CN111454455B - Porous hybrid polymer rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl and preparation method and catalytic application thereof - Google Patents
Porous hybrid polymer rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl and preparation method and catalytic application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 13
- 239000010703 silicon Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 11
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
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- 229910018557 Si O Inorganic materials 0.000 description 2
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- DHSRFGJMOVMDPI-UHFFFAOYSA-N 2-methyloxirane hydrobromide Chemical compound CC1OC1.Br DHSRFGJMOVMDPI-UHFFFAOYSA-N 0.000 description 1
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—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
- 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
- C07D317/34—Oxygen atoms
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- 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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- 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
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Abstract
A porous hybrid polymer rich in POSS derived silicon hydroxyl is shown in one of the following structural formulas, and is prepared by respectively reacting rigid building units of vinyl POSS with tri (4-bromobenzene) amine or tetra (4-bromobenzene) methane through Heck reaction. The prepared porous hybrid polymer has large specific surface area, abundant mesoporous pores and Si-OH active groups derived in situ, and N-PHPs and C-PHPs are used as nonmetal non-halogen heterogeneous catalysts, so that the high-added-value cyclic carbonate can be prepared by the efficient catalytic conversion of carbon dioxide under mild conditions.
Description
Technical Field
The invention relates to the field of preparation and catalytic application of porous polymers, in particular to porous hybrid polymers rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl, a preparation method thereof and application thereof in CO2Application in catalytic conversion.
Background
With the increasing deterioration of global environment, the greenhouse gas CO2The capture and utilization of CO is becoming increasingly important, and CO2The source is rich, and the product can be used as renewable C1 resource to synthesize chemical products with high added value. In a large number of uses of CO2In the strategy of (1), from CO2And epoxy compounds are one of the most promising strategies for the synthesis of cyclic carbonates by cycloaddition reactions. At present, many homogeneous and heterogeneous catalysts have been developed for CO2And (4) transformation. Homogeneous catalysts are generally highly efficient, but suffer from the disadvantages of difficulty in catalyst recovery and product separation. Heterogeneous catalysts can solve these problems relatively speaking, but most heterogeneous catalytic systems often require severe reaction conditions of high temperature and high pressure. At present, against CO2The catalytic activity sites of the cycloaddition reaction, whether a homogeneous catalyst or a heterogeneous catalyst, mainly depend on nucleophilic halogen anions and electrophilic metal sites, and the catalytic system is not green and environment-friendly. Therefore, the green and high-efficiency nonmetal non-halogen heterogeneous catalyst is constructed, and the CO is treated under the conditions of normal pressure and low temperature2The efficient transformation of (A) is a very important research topic.
As a common heterogeneous catalyst, Porous Organic Polymers (POPs) are known to have high surface area, adjustable chemical functionality and excellent chemical stability in CO2There is increasing interest in capture and conversion. These excellent features of POPs not only enhance the CO-pair of the catalyst in the catalytic reaction2The adsorption capacity of the epoxy resin can be effectively promoted, and the mass transfer of the epoxy substrate can be effectively promoted. In addition, various catalytic functional groups can be introduced into the POP framework, so that the POP framework has abundant active sites and can effectively activate CO2Molecules and epoxy substrates. However, the device is not suitable for use in a kitchenIn contrast, the active sites in current POP heterogeneous catalysts are mainly halogen anion sites and metal sites for CO2POP catalysts free of metal and halogen sites for cycloaddition reactions are very rare. Polyhedral oligomeric silsesquioxanes (POSS) are a novel, nanoscale, inorganic-organic hybrid molecule. POSS is considered to be an ideal building block for the construction of porous polymers due to its regular cage structure, functionalized reactable groups, and excellent hydrothermal stability. In general, porous hybrid polymers based on POSS all have large specific surface areas and excellent hydrothermal stability. However, during the preparation of POSS-based porous polymers, the Si-C and Si-O bonds in the POSS cage may be partially cleaved, resulting in partial collapse of the cage structure and subsequent derivatization of the silicon hydroxyl (Si-OH) groups. From the point of view of the synthesis of ordered porous materials, the destruction of POSS cages is not perfect; from a catalytic application perspective, it is these defective POSS cages that provide catalytically active Hydrogen Bond Donor (HBD) Si-OH groups. The Si-OH group can be used as an auxiliary catalytic active site and can greatly promote the activation of epoxy compounds and CO2The transformation of (3). However, no catalyst using Si-OH groups alone as the catalytically active center has been reported. Therefore, the invention develops a porous hybrid organic polymer rich in POSS derived Si-OH based on POSS unit, which is used as a non-metal non-halogen catalyst to realize CO treatment under normal pressure and mild condition under the conditions of no solvent and no promoter2High efficiency catalytic conversion.
