CN106478965A - A kind of water-soluble network-like beta-cyclodextrin cross-linked polymer and its method for purification of organic waste water - Google Patents
A kind of water-soluble network-like beta-cyclodextrin cross-linked polymer and its method for purification of organic waste water Download PDFInfo
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Abstract
The invention discloses the method for belonging to a kind of water-soluble network-like beta-cyclodextrin cross-linked polymer construction method, cross-linked polymer and the purification of organic waste water of field of functional materials.The cross-linked polymer is with derivatized beta cyclodextrin as elementary cell, series connection by specific line style structural compounds is acted on, the hydrophobic cavity of the different derivatized cyclodextrins of connection, network-like structure is constructed out by the self-crosslinking effect between the weak crosslinking of polyfunctional group small molecule and cyclodextrin substituent is controlled, remove through wash-out after linear structure compound and obtain target product, preparation section is easy, and course of reaction is easily controllable, without the need for artificially terminating cross-linking reaction.Beta-cyclodextrin cross-linked polymer prepared by present invention dissolution dispersity in water is good, and the internal structure that network-like and hydrophobic cavity is interconnected is conducive to its quick identification to organic pollution in dyeing waste water and encompasses；The cross-linked polymer for completing to encompass process still repeats utilization after centrifugal concentrating, wash-out pollutant.
Description
Technical field
The invention belongs to technical field of function materials, more particularly to a kind of water-soluble network-like beta-cyclodextrin cross-linked polymer structure
The method of building method, cross-linked polymer and purification of organic waste water.
Background technology
Cyclodextrin compound (Cyclodextrins) be amylose generate under particular organisms enzyme effect a series of by
The general name of the cyclic oligosaccharide that α-Isosorbide-5-Nitrae-glycosidic bond is formed by connecting.Beta-schardinger dextrin is one kind of most study in numerous CDs, and
It is used widely in numerous areas such as selective catalysis, environment separation, bio-pharmaceuticals, food finishing.However, due to molecule
The factors such as interior hydrogen bond and ring rigidity, omit compared with other cyclodextrin compounds in terms of solubility of the beta-schardinger dextrin in water and the ability that encompasses
Aobvious inferior.
It is to strengthen its solubility and to allogenic material bag in water to perform the derivatization reaction to beta-schardinger dextrin and obtain derivative
Receive a kind of effective means of ability.However, the cyclodextrin after derivatization, though its water solubility is significantly improved, is limited to the sky of fixation
Chamber volume, the ability that encompasses to allogenic material are still restricted.It is to strengthen its bag cyclodextrin to be obtained by cross-linking agents
Receive or adsorption capacity one of effective means.With the gel point in cross-linking process or resinification point as boundary, can with cyclodextrin will be
The cross-linked polymer of basic framework is divided into two classes：(1) before system assumes gel point or resinification point, artificial termination crosslinking is anti-
Should, obtain the cross-linked polymer in water with certain solubility；(2) complete cross-linking reaction, obtain with adsorption function
Gel state or the beta-cyclodextrin cross-linked polymer of resin state.
At present, for the research of water soluble Beta-cyclodextrin cross-linked polymer, set up in human hairs such as Rui Nade (Renard) mostly
Table is in the paper " preparation of high molecular polymer water solubility beta-schardinger dextrin-epoxychloropropane and sign " of European polymer journal
(Preparation and characterization of watersoluble high molecular weightβ-
cyclodextrin-epichlorohydrin polymers(European Polymer Journal,33(1):49-57))
Or on the basis of the hungarian patent of Patent No. 222968；I.e. in the strong alkali solution of beta-schardinger dextrin is dissolved with, ring is dripped
Oxygen chloropropane observing response system, are occurring pouring acetone termination cross-linking reaction into reaction system at the beginning of gel is inclined to.This
Although method can obtain having necessarily water miscible beta-cyclodextrin cross-linked polymer, the crosslinking in moment observing response system is needed
Degree, adds cross-linking reaction terminator, it is to avoid the gelation of product and resinification, whole course of reaction controllability be not good in time.
Meanwhile, by the cyclodextrin elementary cell in cross linked water soluble polymer obtained in said method often in unordered connection or heap
Cumuliformis state, most hydrophobic cavity are not mutually connected, this structure to the identification of allogenic material and assembling ability largely according to
Single cyclodextrin compound is so derived from.Therefore, the water soluble Beta-cyclodextrin cross-linked polymer that is studied at this stage does not give full play to friendship
Synergy after connection between different cyclodextrin units and the joint identification to allogenic material and assembling ability.
