CN108164696A - A kind of polyamide detected with extracting metals ion - Google Patents
A kind of polyamide detected with extracting metals ion Download PDFInfo
- Publication number
- CN108164696A CN108164696A CN201810025457.6A CN201810025457A CN108164696A CN 108164696 A CN108164696 A CN 108164696A CN 201810025457 A CN201810025457 A CN 201810025457A CN 108164696 A CN108164696 A CN 108164696A
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- CN
- China
- Prior art keywords
- polyamide
- metal ion
- ion
- organic solvent
- aqueous solution
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
Abstract
The present invention relates to a kind of polyamide detected with extracting metals ion, belong to macromolecule parents self assembly and metal ion field of waste water treatment.Invention prepares polyamide with piperazine aqueous solution using calixarenes organic solution derived from acyl chlorides by interfacial polymerization, the polyamide is dissolved in organic solvent, metal ion can be extracted from its immiscible aqueous solution, and shape foam-like or nanofiber mats or interfacial film Supramolecular self assembly network structure between boundary, the structure has some strength, easy from liquid system can remove.It in the substance input dilute hydrochloric acid of removal and the layering mixed liquor formed with immiscible organic solvent, decomposes, metal ion is dissolved in dilute hydrochloric acid, and polyamide is incorporated in organic solvent layer, realizes the recycling of polyamide.This method can detect that the metal ion of ppm grades of content soluble in water, and realizes its extraction and remove, and be efficient repeatedly used detection fiber material.
Description
Technical field
Detected and the polyamide of extracting metals ion the present invention relates to a kind of, more particularly to soluble polyamide and metal from
The chelating of son belongs to absorption complexing field of functional materials.
Background technology
With industrial development and progress, the usage amount of rare earth and heavy metal is growing day by day, while it is in the form of an ion with water
It is inevitable that body enters environment.The water soluble ion of rare earth metal and heavy metal, which is good for environment, ecology and human body, has damage to make
With recycling not only contributes to the protection and maintenance of environment, can also improve its utilization rate.Thus exploitation has inspection to rare earth metal
It surveys and the material of extracting power, existing social value has economic interests again.Polymer substance is captured molten in water by complexing
The harmful ion of solution is macromolecule binding site to be made to form coordinate bond with metal ion by noncovalent interaction, thus will
Metal ion is removed from water.Since macromolecule binding site is more, and rare earth metal, heavy metal etc. have variable valence, same
Ion can be formed with several sites and is coordinated, thus coordination polymer is mostly supermolecule cross-linked structure, is macroscopically seen as neither
The solid matter also not melted is dissolved, thus can be removed solid by shirtsleeve operation.Both eliminated metal in water from
Son, and can be recycled by breaking coordinate bond, it reuses, is a kind of effectively economic extraction recycling method.Oversubscription
Shape, color of son complexing network etc. can be used as detection metal ion presence or absence and the basis for estimation of its type, thus
This macromolecule is a kind of efficient detection underwater gold category ion again in the presence of the detection reagent with type.
This patent carries out interfacial polymerization or lotion by the organic solution of calixarenes diacid chloride derivative with piperazine aqueous solution
Polycondensation, prepares calixarenes-piperazine derivatives polyamide, the polyamide be connect by fragrant rigid macrocyclic kind building block and the small loop chain of fat and
Into, have a variety of strong contrast factors alternating structure.Abundant self assembly and stimulation-response property are shown in the solution.
The polyamide hydrogen bond donor, metal ion etc. be single or inductions of multiple factors under can form various nanometers, micron and macroscopic view
Supramolecular structure presents the recognition detection of metal ion and the potentiality of extraction recycling.
Invention content
The purpose of the present invention is overcoming the shortcomings of in existing detection and discriminating rare earth ion method, a kind of inspection has been invented
Survey the polyamide with extracting metals ion.Technical scheme of the present invention is summarized as follows：
A kind of polyamide detected with extracting metals ion, it is characterized in that the derivative of calixarenes diacid chloride is dissolved in organic
It is reacted in solvent A with piperazine aqueous solution, in the case where stirring and not stirring, generates interfacial polymerization resultant polyamides；The polyamide
Be dissolved in in the immiscible organic solvent B of water, being placed on the aqueous solution containing metal ion, at boundary formed foam or
The visible complex compound such as nanofiber mats or interfacial film, shows the presence of metal ion；It is molten in complex compound removal water by collecting
The metal ion of solution.
