CN110152632A - A kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide - Google Patents
A kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide Download PDFInfo
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- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention provides a kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide, belong to adsorbent material technical field.Preparation method provided by the invention includes the following steps: (1) for 2,4,6- trihydroxy benzenes -1,3, and 5- trioxin, amination magnetic bead and ethyl alcohol mixing carry out the first aldimine condensation reaction, obtain aldehyde radical magnetic bead；(2) solution of p-phenylenediamine is added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxy benzenes -1,3 is then added, the solution of 5- trioxin carries out the second aldimine condensation reaction, obtains the magnetic COF-TpPa for being enriched with amides pesticide.The magnetic COF-TpPa that preparation method provided by the invention obtains has excellent adsorptivity to amides class pesticide (Prochloraz and Tolfenpyrad), stability is good, has superparamagnetism, is easily isolated, and the preparation method is easy to operate, reaction condition is mildly controllable.
Description
Technical field
The present invention relates to adsorbent material technical fields more particularly to a kind of for being enriched with the magnetic COF- of amides pesticide
TpPa and its preparation method and application.
Background technique
Covalent organic frame (Covalent Organic Framework, COF) material is a kind of light by C, H, B, O, N etc.
Element passes through organic porous material be covalently keyed, structurally ordered, function is controllable, have structure height orderly, compare table
Many advantages, such as area is big, chemical stability and thermal stability are good is mainly used in photoelectricity, catalysis, gas absorption storage, sensing
Equal fields.And application of the covalent organic frame material in pesticide residue enrichment detection is rarely reported, there is presently no can be used for
There is the COF of good accumulation ability to amides pesticide residual.
Currently, the common synthetic method of COF material has solvent-thermal process method, sound wave auxiliary law, microwave method, mechanical milling method
Deng wherein reporting that most, most widely used is solvent-thermal process method, mainly by the way that the presoma of reaction to be dissolved in properly
Medium solution in, synthesized in closed reaction vessel (such as reaction kettle, heat-resistant tube) by the method for high temperature and pressure,
Typical temperature is at 100 DEG C or more, and even up to 200 DEG C.Solvent heat seal synthesizes the whole process of COF in closed reaction vessel
Middle progress can not be observed and be taken a sample to research in real time, and yield is generally lower.In addition, the solvent-thermal process of some COF materials
Process needs the operation such as liquid nitrogen flash freezing and flame sealing (such as " Magnetic covalent organic framework
material:Synthesis and application as a sorbent for polycyclic aromatic
Hydrocarbons ", Xuexiang Shi, 2018), the synthesis of triazines COFs material needs in the zinc chloride of high-temperature fusion
It is reacted, reaction condition is more harsh.Therefore, COF preparation method condition is harsh, cannot produce in enormous quantities, hinder COF material
The extensive use of material.In addition, the covalent organic frame material problem that there is also stability is poor, separation is difficult, further limits
Application of the covalent organic frame material in the enrichment of amides pesticide residue.
Summary of the invention
The purpose of the present invention is to provide a kind of magnetic COF-TpPa and preparation method thereof for being enriched with amides pesticide
And application, the magnetic COF-TpPa that preparation method provided by the invention obtains are excellent to the adsorptivity of amides class pesticide, can use
In the enrichment of the pesticide residue, and excellent in stability, it is easily isolated, preparation method is simple.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of for being enriched with the preparation method of the magnetic COF-TpPa of amides pesticide, including walks as follows
It is rapid:
(1) by 2,4,6- trihydroxy benzenes -1,3,5- trioxin, amination magnetic bead and ethyl alcohol mixing carry out the contracting of the first aldehyde amine
Reaction is closed, aldehyde radical magnetic bead is obtained；
(2) solution of p-phenylenediamine is added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxies is then added
Benzene -1,3, the solution of 5- trioxin carry out the second aldimine condensation reaction, obtain the magnetic COF- for being enriched with amides pesticide
TpPa。
Preferably, the mass ratio of 2,4,6- trihydroxy benzenes -1,3 in the step (1), 5- trioxin and amination magnetic bead is
0.1~0.4:1.
