TWI791369B - Hydrophilic phosphorus ligand and method for separation and recovery of catalyst - Google Patents

Abstract

Provided is a hydrophilic phosphorus ligand with the structure of formula 1,

（式1） wherein, X is

, Y is

, m is an integer from 1 to 20, A independently is *-O(CH ₂) _n-, n is an integer from 1 to 5, *- is a bond close to triphenylphosphine, and – is a bond away from triphenylphosphine.

Description

Method for separation and recovery of hydrophilic phosphorus ligand and catalyst

The embodiment of the present invention relates to methods for separating and recovering hydrophilic phosphorus ligands and catalysts.

Due to the high boiling point of the product obtained in the hydroformylation reaction of olefins, if the product and the catalyst are separated by vacuum distillation, it needs to be carried out at a higher temperature environment. In this high-temperature environment, the rhodium catalyst is unstable and easy to decompose, so quite a lot of research has focused on other milder purification work, such as solvent extraction.

At present, a variety of process methods have been developed for rhodium catalyst recovery after hydroformylation. The hydroformylation process uses extraction to separate the catalyst. However, the separation effect is not good, and the partition coefficient of the product in the extraction solvent is low.

（式1） 其中X為

，Y為

，m為1~20的整數，A獨立地為*-O(CH ₂) _n-，n為1~5的整數，*-為接近三苯基膦的鍵， -為遠離三苯基膦的鍵。 The embodiment of the present invention proposes a hydrophilic phosphorus ligand, which has the structure of formula 1,

(Formula 1) where X is

, Y is

, m is an integer from 1 to 20, A is independently *-O(CH ₂ ) _n -, n is an integer from 1 to 5, *- is a bond close to triphenylphosphine, - is a bond far away from triphenylphosphine key.

（式1） 其中X為

，Y為

，m為1~20的整數，A獨立地為*-O(CH ₂) _n-，n為1~5的整數，*-為接近三苯基膦的鍵， -為遠離三苯基膦的鍵。所述第二層溶液包括反應物。接著，進行氫甲醯化反應（Hydroformylation），亦可應用於氫化反應（Hydrogenation）、烯烴水調聚反應（Telomerization）、碳-碳偶合反應（C-C coupling）、異構化（Isomerization）化學反應，使所述銠金屬觸媒以及所述親水性磷配位體從所述第一層溶液轉移到所述第二層溶液，並使得所述反應物在所述銠金屬觸媒以及所述親水性磷配位體存在下反應，而在所述第二層溶液中形成產物進行分離製程，使所述銠金屬觸媒及所述親水性磷配位體從所述第二層溶液轉移到所述第一層溶液，所述產物留在所述第二層溶液中。 An embodiment of the present invention proposes a method for separating and recovering metal catalysts, including: providing a two-phase solution including a first-layer solution and a second-layer solution. The first layer solution includes (rhodium) metal catalyst and hydrophilic phosphorus ligand. Wherein the hydrophilic phosphorus ligand has a structure of formula 1,

(Formula 1) where X is

, Y is

, m is an integer from 1 to 20, A is independently *-O(CH ₂ ) _n -, n is an integer from 1 to 5, *- is a bond close to triphenylphosphine, - is a bond far away from triphenylphosphine key. The second layer solution includes reactants. Then, carry out hydroformylation reaction (Hydroformylation), which can also be applied to hydrogenation reaction (Hydrogenation), olefin water telomerization reaction (Telomerization), carbon-carbon coupling reaction (CC coupling), isomerization (Isomerization) chemical reactions, The rhodium metal catalyst and the hydrophilic phosphorus ligand are transferred from the first layer solution to the second layer solution, and the reactants are transferred between the rhodium metal catalyst and the hydrophilic phosphorus ligand. React in the presence of phosphorus ligands, and form products in the second layer solution to carry out the separation process, so that the rhodium metal catalyst and the hydrophilic phosphorus ligands are transferred from the second layer solution to the first layer of solution, the product remains in the second layer of solution.

