CN110078888A - With the porous organic polymer and the preparation method and application thereof of thiocarbamide structure connection - Google Patents
With the porous organic polymer and the preparation method and application thereof of thiocarbamide structure connection Download PDFInfo
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Abstract
The invention discloses the porous organic polymers and the preparation method and application thereof connected with thiocarbamide structure.The preparation method is that compound II, compound III are added in organic solvent under argon gas or nitrogen atmosphere, uniform with ultrasonic disperse at room temperature；After chilled deoxygenation, 60~120 DEG C are heated to, is reacted 24~72 hours；It is then cooled to which room temperature, is added acetone to reaction solution, stirs 1~2 hour, using filter, washing, drying, the porous organic polymer POP-S connected with thiocarbamide structure is obtained.The porous organic polymer catalysis material connected with thiocarbamide structure that the present invention synthesizes, there is more thiocarbamide structure in its unit duct, it is acted on the dihydrogen bond of thiocarbamide in POP-S as catalytic active center, beta-nitrostyrene can be efficiently catalyzed to react with diethyl malonate generation Michael, and there is good solvent tolerance, stability and recoverable.
Description
Technical field
The present invention relates to a kind of porous organic polymer, in particular to a kind of porous organo polysilica with the connection of thiocarbamide structure closes
Object and the preparation method and application thereof；Belong to organic porous polymer material.
Background technique
Porous organic polymer (porous organic polymer, POP) replaces traditional reduction with strong covalent bond
It learns key and constructs the rigid backbone with two dimension or three-dimensional structure, the nanoscale cellular structure with controllable size.POP material tool
Have following advantage: (1) skeleton is mostly that light element is constituted, and rigid backbone density is lower, and specific surface area is high；(2) higher thermostabilization
Property and chemical stability, are able to maintain its characteristic in acid, alkali, a variety of common polarity and nonpolar solvent；(3) structure can be set
Meter property is strong, can be pre-designed skeleton structure, required functional group and the atom that need to be introduced of POP etc. according to synthesis purpose, thus
The structure of controlled material.These advantages of POP material make a kind of its heterogeneous catalysis framework material as great potential, closely
More and more concerns have been obtained over year.
Organic micromolecule catalyst refers to the catalyst being only made of nonmetalloids such as C, N, O, S, is after enzymatic
The widely used catalyst of third class after agent and metal complex catalyst.The organic matter of sulfur-bearing urea structure is that one kind has
The organic micromolecule catalyst of very strong hydrogen bond mobilizing function has raw material cheap and easily-available, and reaction condition is mild, is easy to be tied
Structure modification, the unique advantages such as of less demanding to the reaction condition being catalyzed.Only drawback is that this sulfur-bearing urea structure has
The catalytic efficiency of machine object is not high, and catalyst amount is typically larger than 20% or more be catalyzed substrate molar equivalent, after reaction
It is difficult to separate and reuse.This undoubtedly significantly limits them in the application of catalytic field.
Traditional heterogeneous catalysis such as zeolite etc. is with good stability, and is easily recycled, and answers in industry
Leading position is occupied in.However, the structure modifiability and designability of traditional heterogeneous catalysis are very limited, it is difficult
To meet the requirement of diversified catalyst system, therefore the application range of this kind of heterogeneous catalysis is also limited by very large.
Therefore, the novel of a kind of the characteristics of integrating heterogeneous catalysis and organic micromolecule catalyst and advantage is developed heterogeneous to urge
Agent, for developing green catalysis and realizing that efficient catalytic has important theoretical research value and actual application prospect.
Summary of the invention
It is an object of the present invention to provide a kind of porous organic polymer POP-S and its system with the connection of thiocarbamide structure
Preparation Method, the prepared porous organic polymer POP-S with the connection of thiocarbamide structure is to selected model reaction, i.e. β-nitro
Styrene is reacted with the Michael of diethyl malonate has efficient catalytic efficiency, and catalyst amount can be down to reaction bottom
The 0.04mol% of object beta-nitrostyrene；Also there is good solvent with the porous organic polymer POP-S that thiocarbamide structure connects
Tolerance, thermal stability and recoverable.
It is another object of the present invention to provide the porous organic polymer POP-S connected using thiocarbamide structure as it is non-
The application of phase catalyst.
