CN106496577B - The preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent - Google Patents
The preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent Download PDFInfo
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- CN106496577B CN106496577B CN201610857859.3A CN201610857859A CN106496577B CN 106496577 B CN106496577 B CN 106496577B CN 201610857859 A CN201610857859 A CN 201610857859A CN 106496577 B CN106496577 B CN 106496577B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 165
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 52
- 239000002738 chelating agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 239000005864 Sulphur Substances 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 238000005189 flocculation Methods 0.000 claims description 19
- 230000016615 flocculation Effects 0.000 claims description 19
- 229920001021 polysulfide Polymers 0.000 claims description 16
- 229920002401 polyacrylamide Polymers 0.000 claims description 15
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 claims description 10
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- -1 poly(N-isopropylacrylamide) Polymers 0.000 claims description 10
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 9
- 238000010550 living polymerization reaction Methods 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001540 azides Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- ORKNWMCBDOXCCG-UHFFFAOYSA-N 2-(3-ethylsulfanylpropylsulfanyl)ethanethiol Chemical compound C(CSCCCSCC)S ORKNWMCBDOXCCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 14
- 239000000243 solution Substances 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract description 7
- 239000011557 critical solution Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 8
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 description 2
- CNRZJYVUUWUCND-UHFFFAOYSA-N C(CSCCCSCC)S.C(C(=C)C)(=O)O Chemical compound C(CSCCCSCC)S.C(C(=C)C)(=O)O CNRZJYVUUWUCND-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N sodium azide Substances [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to a kind of preparation methods of thermosensitive type polymer molecule brush heavy metal chelating agent, and feature is to include the steps that are as follows: 5~10 parts of thermosensitive type polymer molecule brush is dissolved in 10~50 parts of water；It is stirred 1~10 hour at 20 DEG C~30 DEG C, obtains thermosensitive type polymer molecule brush heavy metal chelating agent micellar solution.Thermosensitive type polymer molecule brush contains the polymer side chain of three kinds of different function, to can play synergistic effect capturing heavy metal ion, reaches efficiently capture and rapid subsidence function；When heating temperature is higher than critical solution temperature, grade aggregation becomes hydrophobicity completely, and rapid subsidence occurs, can achieve the purpose that quick separating low-concentration heavy metal ions.
Description
Technical field
The invention belongs to water treatment technology and polymer-function material fields, and in particular to a kind of thermosensitive type polymer molecule
The preparation method of brush heavy metal chelating agent.
Background technique
Heavy metal ion agent for capturing is a kind of organic compound with chelating functional group, can be from the solution of metal ion
Middle selection capture, separation and precipitation of heavy metals.Currently, mainly having dithiocarbamate salt using more heavy metal chelating agent
Analog derivative (DTC class), trithiocyanuric acid (TMT), small molecule polysulfide etc..DTC analog derivative is as a first generation huge sum of money
Belong to agent for capturing product, is most widely used product, but have the defects that the easy stability of factorization of the sediment of generation is poor, thus
Cause secondary pollution problem.Trithiocyanuric acid (TMT) is used as second generation heavy metal chelating agent product, is also widely used in Industry Waste
There is precipitating not exclusively containing the precipitable most heavy metal ion of three thin bases in water process, trithiocyanuric acid, removal efficiency is low etc.
Problem.Small molecule polysulfide can provide multiple sulfur-bearing coordination sites, be current weight to be able to achieve efficient process industrial wastewater
One of the emphasis direction of metal agent for capturing research and development.Small molecule polysulfide main problem is that the precipitating particle generated is smaller,
Usually nanoscale precipitates, it is more difficult to effectively come out from industrial wastewater precipitation and separation, a large amount of high polymer coagulant is only added
It can effective sedimentation separation.
Currently, heavy metal chelating agent research and development Main way is to reduce medicine consumption around raising removal effect, separative efficiency, subtract
Of low pollution and enhancing environmental consciousness.The heavy metal chelating that the market mainstream uses does not have low-concentration heavy metal to capture sedimentation energy substantially
Power (heavy metal concentration heavy metal ion < 5mg/L).Therefore, it is useless to be unable to reach plating for most of heavy metal chelating agents capture performances
3 national emission standard of water meter.Realize that low-concentration heavy metal agent for capturing captures and the main method of settling property is by effective
Molecular Design realized with synthesis.