The combined catalyst formed by the hydrophilic phosphorus ligand and the metal catalyst of the present invention can make the hydroformylation reaction have high catalytic activity and reaction conversion rate. Moreover, the hydrophilic phosphorus ligand of the present invention can separate the metal catalyst from the product by changing the temperature, so that the metal catalyst can be reused with a high recovery rate, thereby reducing the cost of the manufacturing process.

The invention provides a hydrophilic phosphorus ligand which can form a combined catalyst with a metal catalyst (such as a catalyst). This combined catalyst can be applied to chemical reactions, such as olefin hydroformylation, and during the reaction, the metal catalyst can be brought into the water phase through the mutual solubility of the hydrophilic phosphorus ligand and polar water, and the The aldehyde product remains in the low polarity organic solution, thus allowing for efficient separation of the product and recovery of the catalyst for reuse. At the same time, the recovered rhodium catalyst aqueous solution layer can be re-introduced into the hydroformylation process for recycling, therefore, the use cost of the catalyst in the process can be reduced.

（式1） 其中X為

，Y為

，m為1~20的整數，A獨立地為*-O(CH ₂) _n-，n為1~5的整數，*-為接近三苯基膦的鍵， -為遠離三苯基膦的鍵。若n大於5則羥基環氧單體開環聚合反應性可能變差，難製備親水性磷配體。 The hydrophilic phosphorus ligand of the embodiment of the present invention has the structure of formula I,

(Formula 1) where X is

, Y is

, m is an integer from 1 to 20, A is independently *-O(CH ₂ ) _n -, n is an integer from 1 to 5, *- is a bond close to triphenylphosphine, - is a bond far away from triphenylphosphine key. If n is greater than 5, the ring-opening polymerization reactivity of the hydroxyl epoxy monomer may become poor, making it difficult to prepare hydrophilic phosphorus ligands.

、

、

、

等。 上述親水性磷配位體可以簡稱為PPh ₃-PGC。PPh ₃-PGC的分子量例如為500~50,000 g/mol。若分子量低於500 g/mol會與有機溶劑高度相溶，難進入水相達到分離效果。若分子量高於50,000 g/mol會與水相高度相溶，難進入有機相中進行反應，造成催化反應轉化率不佳。 According to an embodiment of the present invention, the hydrophilic phosphorus ligand can be

,

,

,

wait. The above-mentioned hydrophilic phosphorus ligand may be referred to as PPh ₃ -PGC for short. The molecular weight of PPh ₃ -PGC is, for example, 500 to 50,000 g/mol. If the molecular weight is lower than 500 g/mol, it will be highly compatible with organic solvents, and it will be difficult to enter the water phase to achieve the separation effect. If the molecular weight is higher than 50,000 g/mol, it will be highly compatible with the aqueous phase, and it will be difficult to enter the organic phase for reaction, resulting in poor conversion rate of catalytic reaction.

（式2）

（式3） The hydrophilic phosphorus ligand PPh ₃ -PGC of the embodiment of the present invention can be formed through various methods. For example, an example of the hydrophilic phosphorus ligand PPh ₃ -PGC can be synthesized through the following formulas 2 and 3, but not limited thereto.

(Formula 2)

(Formula 3)

The hydrophilic phosphorus ligand PPh ₃ -PGC of the embodiment of the present invention can be combined with a metal catalyst to form a combined catalyst for application in various chemical processes. The metal catalyst is, for example, a rhodium catalyst, a ruthenium catalyst, an iridium catalyst, or a cobalt catalyst. For example, the rhodium catalyst is a rhodium compound, which can be rhodium trichloride hydrate (RhCl ₃ .xH ₂ O), acetylacetonate group dicarbonyl rhodium (I) (dicarbonyl acetylacetone rhodium, Rh(acac) (CO) ₂ ), (RhCl(CO) ₂ ) ₂ , rhodium carbonyl (carbonyl rhodium, Rh ₆ (CO) ₁₆ or Rh ₄ (CO) ₁₂ ), rhodium (III) Nitrate, Rh(NO ₃ ) ₃ ), or other suitable rhodium compounds. Here, x represents the number of crystal water, and the range of x is 0 to 3, for example.

