RU2059598C1 - Method of synthesis of c5-c7-aldehydes - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: products: C₅-C₇-aldehydes. Reagent 1: C₄-C₆-olefins. Reagent 2: carbon oxide and hydrogen. Reaction condition: rhodium catalyst containing water-soluble ligand of the formula

where X = 3-80 wt.-% modified with Na₃PO₄ at the molar ratio ligand/rhodium = 0.2-2.0. Synthesized products were used for production of plasticizers and surface-active substances.??? EFFECT: improved method of synthesis. 4 tbl

Description

 The invention relates to petrochemical synthesis, and in particular to a two-phase method for producing aliphatic aldehydes, which are used for the production of plasticizers and surfactants.

P-Ar

Ar

где Y₁, Y₂, Y₃ С₁-С₄; М-Na, K;
n₁, n₂, n₃0-3;
m₁, m₂, m₃0-5,
а в качестве родиевой компоненты: [Rh(CO)₄]₂; [Rh(CO)₂Cl] Rh₂O₃, RhCl₃, RhBr₃, Rh(SO₄)₃, Rh(NO₃)₃, Rh(CH₃COO)₃, [Rh(C₈H₁₂)Cl]₂. Двухфазная система формируется из водного раствора фосфорорганического лиганда, родиевого соединения, органического субстрата с растворителями или без него. Гидроформилирование алифатических альдегидов содержащих в молекуле от 2 до 20 атомов углерода, проводится при 20-150^оС, давлении синтез-газа 1-200 бар, концентрации родия 10^-4-5·10^-1 г-ат. Rh л^-1. Производительность катализатора при гидроформилировании по этому способу, например пропена, достигает 29 кг альдегидов г-ат. Rh^-1· ч^-1.A known method of two-phase hydroformylation of olefins on catalytic systems, including a water-soluble phosphorus ligand of the General formula
Ar

P-ar

Ar

where Y ₁ , Y ₂ , Y ₃ C ₁ -C ₄ ; M-Na, K;
n ₁ , n ₂ , n ₃ 0-3;
m ₁ , m ₂ , m ₃ 0-5,
and as the rhodium component: [Rh (CO) ₄ ] ₂ ; [Rh (CO) ₂ Cl] Rh ₂ O ₃ , RhCl ₃ , RhBr ₃ , Rh (SO ₄ ) ₃ , Rh (NO ₃ ) ₃ , Rh (CH ₃ COO) ₃ , [Rh (C ₈ H ₁₂ ) Cl ] ₂ . The two-phase system is formed from an aqueous solution of an organophosphorus ligand, a rhodium compound, an organic substrate with or without solvents. Hydroformylation of aliphatic aldehydes containing from 2 to 20 carbon atoms in a molecule is carried out at 20-150 ^о С, synthesis gas pressure is 1-200 bar, rhodium concentration is 10 ^-4 -5 · 10 ^-1 g-at. Rh l ^-1 . The performance of the catalyst during hydroformylation by this method, for example propene, reaches 29 kg of g-at. Rh ^-1 · h ^-1 .

где х₁, х₂, х₃=0-3; y₁, y₂, y₃=0-5
R алкил-, галоген-, гидрокси-, нитрит-, нитро-, амино-группа;
Х остатки карбоновой кислоты, сульфокислоты или их солей. В качестве родиевой компоненты используют соединения Rhacac(CO)₂, RhCl₃·4H₂O, [Rh(C₈H₁₂)Cl] ₂, [Rh(C₈H₁₂)₄]BF₄. Двухфазная система формируется из водного раствора Р-лиганда, родиевого соединения, органического растворителя и субстрата. В целях лучшего разделения фаз предлагается использовать поверхностно-активные (нейтральные, анионные или катионные) соединения, например соли аммония, полиэтиленгликоль. Гидроформилирование проводится при 40-150^оС, давлении Синтез-газа 300-10000 кПа, концентрация родия 10^-3-3·10^-3 г-атом Rh л^-1. Производительность катализатора при гидроформилировании, например гексена-1, по этому способу достигает 22,8 кг альдегидов г-атом Rh^-1ч^-1. Следует отметить, что водорастворимые каталитические системы на основе сульфированных фосфинов являются единственными, которые используются в промышленной практике в настоящее время.More perfect is the method (prototype) hydroformylation of α-olefins with the number of carbon atoms C ₃ -C ₂₀ in the presence of P-ligands of the General formula
P

where x ₁ , x ₂ , x ₃ = 0-3; y ₁ , y ₂ , y ₃ = 0-5
R is an alkyl, halogen, hydroxy, nitrite, nitro, amino group;
X residues of carboxylic acid, sulfonic acid or their salts. As the rhodium component, the compounds Rhacac (CO) ₂ , RhCl ₃ · 4H ₂ O, [Rh (C ₈ H ₁₂ ) Cl] ₂ , [Rh (C ₈ H ₁₂ ) ₄ ] BF _{4 are used} . The two-phase system is formed from an aqueous solution of the P-ligand, a rhodium compound, an organic solvent and a substrate. In order to better phase separation, it is proposed to use surface-active (neutral, anionic or cationic) compounds, for example, ammonium salts, polyethylene glycol. The hydroformylation is carried out at 40-150 ^{° C,} a pressure of synthesis gas 300-10000 kPa, the concentration of rhodium ^-3 -3 10 × 10 ^-3 g atom Rh l ^-1. The performance of the catalyst during hydroformylation, for example hexene-1, in this way reaches 22.8 kg of aldehydes g-atom Rh ^-1 h ^-1 . It should be noted that water-soluble catalytic systems based on sulfonated phosphines are the only ones that are currently used in industrial practice.

