CN105778056B - One kind is used to detect Fe3+Porous conjugated polymer and its preparation method and application - Google Patents

One kind is used to detect Fe3+Porous conjugated polymer and its preparation method and application Download PDF

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CN105778056B
CN105778056B CN201610280147.XA CN201610280147A CN105778056B CN 105778056 B CN105778056 B CN 105778056B CN 201610280147 A CN201610280147 A CN 201610280147A CN 105778056 B CN105778056 B CN 105778056B
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蔡雪刁
骆楚欣
刘亚婷
张婷
李玲
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Shaanxi Normal University
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Abstract

It is used to detect Fe the invention discloses one kind3+Porous conjugated polymer and its preparation method and application, the construction unit of the polymer isR is represented in formulaIn any one, R ' represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base, itrile group, nitro, COONa.Inventive polymers are using MBH type reaction synthesis, and reaction condition is gentle, environment-friendly and non-metal catalyst residual, Fe3+The aqueous solution of porous conjugated polymer or the fluorescence of tetrahydrofuran solution synthesized by ion pair have obvious quenching effect, available for Fe in aqueous phase or organic phase3+The detection of ion, and to Fe3+The selectivity of ion is high, detection limit is low.

Description

One kind is used to detect Fe3+Porous conjugated polymer and its preparation method and application
Technical field
The invention belongs to technical field of high-molecular polymer, and in particular to the novel porous conjugation of a kind of carbon-carbon double key Polymer, and the preparation method of the polymer and detection Fe3+In application.
Background technology
Organic porous polymer is that a kind of one kind being made up of elements such as C, H, O, N, B has larger specific surface area and big The novel porous materials of metering-orifice structure.Organic porous polymer can be divided into from tool microporous polymer according to the difference of structure (polymers of intrinsic microporosity, PIMs), super cross-linked polymer (hypercross-linked Polymers, HCPs), conjugation microporous polymer (conjugated microporous polymers, CMPs) and covalent organic Skeleton polymer (covalent organic frameworks, COFs).Organic porous polymer due to loose structure and High specific surface area, and the features such as the size in hole, surface area, hydrophilic and hydrophobic, hard and soft can design, be widely used In gas absorption, separation, heterogeneous catalysis and energy storage.
In recent years, high selectivity molecule sensing material causes the great interest of people, so far, report it is most It is crown ether and conjugated polymer.In report, these polymer are generally to Cu2+、Hg2+Show stronger fluorescent quenching or increasing By force.Iron is indispensable trace element in most of organisms, in more than ten kinds of the essential trace elements of the human bodys iron no matter In importance or in content, first place is belonged to.Asiderosis excessively can induce various diseases.The iron metabolism reported at present Disorder can cause the infringement of anaemia and liver and kidney, ultimately result in liver cancer, hepatic sclerosis, arthritis, diabetes or heart decline Exhaust.Iron or the plant manufacture indispensable catalyst of chlorophyll.If a potted flower lacks iron, flower will lose gorgeous face Color, loses that fragrance moved one deeply, and leaf also turns to be yellow withered.Therefore, to Fe in organism3+The detection of content just seems particularly It is important.
The content of the invention
The technical problems to be solved by the invention are that providing one kind is used to detect Fe3+Porous conjugated polymer, and The preparation method and application of the polymer.
Technical scheme is used by solving above-mentioned technical problem：The following institute of construction unit of the porous conjugated polymer Show：
R is represented in formula In any one, R ' represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base, itrile group, nitro ,-COONa.
R ' represents any in carbomethoxy, ethoxycarbonyl, tert-butyl ester base, itrile group, nitro in above-mentioned porous conjugated polymer When a kind of, its preparation method is：Be catalyst with the carbon -7- alkene of 1,8- diazabicylos 11, ethanol be solvent, in counterflow condition Under make the compound shown in 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde and Formulas I be 1 in molar ratio:3 carry out polymerisation, Obtain porous conjugated polymer；
R in Formulas I " represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base, itrile group, nitro.
