CN104058469A - Carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite material and preparation method thereof - Google Patents
Carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of organic-inorganic composites and in particular relates to a carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite material and a preparation method thereof. The hydrotalcite material is prepared by the steps of preparing carboxymethyl modified beta-cyclodextrin intercalated cobalt-iron hydrotalcite, fully mixing the hydrotalcite and epichlorohydrin under the condition of strong alkaline, and then carrying out polymerization reaction on interlayer cyclodextrin and the epichlorohydrin to obtain the carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite material. A chemical formula of the carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite material is [(Co<2+>)1-x(Fe<3+>)x(OH)2]<x+>(CMCDP<n->)x/n.mH2O, wherein x is equal to 0.25-0.33, m is equal to 3-6 and is an amount of interlayer crystal water molecules, and n is equal to 25-50 and is an amount of negative charges carried by carboxymethyl-beta-cyclodextrin polymer. Compared with monomer cyclodextrin intercalated hydrotalcite, the carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite has the advantages of more convenience, stronger stability, higher repeated utilization ratio, larger application range and the like. The preparation method is simple and feasible and is easy to realize.
Description
Technical field
The present invention relates to composite organic-inorganic material field, be specifically related to a kind of carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material and preparation method thereof.
Background technology
Hydrotalcite (Layered Double Hydroxides is called for short LDHs), is an anionoid type stratified material, and its chemical constitution is [M
2+ 1-xm
3+ x(OH)
2]
x+(A
n–)
x/nmH
2o.This material is comprised of the laminate being parallel to each other, and laminate is with permanent positive charge.M
2+, M
3+be divalence and trivalent metal cation, interlayer has tradable negatively charged ion A
n-to maintain charge balance.Between hydrotalcite laminate there is strong covalent bond effect in element, and interlayer anion and laminate attract each other with electrostatic attraction, and whole crystal is electric neutrality.Because having laminate metal ion and interlayer anion Modulatory character, hydrotalcite-like material has been widely used in the fields such as catalysis, absorption, medicament slow release, ion-exchange.
Cyclodextrin is by α-1 by D-glucopyranose units, the cyclic oligosaccharide that 4-glycosidic link is formed by connecting, it is the round table-like molecule that " interior hydrophobic; outer hydrophilic " has certain size cavity, modal cyclodextrin be α-, β-and γ-cyclodextrin, 6,7 and 8 D-(+)-Glucopyranose had respectively.For beta-cyclodextrin, outside surface has 7 primary hydroxyls to be positioned at thin mouthful of end of cavity, and 14 secondary hydroxyls are positioned at wealthy mouthful of end of cavity.Cyclodextrin cavity inside only has hydrogen atom and glucosides Sauerstoffatom, have hydrophobicity, and the hydroxyl of cavity port makes cyclodextrin outside have wetting ability.Hydrophobic and the outside hydrophilic characteristic of its inner chamber makes it according to Van der Waals force, hydrophobic interaction power, the intermolecular matching effect of Subjective and Objective etc. and many organic and inorganic molecule formation inclusion compound and molecular assembly systems, become chemistry and the interested research object of chemical research person.
Since last century Mo, scientists just attempts using the cyclodextrin of modifying as a kind of " object " molecule, introducing hydrotalcite layers, and has studied the cyclodextrin of derivatize in great detail in the absorption inclusion character of the situation of arranging, thermostability and the centering guest molecule of hydrotalcite layers etc.In the research of two more than ten years, lot of experimental data shows anion modified cyclodextrin to insert hydrotalcite layers, realized the immobilization of cyclodextrin, and have easily synthetic, cheap, advantages of environment protection, so this material is generally considered to have the prospect of the field application such as chiral separation racemic modification and absorption organic pollutant in industry.