In the prior art the dosage of thiocarbamide micromolecule catalyst be typically larger than the 20mol% of substrate beta-nitrostyrene with
On.The present invention in POP skeleton by introducing thiocarbamide structure, by urging for the organic micromolecule catalyst with good catalytic
Change active sites with the high-specific surface area of heterogeneous catalysis, high stability, be easily recycled the advantages of combine, with
Preparation is a kind of to be not necessarily to carried metal, and has high catalytic efficiency, is easily isolated and can be recycled the novel heterogeneous of recycling characteristic
Catalyst.It is this kind of high by the Atom economy of the novel heterogeneous catalysis of skeleton of POP, it is not necessarily to carried metal, is had excellent
Recyclable and repeat performance, meet the theory and development trend of Green Chemistry and sustainable development.
The porous organic polymer connected with thiocarbamide structure is made using compound II and compound III as monomer in the present invention
POP-S；Using the dihydrogen bond catalytic action of thiocarbamide contained by POP-S skeleton, it is not necessarily to carried metal, it can efficient catalytic β-nitrobenzene
Ethylene occurs Michael with diethyl malonate and reacts.The structure of porous organic polymer POP-S prepared by the present invention is new
Grain husk has not been reported so far；POP-S is high-efficient to Michael catalytic reaction, the thiocarbamide small molecule of catalyst amount and existing report
Catalyst is compared to significant decrease.Importantly, porous organic polymer POP-S prepared by the present invention is completed in catalysis reaction
Afterwards, it is easy to which recycling and reusing, through being recycled for multiple times after recycling, catalytic capability also has no and is substantially reduced.
The purpose of the present invention is achieved through the following technical solutions:
A kind of porous organic polymer, structural formula are as follows:
Wherein, R1For N or C6H3。
The preparation method of the porous organic polymer: under argon gas or nitrogen atmosphere, by compound II and compound
III is added in organic solvent, uniform with ultrasonic disperse at room temperature；After chilled deoxygenation 2~4 times, it is heated to certain
Reaction temperature, react certain time；It is then cooled to room temperature, is added a large amount of acetone to reaction solution, stirs 1~2 hour, then
It is filtered, washed, dried to get the porous organic polymer POP-S connected with thiocarbamide structure is arrived.
The compound II is three (4- aminophenyl) amine or 1,3,5- tri- (4- aminophenyl) benzene；The compound
III is bitoscanate；The molar ratio of the compound II and compound III are 2: 3~2: 3.5.
To further realize the object of the invention, it is preferable that the organic solvent is mesitylene, N, N- dimethyl formyl
Amine (DMF), ethyl alcohol or Isosorbide-5-Nitrae-dioxane, can also select other organic solvents；The quality of compound II and organic solvent
Volume ratio is 100: 5~100: 20, mass unit mg, volume unit mL.
Preferably, the reaction temperature is 60~120 DEG C, and the certain time is 24~72 hours.
It is reacted with beta-nitrostyrene with the Michael that diethyl malonate occurs for model reaction, by porous organo polysilica
Object POP-S is closed for being catalyzed Michael reaction.
The application of the porous organic polymer with the connection of thiocarbamide structure: by beta-nitrostyrene and malonic acid diethyl
Ester is dissolved in organic solvent, is stirred evenly, and the porous organic polymer POP-S catalyst that alkali is connected with thiocarbamide structure is added, adds
Heat to 25~60 DEG C react 24~48 hours；Then, catalyst is filtered out, solvent is removed in decompression rotation, then is purified with column chromatography, obtains
Product 2- (2- nitro -1- phenylethyl) malonic acid diethyl that beta-nitrostyrene is reacted with the Michael of diethyl malonate
Ester；The molar ratio of beta-nitrostyrene and diethyl malonate is 1: 1~1:5.
The Michael reaction of POP-S catalysis is as shown in reaction equation (1):
Reaction equation (1) is as follows:
Preferably, the organic solvent is mesitylene or toluene；The mass body of beta-nitrostyrene and organic solvent
Product is than being 100: 1~100: 5, mass unit mg, volume unit mL.
Preferably, the molar ratio of the porous organic polymer POP-S catalyst and beta-nitrostyrene is 0.0004: 1
~0.025: 1.
Preferably, the alkali is potassium carbonate, and the molar ratio of the alkali and beta-nitrostyrene is 0.2: 1~1: 1；Institute
State the petrol ether/ethyl acetate mixture that the eluant, eluent that column chromatography uses is volume ratio 20: 1~15: 1.