Summary of the invention
A kind of thermosensitive type polymer molecule brush heavy metal is provided the purpose of the present invention is overcome the deficiencies in the prior art to catch
The preparation method of agent is caught, thermosensitive type polymer molecule brush contains the polymer side chain of three kinds of different function, thus capturing heavy metal
Ion can play synergistic effect, reach efficiently capture and rapid subsidence function；It is being lower than critical solution temperature (LCST < 33 DEG C)
Under the conditions of, thermosensitive type side chain has good water soluble characteristic, and thermosensitive type polymer molecule brush constructs a nanometer heavy metal chelating agent glue
Beam can disperse in aqueous solution；When thermosensitive type polymer molecule brush heavy metal chelating agent is added in heavy metal wastewater thereby, thermosensitive type
The sulfenyl functional group of polymer molecule brush can quickly capture the aggregation that heavy metal ion generates micro-nano structure；In flocculation macromolecule
Under the further effect of side chain, the further aggressiveness of the aggregation of micro-nano structure is at grade aggregation；Face when adjusting temperature is higher than
Under the conditions of boundary's solution temperature (LCST > 33 DEG C), grade aggregation becomes hydrophobicity completely, and rapid subsidence occurs, can reach fast
The purpose of fast separating low concentration heavy metal ion.
In order to achieve the above object, the technical proposal of the invention is realized in this way, is a kind of thermosensitive type polymer point
Sub- brush heavy metal chelating agent, it is characterised in that include the following steps:
Step 1
5~10 parts of thermosensitive type polymer molecule brush is dissolved in 10~50 parts of water；
Step 2
20oC~30oIt is stirred 1~10 hour under C, it is molten to obtain thermosensitive type polymer molecule brush heavy metal chelating agent micella
Liquid；
It is above mass fraction.
In the technical scheme, the partial size of the thermosensitive type polymer molecule brush heavy metal chelating agent micellar solution is 1
~400 nm.
In the technical scheme, the general formula of the thermosensitive type polymer molecule brush: A-g- (B-r-C-r-D), wherein g generation
Table grafting, r represent random distribution, A representation polymer main chain, and B represents more sulphur polymer side chains, and C represents thermosensitive type macromolecule side
Chain, D represent flocculation polymer side chain, and more sulphur polymer side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D are random
Ground is grafted on main polymer chain A；
The polymer of the main polymer chain A is poly (glycidyl methacrylate) (PGMA)；
The polymer of more sulphur polymer side chain B is polymethylacrylic acid 3,7- dithia -1- nonyl mercaptan (PDNTEMA)
Or one of polymethylacrylic acid 4- thiopurine methyltransferase -3,6- dithia -1- spicy thioalcohol (PMDOTEMA)；
The polymer of the thermosensitive type polymer side chain C is poly(N-isopropylacrylamide) (PNIPAM)；
The polymer of the flocculation polymer side chain D is polyacrylamide (PAM).
In the technical scheme, the degree of polymerization of the main polymer chain A is 500~1000, more sulphur polymer side chains
B, the degree of polymerization of thermosensitive type polymer side chain C and the polymer side chain D that flocculates are 40~200, and the grafting rate of B, C and D are 10
~100%.
In the technical scheme, the step of synthesis of the thermosensitive type polymer molecule brush is as follows:
Step 1 synthetic polymer main chain A
PGMA main polymer chain, then each epoxy group list to PGMA main polymer chain are synthesized by controllable living polymerization
Member carries out azide functionalization, obtains P(GMA-N3) main polymer chain；
Step 2 synthesizes more sulphur polymer side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D
More sulphur polymer side chain B are synthesized, first synthesize more sulphur monomers, then carry out controllable living polymerization, synthesis end contains alkynyl
The polysulphide polymer of functional group, more sulphur monomers mainly pass through glycidyl methacrylate and 3,7- dithia -1,9- nonyl
" epoxy group-mercapto occurs under lithium hydroxide catalytic action for two mercaptan or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8-
Base " click chemistry is reacted and is synthesized, and ingredient proportion is controlled in 1:2~5, it is ensured that the epoxy group of glycidyl methacrylate
Occur with a sulfydryl of two mercaptan of 3,7- dithia -1,9- nonyl or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- anti-
It answers；The glycidyl methacrylate contains 1 epoxy group, and 3,7- dithia -1,9- nonyl, two mercaptan contains two mercaptos
Base, pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- contain three sulfydryls；
Thermosensitive type polymer side chain C is synthesized, PNIPAM polymer of the end containing alkynyl is synthesized by controllable living polymerization；
Synthesis flocculation polymer side chain D, synthesizes PAM polymer of the end containing alkynyl by controllable living polymerization；
The synthesis of step 3 final products
By obtained more sulphur macromolecules in the obtained main polymer chain A containing azide functionalities in step 1 and step 2
Side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D are mixed, and each Elementary Function of main polymer chain A is made
Group is chemically reacted with more sulphur polymer side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D, in catalyst
In the presence of carry out a step " nitrine-alkynyl " click chemistry reaction, obtain final products i.e. thermosensitive type polymer molecule brush.