Content of the invention
In view of this, the present invention provides a kind of water-soluble network-like beta-cyclodextrin cross-linked polymer construction method, cross-linked polymeric
Thing and the method for purification of organic waste water, water-soluble network-like beta-cyclodextrin cross-linked polymer can be by the cyclodextrin hydrophobic cavities of connection
The larger hydrophobic potential energy for being formed, quickly recognizes and encompasses the organic pollution in water, can be used for purification of organic waste water.
The preparation principle of beta-cyclodextrin cross-linked polymer of the present invention is derived with the cyclodextrin with specific replacement position
Thing is elementary cell, and under certain ph, the series connection of meridional type structural compounds, the weak crosslinking of crosslinking agent, eluent line style are divided
Sub with partial cross-linked dose after form the network-like structure that is interconnected of hydrophobic cavity, wherein cyclodextrine derivatives, linear structure
The input mass ratio of compound, crosslinking agent and eluant, eluent is：40:7-19:5-11:197-770, described water solubility refer to that normal temperature is normal
Pressure (25 DEG C, 1 standard atmospheric pressure) can dissolve the beta-cyclodextrin cross-linked polymer more than 1g per 100mL deionized water.
A kind of water-soluble network-like beta-cyclodextrin cross-linked polymer construction method, by cyclodextrine derivatives and appropriate amount of deionized water
Pastel is mixed into, concentration is a small amount of watery hydrochloric acid of 0.05-1mol/L and diluted sodium hydroxide solution adjusts pasty state system
PH value between 5.7-8.2 after, with appropriate linear structure compound while be transferred to dispersion sand mill, in 300-800r/min
Grinding rate under grind 20-100min；Then appropriate crosslinking agent is slowly added to in sand mill, and grinding rate is adjusted to
1000-2500r/min, takes out pastel after continuing grinding 40-90min；Pastel is placed in beaker, add eluant, eluent and
At 30-50 DEG C, constant temperature at the uniform velocity vibrates 10-40h；After vibration terminates, filter, take out pastel and be vacuum dried at 40-60 DEG C, obtain
To water-soluble network-like beta-cyclodextrin cross-linked polymer, above-mentioned cyclodextrine derivatives, linear structure compound, crosslinking agent and eluant, eluent
Mass ratio be：40:7-19:5-11:197-770.
Optionally, in the above-mentioned methods, described cyclodextrine derivatives selected from bis--O- methyl-B-cyclodextrin of 2,6-, 2,6-
In two-O- (2- hydroxypropyl)-beta-schardinger dextrin, 2,6-O- semi-annular jade pendant fourth group-beta-cyclodextrin and tri--O- carboxymethyl-beta-cyclodextrin of 2,4,6-
One or more.
Optionally, in the above-mentioned methods, described linear structure compound is selected from octadecylamine, cetylamine, laruyl alcohol, Pork and beans
One or more in cool alcohol and stearyl alcohol.
Optionally, in the above-mentioned methods, the one kind of described crosslinking agent in ethylene glycol, Propylene Glycol and glycerine
Or it is several.
Optionally, in the above-mentioned methods, the one kind or several of described eluant, eluent in chloroform, acetoneand ethyl acetate
Kind.
A kind of network-like beta-cyclodextrin cross-linked polymer of water solubility prepared by said method.
The network-like beta-cyclodextrin cross-linked polymerization of the above-mentioned water solubility of every more than 100mL deionized water dissolving 1g at normal temperatures and pressures
Thing.
A kind of method of purification of organic waste water, above-mentioned water-soluble network-like beta-cyclodextrin cross-linked polymer is thrown in into organic waste
Water, quickly recognizes to the organic pollution in waste water and encompasses.
Optionally, in the above-mentioned methods, complete to encompass the cross-linked polymer of process through centrifugal concentrating, wash-out pollution by above-mentioned
Reuse after thing.
