CN108530625A - A kind of gel and method of the amphipathic copolymerization network with micron hole - Google Patents
A kind of gel and method of the amphipathic copolymerization network with micron hole Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a kind of gel and method of the amphipathic copolymerization network with micron hole, which has the polymer constitutional repeating unit such as formula (1), wherein and R is N heterocycles, it includes：In any one, wherein X includes：Br‑、Cl‑OrN is 6 30；M is 3 30；The gel fraction of gel is more than 70%.The gel of the present invention can be formed in the interior thereof three-dimensional highly branched structure, while also have hydrophobic patch, have better absorption property.
Description
Technical field
The present invention relates to gel rubber material fields, and in particular to a kind of gel of the amphipathic copolymerization network with micron hole
And method.
Background technology
Due to the toxicity and visibility of dyestuff, even at a low concentration, the waste water that industrial wastewater is also most problematic is dyed
One of.Most of organic dyestuff, especially synthetic dyestuffs have complicated aromatic molecule structure, so that it is stablized and are difficult to biology
Degradation, this may have toxicity or mutagenicity and carcinogenicity to bio-diversity.Therefore, effectively removed from water dyestuff for
Protection public health and ecological environment are of great significance.
In numerous methods of development process waste water containing dye, due to economic feasibility, high efficiency and property easy to operate are inhaled
It is attached to be typically considered most widely used dyestuff removal technology.Therefore, it is novel with high adsorption efficiency how to design synthesis
Adsorbent is the important research target of dye wastewater treatment area research personnel.
Hydrogel is considered as effective material that dyestuff adsorbs in contaminant water, in recent years on a molecular scale due to them
Available design, swelling network be conducive to it is guest molecule and it is convenient operation and cause more and more to pay close attention to.However, improving
The performance of hydrogel still has some significant challenges.For example, conventional hydrogels (the i.e. ethylene prepared by typical polymerization methods
Base monomer and cross-linking monomer it is free-radical polymerized) network structure that typically exhibits random crosslinking, its strand will be caused
It tangles and causes adsorption site in network internal, to limit the adsorption capacity of hydrogel.The reticular structure of random crosslinking
Limit the mechanical performance of gained hydrogel.
In order to overcome the above problem, the research about hydrogel adsorbent recently concentrates on designing and being built with conducive to exposure
The new network structure of internal adsorption site.Due to its three-dimensional hyperbranched structure and numerous molecule inner cavities, hyperbranched topology
Structure is the potential candidate for promoting internal functionality exposure and increase guest molecule internal functionality to utilize.
Invention content
The object of the present invention is to provide a kind of gel and method of the amphipathic copolymerization network with micron hole, the gels
Conventional gel is solved without network cross-linked structure, the problem of adsorption energy force difference, three-dimensional highly branched knot can be formed in the interior thereof
Structure, while also there is hydrophobic patch, there is better absorption property.
In order to achieve the above object, the present invention provides a kind of amphipathic copolymerization network gels with micron hole, should
Gel has the polymer constitutional repeating unit such as formula (1)：
In formula (1), R is N heterocycles, it includes：In any one, wherein X includes：Br-、Cl-
Or
In formula (1), n 6-30；M is 3-30.
The gel fraction of the gel is more than 70%.
Preferably, the gel is by having such as the compound B of formula (2) structure and with the chemical combination such as formula (3) structure
Object A is prepared through N- alkylated reactions：
In formula (2), R ' includes：In any one.
In formula (3), R1、R2、R3It is each independently Cl or Br；
In formula (3), n is 6~30；M is 3~30.
The present invention also provides a kind of preparation method of the amphipathic copolymerization network gel with micron hole, which is
The amphipathic copolymerization network gel with micron hole, this method include：
Will the compound B with such as formula (2) structure and compound A with such as formula (3) structure through N- alkylated reaction systems
It is standby to obtain：
In formula (2), R ' includes：In any one.
In formula (3), R1、R2、R3It is each independently Cl or Br；
In formula (3), n is 6~30；M is 3~30.