One or more of mixing of the calixarenes diacid chloride derivative for following structural formula：
Mixing of the organic solvent A for one or more of n-hexane, normal heptane, hexamethylene, petroleum ether, kerosene or diesel oil
Object.
Organic solvent B is one kind in n-hexane, hexamethylene, ether, ethyl acetate, toluene, dimethylbenzene, kerosene or diesel oil
Or several mixture.
Metal ion includes rare earth ion La3+(lanthanum), Ce3+(cerium), Pr3+(praseodymium), Nd3+(neodymium), Pm3+(promethium), Sm2+
(samarium), Eu2+(europium) or Hg2+(mercury), Cd2+(cadmium), Pb2+(lead), Zn2+(zinc), Cu2+The inorganic salt solution of (copper) ion.
Foam-like or the complexing such as nanofiber mats or interfacial film analyte detection are generated between organic phase and water phase, removes metal
Ion is conducive to effectively extract the harmful metal ion in water phase, can avoid introducing water body band by small molecule or soluble reagents
The secondary pollution come, this method are convenient and efficient.After foam, fibrofelt or interface membrane substance slave phase interface are taken out, add in dilute hydrochloric acid and
It with the immiscible pure organic solvent layered system of water, can dissolve, metal ion is dissolved in hydrochloric acid phase, and polyamide returns to organic phase continuation
Recycling uses.
Description of the drawings
Fig. 1 is the ethyl acetate solution of polyamide described in embodiment 3 and Ce (NO3)3The nanofiber formed at boundary
Felt, Fig. 2 are the cyclohexane solution of the polyamide described in embodiment 4 and Pb (NO3)2The foam-like material formed at boundary, figure
3 be the hexane solution of the polyamide described in embodiment 5 and La (NO3)3The foam-like material formed at boundary, Fig. 4 are
The hexane solution of polyamide described in embodiment 6 and Cu (NO3)2The foam-like material formed at boundary.
Embodiment
The synthesis of polyamide
Embodiment 1
To 20mL 50g/L (w/v) to being added dropwise in tertiary butyl p tertButylcalixarene -1,3 diethyl acyl chlorides (A) hexane solution
200mL 30g/L piperazine aqueous solutions stand 3 minutes, collect interfacial product, filtering, deionized water is washed, poly-ly to uncle dry
Butyl cup [4] aromatic hydrocarbons -1,3 diacetyl piperazine (1), quality 0.037g, yield 37%.
Embodiment 2
20mL is being dissolved in just to tert-butyl-calix [6] aromatic hydrocarbons -1,3- diethyl acyl chlorides (B) to 20mL 50g/L (w/v) under stirring
In hexane, 200mL 30g/L piperazine aqueous solutions are added dropwise, piperazine is added dropwise in the hexane solution of the B at the uniform velocity rotated to 50r/s
Aqueous phase solution, treat to generate granulated substance in B organic phases, stand 3 minutes, filtering, deionized water washing filter cake, drying to obtain
Gather to tert-butyl-calix [6] aromatic hydrocarbons -1,3- diacetyl piperazine (2), quality 0.042g, yield 42%.
Detection and extracting metals ion
Embodiment 3
By the poly- acetic acid second to tert-butyl-calix [6] aromatic hydrocarbons-Isosorbide-5-Nitrae-diacetyl piperazine of a concentration of 2g/L of 100ml (w/v)
Ester solution is poured into the Ce (NO of a concentration of 0.002g/L of 1L3)3On aqueous solution.It stands at room temperature after five minutes, it is seen that upper strata second
Acetoacetic ester mutually gradually becomes purple transparency liquid, can judge there is Ce in aqueous solution with this3+In the presence of.It is organic after standing 12 hours
The purple of phase subsides, and darkviolet sheet solid matter is generated at two-phase interface, and transmission electron microscope (TEM) observable should
Substance is accumulated by the nanofiber of a diameter of 10nm.This structure is poly- to tert-butyl-calix [6] aromatic hydrocarbons-Isosorbide-5-Nitrae-diacetyl
Base piperazine in the presence of water, ethyl acetate with Ce3+The metal of formation-organic supramolecular frameworks structure, by the Ce in water3+It grabs
It takes to network.It is (3) by nanofiber mats number.