Preferably, the temperature that the first aldimine condensation reacts in the step (1) is 40~55 DEG C, and the time is 1~2h.
Preferably, the dispersion liquid of aldehyde radical magnetic bead, the solution of p-phenylenediamine and 2,4,6- trihydroxies in the step (2)
Benzene -1,3, the solvent in the solution of 5- trioxin are the mixed liquor of Isosorbide-5-Nitrae-dioxane and trimethylbenzene, the Isosorbide-5-Nitrae-dioxane
Volume ratio with trimethylbenzene is 1:0.2~4.
Preferably, the amination magnetic bead in the step (1) and p-phenylenediamine, 2 in step (2), 4,6- trihydroxy benzene -1,
The mass ratio of 3,5- trioxin is 1:0.15~0.35:0.25~0.4.
Preferably, the temperature that the second aldimine condensation reacts in the step (2) is 15~35 DEG C, and the time is 1~4d.
Preferably, the first aldimine condensation reaction in the step (1) and the second aldimine condensation in step (2) have reacted
Cheng Hou independently further includes Magnetic Isolation and washing.
The present invention also provides the magnetic for being used to be enriched with amides pesticide that the preparation method described in above-mentioned technical proposal obtains
Property COF-TpPa, partial size be 0.33~0.73 μm.
The present invention also provides the magnetic COF-TpPa conducts for being used to be enriched with amides pesticide described in above-mentioned technical proposal
The application of amides pesticide adsorbent.
The present invention provides a kind of for being enriched with the preparation method of the magnetic COF-TpPa of amides pesticide, including walks as follows
Rapid: (1) by 2,4,6- trihydroxy benzenes -1,3, it is anti-to carry out the first aldimine condensation for 5- trioxin, amination magnetic bead and ethyl alcohol mixing
It answers, obtains aldehyde radical magnetic bead；(2) solution of p-phenylenediamine is added to the dispersion liquid of the aldehyde radical magnetic bead, is then added 2,
4,6- trihydroxy benzenes -1,3, the solution of 5- trioxin carry out the second aldimine condensation reaction, obtain for being enriched with amides pesticide
Magnetic COF-TpPa.The present invention is reacted by the first aldimine condensation, makes the amino and 2 of amination magnetic bead surfaces, 4,6- trihydroxies
Benzene -1,3, the aldehyde radical reaction of 5- trioxin, so that 4,6- trihydroxy benzenes -1,3,5- trioxin is grafted on amination magnetic bead table by 2
Face, obtains aldehyde radical magnetic bead, then sequentially adds the solution and 2 of p-phenylenediamine, 4,6- trihydroxy benzenes -1,3,5- trioxin it is molten
Liquid carries out the second aldimine condensation reaction, is further grafted p-phenylenediamine and 2 in aldehyde radical magnetic bead surfaces, 4,6- trihydroxy benzene -1,
The polymer of 3,5- trioxins obtains the magnetic COF-TpPa for being enriched with amides pesticide.
The magnetic COF-TpPa for being enriched with amides pesticide that preparation method provided by the present invention obtains is to amides
Pesticide (Prochloraz and Tolfenpyrad) shows good adsorption effect.Gained of the invention is for being enriched with the magnetism of amides pesticide
Aldehyde radical unit and amido the unit frame all based on phenyl ring in COF-TpPa, and aldehyde radical unit contains hydroxyl abundant, can pass through
The pi-conjugated phenyl ring with Prochloraz and Tolfenpyrad of π-interacts, by hydrogen bond and Prochloraz and Tolfenpyrad
Amido bond interacts, to realize the absorption and enrichment to two kinds of drugs.Meanwhile the material is on magnetic kernel surface
Covalent organic framework polymer is formed, so, there is loose and porous structure, have the strong advantage of large specific surface area, adsorption capacity.
Adsorption experimental results show magnetic COF-TpPa pairs for being used to be enriched with amides pesticide that preparation method provided by the invention obtains
The adsorption rate of two kinds of pesticides reaches 98% or more；When further using the magnetic covalent organic frame material-of eluting solvent processing
After TpPa, pesticide can be eluted and be transferred in elution solution, and eluting rate illustrates 85% or more for being enriched with amides agriculture
The magnetic COF-TpPa of medicine is mainly based upon non-covalent bond effect power to the absorption of these pesticides and the reversible adsorption process that combines,
Magnetic COF-TpPa can be made to be regenerated, to achieve the purpose that reuse by the use of strong eluting solvent.
