RU2005713C1 - Process for preparation of aldehydes - Google Patents

Abstract

FIELD: organic synthesis. SUBSTANCE: C₄ or C₅ aldehydes are prepared by hydroformulation of C₃-C₄ olefins with carbon monoxide-hydrogen mixture the presence rhodium-polyphosphite complex as a catalytic agent at temperatures of 70-120 C and pressure less than 35.15 kg/cm² in molar carbon monoxide hydrogen ratio of 1: 1-2, with rhodium content being of 191-1000 ppm, and molar polyphosphite ligand- rhodium ratio being of 3.2-26.1: 1. Polyphosphite ligand is addend of the general formula given in description of the invention. EFFECT: high yield of the end product.

Description

The invention improves the process for producing C ₄ -C ₅ by hydroformylation of C ₃ -C ₄ olefins. C ₄ -C ₅ aldehydes are valuable intermediates in basic organic synthesis.

A method of producing aldehydes C ₄ -C ₅ olefins by hydroformylation of C ₃ -C ₄ carbon monoxide and hydrogen in the presence of rhodium-polifosfitnogo complex as a catalyst at 70-120 ^{° C} and an absolute pressure generally a mixture of hydrogen, carbon monoxide and olefin of less than 35, 15 at at a molar ratio of carbon monoxide and hydrogen of 1: 1-2 at a rhodium content of 191-1000 ppm and at a molar ratio of polyphosphite ligand and rhodium of 3.2-26.1: 1 [1]. Polyphosphite ligands are polyphosphite ligands.

 Despite the fact that the known method allows to obtain the target product in which the ratio of normal aldehydes and isostructure reaches 79, this method does not allow to regulate within a wide range the molar ratio of normal aldehydes and isostructure.

 The aim of the invention is to improve the regulation of the molar ratio of aldehydes having a normal and isomeric structure.

, где R - водород или группа OCH₃ или -C(CH₃)₃;
W - группа одной из формул

или

,
или

, _или

, или

,
или

, ^или

,
или

, ^или

, или
_или

, или

S

или -(CH₂)_n, где n = 2-8, или -(CH₂)₂-O-(CH₂)₂-, или полифосфитный лиганд формулы

, или полифосфитный лиганд формулы

_O

Полифосфитные лиганды, используемые в соответствии с изобретением, могут быть получены реакцией конденсации фосфорного галида и спирта. Способ получения таких лигандов может содержать: а) реакцию соответствующего органического дифенолового соединения с трихлоридом фосфора, в результате которой получают соответствующие органическое промежуточное соединение фосфорхлоридита, б) реакцию упомянутого промежуточного соединения с диолом (соответствующим W в приведенных формулах), в результате которой получают соответствующее оксизамещенное диорганофосфитное промежуточ- ное соединение; в) взаимодействие упомянутого и органофосфитного промежуточного соединения с трихлориддом фосфора, в результате которого получают соответствующее промежуточное соединение фосфордихлоридита; г) взаимодействие дихлори- дита с соответствующими диодом, в результате которого получают соответствующий целевой полифосфитный лиганд.This object is achieved a method of producing a C ₄ -C ₅ aldehydes by hydroformylation of olefins, C ₃ -C ₄ carbon monoxide and hydrogen in the presence of a rhodium-polifosfitnogo complex as a catalyst at 70-120 ^{° C} and an absolute pressure generally a mixture of hydrogen, carbon monoxide and olefin of less than 35.15 kg / cm ² with a molar ratio of carbon monoxide and hydrogen of 1: 1-2 with a rhodium content of 191-1000 ppm and with a molar ratio of polyphosphite ligand and rhodium of 3.2-26.1: 1, and a distinctive feature is the use in as a polyphosphite ligand igandov general formula

where R is hydrogen or an OCH ₃ or —C (CH ₃ ) ₃ group;
W is the group of one of the formulas

or

,
or

, _or

, or

,
or

, ^or

,
or

, ^or

, or
_or

, or

S

or - (CH ₂ ) _n , where n = 2-8, or - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, or a polyphosphite ligand of the formula

or polyphosphite ligand of the formula

_O

The polyphosphite ligands used in accordance with the invention can be obtained by the condensation reaction of phosphoric halide and alcohol. A method for producing such ligands may contain: a) a reaction of the corresponding organic diphenol compound with phosphorus trichloride, resulting in the corresponding organic intermediate phosphorus chloridite, b) a reaction of the said intermediate with a diol (corresponding to W in the above formulas), as a result of which the corresponding oxysubstituted diorganophosphite intermediate; c) the interaction of the aforementioned and organophosphite intermediate with phosphorus trichloride, as a result of which the corresponding phosphorus dichloridite intermediate is obtained; d) the interaction of dichloridite with the corresponding diode, as a result of which the corresponding target polyphosphite ligand is obtained.

 All condensation reactions are preferably carried out in the presence of a solvent, for example toluene, and an HCl acceptor, for example an amine, and can be carried out in a single synthesis vessel, if necessary. For example, target ligands of a symmetric phosphite type can be directly obtained by reacting two molar equivalents of the intermediate from step (a), phosphorochloridite, with one molar equivalent of a diol corresponding to W. In addition, polyphosphite ligands can be identified and characterized by using spectra of nuclear magnetic resonance using phosphorus-31, and, if necessary, mass spectroscopy during the bombardment of fast atoms.

