CN106496575B - The preparation method of acid sensitive heavy metal chelating agent - Google Patents
The preparation method of acid sensitive heavy metal chelating agent Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of acid sensitive heavy metal chelating agent, feature is to include the steps that are as follows: 5~10 parts of acid sensitive polymer molecule brush is dissolved in 10~50 parts of pH value in 3~5 water；20oC~30oIt is stirred 1~10 hour under C, obtains a nanometer acid sensitive heavy metal chelating agent micellar solution；Acid sensitive heavy metal chelating agent is that acid sensitive polymer molecule brush is assembled in aqueous solution, obtains nanosized micelles, can be used for capturing the heavy metal ion of extremely low concentration.Which solve the effluent containing heavy metal ions difficulties of extremely low concentration, and problem is effectively treated, and further adjusts pH value, improves the hydrophobicity of the aggregation of micro-nano structure, so as to which effectively precipitation and separation comes out from water body.The aggregation stability of generation is good, is not easily decomposed, is not likely to produce secondary pollution.
Description
Technical field
The invention belongs to water treatment technology and polymer-function material fields, and in particular to a kind of acid sensitive heavy metal chelating
The preparation method of 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 preparation side of acid sensitive heavy metal chelating agent is provided the purpose of the present invention is overcome the deficiencies in the prior art
Method, side chain polymethylacrylic acid N, the N- dimethylamino ethyl ester of acid sensitive polymer molecule brush in acid condition, have very
Good water soluble characteristic, acid sensitive polymer molecule brush, which constructs a nanometer heavy metal chelating agent micella, can disperse in aqueous solution, acid-sensitive
Type polymer molecule brush sulfur-containing group is more, can quickly capture the aggregation that heavy metal ion generates micro-nano structure, when pH is from acidity
When becoming alkalinity, the aggregation of micro-nano structure becomes hydrophobicity completely, and rapid subsidence occurs, can reach separating low concentration heavy metal
The purpose of ion.
In order to achieve the above object, the technical proposal of the invention is realized in this way, is that a kind of acid sensitive heavy metal is caught
Catch agent, it is characterised in that include the following steps:
Step 1
It is in 3~5 water by the pH value that 5~10 parts of acid sensitive polymer molecule brush is dissolved in 10~50 parts；
Step 2
20oC~30oIt is stirred 1~10 hour under C, obtains a nanometer acid sensitive heavy metal chelating agent micellar solution；
It is above mass fraction.
In the technical scheme, the partial size of the nanometer acid sensitive heavy metal chelating agent micellar solution is 1~150 nm.
In the technical scheme, the general formula of the acid sensitive polymer molecule brush: A-g- (B-r-C), wherein g representative connects
Branch, r represent random distribution, A representation polymer main chain, and B represents more sulphur polymer side chains, and C represents acid sensitive polymer side chain, side
Chain B and C are randomly grafted on main 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 acid sensitive polymer side chain C is polymethylacrylic acid N, N- dimethylamino ethyl ester
(PDMAEMA)。
In the technical scheme, the degree of polymerization of the main polymer chain A is 500~1000, more sulphur polymer side chain B
And the degree of polymerization of acid sensitive polymer side chain C is 40~200, more sulphur polymer side chain B and acid sensitive polymer side chain C's connects
Branch rate is 10~100%.
In the technical scheme, the step of acid sensitive polymer molecule brush synthesizes 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 and acid sensitive polymer side chain C
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；
Acid sensitive polymer side chain C is synthesized, PDMAEMA of the end containing alkynyl is synthesized by controllable living polymerization and is polymerize
Object；
The synthesis of step 3 final products
By obtained more sulphur macromolecules in the main polymer chain A with azide functionalities obtained in step 1 and step 2
Side chain B and acid sensitive polymer side chain C mixing makes each Elementary Function group and more sulphur polymer side chain B of main polymer chain A
And acid sensitive polymer side chain C is chemically reacted, and it is anti-to carry out a step " nitrine-alkynyl " click chemistry in the presence of a catalyst
It answers, obtains final products i.e. acid sensitive 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, the main polymer chain A is P (GMA-N3)；The C of acid sensitive polymer side chain described in step 2 is
PDMAEMA-C≡CH；The B of polysulphide polymer side chain described in step 2 is PDNTEMA-C ≡ CH, PMDOTEMA-C ≡ CH；Step
Catalyst described in three includes copper sulphate and ascorbic acid, ratio 1:5.
