CN104311548B - Cadmium ion sensor and functional polyurathamc - Google Patents

Cadmium ion sensor and functional polyurathamc Download PDF

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CN104311548B
CN104311548B CN201410628376.7A CN201410628376A CN104311548B CN 104311548 B CN104311548 B CN 104311548B CN 201410628376 A CN201410628376 A CN 201410628376A CN 104311548 B CN104311548 B CN 104311548B
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polyurathamc
cadmium
cadmium ion
functional
ion sensor
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CN104311548A (en
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程新建
余运
吴斌
井丰喜
张春琪
夏智峰
王顺
张爱清
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SUZHOU TAIHU ELECTRIC NEW MATERIAL CO Ltd
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Abstract

The present invention relates to a kind of cadmium ion sensor and there is the functional polyurathamc of detection and Adsorption of Cadmium function, cadmium ion sensor is a kind of naphthalimide thiazolyl acetic acid based compound, after this compound selective binding cadmium ion, while color significant change, fluorescence is obviously enhanced；Functional polyurathamc is with polyurathamc as matrix, is bonded to cadmium ion sensor chemistry on matrix be formed.Cadmium ion sensor of the present invention is 10 in divalent cadmium ion concentration‑7Remain to detect the enhancing of fluorescence during mol/L；Concentration at the divalent cadmium ion added reaches 1 10‑7During mol/L, functional polyurathamc color remains to fade to green from yellow, and adsorption capacity is high, it is possible to reach to detect, the purpose adsorbed and separate, it is adaptable to detect and purify the cadmium ion in ocean, lake, industrial wastewater simultaneously.

Description

Cadmium ion sensor and functional polyurathamc
Technical field
The present invention relates to a kind of cadmium ion sensor and there is the poly-ammonia of foaming of detection and Adsorption of Cadmium function Ester and preparation method thereof.
Background technology
Heavy metal has significant bio-toxicity at environment and health field, and they migrate with various valence state forms And enrichment, but cannot degrade, but enter human body by food chain, with protein and enzyme etc. in human body There is various interaction, make them lose activity, thus cause various possible pathological changes, it is also possible to people Cylinder accumulation causes chronic poisoning to a certain extent.Therefore invent a kind of high selectivity, high sensitivity and can Particularly important to concurrently separate the functional sensor of cadmium ion in enrichment environment.
In prior art, the design of major part sensor is only limitted to detect heavy metal ion；Also some are had to sense The organic molecule that can detect heavy metal is received on macromole by the design of device, can reach recognition detection weight The purpose of metal ion, but, the heavy metal analysis separation macromole being seen in report mostly is water solublity high score Son, is unfavorable for the separation of heavy metal ion.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of naphthalimide-thiazolyl acetic acid based compound, and it is right Cadmium ion has the highest selectivity, is preferable cadmium ion sensor.
Present invention simultaneously provides naphthalimide-thiazolyl acetic acid based compound for detecting cadmium ion particularly bivalence The purposes of cadmium ion and the preparation method of naphthalimide-thiazolyl acetic acid based compound.
The present invention furthermore provides the functional polyurathamc with detection and Adsorption of Cadmium function, should Functional polyurathamc is high to the detection sensitivity of cadmium ion, and detection limit is low, and can fully adsorb cadmium Ion and there is high adsorption capacity, thus this functional polyurathamc can be also used for concentration and separation cadmium from Son.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
Cadmium ion sensor shown in Formulas I:
Above-mentioned compound of formula I has a characteristic that
1, for the solution of compound of formula I of 1mg/L, the concentration at the divalent cadmium ion added reaches 1×10-7During mol/L, the color being visually observed solution i.e. fades to green from yellow, and response speed is fast, Therefore, the quicklook detection of divalent cadmium ion during it can be used for solution.
2, for the solution of above-mentioned compound of formula I of 1mg/L, the concentration at the divalent cadmium ion added reaches To 1 × 10-9During mol/L, remain to detect the increase of fluorescence intensity.
3, this compound has oh group, can be grafted to macromolecule polyalcohol by this carboxylic group On, form functional polymer, the polyurathamc of the most adsorbable cadmium ion.