The chemical process (reaction) that can be applied to the composition formed by the hydrophilic phosphorus ligand PPh ₃ -PGC and the metal catalyst is, for example, the hydroformylation of higher carbon olefins (Hydroformylation), and it can also be applied to the hydrogenation reaction (Hydrogenation) , Olefin water telomerization reaction (Telomerization), carbon-carbon coupling reaction (CC coupling), isomerization (Isomerization) reaction.

The presence of the hydrophilic phosphorus ligand PPh ₃ -PGC in the embodiment of the present invention is helpful for the recovery of the metal catalyst. The application of the combined catalyst formed by the hydrophilic phosphorus ligand PPh ₃ -PGC and the rhodium catalyst to the hydroformylation process of high carbon olefins is illustrated below.

First, a rhodium catalyst and a hydrophilic phosphorus ligand PPh ₃ -PGC are provided. In some embodiments, the molar ratio of the rhodium catalyst to the hydrophilic phosphorus ligand PPh ₃ -PGC ranges from 1 to 300. When the molar ratio of the rhodium catalyst to the hydrophilic phosphorus ligand PPh ₃ -PGC is less than 1, the reaction selectivity will be poor, resulting in a decrease in catalyst stability, easy deactivation, and increased side reactions. When the molar ratio of the rhodium catalyst to the hydrophilic phosphorus ligand PPh ₃ -PGC is greater than 300, the catalytic activity of the catalyst will decrease, the reaction conversion rate will be poor, and the yield of the process will decrease. In some other embodiments, the molar ratio of the rhodium catalyst to the hydrophilic phosphorus ligand PPh3-PGC is 1:10 to 1:150.

The rhodium catalyst and the hydrophilic phosphorus ligand PPh ₃ -PGC are placed in the process solution to form a catalyst solution. The process solution of the high carbon olefin hydroformylation process includes a two-phase solution of a low-polarity organic phase and a high-polarity aqueous solution phase. The low polarity mentioned here means that the polarity is less than 1; the high polarity means that the polarity is equal to 1 or greater than 1. The aforementioned low-polarity candidate organic phase solutions can be alkanes, naphthenes, benzenes, other low-polarity solvents or co-solvents formed by combinations thereof. The above-mentioned highly polar candidate aqueous phase includes water or further includes hydrophilic additives, such as polyethylene glycol, polypropylene glycol, or low-carbon alcohols. In some embodiments, the concentration of the rhodium catalyst ranges from 10 to 1000 ppm. In other embodiments, the rhodium catalyst concentration is 100 to 600 ppm. When the concentration of the rhodium catalyst is less than 10 ppm, the reactivity will be poor, resulting in a decrease in reaction conversion and yield. When the concentration of the rhodium catalyst is greater than 1000ppm, the initial reaction will be too fast, which will lead to abnormal heating of the process and increase of side reactions.

After the rhodium catalyst solution is formed, then, the olefin compound is added into the rhodium catalyst solution and placed in a high-pressure reactor. The aforesaid olefinic compound may be an alkyl or aryl olefinic compound with a carbon number of 1 to 15. Olefins may contain a single carbon-carbon double bond or multiple carbon-carbon double bonds. Olefins containing multiple carbon-carbon double bonds may include dicyclopentadiene (DCPD for short), tricyclopentadiene (TCPD for short), dicyclohexadiene (DCHD for short), cyclohexene Aldehydes (cyclohexene-1-carbaldehyde, CHCA for short), or other suitable cycloalkenes.

Gases, such as hydrogen and carbon monoxide, are introduced under high pressure, so that the olefinic compounds undergo hydroformylation reactions and are converted into aldehyde compounds. The formed aldehyde compounds include those with 1 to 17 carbon atoms.