Yet investigator also finds such cyclodextrin intercalation hydrotalcite material and in application, has an obvious defect.In these materials, anion modified cyclodextrin and hydrotalcite rely on electrostatic attraction to combine, and this bonding force is not strong, and cyclodextrin is easy to be replaced by other higher negatively charged ion of negative charge density; For example, the cyclodextrin of intercalation is easy to be replaced by the carbonate of the water-soluble formation of airborne carbonic acid gas.Therefore these anion modified cyclodextrin intercalated hydrotalcite materials mostly require to carry out under nitrogen protection when application, and this has seriously limited the application of this class material.
In other research field of cyclodextrin, scientific research personnel also adopts cross-linking method that cyclodextrin is reacted with compounds such as epoxide, formaldehyde, allyl groups, prepared cross-linking type cyclodextrin, realized the immobilized of cyclodextrin, facilitated cyclodextrin foodstuff additive, medicine control discharge etc. with the closely-related field of people's lives in application.
At document (1) Eur.Polym.J, 1997, in Vol.33No.1:49-57, the people such as E.Renard be take epoxy chloropropane and have been prepared beta cyclo dextrin polymer as linking agent, inquired into synthetic mechanism, analyze the impact of different synthetic schemess on the performance of product, and furtherd investigate the physico-chemical property of beta-cyclodextrin cross-linked polymer.
At document (2) Chin.J.Chem.Eng., 2012, in Vol.20:784-792, the people such as Jiang Hongguo have obtained cyclodextrin by cyclodextrin and epoxy chloropropane polymerization reaction take place, by multiple characterization method, analyze this polymkeric substance, and studied the application of this polymkeric substance at catalytic field.
At present there is no relevant cyclodextrin both at home and abroad and at the direct polymerization reaction take place of hydrotalcite layers, obtain document and the patent report of cyclodextrin intercalated houghite.
Summary of the invention
The object of the invention is to provide a kind of carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material, carboxymethyl-beta-cyclodextrin in this material exists with polymer form in hydrotalcite layers, its Stability Analysis of Structures, can do not replaced by other negatively charged ion, be particularly suitable for using under air conditions, there is very high using value; The present invention provides its preparation method simultaneously.
Carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material of the present invention, first to prepare carboxymethyl-beta-cyclodextrin (CMCD) intercalation ferro-cobalt hydrotalcite, then this hydrotalcite is put into NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution, the polyreaction of carboxymethyl-beta-cyclodextrin and epoxy chloropropane between genetic horizon, obtains the hydrotalcite material of carboxymethyl-beta-cyclodextrin polyalcohol intercalation.
The hydrotalcite of carboxymethyl-beta-cyclodextrin polymkeric substance of the present invention (CMCDP) intercalation is supramolecular structure, and its crystalline structure is the crystalline structure of houghite material, and its chemical formula is:
[(Co
2+)
1-x(Fe
3+)
x(OH)
2]
x+(CMCDP
n-)
x/n·mH
2O
X=0.25～0.33 wherein, m=3～6, m is the quantity of interlayer crystal water molecule, n=25～50, n is the electronegative quantity of carboxymethyl-beta-cyclodextrin polymkeric substance.
