CO2 switching type surfactant mediated olefin water two-phase hydroformylation method

Abstract

The invention relates to a CO2 switch type surfactant mediated olefin water two-phase hydroformylation method, and aims to solve the problem that water / organic two phases are difficult to split due to emulsification in surfactant assisted water organic two-phase hydroformylation. According to the invention, the guanidyl CO2 switching type surfactant is applied to a rhodium-catalyzed olefin-water two-phase hydroformylation reaction; by introducing CO2 in the hydroformylation process and releasing CO2 after the reaction is finished, emulsification and demulsification of a water organic two-phase catalytic system are mediated, so that efficient mass transfer of olefin in the reaction and rapid separation and recovery of a rhodium catalyst in a post-treatment stage are realized; compared with an existing surfactant-promoted water two-phase hydroformylation technology, the CO2 switch type surfactant-mediated olefin water two-phase hydroformylation method disclosed by the invention solves the problem that a rhodium catalyst cannot be effectively recycled due to the emulsification effect of a surfactant; the rhodium catalyst prepared by the method can be recycled for multiple times, and the catalytic activity and the selectivity are not obviously reduced.

Description

Technical Field

[0001] The invention relates to the technical field of chemistry and chemical engineering, and in particular to a method for two-phase hydroformylation of olefins in water mediated by a CO2 switchable surfactant. Background Art

[0002] Rhodium-catalyzed olefin hydroformylation is a typical atom-economic reaction and an ideal method for preparing aldehydes / alcohols. Homogeneous rhodium catalysts have the advantages of high catalytic activity, good selectivity and mild reaction conditions, but their recovery and recycling have long been one of the difficulties plaguing the field of homogeneous catalysis.

[0003] In order to solve the problem of rhodium catalyst recovery and circulation, water / organic two-phase, organic fluorine two-phase and ionic liquid two-phase catalytic systems have been developed successively. In contrast, the water / organic two-phase system based on water-soluble rhodium catalyst uses cheap green solvent-water as the catalyst carrier, and it still has strong vitality. In 1984, the RCH-RP process based on water-soluble Rh-TPPTS catalyst was successfully applied to the water / organic two-phase hydroformylation of propylene, but due to the extremely low water solubility of high-carbon olefins, this process is only applicable to low-carbon olefins below C6. In order to overcome this problem, some improved water / organic two-phase catalytic systems have been developed, such as: co-solvent method, modified cyclodextrin method, temperature-controlled phase transfer catalysis and micelle catalysis. Among them, micelle catalysis utilizes the emulsification and solubilization effect of surfactants to effectively improve the mass transfer of high-carbon olefins. It has developed rapidly in recent years, and the application of cationic, anionic and non-ionic surfactants in the hydroformylation reaction of high-carbon olefins has been widely reported. Although the application of surfactants has improved the mass transfer of high-carbon olefins between the water / organic phases to a certain extent, the problem of difficulty in phase separation of the water / organic phases caused by the emulsification effect of surfactants remains unsolved, making it difficult to effectively separate and recover the rhodium catalyst, resulting in a large amount of loss (Journal of Chemical Engineering of Colleges and Universities, 2022, 36, 693-701).

[0004] In recent years, CO2 switchable surfactants have received extensive attention. This type of surfactant uses CO2 as the switch trigger of its surface activity, utilizing the weak acidity of CO2 gas. As CO2 is introduced and discharged, it causes the protonation or deprotonation of ionizable precursors in the system, resulting in changes in hydrophilicity, thereby affecting the surface activity of the system (Oilfield Chemistry, 2016, 33, 564-570). This change in surface activity is controllable, reversible and repeatable. At present, its precursor compounds mainly include various types of long-chain alkyl organic bases, such as alkyl amidines, alkyl guanidines and alkyl amines, which derive the corresponding amidine groups (Science, 2006, 313, 958-960), guanidine groups (Tenside Surfact. Det., 2009, 46, 294-297) and amine groups (J. Ind. Eng. Chem., 2018, 60, 348-354) CO2 switchable surfactants. These CO2-switchable surfactants show great application potential in emulsion polymerization, emulsification and demulsification, smart drug delivery and other fields. Summary of the invention

