CN115181248A - Porous organic polymer with quaternary ammonium salt structure and preparation method and application thereof - Google Patents

Porous organic polymer with quaternary ammonium salt structure and preparation method and application thereof Download PDF

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CN115181248A
CN115181248A CN202210911717.6A CN202210911717A CN115181248A CN 115181248 A CN115181248 A CN 115181248A CN 202210911717 A CN202210911717 A CN 202210911717A CN 115181248 A CN115181248 A CN 115181248A
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organic polymer
porous organic
pbtp
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amine
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谢冠群
王瑞
汤甲
李华登
王小霞
田俊
郑轲
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Dongguan University of Technology
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Abstract

The invention discloses a porous organic polymer with a quaternary ammonium salt structure, a preparation method and application thereof. The porous organic polymer has simpler synthesis steps and high catalytic efficiency, and is an ideal and stable catalyst. The catalyst prepared by the method is prepared by Friedel-crafts alkylation and quaternization, and has a basic group so as to facilitate better adsorption and fixation of CO2 and improve the yield of the reaction.

Description

Porous organic polymer with quaternary ammonium salt structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of synthesis of cyclic carbonate, in particular to a porous organic polymer with a quaternary ammonium salt structure and a preparation method and application thereof.
Background
With the rapid development of the industry, CO is caused 2 The excessive discharge brings about not only the development of economy but also the increasingly severe greenhouse effect. CO2 2 The excessive emission of (b) may affect the aspects of human living life, but as a safe and cheap C1 resource, human should be more responsive to CO 2 The efficient utilization of the CO is concerned, so that the waste can be changed into valuable, wherein the atom utilization rate of the cycloaddition reaction path is as high as 100 percent, namely the CO is treated 2 The catalyst and epoxide are catalytically converted into cyclic carbonate with high added value, so that the development of a clean, safe and efficient catalytic synthesis system is particularly important.
There have been many reports on CO 2 The invention discloses a method for synthesizing cyclic carbonate ester by solvent-free catalysis, which is characterized in that organic solvent is not needed in the chemical method, and the catalyst provided by the invention has high catalytic activity, high chemical selectivity, high conversion speed, mild reaction conditions, low cost and easiness in preparation, but coordination of a metal complex is needed. The introduction of the metal complex not only causes secondary pollution to the environment, but also increases the reaction cost. Wherein CN109382128A discloses a catalyst for catalyzing CO 2 The catalyst for synthesizing cyclic carbonate is characterized by that it can make CO react under the condition of normal pressure and no solvent 2 The epoxide is converted to a cyclic carbonate. However, the catalyst system needs to additionally add the co-catalyst TBAB, the co-catalyst increases the cost and is difficult to recover, and secondary pollution to the environment is caused, but the co-catalyst TBAB is not usedIn addition, organic solvent is needed to improve the catalytic effect. The CN103319451B discloses a method for synthesizing cyclic carbonate without a cocatalyst and a solvent, the catalyst has high catalytic efficiency, the yield can reach 99 percent, the reaction time is short, but the catalyst provided by the invention can reach a good catalytic effect only when the pressure is as high as 5 MPa.
The catalytic effect of the metal-free, solvent-free and promoter-free reaction can achieve higher catalytic efficiency under high pressure, but the harshness of the reaction conditions and the safety, easy operation and control of the reaction device are considered. The search for a green route to the synthesis of cyclic carbonates under atmospheric conditions without solvent, metal and promoter is not exhaustive.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a porous organic polymer with a quaternary ammonium salt structure, a preparation method and application thereof, and a novel method for synthesizing a catalyst by amine post-modification of a porous organic polymer prepolymer is explored.
In order to achieve the purpose, the invention adopts the technical scheme that a porous organic polymer with a quaternary ammonium salt structure is obtained by reacting a compound with a benzyl bromide structure on a benzene ring as a monomer with anhydrous ferric trichloride and then modifying the porous organic polymer precursor through amines.