The total concentration of the compound B and compound A is 200~1000mg/mL, and the gel fraction of the gel is more than
70%.
Preferably, the R ' is
The preparation method of the compound B includes：1,3,5- triacryls hexahydro -1,3,5- triazines and imidazoles are passed through
Michael addition reaction obtains compound B.
Preferably, 1,3, the 5- triacryl hexahydros -1,3,5-triazines flows back with imidazoles in absolute methanol, instead
It answers liquid precipitate in ethyl acetate/tetrahydrofuran mixed solvent, washs, filter, it is dry, to obtain the compound B.
Preferably, the preparation method of the compound A includes：Will have as formula (4) structure compound C with it is alpha-brominated
Or chloropropionic acid carries out esterification, obtains compound A.
In formula (4), n is 6~30；M is 3~30.
Preferably, the compound C, alpha-brominated or chloropropionic acid and p-methyl benzenesulfonic acid are heated to reflux in toluene,
Solvent is removed, crude product is obtained, purifies, obtains compound A.
Preferably, the preparation method of the compound C includes：To have compound D and 6- such as formula (5) structure in oneself
Ester under inert gas conditions, reaction is heated in higher boiling non-polar organic solvent, is obtained after reaction by precipitating；
In formula (5), n is 6~30；In the compound C-structure, the molecular wt ratio of PEG and PCL segments is (1000
~10000)：(1000~30000).
The present invention also provides a kind of anionic dyes or anionic heavy metal absorbent, which is described
Amphipathic copolymerization network gel with micron hole；The anionic dyes include：Bromophenol blue, Congo red, methyl orange,
In methyl blue and acid fuchsin any one or it is two or more；The anionic heavy metal includes：WithIn any one or it is two or more.
The present invention also provides a kind of processing method of chromate waste water, two with micron hole described in this method use
Parent's property copolymerization network gel is with Adsorption of Chromium.
The gel and method of the amphipathic copolymerization network with micron hole of the present invention, solve conventional gel without network
It the problem of cross-linked structure, adsorption energy force difference, has the following advantages：
(1) gel of the invention be with hyperbranched topological structure and include ionic liquid group amphipathic network it is solidifying
Glue has the macromonomer containing PEG (polyethylene glycol) and PCL (polycaprolactone) segment, since most of dyestuffs have simultaneously
Ion and hydrophobic structure, electrostatic and hydrophobic patch, which are introduced gel network, will promote its interaction with dye molecule；
(2) present invention introduces adsorbent as adsorption potential using ionic liquid as functional group, and it is (i.e. solidifying to improve sorbing material
Glue) absorption property, have good adjustability of structure and the multiple interaction with dyestuff；
(3) hydrophobic block (such as polycaprolactone) introducing gel network will ensure that gel by the present invention to prepare amphiphilic block body
Hydrophobicity and mechanical performance.
Description of the drawings
Fig. 1 is the SEM image of the amphipathic copolymerization network gel with micron hole of the present invention.
Fig. 2 is the preparation route figure of the amphipathic copolymerization network gel with micron hole of the present invention.
Fig. 3 is the preparation route figure of the amphipathic A monomers of three bromos of the present invention.
Fig. 4 is the H nuclear magnetic spectrograms of B monomer of the end group with imidazoles prepared by experimental example 3 of the present invention.
The measuring mechanical property result figure of sample 1-4 prepared by the test example 4 of Fig. 5 present invention.
Specific implementation mode
Below in conjunction with drawings and examples, the following further describes the technical solution of the present invention.
There is the polymer such as formula (1) to repeat to tie for a kind of amphipathic copolymerization network gel with micron hole, the gel
Structure unit：
In formula (1), R is N heterocycles, it includes：In any one, wherein X includes：Br-、Cl-
OrIn formula (1), n 6-30；M is 3-30.The gel fraction of the gel is more than 70%, as shown in Figure 1, being of the invention
The SEM image of amphipathic copolymerization network gel with micron hole, gel contain a micron hole.When hydrophilic section (PEG segments)
It is about 1 with hydrophobic section (PCL segments) molecular weight ratio:When 1, it is capable of the micron openings of functional dispersion, there is best absorption
Performance.