[0005] In view of the limitations existing in the above-mentioned prior art, the purpose of the present invention is to develop a rhodium-catalyzed two-phase hydroformylation method for olefins in water. Considering the unique emulsification and demulsification properties of CO2 switchable surfactants, the present invention applies guanidine CO2 switchable surfactants to rhodium-catalyzed two-phase hydroformylation of olefins in water; by introducing CO2 during the hydroformylation process and releasing CO2 after the reaction, the emulsification and demulsification of the water / organic two-phase catalytic system are mediated, thereby achieving efficient mass transfer of olefins in the reaction and rapid separation and recovery of the rhodium catalyst in the post-treatment stage. Compared with the existing surfactant-promoted two-phase hydroformylation technology for water, the CO2 switchable surfactant-mediated two-phase hydroformylation method for olefins in water solves the problem that the rhodium catalyst cannot be effectively recovered due to the emulsification effect of the surfactant.

[0006] To achieve the purpose of the present invention, the technical solutions adopted are as follows:

[0007] A method for aqueous two-phase hydroformylation of olefins mediated by a CO2 switchable surfactant, characterized in that: the aqueous two-phase catalytic system is composed of an aqueous phase and an organic phase: the aqueous phase includes water, an alkylguanidine or an alkylguanidinium CO2 switchable surfactant or a mixture of the two, an anionic water-soluble phosphine ligand and a rhodium catalyst formed by the phosphine ligand and a rhodium catalyst precursor; the organic phase is a reaction substrate olefin or a reaction product or a mixture of the two; the hydroformylation reaction is carried out at a certain reaction temperature, a certain synthesis gas pressure and a certain CO2 pressure; after the hydroformylation reaction is completed, an inert gas is introduced into the aqueous two-phase catalytic system at a certain temperature to achieve two-phase separation of the organic phase and the aqueous phase and recovery and recycling of the rhodium catalyst in the aqueous phase.

[0008] A method for two-phase hydroformylation of olefins in water mediated by a CO2 switchable surfactant, characterized in that, under an inert atmosphere, an anionic water-soluble phosphine ligand, a rhodium catalyst precursor and water are mixed in a certain ratio, wherein the molar ratio of the anionic water-soluble phosphine ligand to the rhodium in the rhodium catalyst precursor is 1:1-100:1, the mass ratio of water to the rhodium catalyst precursor is 1000:1-8000:1, the synthesis gas pressure is 0.5MPa-2.0MPa, the reaction temperature is 70°C-110°C, the reaction time is 0.5h-2h, and an aqueous solution of the rhodium catalyst is obtained; then an alkylguanidine or alkylguanidine-based CO2 switchable surfactant, a reaction mixture and a reaction mixture are added; The invention discloses a method for preparing a hydroformylation reaction of a hydroformylation catalyst comprising: preparing a hydroformylation reaction of a hydroformylation catalyst and preparing a hydroformylation catalyst; wherein the molar ratio of the alkylguanidine or alkylguanidine CO2 switchable surfactant to the rhodium in the rhodium catalyst is 10:1-50:1, the molar ratio of the olefin to the rhodium in the rhodium catalyst is 500:1-10000:1, the synthesis gas partial pressure is 1.0MPa-3.0MPa, the CO2 partial pressure is 0.5MPa-3.0MPa, the reaction temperature is 80°C-110°C, and the reaction time is 1h-16h; after the hydroformylation reaction is completed, argon or nitrogen is introduced into the water two-phase catalytic system at 50°C-70°C to achieve two-phase separation of the organic phase and the water phase, recover the water phase containing the rhodium catalyst, and carry out a recycling of the rhodium catalyst.

[0009] A method for the two-phase hydroformylation of olefins in water mediated by a CO2-switchable surfactant, characterized in that an alkylguanidine R 1 TMG and alkylguanidine CO2 switchable surfactants 1 The structural formula of TMG-H][HCO3] is as follows:

[0010]

[0011] Where: R 1 For C8-C 16 n-alkyl, TMG represents the residue of tetramethylguanidine;

[0012] When alkylguanidine R 1 TMG, R 1 TMG was in situ converted into alkylguanidine CO2-switchable surfactants in the presence of H2O and CO2. 1 TMG-H][HCO3], the reaction formula is as follows:

[0013]

[0014] Where: R 1 For C8-C 16 n-Alkyl, TMG represents the residue of tetramethylguanidine.