In an embodiment of the present invention, the compound having a benzyl bromide structure on the benzene ring is any one or a mixture of two or more of 4,4' -bis (bromomethyl) biphenyl, benzyl bromide, 1,3,5-tris (bromomethyl) benzene, 1,3,5-tris (bromomethyl) benzene, and 1,2-bis (bromomethyl) benzene.
In one embodiment of the invention, the amine is N, N, N ', N' -tetramethylethylenediamine, N, N-diisopropylethylamine, triethanolamine, 1,4,7-trimethyl-1,4,7-triazacyclononane, tetramethylpropylenediamine, pentamethyldiethylenetriamine, triethylamine, triethylenediamine, N, N-dipropyl-1-propylamine, N, N-dimethylaniline, N, N, N ', N' -tetramethyl-1,6-hexanediamine, tris [2- (dimethylamino) ethyl ] amine, or a mixture of two or more thereof.
The preparation method of the porous organic polymer with the quaternary ammonium salt structure comprises the following steps:
preparation of a prepolymer: taking a compound with a benzyl bromide structure on a benzene ring as a substrate monomer, dissolving the compound in a three-necked flask filled with 5-50 ml of solvent according to the proportion of 1-4 mmol;
amine post-modification: and sealing and mixing the obtained prepolymer, amine and solvent in a reaction tube according to a certain proportion, then reacting for 12-72 h at 60-120 ℃, and treating after the reaction is finished to obtain the porous organic polymer PBTP- (x) -R, wherein R represents grafted amine.
After the reaction is finished, cooling the system to room temperature, centrifuging, carrying out suction filtration treatment, and drying in vacuum to obtain a gray-brown solid, namely a porous organic polymer named PBTP- (x), wherein x represents the proportion of a substrate monomer 4,4' -bis (bromomethyl) biphenyl and 1,3,5-tris (bromomethyl) benzene, and the color of the solid catalyst is deepened along with the increase of the proportion x.
After the reaction is finished, a tan solid, namely the porous organic polymer, is obtained through washing and drying, and is named as PBTP- (x) -R, wherein R represents amine, and the color of the solid catalyst is slightly changed due to the difference of the amine R.
In one embodiment of the present invention, the solvent used in the preparation of the prepolymer may be any one of toluene, tetrahydrofuran, ethyl acetate, dichloroethane, bromoethane, and acetonitrile, or a mixture of two or more thereof.
In an embodiment of the present invention, the solvent in the amine post-modification is a polar solvent.
In an embodiment of the present invention, the polar solvent is any one of dichloroethane, tetrahydrofuran, toluene, and ethyl acetate, or a mixture of two or more thereof.
In one embodiment of the present invention, the reaction conditions in the preparation of the prepolymer are: fully reacting for 0.5 to 3 hours at the temperature of between 45 and 80 ℃.
In one embodiment of the present invention, the dosage ratio of the porous organic polymer prepolymer, the amine and the solvent is 1:1-5:5-1.
The porous organic polymer with the quaternary ammonium salt structure is used for catalyzing CO 2 And converting into cyclic carbonate.
In one embodiment of the present invention, the porous organic polymer with a quaternary ammonium salt structure is used as a catalyst, carbon dioxide and epoxide are used as reaction substrates, and the reaction is performed under the conditions of a reaction pressure of 0.1MPa and a temperature of 60 to 100 ℃ to obtain cyclic carbonate, wherein the reaction formula is as follows, wherein R is tertiary amine:
Figure BDA0003770814150000031
the invention finally provides a method for catalyzing epoxide and CO by using catalyst PBTP- (x) -R 2 The reaction for converting into cyclic carbonate is specifically: weighing (20-100) mg of catalyst, putting the catalyst into a reaction tube, adding (1-10) mmol of epoxy substrate, putting the epoxy substrate into a magnetic rotor, adding (0-2) ml of DMF solvent into an injector, vacuumizing, and pricking CO 2 A balloon. Reacting in an oil bath kettle at the constant temperature of 60-100 ℃ for 8-24 h. After the reaction is finished, the conversion rate is measured by processing and analyzing by an instrument GC-MS.
