Synthesis method and application of rhodium catalyst loaded on phosphine-containing porous organic polymer / molecular sieve composite carrier

Abstract

The present application relates to a kind of synthesis of rhodium catalyst containing phosphine porous organic polymer / molecular sieve composite carrier and its catalytic tandem olefin hydroformylation- acetalization reaction. Specifically, it is obtained by polymerization reaction of monomer and molecular sieve mixture to obtain composite carrier, and further loaded with rhodium to obtain the corresponding catalyst. The catalyst can catalyze olefin, H2 / CO and organic alcohol one-pot preparation of acetal, belonging to the technical field of organic chemistry. The present application provides high catalytic rate, wide substrate applicability, high regioselectivity and recycling in the catalytic tandem hydroformylation / acetalization reaction.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for synthesizing acetal. Specifically, it relates to the application of a kind of rhodium catalyst supported on porous organic polymer / molecular sieve composite carrier to the reaction of preparing acetal by heating one-pot method of olefins and organic alcohol, and belongs to the technical field of organic chemistry. TECHNICAL BACKGROUND

[0002] Hydroformylation is a process in which an olefin and CO / H2 react to form an aldehyde in the presence of a catalyst. Hydroformylation is an important industrial chemical reaction, which is often used to prepare various aldehyde compounds. Aldehyde compounds are very valuable fine chemicals and important synthetic intermediates. Through the "hydroformylation- acetalization" tandem reaction of olefins, the "one-pot" synthesis of acetal from the functional groups of olefins can be achieved. Acetal is an important organic synthesis intermediate and has wide application value. It is widely used to prepare fungicides, dyes, resins and synthetic fibers and other chemicals, as well as to protect sensitive aldehyde groups from side reactions in organic synthesis. At the same time, the acetal group can be converted to aldehyde group under acidic conditions. Through the hydroformylation-acetalization reaction of olefins, the product acetal can be obtained in one pot, which simplifies the purification step of the intermediate aldehyde, avoids the separation and purification of the aldehyde intermediate, and avoids the disadvantages of the separation process, which is in line with the concept of green development. The currently developed heterogeneous catalysts still have low catalytic activity (TON less than 2000) and low regioselectivity. These shortcomings limit the industrial application of the catalyst. In view of the above problems, we developed a kind of rhodium catalyst supported on composite carrier based on the structural advantages of porous organic polymers and molecular sieves, and successfully applied it to the heterogeneous tandem olefin hydroformylation-acetalization reaction. SUMMARY

[0003] 1. A kind of rhodium catalyst supported on porous organic polymer / molecular sieve composite carrier containing phosphine, characterized by the preparation method comprising the following steps:

[0004] (1) 0.1-10 mmol of polymer monomer L1 and 0.3-50 mmol of polymer monomer L2 are dissolved in 1-100 mL of tetrahydrofuran solution;

[0005] (2) The solution of step (1) is added to the suspension containing molecular sieve, and 5-100 mg of AIBN free radical initiator is added. After the mixture is reacted at 100℃ for 24 hours, the solvent is removed under reduced pressure to obtain the composite carrier POP-L1&L2@molecular sieve;

[0006] (3) Take 0.1-10g of the composite support POP-L1&L2@ molecular sieve synthesized in step (2) and 0.1-0.5mg of Rh salt, and add them to 5-20mL of tetrahydrofuran. Stir at room temperature for 24 hours, remove the solvent, and dry under vacuum to obtain the catalyst Rh / POP-L1&L2@ molecular sieve;

[0007] 2. The method for preparing a type of phosphine-containing porous organic polymer / molecular sieve composite support for rhodium catalyst according to claim 1, characterized in that the polymer monomer L1 in step (1) has the following characteristics:

[0008] R 1 R 2 R 3 R 4 Selected independently

[0009] 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 alkoxy groups,

[0010] 2. The rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support according to claim 1, characterized in that, in step (1), the polymerizing monomer L2 is selected from... One of them;

[0011] 3. The rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support according to claim 1, characterized in that the molecular sieve in step (2) is selected from one or more of the following: MCM-41, ZSM-5, β-Zeolite, ZSM-35(100), ZSM-35(10), ZSM-23, ZSM-22, ZSM-11, KIT-6, SBA-15, MCM-22, MCM-48, SSZ-13, UIO-66, titanium silica molecular sieve TS-1, SAPO-34, SAPO-11, silica nanospheres, mesoporous silica, hierarchical porous silica microspheres, carbon molecular sieve, 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, Y-type molecular sieve, and S-1 all-silica molecular sieve;