Disclosure of Invention
The inventor researches and develops a preparation method of a porous hybrid polymer rich in POSS derived Si-OH through a large amount of experimental researches, and designs and synthesizes a series of POSS-based porous hybrid polymers N-PHPs and C-PHPs. Experimental research shows that the N-PHPs and C-PHPs synthesized by the method can be used as high-efficiency catalysts applied to CO2In the cycloaddition reaction.
As a first aspect of the invention, the invention provides a class of porous hybrid polymers rich in POSS-derived silicon hydroxyl groups,
the structural formula is shown as one of the following formulas:
as a second aspect of the present invention, there is also provided a process for preparing a porous hybrid polymer rich in POSS-derived silicon hydroxyl groups of the above-mentioned class, comprising: dissolving vinyl POSS shown in the following formula 1 and tri (4-bromobenzene) amine shown in the following formula 2 or tetra (4-bromobenzene) methane shown in the following formula 3 in an organic solvent, and preparing the POSS-derived silicon hydroxyl-rich porous hybrid polymer through Heck reaction.
Further, the preparation method specifically comprises the following steps:
s1: weighing a certain amount of the vinyl POSS shown in the formula 1 and the tri (4-bromobenzene) amine shown in the formula 2 or the tetra (4-bromobenzene) methane shown in the formula 3, and dissolving in an organic solvent to obtain a uniform solution;
s2: transferring the uniform solution into a reaction kettle, adding an alkaline acid-absorbing agent and a catalyst, and heating for reaction for a period of time;
s3: and after the reaction is finished, filtering, washing and drying to obtain the porous hybrid polymer rich in POSS derived silicon hydroxyl.
In step S1, the molar ratio of the vinyl POSS represented by formula 1 to the tris (4-bromobenzene) amine represented by formula 2 or the tetrakis (4-bromobenzene) methane represented by formula 3 is 1:1 to 3.
Further, the alkaline acid acceptor is K2CO3。
Further, the catalyst is palladium triphenylphosphine.
Further, the reaction temperature in the step S2 is 120 ℃, and the reaction time is 72 h.
As a third aspect of the invention, there is also provided the use of the above-mentioned POSS-derived Si-OH-rich porous hybrid polymer in CO2Application in catalytic conversion.
Further, the application specifically includes: using an epoxy compound as a substrate, using the porous hybrid polymer rich in POSS derived silicon hydroxyl as a catalyst, and using CO at normal pressure2In the atmosphere, CO is carried out under heating2Cycloaddition reaction with an epoxy compound.
Further, the structural formula of the epoxy compound is shown as the following formula 4
Wherein R is chloromethyl, bromomethyl, phenyl, n-butyl, n-hexyl or benzyloxy.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, the vinyl POSS and the tri (4-bromobenzene) amine or tetra (4-bromobenzene) methane are subjected to Heck reaction to prepare the POSS-derived Si-OH-rich porous hybrid polymer, the reaction conditions required by the preparation process are mild, the reaction time is short, the used equipment is simple, and the preparation method has a wide industrial/large-scale application prospect;
the prepared polymer has excellent catalytic activity by introducing the hydrogen bond donor Si-OH group into the polymer in situ;
the porous hybrid polymer rich in POSS derived Si-OH is prepared by reacting an epoxy compound and CO under the conditions of no solvent and no promoter2The cycloaddition reaction has excellent catalytic performance, and the reaction also has the advantages of small catalyst consumption and easy separation and recovery.
Drawings
FIG. 1 is an XRD spectrum of N-PHP-2, C-PHP-2 in example 1;
FIG. 2 is an IR spectrum of N-PHP-2, C-PHP-2 in example 1;
FIG. 3 is an SEM photograph of N-PHP-2, C-PHP-2 in example 1;
FIG. 4 shows N at 77K for N-PHP-2, C-PHP-2 in example 12Adsorption and desorption curves and an NLDFT aperture distribution diagram;
FIGS. 5-9 are for the respective reaction products of example 31H NMAnd (4) an R spectrogram.
The specific implementation mode is as follows:
the technical solutions of the present invention are specifically described below with reference to examples, and it should be noted that the implementation examples only describe the preferred examples of the present invention, and do not limit the concept and scope of the present invention. Without departing from the design concept of the present invention, those skilled in the art can change the linker of the novel POSS-enriched Si-OH derived porous hybrid polymer, change the reaction conditions of the synthesis method, change the specific surface area of the synthesized polymer and change the specific surface area of the synthesized polymer in CO2Variations in the application of catalytic conversion are within the scope of the present invention.