In an embodiment of the present invention, the epoxide is one or a mixture of two or more of epichlorohydrin, epibromohydrin, tert-butyl glycidyl ether, n-butyl glycidyl ether, styrene oxide, 1,2-epoxyhexane, oxypropylphenyl ether, 1,2-epoxy-5-hexene, allyl glycidyl ether, 1,2-epoxybutane, and cyclohexene oxide.
In one embodiment of the present invention, the dosage ratio of the porous organic polymer with quaternary ammonium salt structure to the epoxide is 1-2.
In one embodiment of the present invention, CO is reacted at a pressure of 0.1MPa 2 Constant temperature 80 ℃,1ml of DMF solvent, 40mg of catalyst,Under the condition of time of 8h, the corresponding cyclic carbonate is prepared by cycloaddition reaction. The catalyst used therein is a product obtained by Friedel-crafts alkylation and quaternization- -a porous organic polymer.
The technical scheme has the following beneficial effects:
the catalyst prepared by the method of the invention is prepared by Friedel-crafts alkylation and quaternization, and the catalyst has a basic group so as to facilitate CO treatment 2 Better adsorption fixation to improve the yield of the reaction. The synthesis steps are simple, the catalytic efficiency is high, and the catalyst is an ideal and stable catalyst. When the amount of the catalyst was increased to 40mg, the catalytic reaction yield was significantly improved by simply extending the reaction time from 8 hours to 24 hours. From the above description, it can be seen that the method of the present invention has great application potential and great value.
Drawings
FIG. 1 is a schematic diagram of a synthetic route for a porous organic polymer according to an embodiment of the present invention;
FIG. 2 is a general reaction scheme of a carbon dioxide cycloaddition reaction according to an embodiment of the present invention;
FIG. 3 is an NMR of a chlorocyclic carbonate product of an epichlorohydrin cycloaddition reaction in one embodiment of the present invention;
FIG. 4 is an NMR of a brominated cyclic carbonate product of a cycloaddition reaction of propylene oxide bromide in one embodiment of the present invention;
FIG. 5 is a GC-MS spectrum in example 1 of the present invention;
FIG. 6 is a GC-MS spectrum of the product cyclic carbonate in an example of the present invention;
FIG. 7 is a GC-MS spectrum of the substrate epichlorohydrin in one example of the invention;
FIG. 8 is a GC-MS spectrum of an internal standard 1,3,5-trimethoxybenzene in one embodiment of the present invention.
FIG. 9 is a GC-MS spectrum of DMF as a solvent in one embodiment of the present invention;
Detailed Description
The invention will now be further described with reference to the following examples and figures 1 to 9.
Example 1
In the embodiment, the synthesis method of the catalyst PBTP- (X) -R is selected, the catalyst with different pore diameters and different quaternary ammonium salt structures is obtained by adjusting the proportion X of the synthesis monomers and carrying out post-modification on different tertiary amine R, and the catalyst is prepared according to the corresponding raw material dosage.
1) The synthesis method of PBTP- (1:4) comprises the following steps: 4,4' -bis (bromomethyl) biphenyl (0.3 mmol, 0.102g) and 1,3,5-tris (bromomethyl) benzene (1.2 mmol, 0.42828g) were added to 100ml three-necked bottles, respectively, 1,2-dichloroethane (8.5 ml) was injected with a syringe, mixed until completely dissolved, and the three-necked bottles were fixed on a mechanical stirring apparatus. Under the protection of nitrogen, weighed anhydrous ferric chloride (1.5mmol, 0.243315g) is added into a three-necked flask and stirred uniformly. Mechanically stirring at 45 deg.C and 80 deg.C respectively for 1h under nitrogen protection. After the reaction is finished, cooling the system to room temperature, performing suction filtration and bubble washing by using a methanol solvent, and repeatedly performing the operation for 5 to 6 times to ensure FeC 3 Is completely removed, and the filter cake is then transferred to a culture dish and dried overnight at 60 ℃ under vacuum to obtain PBTP- (1:4).