4, this compound can be prepared by simple technique, low cost.
To this end, the present invention relates particularly to cadmium ion sensor shown in Formulas I for detecting cadmium ion particularly two Valency cadmium ion (Cd2+) purposes.Use this compound test cadmium ion, have highly sensitive, detection limit is low Advantage.
The another technical scheme that the present invention takes is: the preparation method of a kind of above-mentioned cadmium ion sensor, should Method includes making compound shown in Formula II
With 2-amino-4-thiazolyl acetic acid, in organic solvent, in the presence of catalyst and temperature 70～120 DEG C Lower reaction obtains compound shown in Formulas I.
Further, compound shown in Formula II with the molar ratio of 2-amino-4-thiazolyl acetic acid is 1:2.0～2.5.
Further, catalyst can be selected from three (dibenzalacetone) two palladium, palladium, sodium tert-butoxide, One or more mixture in diphenylphosphine.
Further, described organic solvent can be selected from oxolane, ethanol, N, N-dimethyl formyl One in amine and ethylene glycol monomethyl ether.
According to the present invention, the response time is generally 24～48 hours, after reaction terminates, passes through pillar layer separation Obtain compound shown in Formulas I.
Above-mentioned Formula II compound is commercially available or prepares in accordance with known methods.
The another technical scheme that the present invention takes is: have the functional foaming of detection and Adsorption of Cadmium function Polyurethane, it is connected on polyurathamc be formed by above-mentioned cadmium ion sensor chemistry.
According to the present invention, described polyurathamc is known in the art various polyurathamc, the most especially Limit.Preferably, polyurathamc is soft polyurathamc.
Preferably, cadmium ion sensor mass content in functional polyurathamc is 1wt%～5wt%.
Specifically, functional polyurathamc can prepare by the following method: by many to isocyanates, polyethers Unit's alcohol, the mixing of described cadmium ion sensor, stirring at normal temperature, the most progressively dropping catalyst and foaming agent, often Temperature reaction 5～10 minutes, after reaction terminates, products therefrom through transconversion into heat, ageing, to obtain final product successively.
Above-mentioned isocyanates, polyether polyol, catalyst and foaming agent is all polyurathamc synthesis neck Conventional those in territory, are not particularly limited.
The present invention also adopts the technical scheme that: a kind of above-mentioned having detects and Adsorption of Cadmium function The preparation method of functional polyurathamc, its comprise the steps: by isocyanates, polyether polyol, Compound of formula I mixes, stirring at normal temperature, the most progressively dropping catalyst and foaming agent, normal-temperature reaction 5～10 Minute, after reaction terminates, products therefrom through transconversion into heat, ageing, to obtain final product successively.
According to the present invention, above-mentioned isocyanates, polyether polyol, catalyst and foaming agent is all foaming Polyurethane synthesizes those that field is commonly used, is not particularly limited.
Specifically, described isocyanates can be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, The combination of one or more in isophorone diisocyanate.Polyether polyol can be polytetramethylene glycol, gather The combination of one or more in 1,2-propylene glycol, Polyethylene Glycol, polypropylene glycol.
According to a specific aspect, described polyether polyol is PEG400, the mechanics of gained polyurethane foam Intensity, foaming effect are optimal, and described isocyanates is toluene di-isocyanate(TDI).Described catalyst is two Laurels Acid dibutyl tin and triethanolamine, described foaming agent is water.Isocyanates, Polyethylene Glycol and Formulas I The molar ratio of compound is 3～2:1:0.01～0.1.Catalyst quality consumption is isocyanates, polyether polyols Alcohol and the 0.5 of compound of formula I gross mass～1.5%, foaming agent quality consumption is isocyanates, polyether polyol And the 0.5 of compound of formula I gross mass～1%.
The functional polyurathamc of the present invention has the property that
1, for 1cm3Polyurathamc, in the concentration as little as 1 × 10 of the cadmium ion added-7During mol/L, Polyurathamc color remains to fade to green from yellow, and response speed is fast, and this polyurathamc can be with fast direct The detection cadmium ion seen；
2, macromolecular functionality polyurathamc can abundant Adsorption of Cadmium, adsorption capacity high (for cadmium from Sub-sensor content is the functional polyurathamc of 1wt%, and unit interval internal adsorption capacity can reach 37.66mg.g-1.s-1) can be used for adsorbing, concentration and separation cadmium ion；
3, functional polyurathamc is with polyurathamc as carrier, high comprehensive performance, has common sending out The general characteristic that bubble polyurethane is had.
