CN102225917A - Preparation method of organic/layered double hydroxide (LDH) complex - Google Patents
Preparation method of organic/layered double hydroxide (LDH) complex Download PDFInfo
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- CN102225917A CN102225917A CN2011100971967A CN201110097196A CN102225917A CN 102225917 A CN102225917 A CN 102225917A CN 2011100971967 A CN2011100971967 A CN 2011100971967A CN 201110097196 A CN201110097196 A CN 201110097196A CN 102225917 A CN102225917 A CN 102225917A
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Abstract
The invention provides a preparation method of an organic/layered double hydroxide (LDH) complex. The preparation method comprises the following steps of a) dissolving 1,10-dioxo-4,7,13, 16-tetranitro-18-crown-6 in a CH2Cl2 solvent, adding anhydrous potassium carbonate into the solution and mixing them, heating and refluxing the mixed solution, then adding ethyl bromoacetate into the mixed solution and refluxing it, then filtering and evaporating the refluxed solution to obtain an oil-like substance, adding hydrochloric acid solution into the oil-like substance, heating, refluxing and filtering the mixed solution, and evaporating the filtrate to make crystals be separated out to obtain 4,7,13,16-tetracarboxymethyl-1,10-dioxo-4,7,13, 16-tetraazaoctadecane (TECA), and b) mixing TECA, NaOH and methanamide, adding MgAl-NO3-LDH into the mixture, standing for 10 minutes to 16 hours, and then centrifuging, washing and drying the mixture to obtain a TECA/LDH complex, wherein a mass ratio of TECA to MgAl-NO3-LDH is 1. Through the preparation method, a TECA/LDH complex can be prepared in a short reaction time thus a production period of the TECA/LDH complex is saved; corrosive effects of methanamide on LDH laminates are reduced and compositions of the laminates are maintained well; and a crystallinity and a yield of complex products are improved.
Description
Technical field
The present invention relates to the synthetic field of organic/LDH matrix material, be specifically related to a kind of carboxylic acid derivative of four Azacrown ether containings, by the organic/LDH complex body and the preparation method of this carboxylic acid derivative preparation.
Background technology
The nano material size is between 1-100nm, and the volume effect that it had, surface effects, quantum size effect and macro quanta tunnel effect make nanoparticle have peculiar performance at aspects such as mechanics, magnetics, optics, chemically reactives.Yet the nano material activity is very high, and very instability, so people proposes Organic and improves nano material stability.
Organic is meant organic and the heterozygosis of inorganic materials on nano level, is a kind of special functional materials.Mineral compound has satisfactory electrical conductivity, mechanicalness, thermostability, magnetic and optical property etc., and organism has structure diversity, mechanics plasticity-, luminous etc., the combination in nanometer range of inorganic nano ion and organic substrate, there are effects such as static, hydrogen bond between two-phase interface, influence the biphase chemical physical property by synergistic effect, form over-all properties and be better than each one-component, and have the not available new function matrix material of single component.Organic is a research field of rising and have development prospect in the materials chemistry recently, has excellent optical property, snappiness and toughness, easily processing, corrosion-resistant, can suppress the oxidation and the reunion of nano unit, make system have higher long-acting stability, important application is arranged at aspects such as biomineralization, degradable environment-friendly type material, biomimetic material, electrode modifications.
Layered double hydroxide (layered double hydroxides, be called for short LDH), it is a kind of ideal layered inorganic material of preparation matrix material, it has laminate structure and the commutative anionic character of interlayer, can form organic/LDH matrix material through ion-exchange or intercalation assembling, have very big application potential in fields such as macromolecular material, drug release and transmission, biosensor, sewage-treating agent, optical materials.
The traditional method for preparing organic/LDH matrix material has co-precipitation, ion-exchange and roasting restoring method etc., peel off in addition in the recent period/assortment and swelling/answer method again, but the contriver find with peel off/assortment and swelling/answers legal system are equipped with and occur laminate in the complex body process and form that to change be the phenomenon of Mg/Al than reduction again, and peel off/arrangement method can destroy LDH precursor pattern.