The preparation method of described carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material, comprises the steps:
The preparation of A, hydrotalcite precursor:
Anion N O between prepared layer
3 -or Cl
-, laminate Co
2+, Fe
3+mol ratio Co
2+/ Fe
3+=2～3 hydrotalcite NO
3-LDHs or Cl-LDHs:
By Co
2+soluble salt and Fe
3+soluble salt be mixed with mixing solutions, Co wherein
2+/ Fe
3+=2～3, Co
2+volumetric molar concentration be 0.1～0.7M, Fe
3+volumetric molar concentration be 0.03～0.35M; Take NaOH as alkaline solution, and wherein NaOH volumetric molar concentration is 1.0～5.0M, at room temperature N
2under protective condition; adopting two methods of dripping that soluble salt mixing solutions and alkaline solution are added in four-hole bottle, is 8～10 with 0.1～5.0M NaOH solution adjust pH after having added, by 60～80 ℃ of crystallization 24～72h of gained slurries again; then throw out is filtered, repeatedly with removing CO
2deionized water wash repeatedly, until washings pH=7 obtains hydrotalcite precursor;
Described Co
2+soluble salt be hydrochloride or nitrate, Fe
3+soluble salt be hydrochloride or nitrate, and Co
2+soluble salt and Fe
3+the kind of soluble salt identical;
B, carboxymethyl-beta-cyclodextrin intercalated ferro-cobalt hydrotalcite:
Carboxymethyl-beta-cyclodextrin is dissolved in and removes CO
2deionized water in, then the hydrotalcite precursor that steps A is obtained joins in this solution, N
2protection is heated to 60～80 ℃, stirs lower reaction 24～48h, then throw out is filtered, repeatedly with removing CO
2deionized water wash repeatedly, until washings pH=7 obtains carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs;
C, carboxymethyl-beta-cyclodextrin and epoxy chloropropane are in hydrotalcite layers polymerization:
The carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs that step B is obtained, puts into the Erlenmeyer flask that fills NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution, at N
2protect and stir down and place 5-10h, wherein NaOH solution volumetric molar concentration is 3.0～6.0M, the volume ratio of three kinds of liquid is NaOH: methyl-sulphoxide: epoxy chloropropane=3: 4: 4, this Erlenmeyer flask is put into ultrasonic oscillation device, supersound process 0.5h, when ultrasonic, control temperature and be no more than 25 ℃, add again ethylene glycol 0.5mL, altogether hot 1～2h at 50～70 ℃, then mixed solution is poured out, twice of washing with acetone of product, again repeatedly with distilled water wash repeatedly, until washings pH is 7, taking-up is dried, can obtain the hydrotalcite CMCDP-LDHs of cyclodextrin intercalation.
The intercalation product making is carried out to XRD, infrared spectrum characterization.
By above-mentioned materials carry out XRD, infrared spectrum characterization shows the hydrotalcite of successfully having prepared cyclodextrin intercalation.By the known carboxymethyl-beta-cyclodextrin polymkeric substance of XRD structural parameter, in hydrotalcite layers, take the monolayer alignment mode of the vertical laminate of axis, after polymerization reaction take place, interlamellar spacing does not increase, and shows that carboxymethyl-beta-cyclodextrin does not change at the configuration of interlayer in polymerization process.And its unit cell parameters a value is close with other hydrotalcite, show that product has complete laminate structure.After cyclodextrin intercalated houghite is positioned in sodium carbonate solution and is fully soaked, then do X-ray diffraction analysis, find d
003interlamellar spacing changes not obvious, illustrates that the polymerization carboxymethyl-beta-cyclodextrin of interlayer can not replaced by carbonate.From infrared spectra, can find out, after polyreaction-OH stretching vibration peak intensity weakens gradually, illustrate that CMCD with epoxy chloropropane, polymerization has occurred really, and the further feature peak of cyclodextrin and carboxymethyl do not have considerable change, illustrates and there is no other side reaction generation.
The present invention utilizes the interlayer ion interchangeability of hydrotalcite and veneer structure orientation effect, and the first intercalation of carboxymethyl-beta-cyclodextrin negatively charged ion (CMCD) is entered to hydrotalcite layers, makes organic-inorganic nanocomposite.Again CMCD-LDHs is placed in high density epoxy chloropropane solution (NaOH solution: methyl-sulphoxide: the volume ratio of epoxy chloropropane is 3: 4: 4) enough for a long time, makes epoxy chloropropane fully be diffused into hydrotalcite layers.By the polyreaction of cyclodextrin and epoxy chloropropane in suitable heating trigger layer, make and contain high stability carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite stratified composite.