In some embodiments, the molar ratio of hydrogen to carbon monoxide is between 1:10 and 10:1. In other embodiments, the molar ratio of hydrogen to carbon monoxide is between 3:1 and 1:3. In some embodiments, the temperature of the hydroformylation reaction is between about 50°C and 160°C. In other embodiments, 70°C to 140°C. In some embodiments, the pressure is about 0.5 MPa to 15 MPa, and in other embodiments, the pressure is about 2 MPa to 10 MPa.

After the above hydroformylation reaction is completed, it is left to stand so that the mixture of the rhodium catalyst solution and the aldehyde compound is divided into two layers. One layer mainly contains rhodium catalyst, hydrophilic phosphorus ligand and polar aqueous solution; the other layer mainly contains aldehyde compounds and low-polarity organic solution. The pressure range of the above stratification phenomenon is between normal pressure and 10 MPa, and the temperature range is between 0 ^o C and 100 ^o C.

（式4）

（式5）

（式6）

（式7）

（式8）

（式9）

（式10）

（式11） 其中R可為烷基或含有醇基、醛基及羧酸基等官能基的取代基。 Depending on the structure of the olefin, the product can be a single aldehyde compound or a polyaldehyde compound. The formylation reactions of DCPD, TCPD, DCHD, CHCA and several cycloalkenes to form cycloalkanals are shown in Formula 4 to Formula 11.

(Formula 4)

(Formula 5)

(Formula 6)

(Formula 7)

(Formula 8)

(Formula 9)

(Formula 10)

(Formula 11) wherein R can be an alkyl group or a substituent containing functional groups such as alcohol groups, aldehyde groups, and carboxylic acid groups.

When performing two-phase separation, an additional low-polarity organic solution can be added to improve the efficiency of catalyst separation. Then separate the two-layer solution, and complete the separation step of the aldehyde products and the rhodium catalyst solution. The separated rhodium catalyst solution layer can be added with new olefin and organic solution to carry out the hydroformylation process. The above method can solve the problem of rhodium catalyst recovery and reuse, and effectively separate high-boiling point aldehyde products and rhodium catalyst solution.

1A to 1C show the schematic flow chart of the present invention using hydrophilic phosphorus ligands to assist metal catalyst recovery. 2A to 2C show schematic diagrams of various stages of a combined catalyst of a metal catalyst and a hydrophilic phosphorus ligand.

Referring to FIG. 1A , the process solution 300 is a two-phase solution, including a first layer solution 100 and a second layer solution 200 . The polarity of the first layer solution 100 is higher than that of the second layer solution 200 . The first layer solution 100 is, for example, water, polyethylene glycol, polypropylene glycol, an alcohol compound with a carbon number less than or equal to 4, or a combination thereof. The second-layer solution 200 includes organic solvents, such as alkanes, naphthenes, benzenes, other solvents with a lower polarity than water, or a co-solvent composed of them.

Referring to FIG. 1A and FIG. 2A, before the reaction, the combined catalyst 10 of the metal catalyst and the hydrophilic phosphorus ligand can form a hydrogen bond with the water in the first layer solution 100 because the hydrophilic phosphorus ligand PPh ₃ -PGC, Thus dissolved in the first layer solution 100 . Since the first chemical (or reactant, such as olefin) 20 has a higher carbon number, its polarity is lower, so it will dissolve in the second layer solution (organic layer) 200 which is lower in polarity.

Referring to FIG. 1B and FIG. 2B , the temperature is raised to carry out a chemical reaction (such as a hydroformylation chemical reaction). When the temperature rises to a certain value such as the cloud point (Cloud point, Cp), the hydrogen bond in the hydrophilic phosphorus ligand PPh ₃ -PGC is destroyed, and the non-ionic surface loses its hydrophilic property, so the water layer (that is, the first layer solution 100) precipitates into the non-polar layer (that is, the second layer solution 200), and undergoes a catalytic reaction. That is, the combined catalyst 10 formed by the hydrophilic phosphorus ligand and the metal catalyst is transferred from the first layer solution 100 to the second layer solution 200, and makes the first chemical (such as olefin) 20 react with the hydrophilic phosphorus ligand And the combined catalyst 10 formed by the metal catalyst reacts in the presence of the second chemical (or product, such as aldehyde compound) 30 in the second layer solution 200 .