Above-mentioned gel is by having such as the compound B of formula (2) structure and with if the compound A of formula (3) structure is through N- alkane
Glycosylation reaction prepares：
In formula (2), R ' includes：In any one.
In formula (3), R1、R2、R3It is each independently Cl or Br；In formula (3), n is 6~30；M is 3~30.
The present invention gel can adsorpting anion dye molecule, such as bromophenol blue, Congo red, methyl orange, methyl blue, acid
Property magenta etc. or anionic heavy metal, including：WithIn the structure of the present invention
Containing PCL (polycaprolactone) segment, gel mechanical property and tertiary hydrophobic property are improved, is carried for adsorpting anion dye molecule
For active force.
The preparation method of the gel of the above-mentioned amphipathic copolymerization network with micron hole, as shown in Fig. 2, being of the invention
The preparation route figure of amphipathic copolymerization network gel with micron hole, this method include：
Compound A and B is prepared into the amphiphilic for including ionic liquid group with hyperbranched topological structure by one kettle way
Property network the B monomer of the amphipathic A monomers of three bromos and end group with imidazoles is specifically performed under heating conditions N- alkyl
Change reaction.
The solvent used is organic solvent, and such as dry DMF can be by impregnating to the end of reaction in ethanol solution
To replace the DMF in gel network.
As shown in figure 3, the preparation route figure of the amphipathic A monomers of three bromos for the present invention, is 1000g/ by molecular weight
Mol polyoxyethanyl glycerin ether A-PEG-OH (compound D) are initiator, so that 6- caprolactones (ε-CL) progress ring-opening polymerisation is anti-
It answers, synthesizes amphipathic block presoma (A-PEG-b-PCL-OH), is i.e. then compound C utilizes its terminal hydroxy group and BPA (α-
Bromo acid) O- esterifications, obtain bromine end group A monomers (A-PEG-b-PCL-Br).
The conjunction of the 1 amphipathic block presoma (A-PEG-b-PCL-OH) of polyoxyethanyl glycerin ether-b- polycaprolactones of experimental example
At
A-PEG-OH is utilizing toluene azeotropic water removing using preceding, a certain amount of A-PEG-OH and 6- caprolactones CL is added anti-
It answers in bottle, after leading to argon gas deoxygenation 40min, is rapidly added Sn (Oct)2, after continuing logical argon gas deoxygenation 20min, reaction system is close
Envelope, is placed at 110 DEG C and stirs 16h.After reaction, reaction system is deposited in ice ether, is filtered, products therefrom is in 40 DEG C
Under the conditions of be dried under vacuum to constant weight.
As shown in table 1, it is that the rate of charge table of 1 each raw material of experimental example is obtained by adjusting A-PEG-OH/CL rate of charges
The A-PEG-b-PCL-OH presomas of three kinds of different molecular weights, and according to the theoretical degree of polymerization of polymerized unit in its every arm, divide
A-PEG is not named as it7-b-PCL3- OH (presoma 1), A-PEG7-b-PCL5- OH (presoma 2) and A-PEG7-b-PCL7-OH
(presoma 3).As shown in table 2, it is the characterization result table of presoma 1-3 prepared by experimental example 2：
The rate of charge table of 1 experimental example of table, 1 each raw material
The characterization result table of presoma 1-3 prepared by 2 experimental example 1 of table
Note：aM is measured by SEC/MALLS (molecular exclusion chromatography is combined with multi-angle laser light scattering method)w/MnWith
dn/dc；Mw/MnFor molecular weight distributing index；Dn/dc is refractive index increment；Mn,theroIt is theoretical molecular weight (according to rate of charge
The molecular weight of design)；Mn,HNMRThe number-average molecular weight measured for HNMR；Mn,SECThe number-average molecular weight measured for SEC；bDPEG/DPCL
For the practical practical degree of polymerization of the degree of polymerization/PCL of PEG, the practical degree of polymerization passes through1HNMR is calculated.