In addition, preparation method provided by the invention is easy to operate, it is easy to implement, and exacting terms is not needed, gained material
Material has magnetism, and the mode that can directly adopt Magnetic Isolation is separated and recovered from solution medium.
Detailed description of the invention
For being enriched with the SEM figure of the magnetic COF-TpPa of amides pesticide obtained by Fig. 1 embodiment 1；
For being enriched with the FTIR figure of the magnetic COF-TpPa of amides pesticide obtained by Fig. 2 embodiment 1.
Specific embodiment
(wherein COF is covalent organic material to the magnetic COF-TpPa that the present invention provides a kind of for being enriched with amides pesticide
Material is write a Chinese character in simplified form, Tp 2,4,6- trihydroxy benzene -1,3, the contracting of the English name TriformylPhloroglucinol of 5- trioxin
Write, Pa be p-phenylenediamine English name p-Phenylenediamine abbreviation) preparation method, include the following steps:
(1) by 2,4,6- trihydroxy benzenes -1,3,5- trioxin, amination magnetic bead and ethyl alcohol mixing carry out the contracting of the first aldehyde amine
Reaction is closed, aldehyde radical magnetic bead is obtained；
(2) solution of p-phenylenediamine is added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxies is then added
Benzene -1,3, the solution of 5- trioxin carry out the second aldimine condensation reaction, obtain the magnetic COF- for being enriched with amides pesticide
TpPa。
2,4,6- trihydroxy benzenes -1,3,5- trioxin, amination magnetic bead and ethyl alcohol mixing are carried out the first aldehyde amine by the present invention
Condensation reaction obtains aldehyde radical magnetic bead.In the present invention, in the first aldimine condensation reaction process amination magnetic bead surfaces amino
With 2, the reaction of the first aldimine condensation occurs for 4,6- trihydroxy benzenes -1,3, the aldehyde radical in 5- trioxin, thus by 2,4,6- trihydroxies
Benzene -1,3,5- trioxin are connected on amination magnetic bead, obtain the aldehyde radical magnetic bead that surface is rich in aldehyde radical.
In the present invention, the partial size of the amination magnetic bead is preferably 0.148~0.720 μm.The present invention is to the amino
The source for changing magnetic bead is not particularly limited, and commercial product or self-control can be directly used；In embodiments of the present invention, referring to existing
Technology " Removal of Acidic Interferences in Multi-pesticides Residue Analysis of
Fruits Using Modified Magnetic Nanoparticles Prior to Determination via
Ultra-HPLC-MS/MS, Microchimica Acta, 2015,182 (15): 2521-2528 " prepares amination magnetic bead.
In the present invention, 2,4,6- trihydroxy benzenes -1,3,5- trioxin and amination in the first aldimine condensation reaction
The mass ratio of magnetic bead is preferably 0.1~0.4:1, and more preferably 0.12~0.3.
In the present invention, the amount ratio of the amination magnetic bead and ethyl alcohol is preferably 1g:200~350mL.
The present invention does not have the order by merging of the amination magnetic bead, 2,4,6- trihydroxy benzene -1,3,5- trioxin and ethyl alcohol
There is particular determination, finely dispersed mixed liquor can be obtained.In embodiments of the present invention preferably by amination magnetic bead and 2,
4,6- trihydroxy benzenes -1,3,5- trioxin are dispersed or dissolved in ethyl alcohol respectively, then again by the dispersion liquid of amination magnetic bead and
2,4,6- trihydroxy benzenes -1,3, the solution mixing of 5- trioxin, above-mentioned order by merging can make amination magnetic bead and 2, and 4,6- tri-
Hydroxy benzenes -1,3,5- trioxin are sufficiently mixed uniformly, obtain uniform reaction product in favor of subsequent；The amination magnetic bead
The amount ratio of amination magnetic bead and ethyl alcohol is preferably 1g:60~80mL, more preferably 1g:65~70mL in dispersion liquid；Described 2,
In the solution of 4,6- trihydroxy benzene -1,3,5- trioxin the concentration of 2,4,6- trihydroxy benzene -1,3,5- trioxin be preferably 0.8~
1.5mg/mL.The present invention is not particularly limited the mode of the dispersion and dissolution, can obtain uniform dispersion liquid and solution
, in embodiments of the present invention, the mode of the dispersion and dissolution is preferably the mode of ultrasound.In the embodiment of the present invention, institute
The hybrid mode preferably stirring for stating the dispersion liquid of amination magnetic bead and the solution of 2,4,6- trihydroxy benzene -1,3,5- trioxin is mixed
It closes.
