Porous organic polymers containing bidentate phosphorus ligands, methods of making and using the same

Abstract

The application discloses a kind of porous organic polymers containing bidentate phosphorus ligand and a preparation method and application thereof.The polymer is of general formula I as follows: The above polymer is obtained by polymerization of: General compound and or.The porous organic polymer containing phosphorus ligand provided by the application can be used to catalyze hydroformylation of olefins after forming catalyst with transition metal salt, and has high catalytic rate, good selectivity and cycle, and has practical value.

Description

Technical Field

[0001] This invention relates to a class of organic polymers, their preparation methods, and applications. Specifically, it relates to a class of porous organic polymers containing bidentate phosphorus ligands, their preparation methods, and applications, belonging to the field of organic chemistry technology. Technical Background

[0002] Hydroformylation is the process by which olefins and CO / H2 generate aldehydes under the action of a catalyst. Hydroformylation of olefins is an important method for the industrial synthesis of aldehydes. Aldehydes are valuable fine chemicals and important synthetic intermediates. Achieving heterogeneous catalysis of olefin hydroformylation can effectively solve problems such as catalyst recovery, recycling, and pollution. Porous organic polymers (POPs) are a new type of polymer material that has attracted widespread research interest due to their high specific surface area, stable framework, and controllable structure; and have made great progress in the field of heterogeneous catalysis. POPs constructed from phosphine ligand monomers have the following characteristics: (1) high concentrations of phosphine ligands in the polymer framework can support metals and recover catalysts; (2) effectively regulate the spatial and electronic benefits around the metal center, which helps to improve the selectivity and activity of the catalyst; (3) effectively disperse metal particles to form single-atom active sites. Therefore, in recent years, a variety of phosphine-containing POPs materials have been synthesized and used in heterogeneous catalysis. Solvothermal olefin polymerization is one of the main methods for synthesizing phosphine-containing porous organic polymers. However, there are still problems such as expensive raw materials, complicated synthesis process, and a lot of waste. This patent describes the successful synthesis of a porous organic polymer containing bidentate phosphorus ligands from the natural product magnolol via a three-step reaction. The heterogeneous catalyst constructed by supporting rhodium on this polymer exhibits high catalytic activity, selectivity, and cyclicity in the hydroformylation of olefins. Summary of the Invention

[0003] The purpose of this invention is to provide a class of porous organic polymers containing bidentate phosphorus ligands, their preparation methods and applications, thereby adding a new type of catalyst to heterogeneous catalytic hydroformylation of olefins.

[0004] A class of porous organic polymers containing bidentate phosphorus ligands have the following general structural formula I:

[0005]

[0006] In the above general formula:

[0007] R 1 R 2 R 3 R 4 Selected from C1 to C1 respectively 10 alkane group, C1-C 10 alkoxy groups,

[0008] R 5 R 6 R 7 R 8 R 9 R 10 Each group is independently selected from hydrogen, sulfonic acid group, halogen, nitrile group, C1 to C2 groups. 12 alkane group, C1-C 10 alkyl acyl group, C1-C 10 ester group, C1-C 10 sulfonate group;

[0009] R comes from... Monomer unit;

[0010] The n:m ratio is 1:1 to 1:100;

[0011] The aforementioned porous organic polymer containing bidentate phosphorus ligands is characterized in that: polymer I is obtained by polymerization of compound 1 and R'; the general reaction formula is shown below:

[0012]

[0013] In the general formula, compound 1 is composed of compound 2 and phosphorus chloride. The reaction is carried out to obtain the product; the general reaction formula is shown below:

[0014]

[0015] In the general formula, compound 2 is obtained by the isomerization reaction of compound 3; the general reaction formula is shown below:

[0016]

[0017] R in the above general formula 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 The meanings of R and R are the same as those described in claim 1; R' is selected from...

[0018] The application of the aforementioned porous organic polymer containing bidentate phosphorus ligands is characterized by its use in catalyzing the hydroformylation reaction of olefins.

[0019] The application is characterized in that: a porous organic polymer containing bidentate phosphorus ligands forms an I / Rh catalyst with a transition metal salt, which is then used to catalyze the hydroformylation reaction of olefins;

[0020] The application is characterized in that a class of porous organic polymers containing bidentate phosphorus ligands are selected from the following structures:

[0021]

[0022] Compared with the prior art, the present invention has the following significant effects:

[0023] 1. The porous organic polymer supported catalyst containing bidentate phosphorus ligands provided by the present invention uses natural products as raw materials, has a green synthesis step, and a simple preparation method.

