Organic catalysts for non-aqueous aldol condensations

Abstract

The present disclosure provides a method. In one embodiment, the method includes providing a first blend consisting of nonanal, C8 olefins, and C7-C9 alkanes. The method includes adding a component selected from C4 aldehydes, C5 aldehydes, and combinations thereof to the first blend to form a non-aqueous reaction mixture having an initial water content of 0 wt% to 10 wt% water. The method includes introducing an organic base catalyst into the non-aqueous reaction mixture, heating the non-aqueous reaction mixture to a temperature from 30 °C to 100 °C, and subjecting the non-aqueous reaction mixture to a crossed aldol condensation reaction. The method includes forming a crossed aldol product consisting of components selected from C8 alkenals, C 10 alkenals, C 13 alkenals, C 14 alkenals, and C 18 alkenals, and combinations thereof.

Description

Background Art

[0001] Reuse of purged hydrocarbon material is one of the biggest challenges facing large-scale polyolefin production. For example, the conversion of octene comonomer in ethylene / octene copolymer polymerization production is usually very low, such as between 10% and 20%. This means that 80%-90% of octene can pass through the reactor without being converted into polymer.

[0002] Hydroformylation of an octene / alkane industrial purge stream using a hydroformylation catalyst to produce C 9 Aldehyde, unreacted C 8 The hydroformylation product can then undergo a cross-aldol reaction with butyraldehyde and / or valeraldehyde to produce C 8 -C 18 Aldehydes. By subsequent hydrogenation, these C 8 -C 18 Aldehydes can be used to generate C 8 -C 18 Alcohol. C 8 -C 18 Alcohols are high demand starting materials, for example for end-use applications such as surfactants.

[0003] Industrial-scale cross-aldol reactions are usually carried out using, for example, an inorganic base catalyst such as sodium hydroxide (NaOH) dissolved in aqueous solution. However, when attempting to carry out a cross-aldol reaction with a hydroformylation product prepared from octene isomers / alkanes consisting of a purge stream and butyraldehyde or valeraldehyde, the use of an inorganic base catalyst in aqueous solution is problematic. 8 The presence of olefins and hydrocarbon solvents (alkanes) provides a non-aqueous and non-polar environment for the aldol reaction. 9 Aldehyde and C 4 Aldehyde or C 5 Aldehydes vary greatly in polarity. Their relative solubility in water and in mixtures of alkanes and octenes varies greatly. 4 Aldehyde or C 5 Aldehyde Ratio C 9 Aldehydes are more soluble in the aqueous phase. This leads to the occurrence of C 4 Aldehyde or C 5 The self-condensation reaction of aldehydes, rather than C 4 Aldehyde or C 5 Aldehyde and C 9 The desired cross-condensation reaction between aldehydes. Adding a solvent to make the aldehyde miscible with the inorganic base catalyst (e.g., isopropanol) can promote the cross-condensation reaction. However, solvents such as isopropanol can form multiple azeotropes in the aldol reaction product mixture, making it difficult to recover the organic solvent from the aldol reaction product.

[0004] In addition, the use of inorganic base catalysts in the presence of polar organic solvents requires high concentrations of inorganic base catalysts in order to achieve high conversions of the aldehyde reactant. However, high concentrations of inorganic base catalysts generally lead to undesirable side reactions and undesirable by-products. Side reactions not only reduce the yield of the desired product, but also lead to the formation of carboxylic acids, for example, by the Cannizzaro reaction. Carboxylic acids and their salts in the presence of unreacted olefins and hydrocarbons (such as C 9 In the case of aldol products, severe gelation can result. Gelling of aldol reaction mixtures is problematic because the gel is difficult to handle and further processing of the aldol reaction product is expensive, time-consuming, and energy-intensive.

[0005] Thus, the art recognizes the need for catalysts that can drive the aldol reaction when hydrophobic hydroformylation reaction products (e.g., nonanal) are used as starting materials. There is also a need for catalysts that can generate aldol reaction products containing little or no azeotrope and produce room temperature flowable products when non-aqueous olefin / alkane hydroformylation reaction products are used as starting materials. Summary of the invention

[0006] The present disclosure provides a method. In one embodiment, the method comprises providing a 8 Olefins and C 7 -C 9 The method comprises adding to the first blend a compound selected from C 4 Aldehyde, C 5 aldehydes and combinations thereof to form a non-aqueous reaction mixture having an initial water content of 0 wt % to 10 wt % water. The method comprises introducing an organic base catalyst into the non-aqueous reaction mixture, heating the non-aqueous reaction mixture to a temperature of from 30° C. to 100° C., and subjecting the non-aqueous reaction mixture to a cross-aldol condensation reaction. The method comprises forming a 8 Alkenal, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal, C 18 The components of enals and their combinations constitute the cross-aldol products. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is a schematic diagram of a hydroformylation reactor system for providing hydroformylation conditions according to an embodiment of the present disclosure.