In the present invention, the temperature of the first aldimine condensation reaction is preferably 40~55 DEG C, and more preferably 45~50 DEG C；
The time of the first aldimine condensation reaction is preferably 1~2h.
After the reaction was completed, it is also preferable to include Magnetic Isolations and washing by the present invention for first aldimine condensation.
First aldimine condensation is preferably reacted gained reaction solution and is cooled to room temperature by the present invention, then carries out Magnetic Isolation
And washing.The present invention is not particularly limited the rate of the cooling, and room temperature is cooling.
In the present invention, the Magnetic Isolation preferably by additional magnet the separating obtained aldehyde radical magnetic bead of mode.
In the present invention, the washing solvent for use is preferably ethyl alcohol；The mode of the washing is preferably washing by soaking, institute
It states washing process and is preferably aided with ultrasound；The time washed every time is preferably 3~7min；The number of the washing is preferably 3~5
It is secondary；The dosage of washing solvent for use is preferably 100~200mL/1g amination magnetic bead every time.
After obtaining aldehyde radical magnetic bead, the solution of p-phenylenediamine is added to the dispersion liquid of the aldehyde radical magnetic bead present invention,
Then 2,4,6- trihydroxy benzenes -1,3 are added, the solution of 5- trioxin carries out the second aldimine condensation reaction, obtains for being enriched with acyl
The magnetic COF-TpPa of amine pesticide.In the present invention, the solution of p-phenylenediamine is added to the dispersion of the aldehyde radical magnetic bead
Liquid, p-phenylenediamine occur aldimine condensation with the aldehyde radical of aldehyde radical magnetic bead surfaces and react, and p-phenylenediamine is grafted on aldehyde radical magnetic bead
Surface makes magnetic bead surfaces rich in amino, 2,4,6- trihydroxy benzenes -1,3 is then added, the solution of 5- trioxin is more conducive to
It reacts and is carried out to the direction for generating COF-TpPa.
In the present invention, the solution and 2 of the dispersion liquid of the aldehyde radical magnetic bead, p-phenylenediamine, 4,6- trihydroxy benzenes -1,3,
The solution of 5- trioxin is preferably prepared by the way of ultrasound.
In the present invention, the dispersion liquid of aldehyde radical magnetic bead in second aldimine condensation reaction, the solution of p-phenylenediamine and
2,4,6- trihydroxy benzenes -1,3, the solvent in the solution of 5- trioxin are preferably the mixed liquor of Isosorbide-5-Nitrae-dioxane and trimethylbenzene,
The volume ratio of the 1,4- dioxane and trimethylbenzene is preferably 1:0.2~4.
In the present invention, the dosage of solvent and the amount ratio of amination magnetic bead are preferred in the dispersion liquid of the aldehyde radical magnetic bead
For 60~85mL:1g.
In the present invention, the concentration of the solution of the p-phenylenediamine is preferably 0.002~0.004g/mL.
In the present invention, described 2,4,6- trihydroxy benzenes -1,3, the concentration of the solution of 5- trioxin is preferably 0.0015~
0.003g/mL。
In the present invention, the amination magnetic bead reacted with the second aldimine condensation in the mass ratio of p-phenylenediamine be preferably 1:
0.15~0.35, more preferably 1:0.2~0.3.