Example 1: preparation of POSS-derived Si-OH-rich porous hybrid polymers N-PHPs and C-PHPs
The synthetic route is as follows:
vinyl POSS (VPOSS) and tris (4-bromobenzene) amine (TBPA) were weighed into 10mL of N, N' -dimethylformamide, stirred to dissolve completely, and the two solutions were mixed and charged into a stainless steel reactor lined with polytetrafluoroethylene. Weighing alkaline acid-absorbing agent K2CO32mL of water was added, dissolved by stirring, and transferred to the above reaction vessel. And weighing catalyst triphenylphosphine palladium, adding the catalyst triphenylphosphine palladium into the reaction kettle, and uniformly stirring. And (3) placing the reaction kettle in an oven at 120 ℃ for reaction for 72 hours. And after the reaction is finished, cooling the reaction kettle to room temperature, transferring the solution into a beaker, performing suction filtration, and washing with tetrahydrofuran, deionized water and ethanol respectively. And finally, drying the filter cake in a vacuum oven (80 ℃) for 12 hours to obtain the porous hybrid polymer N-PHPs. A series of porous hybrid polymers N-PHP-N (N is 1,2,3) are obtained by adjusting the molar ratio of VPOSS to TBPA (1: 1-1: 3). The obtained N-PHP-2 has the highest specific surface area and moderate nitrogen content, and is selected as a typical sample for subsequent characterization and application.
The porous hybrid polymer C-PHP-n (n is 1,2,3) can be obtained by replacing TBPA with tetra (4-bromobenzene) methane (TBPM) and repeating the experiment with the molar ratio of VPOSS to TBPM being 1: 1-3.
Structural characterization:
FIG. 1 is an infrared spectrum of N-PHP-2 and C-PHP-2 porous hybrid polymers prepared in example 1 (POSS is an abbreviation for polyhedral oligomeric silsesquioxane, and PHPs is an abbreviation for porous hybrid polymer). As can be seen from the figure, N-PHP-2 and C-PHP-2 substantially retain the Si-O-Si structure of the POSS cage, but due to the coexisting T's in the POSS cagenAnd QnCollapse and regeneration of silicon units with characteristic peak positions from 1110cm of VPOSS monomer-1Is shifted to 1062, 1147 and 1142cm-1To (3). It is at 3674/3650cm-1Si-OH and 967/966cm-1Stretching vibration of the Si-O bond confirmed the presence of Si-OH groups in N-PHP-2 and C-PHP-2. In addition, 1506cm-1The characteristic peaks in (a) are assigned to the C-N bond in tris (4-bromobenzene) amine, further illustrating the successful incorporation of the tris (4-bromobenzene) amine monomer into the polymer backbone. FIG. 2 is an XRD spectrum of N-PHP-2 and C-PHP-2, which has distinct peaks at 20.9-21.5 degrees, indicating that N-PHP-2 and C-PHP-2 are amorphous structures. FIG. 3 is an SEM image of N-PHP-2 and C-PHP-2, showing that they have a fluffy, nano-like morphology. The porous nature of the porous hybrid polymer was confirmed by nitrogen desorption testing at 77K. As shown in FIG. 4A, the N-PHP-2 and C-PHP-2 isotherms are at low relative pressures (P/P)0<0.1) exhibits considerable absorption at high pressures P/P0(0.85-0.99) shows a certain hysteresis ring, which indicates that the materials have a hierarchical pore structure of micropores and mesopores. In addition, they have a high specific surface area, 547 and 715m respectively2g-1. The pore size distribution of the sample was calculated by using NLDFT model, as shown in FIG. 4B, the polymers N-PHP-2 and C-PHP-2 have narrower micropore distribution at 1.41 and 1.29nm, and some disordered mesopore distribution appears at 2.89/3.32, 5.44/4.54 and 11.17/15.31nm, which is similar to N2The type of adsorption desorption isotherms is consistent.