Summary of the invention
The problem that the present invention solves is to provide a kind of carboxylic acid derivative of four Azacrown ether containings and organic/LDH matrix material and the preparation method who is prepared by this carboxylic acid derivative, make the TECA/LDH complex body, the composition of the fine maintenance laminate of preparation process energy reduces the corrosion of solvent to laminate.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of carboxylic acid derivative, structural formula is:
A kind of preparation method of carboxylic acid derivative comprises:
With CH
2Cl
2As dissolution with solvents 1,10-dioxy-4,7,13,16-four nitrogen-18-hat-6 add Anhydrous potassium carbonate then and mix in solution, and reflux adds ethyl bromoacetate again and refluxes, and with resulting solution filtration, evaporation, obtains oily matter;
Add hydrochloric acid soln in described oily matter, reheat refluxes, and filters gained solution then, evaporates, separates out crystal, obtains carboxylic acid derivative 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane.
As preferably, described CH
2Cl
2Volume and described 1,10-dioxy-4,7,13, the ratio of the mole number of 16-four nitrogen-18-hat-6 is 5L/mol～10L/mol.
As preferably, described Anhydrous potassium carbonate and 1,10-dioxy-4,7,13, the mass ratio of 16-four nitrogen-18-hat-6 is 2～5.
As preferably, the volume of described ethyl bromoacetate and described 1,10-dioxy-4,7,13, the mole ratio of 16-four nitrogen-18-hat-6 is 0.5L/mol～1L/mol.
As preferably, HCl and H in the described hydrochloric acid soln
2The volume ratio of O is 1.5～2.5, and the volume of described hydrochloric acid soln and the mass ratio of described oily matter are 8mL/g～15mL/g.
A kind of organic/the LDH complex body, be 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body uses copper anticathode X-ray diffractometer to measure and obtains X-ray diffractogram, and wherein the pass at spacing d and 2 θ angles, Prague is:
A kind of above-mentioned organic/preparation method of LDH complex body, may further comprise the steps:
With 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, NaOH and methane amide mix, and add MgAl-NO again
3-LDH leaves standstill 10min～16h, and centrifugal then, washing, drying obtain 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body, described 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane and MgAl-NO
3The mass ratio of-LDH is 1.
A kind of organic/the LDH complex body, be 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body uses copper anticathode X-ray diffractometer to measure and obtains X-ray diffractogram, and wherein the pass at spacing d and 2 θ angles, Prague is:
A kind of above-mentioned organic/preparation method of LDH complex body, it is characterized in that, may further comprise the steps:
With 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, NaOH and methane amide mix, and add MgAl-NO again
3-LDH leaves standstill 10min～48h, and centrifugal then, washing, drying obtain 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body; Described 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane and MgAl-NO
3The mass ratio of-LDH is 0.5.
More than among the preparation method of two kinds of organic/LDH complex bodys, as preferably, described MgAl-NO
3The preparation method of-LDH comprises:
1) with Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O and HMT mix soluble in water, and heating is reacted, and cool off then, filtration, washing, drying, make MgAl-CO
3-LDH;
2) to MgAl-CO
3Add NaNO among the-LDH
3And HNO
3Mixing solutions, feed N
2, filter, wash after drying, make MgAl-NO
3-LDH.
As preferably, described 1) Mg (NO in
3)
26H
2O, Al (NO
3)
39H
2The mol ratio of O and HMT is 1～2.5: 0.5～1.5: 2～3.
As preferably, with described Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O and HMT mixing are dissolved in the exhaust water, and the volume of described exhaust water is 50mL～80mL/1mmolAl (NO
3)
39H
2O.
As preferably, described 1) temperature of reaction is 120 ℃～150 ℃ in, and the reaction times is 20h～30h.