Beta-cyclodextrin cross-linked polymer prepared by the present invention is cyclodextrine derivatives with specific replacement position by multifunctional
The network-like structure that constructs out under the collective effect of self-crosslinking effect between the weak crosslinking of group's molecule and different substituents；Meanwhile, participate in
The derivatized cyclodextrin elementary cell of crosslinking, its hydrophobic cavity are interconnected, and possess stronger hydrophobic potential energy, improve traditional water
The drawbacks of soluble cyclodextrin cross-linked polymer encompasses limited ability to allogenic material.Water solubility network-like ring paste prepared by the present invention
Smart cross-linked polymer has further the advantage that：
1) preparation process is simple, it is not necessary to artificial observation cross-linking reaction degree；
2) dosage of crosslinking agent is few, and reaction condition is gentle, reacts easily controllable；
3) change linear structure compound molecule chain length, the crosslinking scale of end-product is can control, realizes controllable standby；
4) hydrophobic potential energy is big, can quickly recognize and encompass the light concentration organic pollutant in water and without ultrasonic, smelly
The supplementary means such as oxygen or uv light irradiation；
5) cross-linked polymer after use, through centrifugal concentrating, after secondary wash-out, repeats and utilizes.
Description of the drawings
Fig. 1 is water soluble Beta-cyclodextrin cross-linked polymer network-like structure schematic diagram before and after wash-out in the present invention.
Fig. 2 be embodiment 1 prepare cross linked water soluble polymer and bis--O- of corresponding elementary cell 2,6- (2- hydroxypropyl)-
The proton nmr spectra comparison diagram of beta-schardinger dextrin.
Fig. 3 is the design sketch that cross linked water soluble polymer prepared by embodiment 2 processes methylene blue simulated wastewater.
Fig. 4 is to implement the Contrast on effect that 3 cyclodextrin elementary cells and cross-linked polymer process methylene blue simulated wastewater
Figure.
Specific embodiment
With reference to instantiation, the present invention is elaborated.
Embodiment 1
Bis--O- of 23.5g 2,6- (2- hydroxypropyl)-beta-schardinger dextrin and appropriate amount of deionized water are mixed to form pastel, while
Pastel pH to 7.2 is adjusted using a small amount of 0.1mol/L watery hydrochloric acid with 0.1mol/L diluted sodium hydroxide solution；By pastel with
5.3g laruyl alcohol is transferred in dispersion sand mill in the lump and grinds 60min under the grinding rate of 450r/min；Then accurately measure
3mL (about 3.3g) ethylene glycol, is slowly dropped into dispersion sand mill, while rotating speed is risen to 1500r/min, after continuing grinding 55min
Take out pastel and insert beaker；Pour 330mL ethyl acetate in the beaker for fill pastel into and constant-temperature table is transferred to, 50 DEG C
Under at the uniform velocity vibrate 20h after, filter, take out pastel be vacuum dried i.e. at 50 DEG C obtain water-soluble network-like beta-cyclodextrin cross-linked poly-
Compound, the product are bis--O- of 2,6- (2- hydroxypropyl)-beta-schardinger dextrins through constructing under the weak crosslinking of ethylene glycol and self-crosslinking collective effect
The network-like cross-linked polymer that is interconnected of hydrophobic cavity.Cross-linked polymer and the proton nmr spectra of cyclodextrin elementary cell
Contrast is as shown in Figure 2.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 98.5%.
Embodiment 2
Bis--O- methyl-B-cyclodextrin of 24.4g 2,6- and appropriate amount of deionized water are mixed to form pastel, while using few
Amount 0.1mol/L watery hydrochloric acid adjusts pastel pH to 6.2 with 0.1mol/L diluted sodium hydroxide solution；By pastel and 9.2g 18
Amine is transferred in dispersion sand mill in the lump and grinds 55min under the grinding rate of 300r/min；Then 6mL is accurately measured (about
6.2g) Propylene Glycol, is slowly dropped into dispersion sand mill, while rotating speed is risen to 1800r/min, takes after continuing grinding 40min
Go out pastel and insert beaker；Pour 280mL acetone in the beaker for fill pastel into and constant-temperature table is transferred to, at 40 DEG C at the uniform velocity
After vibration 15h, filter, taking-up pastel is vacuum dried i.e. at 40 DEG C and obtains water-soluble network-like beta-cyclodextrin cross-linked polymer,
It is hydrophobic through constructed under the weak crosslinking of Propylene Glycol and self-crosslinking collective effect that the product is bis--O- methyl-B-cyclodextrin of 2,6-
The network-like cross-linked polymer that cavity is interconnected.The cross-linked polymer processes the effect of methylene blue simulated wastewater referring to Fig. 3.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 99.2%.