In the present invention, the amination magnetic bead reacted with the second aldimine condensation in 2,4,6- trihydroxy benzenes -1,3,5- tri-
The mass ratio of formaldehyde is preferably 1:0.25~0.4.
In the present invention, the solution of the p-phenylenediamine is preferably slowly added into the dispersion liquid of the aldehyde radical magnetic bead,
It is then slowly added into the solution of 2,4,6- trihydroxy benzene -1,3,5- trioxin.In the present invention, slowly charging is conducive to further
Reaction is promoted to carry out to the direction for generating COF-TpPa.
The pressure that the present invention reacts second aldimine condensation is not particularly limited, using condition of normal pressure.
In the present invention, the temperature of the second aldimine condensation reaction is preferably 15~35 DEG C；Second aldimine condensation
The time of reaction is preferably 1~4d；The time of the second aldimine condensation reaction is preferably from 2,4,6- trihydroxy benzene -1,3,5- three
The solution of formaldehyde, which is added, completes Shi Jiqi.
After the reaction was completed, it is also preferable to include Magnetic Isolations and washing by the present invention for second aldimine condensation.In the present invention, described
Washing solvent for use is preferably ethyl alcohol；The mode of the washing is preferably washing by soaking, and the washing process is preferably aided with ultrasound；
The time washed every time is preferably 3~7min；The number of the washing is preferably 3~5 times；The dosage of washing solvent for use every time
Preferably 80~300mL/1g amination magnetic bead.
In the present invention, stirring shape is preferably maintained in the first aldimine condensation reaction and the second aldimine condensation reaction process
State.
The present invention also provides the magnetic for being used to be enriched with amides pesticide that the preparation method described in above-mentioned technical proposal obtains
Property COF-TpPa, partial size be 0.33~0.73 μm.
2,4,6- trihydroxy benzene -1,3,5- three in magnetic COF-TpPa provided by the present invention for being enriched with amides pesticide
It is keyed between formaldehyde and amination magnetic bead by imines, p-phenylenediamine and 2,4,6- trihydroxy benzenes -1,3, between 5- trioxin
It is keyed also by imines, will not occur in the case where water and common organic solvent such as acetonitrile, methanol and a small amount of acid addition
Structure change illustrates that magnetism COF-TpPa provided by the invention has excellent stability in water and organic solvent, makes it
The adsorption process being suitable in liquid medium.
The present invention also provides the magnetic COF-TpPa conducts for being used to be enriched with amides pesticide described in above-mentioned technical proposal
The application of amides pesticide adsorbent；In the present invention, the amides pesticide be preferably in Prochloraz and Tolfenpyrad extremely
Few one kind.
The present invention is not particularly limited the detailed directions of the pesticide adsorbent, using the use of conventional pesticide adsorbent
Method.
Below with reference to embodiment to a kind of magnetic COF-TpPa for being enriched with amides pesticide provided by the invention and its
Preparation method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
By 2,4,6- trihydroxy benzene -1,3 of 0.05g, 5- trioxin is mixed with 50mL ethyl alcohol, and ultrasound uniformly, obtains 2,4,6-
The solution of trihydroxy benzene -1,3,5- trioxin；By 0.3g amination magnetic bead (partial size is 0.148~0.720 μm) and 20mL ethyl alcohol
Mixing, ultrasound uniformly, obtain the dispersion liquid of amination magnetic bead；By the solution and ammonia of 2,4,6- trihydroxy benzene -1,3,5- trioxin
The dispersion liquid of base magnetic bead mixes, in 40 DEG C of reaction 1h；After reaction, it is down to room temperature to temperature, passes through the side of additional magnet
Formula isolates aldehyde radical magnetic bead, then uses ethyl alcohol washing by soaking 3 times (40~50mL every time), and immersion while is aided with ultrasound, washes
Liquid becomes clarification, obtains aldehyde radical magnetic bead；
By the aldehyde radical magnetic bead and 25mL mixed solvent, (1,4- dioxane and trimethylbenzene are the ratio of 1:1 with volume ratio
Example is mixed to get) mixing, ultrasound is uniform, obtains the dispersion liquid of aldehyde radical magnetic bead；By 0.07g p-phenylenediamine and 25mL mixed solvent
(Isosorbide-5-Nitrae-dioxane and trimethylbenzene are mixed to get with volume ratio for the ratio of 1:1) mixing, ultrasound uniformly, obtain p-phenylenediamine
Solution；By the 2,4,6- trihydroxy benzene -1,3,5- trioxin of 0.1g and 50mL mixed solvent (1,4- dioxane and trimethylbenzene with
Volume ratio is that the ratio of 1:1 is mixed to get) mixing, ultrasound uniformly, obtains 2,4,6- trihydroxy benzenes -1,3,5- trioxin it is molten
Liquid；The solution of p-phenylenediamine is slowly added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxies are then slowly added into
Benzene -1,3, the solution of 5- trioxin are stirred to react 3d at 25 DEG C；After the reaction was completed, it is isolated by way of additional magnet
Magnetic COF-TpPa outwells reaction solution, then uses ethyl alcohol washing by soaking 3 times (each 100mL), and immersion while is aided with ultrasound,
Final washing lotion becomes clarification, obtains the magnetic COF-TpPa for being enriched with amides pesticide.
