CN116253887B - POSS-based organic porous polymer for catalyzing cycloaddition reaction of epoxide and carbon dioxide - Google Patents

POSS-based organic porous polymer for catalyzing cycloaddition reaction of epoxide and carbon dioxide Download PDF

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CN116253887B
CN116253887B CN202310230159.1A CN202310230159A CN116253887B CN 116253887 B CN116253887 B CN 116253887B CN 202310230159 A CN202310230159 A CN 202310230159A CN 116253887 B CN116253887 B CN 116253887B
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CN116253887A (en
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肖龙强
侯琳熙
蔡静宇
赵玉来
阴翔宇
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Qingyuan Innovation Laboratory
Fuzhou University
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Fuzhou University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
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    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

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Abstract

The invention discloses a POSS-based organic porous polymer capable of being repeatedly used for catalyzing cycloaddition of epoxide and carbon dioxide under normal pressure and a preparation method thereof. The POSS-based organic porous polymer is prepared by reacting a dibromo compound with vinyl imidazole to generate imidazolium ions, then adding octavinyl-POSS, an initiator azodiisobutyronitrile and a reaction solvent, and reacting under a heating condition. The POSS-based organic porous polymer can catalyze the cycloaddition reaction of epoxide and carbon dioxide to generate cyclic carbonate under mild conditions, can be separated from products by high-speed centrifugation, can be reused, and provides more choices for heterogeneous catalysis of cycloaddition of epoxide and carbon dioxide.