The present invention has following beneficial effect:
In the carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material that the present invention prepares, carboxymethyl-beta-cyclodextrin exists with polymer form in hydrotalcite layers.Because the carboxymethyl-beta-cyclodextrin polymer molecule forming in interlayer is bulky, and with a lot of electric charges, cannot be replaced by negatively charged ion such as carbonates, be particularly suitable for using under air conditions, in use no longer need nitrogen protection.Compare with monomer cyclodextrin intercalation hydrotalcite, that this cyclodextrin intercalated houghite has is more convenient, more stable, can repeating utilization factor the advantage such as higher and Application Areas is larger.Its preparation method is simple, is easy to realize.
Accompanying drawing explanation
Fig. 1 is the structural representation of the hydrotalcite of carboxymethyl-beta-cyclodextrin polyalcohol intercalation.
Fig. 2 is the X-ray powder diffraction figure of hydrotalcite material of the carboxymethyl-beta-cyclodextrin polyalcohol intercalation of embodiment 1 preparation.
The carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of a-;
B-carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite;
C-is soaked in the carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite after sodium carbonate solution;
Fig. 3 is the infrared spectrogram of hydrotalcite material of the carboxymethyl-beta-cyclodextrin anionic polymer intercalation of embodiment 1 preparation.
The carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of a-;
B-carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Steps A: take 11.64g Co (NO
3)
2﹒ 6H
2o, 8.08g Fe (NO
3)
3﹒ 9H
2o is dissolved in 100ml and removes CO
2deionized water in prepare mixing salt solution, separately get 5.60g NaOH and be dissolved in 50ml and remove CO
2deionized water in prepare alkaline solution, N under room temperature
2protection adopts two methods of dripping that mixing salt solution and alkaline solution are added in four-hole bottle, stirs mixing speed 600rpm.With 0.2mol/L NaOH solution, regulating pH value is 8.Gained slurries, in 60 ℃ of crystallization 72h, then filter throw out, repeatedly spend CO
2water washing repeatedly, until washings pH=7 obtains hydrotalcite precursor NO
3-LDHs, its Co
2+/ Fe
3+=2.
Step B: 1.0g carboxymethyl-beta-cyclodextrin (CMCD) solid is dissolved in to 100mL and removes CO
2deionized water after proceed in four-hole bottle, then add and fill the hydrotalcite precursor NO that 15.0g steps A obtains
3-LDHs, N
2protection is heated to 60 ℃, and 600rpm stirs lower reaction 48h.Then throw out is filtered, repeatedly with removing CO
2deionized water wash repeatedly, until washings pH=7 can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs.
Step C: the carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs that 10g step B is obtained, puts into the Erlenmeyer flask that fills NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution 75mL, at N
2protection 300rpm stir the lower 5h of placement, and wherein NaOH solution volumetric molar concentration is 6.0M, and the volume ratio of three kinds of liquid is (V (NaOH): V (methyl-sulphoxide): V (epoxy chloropropane)=3: 4: 4).This Erlenmeyer flask is put into ultrasonic oscillation device, and under ultrasonic frequency 35kHZ condition, supersound process 0.5h can adopt and add the method control temperature of ice cube to be no more than 25 ℃ when ultrasonic.Add again ethylene glycol 0.5mL, at 50 ℃, be total to hot 2h, then mixed solution is poured out, washing with acetone twice for product, more repeatedly with distilled water wash repeatedly, until washings pH is 7, taking-up is dried, and can obtain the hydrotalcite CMCDP-LDHs of cyclodextrin intercalation, and its structural representation is shown in Fig. 1.