[0008] Figure 2A is a photograph of the crossed aldol product from Comparative Sample B with the container in a vertical position.

[0009] Figure 2Bis a photograph of the crossed aldol product from Comparative Sample B with the container in an inverted position.

[0010] Figure 3A is a photograph of the crossed aldol product from Comparative Sample C with the container in a vertical position.

[0011] Figure 3B is a photograph of the crossed aldol product from Comparative Sample C with the container in an inverted position.

[0012] Figure 4A is a photograph of the crossed aldol product from Example 2d of the present invention, wherein the container is in a vertical position.

[0013] Figure 4B is a photograph of the crossed aldol product from Example 2d of the present invention, wherein the container is in an inverted position.

[0014] definition

[0015] Any reference to the Periodic Table of the Elements is to the Periodic Table as published by CRC Press, Inc., 1990-1991. A group of elements in this table is referred to by a new notation for numbering the groups.

[0016] For purposes of U.S. patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference), especially with respect to definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and common general knowledge in the art.

[0017] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include the lower limit and the upper limit. For ranges containing explicit values ​​(e.g., 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two explicit values ​​is included (e.g., above range 1-7 includes subranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0018] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0019] An "alcohol" is a chemical compound having a hydroxyl group (-OH) attached to a hydrocarbon group.

[0020] An "aldehyde" is a chemical compound having a hydrogen atom and a carbonyl functional group (C=O) attached to a hydrocarbon group.

[0021] "Olefins" are hydrocarbons containing a carbon-carbon double bond.

[0022] As used herein, the term "blend" or "polymer blend" is a blend of two or more polymers. The blend may or may not be miscible (not phase separated at the molecular level). The blend may or may not be phase separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art.

[0023] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0024] The terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional components, steps or procedures, whether or not the components, steps or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed by using the term "comprising" may include any additional additives, adjuvants or compounds, whether in polymeric form or otherwise. In contrast, the term "consisting essentially of excludes any other components, steps or procedures (except those that are not essential for operability) from the scope of any subsequent statements. The term "consisting of" excludes any components, steps or procedures that are not specifically described or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination. The use of the singular includes the use of the plural, and vice versa.

[0025] "Alkenal" is an aldehyde compound containing a carbon-carbon double bond. Alkenals can be formed by an aldol (or cross-aldol) condensation reaction of an aldehyde followed by dehydration of the resulting intermediate compound. A non-limiting example of an alkenal is 2-ethylhexanal, which is composed of C 4 Self-condensation of aldehydes produces:

[0026]

[0027] "Enol" is an alcohol containing a carbon-carbon double bond. Enols can be formed by partial hydrogenation of enals.

[0028] "Ethylene polymers" are polymers that contain more than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene polymers" and "polyethylene" are used interchangeably.

[0029] A "hydrocarbon" is a chemical compound containing only hydrogen and carbon atoms. A "hydrocarbyl" (or "hydrocarbyl group") is a hydrocarbon having a valency (usually monovalent).

[0030] As used herein, the term "1-octene" is a 1-octene having a molecular formula of C 8 H 16 The unsaturated hydrocarbon α-olefin whose unsaturation is at the α position. 1-octene has the molecular structure (A) shown below.

[0031] Structure (A)

[0032]

[0033] As used herein, the term "octene isomer" is an isomer of the molecular formula C 8 H 16 And the unsaturated hydrocarbon that the unsaturation (double bond) is not in the alpha position. In other words, the term "isomer of octene" is any octene except 1-octene. Non-limiting examples of octene isomers include cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene and combinations thereof, as well as cis-4-octene, trans-4-octene, branched octene isomers and combinations thereof.