 Polyphosphite ligands are suitable and designed to promote a hydroformylation reaction, especially a hydroformylation reaction with a rhodium catalyst. For example, it was found that polyphosphite ligands give very good stability to the rhodium complex, along with good catalytic activity in hydroformylation of all types of olefins. In addition, due to their chemical structure, the ligands have very good stability properties with respect to side reactions, such as hydrolysis during hydroformylation, as well as during storage.

 In addition, polyphosphate ligands have a high molecular weight and weak volatility properties, and it has been found that such ligands are especially effective when used in homogeneous catalytic hydroformylation reactions of olefinically unsaturated compounds. In addition, the use of polyphosphitic ligands can provide an extremely effective tool for controlling the selectivity of products in hydroformylation reactions. For example, it was found that polyphosphites are very effective ligands for regulating the selectivity of aldehyde products in a wide range of ratios of a normal product to an iso (branched) product, from small to very high, and are especially effective in hydroformylating alpha and internal olefins, including isobutylene.

 Due to their structural properties, polyphosphite ligands possess the properties of catalytic promoters of the hydroformylation reaction and make it possible to obtain the most diverse proportions of normal to iso (branched) aldehyde products, from small to very high. These properties include the steric size of the phosphorus groups of polyphosphite, as well as the steric size of the bridging group W and the bonds of the phosphorus groups one with another. Some of these polyphosphites may have the ability to form chelate complexes with transition metals, such as rhodium.

 The exceptionally good selectivity properties in the preparation of normal isoproducts using such chelating ligand types are a reflection of their ability to cis chelate, which apparently creates a steric environment around rhodium, favoring the formation of linear hydroformylation products. In addition, the total size of the ligand itself, as well as the size of other substituent groups in the polyphosphite molecule, should apparently be considered as important factors regarding the chelation properties of polyphosphite ligands. Too large a steric hindrance can interfere with the ability of the polyphosphite to chelate, while an insufficient steric hindrance can stimulate polyphosphite to become too chelating.

 It must be borne in mind that the possible inability of other polyphosphites to form chelate metal complexes cannot be considered as detracting from their importance as ligand promoters, for example, in hydroformylation reactions it only follows from this that it is impossible to calculate very large ratios for normal : isoaldehyde products which can be prepared using polyphosphites having the described chelation properties.

 Polyphosphite ligands are used both in the form of phosphoric ligands of the catalytic metal complex of transition group VIII, and in the form of a free phosphoric ligand, which is preferably contained in the reaction medium. In addition, it must be borne in mind that in a preferred embodiment of the method, the reaction medium contains a phosphorus ligand of a catalytic complex of a metal of transition group VIII — polyphosphite and an excess of free phosphoric ligand. In the general case, for different purposes, in each individual case, a polyphosphite ligand of the same type and other types of polyphosphite ligands can be used.

The metal of the transition group VIII-phosphorus, catalytic complexes and the metal of the transition group VIII-polyphosphite can be obtained in advance. For example, you can pre-get hydridocarbonyl (polyphosphite) catalyst containing a metal of transition group VIII, and then introduce it into the reaction medium of the hydroformylation process. More preferably, the metal complexes of the transition group VIII-polyphosphite can be obtained from a product preceding the metal catalyst, which can be introduced into the reaction medium to form the active catalyst in place. For example, a precursor product of a rhodium catalyst, such as rhodium dicarbonyl acetylacetonate, Rh ₂ O ₃ , Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , Rh (NO ₃ ) ₃ , etc., can be introduced into the reaction medium together with a polyphosphite ligand to obtain an active catalyst in place. In a preferred embodiment, rhodium dicarbonyl acetylacetonate is used as the rhodium precursor product, which reacts with a polyphosphite in the presence of a solvent, resulting in the formation of a product preceding the rhodium polyphosphite catalyst complex, which is then introduced into the reactor together with an excess of free polyphosphite ligand to obtain place of active catalyst.

 Accordingly, the catalytic complexes of transition metal of group VIII and polyphosphite can be defined as consisting essentially of the metal of transition group VIII in complex with carbon monoxide and polyphosphite ligand, in which the ligand is bound (forms a complex) with a metal, for example, rhodium, chelate and / or in an inappropriate manner. In addition, it must be borne in mind that the catalytic terminology of the “consisting essentially” type does not mean that hydrogen forming a complex with a metal is excluded, in particular in the case of a hydroformylation reaction with a rhodium catalyst, in addition to carbon monoxide and a polyphosphite ligand, rather the opposite hydrogen here, also, is meant. In addition, this terminology does not mean that it excludes the possibility of other organic ligands and / or anions, which can also be included in a complex with a metal. However, such catalytic terminology in a preferred embodiment means that other materials are excluded in amounts that can lead to undesired poisoning or undesired catalyst deactivation. So, it is desirable that rhodium be free from impurities such as rhodium bound by halogen, for example, chlorine, etc., although this may not be absolutely necessary. As already noted, hydrogen and / or carbonyl ligands of the rhodium-polyphosphite active catalytic complex may be contained as a result of the fact that they are ligands bound by the product to the preceding catalyst and / or as a result of in situ formation, for example, as a result of contact with hydrogen and oxide carbon, gases that are used in hydroformylation reactions.