As preferably, described 2) NaNO in
3And HNO
3Mixing solutions in NaNO
3Concentration be 1molL
-1～2molL
-1, HNO
3Concentration be 3mmolL
-1～8mmolL
-1, every gram MgAl-CO
3Add the described NaNO of 0.8L～1.5L among the-LDH
3And HNO
3Mixing solutions.
As preferably, described 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13, the mass ratio of 16-tetraazacyclododecane octadecane and NaOH is 5～15: 3～8, the volume of described methane amide and 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13, the mass ratio of 16-tetraazacyclododecane octadecane is 100mL/g～1000mL/g.
The invention provides a kind of carboxylic acid derivative of four Azacrown ether containings, and by the organic/LDH complex body of this carboxylic acid derivative preparation, the preparation method of this organic/LDH complex body utilizes the strong polarity of formamide solvent, LDH can be in methane amide swelling fast, LDH provides free access for the organic object intercalation of large volume, the strong avidity that has between the crown ether carboxylate anion of combined belt negative charge and positive electricity laminate, avoid the method for proceed step by step in the past, with the disposable adding of reactant, successfully synthesize product TECA/LDH complex body in the shorter reaction time, thereby save the production cycle, reduce the corrosion of methane amide to the LDH laminate, the composition that keeps laminate well, and improve complex body degree of crystallinity, improve product yield.
Description of drawings
Fig. 1 is the IR figure of the TECA of specific embodiment of the invention preparation;
Fig. 2 is the MgAl-CO of the embodiment of the invention 1 preparation
3The XRD figure of-LDH;
Fig. 3 is the MgAl-NO of the embodiment of the invention 1 preparation
3The XRD figure of-LDH;
Fig. 4 is the MgAl-CO of the embodiment of the invention 1 preparation
3-LDH and MgAl-NO
3The IR figure of-LDH;
Fig. 5 is the XRD figure of the TECA/LDH complex body of embodiment of the invention 1-3 preparation;
Fig. 6 is the IR figure of the TECA/LDH complex body of embodiment of the invention 1-3 preparation;
Fig. 7 is the SEM photo of the TECA/LDH complex body of embodiment of the invention 1-3 preparation;
Fig. 8 is the XRD figure of the TECA/LDH complex body of embodiment of the invention 4-7 preparation;
Fig. 9 is the IR figure of the TECA/LDH complex body of embodiment of the invention 4-7 preparation;
Figure 10 is the SEM photo of the TECA/LDH complex body of the embodiment of the invention 4 preparations.
Embodiment
For further understanding the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The invention provides a kind of carboxylic acid derivative of four Azacrown ether containings, structural formula is:
The present invention also provides organic/LDH complex body and the preparation method by the TECA preparation.
One, provided by the invention organic/the LDH complex body is 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body uses copper anticathode X-ray diffractometer to measure and obtains X-ray diffractogram, and wherein the pass at spacing d and 2 θ angles, Prague is:
Detect through infrared spectrometer, the contrast relationship of wave number and absorption peak is in its infrared spectra:
| Wave number (cm -1) | |
| 1573 | -COO -Antisymmetric stretching vibration |
| 1405 | -COO
- |
| 1364 | CO 3 2-Absorb |
| 1101 | The |
| 680 | Mg (Al)- |
| 447 | Mg (Al)-O-Mg (Al) flexural vibration |
The preparation method of this organic/LDH complex body may further comprise the steps:
A) preparation 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane (the present invention is called for short TECA):
With CH
2Cl
2As dissolution with solvents 1,10-dioxy-4,7,13,16-four nitrogen-18-is preced with-6 (the present invention is called for short L, and structure iron is as follows), CH
2Cl
2The ratio of volume and the mole number of L be 5L/mol～10L/mol.In solution, add Anhydrous potassium carbonate then and mix, reflux 15min～40min, the mass ratio of Anhydrous potassium carbonate and L is preferably 2～5.Add ethyl bromoacetate backflow 20h～25h again in solution, the volume of ethyl bromoacetate and the mole ratio of L are 0.5L/mol～1L/mol.Gained solution is filtered, evaporates, obtain oily matter (the present invention is called for short L1), in this oily matter L1, add hydrochloric acid soln, reheat backflow 10h～15h, HCl and H in the hydrochloric acid soln
2The volume ratio of O is 1.5～2.5, and the volume of hydrochloric acid soln and the mass ratio of L1 are 8mL/g～15mL/g.Filter the gained solution evaporation at last, separate out crystal, obtain 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane (TECA):
B) preparation TECA/LDH complex body
TECA, NaOH and methane amide are mixed, and the mass ratio of TECA and NaOH is 5～15: 3～8, and methane amide volume and TECA mass ratio are 100mL/g～1000mL/g.Add MgAl-NO again
3-LDH, TECA and MgAl-NO
3The mass ratio of-LDH is 1.Then with solution left standstill 10min～16h, centrifugal again, washing, 25 ℃～70 ℃ following vacuum-dryings obtains the TECA/LDH complex body.