Embodiment 3
2,4,6- tri--O- carboxymethyl-beta-cyclodextrin of 23.1g and appropriate amount of deionized water are mixed to form pastel, while making
Pastel pH to 6.9 is adjusted with a small amount of 0.1mol/L watery hydrochloric acid with 0.1mol/L diluted sodium hydroxide solution；By pastel and 10.4g
Cetylamine is transferred in dispersion sand mill in the lump and grinds 90min under the grinding rate of 800r/min；Then 3.6mL is accurately measured
(about 4.6g) glycerine, is slowly dropped into dispersion sand mill, while rotating speed is risen to 2200r/min, takes out after continuing grinding 75min
Beaker inserted by pastel；Pour 260mL chloroform in the beaker for fill pastel into and constant-temperature table is transferred to, at the uniform velocity shake at 45 DEG C
After swinging 30h, filter, taking-up pastel is vacuum dried i.e. at 60 DEG C and obtains water-soluble network-like beta-cyclodextrin cross-linked polymer, should
Product is hydrophobic sky of the tri--O- carboxymethyl-beta-cyclodextrin of 2,4,6- through constructing under the weak crosslinking of glycerine and self-crosslinking collective effect
The network-like cross-linked polymer that chamber is interconnected.The cross-linked polymer and the basic cell processing methylene blue simulation of corresponding cyclodextrin
The Contrast on effect of waste water is as shown in Figure 4.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 99.5%.
Embodiment 4
13.9g 2,6-O- semi-annular jade pendant fourth group-beta-cyclodextrin and appropriate amount of deionized water are mixed to form pastel, while using few
Amount 0.1mol/L watery hydrochloric acid adjusts pastel pH to 7.4 with 0.1mol/L diluted sodium hydroxide solution；By pastel and 5.2g Pork and beans
Cool alcohol is transferred in dispersion sand mill in the lump and grinds 35min under the grinding rate of 750r/min；Then 2.2mL is accurately measured
(about 2.8g) glycerine, is slowly dropped into dispersion sand mill, while rotating speed is risen to 2500r/min, takes out after continuing grinding 90min
Beaker inserted by pastel；Pour 225mL ethyl acetate in the beaker for fill pastel into and constant-temperature table is transferred to, even at 30 DEG C
After speed vibration 25h, filter, taking-up pastel is vacuum dried i.e. at 45 DEG C and obtains water-soluble network-like beta-cyclodextrin cross-linked polymerization
Thing, the product are hydrophobic sky of 2, the 6-O- semi-annular jade pendant fourth group-beta-cyclodextrin through constructing under the weak crosslinking of glycerine and self-crosslinking collective effect
The network-like cross-linked polymer that chamber is interconnected.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 99.1%.
Embodiment 5
Bis--O- methyl-B-cyclodextrin of 10.5g 2,6- is mixed with bis--O- of 20.3g 2,6- (2- hydroxypropyl)-beta-schardinger dextrin
Close uniform rear and appropriate amount of deionized water and pastel is tuned into, while using a small amount of 0.1mol/L watery hydrochloric acid and the dilute hydroxide of 0.1mol/L
Sodium solution adjusts pastel pH to 8.2；Pastel and 6.2g stearyl alcohol are transferred in dispersion sand mill in the lump in 380r/min
Grinding rate under grind 100min；Then 3.5mL (about 3.9g) ethylene glycol is accurately measured, dispersion sand mill is slowly dropped into, with
When rotating speed is risen to 1000r/min, take out pastel after continuing grinding 50min and insert beaker；To in the beaker for filling pastel
Pour 310mL chloroform into and constant-temperature table is transferred to, after at the uniform velocity 10h being vibrated at 35 DEG C, filter, take out pastel vacuum at 60 DEG C
The water-soluble network-like beta-cyclodextrin cross-linked polymer of drying to obtain, the product is bis--O- methyl-B-cyclodextrin of 2,6- and 2,6-
Two-O- (2- hydroxypropyl)-beta-schardinger dextrin is through the weak crosslinking of ethylene glycol and structure under two kinds of cyclodextrin elementary cell self-crosslinking collective effects
The network-like cross-linked polymer that the hydrophobic cavity that builds is interconnected.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 98.3%.