The synthesis of the amphipathic A monomers (A-PEG-b-PCL-Br) of 2 three bromo of experimental example
By a certain amount of A-PEG-b-PCL-OH, BPA (alpha-brominated propionic acid), p-TSA (p-methyl benzenesulfonic acid) and 200mL
Dean-Stark devices are added in toluene, are heated to 120 DEG C, and flow back 16h.After reaction, toluene is evaporated off, crude product is dissolved in
In dichloromethane, 2%Na is used successively2CO3Washing 3 times, 5%NaCl solution washs 2 times and deionized water washing is washed 2 times.
Liquid separation, with anhydrous MgSO4Dry organic layer, is removed under reduced pressure solvent, crude product is deposited in ice n-hexane, filters, gained production
Object is dried under vacuum to constant weight at 40 DEG C.
The A monomers that the corresponding esterification modifications of presoma 1-3 prepared by experimental example 1 obtain then are respectively designated as A-PEG7-b-
PCL3- Br (A monomers 1), A-PEG7-b-PCL5- Br (A monomers 2) and A-PEG7-b-PCL7- Br (A monomers 3).As shown in table 3, it is
The characterization result table of A monomers 1-3 prepared by experimental example 2：
The characterization result table of A monomers 1-3 prepared by 3 experimental example 2 of table
Note：aM is measured by SEC/MALLS (molecular exclusion chromatography is combined with multi-angle laser light scattering method)w/MnWith
dn/dc；Mw/MnFor molecular weight distributing index；Dn/dc is refractive index increment；Mn,HNMRThe number-average molecular weight measured for HNMR；
Mn,SECThe number-average molecular weight measured for SEC.
The synthetic method of B monomer of 3 end group of experimental example with imidazoles
It is prepared by 1,3,5- triacryl hexahydro -1,3,5- triazines (TT) and imidazoles (Im) Michael addition reaction
It arrives, specific technical solution is as follows：
TT (5g, 20mmol) and Im (10g, 106mmol) are added in 30mL absolute methanols, reflux is for 24 hours.Reaction terminates
Afterwards, reaction system is deposited in ethyl acetate/tetrahydrofuran (volume ratio 1：1) in the mixed solvent.Using dissolving-precipitation
(methanol-ethyl acetate/tetrahydrofuran) washes twice, filtering, and gained precipitation is dried under vacuum to constant weight at room temperature, obtains B
Monomer (TT Im), as shown in figure 4, the H nuclear magnetic spectrograms of B monomer of the end group with imidazoles prepared for experimental example 3 of the present invention.
Amphiphilic hyper-branched gel (the hbGel-PEG-PCL-TTIm of 4 bromide ionic liquid of embodiment+Br-) preparation
A monomers, B monomer and the DMF of drying are added in reagent bottle, after stirring and dissolving, take out rotor.Reaction bulb is sealed
It is placed in 80 DEG C of oil baths, stands 20h.After reaction, reaction bulb is taken out from oil bath, the system of waiting for is cooled to room temperature, and is taken
Go out sample.The gel of taking-up is placed in DMF and impregnates 2 days (period changes DMF 3 times daily), to wash away unreacted monomer.Then
Gel film is pulled out, is placed in ethanol solution, to replace the DMF in gel network, gel film is pulled out, 25 DEG C are dried under vacuum to
After constant weight, hbGel-PEG-PCL-TTIm is obtained+Br-。
N- alkylated reactions, C are carried out by the A monomers 1-3 and B monomer that are prepared in experimental example 2A+BWith PEG/ in A monomers
PCL ratios, all can be to gained hbGel-PE-PCL-TTIm+Br-The gel fraction of (sample 1-9) has an impact, and as shown in table 4, is
The Gel fraction and equilibrium swelling ratio of sample 1-9 prepared by experimental example 3：
The Gel fraction and equilibrium swelling ratio of sample 1-9 prepared by 4 experimental example 3 of table
Note：Pass through Mn,HNMRCalculate the molecular wt ratio of peg moiety and the parts PCL；bGel fraction passes through yield meter
It calculates；ESR is Equilibrium swelling ratio, i.e. equilibrium swelling ratio.