It is characterized using scanning electron microscope for being enriched with the magnetic COF-TpPa of amides pesticide obtained by the present embodiment, as a result as schemed
Shown in 1.The partial size for being measured the magnetic COF-TpPa obtained by the present embodiment for being enriched with amides pesticide is 0.330~0.730 μ
M, it is bigger than the partial size of amination magnetic bead, illustrate to be grafted other monomers in amination magnetic bead surfaces.
It is characterized for being enriched with the magnetic COF-TpPa of amides pesticide obtained by the present embodiment, as a result such as using infrared spectrogram
Shown in Fig. 2.1577cm in figure-1、1242cm-1、561cm-1There is the feature spectral peak of C=C, C-N and Fe-O key, a side respectively in place
Face illustrates the formation of imine linkage, on the other hand also illustrates in magnetic Fe3O4The surface of microballoon forms COF-TpPa.
Embodiment 2
By 2,4,6- trihydroxy benzene -1,3 of 0.05g, 5- trioxin is mixed with 60mL ethyl alcohol, and ultrasound uniformly, obtains 2,4,6-
The solution of trihydroxy benzene -1,3,5- trioxin；By 0.4g amination magnetic bead (partial size is 0.148~0.720 μm) and 25mL ethyl alcohol
Mixing, ultrasound uniformly, obtain the dispersion liquid of amination magnetic bead；By the solution and ammonia of 2,4,6- trihydroxy benzene -1,3,5- trioxin
The dispersion liquid of base magnetic bead mixes, in 50 DEG C of reaction 1h；After reaction, it is down to room temperature to temperature, passes through the side of additional magnet
Formula isolates aldehyde radical magnetic bead, then uses ethyl alcohol washing by soaking 3 times (each 50mL), and immersion while is aided with ultrasound, and washing lotion becomes
Clarification, obtains aldehyde radical magnetic bead；
By the aldehyde radical magnetic bead and 25mL mixed solvent, (1,4- dioxane and trimethylbenzene are the ratio of 1:1 with volume ratio
Example is mixed to get) mixing, ultrasound is uniform, obtains the dispersion liquid of aldehyde radical magnetic bead；By 0.09g p-phenylenediamine and 30mL mixed solvent
(Isosorbide-5-Nitrae-dioxane and trimethylbenzene are mixed to get with volume ratio for the ratio of 1:1) mixing, ultrasound uniformly, obtain p-phenylenediamine
Solution；By the 2,4,6- trihydroxy benzene -1,3,5- trioxin of 0.12g and 60mL mixed solvent (1,4- dioxane and trimethylbenzene
Be mixed to get with volume ratio for the ratio of 1:1) mixing, ultrasound uniformly, obtains 2,4,6- trihydroxy benzenes -1,3,5- trioxin it is molten
Liquid；The solution of p-phenylenediamine is slowly added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxies are then slowly added into
Benzene -1,3, the solution of 5- trioxin are stirred to react 3d at 25 DEG C；After the reaction was completed, it is isolated by way of additional magnet
Magnetic COF-TpPa outwells reaction solution, then uses ethyl alcohol washing by soaking 3 times (each 80mL), and immersion while is aided with ultrasound, most
Whole washing lotion becomes clarification, obtains the magnetic COF-TpPa for being enriched with amides pesticide.