 In addition, like the well-known catalytic complexes of the transition metal of group VIII and the phosphorus ligand, it is clear that the amount of the catalytic complex contained in the reaction medium during the process should be minimal in order to provide the necessary concentration of the metal of the transition group VIII, and it should serve as the basis for at least that catalytic amount of a metal of transition group VIII, which is necessary for a catalytic effect on a particular hydroformylation process. In general, for most hydroformylation reactions, transition metal concentrations in the range of about 10 ppm to about 1000 ppm in terms of free metal should be sufficient. In addition, when carrying out the process in a hydroformylation reaction with a rhodium catalyst, in a preferred embodiment, in general, 10-500 ppm, preferably 25-350 ppm in terms of free metal, are used.

 The hydroformylation reaction is preferably carried out in the presence of an organic solvent for the catalytic complex of metal of transition group VIII - polyphosphite. You can use any suitable solvent that does not adversely affect the corresponding hydroformylation process, or several different solvents. In general, in the hydroformylation reaction with a rhodium catalyst, aldehyde compounds corresponding to the aldehyde products to be obtained and / or aldehyde liquid condensation by-products with higher boiling points are preferably used as the main solvent, such as, for example aldehyde liquid condensation by-products with a higher boiling point, which are formed in situ during the hydroformylation reaction. In fact, while if desired, any suitable solvent can be used at the initial stage of the reaction when it is carried out on a continuous basis (in the preferred embodiment, aldehyde compounds corresponding to the desired aldehyde products are used), the basic solvent will generally contain as aldehyde products as well as liquid condensation by-products boiling at a higher temperature, due to the very nature of such continuous reactions. Such aldehyde condensation by-products can also be obtained in advance, if necessary, and then used in the same way. The amount of solvent used is not a decisive factor for achieving the objectives of the invention and it is necessary to use only the amount that is sufficient for the formation of a reaction medium with a certain concentration of the metal of transition group VIII necessary for this reaction. In the General case, the amount of solvent used can vary in the range from about 5 to 95 wt. % or more, calculated on the total mass of the reaction medium.

 In addition, it is generally preferred to carry out hydroformylation in continuous plants. The aldehyde product is removed from the liquid reaction medium, and fresh olefin starting material, carbon monoxide and hydrogen are fed into the liquid reaction medium for the next implementation of the “in one pass” principle without recycle of unreacted olefin starting material. In the General case, it is preferable to use a continuous implementation of the reaction, which includes a procedure for recycling liquid and / or gas. Such types of recycling may include recycling a solution of a catalytic complex of a metal of transition group VIII and polyphosphite, which is previously separated from the target aldehyde reaction product, or recirculating gas, and, if necessary, a combination of liquid and gas recycling. In a most preferred embodiment of the hydroformylation process, an apparatus for continuously recycling a liquid catalyst is used.

The desired aldehyde product can be recovered by continuous recycle of the liquid catalyst. Part of the liquid reaction solution (containing the aldehyde product, catalyst, etc.) is removed from the reactor and can be passed through an evaporator-type installation (separator, where the target aldehyde product can be separated by distillation in one or several stages at normal, low or increased pressure from the liquid reaction solution, condensed and collected in the product collector, and then the resulting target product can be purified if necessary. The remaining unevaporated liquid reaction The catalyst-containing solution may then be recycled back to the reactor together with any other volatile materials, for example, unreacted olefin, hydrogen and carbon monoxide, dissolved in the liquid reaction solution after separation from the condensed aldehyde product, for example, by distillation using any known method. In general, it is preferable to isolate the desired aldehyde product from a solution of a product containing a rhodium catalyst under reduced pressure and low temperature, n example at a temperature below ^{150 °} C, preferably at a temperature below 130 ° ^C.

 The hydroformylation process is preferably carried out in the presence of a free polyphosphite ligand, namely a ligand that is not complexed with a transition metal of group VIII of the metal catalyst complex used. Thus, the free polyphosphite ligand may correspond to any of these polyphosphite ligands. However, although it is preferable to use a free polyphosphite ligand of the same type as the polyphosphite ligand of the catalytic complex of the transition metal group VIII and polyphosphite, such ligands do not have to be of the same type that are used in this process, if necessary, they can be of a different type. Despite the fact that hydroformylation processes can be carried out with any excess amount of free polyphosphite ligand, for example, in the presence of at least 1 mol of a free polyphosphite ligand per 1 mol of a metal of transition group VIII containing in the reaction medium, the use of a free polyphosphite ligand is not absolutely necessary. Accordingly, in the general case, the amount of polyphosphite ligand is about 2-100 mol and more, if necessary, preferably 4-50 mol per 1 mol of metal of transition group VIII (for example, rhodium) contained in the reaction medium should be sufficient for most embodiments of the proposed method, in particular when implementing hydroformylation using a rhodium catalyst. The mentioned amounts of the polyphosphite ligand used are the sum of both the amount of polyphosphite that is bound (in complex) to the metal of transition group VIII and the amount of free (outside the complex) polyphosphite ligand that is contained in the reaction medium. Fresh polyphosphite ligand can be fed into the reaction medium of the hydroformylation reaction at any time and by any procedure in order to maintain a predetermined level of free ligand in the reaction medium.