Example 2: catalytic conversion of CO by N-PHP-2 and C-PHP-22Reactivity comparison and recyclability of
Obtained by working example 1The porous hybrid polymer catalysts N-PHP-2 and C-PHP-2 are used for CO2And cycloaddition reaction with epoxy chloropropane. The reaction conditions are as follows: epichlorohydrin (2mmol), the catalyst from example 1 (0.05g), was charged to a 25mL reaction tube, stirred at 80 ℃ and first connected to CO2The air in the reaction tube is discharged through the vent pipe of the gas cylinder, and then a balloon (0.1MPa) filled with carbon dioxide is inserted on the reaction tube to react for 72 hours. After the reaction, a certain amount of ethyl acetate was added to dilute the reaction solution, and the mixture was stirred at room temperature for 20 minutes. The solution was removed, centrifuged, and the supernatant removed and the yield calculated using Gas Chromatography (GC) analysis, the results of which are shown in table 1. As can be seen from Table 1, under the same conditions, the catalysts N-PHP-2 and C-PHP-2 have almost the same catalytic activity and can exhibit excellent catalytic activity.
TABLE 1 CO catalyzed by N-PHP-2 and C-PHP-2 catalysts2Cycloaddition reaction result with epichlorohydrin
The above experiment was repeated using the above catalyst C-PHP-2, and the cycle was repeated 1 to 5 times under the same conditions of reaction temperature and reaction time, and the results of the experiment are shown in Table 2. As can be seen from Table 2, catalyst C-PHP-2 has good recyclability.
TABLE 2C-PHP-2 catalyzed CO2Recycling results of cycloaddition reaction with epichlorohydrin
Example 3: catalysts N-PHP-2 and C-PHP-2 for catalyzing CO2Activity comparison and substrate suitability in cycloaddition reactions with different epoxides
This example uses N-PHP-2 and C-PHP-2 catalysts and various epoxy compounds as substrates to compare the activities of the N-PHP-2 and C-PHP-2 catalysts and CO2Substrate expansibility study of cycloaddition catalytic reaction, epoxy compound is
Wherein, R is chloromethyl, bromomethyl, phenyl, benzyloxy, n-butyl, n-hexyl experimental result is shown in Table 3.
As can be seen from the data in Table 3, the catalytic activity of the catalyst C-PHP-2 is slightly better than that of N-PHP-2, which is probably because the C-PHP-2 has a very high specific surface area and a large number of mesopores, which are beneficial to the mass transfer of the epoxy substrate in the reaction. In addition, both catalysts can have relatively mild conditions and high yield on inert and long-chain epoxy substrates, which shows that the two catalysts have good substrate applicability and can be used as efficient heterogeneous catalysts to realize CO under mild conditions2The catalytic conversion of (2).
TABLE 3 CO catalyzed by N-PHP-2 and C-PHP-2 catalysts2Cycloaddition reaction performance with different epoxy compounds
The following specific experimental procedure, using C-PHP-2 as an example:
3.1 catalytic conversion of CO by C-PHP-22Catalytic performance of reaction with bromopropylene oxide
Propylene oxide bromide (2mmol), the C-PHP-2 catalyst from example 1 (0.05g) was added to a 25mL reaction tube and stirred at 80 deg.C, first with a CO linker2The air in the reaction tube is discharged by the vent tube of the gas cylinder and then filled with CO2The balloon (0.1MPa) was inserted into the reaction tube and reacted for 72 hours. After the reaction, a certain amount of ethyl acetate was added to dilute the reaction solution, and the mixture was stirred at room temperature for 20 minutes. Taking out the solution, centrifuging, taking out the supernatant, evaporating the solvent by using a vacuum rotary evaporator, and calculating the yield of the obtained crude product by nuclear magnetic hydrogen spectrum. Of the reaction products1The H NMR spectrum is shown in FIG. 5.
Under similar reaction conditions, styrene oxide, epoxypropylphenyl ether, 1,2Replacement of bromopropylene oxide by Hexane oxide and 1, 2-Octane oxide, testing of the catalyst C-PHP-2 in the catalytic conversion of CO by changing the reaction temperature (100 ℃ C.) and 120 ℃ C.) under otherwise unchanged conditions2Catalytic performance in reactions with other epoxy compounds. Reaction product1The H NMR spectrum is shown in FIGS. 6 to 9.
Claims (2)
1. The application of the porous hybrid polymer rich in POSS derived silicon hydroxyl in the catalytic conversion of carbon dioxide is characterized in that the structural formula of the porous hybrid polymer rich in POSS derived silicon hydroxyl is shown as one of the following formulas:
the application specifically comprises: using an epoxy compound as a substrate, using the porous hybrid polymer rich in POSS derived silicon hydroxyl as a catalyst, and using CO at normal pressure2In the atmosphere, CO is carried out under heating2Cycloaddition reaction with an epoxy compound.
2. The use of claim 1, wherein the epoxy compound has a formula of formula 4
Wherein R is chloromethyl, bromomethyl, phenyl, n-butyl, n-hexyl or benzyloxy.
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