Referring to FIG. 1C and FIG. 2C , the temperature is lowered after the reaction. After cooling down, the surface of the hydrophilic phosphorus ligand becomes hydrophilic due to the formation of hydrogen bonds, and thus dissolves again in the water layer (ie, the first layer of solution 100 ). That is, the combined catalyst 10 of the metal catalyst and the hydrophilic phosphorus ligand is transferred from the second layer of solution 200 to the first layer of solution 100, thereby being able to interact with the second chemical (or referred to as the product) remaining in the second layer of solution 200 , such as aldehydes) 30 separation.

The hydrophilic phosphorus ligand of the embodiment of the present invention can form a combined catalyst 10 with a metal catalyst, and the combined catalyst 10 can be separated from the water phase and transferred to the organic phase during the heating process. It can also dissolve in the water layer again during the cooling process. By changing the temperature, the metal catalyst can be separated from the product, so that the metal catalyst can be recycled and reused.

Example 1: Synthesis of hydrophilic phosphorus ligand PPh ₃ -PGC

（式12） Weigh (4-Hydroxyphenyl)diphenylphosphine ((4-Hydroxyphenyl)diphenylphosphine, TPPOH, 8.45 g, 0.030 mol) and excess sodium (Na, 1.61 g) into a 250 mL round bottom reaction flask , adding water and oxygen-free THF (50 mL) under nitrogen and stirring for 18 hours to obtain the product TPPONa. The TPPONa solution was filtered and THF was drained, and then dioxane (Dioxane, 50 mL) was added to remove water and oxygen as a reaction solvent to prepare solution A. Take another reaction bottle and add dioxane (50 mL) to remove water and oxygen and hydroxyl functional epoxy resin (HE) to prepare solution B. The hydroxyl functional epoxy resin (HE) may be Tetrahydrofurfuryl alcohol (GC5). The molar ratio of tetrahydrofurfuryl alcohol GC5 (30.6 g, 29.1 mL, 0.30 mol) to TPPONa was 10. Solution B was slowly dropped into solution A under nitrogen, and stirred at room temperature for 3 hours. After the reaction was completed, H ₂ O (3 mL) was added to terminate the reaction, and the solution was removed to complete the synthesis of PPh ₃ -PGC. The results are shown in the table 1.

(Formula 12)

Change the hydroxyl-functional epoxy (HE) of solution B to GC3 following the method described above. The molar ratios of GC3 to TPPONa were 10 and 20, and the results are shown in Table 1.

10 1120 64 PPh ₃-PGC5 2

10 580 N.A. PPh ₃-PGC3 3

20 1650 N.A. PPh ₃-PGC3 Table 1 Experimental example Hydroxy Functional Epoxy Resin (HE) Molar ratio HE/TPPONa Molecular weight Mn (g/mol) Cloud point ( ^o C) Phosphorus ligand 1

10 1120 64 PPh ₃ -PGC5 2

10 580 NA PPh ₃ -PGC3 3

20 1650 NA PPh ₃ -PGC3

According to the results of NMR, when the hydroxyl-functional epoxy resin is GC5, and the molar ratio of GC5 to TPPONa is 10, the molecular weight of PPh3-PGC5 obtained is 1120 g/mol, and the cloud point is 64 ^o C. When the hydroxyl-functional epoxy resin is GC3, and the molar ratio of GC3 to TPPONa is 10, the obtained PPh3-PGC3 molecular weight=580g/mol. When the hydroxyl-functional epoxy resin is GC3, and the molar ratio of GC3 to TPPONa is 20, the obtained PPh3-PGC3 molecular weight=1650g/mo. Because the cloud point measurement has been greater than 100 degrees, higher than the boiling point of water, so no longer measure.