R ' representative-COONa, its preparation method are in above-mentioned porous conjugated polymer：With 1,8- diazabicylos 11 Carbon -7- alkene is oxidant, ethanol is solvent, makes 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde and Formula II institute under reflux conditions The compound shown is 1 in molar ratio:3 carry out polymerisation, isolate and purify product with dialysis, products therefrom is dissolved in into methanol In, sodium hydrate aqueous solution is added, is hydrolyzed under reflux conditions, obtains porous conjugated polymer；
R in Formula II " ' represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base.
In above-mentioned preparation method, the addition of the carbon -7- alkene of 1,8- diazabicylo 11 is preferably 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) Base phenyl)-benzaldehyde mole 40%~60%.
The porous conjugated polymer of the present invention is in detection Fe3+In application, specific detection method is：By porous conjugated polymer It is dissolved in tetrahydrofuran or water, is configured to 1.0 × 10-5Mol/L porous conjugated polymer solution；Then add thereto different The Fe of concentration3+Standard sample, the fluorescence intensity of detection architecture, draw various concentrations Fe3+The maximum fluorescence intensity of corresponding system with Fe3+The standard curve of change in concentration；Then test adds Fe to be measured3+The fluorescence intensity of system, strong according to fluorescence during sample solution Degree combined standard curvilinear equation can determine that Fe3+Content.
The present invention has synthesized a kind of porous conjugated polymer using MBH-type reactions, with conventional method such as：Suzuki is handed over Fork coupling reaction, Still reactions, Kumada reactions, Sonogashira reactions, Sonogashira reactions etc. are compared, the present invention Synthetic method is gentleer, environment-friendly and non-metal catalyst residual, Fe3+Porous conjugated polymers synthesized by ion pair The aqueous solution of thing or the fluorescence of tetrahydrofuran solution have obvious quenching effect, available for Fe in aqueous phase or organic phase3+Ion Detection, and to Fe3+The selectivity of ion is high, detection limit is low.
Brief description of the drawings
Fig. 1 is polymer M1 fluorescence intensity with Fe3+The fluorescence spectra of change in concentration.
Fig. 2 is polymer M1 fluorescence intensity with Fe3+The linear relationship chart of change in concentration.
Fig. 3 is polymer M2 fluorescence intensity with Fe3+The fluorescence spectra of change in concentration.
Fig. 4 is polymer M2 fluorescence intensity with Fe3+The linear relationship chart of change in concentration.
Fig. 5 is polymer M3 fluorescence intensity with Fe3+The fluorescence spectra of change in concentration.
Fig. 6 is polymer M3 fluorescence intensity with Fe3+The linear relationship chart of change in concentration.
Fig. 7 is polymer M4 fluorescence intensity with Fe3+The fluorescence spectra of change in concentration.
Fig. 8 is polymer M4 fluorescence intensity with Fe3+The linear relationship chart of change in concentration.
Fig. 9 is relative intensity of fluorescence comparison diagrams of the polymer M1 in different cationic systems.
Figure 10 is relative intensity of fluorescence comparison diagrams of the polymer M2 in different cationic systems.
Figure 11 is relative intensity of fluorescence comparison diagrams of the polymer M3 in different cationic systems.