[0015] A method for the two-phase hydroformylation of olefins in water mediated by a CO2-switchable surfactant, characterized in that the anionic water-soluble phosphine ligand has the following structural formula:

[0016]

[0017] Wherein: Ar=C6H4-m-SO3Na, n=0,1.

[0018] A method for the two-phase hydroformylation of olefins in water mediated by a CO2 switchable surfactant is characterized in that the rhodium catalyst precursor is acetylacetonato dicarbonyl rhodium Rh(acac)(CO)2, RhCl3·3H2O, [Rh(COD)2]BF4 or [Rh(COD)Cl]2, and COD is 1,5-cyclooctadiene.

[0019] A method for the two-phase hydroformylation of olefins in water mediated by a CO2-switching surfactant, characterized in that the reaction substrate olefin is C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 Straight-chain 1-olefins, Fischer-Tropsch olefins, cyclohexene, styrene, p-methylstyrene, o-methylstyrene, p-tert-butylstyrene, p-isobutylstyrene, p-methoxystyrene, p-chlorostyrene, o-chlorostyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene or a mixture of the above olefins; the reaction product is one or a mixture of several of aldehydes, alcohols, isomerized olefins or alkanes. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with embodiments, but the protection scope of the present invention is not limited to the cases shown in the embodiments.

[0021] Comparative Example 1

[0022] NP-9 / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction

[0023] Under an inert atmosphere, anionic water-soluble phosphine ligand 2,7-bis(SO3Na)Xantphos, rhodium catalyst precursor Rh(acac)(CO)2 and water are added to a stainless steel autoclave, wherein the molar ratio of 2,7-bis(SO3Na)Xantphos to Rh(acac)(CO)2 is 10:1, and the mass ratio of water to Rh(acac)(CO)2 is 3000:1. Then, the autoclave is pressurized to 1.0 MPa with synthesis gas (H2 / CO=1:1), the reaction temperature is 100°C, and the reaction time is 1 hour to obtain an aqueous solution of the rhodium catalyst. Then, the autoclave is rapidly cooled to room temperature, the synthesis gas is vented, and a nonionic surfactant NP-9 (nonyl) is added. Phenol polyoxyethylene ether) and 1-octene, the molar ratio of NP-9 to Rh(acac)(CO)2 is 20:1, the molar ratio of 1-octene to Rh(acac)(CO)2 is 3000:1, under the conditions of synthesis gas (H2 / CO=1:1) pressure 1.0Mpa, reaction temperature 100℃, reaction for 5h; then quickly cooled to room temperature, vented synthesis gas, the water two-phase catalytic system showed an emulsion state, centrifuged by centrifuge to separate the organic phase and the aqueous phase, the organic phase was analyzed by gas chromatography, the conversion rate of 1-octene was 32.7%, the chemical selectivity of aldehyde was 23.1%, the molar ratio of normal aldehyde to isomeric aldehyde was 39.2:1, and the TOF value was 45.3h -1 .

[0024] Comparative Example 2

[0025] AOT / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction

[0026] The surfactant was replaced by anionic surfactant AOT (sodium bis(2-ethylhexyl) succinate sulfonate), and the remaining reaction conditions and steps were the same as those in Comparative Example 1. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 45.0%, the chemical selectivity of aldehyde was 14.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 52.4:1, and the TOF value was 39.2h -1 .

[0027] Comparative Example 3

[0028] CTAB / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction

[0029] The surfactant was replaced by a cationic surfactant CTAB (hexadecyltrimethylammonium bromide), and the remaining reaction conditions and steps were the same as those in Comparative Example 1. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 73.4%, the chemical selectivity of aldehyde was 86.4%, the molar ratio of normal aldehyde to isomeric aldehyde was 64.6:1, and the TOF value was 380.5h-1 .

[0030] Comparative Example 4

[0031] DHDMAB / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction

[0032] The surfactant was replaced by a cationic surfactant DHDMAB (dihexadecyldimethylammonium bromide), and the remaining reaction conditions and steps were the same as those in Comparative Example 1. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 88.0%, the chemical selectivity of aldehyde was 83.7%, the molar ratio of normal aldehyde to isomeric aldehyde was 64.3:1, and the TOF value was 441.9h -1 The loss rate of rhodium to the organic phase was 14.2%.