In the technical scheme, main polymer chain A described in step 1, which can be used, makees controllable free radical polymerization process synthesis,
And carry out Azide and be modified, main polymer chain A is P (GMA-N3)；Controllable free-radical polymerisation can be used in side chain described in step 2
Method；The C of thermosensitive type polymer side chain described in step 2 is PNIPAM-C ≡ CH；The B of polysulphide polymer side chain described in step 2
It is PDNTEMA-C ≡ CH, PMDOTEMA-C ≡ CH；Flocculation polymer side chain D described in step 2 is PAM-C ≡ CH；Step 3
Described in catalyst sulfuric acid copper and ascorbic acid, ratio 1:5.
Compared with prior art, the present invention have following advantages and effects
1, thermosensitive type polymer molecule brush heavy metal chelating agent has high capture and quickly to low concentration heavy metal water
The dual function of sedimentation, the technical problem of low-concentration heavy metal ions can not be captured by solving current heavy metal chelating agent；
2, the aggregation generated is completely hydrophobic, easy to clean small to equipment adhesion strength；
3, the aggregation stability generated is good, is not easily decomposed, is not likely to produce secondary pollution.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of thermosensitive type polymer molecule brush, is prepared by the following steps to obtain:
Step 1 P (GMA-N3) main polymer chain A synthesis
Take 1 part 2- isobutyl ethyl bromide initiator, 700 parts of glycidyl methacrylate (GMA), 1000 part
Diphenyl ether, CuBr and 5 of 5 parts part of N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), 30 DEG C under nitrogen protection
It carries out ATRP to react 9 hours, obtains the poly (glycidyl methacrylate) (PGMA) that the degree of polymerization (DP) is 600；
Take 100 parts of PGMA(DP=600), 200 parts of NaN3And 300 parts of dimethylformamide (DMF), it is anti-at 60 DEG C
It answers 50 hours, obtains P (GMA-N3), as main polymer chain A；
The synthesis of three kinds of side chains of step 2
The synthesis of thermosensitive type polymer side chain C: 1 part of bromo acid propynyl ester initiator, 300 parts of N- isopropyl are taken
Acrylamide (NIPAM), 200 parts of isopropanol and water (v/v, 16/1), 2 parts CuBr and 2 part of N, N, N', N', N "-pentamethyl
Diethylenetriamine (PMDETA), 25 DEG C of progress ATRP react 8 hours under nitrogen protection, and obtaining the degree of polymerization (DP) is 180
PNIPAM-C ≡ CH, that is, thermosensitive type polymer side chain C；
The synthesis of polysulphide polymer side chain B: 100 parts of glycidyl methacrylate, 250 parts of bis- sulphur of 3,7- are taken
Miscellaneous -1,9- nonyl, two mercaptan, 3 parts of lithium hydroxide and 400 parts of methylene chloride, normal-temperature reaction 36 hours, obtains methacrylic acid 3,
7- dithia -1- nonyl mercaptan (DNTEMA)；
Take 1 part of bromo acid propynyl ester initiator, 200 parts of methacrylic acid 3,7- dithia -1- nonyl mercaptan
(DNTEMA), 200 parts of toluene, 2 parts CuBr and 2 part of N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), in nitrogen
The lower 60 DEG C of progress ATRP of gas shielded react 7 hours, obtain the polysulphide polymer for the PDNTEMA-C ≡ CH that the degree of polymerization (DP) is 150
Side chain B；
Flocculate polymer side chain D synthesis: take 2 parts bromo acid propynyl ester initiator, 250 parts of acrylamide
(AM), 200 parts of dimethylformamide (DMF), 2 parts of frerrous chloride (FeCl2) and 2 parts of triphenyl phosphorus (PPh3), it is protected in nitrogen
Under shield, temperature is controlled at 80 DEG C, is carried out ATRP and is reacted 8 hours, is obtained the PAM-C ≡ CH that the degree of polymerization (DP) is 130 and is flocculated height
Molecular side chain D；
The synthesis of step 3 thermosensitive type polymer molecule brush PGMA-g- (PDNTEMA-r-PNIPAM-r-PAM)
Take 10 parts of P (GMA-N3), 15 parts of PAM-C ≡ CH, 35 parts of PNIPAM-C ≡ CH and 30 parts of PDNTEMA-C
≡ CH is dissolved in 500 parts of dimethylformamide (DMF), adds 2 parts of CuSO4And 10 parts of sodium ascorbates, it reacts at 30 DEG C
50 hours, obtain thermosensitive type polymer molecule brush PGMA-g- (PDNTEMA-r-PNIPAM-r-PAM), PAM, PNIPAM and
The grafting rate of PDNTEMA side chain is respectively 15%, 35% and 30%.