Figure 12 is relative intensity of fluorescence comparison diagrams of the polymer M4 in different cationic systems.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
Embodiment 1
By 0.1g (3.18 × 10-4Mol) 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde, 0.288g (9.54 × 10- 4Mol) (2E, 2 ' E)-diethyl -4,4 shown in I-1 '-(1,4- phenylenes) double (but-2-ene acetoacetic esters) and 21.6mg (1.431×10-4Mol) carbon -7- alkene (DBU) of 1,8- diazabicylos 11 is dissolved in 10mL ethanol, back flow reaction 96 hours, After ethanol is removed under reduced pressure, crude product is dissolved with dichloromethane, then successively with the aqueous hydrochloric acid solution and deionized water that pH value is 2 Washing, then it is dry with anhydrous magnesium sulfate and after dichloromethane is removed under reduced pressure, obtain porous conjugated polymer (being denoted as M1), its yield For 74.0%, structural characterization result is as follows：
1H NMR (600MHz, CDCl3)δ：10.12 (1H ,-CHO), 9.39-7.45 (8H, phenyl ring=CH), 6.88-7.33 (3H ,=CH), 4.19 (2H ,-CH2), 1.26 (3H ,-CH3)；FT-IR (KBr)：=CH：2928；C=C：3020、1605；C= O：1722.
Tested through gel permeation chromatography, Mn=7505, Mw=14069 of the polymer, Mw/Mn=1.874.
Embodiment 2
By 0.1g (3.18 × 10-4Mol) 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde, 0.261g (9.54 × 10- 4Mol) (2E, 2 ' E)-dimethyl -4,4 '-(1,4- phenylenes) double (but-2-ene acetoacetic esters) and 21.6mg shown in I-2 (1.431×10-4Mol) DBU is dissolved in 10mL ethanol, back flow reaction 96 hours, molten with dichloromethane after ethanol is removed under reduced pressure Crude product is solved, is then washed successively with the aqueous hydrochloric acid solution and deionized water that pH value is 2, then with anhydrous magnesium sulfate drying and depressurize After removing dichloromethane, porous conjugated polymer (being denoted as M2) is obtained, its yield is 72.0%, and structural characterization result is as follows：
1H NMR (600MHz, CDCl3)δ：10.02 (1H ,-CHO), 7.94-7.45 (16H, phenyl ring=CH), 6.85-7.41 (3H ,=CH), 4.19 (9H ,-CH3)；FT-IR(KBr)：CH=：2930；C=C：3010,1600；C=O：1701.
Tested through gel permeation chromatography, Mn=6566, Mw=11687 of the polymer, Mw/Mn=1.780.
Embodiment 3
By 0.1g (3.18 × 10-4Mol) 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde, 0.399g (9.54 × 10- 4Mol) (2E, 2 ' E)-diethyl-4,4 ' shown in I-3-(9,9- diformazan-9H- fluorenes-2,7- diyls) double (but-2-ene acid second Ester) and 21.6mg (1.431 × 10-4Mol) DBU is dissolved in 10mL ethanol, back flow reaction 96 hours, after ethanol is removed under reduced pressure, Crude product is dissolved with dichloromethane, is then washed successively with the aqueous hydrochloric acid solution and deionized water that pH value is 2, then use anhydrous slufuric acid Magnesium is dry and after dichloromethane is removed under reduced pressure, and obtains porous conjugated polymer (being denoted as M3), its yield is 65.0%, structure table It is as follows to levy result：
1H NMR (600MHz, CDCl3)δ：10.21 (1H ,-CHO), 7.98-7.31 (17H, phenyl ring=CH), 6.81-7.28 (3H ,=CH), 4.19 (2H ,-CH2), 1.69 (6H ,-CH3), 1.69 (6H ,-CH3)；Tested through gel permeation chromatography, the polymerization Mn=6142, Mw=10652 of thing, Mw/Mn=1.734.
