CN106111086B - A kind of absorption Pd2+Ionic polymeric sorbent of metal ion and preparation method thereof - Google Patents
A kind of absorption Pd2+Ionic polymeric sorbent of metal ion and preparation method thereof Download PDFInfo
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- CN106111086B CN106111086B CN201610457063.9A CN201610457063A CN106111086B CN 106111086 B CN106111086 B CN 106111086B CN 201610457063 A CN201610457063 A CN 201610457063A CN 106111086 B CN106111086 B CN 106111086B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
A kind of absorption Pd2+Ionic polymeric sorbent of metal ion and preparation method thereof, belongs to environmental protection and materials science field.The invention discloses a kind of ionic polymeric sorbent, monomer composition is divinylbenzene and unsaturated guanidine ionic liquid, and ionic liquid anion is selected from bromide ion, tetrafluoro boric acid ion, hexafluorophosphate ion and acetate ion；Preparation method is that ionic polymeric sorbent is made by free-radical polymerized, then by anion exchange by divinylbenzene and unsaturated guanidine ionic liquid monomer.The adsorbent can be used for Pd2+The quick adsorption separation of metal ion, has many advantages, such as that adsorption rate is fast, saturated extent of adsorption is high, absorption property is stable and separation is simple.
Description
Technical field
The present invention relates to a kind of absorption Pd2+The ionic polymeric sorbent of metal ion, belongs to environmental protection and material
Scientific domain.
Background technology
Palladium (Pd2+) metal ion is a kind of important noble metal catalyst, in a variety of Minute Organic Synthesis reaction
Show excellent catalytic performance, especially drug synthetic reaction.However, Pd2+The organic synthesis of catalysis is often led to
Homogeneous catalysis system, Pd2+Catalyst is difficult to recycle and reuse, and separation and the purification difficult of product.Therefore homogeneous Pd2 +The separation and recovery of catalyst causes the extensive concern of people.The method of separating metal ions mainly has the precipitation method, ion at present
Exchange and absorption method.The precipitation method it is less efficient, and other impurity will be introduced while precipitate metal ion；Ion exchange
The selectivity of method is poor and exchange capacity is relatively low；Sorbing material used in absorption method is usually cheap and easy to get, does not need to complex appts
The features such as with addition additional chemical substance.Therefore, absorption method become current most common contaminant metal ions processing method it
One, and the research and development of wherein sorbing material are key technologies.Seek it is various with special or excellent properties such as with special choosing
Selecting property, the adsorbent that of low cost, preparation is simple and adsorption efficiency is high are one of most noticeable research heat in the field.
Ionic liquid is the hot research pair of current Green Chemistry as a kind of green reaction medium and " soft " functional material
As.Various ionic macromolecules can be made by autohemagglutination or copolymerization in unsaturated ionic liquid monomer.Ionic macromolecule is not only
Remain the performances such as dissolving, absorption, separation, the catalysis of ionic liquid, and the structure-controllable with high molecular material, stability
The advantages that good, easily separated, thus as the hot research direction of material science and technical field.However, current ionic high score
The application of son also focuses primarily upon catalyticing research field, this significantly limits being widely used for polymeric ionic liquid.To fill
Distribution shoots the high molecular advantage of ionic, needs to expand more application ranges.
Guanidine ionic liquid and divinylbenzene copolymerization are made ionic macromolecule using radical polymerization and inhaled by the present invention
Attached dose, preparation process is simple, and raw material is cheap and easy to get, can directly be soaked in containing Pd2+Pd is adsorbed in the solution of metal ion2+, tool
Have the advantages that adsorption rate is fast, saturated extent of adsorption is high, absorption property is stablized.The method is not yet reported.
Invention content
For existing Pd2+Separation of metal ions and recycling there are the problem of, the present invention provide a kind of preparation process it is simple,
Good adsorption performance, cheap, environmental-friendly, ionic polymeric sorbent easy to use.