 The possibility of implementing the method in the presence of a free polyphosphite ligand is an important advantage due to the fact that it reduces the criticality of applying ligand concentrations, which are determined with very low accuracy, which may be required when using some catalytic complexes, the activity of which can be slowed down, even if during the reaction any amount of free ligand is present, in particular, for example, when implementing the process on a significant industrial scale, this gives possibility of the operator to have more time to make a decision.

 As noted above, a more preferred embodiment of the proposed method involves the preparation of aldehydes by hydroformylation of olefinic unsaturated compounds with carbon monoxide and hydrogen in the presence of a catalytic complex of a transition metal of group VIII and polyphosphite, and a free polyphosphite ligand, in particular a catalytic complex of rhodium and polyphosphite.

 Polyphosphite ligands are an extremely effective tool for controlling the selectivity of products and for obtaining a wide range of linear (normal) to branched isomeric aldehyde products from very small to high as a result of hydroformylation reactions.

 In addition, the ability to hydroformylate both alpha and internal olefins is quite easy, allows hydroformylation of both types of olefins (for example, butene-1 and butene-2 mixtures) simultaneously with the same ease from the same mixture of starting materials. This gives an advantage over the known methods, since such starting materials consisting of mixed alpha-olefin and internal olefin are more affordable and represent the most economical olefin raw materials. In addition, the versatility of polyphosphite ligands allows them to be easily used for continuous hydroformylation of both alpha olefins and internal olefins, for which several reactors connected in series can be used. Such an opportunity allows not only to monitor the subsequent hydroformylation in the second reactor of any unreacted olefin entering it from the first reactor, but it also makes it possible to optimize the reaction conditions for hydroformylation, for example, alpha-olefin in the first reactor, and in addition, to optimize the reaction conditions for hydroformylation of, for example, an internal olefin in a second reactor.

 As already noted, the hydroformylation process can be carried out either in a liquid or in a gaseous state and includes a continuous liquid or gas recycling system, or a combination of such systems. In a preferred embodiment of the hydroformylation process with a rhodium catalyst, a continuous homogeneous catalytic process is used in which the hydroformylation reaction is carried out in the presence of both a free polyphosphite ligand and any suitable known solvent.

Thus, the use of polyphosphite ligands is unique in that they make it possible to obtain rhodium catalysts with very high catalytic activity and stability. In addition, the low volatility possessed by such high molecular weight polyphosphite ligands makes them particularly suitable for hydroformylation of higher olefins, for example, olefins with four or more carbon atoms. For example, volatility is inversely proportional to the molecular weight within a given homologous series. Accordingly, in general, it is desirable to use a phosphoric ligand whose molecular weight exceeds that of the secondary aldehyde example with a higher boiling point corresponding to the aldehyde resulting from the hydroformylation reaction in order to avoid or at least minimize possible Ligand loss upon removal using distillation of the aldehyde product and / or higher boiling point aldehyde condensation by-products from the reaction th system. So, for example, since the molecular weight of the valeraldehyde example is approximately 250 (C ₁₅ H ₃₀ O ₃ ), and all the polyphosphites used have a molecular weight of more than 250, there should not be any excessive loss of the polyphosphite ligand during the removal of such higher aldehyde products and / or aldehyde by-products with a higher boiling point from the reaction system.

, смолы Амберлист

A-21 и т. п. Можно использовать более одного слоя такой основной анионообменной смолы, например, целый ряд таких слоев, и любой такой слой можно легко удалить и/или заменить. В качестве альтернативы, любую часть или весь поток рецикла катализатора, загрязненный оксиалкилфосфиновой кислотой, можно периодически извлекать из непрерывной системы рецикла и обрабатывать как описано выше, чтобы удалить полностью или уменьшить количество оксиалкилфосфиновой кислоты, содержащейся в ней для дальнейшего использования жидкости, содержащей катализатор, в реакции гидроформилирования.In addition, when the process is continuously conducted in the liquid phase using the rhodium-triorganophosphite complex as a catalyst using recycling, hydroxyalkylphosphinic acid can be formed as a by-product as a result of the interaction of the triorganaphosphite ligand and the aldehyde product, which leads to a decrease in the ligand concentration during continuous process. Such an acid is very often insoluble in the common liquid reaction medium of the hydroformylation reaction, and this can lead to precipitation of the undesirable gelatinous by-product and to the promotion of autocatalytic formation of the same product. Polyphosphite ligands must have very good stability against the formation of such an acid. However, this can be avoided by skipping the liquid reaction effluent of a continuous liquid recycle either before or, more preferably, after separating the aldehyde product therefrom, through any suitable weakly basic anion exchange resin, such as, for example, an amine-amberlist resin layer

Amberlist resin

A-21, etc. More than one layer of such a basic anion exchange resin can be used, for example, a number of such layers, and any such layer can be easily removed and / or replaced. Alternatively, any part or all of the catalyst recycle stream contaminated with hydroxyalkylphosphinic acid can be recovered periodically from the continuous recycle system and processed as described above to completely remove or reduce the amount of hydroxyalkylphosphinic acid contained in it for later use of the catalyst containing liquid in hydroformylation reactions.