2) The synthesis method of PBTP- (1:4) -TMPDA comprises the following steps: 80mg of PBTP- (1:4) was weighed and dissolved in a pressure resistant tube equipped with a 1cm diameter magnetic rotor and 5ml of toluene reagent, and 1ml of Tetramethylpropylenediamine (TMPDA) reagent was added to the syringe. Stirring for 72h at 90 ℃ under a sealed condition. After the reaction is finished, cooling the system to room temperature, performing suction filtration and bubble washing by using a methanol solvent, repeatedly operating for 5-6 times to ensure that redundant tertiary amine is completely removed, then transferring a filter cake into a culture dish, and drying overnight at 80 ℃ in vacuum to obtain PBTP- (1:4) -TMPDA. The synthetic route is shown in figure 1.
3) PBTP- (1:4) -TMPDA catalyzes CO 2 Reacting with epoxy chloropropane, wherein the general formula of the catalytic reaction is shown in figure 2:
(1) 20mg of PBTP- (1:4) -TMPDA,5mmol of epichlorohydrin and 1bar of CO 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chloropropylene carbonate with the yield of 21.90 percent.
(2) 40mg of PBTP- (1:4) -TMPDA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chloropropylene carbonic acidThe yield of ester was 59.26%.
(3) 40mg of PBTP- (1:4) -TMPDA,5mmol of epoxy chloropropane, 1ml of DMF,1bar CO2 and constant temperature reaction at 80 ℃ for 24 hours. The yield of chloropropylene carbonate obtained was 70.03%. The GC-MS pictures are shown in FIG. 5, and the NMR spectra are shown in FIG. 3, 1H NMR (400MHz, methanol-d) delta 5.11-5.04 (m, 1H), 4.66-4.55 (m, 1H), 4.39 (dd, J =8.8,5.7Hz, 1H), 3.93 (dd, J =12.4,3.8Hz, 1H), 3.82 (dd, J =12.4,3.8Hz, 1H).
4) PBTP- (1:4) -TMPDA catalyzed CO 2 Reaction with bromopropylene oxide:
(1) 40mg of PBTP- (1:4) -TMPDA,5mmol of epibromohydrin, 1ml of DMF,1bar CO 2 Reacting at the constant temperature of 80 ℃ for 8h to obtain the bromopropylene carbonate with the yield of 58.67%. The nuclear magnetic spectrum is shown in figure 4, 1 H NMR(400MHz，Methanol-d)δ3.52(dd,J＝10.7,4.7Hz,1H)，3.36(dd,J＝10.7,6.8Hz,1H)，3.30–3.19(m,1H)，2.90(dd,J＝4.9,3.9Hz,1H)，2.67(dd,J＝5.0,2.4Hz,1H)。
5) PBTP- (1:4) -TMPDA catalyzed CO 2 Reaction with styrene oxide:
(1) 40mg of PBTP- (1:4) -TMPDA,5mmol of styrene oxide, 1ml of DMF,1bar CO 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the styrene cyclic carbonate with the yield of 23.91 percent.
6) PBTP- (1:4) -TMPDA catalyzed CO 2 Reaction with n-butyl glycidyl ether:
(1) 40mg of PBTP- (1:4) -TMPDA,5mmol of n-butyl glycidyl ether, 1ml of DMF,1bar CO 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the corresponding cyclic carbonate with the yield of 50.38 percent.
Example 2
1) The synthesis method of PBTP- (1:4) comprises the following steps: PBTP- (1:4) was prepared in the same manner as in example 1.
2) The synthesis method of PBTP- (1:4) -PMDETA comprises the following steps: PBTP- (1:4) -PMDETA was prepared in the same manner as in example 1, using Pentamethyldiethylenetriamine (PMDETA) instead of Tetramethylpropanediamine (TMPDA).
3) PBTP- (1:4) -PMDETA catalyzes CO 2 Reaction with epichlorohydrin:
①、40mg PBTP-(1:4)-PMDETA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the cyclic carbonate with the yield of 52.20 percent.
Example 3
1) The synthesis method of PBTP- (1:4) comprises the following steps: PBTP- (1:4) was prepared in the same manner as in example 1.