Porous organic polymer POP-S of the present invention is made by compound II and III reaction, and the synthesis of the POP-S is anti-
It should see reaction equation (2).
Reaction equation (2) is as follows:
The present invention selects beta-nitrostyrene and diethyl malonate for reaction substrate, with beta-nitrostyrene and malonic acid
The Michael reaction of diethylester is model reaction, and the porous organic polymer POP-S connected with thiocarbamide structure is used as the model
The catalyst of reaction.
Relative to existing POPs material, the present invention has the advantages that
(1) present invention has synthesized the porous organic polymer POP-S of a kind of structure novel connected with thiocarbamide structure, list
There is more catalytic center thiocarbamide structure in first duct, just can be used as heterogeneous catalysis without carried metal.
(2) catalysis that Michael is reacted with the porous organic polymer POP-S of thiocarbamide structure connection that the present invention synthesizes
High-efficient, catalyst amount significantly reduces compared with the thiocarbamide micromolecule catalyst of existing report, can efficiently be catalyzed β-nitro
Styrene occurs Michael with diethyl malonate and reacts, and has good solvent tolerance, thermal stability and recyclable benefit
The property used.
(3) present invention successfully combines the catalysis of organic micromolecule catalyst with the skeleton structure of POP material,
It is greatly expanded the application field of porous organic polymer material, according to a kind of novel function having potential application
POP material can be changed.
(4) present invention is with the porous organic polymer POP-S of thiocarbamide structure connection and existing thiocarbamide micromolecule catalyst phase
Than catalyst amount substantially reduces, and efficiency is greatly improved with economy.
Detailed description of the invention
Fig. 1 is that porous organic polymer POP-S obtained by embodiment 1 reacts with it object i.e. compound II and compound
The infrared spectrogram (FT-IR) of III.
Fig. 2 is the solid state nmr spectrogram (Solid-NMR) of porous organic polymer POP-S obtained by embodiment 1.
Fig. 3 is scanning electron microscope (SEM) figure of porous organic polymer POP-S obtained by embodiment 1.
Fig. 4 is the N of porous organic polymer POP-S obtained by embodiment 12Isothermal adsorption and desorption curve.
Fig. 5 is the thermal gravimetric analysis curve (TGA) of porous organic polymer POP-S obtained by embodiment 1.
Fig. 6 is the N of porous organic polymer POP-S obtained by embodiment 22Isothermal adsorption and desorption curve.
Fig. 7 is scanning electron microscope (SEM) figure of porous organic polymer POP-S obtained by embodiment 3.
Fig. 8 is the N of porous organic polymer POP-S obtained by embodiment 32Isothermal adsorption and desorption curve.
Fig. 9 is the N of porous organic polymer POP-S obtained by embodiment 42Isothermal adsorption and desorption curve.
Figure 10-1 is that the porous organic polymer POP-S of embodiment 5 is catalyzed the obtained reaction product 2- of Michael reaction
(2- nitro -1- phenylethyl) diethyl malonate1H NMR spectra.
Figure 10-2 is that the porous organic polymer POP-S of embodiment 5 is catalyzed the obtained reaction product 2- of Michael reaction
(2- nitro -1- phenylethyl) diethyl malonate13C NMR spectra.
Figure 11 is embodiment 8 more circulations catalysis beta-nitrostyrenes of porous organic polymer POP-S and malonic acid two
The yield of the Michael reaction of ethyl ester and the relational graph of cycle-index.
Specific embodiment
For a better understanding of the invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this hair
Bright embodiment is without being limited thereto.
The synthesis of 1 porous organic polymer POP-S of embodiment
By III couples of compound of tri- (4- aminophenyl) amine of 145mg (0.5mmol) compound II and 144mg (0.75mmol)
Benzene diisothiocyanate is dissolved separately in 5mL n,N-Dimethylformamide under argon atmosphere, and compound II solution is added drop-wise to
In compound III solution, ultrasonic disperse 3 minutes, freeze deoxygenation 3 times；After being heated to 60 DEG C, reaction 72 hours, it is cooled to room temperature,
50mL acetone is added, is stirred 1 hour, filtering is successively used methylene chloride, acetone, methanol, water washing, is repeated 3 times, and removes not
The monomer of reaction, obtained solid product are dried in vacuo 24 hours at 80 DEG C, obtain brown solid POP-S216mg (yield
74.7%).