[0034] As used herein, the term "linear internal octene isomer" is a linear unsaturated hydrocarbon consisting of an eight-carbon chain, and the unsaturated group (double bond) is not located at the alpha position. Linear internal octene isomers include cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene, cis-4-octene, trans-4-octene, and combinations thereof. As used herein, the term "branched C 8 "Olefin" is a molecule having the molecular formula C 8 H 16 The main chain length is ≤7 carbon atoms. Compared with the straight chain nature of structure A, the branched chain C 8 Olefins contain at least one hydrocarbon group directly bonded to the main chain. 8 Non-limiting examples of olefins include methylheptenes, such as 3-methyl-2-heptene, 3-methyl-3-heptene, 5-methyl-2-heptene, 5-methyl-3-heptene, and the like. 8 Additional non-limiting examples of olefins include dimethyl hexenes, such as 3,4-dimethyl-2-hexene, 3,4-dimethyl-3-hexene, 2,3-dimethyl-3-hexene, etc. Further non-limiting examples include ethyl hexenes, such as 2-ethyl-1-hexene, etc.

[0035] An "olefin" is an unsaturated aliphatic hydrocarbon having a carbon-carbon double bond.

[0036] "Polymer" is a compound prepared by polymerizing monomers of the same or different types, which provide multiple and / or repeated "units" or "monomer units" constituting the polymer in a polymerized form. Therefore, the general term polymer covers the term homopolymer, which is usually used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is usually used to refer to polymers prepared from at least two types of monomers. It also covers all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" represent copolymers prepared by polymerizing ethylene or octene and one or more other polymerizable α-olefin monomers, respectively, as described above. It should be noted that although polymers are generally referred to as "made of" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than unpolymerized substances. In general, polymers are referred to herein as "units" based on the polymerized form of the corresponding monomers.

[0037] Test Method

[0038] Gas chromatography (GC):

[0039] The composition of the spent solvent and the hydroformylation reaction product was determined by gas chromatography (GC) using the following conditions:

[0040]

[0041] Quantification of this data in Table 1 and Section A of the Examples section is based on using weight percent of the response factors from standard solutions of known concentration.

[0042] The composition of the cross-aldol reaction product was determined by GC using the following conditions:

[0043]

[0044]

[0045] Quantitation in the Examples section is based on the GC area percentage (interchangeably referred to as "GC area" or "GC %) of the FID signal. Peak assignments / confirmation of component structures were based on matching of the electron ionization mass selective detector signal to the National Institute of Standards and Technology library.

[0046] N:I ratio. The hydroformylation reaction of olefins with three or more carbon atoms produces a mixture of both straight chain isomers and branched chain isomers. As used herein, the term "N:I ratio" is the ratio of straight chain or normal (N) aldehyde isomers to branched chain or isoaldehyde (I) isomers. The N:I ratio is calculated by dividing the concentration (weight %) of normal aldehydes by the concentration (weight %) of isoaldehydes. The weight percent concentration of each aldehyde isomer is determined by gas chromatography (GC).

[0047] Turbidity was measured using a Hach Ratio turbidimeter with a range of 0 NTU to 200 NTU. Measurements were performed at room temperature using an 8 dram sample cell. The calibration of the instrument was confirmed using a Gelex turbidity standard. Each sample was allowed to balance for at least 15 seconds so that the readings were stable. If any phase separation occurred in the sample, the organic phase was measured. The organic phase mixture. The results were reported in nephelometric turbidity units (NTU). DETAILED DESCRIPTION

[0048] The present disclosure provides a method. The method comprises providing a 8 Olefins and C 7 -C 9 A first blend of alkanes, and adding to the first blend a compound selected from C 4 Aldehyde, C 5 aldehydes and combinations thereof to form a non-aqueous reaction mixture. The non-aqueous reaction mixture has an initial water content of 0 wt % to 10 wt % water. The method includes introducing an organic base catalyst into the non-aqueous reaction mixture. The method includes heating the non-aqueous reaction mixture to a temperature of from 30° C. to 100° C., and subjecting the non-aqueous reaction mixture to a cross-aldol condensation reaction. The method includes forming a 8 Alkenal, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal and C 18 The components of enals and their combinations constitute the cross-aldol products.