[0024] 2. The porous organic polymer supported catalyst containing bidentate phosphorus ligands provided by this invention is used for the hydroformylation reaction of olefins. The reaction conditions are mild and the yield can be as high as 78%, which is suitable for large-scale production and has practical value. Detailed Implementation

[0025] The present invention will be further described in detail and completely below with reference to the embodiments.

[0026] The propylene-based biphenyl used in the following examples was prepared by the following method:

[0027] 1) Diphenol Preparation

[0028] Under nitrogen protection, the raw materials are added to the reaction flask. 1.0 g, Rh(acac)(CO)₂ (1 mg, 0.004 mmol), tris(4-methoxyphenyl)phosphine (4.22 mg, 0.012 mmol), EtOH (4 mL), heated at 100 °C for 72 hours, the product was purified by column chromatography to obtain propenyl biphenylhydrazine. The product characterization is as follows: 1 H NMR (500MHz, CDCl3) δ7.29(dd,J=8.5,1.5Hz,2H),7.23(d,J=1.5Hz,2H),6.95(d,J=8.5Hz,2H ),6.36(d,J=15.5Hz,2H),6.13(m,2H),5.70(d,J=28.5Hz,2H),1.88(dd,J=19.5,7.0Hz,6H).

[0029] 2) synthesis

[0030] Under a nitrogen atmosphere, dipyrrole phosphorus chloride (297.9 mg, 1.5 mmol), anhydrous triethylamine (0.21 mL, 1.5 mmol), and anhydrous tetrahydrofuran (2 mL) were added separately to a 20 mL Schlenk tube. The tube was cooled to 0 °C, and propenyl biphenyl hydroquinone was added dropwise. A solution of 200 mg, 0.75 mmol, anhydrous tetrahydrofuran (2 mL) was slowly heated to room temperature and stirred overnight. The reaction was stopped, the solvent was removed under reduced pressure, and the product was separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 20) to obtain 421.1 mg of a colorless oil. The product was characterized as follows: 1 H NMR (500MHz, CDCl3) δ7.23(d,J=6.5Hz,4H),6.79(d,J=9.0Hz,2H),6.73(s,8H),6.35(d,J=15.5Hz,2H),6.24(s,8H),6.16(m,2H),1.91–1.84(m,6H).

[0031] 3) Polymer I1 Synthesis

[0032] Under a nitrogen atmosphere, anhydrous tetrahydrofuran (3.0 mL) was added to a 10 mL stopcock bottle. The copolymer unit... (60mg, 0.102mmol) and (172.8 mg, 0.51 mmol). Finally, 5.0 mg of initiator AIBN was added. After stirring at room temperature for 10 min, the mixture was reacted at 100 °C for 24 h. The product was separated by centrifugation, washed with tetrahydrofuran (3 × 3 mL), and rotary evaporated to give a white solid (201.2 mg).

[0033] 4) Polymer I2 Synthesis

[0034] Under a nitrogen atmosphere, anhydrous tetrahydrofuran (3.0 mL) was added to a 10 mL stopcock bottle. The copolymer unit... (60.2 mg, 0.102 mmol) and divinylbenzene (66.4 mg, 0.51 mmol). Finally, 5.0 mg of initiator AIBN was added. After stirring at room temperature for 10 min, the mixture was reacted at 100 °C for 24 h. The product was separated by centrifugation, washed with tetrahydrofuran (3 × 3 mL), and rotary evaporated to give a white solid (108.4 mg).

[0035] 5) Polymer I3 Synthesis

[0036] Under a nitrogen atmosphere, anhydrous tetrahydrofuran (3.0 mL) was added to a 10 mL stopcock bottle. The copolymer unit... (60.2 mg, 0.102 mol) and (196.1 mg, 0.51 mmol). Finally, 5.0 mg of initiator AIBN was added. After stirring at room temperature for 10 min, the mixture was reacted at 100 °C for 24 h. The product was separated by centrifugation, washed with tetrahydrofuran (3 × 3 mL), and rotary evaporated to give a white solid (201.3 mg).

