CN106496575A - The preparation method of acid-sensitive type heavy metal chelating agent - Google Patents
The preparation method of acid-sensitive type heavy metal chelating agent Download PDFInfo
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- 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
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The present invention relates to a kind of preparation method of acid-sensitive type heavy metal chelating agent, feature is to be the step of including：It is in 3～5 water by the pH value that 5～10 parts of acid-sensitive type polymer molecule brush is dissolved in 10～50 parts；20oC～30oStir 1～10 hour under C, obtain the acid-sensitive type heavy metal chelating agent micellar solution of nanometer；Acid-sensitive type heavy metal chelating agent is that acid-sensitive type polymer molecule brush is assembled in the aqueous solution, obtains nanosized micelles, can be used for the heavy metal ion for catching extremely low concentration.The effluent containing heavy metal ions hardly possible effective process problem of extremely low concentration is which solved, pH value is further adjusted, is improved the hydrophobicity of the aggregation of micro-nano structure, so as to precipitate and separate effectively from water body out.The aggregation good stability of generation, is not easily decomposed, is not likely to produce secondary pollution.
Description
Technical field
The invention belongs to water technology and polymer-function material field, and in particular to a kind of acid-sensitive type heavy metal chelating
The preparation method of agent.
Background technology
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 catches, separates and precipitation of heavy metals.At present, more heavy metal chelating agent is applied mainly to have dithiocarbamate salt
Analog derivative（DTC classes）, trithiocyanuric acid（TMT）, small molecule polysulfide etc..DTC analog derivatives are used as a first generation huge sum of money
Category agent for capturing product, is most widely used product, but there is the defect of the easy stability of factorization difference of the sediment of generation, so as to
Cause secondary pollution problem.Trithiocyanuric acid（TMT）As second generation heavy metal chelating agent product, also it is widely used in Industry Waste
Water process, trithiocyanuric acid is containing the precipitable most heavy metal ion of three thin bases, but there is precipitation not exclusively, and removal efficiency is low
Problem.Small molecule polysulfide can provide multiple sulfur-bearing coordination sites, so as to realize efficient process industrial wastewater, be heavy at present
One of emphasis direction of metal agent for capturing research and development.Small molecule polysulfide subject matter is that the precipitation particle for generating is less,
Usually nanoscale is precipitated, it is more difficult to effectively out, only add substantial amounts of high polymer coagulant from industrial wastewater precipitation and separation
Can effectively sedimentation separation.
At present, heavy metal chelating agent research and development Main way is around raising removal effect, separative efficiency, reduces medicine consumption, subtracts
Of low pollution and enhancing environmental consciousness.The heavy metal chelating that the market mainstream is used does not catch sedimentation energy substantially to low-concentration heavy metal
Power（Heavy metal concentration heavy metal ion<5mg/L）.Therefore, most of heavy metal chelating agents seizure performances are unable to reach plating and give up
3 discharging standards of water meter.Realize that low-concentration heavy metal agent for capturing catches and the main method of settling property is by effective
Molecular Design with synthesis realizing.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art and provide a kind of preparation side of acid-sensitive type heavy metal chelating agent
Method, the side chain polymethylacrylic acid N of acid-sensitive type polymer molecule brush, N- dimethylamino ethyl esters in acid condition, with very
Good water soluble characteristic, acid-sensitive type polymer molecule brush is constructed a nanometer heavy metal chelating agent micella and can be disperseed in aqueous, acid-sensitive
Type polymer molecule brush sulfur-containing group is more, can quickly catch the aggregation that heavy metal ion generates micro-nano structure, when pH is from acidity
When becoming alkalescence, the aggregation of micro-nano structure becomes hydrophobicity completely, rapid subsidence occurs, can reach separating low concentration heavy metal
The purpose of ion.
In order to achieve the above object, the technical scheme is that and be achieved in that, which is that a kind of acid-sensitive type heavy metal is caught
Catch agent, it is characterised in that comprise the steps：
Step one
It is in 3～5 water by the pH value that 5～10 parts of acid-sensitive type polymer molecule brush is dissolved in 10～50 parts；
Step 2
20oC～30oStir 1～10 hour under C, obtain the acid-sensitive type heavy metal chelating agent micellar solution of nanometer；
Mass fraction is more than.
In the technical program, the particle diameter of the acid-sensitive type heavy metal chelating agent micellar solution of described nanometer is 1～150 nm.