4, this functional polyurathamc can reach detection, adsorbs and separate the triple of cadmium ion in solution Purpose, is suitable to be applied to detection and remove ocean, lake, cadmium in industrial wastewater ion, and biological field Middle cadmium ion.
The present invention relates particularly to above-mentioned functional polyurathamc for detecting, adsorb and separating solution The purposes of middle divalent cadmium ion.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of embodiment 3 products therefrom；
Fig. 2 is the fluorogram of gained compound of formula I identification cadmium ion in embodiment 3；
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment 1
This example provides the compound shown in a kind of Formulas I, and its synthetic route is as follows:
Formula II compound and 2-amino-4-thiazolyl acetic acid during 1:2 puts into toluene solvant in molar ratio, are added Enter catalyst acetic acid palladium, react 24 hours at 90 DEG C, stopped reaction, be cooled to room temperature, the product obtained Thing purifies through pillar layer separation, i.e. obtains compound shown in Formulas I, productivity 34%.EI-MS (M2+) m/z= 394.98.
Embodiment 2
This example provides the preparation method of compound shown in a kind of Formulas I, and its synthetic route is with embodiment 1, specifically Step is as follows: Formula II compound and 2-amino-4-thiazolyl acetic acid 1:2 in molar ratio are put into toluene solvant In, add catalyst acetic acid palladium, react 36 hours at 90 DEG C, stopped reaction, be cooled to room temperature, The product arrived purifies through pillar layer separation, i.e. obtains compound shown in Formulas I, productivity 41%.EI-MS(M2+) M/z=394.98.
Embodiment 3
This example provides the preparation method of compound shown in a kind of Formulas I, and its synthetic route is with embodiment 1, specifically Step is as follows: Formula II compound and 2-amino-4-thiazolyl acetic acid 1:2 in molar ratio are put into toluene solvant In, add catalyst acetic acid palladium, react 48 hours at 90 DEG C, stopped reaction, be cooled to room temperature, The product arrived purifies through pillar layer separation, i.e. obtains compound shown in Formulas I, productivity 52%.EI-MS(M2+) M/z=394.98.
Seeing Fig. 1, the stretching vibration peak of amido bond (CONH) occurs in 1686cm-1Place, at 1778cm-1 And 1721cm-1Place correspond to the stretching vibration peak of ester bond (COO), and the carbon bromine key at 559cm-1 disappears Lose, and 1345cm-1There is the stretching vibration peak of carbonnitrogen bond in place.Infrared results confirms compound of formula I Success synthesizes.
Embodiment 4
This example provides the preparation method of compound shown in a kind of Formulas I, and its synthetic route is with embodiment 1, specifically Step is as follows: Formula II compound and 2-amino-4-thiazolyl acetic acid 1:2 in molar ratio are put into toluene solvant In, add catalyst acetic acid palladium, react 60 hours at 90 DEG C, stopped reaction, be cooled to room temperature, The product arrived purifies through pillar layer separation, i.e. obtains compound shown in Formulas I, productivity 51%.EI-MS(M2+) M/z=394.98.
Embodiment 5
This example provides the preparation method of compound shown in a kind of Formulas I, and its synthetic route is with embodiment 1, specifically Step is as follows: for 1:5, Formula II compound and 2-amino-4-thiazolyl acetic acid are put into toluene in molar ratio molten In agent, reacting 48 hours, stopped reaction, be cooled to room temperature at 90 DEG C, the product obtained divides through column chromatography From purification, i.e. obtain compound shown in Formulas I, productivity 48%.EI-MS (M2+) m/z=394.98.
Embodiment 6
This example provides the preparation method of compound shown in a kind of Formulas I, and its synthetic route is with embodiment 1, specifically Step is as follows: for 1:10, Formula II compound and 2-amino-4-thiazolyl acetic acid are put into toluene in molar ratio molten In agent, reacting 48 hours, stopped reaction, be cooled to room temperature at 90 DEG C, the product obtained divides through column chromatography From purification, i.e. obtain compound shown in Formulas I, productivity 52%.EI-MS (M2+) m/z=394.98.
