CN111592607A - Application of covalent organic framework material loaded with rhodium catalyst in alkyne polymerization - Google Patents
Application of covalent organic framework material loaded with rhodium catalyst in alkyne polymerization Download PDFInfo
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Abstract
The invention relates to an application of a covalent organic framework material loaded with a rhodium catalyst in alkyne polymerization, belonging to the technical field of covalent organic framework material catalysis, wherein the application is used as a catalyst for catalyzing polymerization reaction of alkyne polymerization and as a catalyst for catalyzing phenylacetylene polymerization, and when alkyl aluminum, an amine reagent or an aluminoxane auxiliary agent is added, the catalytic activity is high and can reach 1.2 × 107g mol‑1h‑1The content of cis-polyphenylacetylene can reach 99%, the molecular weight can reach 4 ten thousand, and the catalyst can be reused for more than 5 times. The reaction system can also be used for catalyzing and polymerizing functional groups (such as [1- (4-ethynylphenyl) -1,2, 2-triphenyl)]Ethylene) to obtain a polymer with a single-chiral helical polymer, a polymer with aggregation-induced emission effect and a polymer with fluorescence functionThe polymer can be used for chiral recognition, preparation of a light-emitting device and fluorescence detection, the problems that an alkyne polymerization catalyst cannot be recycled, the preparation yield of the polymer is low, the process is complex and the cost is high are solved, and the catalyst can be recycled, is green and environment-friendly and has good economy.
Description
Technical Field
The invention relates to an application of a covalent organic framework material TPB-DMTP-COF (thermoplastic vulcanizate-dimethyl-thiofuran-COF) loaded with a rhodium catalyst in polymerization of phenylacetylene and functional alkyne, belonging to the technical field of catalysis of covalent organic framework materials.
Background
Covalent Organic Frameworks (COFs) are porous crystalline polymers with periodic network structures formed by Organic monomers connected by Covalent bonds. The catalyst has the characteristics of regular pore passages, low density, high crystallinity, high stability and the like, and is widely applied to the aspects of gas storage and separation, drug delivery, energy storage, catalysis and the like. Because the organic monomer used for synthesizing the covalent organic framework material contains heteroatoms, when the organic monomer has coordination property, the metal catalyst can be loaded to prepare the heterogeneous catalyst taking the covalent organic framework material as a carrier, the catalyst can utilize the metal catalyst anchored on a ligand as a catalytic active site, and can also utilize a pore channel of the covalent organic framework material to provide a limited space environment to screen reaction products, thereby obtaining a specific product with high selectivity. The supported catalyst prepared by the strategy is mostly used for catalyzing organic reactions, and the application of the supported catalyst to polymerization reactions is not reported.
In the polymerization reaction, the polymerization of alkyne is mostly a homogeneous polymerization system, the rhodium metal catalyst is beneficial to catalyzing the polymerization of alkyne, but the catalyst is high in price, the catalyst cannot be recycled, and the activity of the reaction system and the molecular weight of the polymer are relatively low, so that the catalyst which can be recycled, is good in economy, is high in reaction activity and is good in selectivity of the molecular weight of the polymer is necessary for ten times. In the covalent organic framework material, the TPB-DMTP-COF framework structure is stable, pore channels are regular and open, and nitrogen and oxygen heteroatoms contained in the framework are wide, so that the covalent organic framework material is utilized, a rhodium metal catalyst is loaded after ligand modification and is used for catalyzing alkyne polymerization reaction, under the condition of adding an auxiliary agent, a reaction system achieves high activity and high selectivity, the catalyst can be recycled, the economy of the catalyst is improved, the cost is saved, and the invention has important scientific significance and wide application prospect.
Disclosure of Invention
In view of the above, the present invention aims to provide an application of a covalent organic framework material supporting a rhodium metal catalyst in alkyne polymerization.
In order to achieve the purpose of the invention, the following technical scheme is provided.
The application of the covalent organic framework material loaded with the rhodium metal catalyst in alkyne polymerization is that the covalent organic framework material is used as a catalyst to catalyze the polymerization reaction of alkyne monomers, and the catalyst can be recycled to obtain alkyne polymers with high molecular weight, high selectivity and specific functionality.
Preferably, the covalent organic framework material supported by the rhodium metal catalyst is TPB-DMTP-COF.
The method comprises the following specific application steps:
(1) TPB-DMTP-COF covalent organic framework material and 2, 5-norbornadiene rhodium react for 24 hours in acetone solution at 25 ℃, solid obtained by centrifuging reaction liquid is washed by acetone for four times, and is dried for 1 hour at 40 ℃ in a vacuum state, thus obtaining the covalent organic framework material with the loaded rhodium metal catalyst respectively.
(2) Respectively adding a catalyst and a good solvent into the reactor, and uniformly stirring; adding alkyne monomer, adding alkyl aluminum, amine reagent or aluminoxane cocatalyst, and continuously stirring uniformly; the reaction is stopped when the reaction temperature is 25 ℃ and the reaction is carried out for 2min under stirring.
