CN108530625B - 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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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses the gel and method of a kind of amphipathic copolymerization network with micron hole, which has the polymer constitutional repeating unit such as formula (1), wherein and R is N heterocycle, it includes:In any one, wherein X includes: Br‑、Cl‑OrN is 6-30；M is 3-30；The gel fraction of gel is greater than 70%.Gel of the 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 technique
Due to the toxicity and visibility of dyestuff, even at a low concentration, dyeing industrial wastewater is also most problematic waste water
One of.Most of organic dyestuff, especially synthetic dyestuffs have complicated aromatic molecule structure, stablize it and are difficult to biology
Degradation, this may have toxicity or mutagenicity and carcinogenicity to bio-diversity.Therefore, Cong Shuizhong effectively remove 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, how to design synthesis has the novel of high adsorption efficiency
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, will lead to its strand
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 being 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.
Summary of the invention
The object of the present invention is to provide the gel and method of a kind of amphipathic copolymerization network with micron hole, the gels
Conventional gel is solved without network cross-linked structure, the problem of adsorption capacity difference can be formed in the interior thereof three-dimensional highly branched knot
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 gel with micron hole, should
Gel has the polymer constitutional repeating unit such as formula (1):
In formula (1), R is N heterocycle, 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 greater than 70%.
Preferably, the gel by the compound B with such as formula (2) structure and has the chemical combination such as formula (3) structure
Object A is prepared through N- alkylated reaction:
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 preparation method of the present invention also provides a kind of amphipathic copolymerization network gel with micron hole, the gel are
The amphipathic copolymerization network gel with micron hole, this method includes:
There to be the compound B such as formula (2) structure and have if the compound A of formula (3) structure is through N- alkylated reaction system
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 are 200~1000mg/mL, and the gel fraction of the gel is greater than
70%.
Preferably, the R ' is
The preparation method of the compound B includes: 1,3,5- triacryl hexahydro -1,3,5- triazine and imidazoles are passed through
Michael addition reaction obtains compound B.
Preferably, 1,3, the 5- triacryl hexahydros -1,3,5-triazines and imidazoles flow back in anhydrous 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 compound C such as formula (4) structure 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: will have compound D and 6- such as formula (5) structure in oneself
Ester under inert gas conditions, heats reaction in higher boiling non-polar organic solvent, after reaction by precipitating to obtain；
In formula (5), n is 6~30；In the compound C-structure, the molecular wt ratio of PEG and PCL segment 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, have the two of micron hole described in this method use
Parent's property copolymerization network gel is with Adsorption of Chromium.
The gel and method of amphipathic copolymerization network with micron hole of the invention, solve conventional gel without network
Cross-linked structure, the problem of adsorption capacity difference, has the advantage that
(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 for ionic liquid as functional group, and it is (i.e. solidifying to improve adsorbent material
Glue) absorption property, have good adjustability of structure and the multiple interaction with dyestuff；
(3) hydrophobic block (such as polycaprolactone) is introduced gel network by the present invention will ensure that gel to prepare amphiphilic block body
Hydrophobicity and mechanical performance.
Detailed description of the invention
Fig. 1 is the SEM image of the amphipathic copolymerization network gel with micron hole of the invention.
Fig. 2 is the preparation route figure of the amphipathic copolymerization network gel with micron hole of the invention.
Fig. 3 is the preparation route figure of the amphipathic A monomer of three bromos of the invention.
Fig. 4 is the H nuclear magnetic spectrogram of B monomer of the end group with imidazoles of experimental example 3 of the present invention preparation.
The measuring mechanical property result figure of sample 1-4 prepared by test example 4 Fig. 5 of the invention.
Specific embodiment
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 heterocycle, 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 greater 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 segment)
When being about 1:1 with hydrophobic section (PCL segment) molecular weight ratio, it is capable of the micron openings of functional dispersion, there is best absorption
Performance.
Above-mentioned gel is by the compound B with such as formula (2) structure and has 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.
Gel of the invention can adsorpting anion dye molecule, such as bromophenol blue, Congo red, methyl orange, methyl blue, acid
Property magenta etc. or anionic heavy metal, comprising:WithIn structure of the invention
Containing PCL (polycaprolactone) segment, gel mechanical property and tertiary hydrophobic property are improved, is mentioned 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 includes:
Compound A and B is had to the amphiphilic comprising ionic liquid group of hyperbranched topological structure by one kettle way preparation
Property network the amphipathic A monomer of three bromos and end group are specifically performed under heating conditions N- alkyl with the B monomer of imidazoles
Change reaction.
The solvent used is organic solvent, and such as dry DMF can be by impregnating to the end of reacting in ethanol solution
To replace the DMF in gel network.
It is 1000g/ by molecular weight as shown in figure 3, being the preparation route figure of the amphipathic A monomer of three bromos of the invention
Mol polyoxyethanyl glycerin ether A-PEG-OH (compound D) is initiator, so that 6- caprolactone (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- esterification, obtain bromine end group A monomer (A-PEG-b-PCL-Br).