Embodiment 4
By 0.1g (3.18 × 10-4Mol) 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde, 0.345g (9.54 × 10- 4Mol) (2E, 2 ' E)-diethyl-4,4 ' shown in I-4-(benzo [c] [1,2,5] thiadiazoles-4,7- diyls) double (but-2-enes Acetoacetic ester) and 21.6mg (1.431 × 10-4Mol) DBU is dissolved in 10mL ethanol, back flow reaction 96 hours, second is removed under reduced pressure After alcohol, crude product is dissolved with dichloromethane, is then washed successively with pH value for 2 aqueous hydrochloric acid solution and deionized water, then with nothing Water magnesium sulfate is dry and after dichloromethane is removed under reduced pressure, and obtains porous conjugated polymer (being denoted as M4) its yield as 66.0%, knot Structure characterization result is as follows：
1H NMR (600MHz, CDCl3)δ：10.01 (1H ,-CHO), 7.98-7.41 (16H, phenyl ring=CH), 6.81-7.36 (3H ,=CH), 4.19 (2H ,-CH2), 1.26 (3H ,-CH3)；
Tested through gel permeation chromatography, Mn=6141, Mw=15812 of the polymer, Mw/Mn=2.575.
Embodiment 5
By 0.1g (3.18 × 10-4Mol) 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde, 0.199g (9.54 × 10- 4Mol) (2E, 2 ' E) -4,4 '-(, 4- phenylenes) double (but-2-ene nitriles) and 21.6mg (1.431 × 10-4Mol) DBU is dissolved in In 10mL ethanol, back flow reaction 96 hours, after ethanol is removed under reduced pressure, crude product is dissolved with dichloromethane, then uses pH successively It is worth aqueous hydrochloric acid solution and the deionized water washing for 2, then is gathered with anhydrous magnesium sulfate drying and after dichloromethane is removed under reduced pressure Compound M5, its yield are 77.0%, and structural characterization result is as follows：
1H NMR (600MHz, CDCl3)δ：10.13 (1H ,-CHO), 7.94-7.41 (16H, phenyl ring=CH), 6.81-7.26 (3H ,=CH)；Tested through gel permeation chromatography, Mn=6895, Mw=10811 of the polymer, Mw/Mn=1.568.
Embodiment 6
By 0.1g (3.18 × 10-4Mol) 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde, 0.288g (9.54 × 10- 4Mol) (2E, 2 ' E)-diethyl -4,4 '-(1,4- phenylenes) double (but-2-ene acetoacetic esters) and 14.4mg (0.954 × 10- 4Mol) DBU is dissolved in 10mL ethanol, back flow reaction 96 hours, after ethanol is removed under reduced pressure, dissolves crude product with dichloromethane, Then washed successively with the aqueous hydrochloric acid solution and deionized water that pH value is 2, then with anhydrous magnesium sulfate drying and dichloro is removed under reduced pressure After methane, products therefrom is dissolved in 5mL methanol, adds the 5mL 2mol/L NaOH aqueous solution, and hydrolysis is anti-under reflux conditions Answer 12 hours, be cooled to room temperature, methanol is removed by rotary evaporation, obtains porous conjugated polymer (being denoted as M6).
Embodiment 7
Porous conjugated polymer (M1) prepared by embodiment 1 is in detection Fe3+In application, specific method is as follows：
By 3mL 10-5Mol/L M1 tetrahydrofuran solution is added in 4mL cuvettes, adds Fe thereto3+Standard sample Product, make Fe in gained mixed liquor respectively3+Concentration for 0,3.33,6.67,10,20,26.67,46.67,53.33,60, 66.67th, 73.33,80,86.67,93.3,100 μm of ol/L, various concentrations Fe is measured using XRF3+Correspondingly system is glimmering Light spectrum (see Fig. 1), and it is plotted in various concentrations Fe at 408nm3+The fluorescence intensity of corresponding system is with Fe3+The mark of change in concentration Directrix curve.