Ionic polymeric sorbent of the present invention preparation through the following steps that complete：
A. tetramethylguanidine and 3- bromopropene ethanol solutions are mixed according to stoichiometric, at 50~120 DEG C
It is stirred to react 1~3 day, then removed under reduced pressure solvent, it is washed and be dried to obtain guanidine ionic liquid presoma；
B. it is 1 according to molar ratio by the guanidine ionic liquid presoma of above-mentioned synthesis and divinylbenzene:2~4:1 ratio
It is added in 100mL organic solvents, adds a certain amount of initiator azodiisobutyronitrile, mass fraction is guanidine ionic liquid
The 0.5%~3% of presoma and divinylbenzene gross mass stirs 1~2 day at 50~100 DEG C, filtered, washing and drying
Obtain ionic macromolecule presoma；
C. the ionic macromolecule presoma of above-mentioned synthesis and anion presoma are added to according to stoichiometric
In a certain amount of deionized water, it is stirred at room temperature 1~2 day, it is filtered, wash and be dried to obtain ionic polymeric sorbent.
The preparation method of above-mentioned ionic polymeric sorbent, it is characterised in that organic solvent described in step B for ethyl alcohol,
One kind in methanol, toluene, acetonitrile, dichloromethane, ethyl acetate；Anion presoma described in step C derives from：Tetrafluoro boron
Sour sodium, sodium hexafluoro phosphate and acetic acid；Ionic polymeric sorbent is to Pd2+Metal ion has high adsorption capacity, can
For Pd in solution2+The quick adsorption of metal ion is with detaching.
Advantages of the present invention and effect：
1st, ionic polymeric sorbent preparation process of the invention is simple, and reaction condition is mild.
2nd, ionic polymeric sorbent produced by the present invention is to Pd2+Metal ion is strong with adsorption capacity, adsorption rate
Soon, the advantages that saturated extent of adsorption is high.
3rd, it is easy to operate when ionic polymeric sorbent produced by the present invention uses, it can be by centrifuging or filtering simple point
From.
Description of the drawings
The structure diagram of ionic polymeric sorbent prepared by Fig. 1 present invention.
Scanning electron microscope (SEM) figure of ionic polymeric sorbent prepared by Fig. 2 present invention.
Specific embodiment
The present invention is further illustrated below by specific embodiment, but does not limit the present invention.
【Embodiment 1】
A. tetramethylguanidine and 3- bromopropene ethanol solutions according to stoichiometric are mixed, is stirred at 80 DEG C anti-
Should for 24 hours, then removed under reduced pressure solvent is washed and be dried to obtain guanidine ionic liquid presoma；
B. it is 1 according to molar ratio by the guanidine ionic liquid presoma of above-mentioned synthesis and divinylbenzene:1 ratio is added to
In 100mL ethyl alcohol, a certain amount of initiator azodiisobutyronitrile is added, mass fraction is guanidine ionic liquid presoma and two
The 1% of vinyl benzene gross mass, it is in 80 DEG C of stirrings for 24 hours, filtered, wash and be dried to obtain ionic macromolecule presoma；
C. by the ionic macromolecule presoma of above-mentioned synthesis and anion presoma sodium hexafluoro phosphate according to stoichiometry
Proportioning is added in a certain amount of deionized water, is stirred at room temperature 48h, filtered, wash and be dried to obtain hexafluorophosphate ion type
Polymeric sorbent.
The high molecular structure diagram of ionic is shown in Fig. 1, the scanning electron microscope of hexafluorophosphate ion type polymeric sorbent
(SEM) figure is shown in Fig. 2.
【Embodiment 2】
Operating method only changes anion presoma sodium hexafluoro phosphate in step C into sodium tetrafluoroborate with embodiment 1,
Obtain tetrafluoro boric acid ionic polymeric sorbent.
【Embodiment 3】
Operating method only changes anion presoma sodium hexafluoro phosphate in step C into acetic acid, obtains vinegar with embodiment 1
Acid ion type polymeric sorbent.