Embodiment 6
11.2g 2,6-O- semi-annular jade pendant fourth group-beta-cyclodextrin is mixed all with tri--O- carboxymethyl-beta-cyclodextrin of 6.1g 2,4,6-
Even rear and appropriate amount of deionized water is tuned into pastel, while molten with 0.1mol/L dilute sodium hydroxide using a small amount of 0.1mol/L watery hydrochloric acid
Liquid adjusts pastel pH to 8.2；Pastel and 8.2g laruyl alcohol are transferred to grinding in 700r/min in dispersion sand mill in the lump
80min is ground under mill speed；Then 3.6mL (about 4.5g) glycerine is accurately measured, dispersion sand mill is slowly dropped into, while will turn
Speed rises to 2300r/min, takes out pastel and insert beaker after continuing grinding 85min；Pour into in the beaker for fill pastel
295mL acetone is simultaneously transferred to constant-temperature table, after at the uniform velocity vibrating 30h, filters at 45 DEG C, takes out pastel and is vacuum dried at 40 DEG C
Water-soluble network-like beta-cyclodextrin cross-linked polymer is obtained, and the product is 2,6-O- semi-annular jade pendant fourth group-beta-cyclodextrin and 2,4,6- tri--O-
Hydrophobic sky of the carboxymethyl-beta-cyclodextrin through constructing under the weak crosslinking of glycerine and two kinds of cyclodextrin elementary cell self-crosslinking collective effects
The network-like cross-linked polymer that chamber is interconnected.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 98.7%.
Embodiment 7
Bis--O- methyl-B-cyclodextrin of 11.9g 2,6- is mixed with tri--O- carboxymethyl-beta-cyclodextrin of 12.2g 2,4,6-
Uniform rear and appropriate amount of deionized water is tuned into pastel, while using a small amount of 0.1mol/L watery hydrochloric acid and 0.1mol/L dilute sodium hydroxide
Solution adjusts pastel pH to 5.7；Pastel and 6.0g octadecylamine are transferred in dispersion sand mill in the lump in 650r/min's
20min is ground under grinding rate；Then 3.5mL (about 3.6g) Propylene Glycol is accurately measured, dispersion sand mill is slowly dropped into, with
When rotating speed is risen to 1800r/min, take out pastel after continuing grinding 75min and insert beaker；To in the beaker for filling pastel
Pour 300mL ethyl acetate into and constant-temperature table is transferred to, after at the uniform velocity 40h being vibrated at 50 DEG C, filter, take out pastel at 60 DEG C
Vacuum drying obtains water-soluble network-like beta-cyclodextrin cross-linked polymer, and the product is bis--O- methyl-B-cyclodextrin of 2,6- and 2,
Tri--O- carboxymethyl-beta-cyclodextrin of 4,6- is through the weak crosslinking of Propylene Glycol and two kinds of cyclodextrin elementary cell self-crosslinking collective effects
Under the network-like cross-linked polymer that is interconnected of the hydrophobic cavity constructed.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 99.3%.
Embodiment 8
Bis--O- methyl-B-cyclodextrin of 24.5g 2,6- and appropriate amount of deionized water are mixed to form pastel, while using few
Amount 0.1mol/L watery hydrochloric acid adjusts pastel pH to 6.4 with 0.1mol/L diluted sodium hydroxide solution；By pastel and 3.2g 18
Amine is transferred in dispersion sand mill in the lump with 4.2g cetylamine and grinds 85min under the grinding rate of 400r/min；Then accurate
3.8mL (about 4.2g) ethylene glycol is measured, dispersion sand mill is slowly dropped into, and rotating speed is risen to 2400r/min, continue grinding
Pastel is taken out after 60min inserts beaker；Pour 350mL acetone in the beaker for fill pastel into and constant-temperature table be transferred to,
After at the uniform velocity vibrating 40h at 45 DEG C, filter, taking-up pastel is vacuum dried i.e. at 40 DEG C and obtains water-soluble network-like cyclodextrin friendship
Linked polymer, the product are bis--O- methyl-B-cyclodextrin of 2,6- through constructing under the weak crosslinking of ethylene glycol and self-crosslinking collective effect
The network-like cross-linked polymer that hydrophobic cavity is interconnected.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 98.9%.