Embodiment 7
This example provides a kind of functional polyurathamc with detection and Adsorption of Cadmium function, its synthesis Route is as follows:
Specific as follows: by toluene di-isocyanate(TDI), PEG400, compound of formula I mixing, room temperature stirs Mix, the most progressively dropping catalyst and foaming agent, normal-temperature reaction 5～10 minutes, after reaction terminates, gained Product through transconversion into heat, ageing, to obtain final product successively, wherein, and toluene di-isocyanate(TDI), PEG400 and Formulas I Shown compound molar ratio is 3:0.99:0.01；Catalyst is dibutyl tin laurate and three second Hydramine (the two mass ratio is 4:1), addition is toluene di-isocyanate(TDI), PEG400 and Formulas I The 1% of shown compound gross mass, foaming agent is water, addition toluene di-isocyanate(TDI), PEG400 With 0.8% of compound gross mass shown in Formulas I, the content of gained polyurathamc compounds of formula I is about 1wt%.
Embodiment 8
This example provides the preparation side of a kind of functional polyurathamc with detection and Adsorption of Cadmium function Method, it is substantially with embodiment 7, except for the difference that, toluene di-isocyanate(TDI), PEG400, Formulas I The molar ratio of compound is 3:0.98:0.02.The content of gained polyurathamc compounds of formula I is about 2wt%.
Embodiment 9
This example provides the preparation side of a kind of functional polyurathamc with detection and Adsorption of Cadmium function Method, it is substantially with embodiment 7, except for the difference that, toluene di-isocyanate(TDI), PEG400, Formulas I The molar ratio of compound is 3:0.95:0.05.The content of gained polyurathamc compounds of formula I is about 5wt%.
Embodiment 10
This example provides the preparation side of a kind of functional polyurathamc with detection and Adsorption of Cadmium function Method, it is substantially with embodiment 7, except for the difference that, toluene di-isocyanate(TDI), PEG400, Formulas I The molar ratio of compound is 3:0.90:0.1.The content of gained polyurathamc compounds of formula I is about 10wt%.
Comparative example 1
This example provides a kind of common polyurathamc, and it is substantially with embodiment 7, except for the difference that, without Adding type I.
Comparative example 2
This example provide a kind of functional polyurathamc, its by the compound of following structure according to the present invention Similar method is connected on polyurathamc be formed, and wherein this compound accounts for containing of functional polyurathamc Amount is 1wt%.
Embodiment 11
This example provides compound of formula I to be used for detecting cadmium ion (Cd2+) purposes.
Use molecule nutriology measure respectively embodiment 1～6 gained compound of formula I for visual inspection cadmium from The performance of son.
As a example by embodiment 3 gained compound of formula I, by the cadmium-ion solution of variable concentrations (25 μ L, 10-7 mol/L,10-6mol/L,10-5mol/L,10-4.5mol/L,10-4mol/L,10-3mol/L,10-2mol/L) It is added separately to 4mL, 1g L-1Compound of formula I acetonitrile-aqueous solution in, measure it with molecule nutriology Fluorescence intensity, concrete data are as shown in Figure 2.The most visible, along with the increase of concentration of cadmium ions, Formulas I The fluorescence intensity of polymer solution gradually strengthens.The concentration of cadmium ion as little as 1 × 10-7During mol/L, remain to detection Increase to fluorescence intensity.
Embodiment 12
This example provides the functional polyurathamc of the present invention for detecting, adsorbing and the purposes of cadmium separation ion.
Use static adsorptive method testing example 7～10 gained polyurathamc for visual inspection cadmium ion Performance, record maximum adsorption capacity and can reach 37.66mg/g
As a example by embodiment 8 gained polyurathamc, size is 1cm3Polyurathamc add respectively Enter the cadmium-ion solution (10 of 10mL variable concentrations-2mol/L,10-3mol/L,10-4mol/L,10-4.5mol/L, 10-5mol/L,10-7Mol/L, 0mol L-1), stand, it is seen that the color of polyurathamc is gradually become by yellow For green, and reach 1 × 10 in the concentration of the cadmium ion added-5During mol/L, polyurethane color remains to from Huang Complexion changed is to green, and response speed is fast.