 Any other suitable technique can be used to remove this hydroxyalkylphosphinic acid (by-product) from the hydroformylation reaction, for example, extracting the acid with a weak base, for example sodium bicarbonate. You can use any suitable solvent, such as, for example, a solvent from the group of solvents used in the implementation of the necessary hydroformylation process. In addition, the necessary hydroformylation process may itself dictate various amounts of metal, solvent and ligand, which should be contained as the precursor material. Carbonyl and polyphosphite ligand, if they do not yet form a complex with a metal of the transition group, can form a complex with the metal either before the start of the reaction or in place already during the hydroformylation reaction. For the purpose of illustration, since rhodium is the preferred transition metal of group VIII, and since the hydroformylation reaction is the preferred embodiment of the process, the preferred composition prior to the catalyst of the invention essentially consists of a solubilized material preceding the catalytic complex of rhodium carbonyl and polyphosphite, an organic solvent and free polyphosphite ligand obtained by the formation of a solution of dicarbonyl acetate rhodium acetate, organic solvent and polyphosphite ligand. Polyphosphite easily replaces one of the dicarbonyl ligands of the material preceding the rhodium acetylacetonate complex at room temperature, as evidenced by the release of gaseous carbon monoxide. This substitution reaction can be accelerated by heating. In this case, any suitable organic solvent can be used in which both the material preceding the rhodium dicarbonyl acetylacetonate complex and the material preceding the rhodium-polyphosphate complex are dissolved. The amounts of material preceding the rhodium catalyst complex, organic solvent and polyphosphite, as well as their preferred amounts in such material preceding the catalyst compositions, may correspond to those used by the hydroformylation process. Experience has shown that the acetylacetonate ligand of the composition preceding the catalyst is replaced after the start of the hydroformylation reaction by another ligand, for example, hydrogen, carbon monoxide or a polyphosphite ligand, resulting in the formation of an active rhodium catalytic complex. Acetylacetone, which is released from the composition preceding the catalyst under hydroformylation conditions, is removed from the reaction medium with the aldehyde product and does not adversely affect the hydroformylation reaction. Thus, the use of such preferred compositions preceding the rhodium catalyst complex provides a simple, economical and efficient technique for working with material preceding the rhodium catalyst and initiating a hydroformylation reaction.

 Finally, the aldehyde products obtained by the method have a wide scope, they are especially effective when used as starting materials for the production of alcohols and acids.

The following examples illustrate the present invention. It must be borne in mind that all parts, percentages and proportions indicated in the examples and in the attached claims are massive, unless otherwise specified. In the formulas of the present description, the tertiary butyl radical is represented by the formula —C (CH ₃ ) ₃ or t-Bu. Similarly, —OMe represents a methoxy radical, —C ₆ H ₅ represents a phenyl radical, and sometimes, —H — are used to indicate the absence of any substituent other than hydrogen at this particular position in the formula.

Example 1. A solution of the material preceding the rhodium catalyst complex consisting of a solubilized reaction product of rhodium dicarbonyl acetylacetonate and a polyphosphite ligand is prepared and used to hydroformylate butene-1 into C ₅ aldehydes as follows.

и валеральдегидным тримером в качестве растворителя, чтобы получить в результате раствор, предшествующий родиевому катализатору, содержащий те количества родия и лиганда, которые указаны в табл. 1.Rhodium dicarbonyl acetylacetonate is mixed at ambient temperature with a polyphosphite ligand of the formula

and valeraldehyde trimer as a solvent to obtain a solution preceding the rhodium catalyst containing the amounts of rhodium and ligand indicated in the table. 1.

The resulting solution, preceding the rhodium catalyst, is then used for hydroformylation of butene-1 in a 100 ml stainless steel autoclave equipped with a magnetic stirrer, a gas distributor for supplying gases at the corresponding partial pressure, and a pressure sensor to determine the reaction pressure with an accuracy of ± 0,0007 kg / cm ² and a platinum resistance thermometer for determining reactor solution temperature to within ± 0,1 ° ^C. The reactor was heated externally by means of two heating coils powerfully 300 W each. The temperature of the reaction solution is controlled using a platinum resistance sensor connected to an external proportional temperature controller, thereby controlling the temperature of the external heating coils.

About 14 g of the resulting solution preceding the rhodium catalyst are loaded into an autoclave type reactor under a nitrogen atmosphere and heated to the desired reaction temperature (see table 1). Then the pressure in the reactor is reduced to 0.352 kg / cm ² and approximately 1.5 g of butene-1 is fed into the reactor. Then, carbon monoxide and hydrogen are fed into the reactor through a gas distributor (the corresponding partial pressures are shown in Table 1) and the butene-1 hydroformylation process begins.