Embodiment 9
Bis--O- of 35.3g 2,6- (2- hydroxypropyl)-beta-schardinger dextrin and appropriate amount of deionized water are mixed to form pastel, while
Pastel pH to 7.9 is adjusted using a small amount of 0.1mol/L watery hydrochloric acid with 0.1mol/L diluted sodium hydroxide solution；By pastel with
6.1g laruyl alcohol is transferred in dispersion sand mill in the lump with 8.9g stearyl alcohol and grinds 95min under the grinding rate of 400r/min；
Then 6.9mL (about 8.8g) glycerine is accurately measured, dispersion sand mill is slowly dropped into, while rotating speed is risen to 1400r/min, is continued
Pastel is taken out after continuous grinding 70min and insert beaker；Pour 310mL chloroform in the beaker for fill pastel into and be transferred to constant temperature
Shaking table, after at the uniform velocity vibrating 22h, filters at 38 DEG C, and taking-up pastel is vacuum dried i.e. at 55 DEG C and obtains water-soluble network-like ring
Dextrin cross-linked polymer, the product are that bis--O- of 2,6- (2- hydroxypropyl)-beta-schardinger dextrin is common with self-crosslinking through the weak crosslinking of glycerine
The network-like cross-linked polymer that the hydrophobic cavity that constructs under effect is interconnected.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 98.5%.
Embodiment 10
22g 2,6-O- semi-annular jade pendant fourth group-beta-cyclodextrin and appropriate amount of deionized water are mixed to form pastel, while using a small amount of
0.1mol/L watery hydrochloric acid adjusts pastel pH to 7.3 with 0.1mol/L diluted sodium hydroxide solution；By pastel and 2.9g nutmeg
Alcohol is transferred in dispersion sand mill in the lump with 6.6g stearyl alcohol and grinds 38min under the grinding rate of 440r/min；Then accurate
3.7mL (about 3.9g) Propylene Glycol is measured, dispersion sand mill is slowly dropped into, while rotating speed is risen to 2350r/min, continue to grind
Pastel is taken out after mill 65min and insert beaker；Pour 275mL ethyl acetate in the beaker for fill pastel into and be transferred to constant temperature
Shaking table, after at the uniform velocity vibrating 17h, filters at 45 DEG C, and taking-up pastel is vacuum dried i.e. at 45 DEG C and obtains water-soluble network-like ring
Dextrin cross-linked polymer, the product are that 2,6-O- semi-annular jade pendant fourth group-beta-cyclodextrin is made with self-crosslinking jointly through the weak crosslinking of Propylene Glycol
With under the network-like cross-linked polymer that is interconnected of the hydrophobic cavity constructed.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 99.1%.
Embodiment 11
By bis--O- methyl-B-cyclodextrin of 11.9g 2,6-, bis--O- of 23.5g 2,6- (2- hydroxypropyl)-beta-schardinger dextrin with
12.2g2,4,6- tri--O- carboxymethyl-beta-cyclodextrins mix rear and appropriate amount of deionized water and are tuned into pastel, while using few
Amount 0.1mol/L watery hydrochloric acid adjusts pastel pH to 5.8 with 0.1mol/L diluted sodium hydroxide solution；By pastel and 17.9g 18
Amine is transferred in dispersion sand mill in the lump and grinds 75min under the grinding rate of 660r/min；Then 6.4mL (about 7.1g) is measured
Ethylene glycol, is slowly dropped into dispersion sand mill, while rotating speed is risen to 2150r/min, takes out pastel and put after continuing grinding 90min
Enter beaker；Pour 300mL acetone in the beaker for fill pastel into and constant-temperature table is transferred to, after at the uniform velocity vibrating 30h at 40 DEG C,
Filter, taking-up pastel is vacuum dried i.e. at 45 DEG C and obtains water-soluble network-like beta-cyclodextrin cross-linked polymer, and the product is 2,
Bis--O- methyl-B-cyclodextrin of 6-, 2,6- bis--O- (2- hydroxypropyl)-beta-schardinger dextrin and 2,4,6- tri--O- carboxymethyl-beta-cyclodextrins
The net that hydrophobic cavity through constructing under the weak crosslinking of ethylene glycol and three kinds of cyclodextrin elementary cell self-crosslinking collective effects is interconnected
Network shape cross-linked polymer.
Above-mentioned cross-linked polymer is dissolved in the process of 50mg/L methylene blue simulated wastewater with the injected volume of 200mg/L
100min, centrifugal concentrating, upper strata low viscosity clear liquid is taken, is determined through ultraviolet-visible spectrophotometer, the percent of decolourization to methylene blue
For 98.2%.