Size is 1cm3Functional polyurathamc (wherein cadmium ion sensor content be about 1wt%) it is respectively placed in the cadmium-ion solution of same volume, after the identical time, takes out polyurathamc, Measure initial cadmium-ion solution concentration and final cadmium-ion solution concentration with atomic fluorescence method respectively, then will The data obtained process, and calculate q=(C through unit interval internal adsorption capacity formula0-Ce) * V/ (M*T) (its In, q is unit time internal adsorption capacity；C0Initial concentration and equilibrium concentration is represented respectively with Ce；V Volume for cadmium-ion solution；M is the quality of functional polyurathamc, and T is the time.) foamed The unit interval internal adsorption capacity of polyurethane.Concrete data are as shown in table 1, and maximum unit time internal adsorption holds Amount can reach 37.66mg.g-1.s-1.And tradition polyurathamc is the least by (0.89 for the adsorption of cadmium ion mg.g-1.s-1), by comparing, when other condition is identical, the functional polyurathamc tree of the present invention Fat is 21 times of tradition polyurathamc adsorption capacity.
Table 1
Above-described embodiment only for technology design and the feature of the present invention are described, its object is to allow and is familiar with this skill The personage of art will appreciate that present disclosure and implements according to this, can not limit the protection model of the present invention with this Enclose, all equivalence changes made according to spirit of the invention or modification, all should contain the protection in the present invention Within the scope of.

Claims (10)

1. the cadmium ion sensor shown in Formulas I,
2. cadmium ion sensor described in claim 1 is for detecting the purposes of divalent cadmium ion, and described purposes is Non-diagnostic and the purposes of non-treatment purpose.
3. the preparation method of the cadmium ion sensor described in a claim 1, it is characterised in that: the method Including making compound shown in Formula II
With 2-amino-4-thiazolyl acetic acid in organic solvent, in the presence of catalyst with And reaction obtains the step of compound of formula I at temperature 70～120 DEG C.
Preparation method the most according to claim 3, it is characterised in that: compound shown in Formula II and 2- The molar ratio of amino-4-thiazolyl acetic acid is 1:2.0～2.5, and described catalyst is selected from three (dibenzylidenes third Ketone) two palladiums, palladium, sodium tert-butoxide, one or more mixture in diphenylphosphine；Described Organic solvent is the one in oxolane, ethanol, N,N-dimethylformamide and ethylene glycol monomethyl ether.
5. there is the functional polyurathamc of detection and Adsorption of Cadmium function, it is characterised in that by right Require that the cadmium ion sensor chemistry described in 1 is connected on polyurathamc be formed.
The functional polyurathamc with detection and Adsorption of Cadmium function the most according to claim 5, It is characterized in that, between described cadmium ion sensor and polyurathamc by the hydroxyl of cadmium ion sensor and The NCO chemical bond joining of polyurathamc.
The functional polyurathamc with detection and Adsorption of Cadmium function the most according to claim 5, It is characterized in that, described compound of formula I mass content in described functional polyurathamc is 1wt%～10wt%.
The functional polyurathamc with detection and Adsorption of Cadmium function the most according to claim 5, It is characterized in that, described polyurathamc is soft polyurathamc.
9. detect and Adsorption of Cadmium function according to having described in claim any one of claim 5～8 Functional polyurathamc, it is characterised in that prepare by the following method: by many to isocyanates, polyethers Unit's alcohol, the mixing of described cadmium ion sensor, stirring at normal temperature, the most progressively dropping catalyst and foaming agent, often Temperature reaction 5～10 minutes, after reaction terminates, products therefrom through transconversion into heat, ageing, to obtain final product successively.
10. having described in claim any one of a claim 5 to 9 is detected and Adsorption of Cadmium The functional polyurathamc of function is for detecting, adsorb and separate the purposes of divalent cadmium ion in solution, institute Stating purposes is non-diagnostic and the purposes of non-treatment purpose.
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