Partial size through being measured the magnetic COF-TpPa obtained by the present embodiment for being enriched with amides pesticide is 0.330~
It is 0.630 μm, bigger than the partial size of amination magnetic bead, illustrate to be grafted other monomers in amination magnetic bead surfaces.
Embodiment 3
By 2,4,6- trihydroxy benzene -1,3 of 0.1g, 5- trioxin is mixed with 80mL ethyl alcohol, and ultrasound uniformly, obtains 2,4,6-
The solution of trihydroxy benzene -1,3,5- trioxin；By 0.3g amination magnetic bead (partial size is 0.148~0.720 μm) and 20mL ethyl alcohol
Mixing, ultrasound uniformly, obtain the dispersion liquid of amination magnetic bead；By the solution and ammonia of 2,4,6- trihydroxy benzene -1,3,5- trioxin
The dispersion liquid of base magnetic bead mixes, in 50 DEG C of reaction 1h；After reaction, it is down to room temperature to temperature, passes through the side of additional magnet
Formula isolates aldehyde radical magnetic bead, then uses ethyl alcohol washing by soaking 3 times (each 30mL), and immersion while is aided with ultrasound, and washing lotion becomes
Clarification, obtains aldehyde radical magnetic bead；
By the aldehyde radical magnetic bead and 20mL mixed solvent, (1,4- dioxane and trimethylbenzene are the ratio of 1:1 with volume ratio
Example is mixed to get) mixing, ultrasound is uniform, obtains the dispersion liquid of aldehyde radical magnetic bead；By 0.07g p-phenylenediamine and 30mL mixed solvent
(Isosorbide-5-Nitrae-dioxane and trimethylbenzene are mixed to get with volume ratio for the ratio of 1:1) mixing, ultrasound uniformly, obtain p-phenylenediamine
Solution；By the 2,4,6- trihydroxy benzene -1,3,5- trioxin of 0.09g and 55mL mixed solvent (1,4- dioxane and trimethylbenzene
Be mixed to get with volume ratio for the ratio of 1:1) mixing, ultrasound uniformly, obtains 2,4,6- trihydroxy benzenes -1,3,5- trioxin it is molten
Liquid；The solution of p-phenylenediamine is slowly added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxies are then slowly added into
Benzene -1,3, the solution of 5- trioxin are stirred to react 3d at 25 DEG C；After the reaction was completed, it is isolated by way of additional magnet
Magnetic COF-TpPa outwells reaction solution, then uses ethyl alcohol washing by soaking 3 times (each 80mL), and immersion while is aided with ultrasound, most
Whole washing lotion becomes clarification, obtains the magnetic COF-TpPa for being enriched with amides pesticide.
Partial size through being measured the magnetic COF-TpPa obtained by the present embodiment for being enriched with amides pesticide is 0.430~
It is 0.730 μm, bigger than the partial size of amination magnetic bead, illustrate to be grafted other monomers in amination magnetic bead surfaces.
Application examples 1
It is detected obtained by embodiment 1 with the following method for being enriched with the magnetic COF-TpPa of amides pesticide to amides agriculture
The absorption property of medicine:
(1) standard configuration pesticide aqueous solution is mixed using the pesticide that concentration is 5ppm, the concentration of various pesticides in pesticide aqueous solution
It is 50ppb；
(2) it measures above-mentioned pesticide aqueous solution 5mL to be put into 10mL centrifuge tube, by 1 gained magnetism COF- of 30mg embodiment
TpPa is put into centrifuge tube, and vortex 10min seethes material sufficiently in centrifuge tube to adsorb pesticide；
(3) on the side wall that magnetic COF-TpPa is fixed on centrifuge tube by way of additional magnet, supernatant is then taken
1mL crosses film, enters sample introduction bottle；
(4) remaining supernatant is discarded, 5mL acetonitrile, ultrasound elution 5min is added in centrifuge tube in reserved materials；
(5) on the side wall that material is fixed on centrifuge tube by way of additional magnet, supernatant acetonitrile solution 1mL is then taken
Film is crossed, sample introduction bottle is entered；
(6) the pesticide water solution control and the control of pesticide acetonitrile solution that the concentration that each pesticide is respectively set is 50ppb, respectively take
1mL crosses film and enters sample introduction bottle；
(7) it is tested and analyzed using LC-MS/MS.