Cross-linked polymer in above-described embodiment with derivatization beta-schardinger dextrin as elementary cell, by specific line style structuring
The series connection effect of compound, the hydrophobic cavity of the different derivatized cyclodextrins of connection, by the weak crosslinking of polyfunctional group small molecule and ring paste
Self-crosslinking effect between smart substituent is controlled to construct out network-like structure, removes through wash-out after linear structure compound and obtains target
Product, preparation section are easy, and course of reaction is easily controllable, without the need for artificially terminating cross-linking reaction.Cyclodextrin prepared by the present invention
Cross-linked polymer dissolution dispersity in water is good, and the internal structure that network-like and hydrophobic cavity is interconnected is conducive to which to printing and dyeing
The quick identification of Organic Pollutants in Wastewater is simultaneously encompassed；Complete to encompass the cross-linked polymer of process through centrifugal concentrating, wash-out pollution
Still repeat after thing and utilize.
It is understood that the embodiment of above principle being intended to be merely illustrative of the present and the exemplary enforcement for adopting
Mode, but the invention is not limited in this.For those skilled in the art, in the essence without departing from the present invention
In the case of god and essence, various modifications and improvement can be made, these modifications and improvement are also considered as protection scope of the present invention.
Claims (9)
1. a kind of water-soluble network-like beta-cyclodextrin cross-linked polymer construction method, it is characterised in that by cyclodextrine derivatives with suitable
Amount deionized water is mixed into pastel, and concentration is a small amount of watery hydrochloric acid of 0.05-1mol/L and diluted sodium hydroxide solution is adjusted
After the pH value of section pastel is between 5.7-8.2, with appropriate linear structure compound while being transferred to dispersion sand mill, in 300-
20-100min is ground under the grinding rate of 800r/min；Then appropriate crosslinking agent is slowly added to in sand mill, and will grinding speed
Rate is adjusted to 1000-2500r/min, takes out pastel after continuing grinding 40-90min；Pastel is placed in beaker, addition is washed
De- agent and at 30-50 DEG C constant temperature at the uniform velocity vibrate 10-40h；After vibration terminates, filter, take out pastel vacuum at 40-60 DEG C
Dry, obtain water-soluble network-like beta-cyclodextrin cross-linked polymer, above-mentioned cyclodextrine derivatives, linear structure compound, crosslinking agent,
The mass ratio of eluant, eluent is：40:7-19:5-11:197-770.
2. water-soluble network-like beta-cyclodextrin cross-linked polymer construction method according to claim 1, it is characterised in that described
Cyclodextrine derivatives be selected from bis--O- methyl-B-cyclodextrin of 2,6-, bis--O- of 2,6- (2- hydroxypropyl)-beta-schardinger dextrin, 2,6-O-
One or more in semi-annular jade pendant fourth group-beta-cyclodextrin and tri--O- carboxymethyl-beta-cyclodextrin of 2,4,6-.
3. water-soluble network-like beta-cyclodextrin cross-linked polymer construction method according to claim 2, it is characterised in that described
One or more in octadecylamine, cetylamine, laruyl alcohol, myristyl alcohol and the stearyl alcohol of linear structure compound.
4. water-soluble network-like beta-cyclodextrin cross-linked polymer construction method according to claim 3, it is characterised in that described
One or more in ethylene glycol, Propylene Glycol and the glycerine of crosslinking agent.
5. water-soluble network-like beta-cyclodextrin cross-linked polymer construction method according to claim 4, it is characterised in that described
Eluant, eluent selected from chloroform, one or more in acetoneand ethyl acetate.
6. the network-like beta-cyclodextrin cross-linked polymerization of a kind of water solubility prepared by any one methods described in claim 1-5
Thing.
7. water-soluble network-like beta-cyclodextrin cross-linked polymer according to claim 6, it is characterised in that at normal temperatures and pressures
Described water-soluble network-like beta-cyclodextrin cross-linked polymer per more than 100mL deionized water dissolving 1g.
8. a kind of method of eliminating organic pollutant waste water, it is characterised in that by network-like for water solubility described in claim 6 ring
Dextrin cross-linked polymer is thrown in into organic pollutant wastewater, the organic pollution in waste water is quickly recognized and is encompassed.
9. the method for eliminating organic pollutant waste water according to claim 8, it is characterised in that will complete to encompass process
Cross-linked polymer is reused after centrifugal concentrating and wash-out pollutant.
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