[0037] 6) Synthesis of polymer I1 / Rh catalyst

[0038] Under a nitrogen atmosphere, add to a 100 mL Schlenk tube. The reaction mixture consisted of 90 mg of Rh(acac)(CO)₂ (3.4 mg, 0.0132 mmol) and 5 mL of anhydrous toluene. After stirring at room temperature under nitrogen protection for 24 h, the reaction product was washed with anhydrous THF and centrifuged three times. Finally, toluene was removed by rotary evaporation under reduced pressure, and the mixture was then pumped for 3 h to obtain 85 mg of catalyst.

[0039] 7) The catalytic capacity of polymer I1 / Rh catalyst for catalyzing 1-hexene is S / C = 1 x 10⁻⁶ 4 hydroformylation reaction

[0040] In a glove box, catalyst (5 mg) and anhydrous 1-hexene (0.46 mL, 3.67 mmol) were added to a 100 mL reactor. The nitrogen in the reactor was then replaced three times with CO, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath. The synthesis gas was slowly released, and decane (49 μL) was added as an internal standard. After thorough stirring, the gas phase was measured. The normal-to-isotropic ratio was 50.5, the yield of the straight-chain aldehyde was 78.0%, and the TON value was 9000.

[0041] 8) The catalytic capacity of polymer I1 / Rh catalyst for catalyzing 1-hexene is S / C = 20 x 10⁻⁶ 4 hydroformylation reaction

[0042] In a glove box, catalyst (5.0 mg) and anhydrous 1-hexene (9.11 mL, 73.4 mmol) were added to a 100 mL reactor. The nitrogen in the reactor was then replaced three times with CO, followed by CO (10 atm) and H2 (10 atm). The reactor was stirred in an oil bath at 90 °C for 10 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath. The synthesis gas was slowly released, and then CO (10 atm) and H2 (10 atm) were added, and the reaction was continued for 3 h. This process was repeated twice. Finally, decane (49 μL) was added as an internal standard, and the gas phase was measured after thorough stirring. The normal-to-isotropic ratio was 12.1, the molar percentage of the straight-chain aldehyde was 77.3%, and the TON was 16.7 × 10⁻⁶. 4 .

[0043] 9) The catalytic capacity of polymer I1 / Rh catalyst for catalyzing 1-hexene is S / C = 1 x 10⁻⁶ 4 Cyclic testing of the hydroformylation reaction.

[0044] In a glove box, 50 mg of catalyst and 4.6 mL (36.7 mmol) of anhydrous 1-hexene were added to a 100 mL reactor. The reactor was then purged with CO three times to replace nitrogen, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath, and the syngas was slowly released. The reaction system was centrifuged to separate the upper product and the lower catalyst layer. The separated catalyst was added back to the reactor in a glove box along with 4.6 mL (36.7 mmol) of anhydrous 1-hexene. The reactor was then purged with CO three times to replace nitrogen, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. Decane (49 μL) was added to the upper product as an internal standard, and the gas phase was measured after thorough stirring. This cycle was repeated 10 times. Throughout the ten reactions, the yield of the aldehyde remained above 70%.

[0045] 10) The catalytic capacity of polymer I1 / Rh catalyst for catalyzing 1-octene is S / C = 1 x 10⁻⁶ 4 Isomerization / hydroformylation reaction.

[0046] In a glove box, catalyst (5 mg) and anhydrous 2-octene (0.57 mL, 3.67 mmol) were added to a 100 mL reactor. The nitrogen in the reactor was then replaced three times with CO, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath. The synthesis gas was slowly released, and decane (49 μL) was added as an internal standard. After thorough stirring, the gas phase was measured. The positive-to-iso ratio was 40, the yield of the straight-chain aldehyde was 71.0%, and the TON was 8000.

[0047] 11) The catalytic capacity of polymer I1 / Rh catalyst for catalyzing 2-octene is S / C = 1 x 10⁻⁶ 4 Isomerization / hydroformylation reaction.

[0048] In a glove box, catalyst (5 mg) and anhydrous 2-octene (0.57 mL, 3.67 mmol) were added to a 100 mL reactor. The nitrogen in the reactor was then replaced three times with CO, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath. The synthesis gas was slowly released, and decane (49 μL) was added as an internal standard. After thorough stirring, the gas phase was measured. The positive-to-iso ratio was 7, the yield of the straight-chain aldehyde was 57.7%, and the TON was 6000.