Fig. 1 is that porous organic polymer POP-S made from embodiment 1 reacts with it object i.e. compound II and compound III
Infared spectrum.Compare the infared spectrum figure of these three compounds, it can be seen that compound II is in 3400cm-1And 3340cm-1
N-H flexural vibrations peak and compound III in 2080cm-1N=C=S cumulated double bond vibration peak in porous organic polymer
It disappears substantially in the map of POP-S, shows compound II and compound III is totally consumed；In addition, in the infrared of POP-S
In map, in 1500cm-1The C-N stretching vibration peak and 1238cm of appearance-1C=S stretching vibration peak show gained it is porous organic
The presence of thiocarbamide structure in polymer.The examination of infrared spectrum is red using Bruker Tensor 27FTIR spectrometer
External spectrum instrument, pressing potassium bromide troche sample preparation, porous organic polymer POP-S are dried in advance.
The reaction equation of the present embodiment is as follows:
Fig. 2 is the solid state nmr carbon spectrogram of porous organic polymer POP-S made from embodiment 1.In the spectrogram,
Peak corresponds to the carbon of C=S in thiocarbamide structure at 180ppm, and peak respectively corresponds as to benzene diisothiocyanic acid at 148ppm and 130ppm
The aromatic carbon of ester and three (4- aminophenyl) amine.In conjunction with Fig. 1's as a result, showing in the present embodiment, compound II and compound
Expected reaction has occurred in III, has obtained the porous organic polymer POP-S with expected structure.The test is in Bruker WB
It is carried out on the nuclear magnetic spectrometry of AVANCE II 400MHz.The solid state nmr carbon spectrogram provided by infrared and Fig. 2, association reaction
Principle can prove that prepared POP-S has the structure as shown in reaction equation above, it was demonstrated that manufactured in the present embodiment porous
The structure of organic polymer POP-S.
Fig. 3 is scanning electron microscope (SEM) figure of porous organic polymer POP-S made from embodiment 1.It can be observed from figure
POP-S loose porous layer structure has micron-sized irregular recess hole thereon.Scanning electron microscope used is German Cai
The EV018 of department.
Fig. 4 is the N of porous organic polymer POP-S made from embodiment 12Isothermal adsorption-desorption analysis result.POP-S
Specific surface area with N2Relative pressure is less than 0.1 part in isothermal adsorption-desorption curve, with relative pressure position abscissa, accumulation
Adsorption volume is ordinate, carries out linear fit by BET equation, and gained straight slope is the BET specific surface area of POP-S, is
49m2g-1, it is 9.8nm that NLDFT, which is fitted mean pore size, with mesoporous for main duct size.It is bent obtained by solid circles in Fig. 4
Line is N2Absorption isotherm, hollow circle curve obtained is N2Line is desorbed in isothermal, from adsorption curve reference standard adsorption line
POP-S is II type absorption isotherm, shows wherein to contain meso-hole structure, this is consistent with the analysis result to pore size.Compare table
Areal analysis uses Micromeritics ASAP 2020M surface area and porosity analyzer.
Fig. 5 is the thermal gravimetric analysis curve (TGA) of porous organic polymer POP-S made from embodiment 1.Due to thiourea group
It easily absorbs water, the weightlessness before 50 DEG C is the volatilization of water, and POP-S just has apparent weightlessness at 180 DEG C, and thermal stability is obviously excellent
In general thiourea compound.
The synthesis of 2 porous organic polymer POP-S of embodiment
By III couples of compound of tri- (4- aminophenyl) amine of 145mg (0.5mmol) compound II and 144mg (0.75mmol)
Benzene diisothiocyanate is dissolved separately in 5mL n,N-Dimethylformamide under nitrogen atmosphere, and compound II solution is added drop-wise to
In compound III solution, ultrasonic disperse 3 minutes, freeze deoxygenation 3 times；After being heated to 120 DEG C, reaction 48 hours, it is cooled to room
Temperature adds 50mL acetone, stirs 1 hour, and filtering is successively used methylene chloride, acetone, methanol, water washing, is repeated 3 times, and removes
Unreacted monomer, obtained solid product are dried in vacuo 24 hours at 80 DEG C, obtain brown solid POP-S219mg (yield
75.8%).