[0049] The method includes providing a first blend consisting of or otherwise consisting of the following and containing 0% by weight or greater to 10% by weight water, or 0% by weight or greater to 8% by weight water: nonanal, C 8 Olefins and C 7 -C 9Alkanes. In one embodiment, the first blend is the reaction product of the hydroformylation of a purge stream. As used herein, a "purge stream" is one of several fractions separated or otherwise recovered from the effluent leaving the polymerization reactor after the polymerization reaction occurs. The liquid effluent leaving the polymerization reactor contains solid (granular) polymer products, which are removed. A recycle stream is also removed from the effluent, which is further processed and returned to the polymerization reactor. A purge stream is a stream remaining after (i) the polymer product has been recovered from the effluent and (ii) the recycle stream has been separated from the effluent. The purge stream contains unreacted olefin monomers (including octene isomers) and other hydrocarbons used during the polymerization reaction. It should be understood that the purge stream does not contain or is substantially free of solid polymer products.

[0050] In one embodiment, the purge stream is the effluent from a polymerization reactor in which ethylene and octene are copolymerized. The purge stream comprises unreacted octene isomers and other hydrocarbons.

[0051] In one embodiment, the sweep stream comprises

[0052] (i) 20 to 55 wt% or 25 to 50 wt% of 1-octene;

[0053] (ii) 20 to 60 weight percent of a linear internal octene isomer;

[0054] (iii) 2 to 8 wt% of branched C 8 Olefins; and

[0055] (iv) 5 wt% to 60 wt% hydrocarbon solvent, wherein the weight percentages are based on the total weight of the sweep stream. It is to be understood that components (i)-(iv) total up to 100 wt% of the sweep stream.

[0056] The purge stream is fed to a hydroformylation reactor system. In the hydroformylation reactor system, the hydroformylation reaction bonds a formyl group (-CH=O) and a hydrogen atom to the carbon-carbon double bond of an alkene (i.e., an olefin) to form an aldehyde. Since the purge stream contains octene isomers, subjecting the purge stream to hydroformylation conditions forms a reaction product consisting of nonanal. "Nonanal" is an aldehyde containing nine carbon atoms. The purge stream is a mixture of olefins (primarily octene isomers) and alkanes, so the reaction product from the hydroformylation reaction contains other components in addition to nonanal. Non-limiting examples of other components in the hydroformylation reaction product include C 8 Olefins, C 7 -C 9 Alkanes and combinations thereof.

[0057] The method comprises adding a first blend (the first blend contains nonanal, C 8 Olefins and C7 -C 9 Alkanes) are added with a mixture selected from C 4 Aldehyde, C 5 Aldehydes and their combination components (hereinafter referred to as "C 4 / C 5 % to 8 wt % water. The initial water content is from 0 wt % or greater to 10 wt % water, or from 0 wt % or greater to 8 wt % water, or from 1 wt % to 8 wt % water, or from 0 wt % or greater to 6 wt % water, or from 1 wt % to 4 wt % water. In one embodiment, the initial water content is from 0 wt % or greater to 10 wt % water, or from 0 wt % or greater to 8 wt % water, or from 0 wt % or greater to 6 wt % water, or from 0 wt % or greater to 4 wt % water. The weight percentages are based on the total weight of the non-aqueous reaction mixture.

[0058] The method comprises introducing an organic base catalyst into the non-aqueous reaction mixture. As used herein, an "organic base catalyst" is a compound composed of (i) an alkylammonium cation or an alkylphosphonium cation, wherein the alkyl portion is C 10 -C 30 Hydrocarbyl group (or C 10 -C 20 The organic base catalyst further comprises (ii) an anion which is a hydroxyl group (-OH) or a halogen group (-Cl, -Br). The anion may be a hydroxyl group (-OH) combined with a cation, or a hydroxide anion may be generated in situ in a reaction mixture containing an inorganic base catalyst such as sodium hydroxide (NaOH) and / or potassium hydroxide (KOH). Non-limiting examples of suitable organic base catalysts include tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), tetrabutylphosphonium hydroxide (TBPH), tetrabutylammonium bromide, and combinations thereof.

[0059] In one embodiment, an organic base is introduced into a basic reaction mixture containing NaOH and / or KOH. The ratio of the inorganic base catalyst to the organic base catalyst is 0.1:1 to 1:1. In other words, the method of the present invention uses an organic base catalyst to reduce or significantly reduce the amount of the inorganic base catalyst (NaOH and / or KOH) in the reaction mixture.

[0060] In one embodiment, an organic base is introduced into the reaction mixture to replace an inorganic base catalyst such as sodium hydroxide and / or potassium hydroxide. In other words, the method of the present invention uses an organic base catalyst as the sole catalyst, thereby avoiding or otherwise eliminating the presence of an inorganic base (such as sodium hydroxide and / or potassium hydroxide) in the method.