In the technical program, the formula of the acid-sensitive type polymer molecule brush：A-g- (B-r-C), wherein, g is represented and is connect
Branch, r represent random distribution, A representation polymer main chains, and B represents many sulphur polymer side chains, and C represents acid-sensitive type 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 many sulphur polymer side chain B is polymethylacrylic acid 3,7- dithia -1- nonyl mercaptan（PDNTEMA）Or it is poly-
One kind in methacrylic acid 4- thiopurine methyltransferases -3,6- dithias -1- spicy thioalcohols (PMDOTEMA)；
The polymer of the acid-sensitive type polymer side chain C is polymethylacrylic acid N, N- dimethylamino ethyl esters (PDMAEMA).
In the technical program, the degree of polymerization of the main polymer chain A is 500～1000, many sulphur polymer side chain B
And the degree of polymerization of acid-sensitive type polymer side chain C is 40～200, many sulphur polymer side chain B and acid-sensitive type polymer side chain C connect
Branch rate is 10～100%.
In the technical program, as follows the step of the acid-sensitive type polymer molecule brush synthesizes：
Step one synthetic polymer main chain A
PGMA main polymer chains are synthesized by controllable living polymerization, then each epoxy radicals units of PGMA main polymer chains is entered
Row azide functionalization, obtains P（GMA-N3）Main polymer chain；
Step 2 synthesizes many sulphur polymer side chain B and acid-sensitive type polymer side chain C
Synthesize many sulphur polymer side chain B, first synthesize many sulphur monomers, then carry out controllable living polymerization, synthesize end function containing alkynyl
The polysulphide polymer of group, many sulphur monomers are mainly by GMA and 3,7- dithia -1, two sulphur of 9- nonyls
There is " epoxy radicals sulfydryl " point under lithium hydroxide catalytic action in alcohol or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8-
Hit chemical reaction and synthesize, ingredient proportion is controlled 1：2～5, it is ensured that the epoxide group of GMA and 3,
One sulfydryl of two mercaptan of 7- dithia -1,9- nonyls or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- reacts；Institute
GMA is stated containing 1 epoxide group, 3,7- dithia -1, two mercaptan of 9- nonyls contain two sulfydryls, institute
Pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- is stated containing three sulfydryls；
Synthesize acid-sensitive type polymer side chain C, PDMAEMA polymer of the end containing alkynyl is synthesized by controllable living polymerization；
Step 3 final products synthesize
By the obtained main polymer chain A with azide functionalities in step one and obtained many sulphur polymer side chains in step 2
B and acid-sensitive type polymer side chain C mixing, makes each Elementary Function group and many sulphur polymer side chain B and the acid of main polymer chain A
There is chemical reaction in quick type polymer side chain C, carry out the reaction of a step " nitrine-alkynyl " click chemistry in the presence of a catalyst, obtain
It is acid-sensitive type polymer molecule brush to final products.
In the technical program, main polymer chain A described in step one can be synthesized using controllable free radical polymerization process is made,
And Azide modification is carried out, the main polymer chain A is P (GMA-N3)；Described in step 2, acid-sensitive type polymer side chain C 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, and ratio is 1：5.
The present invention compared with prior art, has the following advantages and effect：
1st, the present invention has synthesized a kind of acid-sensitive type polymer molecule brush, changes the acid-sensitive type heavy metal chelating of nanometer by adjusting pH value
The hydrophilic and hydrophobic of agent micella, so as to realizing catching and settling dual-use function.Acid-sensitive type heavy metal chelating agent is to low-concentration heavy metal
Ion has extremely strong seizure and sedimentation capacity；
2nd, acid-sensitive type heavy metal chelating agent has high removal efficiency, removal efficiency to be more than 99.8% to solvay-type heavy metal wastewater thereby；
3rd, the aggregation good stability for generating, is not easily decomposed, is not likely to produce secondary pollution.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
In following examples, involved number is mass fraction.