Thermosensitive type polymer molecule brush heavy metal chelating agent is made using solution self-assembly method, preparation method are as follows: by 10
The thermosensitive type polymer molecule brush of part is dissolved in 50 parts of water, 25oIt is stirred 8 hours under C, obtains nanometer heat sensitive type polymer
Molecular brush heavy metal chelating agent micellar solution, partial size are 150 nm.
It takes the present embodiment product to do the test of cadmium ion removal efficiency, takes 500 mL containing Cd2+Ion 5 mg/L and EDTA 0.10
The waste water of g/L adds 0.2 mL of the present embodiment product, 25oIt stirs 5 minutes, is heated up in 40 under CoC generates precipitating, mistake at once
Filter, using aas determination liquor C d2+Ion concentration is 0.003 mg/L, removal efficiency 99.94%.
Embodiment two
Preparation method and raw material composition are as in the first embodiment, only to the thermosensitive type polymer molecule brush PGMA- of embodiment one
The degree of polymerization of the main polymer chain A and polysulphide polymer side chain B of g- (PDNTEMA-r-PNIPAM-r-PAM) are adjusted, can be with
The heavy metal chelating agent of different-grain diameter size is made.The degree of polymerization of main polymer chain A and polysulphide polymer side chain B, heavy metal are caught
It catches agent particle size and is shown in Table 1.
The degree of polymerization of main polymer chain A is 500,650,750,850,950 polymer and the polymerization of polysulphide polymer side chain B
Degree is 55,85,125,175, and the degree of polymerization of heat-sensible high polymer side chain C is 180 and the degree of polymerization of flocculation polymer side chain D is
130.It can be prepared according to the method for embodiment one by control raw material or polymerization reaction time；Every kind of thermosensitive type polymer
The grafting rate of PAM, PNIPAM and PDNTEMA side chain in molecular brush PGMA-g- (PDNTEMA-r-PNIPAM-r-PAM) is distinguished
It is 15%, 35% and 30%.
Table 1: the influence of molecular brush main chain and the side chain degree of polymerization to heavy metal chelating agent partial size
As can be seen from Table 1, by adjusting the degree of polymerization of main polymer chain A and polysulphide polymer side chain B, difference can be prepared
The heavy metal chelating agent of particle size.
Embodiment three
Preparation method and raw material composition are as in the first embodiment, only change the heat of the thermosensitive type polymer molecule brush of embodiment one
Grafting rate, that is, each side chain Relative mole percentage ratio of quick type polymer side chain C and flocculation polymer side chain D can be made different
Rate of settling heavy metal chelating agent.Rate of settling test condition: with the Pb of 10 mg/L2+100 mL of ion is test fluid, is added
0.10 mL heavy metal chelating agent, observation sedimentation situation of change, the timing since when putting into heavy metal chelating agent are big when observing
It is the sedimentation time when precipitating, sedimentation time situation of change is shown in Table 2.
Table 2: molecular brush side chain forms the influence to the heavy metal chelating agent sedimentation time
As can be seen from Table 2, it is rubbed by changing the grafting rate of thermosensitive type polymer side chain C and the polymer side chain D of flocculating
That percentage ratio, can prepare the heavy metal chelating agent of the different rates of settling.
Example IV
It is a kind of thermosensitive type polymer molecule brush polysulphide polymer, is prepared by the following steps to obtain:
Step 1 P (GMA-N3) synthesis of main polymer chain A
Take 1 part 2- isobutyl ethyl bromide initiator, 800 parts of glycidyl methacrylate (GMA), 1000 part
Diphenyl ether, CuBr and 5 of 5 parts part of N, N, N', N', N "-pentamethyl-diethylenetriamine (PMDETA), 30 DEG C under nitrogen protection
It carries out ATRP to react 5 hours, obtains the poly (glycidyl methacrylate) (PGMA) that the degree of polymerization (DP) is 700.