In the present embodiment, product chemical formula is: [(Co
2+)
0.67(Fe
3+)
0.33(OH)
2]
0.33+(CMCDP
33.62-)
0.00984H
2o.From X-ray diffraction Fig. 1, hydrotalcite has six comparatively desirable side's laminate structures, and crystalline phase is single, and degree of crystallinity is better.The d of cyclodextrin intercalated houghite (CMCDP-LDHs)
003interlamellar spacing is 1.559nm, compared with the interlamellar spacing of cyclodextrin intercalation hydrotalcite before polymerization (CMCD-LDHs), does not obviously increase.This phenomenon shows in polymerization process, and the agent structure of carboxymethyl-beta-cyclodextrin and cyclodextrin, at the configuration of hydrotalcite layers, considerable change does not occur, and just between cyclodextrin, by hydroxyl and propylene oxide generation polymerization, formed polymkeric substance.Cyclodextrin intercalated houghite is positioned in 0.1M sodium carbonate solution and is soaked after 4h, then do X-ray diffraction analysis, find d
003interlamellar spacing is 1.571nm, illustrates that the carboxymethyl-beta-cyclodextrin polymkeric substance of interlayer can not replaced by carbonate.
By infrared spectra Fig. 2, find out that CMCD-LDHs and CMCDP-LDHs are at 1607,1421cm
– 1all having there is the asymmetric of carboxyl and symmetrical stretching vibration peak in place, has confirmed that considerable change does not occur the agent structure of carboxymethyl-beta-cyclodextrin in polyreaction.And be positioned at 3458cm
-1place-OH stretching vibration peak intensity weakens gradually, illustrate that polymerization has occurred the certain and epoxy chloropropane of CMCD.
Embodiment 2
Steps A: take 9.52g CoCl
2﹒ 6H
2o, 5.40g FeCl
3﹒ 6H
2o is dissolved in 100ml and removes CO
2deionized water preparation mixing salt solution, separately get 8.00g NaOH and be dissolved in 50ml and remove CO
2in water, prepare alkaline solution, N under room temperature
2protection adopts two methods of dripping that salts solution and alkaline solution are added in four-hole bottle, and 600rpm stirs.With 1.0mol/L NaOH solution, regulating pH value is 10.Gained slurries, in 80 ℃ of crystallization 24h, then filter throw out, repeatedly spend CO
2water washing repeatedly, until washings pH=7 obtains hydrotalcite precursor Cl-LDHs, its Co
2+/ Fe
3+=2.
Step B: 1.0g carboxymethyl-beta-cyclodextrin (CMCD) solid is dissolved in to 100mL and removes CO
2deionized water after proceed in four-hole bottle, then add and fill the hydrotalcite precursor Cl-LDHs that 14.0g steps A obtains, N
2protection is heated to 80 ℃, and 600rpm stirs lower reaction 24h.Then throw out is filtered, repeatedly spend CO
2water washing repeatedly, until washings pH=7 can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs.
Step C: the carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs that 10.0g step B is obtained, puts into the Erlenmeyer flask that fills NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution 75mL, at N
2protection, 300rpm stirs the lower 10h of placement, and wherein NaOH solution volumetric molar concentration is 3.0M, and the volume ratio of three kinds of liquid is (V (NaOH): V (methyl-sulphoxide): V (epoxy chloropropane)=3: 4: 4).This Erlenmeyer flask is put into ultrasonic oscillation device, and under ultrasonic frequency 35kHZ condition, supersound process 0.5h can adopt and add the method control temperature of ice cube to be no more than 25 ℃ when ultrasonic.Add again ethylene glycol 0.5mL, at 70 ℃, be total to hot 1h, then mixed solution is poured out, washing with acetone twice for product, more repeatedly with distilled water wash repeatedly, until washings pH is 7, taking-up is dried, and can obtain the hydrotalcite CMCDP-LDHs of cyclodextrin intercalation.