The reactant MgAl-NO that uses among the above preparation method
3-LDH can prepare by the following method:
1) preparation MgAl-CO
3-LDH (HMT hydrolysis method):
With Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O and HMT (hexamethylenetetramine) mix soluble in water, are heated to 120 ℃～150 ℃ reaction 20h～30h, Mg (NO
3)
26H
2O, Al (NO
3)
39H
2The mol ratio of O and HMT is preferably 1～2.5: 0.5～1.5: 2～3; Preferably be dissolved in the exhaust water, exhaust water refers to get rid of CO
2Water, boiled 5min promptly can obtain with distilled water, exhaust volume of water here is preferably 50mL～80mL/1mmolAl (NO
3)
39H
2O.
To react back solution cooling, filtration, washing, drying then, make MgAl-CO
3-LDH.
2) preparation MgAl-NO
3-LDH (acid-salt method):
To MgAl-CO
3Add NaNO among the-LDH
3And HNO
3Mixing solutions, NaNO
3And HNO
3Mixing solutions in NaNO
3Concentration be 1molL
-1～2molL
-1, HNO
3Concentration be 3mmolL
-1～8mmolL
-1, every gram MgAl-CO
3Add this NaNO of 0.8L～1.5L among the-LDH
3And HNO
3Mixing solutions.
Available ultrasonic that solution stirring is even, feed N again
25min～10min stirs 15h～24h, filters then, preferably cleans with exhaust water, 35 ℃～50 ℃ following vacuum-dryings, makes MgAl-NO
3-LDH.
Embodiment 1:
1, preparation MgAl-NO
3-LDH:
With 3.20gMg (NO
3)
26H
2O (0.02mmol), 2.34gAl (NO
3)
39H
2O (0.01mmol) and 2.28gHMT (0.026mmol) add 50ml distilled water, 140 ℃ of reaction 24h in the reactor, and room temperature cooling, suction filtration, washing, seasoning make MgAl-CO
3-LDH.
MgAl-CO
3The XRD figure of-LDH is seen Fig. 2.Interlamellar spacing d
Basal=0.76nm shows formation CO
3-LDH is 0.76, the sharp-pointed diffraction peak respectively corresponding its (003) at 0.38nm place, the diffraction of (006) face.
Claim 1.0g MgAl-CO again
3-LDH adds 1L and contains NaNO
3(concentration is 1.5molL
-1) and HNO
3(concentration is 5mmolL
-1) mixing solutions in, ultrasonic 20min, logical N
25min stirs 24h, and suction filtration, exhaust washing, 40 ℃ of vacuum-dryings make MgAl-NO
3-LDH.
MgAl-NO
3The XRD of-LDH sees Fig. 3.Interlamellar spacing d
Basal=0.89nm shows formation NO
3-LDH is 0.89, the sharp-pointed diffraction peak respectively corresponding (003) at 0.45nm place, the diffraction of (006) face.