Application Example 1
Configuration contains Pd2+The chloroformic solution 100mL, Pd of ion2+Ion concentration is 100mg/L, with hexafluorophosphate ion type
Polymeric sorbent (0.02g) filters out adsorbent, Pd in solution after absorption after room temperature shakes absorption 10min2+Ion it is dense
It spends for 0.03mg/L, adsorption rate 99.94%.
Claims (5)
1. a kind of absorption Pd2+The ionic polymeric sorbent of metal ion, it is characterised in that there is below formula：
Wherein：X represents ionic liquid anion, selected from tetrafluoro boric acid ion, hexafluorophosphate ion, acetate ion；n:M's rubs
You are than being 1:2~4:1.
2. a kind of absorption Pd2+The preparation method of the ionic polymeric sorbent of metal ion, it is characterised in that include following step
Suddenly：
A. tetramethylguanidine and 3- bromopropene ethanol solutions according to stoichiometric are mixed, is stirred at 50~120 DEG C
Reaction 1~3 day, then removed under reduced pressure solvent are washed and be dried to obtain guanidine ionic liquid presoma；
B. it is 1 according to molar ratio by the guanidine ionic liquid presoma of above-mentioned synthesis and divinylbenzene:2~4:1 ratio adds in
Into 100mL organic solvents, a certain amount of initiator azodiisobutyronitrile is added, mass fraction is guanidine ionic liquid forerunner
The 0.5%~3% of body and divinylbenzene gross mass stirs 1~2 day at 50~100 DEG C, filtered, wash and be dried to obtain
Ionic macromolecule presoma；
C. the ionic macromolecule presoma of above-mentioned synthesis and anion presoma are added to centainly according to stoichiometric
In the deionized water of amount, it is stirred at room temperature 1~2 day, it is filtered, wash and be dried to obtain ionic polymeric sorbent.
3. preparation method according to claim 2, which is characterized in that organic solvent described in step B for ethyl alcohol, methanol,
One kind in toluene, acetonitrile, dichloromethane, ethyl acetate.
4. preparation method according to claim 2, which is characterized in that anion presoma described in step C derives from：Four
Sodium fluoborate, sodium hexafluoro phosphate and acetic acid.
5. ionic polymeric sorbent according to claim 1, it is characterised in that the adsorbent can be used for Pd in solution2+
The absorption of metal ion is with detaching.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610457063.9A CN106111086B (en) | 2016-06-22 | 2016-06-22 | A kind of absorption Pd2+Ionic polymeric sorbent of metal ion and preparation method thereof |
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| CN106111086B true CN106111086B (en) | 2018-06-08 |
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| CN106890628B (en) * | 2017-02-07 | 2019-03-01 | 江南大学 | A kind of organic polymer adsorbent and preparation method thereof for removing precious metal ion in pharmaceutical synthesis system |
| CN107141408A (en) * | 2017-06-12 | 2017-09-08 | 厦门建霖健康家居股份有限公司 | A kind of antibacterial polymer and preparation method thereof |
| CN112011120B (en) * | 2019-05-29 | 2022-04-26 | 合肥杰事杰新材料股份有限公司 | Modified resin material for purifying domestic water and preparation method thereof |
| CN110577260B (en) * | 2019-08-27 | 2021-12-24 | 昆明理工大学 | Liquid cathode and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884315A (en) * | 2006-05-19 | 2006-12-27 | 浙江大学 | Anion type polymer containing tetramethylguanidine cation and its preparation method and uses |
| CN1884323A (en) * | 2006-05-19 | 2006-12-27 | 浙江大学 | Cross-linked anion polymer containing tetramethylguanidine cation and its preparation method and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2135862A4 (en) * | 2007-03-06 | 2014-10-01 | Nippon Steel & Sumikin Chem Co | Cyclic guanidine ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1884315A (en) * | 2006-05-19 | 2006-12-27 | 浙江大学 | Anion type polymer containing tetramethylguanidine cation and its preparation method and uses |
| CN1884323A (en) * | 2006-05-19 | 2006-12-27 | 浙江大学 | Cross-linked anion polymer containing tetramethylguanidine cation and its preparation method and uses |
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