The conjunction of the 1 amphipathic block presoma (A-PEG-b-PCL-OH) of polyoxyethanyl glycerin ether-b- polycaprolactone of experimental example
At
A-PEG-OH is utilizing toluene azeotropic water removing using preceding, a certain amount of A-PEG-OH and 6- caprolactone 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.
It as shown in table 1, is that the feed ratio table of each raw material of experimental example 1 is obtained by adjusting A-PEG-OH/CL feed ratio
The A-PEG-b-PCL-OH presoma 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, the characterization result table of the presoma 1-3 prepared for experimental example 2:
The feed ratio table of each raw material of 1 experimental example of table 1
The characterization result table of the presoma 1-3 of 2 experimental example 1 of table preparation
Note:aPass through SEC/MALLS (molecular exclusion chromatography and multi-angle laser light scattering method are combined) measurement Mw/MnWith
dn/dc；Mw/MnFor molecular weight distributing index；Dn/dc is refractive index increment；Mn,theroIt is theoretical molecular weight (according to feed ratio
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 through1H NMR is calculated.
The synthesis of the amphipathic A monomer (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 device is added in toluene, is heated to 120 DEG C, and flow back 16h.After reaction, toluene is evaporated off, crude product is dissolved in
In methylene chloride, 2%Na is successively used2CO3Washing 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, and gained produces
Object is dried under vacuum to constant weight at 40 DEG C.
The A monomer that the corresponding esterification modification of presoma 1-3 prepared by experimental example 1 obtains then is respectively designated as A-PEG7-b-
PCL3- Br (A monomer 1), A-PEG7-b-PCL5- Br (A monomer 2) and A-PEG7-b-PCL7- Br (A monomer 3).As shown in table 3, it is
The characterization result table of A monomer 1-3 prepared by experimental example 2:
The characterization result table of the A monomer 1-3 of 3 experimental example 2 of table preparation
Note:aPass through SEC/MALLS (molecular exclusion chromatography and multi-angle laser light scattering method are combined) measurement Mw/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- triazine (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 anhydrous methanol, 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 dissolution-precipitating
(methanol-ethyl acetate/tetrahydrofuran) washes twice, filtering, and gained precipitating is dried under vacuum to constant weight at room temperature, obtains B
Monomer (TT Im), as shown in figure 4, the H nuclear magnetic spectrogram of B monomer of the end group with imidazoles for experimental example 3 of the present invention preparation.
Amphiphilic hyper-branched gel (the hbGel-PEG-PCL-TTIm of 4 bromide ionic liquid of embodiment+Br-) preparation
A monomer, B monomer and the DMF of drying are added in reagent bottle, after stirring and dissolving, take out rotor.Reaction flask is sealed
It is placed in 80 DEG C of oil baths, stands 20h.After reaction, reaction flask is taken out from oil bath, is cooled to room temperature to system, taken
Sample out.The gel of taking-up is placed in DMF and is impregnated 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 reaction, C are carried out by the A monomer 1-3 and B monomer that prepare in experimental example 2A+BWith PEG/ in A monomer
PCL ratio, 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 the sample 1-9 of 4 experimental example 3 of table preparation
Note: pass through Mn,HNMRCalculate the molecular wt ratio of peg moiety and the part PCL；bGel fraction passes through yield meter
It calculates；ESR is Equilibrium swellingratio, 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 ratio in A monomer+Br-Gel fraction have an impact, CA+BAll be conducive to the raising of gel fraction with the increase of PCL component.hbGel-PE-PCL-TTIm+
Br-Crosslinking points mainly generated by the N- alkylated reaction of A-PEG-b-PCL-Br and TTIm (imidazoles), and between its crosslinking points
Theoretical chain length is controlled by the brachium of A monomer.Thus higher CA+BAll be conducive to gel fraction with biggish A monomer molecule 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 amphiphilic block body and will ensure that the hydrophobicity and engineering properties of 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 segment 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 prepared for test example 4 of the 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+Concentration is 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 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.
It is discussed in detail although the contents of the present invention have passed through 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 above content, for of the invention
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 heterocycle, 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 greater 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 the compound B with such as formula (2) structure and there is the compound A such as formula (3) structure to obtain through the preparation of N- alkylated reaction
:
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
Benefit require 1 described in micron hole amphipathic copolymerization network gel, this method includes:
To there is the compound B such as formula (2) structure and there is the compound A such as formula (3) structure to obtain through the preparation of N- alkylated reaction
:
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 are 200~1000mg/mL, and the gel fraction of the gel is greater 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 and imidazoles flow back in anhydrous 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 according to any one of claim 3-5 with micron hole
Method, which is characterized in that the preparation method of the compound A includes:
To have such as the compound C of formula (4) structure and alpha-brominated or alpha-chloro propionic acid to carry out esterification, 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- caprolactone under inert gas conditions, higher boiling nonpolarity it is organic molten
Reaction is heated in agent, after reaction by precipitating to obtain；
In formula (5), n is 6~30；
In the compound C-structure, the molecular wt ratio of PEG and PCL segment 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
With the amphipathic copolymerization network gel in micron hole described in asking 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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