Example 2: Hydroformylation reaction

Weigh the rhodium catalyst Rh(acac)(CO) ₂ (37.4 mg, 0.145 mmol) and PPh ₃ -PGC5 (0.974 g, 0.87 mmol) in the glove box, put them into the reaction flask, add cyclohexane Alkanes (21 ml, deoxygenated) were stirred to dissolve. Weighed DCPD (38.3 g, 290 mmol) into another reaction flask, added cyclohexane (4 mL), and deoxygenated by nitrogen for 30 minutes. Vacuumize the reactor to replace nitrogen three times, inject the rhodium catalyst solution into the reactor, and inject H ₂ O/PEG600 (50 mL, deoxygenated) with a volume ratio of 1/1. PEG600 is polyethylene glycol (Polyethylene glycol, Mw = 600g/mol). After that, inject the DCPD solution into the reactor, replace the nitrogen in the reactor with a mixed gas (H ₂ /CO=1/1) and build up the pressure to 30 Kg/cm ² , raise the temperature of the reactor to 120 ^o C, Then build up the pressure to 50 Kg/cm ² and react for 12 hours. After the reaction, the temperature was lowered to room temperature, and the reaction solution was separated into two layers to obtain sample W-9. After that, it was analyzed by gas chromatography (GC) (carvone was used as internal standard).

From the results, the conversion rate of DCPD was 99.5%, the selectivity of TCD-MAL was 4.1%, and the selectivity of TCD-DAL was 95.9%. The two-layer solutions were analyzed separately. The separation rate of rhodium catalyst in the upper layer solution (Cyclohexane) and the lower layer solution (H ₂ O/PEG600) was calculated to be 93.9% by ICP-OES analysis and detection data. The separation rate of TCD-DAL in the upper layer solution and the lower layer solution was calculated to be 98.4% through GC analysis (carvone is the internal standard), the aldehyde product partition coefficient (partition coefficient) = 61.5, and the rhodium metal partition coefficient (Kp, partition coefficient) = 15.4. (The definition of partition coefficient here is the result of dividing the concentration of the component in the two-layer solution)

Example 3: Hydroformylation reaction with a combination of various metal catalysts and PPh ₃ -PGC5

（式13） 通常，除了形成產物TCD-MAL以及TCD-DAL之外，還會形成副產物TCD-MM、TCD-DM以及H-DCPD，其結構如以下所示：

其結果如表2所示。 Various combination catalysts are formed with various metal catalysts Rh(acac)(CO) ₂ , RhCl ₃ , IrCl ₃ , Ru ₃ (CO) ₁₂ , RuCl ₃ and PPh ₃ -PGC. Hydroformylation was carried out via a method similar to Example 2. But the molar ratio of DCPD: metal catalyst: PPh ₃ -PGC is 2000:1:6. Also, cyclohexane/H ₂ O/PEG600=1/1/1 (volume ratio). The reaction formula of hydroformylation reaction is shown in formula 13

(Formula 13) Usually, in addition to the formation of products TCD-MAL and TCD-DAL, by-products TCD-MM, TCD-DM and H-DCPD are also formed, the structures of which are shown below:

The results are shown in Table 2.

Table 2

The results in Table 2 show that the combined catalysts formed by PPh ₃ -PGC5 and various metal catalysts have very high catalytic activity and high reaction selectivity.

Example 4: Hydroformylation of two-phase solutions in various proportions

The metal catalyst Rh(acac)(CO) ₂ and PPh ₃ -PGC5 were used to form a combined catalyst, and the hydroformylation reaction was carried out by a method similar to Example 2. But the solvent used is toluene, cyclohexane, H ₂ O and PEG600 in various proportions. The results are shown in Table 3.

表3 ^a S = DCPD, P = PPh ₃-PGC5; ^b H ₂/CO = 1 /1; ^c 溶劑/DCPD = 1/1 (重量比)

Table 3 ^a S = DCPD, P = PPh ₃ -PGC5; ^b H ₂ /CO = 1 /1; ^c solvent / DCPD = 1/1 (weight ratio)

The results in Table 3 show that Rh(acac)(CO) ₂ /PPh ₃ -PGC5 has quite high catalytic activity and high reaction conversion rate in several different types and proportions of solvents (W-1~W-9). .