[0033] Example 5

[0034] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0035] Under an inert atmosphere, an anionic water-soluble phosphine ligand 2,7-bis(SO3Na)Xantphos, a rhodium catalyst precursor Rh(acac)(CO)2 and water are added to a stainless steel autoclave, wherein the molar ratio of 2,7-bis(SO3Na)Xantphos to Rh(acac)(CO)2 is 10:1, and the mass ratio of water to Rh(acac)(CO)2 is 3000:1. Then, the autoclave is pressurized to 1.0 MPa with synthesis gas (H2 / CO=1:1), the reaction temperature is 100°C, and the reaction time is 1 hour to obtain an aqueous solution of the rhodium catalyst. Then, the autoclave is rapidly cooled to room temperature, the synthesis gas is vented, and a CO2 switchable surfactant [R 1 TMG-H][HCO3](R 1 C 16 normal alkyl) and 1-octene, [R 1The molar ratio of TMG-H][HCO3] to Rh(acac)(CO)2 is 20:1, and the molar ratio of 1-octene to Rh(acac)(CO)2 is 3000:1. Under the conditions of synthesis gas (H2 / CO=1:1) partial pressure of 1.0 MPa, CO2 partial pressure of 2.0 MPa, and reaction temperature of 100°C, the reaction is carried out for 5 hours; then the reaction is rapidly cooled to room temperature, the synthesis gas is vented, and the aqueous two-phase catalytic system is in an emulsion state. Argon is introduced into the catalytic system at 60°C for 20 minutes, and the organic phase and the aqueous phase are separated into two phases. The organic phase is analyzed by gas chromatography, showing that the conversion rate of 1-octene is 86.9%, the chemical selectivity of aldehyde is 90.0%, the molar ratio of normal aldehyde to isomeric aldehyde is 60.8:1, and the TOF value is 469.3h -1 .

[0036] Example 6

[0037] R 1 TMG / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0038] Under an inert atmosphere, an anionic water-soluble phosphine ligand 2,7-bis(SO3Na)Xantphos, a rhodium catalyst precursor Rh(acac)(CO)2 and water are added to a stainless steel autoclave, wherein the molar ratio of 2,7-bis(SO3Na)Xantphos to Rh(acac)(CO)2 is 10:1, and the mass ratio of water to Rh(acac)(CO)2 is 3000:1. Then, the autoclave is pressurized to 1.0 MPa with synthesis gas (H2 / CO=1:1), the reaction temperature is 100°C, and the reaction time is 1 hour to obtain an aqueous solution of the rhodium catalyst. Then, the autoclave is rapidly cooled to room temperature, the synthesis gas is vented, and an alkylguanidine R is added. 1 TMG(R 1 C 16 n-alkyl) and 1-octene, R 1 The molar ratio of TMG to Rh(acac)(CO)2 was 20:1, and the molar ratio of 1-octene to Rh(acac)(CO)2 was 3000:1. The reaction was carried out for 5 hours under the conditions of syngas (H2 / CO=1:1) partial pressure of 1.0 MPa, CO2 partial pressure of 2.0 MPa, and reaction temperature of 100°C. The reaction was then rapidly cooled to room temperature, the syngas was vented, and the aqueous two-phase catalytic system was in an emulsion state. Argon was introduced into the catalytic system at 60°C for 20 minutes to separate the organic phase and the aqueous phase. Gas chromatography analysis of the organic phase showed that the conversion rate of 1-octene was 82.9%, the chemical selectivity of aldehydes was 82.7%, the molar ratio of normal aldehydes to isomeric aldehydes was 60.8:1, and the TOF value was 411.3h -1 .

[0039] Example 7

[0040] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 14 normal alkyl)

[0041] The CO2 switchable surfactant was replaced by [R 1 TMG-H][HCO3](R 1 C 14 The reaction time of hydroformylation was extended to 12 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 82.4%, the chemical selectivity of aldehyde was 88.9%, the molar ratio of normal aldehyde to isomeric aldehyde was 58.2:1, and the TOF value was 183.1 h -1 .

[0042] Example 8

[0043] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 12 normal alkyl)

[0044] The CO2 switchable surfactant was replaced by [R 1 TMG-H][HCO3](R 1 C 12 The reaction time of hydroformylation was extended to 16 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 75.6%, the chemical selectivity of aldehyde was 93.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 57.5:1, and the TOF value was 132.5 h -1 .