The previous solution and reaction conditions: 250 ppm per 1 million rhodium, 2 wt. Ligand bisfosfitnogo%, temperature 70 ° ^C, pressure abs. 7.03 kg / cm ² (CO: H ₂ ) 1: 2 molar ratio), 2.462 kg / cm ² for butene-1 (2.5 ml of butene-1) (molar ratio of ligand / rhodium is approximately 8.6).

PRI me R 2. Similar to example 1, but carry out hydroformylation of propylene instead of butene-1 and use a pre-mixed gas composition of carbon monoxide, hydrogen and propylene after providing a reaction pressure of 1.406 kg / cm ² with nitrogen, then vary the solution preceding the rhodium catalyst complex, and the reaction conditions of hydroformylation in accordance with the data in table. 2.

BACKGROUND solution and reaction conditions: 250 ppm rhodium, 4 mole equivalents of ligand per bisphosphonate 1 mole equivalent of rhodium, ⁷⁰ ° C abs. pressure 6.328 kg / cm ² CO: H ₂ . Propylene (1: 1: 1 molar ratio).

, в которой W является двухвалентной мостиковой группой, указанной в табл. 3.PRI me R 3. Similar to example 1, with hydroformylation of butene-1 is repeated using various polyphosphite ligands having the formula

, in which W is a divalent bridge group indicated in table. 3.

The previous solution and reaction conditions: 250 ppm rhodium, 2 wt. Ligand bisfosfitnogo%, temperature ⁷⁰ ° C abs. pressure 7.03 kg / cm ² , CO: H ₂ (molar ratio 1: 2), 2.5 ml butene-1 (pressure 2,461 kg / cm ² butene-1).

- W - P

, в которой W является двухвалентной мостиковой группой (см. табл. 4).PRI me R 4. In example 1, while repeating the reaction of hydroformylation of propylene using various bis-phosphite ligands having the formula

- W - P

, in which W is a divalent bridging group (see table. 4).

BACKGROUND solution and reaction conditions: 250 ppm rhodium, 4 mole equivalents of bis-phosphite ligand per 1 mole equivalent of rhodium, ⁷⁰ ° C abs. pressure 6.328 kg / cm ² , CO: H ₂ : propylene (molar ratio 1: 1: 1).

 PRI me R 5. Carry out a continuous process of hydroformylation of butene-1 using a polyphosphite ligand as follows.

примерно 8,5 моль-эквивалент на 1 моль-эквивалент родия и Тексанол

(моноизобутират 2,2,4-триметил-1,3-пентандиола в качестве растворителя. После герметизации реактора систему снова продувают азотом и масляную ванну нагревают для обеспечения необходимой реакционной температуры гидроформилирования. Реакцию гидроформилирования осуществляют при полном давлении газа примерно 11,25 кг/см², а парциальные давления водорода, окиси углерода и бутена-1 приведены в табл. 5. Потоки газового сырья (окиси углерода, водорода, бутена-1 и азота) регулируют отдельно при помощи масс-расходомеров, а газы, диспергированные в предшествующие растворы, - при помощи вмонтированных измерителей барботажа. Непрореагировавшую часть газообразного сырья отгоняют из С₅-альдегидных продуктов и газ на выходе анализируют спустя примерно 5 дней непрерывной работы.Hydroformylation is carried out in a glass reactor, operating on the principle of continuous single passage of butene-1 into the hydroformylation zone. The reactor, consisting of a tank designed for a capacity of 0.8 l, is immersed in an oil bath so that it is possible to monitor the contents of the reactor. About 20 ml of the freshly prepared preceding rhodium catalyst solution is charged to the reactor by injection after purging the system with nitrogen. The preceding solution contains about 250 ppm rhodium in the form of a dicarbonyl acetylacetonate / about 2% bisphosphate ligand / having the formula

approximately 8.5 mol equivalent per 1 mol equivalent of rhodium and texanol

(2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as solvent. After sealing the reactor, the system is purged with nitrogen again and the oil bath is heated to provide the required hydroformylation reaction temperature. The hydroformylation reaction is carried out at a total gas pressure of about 11.25 kg / ^cm2, and the partial pressures of hydrogen, carbon monoxide, and butene-1 are shown in Table. 5. The material gas flows (carbon monoxide, hydrogen and butene-1 and nitrogen) is controlled separately by mass flow meters and the gases dispersed in the pre- ETS solutions -. using gauges mounted bubbling Unreacted part of the gaseous feedstock is distilled off from the C ₅ -aldegidnyh product and gas at the outlet was analyzed after about 5 days of continuous operation.

 Polyphosphite ligands.

Лиганда A

P

O

O

P

Лиганда B

Лиганда C

Лиганда D

P

O

O

P

Лиганда E

P

O

Лиганда F

Лиганда G

P

O

CH

CH

O

P

Лиганда H

Лиганда I

P

O

O

P

Лиганда J

Лиганда K

P

O

(CH₂)

O

P

Лиганда L : n= 2; n= 3; n= 4; n= 5; n= 6; n= 7; n= 8

Лиганда M

Лиганда N

Лиганда O

Лиганда P

P

O

O

P

Лиганда Q
П р и м е р 6. Получают серию различных композиций, предшествующих родиевому каталитическому комплексу, содержащих существенно сольюбилизованный реакционный продукт дикарбонил ацетилацетоната родия и полифосфитный лиганд, а затем их используют для гидроформилирования бутена-1 в С₅-альдегиды следующим образом.The following polyphosphite ligands are prepared and then used in Examples 6-9, 11 and 12.