Description

POSS-based organic porous polymer for catalyzing cycloaddition reaction of epoxide and carbon dioxide
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a POSS (polyhedral oligomeric silsesquioxane) -based organic porous polymer capable of being repeatedly used for catalyzing cycloaddition of epoxide and carbon dioxide under normal pressure and a preparation method thereof.
Background
Excessive carbon dioxide emissions can lead to a number of environmental problems such as climate change and global warming. In order to reduce the carbon dioxide content in air, many researchers have focused on the capture, storage and utilization of carbon dioxide. Carbon dioxide is a chemical material that is abundant, inexpensive, non-toxic and thermodynamically stable. Therefore, there is a need to develop effective catalysts to reduce the activation energy of carbon dioxide reactions, converting carbon dioxide into useful materials in the chemical industry.
The epoxide and the carbon dioxide can be catalyzed by a catalyst to generate the cyclic carbonate, and the added value is high, and the atom utilization rate reaches 100 percent, so that the cyclic carbonate is widely paid attention. Most catalysts are used in the study, including phosphines, quaternary ammonium salts, transition metal complexes and alkali metal salts. However, there are still problems with the use of homogeneous catalysts, such as the need to remove the catalyst from the reaction mixture after the reaction, and the recovery of the catalyst, which encourages the development of renewable catalysts. It is therefore necessary to find a catalyst which is gentle in reaction conditions, environmentally friendly and capable of recycling.
Disclosure of Invention
The invention aims to provide a POSS-based organic porous polymer which can be repeatedly used for catalyzing cycloaddition of epoxide and carbon dioxide under normal pressure and a preparation method thereof. The polymer can catalyze the cycloaddition reaction of epoxide and carbon dioxide to generate cyclic carbonate under mild conditions, can be separated from products by high-speed centrifugation, can be reused, and provides more choices for heterogeneous catalysts for cycloaddition of epoxide and carbon dioxide.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a POSS-based organic porous polymer has the following unit structural formula:
，
wherein R is a linear alkane or an aromatic hydrocarbon containing 1-10 carbon atoms.
The preparation method of the POSS-based organic porous polymer comprises the following steps:
1) Mixing dibromo compound and vinyl imidazole with acetonitrile according to a certain proportion, stirring and reacting at 50-100 ℃ for 6-24 h to obtain imidazolium ions;
2) And adding octavinyl-POSS, azodiisobutyronitrile and a reaction solvent into the obtained imidazolium ions, and performing a heating reaction under the condition of nitrogen to obtain the POSS-based organic porous polymer.
Further, the molar ratio of dibromo compound to vinylimidazole used in step 1) is 1 (1-2). The dibromo compound is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, alpha '-dibromo-p-xylene, 4' -bis (bromoethyl) biphenyl and 2, 6-bis (bromomethyl) naphthalene.
Further, the molar ratio of the imidazolium ion, octavinyl-POSS, azobisisobutyronitrile used in step 2) is (1-10): 1 (0.1-10).
Further, the reaction solvent in the step 2) is one or more of tetrahydrofuran, dimethyl sulfoxide, 1, 4-dioxane, N-dimethylformamide, N-butanol and methanol.
Further, the temperature of the heating reaction in the step 2) is 70-160 ℃ for 1-6 days.
The POSS-based organic porous polymer can be repeatedly used for catalyzing the addition reaction of epoxide and carbon dioxide, and the application method comprises the following steps:
(1) Adding the POSS-based organic porous polymer and epoxide into a Schlenk tube, sealing, and filling CO 2 three times at room temperature to remove air in the tube;
(2) After CO 2 is filled in the reaction tube, reacting for 6-60 hours at 50-150 ℃;
(3) Centrifuging the POSS-based organic porous polymer and the reaction product cyclic carbonate.
Further, the epoxide is any one of propylene oxide, epichlorohydrin, bromopropane, styrene oxide, phenyl glycidyl ether, cyclohexene oxide, cyclopentane oxide, butylene oxide and octane oxide.
The invention has the beneficial effects that:
(1) According to the invention, the pore diameter and the distribution of catalytic active sites of the polymer are regulated and controlled by the types of dibromo compounds, so that the POSS-based organic porous polymer can be used for catalyzing cycloaddition of epoxide and carbon dioxide under normal pressure, and has higher catalytic efficiency.
(2) The polymer prepared by the invention has the advantages of normal pressure and mild temperature of the cycloaddition reaction pressure of the catalytic epoxide and the carbon dioxide.
(3) The polymer prepared by the invention can catalyze various epoxide substrates, and the catalyst is not deactivated after repeated use for a plurality of times.
(4) The polymer prepared by the invention does not need a cocatalyst or a solvent in the cycloaddition reaction.
Drawings
FIG. 1 is an infrared spectrum of the POSS-based organic porous polymer P2 produced in example 1. Successful preparation of POSS-based organic porous polymer P2 is demonstrated in the figure.
FIG. 2 is a graph showing comparison of specific surface areas and pore size distribution of POSS-based organic porous polymers PIL4, PIL5, PIL6, PIL7, and PIL8 obtained in example 2. As can be seen from FIG. 2, the specific surface area of the obtained POSS-based organic porous polymer is from 103.7m 2/g to 50.4m 2/g, and the pore size distribution is 9.5-17.5nm, which proves that the regulation and control of the loose porosity of the POSS-based organic porous polymer can be realized by adjusting the proportion of the connecting agent.
FIG. 3 shows the solid nuclear magnetic 29 Si NMR and 13 C NMR of the POSS-based organic cellular polymer obtained in example 6. The pictures demonstrate successful synthesis of the polymer.
Detailed Description
The preparation of the POSS-based organic porous polymer comprises the following steps:
1) Mixing dibromo compound and vinyl imidazole according to the mole ratio of 1 (1-2), dissolving acetonitrile, stirring and reacting at 50-100 ℃ for 6-24 h to obtain imidazolium ions;
2) Adding octavinyl-POSS and azodiisobutyronitrile into the obtained imidazolium ions according to the molar ratio of (1-10) 1 (0.1-10), adding a reaction solvent, and heating and reacting for 1-6 days at 70-160 ℃;
3) And collecting the obtained solid at room temperature after the reaction is finished, washing the solid three times by using a solvent which does not dissolve the polymer, and drying the solid in vacuum to obtain the POSS-based organic porous polymer.
Wherein the dibromo compound is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, alpha '-dibromo-p-xylene, 4' -bis (bromoethyl) biphenyl and 2, 6-bis (bromomethyl) naphthalene. The reaction solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, 1, 4-dioxane, N-dimethylformamide, N-butanol and methanol.
The technical scheme of the invention is further described, but the invention is not limited to the technical scheme.
Example 1
1-Vinylimidazole (1.88 g,0.02 mol) and dibromoethane (1.87 g,0.01 mol) were dissolved in 25ml of acetonitrile, the reaction was continuously stirred at 75℃for 24 h, the solid was collected by filtration, and after washing three times with ethyl acetate and diethyl ether each, a white solid of dibromoethylimidazolium ion (IL 2) was obtained by vacuum drying.
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10 mL Tetrahydrofuran (THF) and dibromoethane imidazolium ion (0.6 mmol,2.256 g) was uniformly dispersed in 10 mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and the IL2 dimethyl sulfoxide solution were added together into a glass flask of 50mL, and 2,2' -azobisisobutyronitrile (0.866mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70℃under nitrogen atmosphere for 24h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried overnight in a vacuum oven to give a white solid with a yield of 96%, designated P2.
Example 2
1-Vinylimidazole (1.88 g,0.02 mol) and 1, 3-dibromopropane (2.01 g,0.01 mol) were dissolved in 25ml of acetonitrile, and the reaction was continuously stirred at 75℃for 24 h, and the solid was collected by filtration, washed three times with ethyl acetate and diethyl ether, and then dried under vacuum to obtain a white solid (IL 3) of dibromopropane imidazolium ion.