[0045] Example 9

[0046] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 is C8 normal alkyl)

[0047] The CO2 switchable surfactant was replaced by [R 1 TMG-H][HCO3](R 1The molar ratio of 1-octene to Rh(acac)(CO)2 was 1000:1, the hydroformylation reaction time was extended to 8h, and the remaining reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 85.8%, the chemical selectivity of aldehyde was 91.2%, the molar ratio of normal aldehyde to isomeric aldehyde was 55.0:1, and the TOF value was 97.8h -1 .

[0048] Example 10

[0049] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0050] [R 1 The molar ratio of TMG-H][HCO3] to Rh(acac)(CO)2 was adjusted to 40:1, and the remaining reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 86.3%, the chemical selectivity of aldehyde was 82.6%, the molar ratio of normal aldehyde to isomeric aldehyde was 54:1, and the TOF value was 427.7h -1 .

[0051] Embodiment 11

[0052] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0053] The mass ratio of water to Rh(acac)(CO)2 was adjusted to 8000:1, and the remaining reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 76.5%, the chemical selectivity of aldehyde was 91.1%, the molar ratio of normal aldehyde to isomeric aldehyde was 64.8:1, and the TOF value was 418.1h -1 .

[0054] Example 12

[0055] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0056] The reaction temperature was adjusted to 110° C., and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 95.3%, the chemical selectivity of aldehyde was 76.0%, the molar ratio of normal aldehyde to isomeric aldehyde was 44.8:1, and the TOF value was 434.6 h -1 .

[0057] Embodiment 13

[0058] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0059] The partial pressure of synthesis gas (H2 / CO=1:1) was adjusted to 3.0 MPa, the reaction time was 10 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 91.6%, the chemical selectivity of aldehyde was 92.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 62.3:1, and the TOF value was 254.2 h -1 .

[0060] Embodiment 14

[0061] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0062] The molar ratio of 2,7-bis(SO3Na)Xantphos to Rh(acac)(CO)2 was adjusted to 2:1, and the remaining reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 91.4%, the chemical selectivity of aldehyde was 89.9%, the molar ratio of normal aldehyde to isomeric aldehyde was 60:1, and the TOF value was 493h -1 .

[0063] Embodiment 15

[0064] [R 1 TMG-H][HCO3] / Rh-TPPTS / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0065] The water-soluble phosphine ligand was replaced with TPPTS, the reaction time was 2 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The gas chromatography analysis results showed that the conversion rate of 1-octene was 95.6%, the chemical selectivity of aldehyde was 94.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.3:1, and the TOF value was 1355 h -1 .

[0066] Example 16

[0067] [R 1 TMG-H][HCO3] / Rh-BISBIS-Na / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl, n=1)

[0068] The water-soluble phosphine ligand was replaced with BISBIS-Na, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 84.6%, the chemical selectivity of aldehyde was 93.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 53.6:1, and the TOF value was 474.6h -1 .

[0069] Embodiment 17

[0070] [R 1 TMG-H][HCO3] / Rh-BINAS-Na / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl, n=1)

[0071] The water-soluble phosphine ligand was replaced with BINAS-Na, the reaction time was 2 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The gas chromatography analysis results showed that the conversion rate of 1-octene was 98.3%, the chemical selectivity of aldehyde was 94.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 62:1, and the TOF value was 1393 h -1 .

[0072] Embodiment 18

[0073] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-octene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0074] The rhodium catalyst precursor was replaced by RhCl3·3H2O, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-octene was 87.2%, the chemical selectivity of aldehyde was 87.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 61.8:1, and the TOF value was 457.8h-1 .

[0075] Embodiment 19

[0076] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-hexene water two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0077] The substrate olefin was replaced by 1-hexene, and the other reaction conditions and steps were the same as those in Comparative Example 5. The gas chromatography analysis results showed that the conversion rate of 1-hexene was 96.3%, the chemical selectivity of aldehyde was 93.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 63.5:1, and the TOF value was 540.2h -1 .

[0078] Embodiment 20

[0079] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-decene water two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0080] The substrate olefin was replaced by 1-decene, the reaction time was extended to 10 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-decene was 83.1%, the chemical selectivity of aldehyde was 92.9%, the molar ratio of normal aldehyde to isomeric aldehyde was 59.8:1, and the TOF value was 231.6 h -1 .