The infrared spectrum of porous organic polymer POP-S and solid state nmr spectrogram prepared by the present embodiment respectively with Fig. 1,
Fig. 2 is consistent, and scanning electron microscope (SEM) photograph is similar to Fig. 3, no longer repeats；Its nitrogen adsorption desorption curve as shown in fig. 6, POP-S ratio table
Area is with N2Relative pressure accumulates adsorbent less than 0.1 part with relative pressure position abscissa in isothermal adsorption-desorption curve
Product is ordinate, carries out linear fit by BET equation, it is 31m that gained straight slope, which is the BET specific surface area of POP-S,2g-1,
It is 9.2nm that NLDFT, which is fitted mean pore size,, can by adsorption curve reference standard adsorption line with mesoporous for main duct size
Know that POP-S is II type absorption isotherm, show wherein to contain meso-hole structure, this is consistent with the analysis result to pore size.
The synthesis of 3 porous organic polymer POP-S of embodiment
By III couples of compound of tri- (4- aminophenyl) amine of 145mg (0.5mmol) compound II and 144mg (0.75mmol)
Benzene diisothiocyanate is dissolved separately in 5mL ethyl alcohol under argon atmosphere, and compound II solution is added drop-wise to compound III solution
In, it ultrasonic disperse 3 minutes, freezes deoxygenation 3 times；After being heated to 60 DEG C, reaction 72 hours, it is cooled to room temperature, filters, successively with two
Chloromethanes, acetone, methanol, water washing, are repeated 3 times, and remove unreacted monomer, and obtained solid product is dried in vacuo at 80 DEG C
24 hours, obtain brown particle solid POP-S 232mg (yield 80.3%).
The infrared spectrum of porous organic polymer POP-S and solid state nmr spectrogram prepared by the present embodiment respectively with Fig. 1,
Fig. 2 is consistent, no longer repeats；Its scanning electron microscope (SEM) photograph from figure as shown in fig. 7, can be observed the homogeneous spherical knot of POP-S
Structure.The nitrogen adsorption desorption curve of porous organic polymer POP-S prepared by the present embodiment as shown in figure 8, POP-S specific surface
Product is with N2Relative pressure accumulates adsorption volume less than 0.1 part with relative pressure position abscissa in isothermal adsorption-desorption curve
For ordinate, linear fit is carried out by BET equation, it is 23m that gained straight slope, which is the BET specific surface area of POP-S,2g-1,
It is 7.9nm that NLDFT, which is fitted mean pore size, and the POP-S known to adsorption curve reference standard adsorption line is IV type isothermal adsorption
Line shows wherein to contain meso-hole structure, this is consistent with the analysis result to pore size.
The synthesis of 4 porous organic polymer POP-S of embodiment
By III couples of compound of tri- (4- aminophenyl) amine of 145mg (0.5mmol) compound II and 144mg (0.75mmol)
Benzene diisothiocyanate is dissolved separately in 5mL1 under nitrogen atmosphere, and compound II solution is added drop-wise to chemical combination by 4- dioxane
In object III solution, ultrasonic disperse 3 minutes, freeze deoxygenation 3 times；After being heated to 60 DEG C, reaction 72 hours, it is cooled to room temperature, mistake
Filter successively uses methylene chloride, acetone, methanol, water washing, is repeated 3 times, removes unreacted monomer, obtained solid product is 80
It is dried in vacuo 24 hours at DEG C, obtains brown solid POP-S 254mg (yield 87.9%).
The infrared spectrum of porous organic polymer POP-S and solid state nmr spectrogram prepared by the present embodiment respectively with Fig. 1,
Fig. 2 is consistent, and scanning electron microscope (SEM) photograph is similar to Fig. 7, no longer repeats；Its nitrogen adsorption desorption curve as shown in figure 9, POP-S ratio table
Area is with N2Relative pressure accumulates adsorbent less than 0.1 part with relative pressure position abscissa in isothermal adsorption-desorption curve
Product is ordinate, carries out linear fit by BET equation, it is 43m that gained straight slope, which is the BET specific surface area of POP-S,2g-1。
It is 12.3nm that NLDFT, which is fitted mean pore size, and the POP-S known to adsorption curve reference standard adsorption line is IV type isothermal adsorption
Line, this is consistent with the analysis result to pore size.