(3) Centrifuging the reaction solution, easily precipitating the catalyst solid, and adding a chain terminator into the upper layer reaction solution to terminate the reaction; and (2) settling the reaction solution by using anhydrous methanol containing 2, 6-di-tert-butyl-p-cresol or glacial acetic acid to separate out solid substances, removing the solvent from the solid substances, drying in a vacuum constant temperature box to constant weight to obtain a polymerization product, and washing the precipitated catalyst for three times by using the solvent selected for polymerization, so that the catalyst can be directly used in new polymerization reaction.
Wherein the molar ratio of the alkyl aluminum, the amine reagent or the methylaluminoxane and other cocatalysts to the monomer to the catalyst is 1-10: 200-5000: 1.
Preferably at 40 ℃ under vacuum.
The good solvent is more than one of n-hexane, n-heptane, benzene, toluene, cyclohexane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, chloroform, dichloromethane, trichloromethane, tetrahydrofuran and water.
The alkyl aluminum reagent is of the molecular formula AlX3Alkyl aluminum of formula HAlX2Of the formula AlX2Alkyl aluminum chloride of Cl or aluminoxane, and X is alkyl. The amine reagent is of the formula NX3And X is an alkyl group.
The chain terminator is methanol and ethanol solution of 2, 6-di-tert-butyl-p-cresol, ethanol solution of 2,3, 4-trimethylphenol, ethanol solution of m-diphenol, ethanol solution of 2, 6-diethylphenol, ethanol solution of p-tert-butylphenol or methanol and ethanol solution of glacial acetic acid.
4. Use of a rhodium catalyst loaded covalent organic framework in the polymerization of alkynes according to claim 3, characterized in that: in the step (3), the mass fraction of phenols of the chain terminator is 5-15%, and the volume fraction of methanol and ethanol solution of glacial acetic acid is 0.1-0.2%.
5. The use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 3 in the polymerisation of alkynes, characterized in that: and (3) drying at 40 ℃ in vacuum.
6. Use of a metal organic framework material supporting a rhodium metal catalyst according to claim 3 in the polymerisation of alkynes, characterized in that: the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tricyclohexyl aluminum or trioctyl aluminum;
the alkyl aluminum hydride is dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride or dioctyl aluminum hydride;
the alkyl aluminum chloride is dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride or dioctyl aluminum chloride;
the aluminoxane is methyl aluminoxane, ethyl aluminoxane, n-propyl aluminoxane or n-butyl aluminoxane;
the amine reagent is triethylamine, triisopropylamine, aniline, (R) - (+) -alpha-methylbenzylamine, S-1-phenylethylamine.
8. The use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 3 in the polymerisation of alkynes, characterized in that: the alkyne monomer is phenylacetylene, fluoro phenylacetylene, chloro phenylacetylene, bromo phenylacetylene, iodo phenylacetylene, methyl phenylacetylene, ethyl phenylacetylene, propyl phenylacetylene, butyl phenylacetylene, vinyl phenylacetylene, propenyl phenylacetylene, butenyl phenylacetylene, phenylenediacetylene, [1- (4-ethynylphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-phenylethynylphenyl) -1,2, 2-triphenyl ] ethylene, biphenyl acetylene, 4-bromo-2-acetylene-1-fluorobenzene, 4-acetylene methyl benzoate, 6-ethynyl-4, 4-dimethyl dihydrobenzene thiopyran, 4 '-diacetylene biphenyl, 4-ethynylene tolane, 2-ethynyl-2' -vinyl-biphenyl, 1-bromo-3, 5-diacetylynylbenzene, 2-ethynyl-3 ', 5 ' -dimethyl-1, 1 ' -biphenyl, (2- (dodecyloxy) -5-ethynyl-1, 3-phenylene) dimethanol, N- (4-ethynylphenyl) -6- (4- (1,2, 2-triphenylethenyl) phenoxy) hexanamide, 5- (dimethylamino) -N- (4-ethynylphenyl) naphthalene-1-sulfonamide.
9. The use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 4 in the polymerisation of alkynes, characterized in that: chain terminators used after the polymerization are: methanol solution of 2, 6-di-tert-butyl-p-cresol, ethanol solution of 2,3, 4-trimethylphenol, ethanol solution of m-diphenol, ethanol solution of 2, 6-diethylphenol or ethanol solution of p-tert-butylphenol; preferably, the mass fraction of 2, 6-di-tert-butyl-p-cresol, 2,3, 4-trimethylphenol, m-diphenol, 2, 6-diethylphenol or p-tert-butylphenol is 5 to 15 percent, or glacial acetic acid methanol or ethanol solution, wherein the volume fraction of the glacial acetic acid is 0.1 to 0.2 percent.