Take 100 parts of PGMA(DP=700), 200 parts of NaN3And 300 parts of dimethylformamide (DMF), it is anti-at 60 DEG C
It answers 50 hours, obtains P (GMA-N3), as main polymer chain A；
The synthesis of three kinds of side chains of step 2
The synthesis of thermosensitive type polymer side chain C: 1 part of bromo acid propynyl ester initiator, 250 parts of N- isopropyl are taken
Acrylamide (NIPAM), 100 parts of isopropanol and water (v/v, 16/1), 2 parts CuBr and 2 part of N, N, N', N', N "-pentamethyl
Diethylenetriamine (PMDETA), 25 DEG C of progress ATRP react 8 hours under nitrogen protection, and obtaining the degree of polymerization (DP) is 140
PNIPAM-C ≡ CH, that is, thermosensitive type polymer side chain C；
The synthesis of polysulphide polymer side chain B: 100 parts of glycidyl methacrylate, 400 parts of 4- thiopurine methyltransferase-are taken
Pungent two mercaptan of 3,6- dithias -1,8-, 3 parts of lithium hydroxide and 400 parts of methylene chloride, normal-temperature reaction 36 hours, obtain methyl
Acrylic acid 4- thiopurine methyltransferase -3,6- dithia -1- spicy thioalcohol (MDOTEMA)；
Take 1 part of bromo acid propynyl ester initiator, 300 parts of methacrylic acid 4- thiopurine methyltransferase -3,6- dithia -1-
Spicy thioalcohol (MDOTEMA), 200 parts of toluene, 2 parts CuBr and 2 part of N, N, N', N', N "-pentamethyl-diethylenetriamine
(PMDETA), 60 DEG C of progress ATRP react 8 hours under nitrogen protection, obtain the PMDOTEMA-C ≡ that the degree of polymerization (DP) is 170
CH, that is, polysulphide polymer side chain B；
Flocculate polymer side chain D synthesis: take 1 part bromo acid propynyl ester initiator, 100 parts of acrylamide
(AM), 200 parts of dimethylformamide (DMF), 2 parts of frerrous chloride (FeCl2) and 2 parts of triphenyl phosphorus (PPh3), it is protected in nitrogen
Under shield, temperature is controlled at 80 DEG C, is carried out ATRP and is reacted 5 hours, is obtained the PAM-C ≡ CH that the degree of polymerization (DP) is 90 and is flocculated high score
Sub- side chain D；
The synthesis of step 3 thermosensitive type polymer molecule brush PGMA-g- (PMDOTEMA-r-PNIPAM-r-PAM)
Take 10 parts of P (GMA-N3), 20 parts of PAM-C ≡ CH, 30 parts of PNIPAM-C ≡ CH and 40 parts of PMDOTEMA-
C ≡ CH is dissolved in 500 parts of dimethylformamide (DMF), adds 3 parts of CuSO4And 10 parts of sodium ascorbates, it reacts at 30 DEG C
50 hours, obtain thermosensitive type polymer molecule brush PGMA-g- (PMDOTEMA-r-PNIPAM-r-PAM), PAM, PNIPAM and
The grafting rate of PMDOTEMA side chain is respectively 20%, 30% and 40%.
Thermosensitive type polymer molecule brush heavy metal chelating agent is made using solution self-assembly method, preparation method are as follows: by 10
The thermosensitive type polymer molecule brush of part is dissolved in 40 parts of water, 25oIt is stirred 5 hours under C, obtains nanometer heat sensitive type polymer
Molecular brush heavy metal chelating agent micellar solution, partial size are 350 nm.