Embodiment one
Which is a kind of acid-sensitive type polymer molecule brush, is prepared by following steps：
Step one P (GMA-N3) main polymer chain A synthesis
Take 1 part 2- isobutyl ethyl bromide initiators, 600 parts of GMA（GMA）, 1000 part hexichol
Ether, CuBr and 5 part of 5 parts of N, N, N', N', N "-pentamethyl-diethylenetriamine（PMDETA）, 30 DEG C are carried out under nitrogen protection
ATRP reacts 7 hours, obtains the degree of polymerization（DP）For 500 poly (glycidyl methacrylate)（PGMA）；
Take 100 parts of PGMA（DP=500）, 200 parts of NaN3And 300 parts of dimethylformamide（DMF）, 50 are reacted at 60 DEG C
Hour, obtain P (GMA-N3), as main polymer chain A；
The synthesis of two kinds of side chains of step 2
The synthesis of acid-sensitive type polymer side chain C：Take 1 part bromo acid propynyl ester initiator, 150 parts of methacrylic acid N,
N- dimethylamino ethyl esters（DMAEMA）, 100 parts methyl alcohol, 2 parts CuCl and 2 part of 2,2- bipyridyls, under nitrogen protection 50
DEG C carry out ATRP to react 6 hours, obtain the degree of polymerization（DP）PDMAEMA-C ≡ CH for 110 are acid-sensitive type polymer side chain C；
The synthesis of many sulphur polymer side chain B：Take 100 parts GMA, 250 parts of 3,7- dithia -1,
Two mercaptan of 9- nonyls, the dichloromethane of 3 parts of lithium hydroxide and 400 parts, normal-temperature reaction 36 hours obtain methacrylic acid 3, bis- sulphur of 7-
Miscellaneous -1- nonyls mercaptan（DNTEMA）；
Take 1 part bromo acid propynyl ester initiator, 200 parts of methacrylic acid 3,7- dithia -1- nonyl mercaptan
（DNTEMA）, 200 parts toluene, 2 parts CuBr and 2 part of N, N, N', N', N "-pentamethyl-diethylenetriamine（PMDETA）, in nitrogen
Lower 60 DEG C of gas shielded carries out ATRP reactions 8 hours, obtains the degree of polymerization（DP）PDNTEMA-C ≡ CH for 140 are many sulphur macromolecules
Side chain B；
The synthesis of the acid-sensitive type polymer molecule brush PGMA-g- (PDNTEMA-r-PDMAEMA) of step 3
Take 10 parts of P (GMA-N3), the PDNTEMA-C ≡ CH of 40 parts of PDMAEMA-C ≡ CH and 20 parts be dissolved in 500 parts of diformazan
Base formamide（DMF）, add 2 parts of CuSO4And 10 parts of sodium ascorbates, react 50 hours at 30 DEG C, obtain acid-sensitive type and gather
Adduct molecule brush PGMA-g- (PDNTEMA-r-PDMAEMA), the percent grafting of PDMAEMA and PDNTEMA side chains are respectively 40% He
20%.
The acid-sensitive type heavy metal chelating agent of nanometer is obtained using solution self-assembly method, and its preparation method is：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 4.0,25oUnder C, stirring 5 is little
When, the acid-sensitive type heavy metal chelating agent micellar solution of nanometer is obtained, particle diameter is 50 nm.
Take the present embodiment product and do the test of lead ion removal efficiency, 500 mL are taken 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, stirs 5 points
Clock, is adjusted pH value of waste water to 8.0 using 0.1 mol/L NaOH, produces precipitation at once, filter, surveyed using atomic absorption method
Determine filtrate Pb2+Ion concentration is 0.01 mg/L, and removal efficiency is 99.75%.
Embodiment two
Preparation method and raw material are constituted with embodiment one, the only acid-sensitive type polymer molecule brush PGMA-g- to embodiment one
(PDNTEMA-r-PDMAEMA) main polymer chain A and the degree of polymerization of many sulphur polymer side chain B is adjusted, and can be obtained not
Acid-sensitive type heavy metal chelating agent with particle size.The degree of polymerization of main polymer chain A and many sulphur polymer side chain B, acid-sensitive type weight
Metal agent for capturing 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 many sulphur polymer side chain B is
50th, 100,150, the 200 and acid-sensitive type polymer side chain C degree of polymerization is 110.Can be former by controlling according to the method for embodiment one
Material or polymerization reaction time and prepare.In every kind of acid-sensitive type polymer molecule brush PGMA-g- (PDNTEMA-r-PDMAEMA)
PDMAEMA and PDNTEMA side chains percent grafting be respectively 40% and 20%.
Table 1：The impact of molecular brush main chain and the side chain degree of polymerization to acid-sensitive type heavy metal chelating agent particle diameter
As can be seen from Table 1, by the degree of polymerization of regulation main polymer chain A and many sulphur polymer side chain B, different-grain diameter can be prepared
The acid-sensitive type heavy metal chelating agent of size.