Example 5: Extraction method 1 (additional addition of 1 times cyclohexane)

In Example 2, after the reaction, the temperature was lowered to room temperature, and an additional 1-times of cyclohexane (25 mL, deoxygenated) was added, stirred for 1 hour, and then separated into layers to obtain sample W-10. Using GC analysis (carvone as internal standard), the separation rate of rhodium catalyst in the upper layer solution (Cyclohexane) and the lower layer solution (H ₂ O/PEG600) was calculated to be 97.7% by ICP-OES analysis and detection data. The separation rate of TCD-DAL in the upper layer solution and the lower layer solution was calculated to be 99.0% by GC analysis (carvone is the internal standard), the partition coefficient of aldehyde products (Kp, partition coefficient)=99, and the partition coefficient of rhodium metal ( Kp, partition coefficient) = 42.5. The results are shown in Table 4.

Example 6: Extraction method 2 (additional 2 times cyclohexane)

After the reaction in Example 2, the temperature was lowered to room temperature, and an additional 2 times of cyclohexane (50 mL, deoxygenated) was added, and after stirring for 1 hour, the mixture was left to stand and separated to obtain sample W-11. Using GC analysis (carvone as internal standard), the separation rate of rhodium catalyst in the upper layer solution (Cyclohexane) and the lower layer solution (H ₂ O/PEG600) was calculated to be 98.2% by ICP-OES analysis and detection data. The separation rate of TCD-DAL in the upper layer solution and the lower layer solution was calculated to be 99.5% through GC analysis (carvone is the internal standard), the aldehyde product partition coefficient (partition coefficient)=199, and the rhodium metal partition coefficient (Kp, partition coefficient) = 54.6. The results are shown in Table 4.

Table 4

The results in Table 4 show that after the reaction is cooled to room temperature, adding additional solvent helps to increase the recovery to 98.2%, and the partition coefficient of the product can reach 199.

Example 7: Recycling and reuse of metal catalysts

The rhodium catalyst after the reaction of Example 2 is recovered and reused 1 to 4 times, and the results are shown in Table 5.

table 5

The results in Table 5 show that the present invention can make the recovered metal catalyst Rh(acac)(CO) ₂ still have high catalytic activity after repeated use through PPh ₃ -PGC5.

The combined catalyst formed by the hydrophilic phosphorus ligand and the metal catalyst of the present invention can improve the catalytic activity and reaction conversion rate of the chemical reaction. Moreover, the hydrophilic phosphorus ligand of the present invention can separate the metal catalyst from the product by changing the temperature, so that the metal catalyst can be reused with a high recovery rate, thereby reducing the cost of the manufacturing process. Furthermore, adding additional solvent after running the reaction helps to improve the recovery of the catalyst.

10: Combined Catalyst 20: First Chemical/Reactant 30:Secondary chemical/product 100: the first layer of solution 200: second layer solution 300: process solution

1A to 1C show schematic diagrams of the present invention using hydrophilic phosphorus ligands to assist recovery of metal catalysts. 2A to 2C show schematic diagrams of various stages of a combined catalyst of a metal catalyst and a hydrophilic phosphorus ligand.

10: Combined Catalyst

20: First Chemical/Reactant

30:Secondary chemical/product

100: the first layer of solution

200: second layer solution

300: process solution

Claims (19)

A kind of hydrophilic phosphorus ligand, has the structure of formula 1,

(Formula 1) where X is

, Y is

, m is an integer from 1 to 20, A is independently *-O(CH ₂ ) _n -, n is an integer from 1 to 5, *- is a bond close to triphenylphosphine, - is a bond far away from triphenylphosphine key. The hydrophilic phosphorus ligand according to claim 1, wherein the molecular weight of the hydrophilic phosphorus ligand is 500-50,000 g/mol. A method for catalyst separation and recovery, comprising: providing a two-phase solution comprising a first layer solution and a second layer solution, wherein the first layer solution includes a metal catalyst and a hydrophilic phosphorus ligand; and the second layer solution The layer solution includes reactants, wherein the hydrophilic phosphorus ligand has a structure of formula 1,