In the present embodiment, product chemical formula is: [(Co
2+)
0.68(Fe
3+)
0.32(OH)
2]
0.32+(CMCDP
25.42-)
0.0133H
2o.From X-ray diffractogram, hydrotalcite has six comparatively desirable side's laminate structures, and crystalline phase is single, and degree of crystallinity is better.The d of cyclodextrin intercalated houghite (CMCDP-LDHs)
003interlamellar spacing is 1.562nm, compared with the interlamellar spacing of cyclodextrin intercalation hydrotalcite before polymerization (CMCD-LDHs), does not obviously increase.This phenomenon shows in polymerization process, and the agent structure of carboxymethyl-beta-cyclodextrin and cyclodextrin, at the configuration of hydrotalcite layers, considerable change does not occur, and just between cyclodextrin, by hydroxyl and propylene oxide generation polymerization, formed large polymkeric substance.Cyclodextrin intercalated houghite is positioned in 0.1M sodium carbonate solution and is soaked after 4h, then do X-ray diffraction analysis, find d
003interlamellar spacing is 1.583nm, illustrates that the polymerization carboxymethyl-beta-cyclodextrin of interlayer can not replaced by carbonate.
By infrared spectrogram, find out that CMCD-LDHs and CMCDP-LDHs are at 1605,1422cm
– 1all having there is the asymmetric of carboxyl and symmetrical stretching vibration peak in place, has confirmed that considerable change does not occur the agent structure of carboxymethyl-beta-cyclodextrin in polyreaction.And be positioned at 3443cm
-1place-OH stretching vibration peak intensity weakens gradually, these feature description CMCD really and epoxy chloropropane there is polymerization.
Embodiment 3
Steps A: take 11.64g Co (NO
3)
2﹒ 6H
2o, 5.37g Fe (NO
3)
3﹒ 9H
2o is dissolved in 100ml and removes CO
2deionized water preparation mixing salt solution, separately get 5.60g NaOH and be dissolved in 50ml and remove CO
2in water, prepare alkaline solution, N under room temperature
2protection adopts two methods of dripping that salts solution and alkaline solution are added in four-hole bottle, stirs mixing speed 600rpm.With 0.5mol/L NaOH solution, regulating pH value is 9.Gained slurries, in 70 ℃ of crystallization 48h, then filter throw out, repeatedly spend CO
2water washing repeatedly, until washings pH=7 obtains hydrotalcite precursor NO
3-LDHs, its Co
2+/ Fe
3+=3.
Step B: 1.0g carboxymethyl-beta-cyclodextrin (CMCD) solid is dissolved in to 100mL and removes CO
2deionized water after proceed in four-hole bottle, then add and fill the hydrotalcite precursor NO that 16.0g steps A obtains
3-LDHs, N
2protection is heated to 70 ℃, and 600rpm stirs lower reaction 36h.Then throw out is filtered, repeatedly with removing CO
2deionized water wash repeatedly, until washings pH=7 can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs.
Step C: the carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs that 10.0g step B is obtained, puts into the Erlenmeyer flask that fills NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution 75mL, at N
2protection is also placed 8h under 300rpm stirs, and wherein NaOH solution volumetric molar concentration is 4.0M, and the volume ratio of three kinds of liquid is (V (NaOH): V (methyl-sulphoxide): V (epoxy chloropropane)=3: 4: 4).This Erlenmeyer flask is put into ultrasonic oscillation device, and under ultrasonic frequency 35kHZ condition, supersound process 0.5h can adopt and add the method control temperature of ice cube to be no more than 25 ℃ when ultrasonic.Add again ethylene glycol 0.5mL, at 60 ℃, be total to hot 1.5h, then mixed solution is poured out, washing with acetone twice for product, more repeatedly with distilled water wash repeatedly, until washings pH is 7, taking-up is dried, and can obtain the hydrotalcite CMCDP-LDHs of cyclodextrin intercalation.
In the present embodiment, product chemical formula is: [(Co
2+)
0.75(Fe
3+)
0.25(OH)
2]
0.25+(CMCDP
28.29-)
0.00884H
2o.From X-ray diffractogram, hydrotalcite has six comparatively desirable side's laminate structures, and crystalline phase is single, and degree of crystallinity is better.The d of cyclodextrin intercalated houghite (CMCDP-LDHs)
003interlamellar spacing is 1.568nm, compared with the interlamellar spacing of cyclodextrin intercalation hydrotalcite before polymerization (CMCD-LDHs), does not obviously increase.This phenomenon shows in polymerization process, and the agent structure of carboxymethyl-beta-cyclodextrin and cyclodextrin, at the configuration of hydrotalcite layers, considerable change does not occur, and just between cyclodextrin, by hydroxyl and propylene oxide generation polymerization, formed large polymkeric substance.Cyclodextrin intercalated houghite is positioned in 0.1M sodium carbonate solution and is soaked after 4h, then do X-ray diffraction analysis, find d
003interlamellar spacing is 1.596nm, illustrates that the polymerization carboxymethyl-beta-cyclodextrin of interlayer can not replaced by carbonate.