[0012] 4. The phosphine-containing porous organic polymer / molecular sieve composite support for rhodium catalyst according to claim 1, characterized in that, in step (3), the rhodium salt is selected from one of Rh(acac)(CO)2, Rh(acac)(C2H4), [Rh(C2H4)2Cl]2, [Rh(COD)Cl]2, [Rh(NBD)Cl]2, [Rh(CO)2Cl]2, Rh(PPh3)Cl or Rh(CO)2Cl2; acac represents acetylacetone, COD represents cyclooctadiene, and NBD represents dicycloheptadiene;

[0013] 5. The application of the phosphine-containing porous organic polymer / molecular sieve composite support supported rhodium catalyst according to claim 1, characterized in that it is used to catalyze the hydroformylation / acetal tandem reaction of heterogeneous olefins;

[0014] 6. The application according to claim 5, characterized in that the catalyst is used to catalyze the hydroformylation / acetalization tandem reaction of olefins as follows: under an inert atmosphere, an olefin substrate, CO, and H2 are added to a reactor containing the catalyst, and the hydroformylation-acetalization 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.

[0015] Compared with the prior art, the present invention has the following significant effects:

[0016] 1. The present invention provides a type of phosphine-containing porous organic polymer / molecular sieve composite support supported rhodium catalyst for the hydroformylation-acetalization reaction of olefins, which has high catalytic rate (TON up to 10000) and substrate applicability.

[0017] 2. The present invention provides a class of phosphine-containing porous organic polymer / molecular sieve composite support for supporting rhodium catalysts in the hydroformylation-acetalization reaction of olefins, which has high regioselectivity (l / b = 30.2-87.9).

[0018] 3. The present invention provides a class of phosphine-containing porous organic polymer / molecular sieve composite support rhodium catalysts for the hydroformylation-acetalization reaction of olefins. All catalysts are recyclable and can maintain high catalytic activity after multiple cycles. Detailed Implementation

[0019] The present invention will be further described in detail and completely below with reference to the embodiments.

[0020] Example 1

[0021] The rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support used in the following examples was prepared via the following reaction process:

[0022] (1) Take monomer L1 (250.00 mg) and polymer monomer L2 (331.10 mg) dissolved in 5.0 mL of tetrahydrofuran solution;

[0023] (2) The solution from step (1) was added to a suspension containing 581 mg of ZSM-35(10) molecular sieve, and then 5 mg of AIBN free radical initiator was added. After the mixture was reacted at 100 °C for 24 hours, the solvent was removed under reduced pressure to obtain the composite carrier POP-BINAPa&PPh3@ZSM-35(10);

[0024] (3) Take 0.4 g of the composite support POP-BINAPa&PPh3@ZSM-35(10) synthesized in step (2) and 7.0 mg of Rh(acac)(CO)2, and add it to 5 mL of tetrahydrofuran. Stir at room temperature for 24 hours, remove the solvent, and dry under vacuum to obtain the catalyst Rh / POP-BINAPa&PPh3@ZSM-35(10);

[0025] Example 2

[0026] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-pentene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0027] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-pentene (0.42 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 90.2%, the l / b ratio was 84.8, and the TON value was 9989.

[0028] Example 3

[0029] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-hexene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0030] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-hexene (0.47 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 96.9%, the l / b ratio was 87.9, and the TON value was 9991.

[0031] Example 4

[0032] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-heptene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0033] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-hepten (0.54 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 89.2%, the l / b ratio was 83.2, and the TON value was 9986.

[0034] Example 5

[0035] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-octene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0036] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-octene (0.60 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 91.0%, the l / b ratio was 72.8, and the TON value was 9985.

[0037] Example 6

[0038] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-nonene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0039] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-nonene (0.66 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 84.0%, the l / b ratio was 33.7, and the TON value was 9923.

[0040] Example 7

[0041] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-decene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0042] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-decene (0.72 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 75.4%, the l / b ratio was 30.2, and the TON value was 9975.

[0043] Example 8

[0044] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-cyclohexene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of MeOH

[0045] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), cyclohexene (0.39 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 84.5%, the l / b ratio was 30.2, and the TON value was 9944.

[0046] Example 9

[0047] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-hexene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of EtOH

[0048] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), EtOH (3.0 mL), 1-hexene (0.47 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 92.2%, the l / b ratio was 75.1, and the TON value was 9940.