Advantageous effects
1. The invention provides an application of a covalent organic framework material loaded with a rhodium metal catalyst in alkyne polymerization, wherein the application is used as a catalyst to catalyze the polymerization reaction of alkyne monomers, the catalyst is utilized to form an alkyne polymerization reaction system together with an alkyl aluminum reagent or an amine reagent and the monomers, the polymerization activity is high, the selectivity is good, the molecular weight of the obtained alkyne polymer is high, and the application of the loaded covalent organic framework material in alkyne polymerization is expanded;
2. the invention provides an application of a metal organic framework material loaded with a rhodium metal catalyst in alkyne polymerization, the application is used as a catalyst for catalyzing polymerization reaction of alkyne monomers, particularly for catalyzing polymerization reaction of phenylacetylene, and the polymerization activity can reach 1.2 × 107gmol-1h-1The selectivity is good, the selectivity of the cis-form polyphenylacetylene is up to 99 percent, and the molecular weight is up to 4 ten thousand;
3. the invention provides an application of a covalent organic framework material loaded with a rhodium metal catalyst in alkyne polymerization, the covalent organic framework material loaded with rhodium can be used in an alkyne polymerization system as a heterogeneous catalyst, the catalyst has good regeneration, can be recycled for 5 times without damaging the catalyst structure, has high polymerization yield, realizes green cyclic regeneration of the catalyst, reduces polymerization cost, and is suitable for industrial production;
4. the invention provides an application of a covalent organic framework material loaded with a rhodium metal catalyst in alkyne polymerization, which is used as a catalyst for catalyzing polymerization reaction of alkyne monomers, can be used for catalyzing alkyne monomers with functional groups (such as [1- (4-ethynylphenyl) -1,2, 2-triphenyl ] ethylene) by the catalyst, and obtains polymers with single-chiral helical polymers, aggregation-induced luminous effects and fluorescent functions by catalytic polymerization, thereby expanding the preparation method of the functional polymers.
Drawings
FIG. 1 is a schematic representation of the preparation of the rhodium metal catalyst supported covalent organic framework material TPB-DMTP-COF-Xwt% Rh in example 1.
FIG. 2 is a powder X-ray diffraction pattern of the covalent organic framework material TPB-DMTP-COF-Xwt% Rh supported by the rhodium metal catalyst and the covalent organic framework not supported by the rhodium metal catalyst of example 1.
FIG. 3 is a scanning electron micrograph of the covalent organic framework material TPB-DMTP-COF-Xwt% Rh supported by the rhodium metal catalyst in example 1.
FIG. 4 is the physical adsorption desorption curve of nitrogen gas of the rhodium metal catalyst supported covalent organic framework material TPB-DMTP-COF-Xwt% Rh in example 1
FIG. 5 is a nuclear magnetic hydrogen spectrum of a polymer obtained by polymerizing phenylacetylene catalyzed by a covalent organic framework material loaded by a rhodium metal catalyst in example 3.
Figure 6 is a Gel Permeation Chromatography (GPC) spectrum of a polymer obtained from the polymerization of phenylacetylene catalyzed by a covalent organic framework material supported by a rhodium metal catalyst of example 3.
FIG. 7 is a nuclear magnetic hydrogen spectrum of a polymer obtained by polymerizing phenylacetylene catalyzed by a covalent organic framework material loaded by a rhodium metal catalyst in example 7.
Figure 8 is a Gel Permeation Chromatography (GPC) spectrum of a polymer obtained from the polymerization of phenylacetylene catalyzed by a covalent organic framework material supported by a rhodium metal catalyst of example 7.
FIG. 9 is a nuclear magnetic hydrogen spectrum of a polymer obtained by polymerizing phenylacetylene catalyzed by a covalent organic framework material loaded by a rhodium metal catalyst in example 8.
Figure 10 is a Gel Permeation Chromatography (GPC) spectrum of a polymer obtained from the polymerization of phenylacetylene catalyzed by a covalent organic framework material supported by a rhodium metal catalyst of example 8.
FIG. 11 is a nuclear magnetic hydrogen spectrum of a polymer obtained by polymerizing phenylacetylene catalyzed by a covalent organic framework material loaded by a rhodium metal catalyst in example 11.
Figure 12 is a Gel Permeation Chromatography (GPC) spectrum of a polymer obtained from the polymerization of phenylacetylene catalyzed by a covalent organic framework material supported by a rhodium metal catalyst of example 11.
FIG. 13 shows a rhodium metal catalyst [ Rh (nbd) (Cl) in example 15]2Catalyzing phenylacetylene to polymerize to obtain the nuclear magnetic hydrogen spectrum of the polymer.
FIG. 14 shows the rhodium metal catalyst [ Rh (nbd) (Cl) in example 15]2Gel Permeation Chromatography (GPC) of the catalyzed phenylacetylene to give a polymer.
Figure 15 is a circular dichroism spectrum of a polymer derived from the polymerization of (2- (dodecyloxy) -5-ethynyl-1, 3-phenylene) dimethanol catalyzed by a covalent organic framework material supported by a rhodium metal catalyst of example 18.