By data preparation, calculates remaining pesticide percentage composition (being denoted as " unadsorbed pesticide volume ") in pesticide aqueous solution and inhale
The percentage composition of the pesticide under magnetic COF-TpPa elution after attached pesticide is (to account for the percentage composition of pesticide acetonitrile solution control
Meter is denoted as " elution pesticide volume "), the results are shown in Table 1:
For being enriched with adsorptivity of the magnetic COF-TpPa to 2 kinds of amides pesticides of amides pesticide obtained by 1 embodiment 1 of table
It can result
As can be seen from the data in table 1, provided by the present invention for being enriched with the magnetic COF-TpPa of amides pesticide to Prochloraz
Have excellent absorption property with Tolfenpyrad, adsorption rate (i.e. the unadsorbed pesticide volume of 1-) 98% or more, meanwhile, adsorb agriculture
Magnetic COF-TpPa after medicine is eluted, and elution pesticide volume 85% or more, approaches the theoretical adsorption capacity of magnetism COF-TpPa,
Illustrate that the pesticide on magnetic COF-TpPa is easy to be washed away, the magnetic COF-TpPa recovery extent after elution is higher, repeats
It uses.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. it is a kind of for being enriched with the preparation method of the magnetic COF-TpPa of amides pesticide, include the following steps:
(1) by 2,4,6- trihydroxy benzenes -1,3, it is anti-to carry out the first aldimine condensation for 5- trioxin, amination magnetic bead and ethyl alcohol mixing
It answers, obtains aldehyde radical magnetic bead；
(2) solution of p-phenylenediamine is added to the dispersion liquid of the aldehyde radical magnetic bead, 2,4,6- trihydroxy benzene -1 is then added,
The solution of 3,5- trioxins carries out the second aldimine condensation reaction, obtains the magnetic COF-TpPa for being enriched with amides pesticide.
2. preparation method according to claim 1, which is characterized in that 2,4,6- trihydroxy benzenes -1,3 in the step (1),
The mass ratio of 5- trioxin and amination magnetic bead is 0.1~0.4:1.
3. preparation method according to claim 1 or 2, which is characterized in that the first aldimine condensation reacts in the step (1)
Temperature be 40~55 DEG C, the time be 1~2h.
4. preparation method according to claim 1, which is characterized in that the dispersion liquid of aldehyde radical magnetic bead in the step (2),
Solvent in the solution of p-phenylenediamine and the solution of 2,4,6- trihydroxy benzene -1,3,5- trioxin is 1,4- dioxane and front three
The volume ratio of the mixed liquor of benzene, the Isosorbide-5-Nitrae-dioxane and trimethylbenzene is 1:0.2~4.
5. preparation method according to claim 1, which is characterized in that amination magnetic bead and step in the step (1)
(2) p-phenylenediamine in, 2,4,6- trihydroxy benzene -1,3,5- trioxin mass ratio be 1:0.15~0.35:0.25~0.4.
6. according to claim 1 with 4~5 described in any item preparation methods, which is characterized in that the second aldehyde in the step (2)
The temperature of amine condensation reaction is 15~35 DEG C, and the time is 1~4d.
7. preparation method according to claim 1, which is characterized in that the first aldimine condensation reaction in the step (1)
It after the reaction was completed with the second aldimine condensation in step (2), independently further include Magnetic Isolation and washing.
8. the magnetic COF-TpPa for being used to be enriched with amides pesticide that the described in any item preparation methods of claim 1~7 obtain,
Its partial size is 0.33~0.73 μm.
9. according to any one of claims 8 for being enriched with magnetic COF-TpPa the answering as amides pesticide adsorbent of amides pesticide
With.
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