As can be seen from the above Table 4, CA+BIt, all can be to gained hbGel-PE-PCL-TTIm with PEG/PCL ratios in A monomers+Br-Gel fraction have an impact, CA+BAll be conducive to the raising of gel fraction with the increase of PCL components.hbGel-PE-PCL-TTIm+
Br-Crosslinking points mainly generated by the N- alkylated reactions of A-PEG-b-PCL-Br and TTIm (imidazoles), and between its crosslinking points
Theoretical chain length is controlled by the brachium of A monomers.Thus higher CA+BAll be conducive to gel fraction with larger A monomer molecules amount to increase.
CA+BThe gel fraction of sample 6 has reached 89.9% when=300mg/mL.In addition, the present invention draws hydrophobic block (such as polycaprolactone)
Enter gel network to prepare the hydrophobicity and engineering properties that amphiphilic block body will ensure that gel, as shown in table 4, with CA+BIncreasing
Greatly, the equilibrium swelling ratio of sample 1,4,7, sample 2,5,8 and sample 3,6,9 is substantially reduced, and hydrophobicity is become better and better；With
Mn,PEG/Mn,PCLThe reduction of ratio, i.e., the increase of PCL segments accounting, hydrophobicity are also become better and better in sample.
As shown in figure 5, the measuring mechanical property result figure of the sample 1-4 for the preparation of test example 4 of the present invention, passes through compression
Test, it can be seen that with CA+BIncrease, the mechanical performance of sample 1,4,7, sample 2,5,8 and sample 3,6,9 becomes better and better,
With Mn,PEG/Mn,PCLThe reduction of ratio, mechanical performance are also become better and better, anti-pressure ability enhancing.
Absorption bromophenol blue performance test is carried out to above-mentioned sample 1-9, is obtained by adsorption isotherm, adsorbs bromophenol blue most
Big adsorbance is about 400mg/g.
Adsorbing hexavalent chromium ions test is carried out to above-mentioned sample 3,6,9, is carried out using the simulated wastewater containing hexavalent chromium
Absorption test：Waste water 50mL, Cr6+A concentration of 10mg/mL, amount of samples 5mg, Cr6+Removal rate is respectively 91.5%, 95.6%,
99.2%.
In conclusion the gel of the amphipathic copolymerization network with micron hole of the present invention can be formed in the interior thereof three
Highly branched structure is tieed up, while also there is hydrophobic patch, there is better absorption property.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of amphipathic copolymerization network gel with micron hole, which is characterized in that the gel has the polymerization such as formula (1)
Object constitutional repeating unit：
In formula (1), R is N heterocycles, it includes：In any one, wherein X includes：Br-、Cl-Or
In formula (1), n is 6~30；M is 3~30；
The gel fraction of the gel is more than 70%.
2. the amphipathic copolymerization network gel according to claim 1 with micron hole, which is characterized in that described is solidifying
Glue is by having such as the compound B of formula (2) structure and being obtained through the preparation of N- alkylated reactions with the compound A such as formula (3) structure
：
In formula (2), R ' includes：In any one；
In formula (3), R1、R2、R3It is each independently Cl or Br；
In formula (3), n is 6~30；M is 3~30.
3. a kind of preparation method of the amphipathic copolymerization network gel with micron hole, which is characterized in that the gel is as weighed
Profit requires the amphipathic copolymerization network gel with micron hole described in 1, this method to include：
Compound B with such as formula (2) structure and compound A with such as formula (3) structure is obtained through the preparation of N- alkylated reactions
：
In formula (2), R ' includes：In any one；
In formula (3), R1、R2、R3It is each independently Cl or Br；
In formula (3), n is 6~30；M is 3~30；
The total concentration of the compound A and compound B is 200~1000mg/mL, and the gel fraction of the gel is more than
70%.