FIG. 16 is an ultraviolet absorption spectrum of a polymer prepared from the polymerization of [1- (4-ethynylphenyl) -1,2, 2-triphenyl ] ethenyl, [1- (4-phenylethynylphenyl) -1,2, 2-triphenyl ] ethenyl, and N- (4-ethynylphenyl) -6- (4- (1,2, 2-triphenylethenyl) phenoxy) hexanamide catalyzed by a covalent organic framework material supported by a rhodium metal catalyst in example 19.
FIG. 17 is a fluorescence spectrum of a polymer obtained from the polymerization of [1- (4-ethynylphenyl) -1,2, 2-triphenyl ] ethene, [1- (4-phenylethynylphenyl) -1,2, 2-triphenyl ] ethene, and N- (4-ethynylphenyl) -6- (4- (1,2, 2-triphenylethenyl) phenoxy) hexanamide catalyzed by a covalent organic framework material supported by a rhodium metal catalyst in example 19.
FIG. 18 is a fluorescence quenching spectrum of a polymer obtained by polymerizing 5- (dimethylamino) -N- (4-ethynylphenyl) naphthalene-1-sulfonamide catalyzed by a covalent organic framework material supported by a rhodium metal catalyst in example 20.
FIG. 19 is a powder X-ray diffraction pattern of example 21 using a covalent organic framework material supported by a rhodium metal catalyst as a recycled catalyst to catalyze the polymerization of phenylacetylene and recycle the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the following embodiments.
The main reagent information mentioned in the following examples is shown in Table 1, and the main instruments and equipment are shown in Table 2.
TABLE 1
TABLE 2
The polymerization product obtained in the following example, wherein Activity is polymerization Activity and the unit is g.mol-1·h-1M is phenylacetylene, halogenated phenylacetylene, alkyl substituted phenylacetylene, [1- (4-ethynylphenyl) -1,2, 2-triphenyl]Ethylene, [1- (4-phenylethynylphenyl) -1,2, 2-triphenyl radical]Ethylene or phenylacetylene containing heteroatoms.
The activity calculation formula is as follows:
wherein: a: polymerization activity;
mpolymer: polymer mass (g);
nRh: the amount (mol) of Rh species in the catalyst;
t is reaction time (h);
mcatalyststhe mass of the catalyst (g);
ωRh: mass fraction of Rh metal in the catalyst;
MRh: molar mass (g/mol) of Rh metal.
The polyphenylacetylene microstructure can be composed of1The H-NMR spectrum shows that the selectivity is specifically calculated by the following formula:
％cis＝[IH1/(Itotal)/6]×100
wherein, IH1Is composed of1Integral at 5.84ppm of alkyne proton on phenylacetylene in H spectrum, ItotalIs composed of1Benzene ring in H spectrumThe upper aromatic substrate peak 6.94ppm, 6.78ppm (trans), 6.63ppm and 5.84ppm alkyne proton on phenylacetylene were all integrated.
Example 1
(1) Four equal parts of covalent organic framework material TPB-DMTP-COF (10mg) are respectively reacted with 2, 5-norbornadiene rhodium (1.3 mg, 2.6mg, 6.5mg and 13.0mg) in acetone solution at 25 ℃ for 24 hours, solid obtained by centrifuging reaction liquid is washed with acetone for four times, and dried at 40 ℃ for 1 hour under a vacuum state, so that four rhodium catalysts with different loading amounts of covalent organic framework material TPB-DMTP-COF-2.74 wt% Rh, TPB-DMTP-COF-4.00 wt% Rh, TPB-DMTP-COF-6.00 wt% Rh and TPB-DMTP-COF-11.38 wt% Rh can be respectively obtained. (see fig. 1,2, 3, 4).
The rhodium catalyst supported covalent organic framework material prepared in this example was tested as follows:
(1) powder X-ray diffraction detection
TPB-DMTP-COF covalent organic framework material and covalent organic framework material loaded with rhodium metal catalyst TPB-DMTP-COF-Xwt% Rh peak position is completely consistent with the standard map simulated by the TPB-DMTP-COF covalent organic framework material, and the covalent organic framework material loaded with the rhodium catalyst in the example 1 is proved not to collapse and can be used for catalysis of the subsequent steps (shown in figure 2).
(2) Scanning electron microscope detection
The scanning electron micrograph of the rhodium catalyst-supported covalent organic framework material prepared in this example is shown in fig. 3. It can be seen from FIG. 3 that the loaded covalent organic framework material is still granular, has a crystal size of between 100nm and 200nm, and is relatively uniform in size.
(3) Nitrogen adsorption desorption detection
The adsorption and desorption curves of the covalent organic framework material loaded by the rhodium catalyst prepared in the embodiment are shown in figure 4. It can be seen from FIG. 4 that as the loading amount increases, the nitrogen adsorption amount decreases, indicating that the channels are caused by the coordinated metal.