Fig. 4 is MgAl-CO
3-LDH and MgAl-NO
3The IR figure of-LDH.Figure a is MgAl-CO
3The IR figure of-LDH is at 1364cm
-1CO appears in the place
3 2-Characteristic absorbance; Figure b is MgAl-NO
3The IR figure of-LDH, 1384cm
-1The place is NO
3 -Characteristic absorbance, CO
3 2-Characteristic absorption band disappear. show CO
3-LDH successfully is exchanged for NO
3-LDH.
2, preparation TECA:
Claim 0.52g L in round-bottomed flask, add 15mL CH
2Cl
2As solvent, add Anhydrous potassium carbonate 1.5g, reflux half an hour add ethyl bromoacetate again, backflow 24h filters resulting solution, revolve steaming, obtains the oily matter of L1.Press HCl: H
2O=2: 1 volume ratio adds hydrochloric acid and water mixed liquid 20mL, and reflux 12h filters the gained solution evaporation, separates out the TECA crystal, filters and collect crystal.
3, preparation TECA/LDH complex body
Claim 0.075gTECA, 0.04gNaOH, add the 30mL methane amide, ultrasonic dissolving fully adds 0.075gMgAl-NO
3-LDH shakes up, and leaves standstill 10min, and is centrifugal then, exhaust washing four times, 40 ℃ of vacuum-dryings.
Embodiment 2:
Embodiment 3:
TECA to the embodiment preparation characterizes:
Please refer to Fig. 1, Fig. 1 is the IR figure of TECA.As seen from the figure, N-H stretching vibration absorption band completely dissolve in the crown ether cycle illustrates that the H atom on the N-H is replaced fully.1747 and 1429cm
-1The absorption at place is respectively-and the unsymmetrically of COOH and symmetrical stretching vibration absorb, and 1199 and 1116cm
-1Be the characteristic absorbance of C-O-C in the crown ether cycle, 2915cm
-1Stretching vibration absorption for saturated C-H.Can judge the carboxylic acid derivative TECA that successfully obtains four Azacrown ether containings thus.
The structural characterization of complex body:
The resulting sample of embodiment 1-3 is carried out X-ray powder diffraction (XRD), infrared analysis (IR) and scanning electron microscope (SEM) test.
(1) XRD analysis: Fig. 5 is the XRD figure of the TECA/LDH complex body of embodiment of the invention 1-3 preparation.The XRD figure of (a) TECA/LDH complex body of preparing during for 10min for embodiment 1 time of repose wherein, (a ') be the Small angle XRD figure of correspondence (a); (b) XRD figure of the TECA/LDH complex body for preparing during for 12h for embodiment 2 time of repose, (b ') be the Small angle XRD figure of correspondence (b); (c) XRD figure of the TECA/LDH complex body for preparing during for 16h for embodiment 3 time of repose, (c ') be the Small angle XRD figure of correspondence (c).
Complex body (figure c, the c ') product of reaction 10min gained complex body (figure a, a ') and 16h gained has one to overlap XRD diffraction peak: d=1.80, and 0.90,0.60,0.45,0.36 and 0.30nm, diffraction peak is sharp-pointed and symmetrical, illustrates that product degree of crystallinity is higher.D=1.80nm=1.32+0.48nm, the about 1.32nm of corresponding interfloor height is that the vertical laminate of TECA is arranged.
This experiment swelling speed is very fast, can finish at short notice, and this method can effectively reduce CO by shortening the reaction times
2Interference, avoid CO
3 2-Enter interlayer and form dephasign.
(2) infrared analysis: Fig. 6 is the IR figure of the TECA/LDH complex body of embodiment of the invention 1-3 preparation.The IR figure of (a) TECA/LDH complex body of preparing during for 10min for embodiment 1 time of repose wherein; (b) the IR figure of the TECA/LDH complex body for preparing during for 12h for embodiment 2 time of repose; (c) the IR figure of the TECA/LDH complex body for preparing during for 16h for embodiment 3 time of repose.
1364cm
-1The place is absorbed as CO
3 2-Characteristic absorption band, CO as seen from the figure
3 2-There is trace to change with the relative quantity of TECA with the reaction times.
