阅读说明：本技术 负载铑催化剂的共价有机骨架材料在炔烃聚合中的应用 (Application of covalent organic framework material loaded with rhodium catalyst in alkyne polymerization ) 是由 李晓芳 曹清彬 章力 高飞 于 2020-05-22 设计创作，主要内容包括：本发明涉及一种负载铑催化剂的共价有机骨架材料在炔烃聚合中的应用,属于共价有机骨架材料催化技术领域。所述应用是作为催化剂催化炔烃聚合的聚合反应,作为催化剂催化苯乙炔聚合,当加入烷基铝、胺试剂或铝氧烷助剂时,催化活性高,可达1.2×10<Sup>7</Sup>g mol<Sup>-1</Sup>h<Sup>-1</Sup>,顺式聚苯乙炔含量可达99％,分子量达4万,催化剂可重复使用5次以上。还可以利用该反应体系,催化聚合带功能性基团(如[1-(4-乙炔基苯基)-1,2,2-三苯基]乙烯)的炔烃单体,得到具有单手性螺旋聚合物、聚集诱导发光效应的聚合物、荧光功能的聚合物,该功能聚合物可用于手性识别、发光器件的制备、荧光检测,本发明解决了炔烃聚合催化剂无法回收再利用,聚合物制备产率低、过程复杂、成本高的问题,该催化剂可循环再生绿色环保且经济性好。(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 × 10 7 g mol ‑1 h ‑1 The 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.)

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.

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;

m_polymer: polymer mass (g);

n_Rh: the amount (mol) of Rh species in the catalyst;

t is reaction time (h);

m_catalyststhe mass of the catalyst (g);

ω_Rh: mass fraction of Rh metal in the catalyst;

M_Rh: 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＝[I_H1/(I_total)/6]×100

wherein, I_H1Is composed of¹Integral at 5.84ppm of alkyne proton on phenylacetylene in H spectrum, I_totalIs 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.