Example 2
(1) Adding 1mg of covalent organic framework catalyst TPB-DMTP-COF-2.74 wt% of Rh and 3ml of toluene loaded with rhodium into an eggplant bottle, and uniformly stirring by using a magnetic stirrer; adding 3400 equivalent of phenylacetylene and 1 equivalent of trimethylaluminum cocatalyst, and continuing to stir uniformly by magnetic force; stirring and reacting for 2min at 25 ℃;
(2) after the reaction, taking the reaction solution out of the eggplant bottle, adding the reaction solution into a centrifuge tube for centrifugation, adding 1mL of methanol solution with the volume fraction of 0.2% of glacial acetic acid into the supernatant to terminate the reaction, settling the reaction solution by using anhydrous methanol to separate out solid substances, drying the solid substances at 40 ℃ in vacuum to constant weight to obtain a polymerization product, weighing the polymerization product, obtaining the yield of 25% and the activity of 1 × 10 according to the activity formula7g/molRhH, the catalyst solid precipitated in the lower layer of the centrifuge tube can be reused for a new polymerization reaction.
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Nuclear magnetic spectrum (hydrogen spectrum) of the polymerization product prepared in this example. From the formula, it can be calculated that cis-polyphenylacetylene reaches 97% by integration at 5.84 in ppm of hydrogen spectrum and integration at 6.94, 6.78 and 6.63 in ppm.
(2) GPC measurement
The number average molecular weight M of the polymer product obtained in this example was found by integration from the GPC measurement result of the polymer productn30000 molecular weight distribution Mw/Mn＝2.04。
Example 3
(1) The catalyst was changed to TPB-DMTP-COF-4.00 wt% Rh, and the remainder was the same as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Analysis of the NMR spectrum of the polymer product prepared in this example revealed that the integral at ppm of hydrogen of 5.84 is shown in FIG. 5, and the integral at ppm of 6.94, 6.78 and 6.63, and that the cis-polyphenylacetylene was 94% as calculated from the above formula.
(2) GPC measurement
The integral of the GPC measurement result of the polymerization product prepared in this example shows that the number average molecular weight M of the polymerization product is shown in FIG. 6n20000 molecular weight distribution Mw/Mn＝2.13。
Example 4
(1) The catalyst was changed to TPB-DMTP-COF-6.00 wt% Rh, and the remainder was the same as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that cis-polyphenylacetylene was 96% as calculated from the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen20000 molecular weight distribution Mw/Mn＝2.07。
Example 5
(1) The catalyst was changed to TPB-DMTP-COF-11.38 wt% Rh, and the remainder was the same as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that the amount of cis-polyphenylacetylene reached 97% as calculated by the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen20000 molecular weight distribution Mw/Mn＝2.04。
Example 6
(1) The amount of phenylacetylene monomer added was changed to 5000 equivalents, and the procedure was otherwise the same as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
The NMR spectrum of the polymer prepared in this example is shown. From the formula, it can be calculated that cis-polyphenylacetylene reaches 95% by integration at 5.84 in ppm of hydrogen spectrum and integration at 6.94, 6.78 and 6.63 in ppm.
(2) GPC measurement
The number average molecular weight M of the polymer product obtained in this example was found by integration from the GPC measurement result of the polymer productn30000 molecular weight distribution Mw/Mn＝2.51。
Example 7
(1) The procedure of example 2 was otherwise the same as in step (1) except that the trimethylaluminum assistant was changed to methylaluminoxane;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
The NMR analysis of the polymer product prepared in this example showed that the hydrogen spectrum in ppm was integrated at 5.84 and in ppm was integrated at 6.94, 6.78 and 6.63, as shown in FIG. 7, and it was found that cis-polyphenylacetylene reached 96% by the above formula.
(2) GPC measurement
The integral of GPC measurement result of the polymer product prepared in this example shows that FIG. 8 shows that the number average molecular weight M of the polymer productn20000 molecular weight distribution Mw/Mn＝1.99。
Example 8
(1) The procedure of example 2 was otherwise the same as for the procedure (1) except that the trimethylaluminum assistant was changed to a triethylamine assistant;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
The NMR analysis of the polymer product prepared in this example showed that the hydrogen spectrum was integrated at ppm of 5.84 and at ppm of 6.94, 6.78 and 6.63, as shown in FIG. 9, and that the cis-polyphenylacetylene was 97% as calculated from the above formula.
(2) GPC measurement
The integral of GPC measurement result of the polymerization product prepared in this example is shown in FIG. 10, and the number average molecular weight M of the polymerization productn20000 molecular weight distribution Mw/Mn＝2.40。
Example 9
(1) Changing 3ml of toluene solvent into 3ml of deionized water, and adding no trimethylaluminum auxiliary agent, the rest is the same as the step (1) of the example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that cis-polyphenylacetylene was 95% as calculated from the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen30000 molecular weight distribution Mw/Mn＝1.43。
Example 10
(1) Changing 3ml of toluene solvent into 3ml of tap water, and adding no trimethylaluminum auxiliary agent, the rest is the same as the step (1) of the example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Nuclear magnetic spectrum (hydrogen spectrum) of the polymerization product prepared in this example. From the integration at 5.84 in ppm of the hydrogen spectrum in FIG. 9 and the integration at 6.94, 6.78 and 6.63 in ppm, it can be calculated from the formula that the cis-polyphenylacetylene reaches 97%.