(3) the SEM pattern characterizes: Fig. 7 is the SEM photo of the TECA/LDH complex body of embodiment of the invention 1-3 preparation.Can see that complex body is the hexagon pattern of homogeneous, side dimension is about 1 μ m, and thickness is about 0.1 μ m, shows that the degree of crystallinity of complex body is very high.
The complex body compositional analysis:
By table 2 data as seen, preparation method's gained complex body provided by the invention has kept the laminate of LDH presoma to form, and the Mg/Al mol ratio is constant, is 2: 1.
The compositional analysis of table 2 embodiment 1-3 differential responses time gained complex body
Two, the present invention also provides another kind of TECA/LDH complex body, uses copper anticathode X-ray diffractometer to measure and obtains X-ray diffractogram, and wherein the pass at spacing d and 2 θ angles, Prague is:
Detect through infrared spectrometer, the contrast relationship of wave number and absorption peak is in its infrared spectra:
| Wave number (cm -1) | |
| 1624 | H 2O-H flexural vibration among the O |
| 1578 | -COO -Antisymmetric stretching vibration |
| 1401 | -COO -Symmetrical stretching vibration |
| 1384 | NO
3 -Middle |
| 1365 | CO
3 2-Middle |
| 1105 | The C-O-C stretching vibration |
| 686 | Mg (Al)- |
| 447 | Mg (Al)-O-Mg (Al) flexural vibration |
A) preparation of TECA is identical with first kind of preparation method among the preparation method of this TECA/LDH complex body, when step b) prepares the TECA/LDH complex body, and TECA and MgAl-NO
3The mass ratio of-LDH is 0.5.The solution left standstill time is 10min～48h then, and other condition is all identical.
Embodiment 4:
Embodiment 5:
TECA and MgAl-NO
3The time of repose that-LDH mixes after shaking up is 12h, and other step is identical with embodiment 4.
Embodiment 6:
TECA and MgAl-NO
3The time of repose that-LDH mixes after shaking up is 24h, and other step is identical with embodiment 4.
Embodiment 7:
TECA and MgAl-NO
3The time of repose that-LDH mixes after shaking up is 48h, and other step is identical with embodiment 4.
The structural characterization of complex body:
The resulting sample of embodiment 4-7 is carried out X-ray powder diffraction (XRD), infrared analysis (IR) and scanning electron microscope (SEM) test.
(1) XRD analysis: Fig. 8 is the XRD figure of the TECA/LDH complex body of embodiment of the invention 4-7 preparation.The XRD figure of (a) TECA/LDH complex body of preparing during for 10min for embodiment 4 time of repose wherein, (a ') be the Small angle XRD figure of correspondence (a); (b) XRD figure of the TECA/LDH complex body for preparing during for 12h for embodiment 5 time of repose, (b ') be the Small angle XRD figure of correspondence (b); (c) XRD figure of the TECA/LDH complex body for preparing during for 24h for embodiment 6 time of repose, (c ') be the Small angle XRD figure of correspondence (c); (d) XRD figure of the TECA/LDH complex body for preparing during for 48h for embodiment 7 time of repose, (d ') be the Small angle XRD figure of correspondence (d).
As seen from the figure, complex body is at d
BasalOne cover diffraction peak appears in=1.50nm, 0.75nm, 0.50nm place, and diffraction peak is sharp-pointed and symmetrical, illustrates that the product crystallinity is fine.1.50nm d
BasalThe corresponding interfloor height of interlayer is 1.02nm (1.50-0.48nm), is the arrangement mode of the vertical laminate of crown ether molecule.Small angle range (2-8 °) XRD tests discovery, at d
Basal=2.35nm (=1.50+0.85nm) secondary occurs to pass rank (staging) structure, be crown ether phase (1.50nm) and NO that vertical laminate is arranged
3 -/ CO
3 2-The ordered arrangement of intercalation phase (0.85nm).This staging structure has promptly appearred in the sample of short period of time 10min (figure a, a '), illustrates that the swelling speed of this method is very fast, and very strong avidity is arranged between crown ether molecule TECA and laminate, and intercalation can be finished at short notice.