[0049] 12) The catalytic capacity of polymer I2 / Rh catalyst for catalyzing 1-hexene is S / C = 1 x 10⁻⁶ 4 hydroformylation reaction

[0050] In a glove box, catalyst (4 mg) and anhydrous 1-hexene (0.46 mL, 3.67 mmol) were added to a 100 mL reactor. The nitrogen in the reactor was then replaced three times with CO, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath. The synthesis gas was slowly released, and decane (49 μL) was added as an internal standard. After thorough stirring, the gas phase was measured. The N / I ratio was 49, the yield of the straight-chain aldehyde was 76.0%, and the TON was 8500.

[0051] 13) The catalytic capacity of polymer I3 / Rh catalyst for catalyzing 1-hexene is S / C = 1 x 10⁻⁶ 4 hydroformylation reaction

[0052] In a glove box, catalyst (5.3 mg) and anhydrous 1-hexene (0.46 mL, 3.67 mmol) were added to a 100 mL reactor. The nitrogen in the reactor was then replaced three times with CO, followed by CO (10 atm) and H2 (10 atm). The reaction was stirred in an oil bath at 90 °C for 3 h. After the reaction was complete, the reactor was cooled to room temperature using an ice-water bath. The synthesis gas was slowly released, and decane (49 μL) was added as an internal standard. After thorough stirring, the gas phase was measured. The N / I ratio was 46, the yield of the straight-chain aldehyde was 72%, and the TON value was 8200.

[0053] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions claimed by the present invention.

Claims

1. A method for preparing a porous organic polymer containing bidentate phosphorus ligands, characterized in that... The method is as follows: (1) Compound 1 reacts with R' to produce polymer I, and the general reaction formula is shown below: ； (2) Compound 1 is formed by compound 2 and and The reaction is carried out to obtain the following general reaction formula: ； (3) Compound 2 is obtained from compound 3 via an olefin isomerization reaction; the general reaction formula is shown below: ； In the above general formula: R 1 R 2 R 3 R 4 Selected from C1 to C1 respectively 10 alkane group, C1-C 10 alkoxy groups, , , , or ; R 5 R 6 R 7 R 8 R 9 R 10 Each group is independently selected from hydrogen, sulfonic acid group, halogen, nitrile group, C1 to C2 groups. 12 alkane group, C1-C 10 alkyl acyl group, C1-C 10 ester group, C1-C 10 sulfonate group; R' comes from respectively , or Compounds; The n:m ratio is 1:1 to 1:

100.

2. The application of the porous organic polymer prepared by the preparation method according to claim 1, characterized in that: Used to catalyze the hydroformylation of olefins.

3. The application of the porous organic polymer according to claim 2, characterized in that: Porous organic polymers containing bidentate phosphorus ligands form I / Rh catalysts with transition metal salts, which are then used to catalyze the hydroformylation of olefins.

4. The application of the porous organic polymer according to claim 3, characterized in that, Porous organic polymers containing bidentate phosphorus ligands are selected from the following structures: ， ， 。 5. The application of the porous organic polymer according to claim 3, characterized in that, The preparation of the I / Rh catalyst includes the following steps: Under an inert gas atmosphere, a porous organic polymer containing bidentate phosphorus ligands is added to toluene at a mass ratio of 1:1 to 500:1 to Rh(acac)(CO)₂ metal salt. The mixture is stirred at 0–100 °C for 0.1–20 hours, and the solvent is removed to obtain the desired product. / Rh catalyst.

6. The application of the porous organic polymer according to claim 3, characterized in that: The procedure for using the I / Rh catalyst to catalyze the hydroformylation of olefins is as follows: Under an inert atmosphere, an olefin substrate, CO, and H2 are added to a reactor containing the catalyst, and the hydroformylation reaction is carried out at 0–300 °C; the olefin substrate is a terminal olefin or an internal olefin; the molar ratio of the olefin substrate to the Rh salt in the catalyst is 100:1 to 100000:1, the CO pressure is 0.5–200 atm, and the H2 pressure is 0.5–200 atm.

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