019-07-10 | 2019-10-22 | 浙江海印数码科技有限公司 | A kind of preparation method of the modified plural gel seperation film of transient state hydrogel and its application method in dye wastewater |
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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 |
| US20110098425A1 (en) * | 2009-10-28 | 2011-04-28 | Giesbrecht Garth R | Catalyst Compounds and Use Thereof |
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| US20110098425A1 (en) * | 2009-10-28 | 2011-04-28 | Giesbrecht Garth R | Catalyst Compounds and Use Thereof |
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| CN108148078A (en) * | 2018-01-23 | 2018-06-12 | 南华大学 | A kind of copper（II）Complex, hydrogel and its preparation method and application |
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