(2) infrared analysis: Fig. 9 is the IR figure of the TECA/LDH complex body of embodiment of the invention 4-7 preparation.The IR figure of (a) TECA/LDH complex body of preparing during for 10min for embodiment 4 time of repose wherein; (b) the IR figure of the TECA/LDH complex body for preparing during for 12h for embodiment 5 time of repose; (c) the IR figure of the TECA/LDH complex body for preparing during for 24h for embodiment 6 time of repose; (d) the IR figure of the TECA/LDH complex body for preparing during for 48h for embodiment 7 time of repose.
As seen from the figure, 1587cm is arrived in the difference red shift in complex body of the carboxyl of TECA and crown ether cycle C-O absorption of vibrations
-1(belong to-COO
-) and 1105cm
-1, illustrate that there are interaction in crown ether molecule (TECA) and LDH laminate and middle water.Complex body is at 1384cm
-1And 1365cm
-1NO appears respectively in the place
3 -CO
3 2-Characteristic absorbance, illustrate that there is NO in interlayer
3 -And CO
3 2-, its reason is reducing to NO of crown ether concentration
3 -And CO
3 2-Enter interlayer chance is provided, the effect of compensation charge is also played in the existence of these two kinds of inorganic anions, and the formation for the staging structure simultaneously provides possibility.In addition, 686cm
-1And 447cm
-1Absorption band, belong to the absorption of vibrations of M-O on the laminate, further specify the formation of complex body.
(3) the SEM pattern characterizes: Figure 10 is the SEM photo of the TECA/LDH complex body of the embodiment of the invention 4 preparations.As seen complex body is the hexagon pattern of homogeneous, and (scheme a), side dimension 2～4 μ m (figure b) show that the degree of crystallinity of complex body is very high to the about 0.1 μ m of thickness, illustrate that this method preparation is applicable to the preparation of the complex body of tool staging structure, exists broad applicability.
More than to provided by the present invention a kind of organic/LDH complex body and preparation method be described in detail.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, also can carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (12)
1. the carboxylic acid derivative of an Azacrown ether containing is characterized in that, structural formula is:
Name is called 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane.
2. the preparation method of a carboxylic acid derivative is characterized in that, comprising:
With CH
2Cl
2As dissolution with solvents 1,10-dioxy-4,7,13,16-four nitrogen-18-hat-6 add Anhydrous potassium carbonate then and mix in solution, and reflux adds ethyl bromoacetate again and refluxes, and with resulting solution filtration, evaporation, obtains oily matter;
Add hydrochloric acid soln in described oily matter, reheat refluxes, and filters gained solution then, evaporates, separates out crystal, obtains carboxylic acid derivative 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane.
3. preparation method according to claim 2 is characterized in that, described CH
2Cl
2Volume and described 1,10-dioxy-4,7,13, the ratio of the mole number of 16-four nitrogen-18-hat-6 is 5L/mol～10L/mol; Described Anhydrous potassium carbonate and 1,10-dioxy-4,7,13, the mass ratio of 16-four nitrogen-18-hat-6 is 2～5; The volume of described ethyl bromoacetate and described 1,10-dioxy-4,7,13, the mole ratio of 16-four nitrogen-18-hat-6 is 0.5L/mol～1L/mol.
4. preparation method according to claim 2 is characterized in that, HCl and H in the described hydrochloric acid soln
2The volume ratio of O is 1.5～2.5, and the volume of described hydrochloric acid soln and the mass ratio of described oily matter are 8mL/g～15mL/g.
5. organic/LDH complex body is characterized in that, is 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body uses copper anticathode X-ray diffractometer to measure and obtains X-ray diffractogram, and wherein the pass at spacing d and 2 θ angles, Prague is:
A claim 5 described organic/preparation method of LDH complex body, it is characterized in that, may further comprise the steps:
With 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, NaOH and methane amide mix, and add MgAl-NO again
3-LDH leaves standstill 10min～16h, and centrifugal then, washing, drying obtain 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body;
Described 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane and MgAl-NO
3The mass ratio of-LDH is 1.