Embodiment 4
By the poly- ethyl acetate to tertiary butyl p tertButylcalixarene -1,3 diacetyl piperazine of a concentration of 2g/L of 100ml (w/v)
Solution is poured into the Pb (NO of a concentration of 0.002g/L of 1L3)2On aqueous solution.When standing 1h at room temperature, upper strata ethyl acetate phase is in
Cloudy state, after standing 12h, organic phase clarification, and foam-like material is generated at visible two-phase interface, it can be judged with this water-soluble
There is Pb in liquid2+In the presence of.The foam is gathered to tertiary butyl p tertButylcalixarene -1,3 diacetyl piperazine in the presence of water, ethyl acetate
With Pb2+The metal of formation-organic supermolecular complexing network structure.It is (4) by foaming structure number.
Embodiment 5
By the poly- to tert-butyl-calix [8] aromatic hydrocarbons -1,5, the acetic acid second of-diacetyl piperazine of a concentration of 2g/L of 100ml (w/v)
Ester solution is poured into the La (NO of a concentration of 0.002g/L of 1L3)3On aqueous solution.When standing 0.5h at room temperature, upper strata ethyl acetate
Mutually in cloudy state, after standing 12h, organic phase is clarified, and white interphase film is generated at visible two-phase interface, can be judged with this
There is La in aqueous solution3+In the presence of.The interfacial film is gathered to tert-butyl-calix [8] aromatic hydrocarbons -1,5- diacetyl piperazine in water, ethyl acetate
In the presence of with La3+The metal of formation-organic supermolecular complexing network structure.It is (5) by interfacial film number.
Embodiment 6
By the poly- ethyl acetate to tertiary butyl p tertButylcalixarene -1,3 diacetyl piperazine of a concentration of 2g/L of 100ml (w/v)
Solution is poured into the Cu (NO of a concentration of 0.002g/L of 1L3)2On aqueous solution.When standing 1h at room temperature, upper strata ethyl acetate phase is in
Cloudy state, after standing 12h, organic phase clarification, and foam-like material is generated at visible two-phase interface, it can be judged with this water-soluble
There is Cu in liquid2+In the presence of.The foam is gathered to tertiary butyl p tertButylcalixarene -1,3 diacetyl piperazine in the presence of water, ethyl acetate
With Cu2+The metal of formation-organic supermolecular complexing network structure.It is (6) by foaming structure number.
Embodiment 7
By the poly- acetic acid second to tert-butyl-calix [8] aromatic hydrocarbons-Isosorbide-5-Nitrae-diacetyl piperazine of a concentration of 2g/L of 100ml (w/v)
Ester solution is poured into the Nd (NO of a concentration of 0.002g/L of 1L3)3On aqueous solution.It stands at room temperature after five minutes, it is seen that upper strata second
Acetoacetic ester mutually gradually becomes purple transparency liquid, can judge there is Nd in aqueous solution with this3+In the presence of.It is organic after standing 12 hours
The purple of phase subsides, and darkviolet sheet solid matter is generated at two-phase interface, and transmission electron microscope (TEM) observable should
Substance is accumulated by the nanofiber of a diameter of 20nm.Nanofiber mats are poly- to tert-butyl-calix [6] aromatic hydrocarbons-Isosorbide-5-Nitrae-diethyl
Acyl piperazine in the presence of water, ethyl acetate with Nd3+The metal of formation-organic supermolecular complexing network structure, will be in water
Nd3+Among crawl to network.It is (7) by nanofiber mats number.
The recycling of metal ion
Embodiment 8
The nanofiber mats 3 (0.05g) in embodiment 3 are thrown in the hydrochloric acid of 20mL a concentration of 5% (w/v), added in
100mL ethyl acetate, ultrasonic vibration 1 hour stand 12 hours, and 3 disappear, electronics coupled plasma emission spectroscopy (ICP-
OES) detection is as it can be seen that hydrochloric acid phase Ce3+Ion concentration is 0.0014g/L.It can detect the polyamide recycled in ethyl acetate phase
1, which can continue to serve as the detection and recycling of metal ion.