[0061] Once the organic base catalyst is introduced into the non-aqueous reaction mixture, the method includes heating the non-aqueous reaction mixture to a temperature of from 30°C to 100°C, or to a temperature of from 40°C to 70°C, or to a temperature of from 50°C to 60°C, and subjecting the non-aqueous reaction mixture to a cross-aldol condensation reaction. In the cross-aldol condensation step, the organic base catalyst catalyzes an aldehyde-alcohol condensation reaction to form a cross-aldol product and a condensed water by-product. The cross-aldol product is selected from C 8 Alkenal, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal, C 18 The cross-hydroxyaldehyde product may also include alcohol solvent; water; unreacted aldehyde; other C 8 , C 10 , C 13 , C 14 , C 18 In one embodiment, the cross-aldol product includes a large amount of C 8 Alkenal, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal, C 18 Enals, wherein "substantial" is greater than 50% of the total GC area of ​​the crossed aldol reaction products.

[0062] As used herein, the term "substance" is a mixture of alcohols, enals, enols, and aldehydes, wherein each alcohol, enal, enol, and aldehyde in the substance has the same number of carbon atoms. 8 Matter is C 8 Alcohol, C 8 Alkenal, C 8 Enol and C 8 A mixture of aldehydes. 10 Matter is C 10 Alcohol, C 10 Alkenal, C 10 Enol and C 10 A mixture of aldehydes. 13 Matter is C 13 Alcohol, C 10 Alkenal, C 13 Enol and C 13 A mixture of aldehydes. 14 Matter is C 14 Alcohol, C 14 Alkenal, C 14 Enol and C 14 A mixture of aldehydes. 18 Matter is C 18 Alcohol, C 18 Alkenal, C18 Enol and C 18 A mixture of aldehydes.

[0063] The method includes forming a cross-aldol product that is a liquid that can flow at 23°C and has a turbidity value of less than 1.0 NTU, or from 0 NTU or greater than 0 NTU to 1.0 NTU. The cross-aldol product produced using an inorganic base catalyst (e.g., NaOH) in the presence of (i) low initial water content (0 wt% to 10 wt% initial water), (ii) olefins and (iii) alkanes is a non-flowing gel at 23°C and has a turbidity greater than 200 NTU. The applicant has found that the cross-aldol product produced using an organic base catalyst in the presence of (i) low initial water content (0 wt% to 10 wt% initial water), (ii) olefins and (iii) alkanes is flowable at 23°C and has a turbidity less than 1.0 NTU. In one embodiment, the method includes forming a cross-aldol product that is a liquid that flows at 23°C and has a turbidity value from 0 NTU to 1.0 NTU, or from greater than 0 NTU to 0.9 NTU, or from 0.05 NTU to 0.5 NTU.

[0064] In one embodiment, the method comprises adding C to the first blend. 4 The method comprises introducing an organic base catalyst (TBAH) at a molar ratio of organic base catalyst to total aldehyde of 0.0036:1 to 0.0286:1, and forming a 8 Alkenal, C 13 Alkenal, C 18 The cross-hydroxyaldehyde product may also include alcohol solvent; water; unreacted aldehyde; other C 8 , C 13 and C 18 Substances (except the above-mentioned aldehydes). The cross-hydroxyaldehyde products include a large amount of C 8 Alkenal, C 13 Alkenal and C 18 Alkenal, wherein "substantial amount" is greater than 50% of the total GC area of ​​the cross-aldol reaction product. The cross-aldol product is mobile at 23°C and has a turbidity value from 0 NTU to 1.0 NTU, or greater than 0 NTU to 0.9 NTU, or from 0.05 NTU to 0.5 NTU. 4 Aldehyde and / or C 9 Aldehyde conversion to C 8 / C 13 / C 18 The conversion of the substance is from 90% to 99%, or from 92% to 98%, or from 93% to 97%.