4. the preparation method of the amphipathic copolymerization network gel according to claim 3 with micron hole, feature exist
In the R ' is
The preparation method of the compound B includes：
By 1,3,5- triacryl hexahydro -1,3,5-triazines and imidazoles through Michael addition reaction, compound B is obtained.
5. the preparation method of the amphipathic copolymerization network gel according to claim 4 with micron hole, feature exist
In described 1,3,5- triacryl hexahydros -1,3,5-triazines flows back with imidazoles in absolute methanol, and reaction solution is deposited in second
Acetoacetic ester/tetrahydrofuran mixed solvent washs, and filters, dry, to obtain the compound B.
6. the preparation side of the amphipathic copolymerization network gel with micron hole according to any one of claim 3-5
Method, which is characterized in that the preparation method of the compound A includes：
There to be the compound C such as formula (4) structure to carry out esterification with alpha-brominated or alpha-chloro propionic acid, and obtain compound A；
In formula (4), n is 6~30；M is 3~30.
7. the preparation method of the amphipathic copolymerization network gel according to claim 6 with micron hole, feature exist
In the compound C, alpha-brominated or alpha-chloro propionic acid and p-methyl benzenesulfonic acid are heated to reflux in toluene, are removed solvent, are obtained
To crude product, purifying obtains compound A.
8. the preparation method of the amphipathic copolymerization network gel according to claim 7 with micron hole, feature exist
In the preparation method of the compound C includes：
To have as formula (5) structure compound D and 6- caprolactones under inert gas conditions, it is organic molten in higher boiling nonpolarity
Reaction is heated in agent, is obtained after reaction by precipitating；
In formula (5), n is 6~30；
In the compound C-structure, the molecular wt ratio of PEG and PCL segments is (1000~10000)：(1000~
30000)。
9. a kind of anionic dyes or anionic heavy metal absorbent, which is characterized in that the adsorbent is to be wanted according to right
Seek the amphipathic copolymerization network gel with micron hole described in 1 or 2；The anionic dyes include：Bromophenol blue, just
In arnotto, methyl orange, methyl blue and acid fuchsin any one or it is two or more；The anionic heavy metal includes：WithIn any one or it is two or more.
10. a kind of processing method of chromate waste water, which is characterized in that this method is had using according to claim 1 or 2
The amphipathic copolymerization network gel in micron hole is with Adsorption of Chromium.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060020064A1 (en) * | 2004-07-22 | 2006-01-26 | Clariant Gmbh | Flame-retardant polymer molding compositions |
| CN102883805A (en) * | 2010-04-28 | 2013-01-16 | 株式会社日立高新技术 | Adsorbent and method for producing same |
| CN103570873A (en) * | 2013-10-23 | 2014-02-12 | 深圳新宙邦科技股份有限公司 | Composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical device |
| US20150119488A1 (en) * | 2013-10-30 | 2015-04-30 | Dentsply International Inc. | Polymerizable resins containing a 1,3,5-hexahydro-1,3,5-triazine moiety, methods of making, and dental compositions containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060020064A1 (en) * | 2004-07-22 | 2006-01-26 | Clariant Gmbh | Flame-retardant polymer molding compositions |
| CN102883805A (en) * | 2010-04-28 | 2013-01-16 | 株式会社日立高新技术 | Adsorbent and method for producing same |
| CN103570873A (en) * | 2013-10-23 | 2014-02-12 | 深圳新宙邦科技股份有限公司 | Composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical device |
| US20150119488A1 (en) * | 2013-10-30 | 2015-04-30 | Dentsply International Inc. | Polymerizable resins containing a 1,3,5-hexahydro-1,3,5-triazine moiety, methods of making, and dental compositions containing the same |
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