As seen from Figure 1, M1 fluorescence intensity is by Fe3+The influence of concentration changes it is obvious that along with Fe3+The increase of concentration, The fluorescence intensity of system is gradually reduced.From Figure 2 it can be seen that Fe3+Concentration in 0~10 μm of ol/L, fluorescence intensity and Fe3+Concentration Linear, linear equation is：
Y=571.9693-16.16387x1
Y is fluorescence intensity in formula, x1For Fe3+Concentration, coefficient R2For 0.976.Fluorescence intensity and Fe as can be seen here3+It is dense The linear relationship of degree is fine.Minimum detectability is calculated using the formula of minimum detectability, M1 is to Fe3+Detection sensitivity it is very high, Detection limit has reached 1.203 × 10-7mol/L。
Embodiment 8
Porous conjugated polymer (M2) prepared by embodiment 2 is in detection Fe3+In application, specific method is as follows：
By 3mL 10-5Mol/L M2 tetrahydrofuran solution is added in 4mL cuvettes, adds Fe thereto3+Standard sample Product, make Fe in gained mixed liquor respectively3+Concentration for 0,3.33,6.67,13.33,16.67,20,26.67,33.33,40, 46.67th, 53.33,60,66.67,73.33,80 μm of ol/L, various concentrations Fe is measured using XRF3+Correspondingly system is glimmering Light spectrum (see Fig. 3), and it is plotted in various concentrations Fe at 412nm3+The fluorescence intensity of corresponding system is with Fe3+The mark of change in concentration Directrix curve.
As seen from Figure 3, M2 fluorescence intensity is by Fe3+The influence of concentration changes it is obvious that along with Fe3+The increase of concentration, The fluorescence intensity of system is gradually reduced.From fig. 4, it can be seen that Fe3+Concentration in 0~20 μm of ol/L, fluorescence intensity and Fe3+Concentration Linear, linear equation is：
Y=534.8515-14.73658x2
Y is fluorescence intensity in formula, x2For Fe3+Concentration, coefficient R2For 0.981.Fluorescence intensity and Fe as can be seen here3+It is dense The linear relationship of degree is fine.Minimum detectability is calculated using the formula of minimum detectability, M2 is to Fe3+Detection sensitivity it is very high, Detection limit has reached 1.839 × 10-6mol/L。
Embodiment 9
Porous conjugated polymer (M3) prepared by embodiment 3 is in detection Fe3+In application, specific method is as follows：
By 3mL 10-5Mol/L M3 tetrahydrofuran solution is added in 4mL cuvettes, adds Fe thereto3+Standard sample Product, make Fe in gained mixed liquor respectively3+Concentration for 0,3.33,6.67,10,13.3,16.67,20,26.67,33.33,40, 46.67th, 53.33,60,66.67,73.33,80,86.67,93.33,100 μm of ol/L, measured using XRF different dense Spend Fe3+The fluorescence spectrum (see Fig. 5) of corresponding system, and it is plotted in various concentrations Fe at 405nm3+The fluorescence intensity of corresponding system With Fe3+The standard curve of change in concentration.
As seen from Figure 5, M3 fluorescence intensity is by Fe3+The influence of concentration changes it is obvious that along with Fe3+The increase of concentration, The fluorescence intensity of system is gradually reduced.As seen from Figure 6, Fe3+Concentration in 0~20 μm of ol/L, fluorescence intensity and Fe3+Concentration Linear, linear equation is：
Y=516.5664-13.2266x3
Y is fluorescence intensity in formula, x3For Fe3+Concentration, coefficient R2For 0.976.Visible fluorescence intensity and Fe3+Concentration Linear relationship is fine.Minimum detectability is calculated using the formula of minimum detectability, M3 is to Fe3+Detection sensitivity it is very high, detection Limit has reached 8.487 × 10-7mol/L。
Embodiment 10
Porous conjugated polymer (M4) prepared by embodiment 4 is in detection Fe3+In application, specific method is as follows：
By 3mL 10-5Mol/L M4 tetrahydrofuran solution is added in 4mL cuvettes, adds Fe thereto3+Standard sample Product, make Fe in gained mixed liquor respectively3+Concentration for 0,3.33,6.67,10,13.3,16.67,20,26.67,33.33,40, 46.67th, 53.33,60,66.67,73.33,80,86.67,93.33,100 μm of ol/L, measured using XRF different dense Spend Fe3+The fluorescence spectrum (see Fig. 7) of corresponding system, and it is plotted in various concentrations Fe at 435nm3+The fluorescence intensity of corresponding system With Fe3+The standard curve of change in concentration.