Compared with prior art, the present invention have following advantages and effects
1, the present invention has synthesized a kind of acid sensitive polymer molecule brush, changes nanometer acid sensitive heavy metal by adjusting pH value
The hydrophilic and hydrophobic of agent for capturing micella, to realize capture and sedimentation dual function.Acid sensitive heavy metal chelating agent is to low concentration weight
Metal ion has extremely strong capture and sedimentation capacity；
2, acid sensitive heavy metal chelating agent has high removal efficiency to solvay-type heavy metal wastewater thereby, and removal efficiency is greater than
99.8%；
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 acid sensitive 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, 600 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 7 hours, obtains the poly (glycidyl methacrylate) (PGMA) that the degree of polymerization (DP) is 500；
Take 100 parts of PGMA(DP=500), 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 two kinds of side chains of step 2
The synthesis of acid sensitive polymer side chain C: take 1 part bromo acid propynyl ester initiator, 150 parts of metering system
Sour N, N- dimethylamino ethyl ester (DMAEMA), 100 parts of methanol, 2 parts CuCl and 2 part of 2,2- bipyridyl, in nitrogen protection
Lower 50 DEG C of progress ATRP react 6 hours, obtain the PDMAEMA-C ≡ CH i.e. acid sensitive polymer side chain that the degree of polymerization (DP) is 110
C；
The synthesis of more sulphur 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 8 hours, obtain the i.e. more sulphur macromolecules of PDNTEMA-C ≡ CH that the degree of polymerization (DP) is 140
Side chain B；
The synthesis of step 3 acid sensitive polymer molecule brush PGMA-g- (PDNTEMA-r-PDMAEMA)
Take 10 parts of P (GMA-N3), 40 parts of PDMAEMA-C ≡ CH and 20 parts of PDNTEMA-C ≡ CH be dissolved in 500 parts
Dimethylformamide (DMF), adds 2 parts of CuSO4And 10 parts of sodium ascorbates, it reacts 50 hours at 30 DEG C, obtains acid-sensitive
Type polymer molecule brush PGMA-g- (PDNTEMA-r-PDMAEMA), the grafting rate of PDMAEMA and PDNTEMA side chain are respectively
40% and 20%.
Nanometer acid sensitive heavy metal chelating agent is obtained using solution self-assembly method, preparation method are as follows: acid-sensitive by 10 parts
Type polymer molecule brush is dissolved in 50 parts of water, using 0.1 mol/L salt acid for adjusting pH value to 4.0,25oStirring 5 is small under C
When, a nanometer acid sensitive heavy metal chelating agent micellar solution is obtained, partial size is 50 nm.
It takes the present embodiment product to do the test of lead ion removal efficiency, takes 500 mL containing Pb2+Ion 4 mg/L and EDTA 0.10
The waste water of g/L adjusts pH value of waste water to 4.0 using 0.1 mol/L hydrochloric acid, adds 0.2 mL of the present embodiment product, stir 5 points
Clock adjusts pH value of waste water to 8.0 using 0.1 mol/L sodium hydroxide, generates precipitating at once, and filtering is surveyed using atomic absorption method
Determine filtrate Pb2+Ion concentration is 0.01 mg/L, removal efficiency 99.75%.
Embodiment two
Preparation method and raw material composition are as in the first embodiment, only to the acid sensitive polymer molecule brush PGMA- of embodiment one
The degree of polymerization of the main polymer chain A of g- (PDNTEMA-r-PDMAEMA) and more sulphur polymer side chain B are adjusted, and can be made
The acid sensitive heavy metal chelating agent of different-grain diameter size.The degree of polymerization, the acid sensitive of main polymer chain A and more sulphur polymer side chain B
Heavy metal chelating agent particle size is shown in Table 1.
The degree of polymerization of main polymer chain A is 600,700,800,900,1000, and the degree of polymerization of more sulphur polymer side chain B is
50, the degree of polymerization of 100,150,200 and acid sensitive polymer side chain C is 110.It can be former by control according to the method for embodiment one
Material or polymerization reaction time and be prepared.In every kind of acid sensitive polymer molecule brush PGMA-g- (PDNTEMA-r-PDMAEMA)
The grafting rate of PDMAEMA and PDNTEMA side chain be respectively 40% and 20%.
Table 1: the influence of molecular brush main chain and the side chain degree of polymerization to acid sensitive 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 more sulphur polymer side chain B, difference can be prepared
The acid sensitive heavy metal chelating agent of particle size.
Embodiment three
Preparation method and raw material composition are as in the first embodiment, only change the side of the acid sensitive polymer molecule brush of embodiment one
The grafting rate of chain, that is, each side chain Relative mole percentage ratio, can be made the acid sensitive heavy metal chelating agent of different-grain diameter size.
Change of size size is shown in Table 2.
Table 2: the influence of the pairs of acid sensitive heavy metal chelating agent partial size of molecular brush side chain group
As can be seen from Table 2, by changing the mole percent ratio of the grafting rate of side chain, different-grain diameter size can be prepared
Acid sensitive heavy metal chelating agent.