[0049] Example 10

[0050] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-hexene (substrate: catalyst) Rh =1×10 4 )and n Hydroformylation-acetalization reaction of PrOH

[0051] In the glove box, place Rh / POP-BINAPa&PPh3@ZSM-35(10)(6.0mg), n PrOH (3.0 mL), 1-hexene (0.47 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, followed by the introduction of CO (10 bar) and H2 (10 bar). The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was complete, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 83.4%, the l / b ratio was 68.7, and the TON value was 9980.

[0052] Example 11

[0053] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-hexene (substrate: catalyst) Rh =1×10 4 )and n Hydroformylation-acetalization reaction of BuOH

[0054] In the glove box, place Rh / POP-BINAPa&PPh3@ZSM-35(10)(6.0mg), n BuOH (3.0 mL), 1-hexene (0.47 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 82.6%, the l / b ratio was 58.2, and the TON value was 10000.

[0055] Example 12

[0056] Phosphorus-containing porous organic polymer / molecular sieve composite support for rhodium catalyst catalysis of 1-hexene (substrate: catalyst) Rh =1×10 4 Hydroformylation-acetalization reaction of n-pentanol

[0057] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), n-pentanol (3.0 mL), 1-hexene (0.47 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, centrifuged, and the gas phase was measured. The yield was 76.8%, the l / b ratio was 41.2, and the TON value was 43000.

[0058] Example 13

[0059] Cyclic experiments of rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support in a tandem hydroformylation-acetalization reaction.

[0060] In a glove box, Rh / POP-BINAPa&PPh3@ZSM-35(10) (6.0 mg), MeOH (3.0 mL), 1-hexene (0.47 mL), and decane (12 μL) were added to a high-pressure reactor and stirred. The mixture was purged three times with H2, and then CO (10 bar) and H2 (10 bar) were introduced. The high-pressure reactor was then stirred and reacted in an oil bath at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature, and the catalyst was recovered by centrifugation and reused in the next reaction. The filtrate was analyzed by GC. The serial data are as follows:

[0061]

[0062] 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. An application of a rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support, characterized in that, The catalyst is used to catalyze the heterogeneous hydroformylation / acetal tandem reaction of olefins, and the preparation method of the catalyst is as follows: (1) Dissolve 0.1-10 mmol of polymeric monomer L1 and 0.3-50 mmol of polymeric monomer L2 in 1-100 mL of tetrahydrofuran solution; (2) Add the solution from step (1) to a suspension containing molecular sieve, and then add 5-100 mg of AIBN free radical initiator. After the mixture reacts at 100 °C for 24 hours, remove the solvent under reduced pressure to obtain the composite carrier POP-L1&L2@molecular sieve. (3) Take 0.1-10 g of the composite support POP-L1&L2@ molecular sieve synthesized in step (2) and 0.1-0.5 mg of Rh salt, and add them to 5-20 mL of tetrahydrofuran. Stir at room temperature for 24 hours, remove the solvent, and then dry under vacuum to obtain the catalyst Rh / POP-L1&L2@ molecular sieve; The polymer monomer L1 in step (1) has the following characteristics: ， R 1 R 2 R 3 R 4 Selected independently , 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 alkoxy groups, ; In step (1), the polymer monomer L2 is selected from... , One of them.

2. The application of the rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support according to claim 1, characterized in that, In step (2), the molecules are screened from one or more of MCM-41, ZSM-5, β-Zeolite, ZSM-35-100, ZSM-35-10, SBA-15, MCM-22, and MCM-48.

3. The application of the rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support according to claim 1, characterized in that, In step (3), the rhodium salt is selected from one of Rh(acac)(CO)2, Rh(acac)(C2H4), [Rh(C2H4)2Cl]2, [Rh(COD)Cl]2, [Rh(NBD)Cl]2, [Rh(CO)2Cl]2, and Rh(PPh3)Cl; acac represents acetylacetone, COD represents cyclooctadiene, and NBD represents dicycloheptadiene.

4. The application of the rhodium catalyst supported on a phosphine-containing porous organic polymer / molecular sieve composite support according to claim 1, characterized in that, The prepared catalyst was used to catalyze the hydroformylation / acetalization tandem reaction of olefins as follows: Under an inert atmosphere, an olefin substrate, CO, and H2 were added to a reactor containing the catalyst, and the hydroformylation-acetalization reaction was carried out at 0–300 °C; the olefin substrate was a terminal olefin or an internal olefin; the molar ratio of the olefin substrate to the Rh salt in the catalyst was 100:1 to 100000:1, the CO pressure was 0.5–200 atm, and the H2 pressure was 0.5–200 atm.

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