2) The synthesis method of PBTP- (1:4) -TEMED comprises the following steps: PBTP- (1:4) -TEMED was prepared as in example 1, substituting N, N, N ', N' -Tetramethylethylenediamine (TEMED) for Tetramethylpropylenediamine (TMPDA).
3) PBTP- (1:4) -TEMED catalyzed CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (1:4) -TEMED,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the cyclic carbonate with the yield of 53.43 percent.
Example 4
1) The synthesis method of PBTP- (1:4) comprises the following steps: PBTP- (1:4) was prepared in the same manner as in example 1.
2) The synthesis method of PBTP- (1:4) -TMHDA comprises the following steps: the procedure is as in example 1, N, N, N ', N' -tetramethyl-1,6-hexanediamine (TMHDA) is used in place of Tetramethylpropanediamine (TMPDA), to prepare PBTP- (1:4) -TMHDA.
3) PBTP- (1:4) -TMHDA catalyzes CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (1:4) -TMHDA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the cyclic carbonate with the yield of 45.00 percent.
Example 5
1) The synthesis method of PBTP- (1:4) comprises the following steps: PBTP- (1:4) was prepared in the same manner as in example 1.
2) The synthesis method of PBTP- (1:4) -DIPEA: PBTP- (1:4) -DIPEA was prepared in the same manner as in example 1, except that Tetramethylpropanediamine (TMPDA) was replaced with N, N-Diisopropylethylamine (DIPEA).
3) PBTP- (1:4) -DIPEA catalyzed CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (1:4) -DIPEA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the cyclic carbonate with the yield of 18.36 percent.
Example 6
1) The synthesis method of PBTP- (1:4) comprises the following steps: PBTP- (1:4) was prepared in the same manner as in example 1.
2)PBTP-(1:4)-Me 3 The method for synthesizing TACN comprises the following steps: the procedure is as in example 1, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me) 3 TACN) instead of Tetramethylpropanediamine (TMPDA) to prepare PBTP- (1:4) -Me 3 TACN。
3)PBTP-(1:4)-Me 3 TACN catalyzed CO 2 Reaction with epichlorohydrin:
①、40mg PBTP-(1:4)-Me 3 TACN,5mmol of epichlorohydrin, 1ml of DMF,1bar CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the cyclic carbonate with the yield of 34.17 percent.
Example 7
1) The synthesis method of PBTP- (1:8) comprises the following steps: the method is the same as example 1, and the adopted amounts are respectively as follows: 4,4' -bis (bromomethyl) biphenyl (0.2mmol, 0.068g), 1,3,5-tris (bromomethyl) benzene (1.6mmol, 0.57104g), anhydrous ferric trichloride (1.8mmol, 0.291978g), 1,2-dichloroethane (10 ml). The PBTP- (1:8) is prepared under the same other conditions.
2) The synthesis method of PBTP- (1:8) -TMPDA comprises the following steps: 80mg of PBTP- (1:8) was weighed into a pressure tube containing a 1cm diameter magnetic rotor and 5ml of toluene reagent, and 1ml of Tetramethylpropylenediamine (TMPDA) reagent was added to the syringe. Stirring for 72h at 90 ℃ under a closed condition to obtain the required PBTP- (1:8) -TMPDA.
3) PBTP- (1:8) -TMPDA catalyzes CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (1:8) -TMPDA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chlorocyclic carbonate with the yield of 51.17 percent.
Example 8
1) Method for synthesizing PBTP- (1: the method is the same as example 1, and the adopted amounts are respectively as follows: 4,4' -bis (bromomethyl) biphenyl (0.1mmol, 0.034g), 1,3,5-tris (bromomethyl) benzene (1.6 mmol, 0.57104g), anhydrous ferric chloride (1.7 mmol, 0.27575757g), 1,2-dichloroethane (9.5 ml). The other conditions were not changed, and the desired PBTP- (1.
2) Method for synthesizing PBTP- (1: 80mg of PBTP- (1. Stirring for 72h at 90 ℃ under a closed condition to obtain the PBTP- (1.
3) PBTP- (1 2 Reaction with epichlorohydrin:
(1) 40mg PBTP- (1 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chloro cyclic carbonate with the yield of 50.72 percent.