Example IV
It is a kind of acid sensitive 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, 900 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 800；
Take 100 parts of PGMA(DP=800), 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 two kinds of side chains of step 2
The synthesis of acid sensitive polymer side chain C: take 1 part bromo acid propynyl ester initiator, the 150 of 300 parts parts
N,N-dimethylaminoethyl methacrylate (DMAEMA), 100 parts of methanol, 2 parts CuCl and 2 part of 2,2- bipyridyl,
The lower 50 DEG C of progress ATRP of nitrogen protection react 3 hours, and it is high to obtain the PDMAEMA-C ≡ CH that the degree of polymerization (DP) is 180 i.e. acid sensitive
Molecular side chain C；
The synthesis of more sulphur 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, 100 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 4 hours under nitrogen protection, obtain the PMDOTEMA-C ≡ CH that the degree of polymerization (DP) is 70
I.e. more sulphur polymer side chain B；
The synthesis of step 3 acid sensitive polymer molecule brush PGMA-g- (PMDOTEMA-r-PDMAEMA)
Take 10 parts of P (GMA-N3), 60 parts of PDMAEMA-C ≡ CH and 20 parts of PMDOTEMA-C ≡ CH be dissolved in 500 parts
Dimethylformamide (DMF), add 3 parts of CuSO4And 10 parts of sodium ascorbates, it reacts 50 hours at 30 DEG C, obtains acid
Quick type polymer molecule brush PGMA-g- (PMDOTEMA-r-PDMAEMA), the grafting rate difference of PDMAEMA and PMDOTEMA side chain
For 60% and 20%.
Nanometer acid sensitive heavy metal chelating agent is obtained using solution self-assembly method, preparation method are as follows: acid-sensitive by 10 parts
Type polymer molecule brush is dissolved in 30 parts of water, using 0.1 mol/L salt acid for adjusting pH value to 3.0,30oStirring 9 is small under C
When, a nanometer acid sensitive heavy metal chelating agent micellar solution is obtained, partial size is 30 nm.
It takes the present embodiment product to do the test of lead ion removal efficiency, takes 500 mL containing Pb2+Ion 4 mg/L and EDTA 0.10
The waste water of g/L adjusts pH value of waste water to 4.0 using 0.1 mol/L hydrochloric acid, adds 0.2 mL of the present embodiment product, stir 5 points
Clock adjusts pH value of waste water to 8.0 using 0.1 mol/L sodium hydroxide, generates precipitating at once, and filtering is surveyed using atomic absorption method
Determine filtrate Pb2+Ion concentration is 0.005 mg/L, removal efficiency 99.88%.
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 acid sensitive heavy metal chelating agent, it is characterised in that include the following steps:
Step 1
It is in 3~5 water by the pH value that 5~10 parts of acid sensitive polymer molecule brush is dissolved in 10~50 parts, they are mass parts
Number；
Step 2
20oC~30oIt is stirred 1~10 hour under C, obtains a nanometer acid sensitive heavy metal chelating agent micellar solution, the nanometer
The partial size of acid sensitive heavy metal chelating agent micellar solution is 1~150 nm；
The general formula of the acid sensitive polymer molecule brush: A-g- (B-r-C), wherein g represents grafting, and r represents random distribution, A generation
Table main polymer chain, B represent more sulphur polymer side chains, and C represents acid sensitive polymer side chain, and side chain B and C are randomly grafted on master
On 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 gathers
One of methacrylic acid 4- thiopurine methyltransferase -3,6- dithia -1- spicy thioalcohol (PMDOTEMA)；
The polymer of the acid sensitive polymer side chain C is polymethylacrylic acid N, N- dimethylamino ethyl ester (PDMAEMA).
2. the preparation method of acid sensitive heavy metal chelating agent according to claim 1, it is characterised in that the polymerization owner
The degree of polymerization of chain A is 500~1000, the degree of polymerization of more sulphur polymer side chain B and acid sensitive polymer side chain C is 40~
The grafting rate of 200, more sulphur polymer side chain B and acid sensitive polymer side chain C are 10~100%.
3. the preparation method of acid sensitive heavy metal chelating agent according to claim 1, it is characterised in that the acid sensitive is poly-
The step of adduct molecule brush synthesizes 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 and acid sensitive polymer side chain C
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；
Acid sensitive polymer side chain C is synthesized, PDMAEMA polymer of the end containing alkynyl is synthesized by controllable living polymerization；
The synthesis of step 3 final products
By obtained more sulphur polymer side chains in the main polymer chain A with azide functionalities obtained in step 1 and step 2
B and acid sensitive polymer side chain C mixing makes each Elementary Function group and more sulphur polymer side chain B and acid of main polymer chain A
Quick type polymer side chain C is chemically reacted, and is carried out the reaction of a step " nitrine-alkynyl " click chemistry in the presence of a catalyst, is obtained
To final products, that is, acid sensitive polymer molecule brush.
4. the preparation method of acid sensitive heavy metal chelating agent according to claim 3, it is characterised in that described in step 1
Main polymer chain A, which can be used, makees controllable free radical polymerization process synthesis, and carries out Azide and be modified, and the main polymer chain A is P
(GMA-N3)；The C of acid sensitive polymer side chain described in step 2 is PDMAEMA-C ≡ CH；Polysulphide polymer described in step 2
Side chain B is PDNTEMA-C ≡ CH, PMDOTEMA-C ≡ CH；Catalyst described in step 3 includes copper sulphate and ascorbic acid, than
Example is 1:5.
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