The disadvantages of these methods are:
sophisticated technology for the preparation of organophosphorus ligand, including Grignard synthesis, arylphosphine sulfonation step, requiring the use of oleum with a high content of SO ₃ . The synthesis technology is also complicated by the fact that the washing and recrystallization of such ligands is accompanied by the formation of large quantities of wastewater;
the use of organophosphorus sulfonated ligands requires deaeration of the working medium at the stage of catalyst formation;
low productivity of the catalytic system when using high concentrations of expensive rhodium;
insufficient stability of the catalytic system associated with its deactivation;
the need to feed the reaction system with a ligand sulfonated phosphine.

CH

CH

H

где х=3-90% (мол.) мол.м. 30000-80000, при молярном соотношении СПЛ /Rh= 0,2-2,0.The objective of the invention is to simplify the process technology of two-phase hydroformylation of olefins and increase its productivity. It is solved by creating a new catalytic system based on RhCl ₃ · 4H ₂ O and a water-soluble macroligand copolymer of dimethyl diallylammonium chloride and dimethyl diallylammonium dihydrogen phosphate and an additional modifier Na ₃ PO ₄ or Na ₂ SO ₄ (in a narrow range of ionic forces) at pH = 5.4-9, 8. General Macroligand Formula (CPL):

CH

CH

H

where x = 3-90% (mol.) mol.m. 30000-80000, with a molar ratio of CPF / Rh = 0.2-2.0.

 Hydroformylation is carried out in an autoclave reactor with a stirrer, into which an aqueous solution of a catalytic complex with a certain pH is loaded, an organic solvent in a volume ratio of 1: 1. A certain pressure and temperature are set and an olefin is introduced. After hydroformylation, the reaction mass consists of two phases: organic, containing aldehydes, and water, containing a catalytic complex. After separation of the organic layer, the aqueous catalyst layer is returned to the reactor.

PRI me R s 1-7 (comparative). 30 ml of water, 30 ml of n-xylene, 7.5 · 10 ^-3 g of RhCl ₃ 4H ₂ O are loaded into the atoclav. 0.2 g of CPL PDMADAAH and PDDAADP (x = 80 mol.m. 30000), create a pH of the aqueous layer 9.8 (molar ratio SPL: Rh = 0.27). Set the pressure of the synthesis gas 6 MPa, the temperature was ⁹⁰ ° C and fed 38.2 g of 2-butenes. The reaction is carried out for 1.5 hours to 50% olefin conversion. After the experiment, the autoclave is cooled, the pressure of the synthesis gas is released, the catalytic layer is separated from the organic layer and returned to the reactor. This operation is carried out several times to assess the stability of the catalyst. The results are presented in table 1.

These examples illustrate that the catalytic system based on RhCl ₃ · 4H ₂ O and CPL PDMDAAH and PDMDAADP has limited stability. The loss of productivity in the 7th cycle of operation is 30% at pH = 9.8.

 PRI me R 8. The experiment is carried out analogously to example 1, but at a pH of the aqueous catalytic layer of 5.4. Aldehyde productivity is 550 kg / g-at. Rh h. This catalytic system at pH = 5.4 has limited stability, since already in the second cycle the productivity loss is 60%. The molar ratio of CPL / Rh = 2.

PRI me R 9. Polycationite is dissolved in a pre-prepared solution of H ₂ SO ₄ having an ionic strength of 0.2-0.3N, an aqueous solution of RhCl ₃ · 4H ₂ O is added dropwise and stirred for two hours. The resulting solution of the catalytic system has an initial pH of 11.9. To create a more acidic environment, 0.1 N was added dropwise to the solution. H ₃ PO ₄ solution.

PRI me R 9A (preparation of the catalytic system). 0.2 g of CPL PDMDAAH and PDMDAADP (X = 80, mol.m. 30000) and 25 ml of an aqueous solution of Na ₃ PO ₄ (0.3 N) are loaded into the flask and stirred until the polymer is completely dissolved, then 7 drops are added. 5 · 10 ^-3 g of RhCl ₃ · 4H ₂ O (2.62 · 10 ^-5 g-atom of Rh), dissolved in 5 ml of an aqueous solution of Na ₃ PO ₄ (0.3 N.), and stirred for 2 h. The initial pH of the treated solution is 11.7. The molar ratio of CPF: Rh = 0.27.