Octavinyl-POSS (1 mmol,0.633 g) was dissolved in 10 mL Tetrahydrofuran (THF) and dibromopropane imidazolium ion (2 mmol,0.780 g) was uniformly dispersed in 10 mL DMSO. Then, the octavinyl-POSS tetrahydrofuran solution and the IL3 DMSO solution were added together into a 50 mL glass flask, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70 ℃ under nitrogen atmosphere for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with THF several times and dried overnight in a vacuum oven to give a white solid in 96% yield designated PIL-2.
A series of samples PIL-n (n represents the molar ratio of IL3 to octavinyl-POSS) were synthesized by varying the molar ratio of octavinyl-POSS to IL3 according to the procedure described above.
Example 3
1-Vinylimidazole (1.88 g,0.02 mol) and 1, 4-dibromobutane (2.15 g,0.01 mol) were dissolved in 25ml of acetonitrile, the reaction was continuously stirred at 75℃for 24 h, the solid was collected by filtration, and after washing three times with ethyl acetate and diethyl ether, a white solid of 1, 4-dibromobutane imidazolium ion (IL 4) was obtained by vacuum drying.
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10 mL Tetrahydrofuran (THF), and 1, 4-dibromobutane imidazolium ion (0.6 mmol,2.424 g) was uniformly dispersed in 10 mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and the IL4 dimethyl sulfoxide solution were added together into a glass flask of 50 mL, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70℃under nitrogen atmosphere for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried overnight in a vacuum oven to give a white solid with a yield of 96%, designated P3.
Example 4
1-Vinylimidazole (1.88 g,0.02 mol) and 1, 5-dibromopentane (2.29 g,0.01 mol) were dissolved in 25ml of acetonitrile, the reaction was continuously stirred at 75℃for 24 h, the solid was collected by filtration, and after washing three times with ethyl acetate and diethyl ether each, a white solid of dibromopentaneimidazolium ion (IL 5) was obtained by vacuum drying.
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10 mL Tetrahydrofuran (THF), and dibromopentamizolium ions (0.6 mmol,2.508 g) were uniformly dispersed in 10 mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and the IL5 dimethyl sulfoxide solution were added together into a glass flask of 50 mL, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70℃under nitrogen atmosphere for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried overnight in a vacuum oven to give a white solid with a yield of 96%, designated P5.
Example 5
1-Vinylimidazole (1.88 g,0.02 mol) and 1, 6-dibromohexane (2.43 g,0.01 mol) were dissolved in 25ml of acetonitrile, and the reaction was continuously stirred at 75℃for 24 h, and the solid was collected by filtration, washed three times with ethyl acetate and diethyl ether, and then dried under vacuum to obtain a white solid of dibromohexane imidazolium ion (IL 6).
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10 mL Tetrahydrofuran (THF), and dibromohexane imidazolium ions (0.6 mmol,2.59 g) were uniformly dispersed in 10 mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and IL6 dimethyl sulfoxide solution were added together to a 50 mL glass flask, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) was added as an initiator, and reacted under nitrogen at 70 ℃ with stirring for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried overnight in a vacuum oven to give a white solid with a yield of 96%, designated P5.
Example 6
1-Vinylimidazole (1.88 g,0.02 mol) and α, α '-dibromoparaxylene (2.63 g,0.01 mol) were dissolved in 25ml of acetonitrile, and the reaction was continuously stirred at 75℃for 24 h, and the solid was collected by filtration, washed three times with ethyl acetate and diethyl ether, and then dried under vacuum to obtain a white solid of α, α' -dibromoparaxylylimidazolium ion (IL 7).
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10mL Tetrahydrofuran (THF) and α, α' -dibromop-xylylenidium bromide ion (0.6 mmol,2.713 g) was uniformly dispersed in 10mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and the IL7 dimethyl sulfoxide solution were added together into a glass flask of 50mL, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70℃under nitrogen atmosphere for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried in a vacuum oven overnight to give a white solid in 97% yield designated P6.
Example 7
1-Vinylimidazole (1.88 g,0.02 mol) and 4,4 '-bis (bromoethyl) biphenyl (3.4 g,0.01 mol) were dissolved in 25ml of acetonitrile, and the reaction was continuously stirred at 75℃for 24 h, and the solid was collected by filtration, washed three times with ethyl acetate and diethyl ether, and dried under vacuum to obtain a white solid (IL 8) of 4,4' -bis (bromoethyl) biphenylimidazolium ion.
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10 mL Tetrahydrofuran (THF), and 4,4' -bis (bromoethyl) biphenimidazolium ions (0.2 mmol,3.169 g) were uniformly dispersed in 10 mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and the IL8 dimethyl sulfoxide solution were added together into a glass flask of 50 mL, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70℃under nitrogen atmosphere for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried overnight in a vacuum oven to give a white solid with a yield of 96%, designated P7.
Example 8
1-Vinylimidazole (1.88 g,0.02 mol) and 2, 6-bis (bromomethyl) naphthalene (3.14 g,0.01 mol) were dissolved in 25ml of acetonitrile, and the reaction was continuously stirred at 75℃for 24h, and the solid was collected by filtration, washed three times with ethyl acetate and diethyl ether, and dried under vacuum to give a white solid of 2, 6-bis (bromomethyl) naphthaleneimidazolium ion (IL 9).
Octavinyl-POSS (0.1 mmol,0.633 g) was dissolved in 10mL Tetrahydrofuran (THF), and 2, 6-bis (bromomethyl) naphthaleneimidazolium ion (0.2 mmol,3.01 g) was uniformly dispersed in 10mL dimethyl sulfoxide (DMSO). Then, the octavinyl-POSS tetrahydrofuran solution and the IL9 dimethyl sulfoxide solution were added together into a glass flask of 50mL, and 2,2' -azobisisobutyronitrile (0.866 mmol,0.142 g) as an initiator was added thereto, and the reaction was stirred at 70℃under nitrogen atmosphere for 24 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and after the product was separated by filtration, the product was washed with DMSO and THF, respectively, and dried in a vacuum oven overnight to give a white solid in 97% yield designated P8.
Application example 1
0.08G of the polymer P2 obtained in example 1 was placed in a Schlenk tube, 1ml of epichlorohydrin was added, the tube was sealed, the air in the tube was replaced six times with CO 2 at room temperature, the reaction was carried out at 80℃for 12 hours, and after the completion of the reaction, the catalyst and the product were separated by high-speed centrifugation. The conversion was 95% as determined by gas chromatography.
Application example 2
The addition reaction of epoxide with carbon dioxide was carried out using the products PIL2, PIL4, PIL5, PIL6, PIL7, PIL8 and PIL10 (0.06 g) in example 2 as catalysts in the same manner as in application example 1, and the catalytic properties were as shown in Table 1.
TABLE 1
Application example 3
As with application example 1, the addition reaction of epoxide with carbon dioxide was carried out using the product P3 (0.08 g) of example 3 as a catalyst, and the result showed that the conversion was 98.05%.
Application example 4
As with application example 1, the addition reaction of epoxide with carbon dioxide was carried out using the product P4 (0.08 g) of example 4 as a catalyst, and the result showed that the conversion was 99%.
Application example 5
As with application example 1, the addition reaction of epoxide with carbon dioxide was carried out using the product P6 (0.08 g) of example 6 as a catalyst, and the result showed that the conversion was 95%.
Application example 6
Polymer P6 collected after the completion of the reaction in application example 5 was dried and subjected to 4 addition reactions under reaction conditions of 80℃for 12 hours. The 4 times conversion was 93.8%, 93%, 92.8%, respectively, as determined by gas chromatography. It proves to have good reusability.
Application example 7
The epoxide used was replaced by epibromohydrin, the conversion of which was 92%, as in application example 1.
Application example 8
The epoxide used was replaced by propylene oxide in the same way as in application example 1, with a conversion of 90%.
Application example 9
The epoxide used was replaced by phenyl glycidyl ether, the conversion of which was 85%,
Application example 10
The epoxide used was replaced by cyclopentane epoxide, the conversion being 82%, as in application example 1.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (2)