(2) GPC measurement
The number average molecular weight M of the polymer product obtained in this example was found by integration from the GPC measurement result of the polymer productn30000 molecular weight distribution Mw/Mn＝1.41。
Example 11
(1) The solvent was changed to tetrahydrofuran, and the rest was the same as in step (1) of example 9;
(2) same as example 2, step (2).
(1) Nuclear magnetic resonance detection
The NMR analysis of the polymer product prepared in this example revealed that FIG. 11 shows the integration at 5.84 in ppm of hydrogen and the integration at 6.94, 6.78 and 6.63 in ppm, and that cis-polyphenylacetylene was 95% as calculated from the above formula.
(2) GPC measurement
FIG. 12 is an integral of the GPC measurement results of the polymer product produced in this example, and the number average molecular weight M of the polymer productn30000 molecular weight distribution Mw/Mn＝2.40。
Example 12
(1) The solvent was changed to methylene chloride, and the rest of the procedure was the same as in step (1) of example 2;
(2) same as example 2, step (2).
(1) Nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that cis-polyphenylacetylene was 96% as calculated from the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen20000 molecular weight distribution Mw/Mn＝2.19。
Example 13
(1) The cocatalyst was replaced by triethylaluminum, and the procedure was otherwise the same as in step (1) of example 2;
(2) same as example 2, step (2).
(1) Nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that cis-polyphenylacetylene was 96% as calculated from the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen30000 molecular weight distribution Mw/Mn＝4.08。
Example 14
(1) The catalyst is changed into a catalyst added with [ Rh (nbd) (Cl)]2Otherwise, the same procedure as in (1) of example 2 was repeated;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Nuclear magnetic spectrum (hydrogen spectrum) of the polymerization product prepared in this example. From the formula, it can be calculated that cis-polyphenylacetylene reaches 95% by integration at 5.84 in ppm of hydrogen spectrum and integration at 6.94, 6.78 and 6.63 in ppm.
(2) GPC measurement
The number average molecular weight M of the polymer product obtained in this example was found by integration from the GPC measurement result of the polymer productn20000 molecular weight distribution Mw/Mn＝4.15。
Example 15
(1) The catalyst is changed into a catalyst added with [ Rh (nbd) (Cl)]2The cocatalyst is changed into methylaluminoxane, and the rest is the same as the step (1) of the example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
The NMR spectrum of the polymerization product prepared in this example is shown in FIG. 13 (hydrogen spectrum). From the integration at 5.84 for ppm of hydrogen spectrum in FIG. 13 and the integrations at 6.94, 6.78 and 6.63 for ppm, it can be calculated from the formula that cis-polyphenylacetylene reaches 95%.
(2) GPC measurement
The GPC measurement result of the polymerization product prepared in this example was integrated from FIG. 14, and the number average molecular weight M of the polymerization product was foundn20000 molecular weight distribution Mw/Mn＝2.82。
Example 16
(1) The cocatalyst is changed into triethylamine, and the rest is the same as the step (1) of the example 15;
(2) same as in example 15, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that 94% of cis-polyphenylacetylene was obtained from the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen30000 molecular weight distribution Mw/Mn＝2.30。
Example 17
(1) The solvent was changed to tetrahydrofuran, and the rest was the same as in step (1) of example 14;
(2) same as in step (2) of example 14.
The following tests were carried out on the polymerization product prepared in this example:
(1) nuclear magnetic resonance detection
Analysis of the nmr spectrum of the polymer product prepared in this example revealed that ppm of hydrogen was integrated at 5.84 and ppm was integrated at 6.94, 6.78 and 6.63, and that the amount of cis-polyphenylacetylene reached 97% as calculated by the above formula.
(2) GPC measurement
The number average molecular weight M of the polymer product was found by integration of the GPC measurement results of the polymer product prepared in this examplen10000, molecular weight distribution Mw/Mn＝4.81。
Example 18
(1) The polymerization monomer was changed to (2- (dodecyloxy) -5-ethynyl-1, 3-phenylene) dimethanol and the reaction time was changed to 0.5 hour by adding (R) - (+) - α -methylbenzylamine or S-1-phenylethylamine as a chiral inducer, the rest of the procedure was the same as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) circular dichroism spectrum
The chiral helical effect of the polymerization product prepared in this example is detected by circular dichroism spectroscopy in different solvents with the same concentration, and the spectral signal is weakened with the increase of the polarity of the solvent, which indicates that the polarity of the solvent has a certain influence on the hydrogen bond of the chiral helical polymer. Furthermore, when the chiral inducing agent was changed, the spectral signals exhibited the opposite phenomenon, which corresponds to the theoretical figure 15.
Example 19
(1) The polymerization monomers were changed to [1- (4-ethynylphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-phenylethynylphenyl) -1,2, 2-triphenyl ] ethylene or N- (4-ethynylphenyl) -6- (4- (1,2, 2-triphenylethenyl) phenoxy) hexanamide, and the reaction time was changed to 0.5 hour, which was otherwise the same as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) ultraviolet absorption spectrum
The aggregation-induced emission effect of the polymerization product prepared in this example was measured by uv absorption spectroscopy, and in solutions with different water contents, the polymers in the solution aggregated with increasing water content, and exhibited an aggregation-induced emission phenomenon, and the uv absorption peak was increased with increasing water content, as shown in fig. 16.