[0065] In one embodiment, the method comprises adding C to the first blend. 5 The method comprises introducing an organic base catalyst (TBAH) at a molar ratio of organic base to total aldehyde of 0.0036:1 to 0.0286:1, and forming a 10 Alkenal, C 14 Alkenal, C 18 The cross-hydroxyaldehyde product may also include alcohol solvent; water; unreacted aldehyde; and other C 10 , C 14 , C 18 Substances (except the above-mentioned aldehydes). The cross-hydroxyaldehyde products include a large amount of C 10 Alkenal, C 14 Alkenal and C 18 Alkenal, wherein "substantial amount" is greater than 50% of the total GC area of ​​the cross-aldol reaction product. The cross-aldol product is mobile at 23°C and has a turbidity value from 0 NTU to 1.0 NTU, or greater than 0 NTU to 0.9 NTU, or from 0.05 NTU to 0.5 NTU. 5 Aldehyde and / or C 9 Aldehyde conversion to C 10 / C 14 / C 18 The conversion of the substance is from 90% to 99%, or from 92% to 98%, or from 93% to 97%.

[0066] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0067] Example

[0068] The composition of the purge stream recovered from an ethylene / octene polymerization production process is provided in Table 1 below.

[0069] Table 1

[0070] Purge flow (weight%) Hydrocarbon solvents 6.1 Branched C9 Olefins 4.8 1-Octene 42.4 trans-4-octene 2.4 trans-3-octene and cis-4-octene (co-eluting) 9.9 cis-3-octene 2.0 Octane 0.6 trans-2-octene 17.0 cis-2-octene 14.8

[0071] The ligands used in the hydroformylation catalysts in Examples (IE) of the present invention are provided in Table 2 below.

[0072] Table 2

[0073]

[0074] A. Subjecting the Purge Stream to Hydroformylation Conditions (Hydroformylation Reaction 1)

[0075] like Figure 1 As shown, hydroformylation conditions are provided in the reactor system. The reactor system is composed of three 1 liter stainless steel stirred tank reactors (Rx 1, Rx 2, Rx 3) connected in series. Each reactor is equipped with a vertically mounted agitator and a circular tubular bubbler near the bottom for feeding olefins and / or synthesis gas to the reactor. The bubbler contains a plurality of holes, and these holes have sufficient size to provide the desired gas stream to the liquid body. Each reactor has a silicone oil shell, as a way of controlling the reactor temperature. Reactor 1 is further connected to reactor 2 via a pipeline and reactor 2 is further connected to reactor 3 via a pipeline, to transfer any unreacted gas and allow a part of the liquid solution containing aldehyde product and catalyst (for example, via pressure difference or by pumping) to flow from reactor 1 to reactor 2 and flow from reactor 2 to reactor 3. Therefore, the unreacted olefins of reactor 1 are further hydroformylated in reactor 2, and then hydroformylated in reactor 3. In an alternative configuration, reactor 3 (Rx 3) can be bypassed so that only two reactors are adopted.

[0076] Each reactor also contains a pneumatic level controller for maintaining the desired liquid level in the reactor. Reactor 1 also contains a pipeline for introducing olefins, carbon monoxide and hydrogen through a bubbler, and supplementary carbon monoxide and hydrogen are transferred to reactors 2 and 3 via a transfer line, which also carries unreacted gas from reactor 1 to reactor 2 and from reactor 2 to reactor 3. If necessary, each reactor also includes a blow-out exhaust port to control the removal of unreacted gas. A portion of the liquid reaction solution is pumped from the last reactor in series to a gasifier, which consists of a heated zone, in which a portion of the flowing gas (stripping gas) stream is used to purge a portion of the volatile components into a water-cooled condenser, where the portion can be collected as a liquid in a product receiver (crude product). Non-volatile substances pass through an aqueous extraction zone consisting of a contact zone and a separation zone. The purpose of aqueous extraction is to extract acidic byproducts, thereby preventing additional hydrolysis of phosphite ligands, as described in US5741944. After the aqueous extraction, the organic non-volatiles are pumped back to Reactor 1 through the recycle line.

[0077] The purge flow is introduced into the reactor 1 ( Figure 1 The "olefin" in refers to the purge stream). The composition of the purge stream from the ethylene-octene polymerization production process / purge stream is provided in Table 1 above.

[0078] Two reactors (Rx 1 and Rx 2, bypassing Rx 3) were used for the hydroformylation reaction. A mixture of rhodium dicarbonyl acetylacetonate (394 ppm rhodium), ligand A (Table 2 above) (0.7 wt %; 2.0 molar equivalents of ligand A per mole of rhodium), tetraethylene glycol dimethyl ether (about 15 wt %) and mixed C 4 Two liters of a catalyst solution of 1,2-butyraldehyde (about 85 wt. %; about 30:1 ratio of n-butyraldehyde to iso-butyraldehyde) was charged to Figure 1 In the reactor system shown in FIG. , the syngas (CO:H 2 The reactor was heated to 70°C at 1:1 ratio (ratio = 1:1). Reactor 1 and Reactor 2 pressures were maintained at 244 psig and 220 psig, respectively. Waste solvent was fed to Reactor 1 at a rate of 138 g / hr. The gasifier system was operated with a stripping gas consisting of 1:1 syngas at a flow rate of 790 sLph; the gasifier pressure was maintained at 7 psig, and the catalyst temperature was 101°C.