Example 9
1) The synthesis method of PBTP- (1:2) comprises the following steps: the method is the same as example 1, and the adopted amounts are respectively as follows: 4,4' -bis (bromomethyl) biphenyl (0.5mmol, 0.17g), 1,3,5-tris (bromomethyl) benzene (1mmol, 0.3569g), anhydrous ferric trichloride (1.5mmol, 0.243315g), 1,2-dichloroethane (8.5 ml), with the other conditions unchanged. PBTP- (1:2) is obtained.
2) The synthesis method of PBTP- (1:2) -TMPDA comprises weighing 80mg of PBTP- (1:2) and dissolving in a pressure-resistant tube containing a magnetic rotor with a diameter of 1cm and 5ml of toluene reagent, and adding 1ml of Tetramethylpropanediamine (TMPDA) into the syringe. Stirring for 72h at 90 ℃ under a closed condition to obtain the PBTP- (1:2) -TMPDA.
3) PBTP- (1:2) -TMPDA catalyzed CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (1:2) -TMPDA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 And reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chloro cyclic carbonate with the yield of 60.93 percent.
Example 10
1) The synthesis method of PBTP- (1:1) comprises the following steps: the method is the same as example 1, and the adopted amounts are respectively as follows: 4,4' -bis (bromomethyl) biphenyl (1mmol, 0.34g), 1,3,5-tris (bromomethyl) benzene (1mmol, 0.3569g), anhydrous ferric chloride (2mmol, 0.32442g), 1,2-dichloroethane (11 ml). The PBTP- (1:1) is prepared under the same other conditions.
2) The synthesis method of PBTP- (1:1) -TMPDA comprises weighing 80mg of PBTP- (1:1) and dissolving in a pressure-resistant tube containing a magnetic rotor with a diameter of 1cm and 5ml of toluene reagent, and adding 1ml of Tetramethylpropanediamine (TMPDA) into the syringe. Stirring for 72h at 90 ℃ under a closed condition to obtain the PBTP- (1:1) -TMPDA.
3) PBTP- (1:1) -TMPDA catalyzed CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (1:1) -TMPDA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 Reacting at the constant temperature of 80 ℃ for 8h to obtain the chloro cyclic carbonate with the yield of 56.26%.
Example 11
1) The PTP synthesis method comprises the following steps: the method is the same as example 1, and the adopted amounts are respectively as follows: 1,3,5-tris (bromomethyl) benzene (1mmol, 0.3569g), anhydrous ferric chloride (1mmol, 0.16221g), 1,2-dichloroethane (5.5 ml). PTP was prepared under otherwise unchanged conditions.
2) The PTP-TMPDA was synthesized by weighing 80mg of PTP and dissolving it in a pressure-resistant tube containing a magnetic rotor of 1cm diameter and 5ml of toluene reagent, and adding 1ml of Tetramethylpropylenediamine (TMPDA) into the syringe. Stirring for 72h at 90 ℃ under a closed condition to obtain PTP-TMPDA.
3) PTP-TMPDA catalyzed CO 2 Reaction with epichlorohydrin:
(1) 40mg PTP-TMPDA,5mmol epichlorohydrin, 1ml DMF,1bar CO 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chloro cyclic carbonate with the yield of 34.37 percent.
Example 12
1) The synthesis method of PBTP- (2:1) comprises the following steps: the method is the same as example 1, and the adopted amounts are respectively as follows: 4,4' -bis (bromomethyl) biphenyl (1mmol, 0.34g), 1,3,5-tris (bromomethyl) benzene (0.5mmol, 0.17845g), anhydrous ferric trichloride (1.5mmol, 0.243315g), 1,2-dichloroethane (8.5 ml). The PBTP- (2:1) is prepared under the same other conditions.
2) The synthesis method of PBTP- (2:1) -TMPDA comprises weighing 80mg of PBTP- (2:1) and dissolving in a pressure-resistant tube containing a magnetic rotor with a diameter of 1cm and 5ml of toluene reagent, and adding 1ml of Tetramethylpropanediamine (TMPDA) into the syringe. Stirring for 72h at 90 ℃ under a closed condition to obtain the PBTP- (2:1) -TMPDA.