(Formula 1) where X is

, Y is

, m is an integer from 1 to 20, A is independently *-O(CH ₂ ) _n -, n is an integer from 1 to 5, *- is a bond close to triphenylphosphine, - is a bond far away from triphenylphosphine bond; carry out a chemical reaction, so that the metal catalyst and the hydrophilic phosphorus ligand are transferred from the first layer of solution to the second layer of solution, and make the reactant in the metal catalyst and the Reacting in the presence of the hydrophilic phosphorus ligand to form a product in the second layer solution; and performing a separation process to separate the metal catalyst and the hydrophilic phosphorus ligand from the second layer The solution transfers to the first layer of solution and the product remains in the second layer of solution. The method for catalyst separation and recovery as described in claim 3, wherein the molecular weight of the hydrophilic phosphorus ligand is 500~50,000 g/mol. The method for catalyst separation and recovery according to claim 3, wherein the polarity of the solution in the first layer is greater than the polarity of the solution in the second layer. The method for catalyst separation and recovery as described in claim item 5, wherein the first layer solution includes water, polyethylether (polyethylene glycol), polypropylether (polypropylene glycol), alcohol compounds with a carbon number less than or equal to 4, or combination. The method for catalyst separation and recovery as claimed in item 5, wherein the second layer of solution includes an organic solvent, and the organic solvent includes alkanes, naphthenes, benzenes, solvents with lower polarity than water or their composition co-solvent. The method for catalyst separation and recovery as claimed in claim 3, wherein the separation process further includes adding additional organic solvent. The method for catalyst separation and recovery as claimed in claim 3, wherein the catalyst includes a rhodium catalyst. The method for catalyst separation and recovery as described in claim item 9, wherein the rhodium catalyst includes rhodium trichloride hydrate (RhCl ₃ .xH ₂ O), acetylacetonate group dicarbonyl rhodium (I) (dicarbonyl acetylacetone rhodium, Rh(acac)(CO) ₂ ), (RhCl(CO) ₂ ) ₂ , rhodium carbonyl (carbonyl rhodium, Rh ₆ (CO) ₁₆ or Rh ₄ (CO) ₁₂ ), rhodium nitrate (Rhodium (III) Nitrate , Rh(NO ₃ ) ₃ ). The method for catalyst separation and recovery according to claim 3, wherein said performing a chemical reaction includes performing a hydroformylation reaction, said reactants include olefins, and said products include aldehyde compounds. The method for catalyst separation and recovery as claimed in claim 11, wherein the olefins include olefins with a single carbon-carbon double bond, or olefins with multiple carbon-carbon double bonds, and the olefins with multiple carbon-carbon double bonds Olefins include dicyclopentadiene, tricyclopentadiene, dicyclohexadiene or cyclohexenal. The method for catalyst separation and recovery according to claim 11, wherein the aldehyde compounds include aldehyde compounds with 1 to 12 carbon atoms. The method for catalyst separation and recovery as claimed in item 11, wherein the hydroformylation reaction includes feeding hydrogen and carbon monoxide. The method for catalyst separation and recovery according to claim 14, wherein the pressure of introducing hydrogen and carbon monoxide is between 0.5MPa and 15MPa. The method for catalyst separation and recovery as claimed in item 11, wherein the temperature for the hydroformylation chemical reaction is between 50°C and 160°C. The method for catalyst separation and recovery according to claim 3, wherein the pressure range for the separation process is between normal pressure and 10 MPa. The method for catalyst separation and recovery according to claim 11, wherein the temperature for performing the separation process is lower than the temperature for performing the hydroformylation chemical reaction. The method for catalyst separation and recovery as described in claim 3, wherein the temperature range for the separation process is between 0 ^o C and 100 ^o C.

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