1. A preparation method of a POSS-based organic porous polymer is characterized in that: the method comprises the following steps:
1) Mixing dibromo compound and vinyl imidazole with acetonitrile according to a certain proportion, stirring and reacting at 50-100 ℃ for 6-24 h to obtain imidazolium ions;
2) Adding octavinyl-POSS, azodiisobutyronitrile and a reaction solvent into the obtained imidazolium ions, and performing a heating reaction under the condition of nitrogen to generate the POSS-based organic porous polymer; the unit structural formula is as follows:
，
wherein R is straight-chain alkane or aromatic hydrocarbon containing 1-10 carbon atoms;
The molar ratio of dibromo compound to vinylimidazole used in step 1) is 1 (1-2); the dibromo compound is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, alpha '-dibromo-p-xylene, 4' -bis (bromoethyl) biphenyl and 2, 6-bis (bromomethyl) naphthalene;
The molar ratio of the imidazolium ions, the octavinyl-POSS and the azodiisobutyronitrile used in the step 2) is (1-10): 1 (0.1-10); the temperature of the heating reaction is 70-160 ℃ and the time is 1-6 days.
2. The method for preparing the POSS-based organic porous polymer according to claim 1, wherein: the reaction solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, 1, 4-dioxane, N-dimethylformamide, N-butanol and methanol.
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