It takes the present embodiment product to do the test of cadmium ion removal efficiency, takes 500 mL containing Cd2+Ion 5 mg/L and EDTA 0.10
The waste water of g/L adds 0.2 mL of the present embodiment product, 25oIt stirs 5 minutes, is heated up in 50 under CoC generates precipitating, mistake at once
Filter, using aas determination liquor C d2+Ion concentration is 0.001 mg/L, removal efficiency 99.98%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (4)
1. a kind of preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent, it is characterised in that include the following steps:
Step 1
5~10 parts of thermosensitive type polymer molecule brush is dissolved in 10~50 parts of water, they are mass fraction；
Step 2
It is stirred 1~10 hour at 20 DEG C~30 DEG C, it is molten to obtain thermosensitive type polymer molecule brush heavy metal chelating agent micella
Liquid, the partial size of thermosensitive type polymer molecule brush heavy metal chelating agent micellar solution are 1~400 nm；
The general formula of the thermosensitive type polymer molecule brush: A-g- (B-r-C-r-D), wherein g represents grafting, and r represents random point
Cloth, A representation polymer main chain, B represent more sulphur polymer side chains, and C represents thermosensitive type polymer side chain, and D represents flocculation macromolecule
Side chain, more sulphur polymer side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D are randomly grafted on main polymer chain
On A；
The polymer of the main polymer chain A is poly (glycidyl methacrylate) (PGMA)；More sulphur polymer side chain B
Polymer be polymethylacrylic acid 3,7- dithia -1- nonyl mercaptan (PDNTEMA) or polymethylacrylic acid 4- thiopurine methyltransferase -3,6-
One of dithia -1- spicy thioalcohol (PMDOTEMA)；
The polymer of the thermosensitive type polymer side chain C is poly(N-isopropylacrylamide) (PNIPAM)；
The polymer of the flocculation polymer side chain D is polyacrylamide (PAM).
2. the preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent according to claim 1, it is characterised in that
The degree of polymerization of the main polymer chain A is 500~1000, more sulphur polymer side chain B, thermosensitive type polymer side chain C and wadding
The degree of polymerization of solidifying polymer side chain D is 40~200, and the grafting rate of B, C and D are 10~100%.
3. the preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent according to claim 1, it is characterised in that
The step of synthesis of the thermosensitive type polymer molecule brush, is as follows:
Step 1 synthetic polymer main chain A
Synthesize PGMA main polymer chain by controllable living polymerization, then to each epoxy group unit of PGMA main polymer chain into
Row azide functionalization, obtains P(GMA-N3) main polymer chain；
Step 2 synthesizes more sulphur polymer side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D
More sulphur polymer side chain B are synthesized, first synthesize more sulphur monomers, then carry out controllable living polymerization, synthesize end function containing alkynyl
The polysulphide polymer of group, more sulphur monomers mainly pass through glycidyl methacrylate and 3, two sulphur of 7- dithia -1,9- nonyl
" epoxy group-sulfydryl " point occurs under lithium hydroxide catalytic action for alcohol or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8-
It hits chemical reaction and synthesizes, ingredient proportion is controlled in 1:2~5, it is ensured that the epoxy group of glycidyl methacrylate and 3,
One sulfydryl of two mercaptan of 7- dithia -1,9- nonyl or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- reacts；Institute
Glycidyl methacrylate is stated containing 1 epoxy group, 3,7- dithia -1,9- nonyl, two mercaptan contains two sulfydryls, institute
4- pungent two mercaptan of thiopurine methyltransferase -3,6- dithia -1,8- is stated containing three sulfydryls；
Thermosensitive type polymer side chain C is synthesized, PNIPAM polymer of the end containing alkynyl is synthesized by controllable living polymerization；
Synthesis flocculation polymer side chain D, synthesizes PAM polymer of the end containing alkynyl by controllable living polymerization；
The synthesis of step 3 final products
By obtained more sulphur polymer side chains in the obtained main polymer chain A containing azide functionalities in step 1 and step 2
B, thermosensitive type polymer side chain C and flocculation polymer side chain D are mixed, and make each Elementary Function group of main polymer chain A
It chemically reacts with more sulphur polymer side chain B, thermosensitive type polymer side chain C and flocculation polymer side chain D, exists in catalyst
The reaction of lower progress one step " nitrine-alkynyl " click chemistry, obtains final products i.e. thermosensitive type polymer molecule brush.
4. the preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent according to claim 3, it is characterised in that
Main polymer chain A described in step 1, which can be used, makees controllable free radical polymerization process synthesis, and carries out Azide and be modified, polymer
Main chain A is P (GMA-N3)；Controllable free radical polymerization process can be used in side chain described in step 2；Thermosensitive type described in step 2
Polymer side chain C is PNIPAM-C ≡ CH；The B of polysulphide polymer side chain described in step 2 be PDNTEMA-C ≡ CH,
PMDOTEMA-C≡CH；Flocculation polymer side chain D described in step 2 is PAM-C ≡ CH；Catalyst sulfuric acid described in step 3
Copper and ascorbic acid, ratio 1:5.
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