As seen from Figure 7, M4 fluorescence intensity is by Fe3+The influence of concentration changes it is obvious that along with Fe3+The increase of concentration, The fluorescence intensity of system is gradually reduced.As seen from Figure 8, Fe3+Concentration in 0~13.33 μm of ol/L, fluorescence intensity and Fe3+It is dense Spend linear, linear equation is：
Y=504.14041-5.00456x4
Y is fluorescence intensity in formula, x4For Fe3+Concentration, coefficient R2For 0.996.Visible fluorescence intensity and Fe3+Concentration Linear relationship is fine.Minimum detectability is calculated using the formula of minimum detectability, M4 is to Fe3+Detection sensitivity it is very high, detection Limit has reached 7.158 × 10-6mol/L。
In order to prove the porous conjugated polymer of the present invention to Fe3+Embodiment 1 is respectively adopted in the selectivity of detection, inventor ~4 porous conjugated polymer is to Mg2+、Al3+、Ni2+、K+、Fe3+、Cu2+、Ba2+、Ca2+、Zn2+、 Mn2+、Pb2+、Ag+、Hg2+、 Cd2+(wherein porous conjugated polymer concentration is 1.0 × 10-5Mol/L, it is formulated by solvent of tetrahydrofuran, detection architecture Middle concentration of metal ions is 1.0 × 10-4Mol/L) it is tested, as a result sees Fig. 9~12.As seen from the figure, as addition Fe3+When, The fluorescent quenching effect of detection architecture is most strong, and other ions illustrate that the porous conjugation of the present invention is poly- almost without fluorescent quenching effect Compound is capable of the detection Fe of high selectivity3+。

Claims (6)

1. one kind is used to detect Fe3+Porous conjugated polymer, it is characterised in that the construction unit of the polymer is as follows：
R is represented in formula In any one, R ' represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base, itrile group, nitro ,-COONa.
2. the preparation method of the porous conjugated polymer described in claim 1, wherein R ' represent carbomethoxy, ethoxycarbonyl, the tert-butyl ester Any one in base, itrile group, nitro, it is characterised in that：Using the carbon -7- alkene of 1,8- diazabicylos 11 as catalyst, ethanol For solvent, 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde is set to be in molar ratio with the compound shown in Formulas I under reflux conditions 1:3 carry out polymerisation, obtain porous conjugated polymer；
R is represented in Formulas I In any one, R " represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base, itrile group, nitro.
3. the preparation method of porous conjugated polymer according to claim 2, it is characterised in that：The 1,8- diazas two The addition of the carbon -7- alkene of ring 11 is the 40%~60% of 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde mole.
4. the preparation method of the porous conjugated polymer described in claim 1, wherein R ' representatives-COONa, it is characterised in that：With Carbon -7- the alkene of 1,8- diazabicylo 11 is catalyst, ethanol is solvent, makes 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base benzene under reflux conditions Base) compound shown in-benzaldehyde and Formula II is 1 in molar ratio:3 carry out polymerisation, and product is isolated and purified with dialysis, will Products therefrom is dissolved in methanol, is added sodium hydrate aqueous solution, is made product back hydrolysis in the basic conditions, obtain porous conjugation Polymer；
R is represented in Formula II In any one, R " ' represents any one in carbomethoxy, ethoxycarbonyl, tert-butyl ester base.
5. the preparation method of porous conjugated polymer according to claim 4, it is characterised in that：The 1,8- diazas two The addition of the carbon -7- alkene of ring 11 is the 40%~60% of 3,5- bis--(PARA FORMALDEHYDE PRILLS(91,95) base phenyl)-benzaldehyde mole.
6. the porous conjugated polymer described in claim 1 is in detection Fe3+In application.
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