The catalytic performance test of 5 porous organic polymer POP-S of embodiment
Beta-nitrostyrene is selected to be reacted with the Michael of diethyl malonate for template reaction, the specific steps are as follows: with
The molal quantity of beta-nitrostyrene is 1, and the diethyl malonate that 2 equivalents are added is dissolved in mesitylene, and the carbon of 0.2 equivalent is added
The POP-S catalyst of sour potassium and 0.08 equivalent reacts 24 hours at 40 DEG C；Then, catalyst is filtered out, solvent is removed in decompression rotation,
Again using volume ratio be 20: 1 petrol ether/ethyl acetate mixture as eluant, eluent, purified with column chromatography to get to the reaction
Product, yield 69.3%.
The Michael of porous organic polymer POP-S catalysis is reacted as shown in reaction equation 1:
Figure 10-1 and Figure 10-2 is respectively the obtained reaction product 2- of the present embodiment 5 (2- nitro-1- phenylethyl) third
Diethyl adipate1H NMR spectra and13C NMR spectra.1H NMR(400MHz,CDCl3)δ:7.32-7.26(m,3H),7.24-
7.23 (m, 2H), 4.93-4.84 (m, 2H), 4.25-4.19 (m, 3H), 4.00 (q, J=4.4Hz, 2H), 3.82 (d, J=6Hz,
1H), 1.26 (t, J=4.8Hz, 3H), 1.04 (t, J=4.8Hz, 3H).13C NMR(400MHz,CDCl3)δ:167.49,
166.84,136.27,128.95,128.36,128.04,77.67,62.16,61.89,55.00,42.89,13.97,13.74。
The catalytic performance test of 6 porous organic polymer POP-S of embodiment
Beta-nitrostyrene is selected to be reacted with the Michael of diethyl malonate for template reaction, the specific steps are as follows: with
The molal quantity of beta-nitrostyrene is 1, and the diethyl malonate that 1.5 equivalents are added is dissolved in mesitylene, and the carbon of 1 equivalent is added
The POP-S catalyst of sour potassium and 0.08 equivalent reacts 48 hours at 60 DEG C；Then, catalyst is filtered out, solvent is removed in decompression rotation,
Again using volume ratio be 20: 1 petrol ether/ethyl acetate mixture as eluant, eluent, purified with column chromatography to get to the reaction
Product, yield 67.1%.
The Michael of porous organic polymer POP-S catalysis is reacted as shown in reaction equation 1.
The influence that 7 different proportion catalyst of embodiment reacts beta-nitrostyrene with the Michael of diethyl malonate
Table 1 is the addition different proportion porous organic polymer POP-S catalysis under reaction condition same as Example 5
The products collection efficiency comparison of Michael reaction.The additive amount of POP-S catalyst from 2.5mol% to 0.04mol%, reaction yield without
Large change, 64% or more, and dosage far below reported thiocarbamide micromolecule catalyst be up to the 20mol% of substrate with
On dosage, this show porous organic polymer POP-S have outstanding catalytic activity.Due to thiourea group can in substrate
The functional groups such as C=O, C=N and N=O form dihydrogen bond effect, reduce the cloud density of electrophilic reagent, activate electrophilic examination
Agent makes it easier to by nucleopilic reagent attack, and reaction is quickly and efficiently carried out.Thiourea group in POP-S skeleton is more,
Dihydrogen bond catalytic effect is strong, along with special cellular structure, large specific surface area, so that POP-S can be high with the dosage of very little
Effect catalysis beta-nitrostyrene occurs Michael with diethyl malonate and reacts.
1. different proportion porous organic polymer POP-S of table is catalyzed Michael reaction
In table 1, the dosage of catalyst and alkali is to calculate basis with the molal quantity of substrate beta-nitrostyrene.
The circulation catalytic performance test of 8 porous organic polymer POP-S of embodiment
Selecting the Michael of beta-nitrostyrene and diethyl malonate reaction is template reaction, is closed to porous organo polysilica
The circulation catalytic capability of object POP-S is tested, and steps are as follows: 75mg (0.5mmol) beta-nitrostyrene and 160mg
(1mmol) diethyl malonate is dissolved in 1mL mesitylene, and 13.8mg (0.1mmol) potassium carbonate and 4.9mg is added
(0.002mmol) POP-S catalyst reacts 24 hours at 40 DEG C；Then, catalyst is filtered out, solvent is removed in decompression rotation, with volume
It is eluant, eluent than the petrol ether/ethyl acetate mixture for 20: 1, is purified with column chromatography to get the product 2- of the reaction is arrived
(2- nitro -1- phenylethyl) diethyl malonate.