(2) Fluorescence spectroscopy
The aggregation-induced emission effect of the polymerization product prepared in this example was measured by fluorescence spectroscopy, and in solutions with different water contents, the polymer aggregates in the solution with increasing water content, exhibiting an aggregation-induced emission phenomenon, and the absorption peak of the fluorescence spectroscopy increased with increasing water content, as shown in fig. 17.
Example 20
(1) The polymerization monomer was changed to 5- (dimethylamino) -N- (4-ethynylphenyl) naphthalene-1-sulfonamide, and the reaction time was changed to 0.5 hour, as in step (1) of example 2;
(2) same as example 2, step (2).
The following tests were carried out on the polymerization product prepared in this example:
(1) fluorescence spectroscopy
The fluorescence quenching effect of the polymerization product prepared in this example is detected by fluorescence spectroscopy, the fluorescence gradually decreases with the addition of trifluoroacetic acid solution, the fluorescence quenching phenomenon is shown, the absorption peak of the fluorescence spectrum increases with the increase of the addition amount when triethylamine solution is added, and the final recovered initial fluorescence intensity is shown in fig. 18.
Example 21
(1) Washing the catalyst centrifuged in the embodiment 2 with toluene for three times, continuously putting the catalyst into use, adding 1 equivalent of trimethylaluminum after 3400 equivalent of phenylacetylene is added, continuously and uniformly stirring the mixture by magnetic force, stirring the mixture at 25 ℃ for reaction for 2min, centrifuging the reaction solution after the reaction is finished, obtaining a precipitated catalyst, continuously reacting the catalyst, and circularly using the catalyst for 5 times, wherein the rest is the same as the step (1) in the embodiment 2;
(2) same as example 2, step (2).
The polymerization product or catalyst prepared in this example was tested as follows:
(1) nuclear magnetic resonance detection
The NMR spectrum of the polymerization product prepared in this example is shown in FIG. 19 (hydrogen spectrum). From the integration at 5.84 for ppm and at 6.94, 6.78 and 6.63 for ppm in the hydrogen spectrum of FIG. 17, it can be calculated from the above formula that after 1,3 and 5 cycles, the cis-polyphenylacetylene reaches 99%, 99% and 98%, respectively.
(2) Cyclic reaction process monitoring
In this example, the reaction solution obtained by recycling was easily separated from the catalyst by centrifugation, and the separated catalyst was introduced into a new polymerization reaction.
(3) X-ray diffraction detection of catalyst powder
In this example, the recycled regenerated catalyst was tested, and the catalyst before the recycling reaction and after the recycling reaction for 3 and 5 times was characterized, and the catalyst still maintains a certain crystallinity after the recycling reaction for 5 times.
(4) Performing nitrogen physical adsorption detection on catalyst powder
In this example, the catalyst after being recycled and regenerated is detected, and the catalyst is characterized after being recycled for 5 times, and the pore volume and the specific surface area of the catalyst are reduced.
Claims (8)
1. The application of the covalent organic framework material loaded with the rhodium metal catalyst in alkyne polymerization is that the covalent organic framework material is used as the catalyst to catalyze the polymerization reaction of alkyne monomers, and the catalyst can be recycled to obtain the alkyne polymer with high molecular weight, high selectivity and specific functionality.
2. The use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 1 in the polymerisation of alkynes, characterized in that: the covalent organic framework material loaded by the rhodium metal catalyst is TPB-DMTP-COF.
3. Use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 1 or 2 in the polymerisation of alkynes, characterized in that: the application steps are as follows:
(1) TPB-DMTP-COF covalent organic framework material and 2, 5-norbornadiene rhodium react for 24 hours in acetone solution at 25 ℃, solid obtained by centrifuging reaction liquid is washed by acetone for four times, and is dried for 1 hour at 40 ℃ in a vacuum state, thus obtaining the covalent organic framework material with the loaded rhodium metal catalyst respectively.
(2) Respectively adding a catalyst and a good solvent into the reactor, and uniformly stirring; adding alkyne monomer, adding alkyl aluminum, amine reagent or aluminoxane cocatalyst, and continuously stirring uniformly; the reaction is stopped when the reaction temperature is 25 ℃ and the reaction is carried out for 2min under stirring.
(3) Centrifuging the reaction solution, easily precipitating the catalyst solid, and adding a chain terminator into the upper layer reaction solution to terminate the reaction; and (2) settling the reaction solution by using anhydrous methanol containing 2, 6-di-tert-butyl-p-cresol or glacial acetic acid to separate out a solid substance, removing the solvent from the solid substance, drying in a vacuum constant temperature box to constant weight to obtain a polymerization product, and washing the precipitated catalyst for three times by using the solvent selected for polymerization, so that the catalyst can be directly used in new polymerization reaction.