7. organic/LDH complex body is characterized in that, is 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body uses copper anticathode X-ray diffractometer to measure and obtains X-ray diffractogram, and wherein the pass at spacing d and 2 θ angles, Prague is:
A claim 7 described organic/preparation method of LDH complex body, it is characterized in that, may further comprise the steps:
With 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, NaOH and methane amide mix, and add MgAl-NO again
3-LDH leaves standstill 10min～48h, and centrifugal then, washing, drying obtain 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane/LDH complex body;
Described 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13,16-tetraazacyclododecane octadecane and MgAl-NO
3The mass ratio of-LDH is 0.5.
9. according to claim 6 or 8 described preparation methods, it is characterized in that described MgAl-NO
3The preparation method of-LDH comprises:
1) with Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O and HMT mix soluble in water, and heating is reacted, and cool off then, filtration, washing, drying, make MgAl-CO
3-LDH;
2) to MgAl-CO
3Add NaNO among the-LDH
3And HNO
3Mixing solutions, feed N2, filter, the washing after drying, make MgAl-NO
3-LDH.
10. preparation method according to claim 9 is characterized in that, described 1) and middle Mg (NO
3)
26H
2O, Al (NO
3)
39H
2The mol ratio of O and HMT is 1～2.5: 0.5～1.5: 2～3, and mixing is dissolved in the exhaust water, and described exhaust volume of water is 50mL～80mL/1mmolAl (NO
3)
39H
2O; Temperature of reaction is 120 ℃～150 ℃, and the reaction times is 20h～30h.
11. preparation method according to claim 9 is characterized in that, described 2) and middle NaNO
3And HNO
3Mixing solutions in NaNO
3Concentration be 1molL
-1～2molL
-1, HNO
3Concentration is 3mmolL
-1～8mmolL
-1, every gram MgAl-CO
3Add the described NaNO of 0.8L～1.5L among the-LDH
3And HNO
3Mixing solutions.
12., it is characterized in that described 4 according to claim 6 or 8 described preparation methods, 7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13, the mass ratio of 16-tetraazacyclododecane octadecane and NaOH is 5～15: 3～8, the volume of described methane amide and 4,7,13,16-tetracarboxylic acid methyl isophthalic acid, 10-dioxy-4,7,13, the mass ratio of 16-tetraazacyclododecane octadecane is 100mL/g～1000mL/g.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103093967A (en) * | 2013-01-24 | 2013-05-08 | 西北师范大学 | Preparation and application of laminated structure cobalt and aluminum double hydroxide-reduction and oxidation graphene composite materials |
| CN103230776A (en) * | 2013-04-26 | 2013-08-07 | 北京师范大学 | Lamellar hydroxide composite material and preparation method thereof |
| CN104151367A (en) * | 2014-08-06 | 2014-11-19 | 北京师范大学 | Rare earth lanthanum complex and synthetic method thereof |
| CN104151368A (en) * | 2014-08-06 | 2014-11-19 | 北京师范大学 | Rare earth europium complex and synthetic method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103093967A (en) * | 2013-01-24 | 2013-05-08 | 西北师范大学 | Preparation and application of laminated structure cobalt and aluminum double hydroxide-reduction and oxidation graphene composite materials |
| CN103230776A (en) * | 2013-04-26 | 2013-08-07 | 北京师范大学 | Lamellar hydroxide composite material and preparation method thereof |
| CN103230776B (en) * | 2013-04-26 | 2016-01-20 | 北京师范大学 | A kind of Lamellar hydroxide composite material and preparation method thereof |
| CN104151367A (en) * | 2014-08-06 | 2014-11-19 | 北京师范大学 | Rare earth lanthanum complex and synthetic method thereof |
| CN104151368A (en) * | 2014-08-06 | 2014-11-19 | 北京师范大学 | Rare earth europium complex and synthetic method thereof |
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