By infrared spectrogram, find out that CMCD-LDHs and CMCDP-LDHs are at 1602,1423cm
– 1all having there is the asymmetric of carboxyl and symmetrical stretching vibration peak in place, has confirmed that considerable change does not occur the agent structure of carboxymethyl-beta-cyclodextrin in polyreaction.And be positioned at 3445cm
-1place-OH stretching vibration peak intensity weakens gradually, these feature description CMCD really and epoxy chloropropane there is polymerization.
Claims (2)
1. a carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material, it is characterized in that: first prepare carboxymethyl-beta-cyclodextrin intercalated ferro-cobalt hydrotalcite, then this hydrotalcite is put into NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution, the polyreaction of carboxymethyl-beta-cyclodextrin and epoxy chloropropane between genetic horizon, obtains the hydrotalcite material of carboxymethyl-beta-cyclodextrin polyalcohol intercalation; Its chemical formula is:
[(Co
2+)
1-x(Fe
3+)
x(OH)
2]
x+(CMCDP
n-)
x/n·mH
2O
X=0.25～0.33 wherein, m=3～6, m is the quantity of interlayer crystal water molecule, n=25～50, n is the electronegative quantity of carboxymethyl-beta-cyclodextrin polymkeric substance.
2. a method of preparing carboxymethyl-beta-cyclodextrin polymer-intercalated hydrotalcite material claimed in claim 1, is characterized in that comprising the steps:
The preparation of A, hydrotalcite precursor:
Anion N O between prepared layer
3 -or Cl
-, laminate Co
2+, Fe
3+mol ratio Co
2+/ Fe
3+=2～3 hydrotalcite NO
3-LDHs or Cl-LDHs:
By Co
2+soluble salt and Fe
3+soluble salt be mixed with mixing solutions, Co wherein
2+/ Fe
3+=2～3, Co
2+volumetric molar concentration be 0.1～0.7M, Fe
3+volumetric molar concentration be 0.03～0.35M; Take NaOH as alkaline solution, and wherein NaOH volumetric molar concentration is 1.0～5.0M, at room temperature N
2under protective condition; adopting two methods of dripping that soluble salt mixing solutions and alkaline solution are added in four-hole bottle, is 8～10 with 0.1～5.0M NaOH solution adjust pH after having added, by 60～80 ℃ of crystallization 24～72h of gained slurries again; then throw out is filtered, repeatedly with removing CO
2deionized water wash repeatedly, until washings pH=7 obtains hydrotalcite precursor;
Described Co
2+soluble salt be hydrochloride or nitrate, Fe
3+soluble salt be hydrochloride or nitrate, and Co
2+soluble salt and Fe
3+the kind of soluble salt identical;
B, carboxymethyl-beta-cyclodextrin intercalated ferro-cobalt hydrotalcite:
Carboxymethyl-beta-cyclodextrin is dissolved in and removes CO
2deionized water in, then the hydrotalcite precursor that steps A is obtained joins in this solution, N
2protection is heated to 60～80 ℃, stirs lower reaction 24～48h, then throw out is filtered, repeatedly with removing CO
2deionized water wash repeatedly, until washings pH=7 obtains carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs;
C, carboxymethyl-beta-cyclodextrin and epoxy chloropropane are in hydrotalcite layers polymerization:
The carboxymethyl-beta-cyclodextrin intercalated hydrotalcite CMCD-LDHs that step B is obtained, puts into the Erlenmeyer flask that fills NaOH solution-methyl-sulphoxide-epoxy chloropropane mixed solution, at N
2protect and stir down and place 5-10h, wherein NaOH solution volumetric molar concentration is 3.0～6.0M, the volume ratio of three kinds of liquid is NaOH: methyl-sulphoxide: epoxy chloropropane=3: 4: 4, this Erlenmeyer flask is put into ultrasonic oscillation device, supersound process 0.5h, when ultrasonic, control temperature and be no more than 25 ℃, add again ethylene glycol 0.5mL, altogether hot 1～2h at 50～70 ℃, then mixed solution is poured out, twice of washing with acetone of product, again repeatedly with distilled water wash repeatedly, until washings pH is 7, taking-up is dried, can obtain the hydrotalcite CMCDP-LDHs of cyclodextrin intercalation.