Embodiment 9
5 median surface film 5 (0.05) of embodiment is put into the hydrochloric acid of 100mL a concentration of 5% (w/v), add in 100mL second
Acetoacetic ester, ultrasonic vibration 1 hour, after standing 12h, 5 disappear, and electronics coupled plasma emission spectroscopy (ICP-OES) detection can
See, hydrochloric acid phase La3+Ion concentration is 0.0018g/L.It can detect the polyamide 1 recycled, the acetic acid second in ethyl acetate phase
Ester solution can continue to serve as the detection, extraction and recycling of metal ion.
Claims (5)
1. a kind of polyamide detected with extracting metals ion, it is characterized in that the derivative of calixarenes diacid chloride is dissolved in organic molten
It is reacted in agent A with piperazine aqueous solution, in the case where stirring and not stirring, generates interfacial polymerization resultant polyamides；The polyamide is molten
Xie Yu forms foam or is received at boundary in the immiscible organic solvent B of water, being placed on the aqueous solution containing metal ion
The visible complex compound of rice fibrofelt or interfacial film etc., shows the presence of metal ion；It is dissolved by collecting complex compound and removing in water
Metal ion.
2. according to claims 1, one or more of mixing of the calixarenes diacid chloride derivative for following structural formula：
。
3. according to claims 1, organic solvent A is one kind or several in n-hexane, normal heptane, hexamethylene or petroleum ether
The mixture of kind.
4. according to claims 1, organic solvent B is n-hexane, hexamethylene, ether, ethyl acetate, toluene and dimethylbenzene
One or more of mixture.
5. according to claims 1, metal ion includes rare earth ion La3+(lanthanum), Ce3+(cerium), Pr3+(praseodymium), Nd3 +(neodymium), Pm3+(promethium), Sm2+(samarium), Eu2+(europium) or Hg2+(mercury), Cd2+(cadmium), Pb2+(lead), Zn2+(zinc), Cu2+(copper) ion
Inorganic salt solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810025457.6A CN108164696A (en) | 2018-01-11 | 2018-01-11 | A kind of polyamide detected with extracting metals ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810025457.6A CN108164696A (en) | 2018-01-11 | 2018-01-11 | A kind of polyamide detected with extracting metals ion |
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| Publication Number | Publication Date |
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| CN108164696A true CN108164696A (en) | 2018-06-15 |
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| CN201810025457.6A Pending CN108164696A (en) | 2018-01-11 | 2018-01-11 | A kind of polyamide detected with extracting metals ion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251331A (en) * | 2018-09-19 | 2019-01-22 | 天津工业大学 | A kind of Polyamine capsule dispersion liquid removing underwater gold category ion |
| CN110988270A (en) * | 2019-12-24 | 2020-04-10 | 南通中智检测服务有限公司 | Method for measuring content of quick-acting metal in solid water-insoluble fertilizer |
Citations (2)
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|---|---|---|---|---|
| EP0309291A1 (en) * | 1987-09-24 | 1989-03-29 | LOCTITE (IRELAND) Ltd. | Nitrogen-containing oxacalixarene and calixarene derivatives, polymers including groups related to such derivatives, polymers including groups related to such derivatives, and use of such compounds |
| US20130001153A1 (en) * | 2011-07-01 | 2013-01-03 | International Business Machines Corporation | Thin film composite membranes embedded with molecular cage compounds |
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2018
- 2018-01-11 CN CN201810025457.6A patent/CN108164696A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0309291A1 (en) * | 1987-09-24 | 1989-03-29 | LOCTITE (IRELAND) Ltd. | Nitrogen-containing oxacalixarene and calixarene derivatives, polymers including groups related to such derivatives, polymers including groups related to such derivatives, and use of such compounds |
| US20130001153A1 (en) * | 2011-07-01 | 2013-01-03 | International Business Machines Corporation | Thin film composite membranes embedded with molecular cage compounds |
Non-Patent Citations (3)
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|---|
| 刘冬青等: "络合阴离子的杯芳烃受体的研究进展", 《有机化学》 * |
| 张力婉等: "界面聚合制备含杯芳烃结构的交联膜", 《河南工程学院学报（自然科学版）》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251331A (en) * | 2018-09-19 | 2019-01-22 | 天津工业大学 | A kind of Polyamine capsule dispersion liquid removing underwater gold category ion |
| CN110988270A (en) * | 2019-12-24 | 2020-04-10 | 南通中智检测服务有限公司 | Method for measuring content of quick-acting metal in solid water-insoluble fertilizer |
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Application publication date: 20180615 |