3) PBTP- (2:1) -TMPDA catalyzed CO 2 Reaction with epichlorohydrin:
(1) 40mg of PBTP- (2:1) -TMPDA,5mmol of epichlorohydrin, 1ml of DMF,1bar of CO 2 Reacting at the constant temperature of 80 ℃ for 8 hours to obtain the chloro cyclic carbonate with the yield of 34.73 percent.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any changes and alterations made without inventive step within the spirit and scope of the claims are intended to fall within the scope of the invention.

Claims (10)

1. The porous organic polymer with the quaternary ammonium salt structure is characterized in that a compound with a benzyl bromide structure on a benzene ring is used as a monomer to react with anhydrous ferric trichloride to obtain a porous organic polymer pre-polymer, and the porous organic polymer pre-polymer is modified by amines to obtain the porous organic polymer.
2. The porous organic polymer according to claim 1, wherein the compound having a benzyl bromide structure on the benzene ring is any one or a mixture of two or more of 4,4' -bis (bromomethyl) biphenyl, benzyl bromide, 1,3,5-tris (bromomethyl) benzene, 1,3,5-tris (bromomethyl) benzene, 1,2-bis (bromomethyl) benzene.
3. The porous organic polymer according to claim 1, wherein the amine is any one or a mixture of two or more of N, N, N ', N' -tetramethylethylenediamine, N, N-diisopropylethylamine, triethanolamine, 1,4,7-trimethyl-1,4,7-triazacyclononane, tetramethylpropylenediamine, pentamethyldiethylenetriamine, triethylamine, triethylenediamine, N, N-dipropyl-1-propylamine, N, N-dimethylaniline and the like, N, N, N ', N' -tetramethyl-1,6-hexanediamine, and tris [2- (dimethylamino) ethyl ] amine.
4. A preparation method of a porous organic polymer with a quaternary ammonium salt structure is characterized by comprising the following steps:
preparation of a prepolymer: taking a compound with a benzyl bromide structure on a benzene ring as a substrate monomer, dissolving the compound in a three-necked flask filled with 5-50 ml of solvent according to the proportion of 1-4 mmol; after the reaction is finished, processing to obtain a porous organic polymer prepolymer PBTP- (x), wherein x represents the proportion of substrate monomers;
amine post-modification: and hermetically mixing the obtained prepolymer, amine and solvent in a reaction tube according to a certain proportion, then reacting for 12-72 h at 60-120 ℃, cooling the system to room temperature after the reaction is finished, centrifuging, carrying out suction filtration treatment on methanol, placing a filter cake in a culture dish, and drying in vacuum to obtain the porous organic polymer PBTP- (x) -R, wherein R represents grafted amine.
5. The process according to claim 1, wherein the solvent used in the preparation of the prepolymer is selected from the group consisting of toluene, tetrahydrofuran, ethyl acetate, dichloroethane, bromoethane, and acetonitrile, and mixtures of two or more thereof.
6. The method according to claim 1, wherein the solvent used in the amine post-modification is a polar solvent.
7. The process according to claim 1, wherein the reaction conditions in the preparation of the prepolymer are: fully reacting for 0.5 to 3 hours at the temperature of between 45 and 80 ℃.
8. The porous organic polymer of claim 1, wherein the porous organic polymer precursor, the amine, and the solvent are added in an amount ratio of 1:1-5:5-1.
9. The method for catalyzing CO by using the porous organic polymer with quaternary ammonium salt structure as claimed in claim 4 2 Use in the conversion to cyclic carbonates.
10. Use according to claim 9, characterised in that the porous organic polymer with quaternary ammonium structure is used as a catalyst, with CO 2 And epoxide (formula I) as reaction substrate, reacting under the conditions of reaction pressure of 0.1MPa and temperature of 60-100 ℃ to obtain corresponding cyclic carbonate (formula II), and reactingThe formula is as follows, wherein R is a tertiary amine:
Figure FDA0003770814140000021
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