[0081] Embodiment 21

[0082] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-dodecene water two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0083] The substrate olefin was replaced by 1-dodecene, the reaction time was extended to 10 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-dodecene was 86.8%, the chemical selectivity of aldehyde was 93.4%, the molar ratio of normal aldehyde to isomeric aldehyde was 55.2:1, and the TOF value was 243.2 h -1 .

[0084] Embodiment 22

[0085] [R 1TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-tetradecene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0086] The substrate olefin was replaced by 1-tetradecene, the reaction time was extended to 10 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-tetradecene was 80.7%, the chemical selectivity of aldehyde was 95.3%, the molar ratio of normal aldehyde to isomeric aldehyde was 65.5:1, and the TOF value was 230.7 h -1 .

[0087] Embodiment 23

[0088] [R 1 TMG-H][HCO3] / Rh-TPPTS / styrene water two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0089] The substrate olefin was replaced by styrene, the water-soluble phosphine ligand was replaced by TPPTS, the reaction time was 2 h, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of styrene was 98.5%, the chemical selectivity of aldehyde was 98.0%, the molar ratio of isomeric aldehyde to normal aldehyde was 4.5:1, and the TOF value was 1448 h -1 .

[0090] Embodiment 24

[0091] [R 1 TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / Fischer-Tropsch synthesis 1-heptene aqueous two-phase hydroformylation reaction (R 1 C 16 normal alkyl)

[0092] The substrate olefin was replaced by 1-heptene synthesized by Fischer-Tropsch, and the other reaction conditions and steps were the same as those in Comparative Example 5. The results of gas chromatography analysis were as follows: the conversion rate of 1-heptene synthesized by Fischer-Tropsch was 87.1%, the chemical selectivity of aldehyde was 88.2%, the molar ratio of normal aldehyde to isomeric aldehyde was 68.7:1, and the TOF value was 460.9h -1 .

[0093] Examples 25-30

[0094] [R 1 Cyclic Experiment of Rhodium Catalyst in TMG-H][HCO3] / Rh-2,7-bis(SO3Na)Xantphos / 1-Octene Water Two-Phase Hydroformylation System

[0095] Under an inert atmosphere, an anionic water-soluble phosphine ligand 2,7-bis(SO3Na)Xantphos, a rhodium catalyst precursor Rh(acac)(CO)2 and water are added to a stainless steel autoclave, wherein the molar ratio of 2,7-bis(SO3Na)Xantphos to Rh(acac)(CO)2 is 10:1, and the mass ratio of water to Rh(acac)(CO)2 is 3000:1. Then, the autoclave is pressurized to 1.0 MPa with synthesis gas (H2 / CO=1:1), the reaction temperature is 100°C, and the reaction time is 1 hour to obtain an aqueous solution of the rhodium catalyst. Then, the autoclave is rapidly cooled to room temperature, the synthesis gas is vented, and a CO2 switchable surfactant [R 1 TMG-H][HCO3](R 1 C 16 normal alkyl) and 1-octene, [R 1 The molar ratio of TMG-H][HCO3] to Rh(acac)(CO)2 was 20:1, and the molar ratio of 1-octene to Rh(acac)(CO)2 was 3000:1. The reaction was carried out for 5 hours under the conditions of synthesis gas (H2 / CO=1:1) partial pressure of 1.0 MPa, CO2 partial pressure of 2.0 MPa, and reaction temperature of 100°C. The reaction was then rapidly cooled to room temperature, the synthesis gas was vented, and the aqueous two-phase catalytic system was in an emulsion state. Argon was introduced into the catalytic system at 60°C for 20 minutes to achieve two-phase separation of the organic phase and the aqueous phase. The reaction mixture was separated into an organic phase containing the product aldehyde and an aqueous phase containing the catalyst by simple liquid / solid two-phase separation; after adding new 1-octene to the aqueous phase, the next catalytic cycle was carried out under the same reaction conditions; the results of gas chromatography analysis showed that after 6 catalytic cycles, the conversion rate of 1-octene, the aldehyde selectivity and the normal-iso ratio remained basically unchanged, and the cumulative TON value reached 13707; ICP analysis showed that the loss of metal rhodium in a single cycle was about 0.6%, and the loss rate of phosphine was about 0.4%; the results of the cycle experiment are shown in Examples 25-30 in Table 1.