Embodiment three
Preparation method and raw material composition only change the side chain of the acid-sensitive type polymer molecule brush of embodiment one with embodiment one
Percent grafting is each side chain Relative mole percentage ratio, and the acid-sensitive type heavy metal chelating agent of different-grain diameter size can be obtained.Particle diameter
Change size is shown in Table 2.
Table 2：The impact of molecular brush side chain group acid-sensitive type heavy metal chelating agent particle diameter in pairs
As can be seen from Table 2, by the mole percent ratio of the percent grafting of change side chain, the acid-sensitive of different-grain diameter size can be prepared
Type heavy metal chelating agent.
Example IV
Which is a kind of acid-sensitive type polymer molecule brush, is prepared by following steps：
Step one P (GMA-N3) main polymer chain A synthesis
Take 1 part 2- isobutyl ethyl bromide initiators, 900 parts of GMA（GMA）, 1000 part hexichol
Ether, CuBr and 5 part of 5 parts of N, N, N', N', N "-pentamethyl-diethylenetriamine（PMDETA）, 30 DEG C are carried out under nitrogen protection
ATRP reacts 5 hours, obtains the degree of polymerization（DP）For 800 poly (glycidyl methacrylate)（PGMA）；
Take 100 parts of PGMA（DP=800）, 200 parts of NaN3And 300 parts of dimethylformamide（DMF）, 50 are reacted at 60 DEG C
Hour, obtain P (GMA-N3), as main polymer chain A；
The synthesis of two kinds of side chains of step 2
The synthesis of acid-sensitive type polymer side chain C：Take 1 part bromo acid propynyl ester initiator, 150 parts of 300 parts of methyl
Acrylic acid N, N- dimethylamino ethyl ester（DMAEMA）, 100 parts methyl alcohol, 2 parts CuCl and 2 part of 2,2- bipyridyls, in nitrogen
Protect lower 50 DEG C to carry out ATRP to react 3 hours, obtain the degree of polymerization（DP）PDMAEMA-C ≡ CH for 180 are acid-sensitive type macromolecule
Side chain C；
The synthesis of many sulphur polymer side chain B：Take 100 parts GMA, 400 parts of 4- thiopurine methyltransferase -3,6-
Dithia -1, pungent two mercaptan of 8-, the dichloromethane of 3 parts of lithium hydroxide and 400 parts, normal-temperature reaction 36 hours obtain metering system
Sour 4- thiopurine methyltransferases -3,6- dithias -1- spicy thioalcohols (MDOTEMA)；
Take 1 part bromo acid propynyl ester initiator, 100 parts of the pungent sulphur of methacrylic acid 4- thiopurine methyltransferase -3,6- dithia -1-
Alcohol (MDOTEMA), 200 parts of toluene, 2 parts CuBr and 2 part of N, N, N', N', N "-pentamethyl-diethylenetriamine（PMDETA）,
60 DEG C carry out ATRP reactions 4 hours under nitrogen protection, obtain the degree of polymerization（DP）PMDOTEMA-C ≡ CH for 70 are that many sulphur are high
Molecular side chain B；
The synthesis of the acid-sensitive type polymer molecule brush PGMA-g- (PMDOTEMA-r-PDMAEMA) of step 3
Take 10 parts of P (GMA-N3), the PMDOTEMA-C ≡ CH of 60 parts of PDMAEMA-C ≡ CH and 20 parts be dissolved in 500 parts two
NMF（DMF）, add 3 parts of CuSO4And 10 parts of sodium ascorbates, react 50 hours at 30 DEG C, obtain acid-sensitive type
Polymer molecule brush PGMA-g- (PMDOTEMA-r-PDMAEMA), the percent grafting of PDMAEMA and PMDOTEMA side chains are respectively
60% and 20%.
The acid-sensitive type heavy metal chelating agent of nanometer is obtained using solution self-assembly method, and its preparation method is：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 3.0,30oUnder C, stirring 9 is little
When, the acid-sensitive type heavy metal chelating agent micellar solution of nanometer is obtained, particle diameter is 30 nm.