Wherein the molar ratio of the alkyl aluminum, the amine reagent or the methylaluminoxane and other cocatalysts to the monomer to the catalyst is 1-10: 200-5000: 1.
Preferably at 40 ℃ under vacuum.
The good solvent is more than one of n-hexane, n-heptane, benzene, toluene, cyclohexane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, chloroform, dichloromethane, trichloromethane, tetrahydrofuran and water.
The alkyl aluminum reagent is of the molecular formula AlX3Alkyl aluminum of formula HAlX2Of the formula AlX2Alkyl aluminum chloride of Cl or aluminoxane, and X is alkyl. The amine reagent is of the formula NX3And X is an alkyl group.
The chain terminator is methanol and ethanol solution of 2, 6-di-tert-butyl-p-cresol, ethanol solution of 2,3, 4-trimethylphenol, ethanol solution of m-diphenol, ethanol solution of 2, 6-diethylphenol, ethanol solution of p-tert-butylphenol or methanol and ethanol solution of glacial acetic acid.
4. Use of a rhodium catalyst loaded covalent organic framework in the polymerization of alkynes according to claim 3, characterized in that: in the step (3), the mass fraction of phenols of the chain terminator is 5-15%, and the volume fraction of methanol and ethanol solution of glacial acetic acid is 0.1-0.2%.
5. Use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 3 in the polymerisation of alkynes, characterized in that: and (3) drying at 40 ℃ in vacuum.
6. Use of a metal organic framework material supporting a rhodium metal catalyst according to claim 3 in the polymerisation of alkynes, characterized in that: the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tricyclohexyl aluminum or trioctyl aluminum;
the alkyl aluminum hydride is dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride or dioctyl aluminum hydride;
the alkyl aluminum chloride is dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride or dioctyl aluminum chloride;
the aluminoxane is methyl aluminoxane, ethyl aluminoxane, n-propyl aluminoxane or n-butyl aluminoxane;
the amine reagent is triethylamine, triisopropylamine, aniline, (R) - (+) -alpha-methylbenzylamine, S-1-phenylethylamine.
7. Use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 3 in the polymerisation of alkynes, characterized in that: the alkyne monomer is phenylacetylene, fluoro phenylacetylene, chloro phenylacetylene, bromo phenylacetylene, iodo phenylacetylene, methyl phenylacetylene, ethyl phenylacetylene, propyl phenylacetylene, butyl phenylacetylene, vinyl phenylacetylene, propenyl phenylacetylene, butenyl phenylacetylene, phenylenediacetylene, [1- (4-ethynylphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-phenylethynylphenyl) -1,2, 2-triphenyl ] ethylene, biphenyl acetylene, 4-bromo-2-acetylene-1-fluorobenzene, methyl 4-acetylenecarboxylate, 6-ethynyl-4, 4-dimethyldihydrobenzothiopyran, 4 '-diacetylene biphenyl, 4-ethynyl diphenylacetylene, 2-ethynyl-2' -vinyl-biphenyl, 1-bromo-3, 5-diacetylynylbenzene, 2-ethynyl-3 ', 5 ' -dimethyl-1, 1 ' -biphenyl, (2- (dodecyloxy) -5-ethynyl-1, 3-phenylene) dimethanol, N- (4-ethynylphenyl) -6- (4- (1,2, 2-triphenylvinyl) phenoxy) hexanamide, 5- (dimethylamino) -N- (4-ethynylphenyl) naphthalene-1-sulfonamide.
8. The use of a covalent organic framework material supporting a rhodium metal catalyst according to claim 4 in the polymerisation of alkynes, characterized in that: chain terminators used after the polymerization are: methanol solution of 2, 6-di-tert-butyl-p-cresol, ethanol solution of 2,3, 4-trimethylphenol, ethanol solution of m-diphenol, ethanol solution of 2, 6-diethylphenol or ethanol solution of p-tert-butylphenol; preferably, the mass fraction of 2, 6-di-tert-butyl-p-cresol, 2,3, 4-trimethylphenol, m-diphenol, 2, 6-diethylphenol or p-tert-butylphenol is 5 to 15 percent, or glacial acetic acid methanol or ethanol solution, wherein the volume fraction of the glacial acetic acid is 0.1 to 0.2 percent.
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| CN114316172B (en) * | 2021-12-29 | 2023-08-08 | 遵义医科大学珠海校区 | Fluorescent covalent organic framework material for detecting fluoride ions and preparation method thereof |
| CN116328844A (en) * | 2023-02-28 | 2023-06-27 | 河北工业大学 | Preparation method and application of core-shell hollow sphere heterojunction photocatalyst constructed by utilizing rhodium electronic medium fixed by covalent organic framework material |
| CN116328844B (en) * | 2023-02-28 | 2024-04-26 | 河北工业大学 | Preparation method and application of core-shell hollow sphere heterojunction photocatalyst constructed by utilizing rhodium electronic medium fixed by covalent organic framework material |
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