The catalyst filtered out successively uses methylene chloride, acetone, methanol, water washing, is repeated 3 times, and removes unreacted substrate,
Much filtrate is dried in vacuo 24 hours at 80 DEG C, the catalyst recycled i.e. porous organic polymer POP-S；By recycling
POP-S is reacted for being catalyzed beta-nitrostyrene with the Michael of diethyl malonate.It so reuses, measurement is porous to be had
The circulation catalytic capability of machine polymer P OP-S.
Figure 11 is the present embodiment using porous organic polymer POP-S as catalyst, repeatedly circulation catalysis beta-nitrostyrene
With the relational graph of the Michael of the diethyl malonate yield reacted and cycle-index.As can be seen from figure 11 that porous organic polymer
In the catalysis of this 5 times circulations, yield is basically unchanged POP-S, can still keep its catalytic efficiency, show it is excellent it is recyclable again
Utilization level.
The solvent tolerance of 9 porous organic polymer POP-S of embodiment is tested
The selection stronger polarity of dissolubility such as organic solvent dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF),
Ethyl alcohol tests the solvent tolerance of porous organic polymer POP-S obtained by embodiment 1, and steps are as follows: 5mg
POP-S is placed in 50mL round-bottomed flask, and one of above-mentioned solvent is added, and is heated to 100 DEG C and is kept for 1 hour.Then filtering
Separation, obtained solid 80 DEG C drying 24 hours in vacuum drying oven.POP-S after drying carries out FT-IR, Solid-NMR respectively
It is tested with SEM, acquired results are compared with corresponding Fig. 1, Fig. 2 and Fig. 3 respectively, have no significant difference.This shows the present invention
The porous organic polymer POP-S with the connection of thiocarbamide structure of preparation has good solvent tolerance.
Embodiments of the present invention are simultaneously not restricted by the embodiments, other any real without departing from spirit of the invention
Made changes, modifications, substitutions, combinations, simplifications under matter and principle, should be equivalent substitute mode, are included in the present invention
Protection scope within.
Claims (10)
1. a kind of porous organic polymer connected with thiocarbamide structure, which is characterized in that its structural formula are as follows:
Wherein, R1For N or C6H3。
2. the preparation method of the porous organic polymer described in claim 1 with the connection of thiocarbamide structure, feature include as follows
Step: under argon gas or nitrogen atmosphere, compound II and compound III is added in organic solvent, used at room temperature
Ultrasonic disperse is uniform；After chilled deoxygenation, 60~120 DEG C are heated to, is reacted 24~72 hours；It is then cooled to room temperature, to anti-
It answers liquid that acetone is added, stirs 1~2 hour, using filter, washing, drying, obtain closing with the porous organo polysilica that thiocarbamide structure connects
Object POP-S；
The compound II is three (4- aminophenyl) amine or 1,3,5- tri- (4- aminophenyl) benzene；
The compound III is bitoscanate；
The molar ratio of the compound II and compound III are 2: 3~2: 3.5.
3. the preparation method of the porous organic polymer according to claim 2 with the connection of thiocarbamide structure, which is characterized in that
The organic solvent is mesitylene, N,N-dimethylformamide (DMF), ethyl alcohol or 1,4- dioxane.
4. the preparation method of the porous organic polymer according to claim 2 with the connection of thiocarbamide structure, which is characterized in that
The mass volume ratio of the compound II and organic solvent are 100: 5~100: 20, mass unit mg, and volume unit is
mL。
5. the preparation method of the porous organic polymer according to claim 2 with the connection of thiocarbamide structure, which is characterized in that
The number of the freezing deoxygenation is 2~4 times.
6. the preparation method of the porous organic polymer according to claim 2 with the connection of thiocarbamide structure, which is characterized in that
The dosage addition of the acetone is 5~10 times of organic solvent volume.
7. it is described in claim 1 using the porous organic polymer that thiocarbamide structure connects as the application of heterogeneous catalysis,
It is characterized in that: beta-nitrostyrene and diethyl malonate is dissolved in organic solvent, stir evenly, potassium carbonate and thiocarbamide is added
The porous organic polymer POP-S catalyst of structure connection is heated to 25~60 DEG C and reacts 24~48 hours；Then, it filters out and urges
Agent, solvent is removed in decompression rotation, then is purified with column chromatography, and the Michael for obtaining beta-nitrostyrene and diethyl malonate is anti-
Product 2- (2- nitro -1- phenylethyl) diethyl malonate answered；The molar ratio of beta-nitrostyrene and diethyl malonate
For 1: 1~1:5.