Ligand A

P

O

O

P

Ligand B

Ligand C

Ligand D

P

O

O

P

Ligand E

P

O

Ligand F

Ligand G

P

O

CH

CH

O

P

Ligand H

Ligand I

P

O

O

P

Ligand J

Ligand K

P

O

(CH ₂ )

O

P

Ligand L: n = 2; n is 3; n is 4; n is 5; n is 6; n is 7; n = 8

Ligand M

Ligand N

Ligand O

Ligand P

P

O

O

P

Ligand Q
Example 6. A series of various compositions is obtained that precede the rhodium catalyst complex containing a substantially solubilized reaction product of rhodium dicarbonyl acetylacetonate and a polyphosphite ligand, and then they are used to hydroformylate butene-1 to C ₅ aldehydes as follows.

с тем, чтобы получить предшествующий родиевому катализатору раствор, содержащий примерно 350 ppm родия в пересчете на свободный металл и примерно 1 мас. % лиганда (содержание лиганда варьируют в соответствии табл. 6). Примерно 5 мас. % толуола добавляют в материал, предшествующий катализатору, в качестве внутреннего стандарта для газовой хроматографии.Rhodium dicarbonyl acetylacetonate is mixed with a sufficient amount of polyphosphite ligand and diluted with a sufficient amount of solvent. Texanol

in order to obtain a solution preceding the rhodium catalyst containing about 350 ppm rhodium in terms of free metal and about 1 wt. % ligand (ligand content varies in accordance with table. 6). About 5 wt. % toluene is added to the material preceding the catalyst as an internal standard for gas chromatography.

In each hydroformylation reaction, approximately 15 ml of the solution preceding the rhodium catalyst is charged into an autoclave type reactor under a nitrogen atmosphere. Further, in the reactor, a vacuum of about 0.281 kg / cm ^2, then the reactor was heated to the hydroformylation reaction to 90 ^C. The reactor was then 2 ml (approximately 1.2 grams) of butene-1 and abs. a pressure of 7.03 kg / cm ² CO: H ₂ in a molar ratio of 1: 1. Under these conditions, butene-1 is subjected to hydroformylation. After each pressure drop in the reactor of 0.352 kg / cm ² , fresh CO: H ₂ mixture is fed into the reactor in order to restore the original pressure in the reactor. After 10 consecutive pressure drops in the reactor by 0.352 kg / cm ² , which corresponds to a conversion of about 30% butene-1, the reaction is converted and the total reaction time is noted (i.e., the time elapsed since the first time the CO: H mixture was fed ₂ at an asb.pressure of 7.03 kg / cm ² until the reaction terminates). After extraction from the reactor, the reaction mixture was analyzed for the total amount of C ₅ -aldehyde obtained by gas chromatography using toluene as an internal standard.

 The results are shown in table. 6.

 PRI me R 7. Butene-2 (approximately 50: 50 molar mixture of cis and transbutene-2) is subjected to hydroformylation according to the same scheme as in example 6, using the same series of solutions preceding the rhodium catalyst complex (see table 7).

 PRI me R 8. Isobutylene is subjected to hydrophilicity according to the scheme of example 6, using the same series of solutions preceding the rhodium catalyst complex. Get one product - 3-methylbutyraldehyde.

EXAMPLE EXAMPLE 9. For the hydroformylation of propylene, the same series of solutions that in Example 6. Instead of butene-1 into the reactor at 90 ° ^C with a pressure of about 2,672 kg / cm ² of propylene and then pressurized 7.03 kg / cm ² mixture of CO: H ₂ in a molar ratio of 1: 1.

, не промотирует гидроформилирование пропилена или бутена-1 при использовании в избыточном количестве относительно родия. Однако этот лиганд промотирует гидроформилирование пропилена при его применении в соотношении 2: 1 лиганда и родия в пересчете на стехиометрию. Например, отношение линейного бутиральдегида к разветвленному изомеру 2,0-1 и скорость реакции, 1,16 грамм-моль/л альдегидного продукта получают при использовании родия в концентрации 500 ppm 0,3 мас. % бис-фосфитного лиганда и давлении смеси газов CO: H₂: пропилен (молярное отношение 1: 1: 1) 6,328 кг/см², абс. при 70^оС.
П р и м е р 11. Непрерывное гидроформилирование бутена-2 (смесь примерно в молярном соотношении 1: 1 цис- и транс-бутена-2) осуществляют по примеру 5 с использованием в качестве полифосфитного лиганда лиганда Е и раствора предшествующего родиевого комплекса (примерно 3,2 моль-эквивалента лиганда на 1 моль-эквивалент родия).PRI me R 10. Symmetric unsubstituted polyphosphite ligand of the formula

does not promote hydroformylation of propylene or butene-1 when used in excess relative to rhodium. However, this ligand promotes the hydroformylation of propylene when used in a 2: 1 ratio of ligand and rhodium in terms of stoichiometry. For example, the ratio of linear butyraldehyde to the branched isomer 2.0-1 and the reaction rate, 1.16 gram mol / L aldehyde product is obtained using rhodium at a concentration of 500 ppm of 0.3 wt. % bis-phosphite ligand and the pressure of the gas mixture CO: H ₂ : propylene (molar ratio 1: 1: 1) 6.328 kg / cm ² , abs. at 70 ^about C.
PRI me R 11. Continuous hydroformylation of butene-2 (mixture in approximately molar ratio 1: 1 of cis- and trans-butene-2) is carried out as in example 5 using ligand E and a solution of the previous rhodium complex as a polyphosphite ligand (approximately 3.2 mol equivalent of ligand per 1 mol equivalent of rhodium).