Take the present embodiment product and do the test of lead ion removal efficiency, 500 mL are taken 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, stirs 5 points
Clock, is adjusted pH value of waste water to 8.0 using 0.1 mol/L NaOH, produces precipitation at once, filter, surveyed using atomic absorption method
Determine filtrate Pb2+Ion concentration is 0.005 mg/L, and removal efficiency is 99.88%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement that is made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of acid-sensitive type heavy metal chelating agent, it is characterised in that comprise the steps：
Step one
It is in 3～5 water by the pH value that 5～10 parts of acid-sensitive type polymer molecule brush is dissolved in 10～50 parts；
Step 2
20oC～30oStir 1～10 hour under C, obtain the acid-sensitive type heavy metal chelating agent micellar solution of nanometer；
Mass fraction is more than.
2. the preparation method of acid-sensitive type heavy metal chelating agent according to claim 1, it is characterised in that described nm acid
The particle diameter of quick type heavy metal chelating agent micellar solution is 1～150 nm.
3. the preparation method of a kind of acid-sensitive type heavy metal chelating agent according to claim 1, it is characterised in that described acid-sensitive
The formula of type polymer molecule brush：A-g- (B-r-C), wherein, g represents grafting, and r represents random distribution, A representation polymer masters
Chain, B represent many sulphur polymer side chains, and C represents acid-sensitive type polymer side chain, and 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 many sulphur polymer side chain B is polymethylacrylic acid 3,7- dithia -1- nonyl mercaptan（PDNTEMA）Or it is poly-
One kind in methacrylic acid 4- thiopurine methyltransferases -3,6- dithias -1- spicy thioalcohols (PMDOTEMA)；
The polymer of the acid-sensitive type polymer side chain C is polymethylacrylic acid N, N- dimethylamino ethyl esters (PDMAEMA).
4. the preparation method of acid-sensitive type heavy metal chelating agent according to claim 3, it is characterised in that the polymerization owner
The degree of polymerization of chain A is 500～1000, the degree of polymerization of many sulphur polymer side chain B and acid-sensitive type polymer side chain C is 40～
The percent grafting of 200, many sulphur polymer side chain B and acid-sensitive type polymer side chain C is 10～100%.
5. the preparation method of acid-sensitive type heavy metal chelating agent according to claim 3, it is characterised in that the acid-sensitive type gathers
The step of adduct molecule brush synthesizes is as follows：
Step one synthetic polymer main chain A
PGMA main polymer chains are synthesized by controllable living polymerization, then each epoxy radicals units of PGMA main polymer chains is entered
Row azide functionalization, obtains P（GMA-N3）Main polymer chain；
Step 2 synthesizes many sulphur polymer side chain B and acid-sensitive type polymer side chain C
Synthesize many sulphur polymer side chain B, first synthesize many sulphur monomers, then carry out controllable living polymerization, synthesize end function containing alkynyl
The polysulphide polymer of group, many sulphur monomers are mainly by GMA and 3,7- dithia -1, two sulphur of 9- nonyls
There is " epoxy radicals sulfydryl " point under lithium hydroxide catalytic action in alcohol or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8-
Hit chemical reaction and synthesize, ingredient proportion is controlled 1：2～5, it is ensured that the epoxide group of GMA and 3,
One sulfydryl of two mercaptan of 7- dithia -1,9- nonyls or pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- reacts；Institute
GMA is stated containing 1 epoxide group, 3,7- dithia -1, two mercaptan of 9- nonyls contain two sulfydryls, institute
Pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- is stated containing three sulfydryls；
Synthesize acid-sensitive type polymer side chain C, PDMAEMA polymer of the end containing alkynyl is synthesized by controllable living polymerization；
Step 3 final products synthesize
By the obtained main polymer chain A with azide functionalities in step one and obtained many sulphur polymer side chains in step 2
B and acid-sensitive type polymer side chain C mixing, makes each Elementary Function group and many sulphur polymer side chain B and the acid of main polymer chain A
There is chemical reaction in quick type polymer side chain C, carry out the reaction of a step " nitrine-alkynyl " click chemistry in the presence of a catalyst, obtain
It is acid-sensitive type polymer molecule brush to final products.
6. the preparation method of acid-sensitive type polymer molecule brush according to claim 5, it is characterised in that described in step one
Main polymer chain A can be synthesized using controllable free radical polymerization process is made, and carry out Azide modification, and the main polymer chain A is P
(GMA-N3)；Acid-sensitive type polymer side chain C 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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| 常忆凌，等: "《药剂学》", 31 July 2005, 中国地质大学出版社 * |
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