8. porous organic polymer the answering as heterogeneous catalysis according to claim 7 connected using thiocarbamide structure
With, which is characterized in that the organic solvent be mesitylene, methylene chloride, methanol, n,N-Dimethylformamide (DMF) or
1,4- dioxane；The mass volume ratio of beta-nitrostyrene and organic solvent is 100: 1~100: 5, mass unit mg, body
Product unit is mL.
9. porous organic polymer the answering as heterogeneous catalysis according to claim 7 connected using thiocarbamide structure
With, which is characterized in that the molar ratio of the porous organic polymer POP-S catalyst and beta-nitrostyrene be 0.0004: 1~
0.025∶1。
10. porous organic polymer the answering as heterogeneous catalysis according to claim 7 connected using thiocarbamide structure
With, which is characterized in that the molar ratio of the potassium carbonate and beta-nitrostyrene is 0.2: 1~1: 1；The solvent is equal front three
Benzene or toluene, the eluant, eluent that the column chromatography uses are the petrol ether/ethyl acetate mixture of volume ratio 20: 1~15: 1.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03200748A (en) * | 1989-12-28 | 1991-09-02 | Mitsui Toatsu Chem Inc | Production of alkyldiamines |
| US20070066738A1 (en) * | 2005-09-16 | 2007-03-22 | Gallucci Robert R | Flame retardant polysulfone blends |
| CN102134395A (en) * | 2010-12-22 | 2011-07-27 | 北京航空航天大学 | Modified light flexible polyimide foam material and preparation method thereof |
| CN103360560A (en) * | 2012-03-30 | 2013-10-23 | 株式会社尼德克 | Multi-branched-chain high-refractive-index material and multi-branched-chain high-refractive-index material of organic-inorganic compound |
| CN105602509A (en) * | 2016-01-20 | 2016-05-25 | 上海嘉好胶粘制品有限公司 | Environment-friendly anti-aging automobile inner decorating glue and preparation method thereof |
| CN105669946A (en) * | 2014-11-18 | 2016-06-15 | 合众（佛山）化工有限公司 | Method for preparing polyether modified HMDI waterborne polyurethane curing agent |
| CN107538584A (en) * | 2017-08-31 | 2018-01-05 | 中国林业科学研究院木材工业研究所 | A kind of synthesis of phosphonitrile class reactive flame retardant and its preparation method of fire-retardant wood-based materialses |
-
2019
- 2019-04-04 CN CN201910268843.2A patent/CN110078888B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03200748A (en) * | 1989-12-28 | 1991-09-02 | Mitsui Toatsu Chem Inc | Production of alkyldiamines |
| US20070066738A1 (en) * | 2005-09-16 | 2007-03-22 | Gallucci Robert R | Flame retardant polysulfone blends |
| CN102134395A (en) * | 2010-12-22 | 2011-07-27 | 北京航空航天大学 | Modified light flexible polyimide foam material and preparation method thereof |
| CN103360560A (en) * | 2012-03-30 | 2013-10-23 | 株式会社尼德克 | Multi-branched-chain high-refractive-index material and multi-branched-chain high-refractive-index material of organic-inorganic compound |
| CN105669946A (en) * | 2014-11-18 | 2016-06-15 | 合众（佛山）化工有限公司 | Method for preparing polyether modified HMDI waterborne polyurethane curing agent |
| CN105602509A (en) * | 2016-01-20 | 2016-05-25 | 上海嘉好胶粘制品有限公司 | Environment-friendly anti-aging automobile inner decorating glue and preparation method thereof |
| CN107538584A (en) * | 2017-08-31 | 2018-01-05 | 中国林业科学研究院木材工业研究所 | A kind of synthesis of phosphonitrile class reactive flame retardant and its preparation method of fire-retardant wood-based materialses |
Non-Patent Citations (1)
| Title |
|---|
| 郝桂霞等: ""缩氨基硫脲类受体的合成和表征"", 《江西化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778503A (en) * | 2021-01-25 | 2021-05-11 | 华南理工大学 | Organic porous polymer and preparation method and application thereof |
| CN112778503B (en) * | 2021-01-25 | 2022-07-26 | 华南理工大学 | Organic porous polymer and preparation method and application thereof |
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