[0096] Table 1 Cycle experiment of rhodium catalyst

[0097]

[0098] a Additional 2,7-bis(SO3Na)Xantphos was added (50% of the initial input).

Claims

1. A method for the two-phase hydroformylation of olefins in water mediated by a CO2-switchable surfactant, characterized in that: The aqueous two-phase catalytic system is composed of an aqueous phase and an organic phase: the aqueous phase includes water, alkylguanidine or alkylguanidine-based CO2 switchable surfactant or a mixture of the two, an anionic water-soluble phosphine ligand and a rhodium catalyst formed by the phosphine ligand and a rhodium catalyst precursor; the organic phase is a reaction substrate olefin or a reaction product or a mixture of the two; the hydroformylation reaction is carried out at a certain reaction temperature, a certain synthesis gas pressure and a certain CO2 pressure; after the hydroformylation reaction is completed, an inert gas is introduced into the aqueous two-phase catalytic system at a certain temperature to achieve two-phase separation of the organic phase and the aqueous phase and recovery and recycling of the rhodium catalyst in the aqueous phase.

2. The method for the CO2-switchable surfactant-mediated two-phase hydroformylation of olefins in water according to claim 1, characterized in that: Under an inert atmosphere, an anionic water-soluble phosphine ligand, a rhodium catalyst precursor and water are mixed in a certain ratio, wherein the molar ratio of the anionic water-soluble phosphine ligand to the rhodium in the rhodium catalyst precursor is 1:1-100:1, the mass ratio of water to the rhodium catalyst precursor is 1000:1-8000:1, the synthesis gas pressure is 0.5MPa-2.0MPa, the reaction temperature is 70℃-110℃, and the reaction time is 0.5h-2h to obtain an aqueous solution of the rhodium catalyst; then, an alkylguanidine or alkylguanidine-based CO2 switchable surfactant and a reaction substrate olefin are added, wherein the alkylguanidine or alkylguanidine-based C The molar ratio of the O2 switchable surfactant to the rhodium in the rhodium catalyst is 10:1-50:1, the molar ratio of the olefin to the rhodium in the rhodium catalyst is 500:1-10000:1, the synthesis gas partial pressure is 1.0MPa-3.0MPa, the CO2 partial pressure is 0.5MPa-3.0MPa, the reaction temperature is 80℃-110℃, and the reaction time is 1h-16h; after the hydroformylation reaction is completed, argon or nitrogen is introduced into the water two-phase catalytic system at 50℃-70℃ to achieve two-phase separation of the organic phase and the aqueous phase, and the aqueous phase containing the rhodium catalyst is recovered to circulate the rhodium catalyst.

3. A method for the CO2-switchable surfactant-mediated two-phase hydroformylation of olefins in water according to claims 1 and 2, characterized in that: Alkylguanidine R 1 TMG and alkylguanidine CO2 switchable surfactants 1 The structural formula of TMG-H][HCO3] is as follows: Where: R 1 For C8-C 16 n-Alkyl, TMG represents the residue of tetramethylguanidine.

4. A method for the CO2-switchable surfactant-mediated two-phase hydroformylation of olefins in water according to claims 1 and 2, characterized in that: The structural formula of the anionic water-soluble phosphine ligand is as follows: Wherein: Ar=C6H4-m-SO3Na, n=0,1.

5. A method for the CO2-switchable surfactant-mediated two-phase hydroformylation of olefins in water according to claims 1 and 2, characterized in that: The rhodium catalyst precursor is acetylacetonato dicarbonyl rhodium Rh(acac)(CO)2, RhCl3·3H2O, [Rh(COD)2]BF4 or [Rh(COD)Cl]2, and COD is 1,5-cyclooctadiene.

6. A method for the CO2-switchable surfactant-mediated two-phase hydroformylation of olefins in water according to claims 1 and 2, characterized in that: The reaction substrate olefins are C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 Straight-chain 1-olefins, Fischer-Tropsch olefins, cyclohexene, styrene, p-methylstyrene, o-methylstyrene, p-tert-butylstyrene, p-isobutylstyrene, p-methoxystyrene, p-chlorostyrene, o-chlorostyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene or a mixture of the above olefins; the reaction product is one or a mixture of several of aldehydes, alcohols, isomerized olefins or alkanes.

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