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| CN106146809A (en) * | 2016-07-04 | 2016-11-23 | 淄博职业学院 | Poly-3 carboxy thiophenes/thiophene intercalated hydrotalcite composite material and preparation technology thereof |
| CN106633215A (en) * | 2016-10-24 | 2017-05-10 | 北京师范大学 | Sulfonated beta-cyclodextrin-LDH complex and synthesis method thereof |
| CN112390984A (en) * | 2020-10-28 | 2021-02-23 | 陕西科技大学 | Cyclodextrin inclusion compound modified hydrotalcite-like flame-retardant composite material and preparation method thereof |
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| US20060189481A1 (en) * | 2003-07-07 | 2006-08-24 | Instituto Mexicano Del Petroleo. | Obtaining multimetallic oxides derived from hydrotalcite type compounds |
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
| CN101323953A (en) * | 2008-07-11 | 2008-12-17 | 北京化工大学 | Vertical substrate grown cyclodextrin intercalation hydrotalcite film and preparation thereof |
| CN102659081A (en) * | 2012-04-27 | 2012-09-12 | 淄博职业学院 | Layered double hydroxides (LDHs) loading highly-dispersed fullerenes and preparing method of LDHs |
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| US20060189481A1 (en) * | 2003-07-07 | 2006-08-24 | Instituto Mexicano Del Petroleo. | Obtaining multimetallic oxides derived from hydrotalcite type compounds |
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
| CN101323953A (en) * | 2008-07-11 | 2008-12-17 | 北京化工大学 | Vertical substrate grown cyclodextrin intercalation hydrotalcite film and preparation thereof |
| CN102659081A (en) * | 2012-04-27 | 2012-09-12 | 淄博职业学院 | Layered double hydroxides (LDHs) loading highly-dispersed fullerenes and preparing method of LDHs |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106146809A (en) * | 2016-07-04 | 2016-11-23 | 淄博职业学院 | Poly-3 carboxy thiophenes/thiophene intercalated hydrotalcite composite material and preparation technology thereof |
| CN106146809B (en) * | 2016-07-04 | 2018-08-14 | 淄博职业学院 | Poly- 3- carboxy thiophenes/thiophene intercalated hydrotalcite composite material and its preparation process |
| CN106633215A (en) * | 2016-10-24 | 2017-05-10 | 北京师范大学 | Sulfonated beta-cyclodextrin-LDH complex and synthesis method thereof |
| CN106633215B (en) * | 2016-10-24 | 2019-04-09 | 北京师范大学 | Sulfonated β-cyclodextrin-LDH complex and its synthetic method |
| CN112390984A (en) * | 2020-10-28 | 2021-02-23 | 陕西科技大学 | Cyclodextrin inclusion compound modified hydrotalcite-like flame-retardant composite material and preparation method thereof |
| CN112390984B (en) * | 2020-10-28 | 2022-07-26 | 陕西科技大学 | Cyclodextrin inclusion compound modified hydrotalcite-like flame-retardant composite material and preparation method thereof |
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