 Example 10. In the reactor load the catalytic complex obtained according to example 9A, creating a pH = 5.4, (CPL PDMDAAX and PDMDAADP, x = 80, mol.m. 30000, CPL / Rh = 0.27). Hydroformylation of hexane-1 according to Example 1 is carried out for 1.2 hours to 50% olefin conversion. Aldehyde productivity is 868.3 kg / g-at. Rh h. The content of n-iso-aldehydes is, wt. 51.3 and 48.7 respectively.

 PRI me R 11-18. The aqueous catalyst layer is loaded into the reactor after the process of Example 10 and hydroformylation is carried out according to Example 10. After the experiment, the aqueous catalyst layer is returned to the reactor. This procedure is carried out several times. The results are shown in table. 2.

PRI me R 19. In the autoclave load the catalytic complex obtained according to example 9, creating a pH = 9.8. (DPMDAAH and PDMDAADP Mm = 30000, molar ratio CPL / Rh = 0.27) and 30 ml of n-xylene are added. Set the pressure of the synthesis gas 6 MPa, the temperature was ⁹⁰ ° C and fed 38.2 kg of 2-butenes. The reaction is carried out for 2 hours to 50% olefin conversion. After the experiment, the autoclave is cooled, the pressure of the synthesis gas is released, and the aqueous catalytic layer is separated from the organic layer containing 29.4 g of aldehydes. Productivity for aldehydes is 561 kg / g-atom Rh h. The content of n-iso-aldehydes is, wt. 22.4 and 77.6 respectively.

 PRI me R 20. In the atoclav load the catalytic complex obtained according to example 9A, creating a pH = 5.4 (SPL, mol.m. 30000. SPL / Rh = 0.27). Hydroformylation of 2-butenes is carried out according to example 1 for 1.8 hours to 50% olefin conversion. Productivity for aldehydes is 623.3 kg / g-atom Rh h, with the content of n-, iso-aldehydes, wt. 22.7 and 77.3 respectively.

 PRI me R s 21-27. The aqueous catalyst layer is loaded into the atoclav after the process of Example 19 and hydroformylation is carried out according to Example 1. After the experiment, the aqueous catalyst layer is returned to the reactor. This operation is carried out several times. The results are presented in table.3.

Thus, the table shows that the catalytic complex (SPL PDMDAAH and PDMDAADF mol.m. 30000, CPL / Rh = 0.27, the rhodium content of 2.62 · 10 ^-5 g-at.), Dissolved in 0.2- 0.3 n an aqueous solution of Na ₃ PO ₄ remains active in the 7th catalytic cycle, while in comparative examples 1-8, a similar catalytic complex has limited stability.

 PRI me R s 28-31. The catalytic complex obtained according to example 9 is charged into the reactor, creating different pHs. (CPF DPMDAAH and PDMDAADF, x = 80, mol. M. 30,000. CPF / Rh = 0.27). Hydroformylation of various substrates is carried out according to Example 1. The results obtained are presented in Table 4.

 Thus, it follows from the data obtained (Table 4) that this technique not only improves the stability of the catalytic system, but in some cases leads to an increase in its activity.

 PRI me R 32 (comparative). In the autoclave load the catalytic complex obtained according to example 9, creating a pH = 3.4. (CPF PDMDAAH and PDMDAADP, mol. M. 30000, CPF / Rh = 9.27) and carry out hydroformylation of 2-butenes according to Example 1 for 3.6 hours to 50% olefin conversion. Productivity for aldehydes is 307 kg / g-atom Rh h. The content of n-iso-aldehydes is, wt. 26.8 and 73.2 respectively. At pH-5, the activity of the catalytic system decreases and it has been shown that the catalytic complex partially passes into the organic phase.

 PRI me R s 21-27. The aqueous layer is loaded into the autoclave after the experiment of Example 20 and hydroformylation is carried out according to Example 20. After the experiment, the aqueous catalyst layer is returned to the reactor. This procedure is carried out several times. The results are shown in table.3.

 PRI me R s 28-34. The catalytic complex obtained according to Example 9A was charged into the reactor, creating a pH = 9.8. Hydroformylation of butene-2 according to Example 1 was carried out for 1.3 hours to 50% olefin conversion. After the experiment, the autoclave is cooled, the pressure of the synthesis gas is released, the catalytic layer is separated from the organic layer and returned to recycling. This operation is done several times. The results are presented in table 4.

Claims (1)

METHOD FOR PRODUCING C * 005 C * 007 ALDEHYDES by hydroforming C ₄ C ₆ olefins with carbon monoxide and hydrogen at elevated temperatures and pressures in the presence of a rhodium catalyst containing a water-soluble ligand, characterized in that a copolymer of dimethyldiallylammonium chloride and dimethyl di amide dimethyl di amide dimethyl di amide dimethyl di amide dimethyl di amide dimethyl di amide dimethyl di amide

where x 3 80 mol. modified Na ₃ PO ₄ with a rhodium ligand molar ratio of 0.2 2.0.

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