 Example 12. The stability of rhodium complexes, that is, various rhodium polyphosphite complexes using polyphosphite ligands J, L and Q, is determined in accordance with the following test procedure.

подвергают дегазации в стеклянном сосуде, снабженном мембранной перегородкой, при помощи откачки газа и последующего заполнения азотом. 10 моль-эквивалент соответствующего лиганда (на 1 моль-эквивалент родия) добавляют в атмосфере азота и смесь тщательно перемешивают до получения однородной смеси. Затем добавляют тетрародий додекарбонил (0,018 г, чтобы получить раствор комплекса, содержащий родий в концентрации 1000 ppm. Этот раствор загружают в автоклав емкостью 100 мл, продутый азотом, снабженный магнитной мешалкой, который затем подсоединяют к газовому коллектору, продутому газообразным азотом. Автоклав трижды продувают смесью CO: H₂ (в молярном соотношении 1: 1) при давлении 4,219 кг/см², абс. , затем окончательно заполняют смесью CO: H₂ (в молярном соотношении 1: 1) под давлением 4,219 кг/см² абс. и содержимое перемешивают в течение 1 ч при 120^оС. Далее давление сбрасывают и автоклав три раза продувают водородом. Затем раствор помещают под давлением 0,7 кг/см², абс. и перемешивают в течение 20 ч при 120^оС. Затем раствор охлаждают и порции объемом от 2-3 мл фильтруют через фильтр Миллипор

(5 мк), а концентрацию родия в фильтрате определяют при помощи атомной спектроскопии поглощения пламени. Концентрация родия в процентах, удерживаемые в растворе, определяют при помощи деления обнаруженного значения концентрации родия на используемую начальную концентрацию родия. Полученные результаты приведены в табл. 11.10 ml texanol

subjected to degassing in a glass vessel equipped with a membrane partition, by pumping gas and subsequent filling with nitrogen. 10 mol equivalent of the corresponding ligand (per 1 mol equivalent of rhodium) is added in a nitrogen atmosphere and the mixture is thoroughly mixed until a homogeneous mixture is obtained. Then tetrarodium dodecarbonyl (0.018 g) is added to obtain a complex solution containing rhodium at a concentration of 1000 ppm. This solution is charged into a 100 ml nitrogen autoclave equipped with a magnetic stirrer, which is then connected to a gas manifold purged with nitrogen gas. The autoclave is purged three times. with a mixture of CO: H ₂ (in a molar ratio of 1: 1) at a pressure of 4.219 kg / cm ² , abs., then finally filled with a mixture of CO: H ₂ (in a molar ratio of 1: 1) under a pressure of 4.219 kg / cm ² abs. and the contents are stirred for 1 h at 120 ^about C. Dale ie the pressure was released and the autoclave was purged three times with hydrogen. Then the solution is placed under a pressure of 0.7 kg / cm ² abs., and stirred for 20 hours at 120 ^C. The solution was then cooled and the batch volume of 2-3 ml is filtered through a filter Millipore

(5 microns), and the concentration of rhodium in the filtrate is determined using atomic flame absorption spectroscopy. The percent rhodium concentration held in solution is determined by dividing the detected value of the rhodium concentration by the initial rhodium concentration used. The results are shown in table. eleven.

 As can be seen from the above experimental data, this method allows to improve the regulation of the molar ratio between aldehydes having a normal and isomeric structure through the use of the above polyphosphate ligands. (56) USSR patent N 1537133, class. C 07 C 45/50, 1986

Claims (1)

METHOD FOR PRODUCING C ₄ -C ₅ ALDEHYDES by hydroformylation of C ₃ - C ₄ olefins with carbon monoxide and hydrogen in the presence of a rhodium-polyphosphite complex as a catalyst at 70 - 120 ^o C and a total absolute pressure of a mixture of hydrogen, carbon monoxide and olefin less than 35.15 kg / cm ² when the molar ratio between carbon monoxide and the molar ratio between polyphosphite ligand and rhodium is 3.2 - 26.1: 1, characterized in that, in order to improve regulation of the molar ratio between aldehydes having normal and isomeric structure, a polyphosphite ligand of the general formula is used as a polyphosphite ligand

where R is hydrogen or a group —OCH ₃ or —C (CH ₃ ) ₃ ;
W is the group of one of the formulas

S

or - (CH _2n ) -, where n = 2 - 8, or - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, or a polyphosphite ligand of the formula

or polyphosphite ligand of the formula

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