[0079] After several days of continuous operation, the headspace butyraldehyde and tetraethylene glycol dimethyl ether were removed, leaving a reactor process fluid consisting of nonanal, heavy aldehydes (byproducts of the in-situ aldol condensation), unreacted olefins, and hydrocarbon solvent (continuously introduced as part of the spent solvent). The reaction product consisting of nonanal (nonanal reaction product) was collected at a rate of 155 g / hour. The composition of the nonanal reaction product is shown in Table 3 below.

[0080] B. Subjecting the Purge Stream to Hydroformylation Conditions (Hydroformylation Reaction 2)

[0081] like Figure 1 Hydroformylation conditions were provided in a 2-reactor system as shown and described above in Hydroformylation Reaction 1. A mixture consisting of rhodium dicarbonyl acetylacetonate (150 ppm rhodium), Ligand B (0.75 wt %; 7.0 molar equivalents per mole of rhodium) and C from Example 1A was added. 9 Two liters of catalyst solution consisting of aldehyde products was loaded into the microdevice. Then, under the flow of syngas (CO:H 2 The reactor was heated to 90°C at a ratio of 1:1 (ratio = 1:1). The pressures of Reactor 1 and Reactor 2 were maintained at 472 psig and 438 psig, respectively. The spent solvent was fed to Reactor 1 at a rate of 175 g / hr. The gasifier system was operated with a stripping gas consisting of 1:1 syngas at a flow rate of 790 sLph; the gasifier pressure was maintained at 7 psig, and the catalyst temperature was 100°C to 105°C. C was collected at a rate of 212 g / hr. 9 Aldehyde products; the composition is shown in Table 3.

[0082] Table 3. Composition of nonanal reaction products .

[0083]

[0084] C. Cross-aldol condensation reaction

[0085] 1-Dodecane was used as a GC internal standard to calculate C 4 and C 9 Conversion. A butyraldehyde masterbatch containing 1 mol% internal standard was prepared from a mixture of 1-dodecane (17 g, 0.1 mol) and butyraldehyde (720 g, 10.0 mol). The butyraldehyde masterbatch was used for the later cross-aldol chemistry. C was calculated using the GC method 4 and C 9 The C between the aldehyde raw material mixture feed and the product mixture 4 and C 9 Aldehyde conversion. GC area integration / 1-dodecane is used to estimate product yield. For example, C 8 / 1-dodecane area ratio indicates C 8 Product yield, C 13 / 1-Dodecane area ratio indicates C 13 Product yield, C 18 / 1-Dodecane area ratio indicates C 18 Product yield, (C 8 +C 13 +C 18 ) total / 1-dodecane represents C 8 , C 13 and C 18 Product yield.

[0086] i. Comparative Sample (CS) A

[0087] Comparative Sample A is the reaction product of nonanal from hydroformylation reaction 1 (Table 3 above) with butyraldehyde catalyzed NaOH (水溶液) A mixture of butyraldehyde (25.3 g; 0.350 mol) and the nonanal reaction product (38.2 g; 0.175 mol of n-nonanal) from hydroformylation reaction 1 was prepared and loaded into a 300 mL Parr reactor, purged three times with nitrogen, and sealed under nitrogen. A solution of NaOH catalyst (1.2 g; 30 mmol) and water (42 g) was prepared and added to the Parr reactor at a feed rate of 20 mL / min using a Gilson pump at 30 ° C. After addition, the reaction mixture was heated to 60 ° C with vigorous stirring, and the temperature was maintained at 60 ° C for 60 minutes. The reaction mixture was cooled to 40 ° C and quenched with 0.9 equivalents of acetic acid. The neutralized reaction mixture was transferred to a separatory funnel, and the organic phase was collected. The conversion of butyraldehyde and nonanal and C were calculated according to gas chromatography. 8 , C 13 and C 18The product yields of enals were calculated based on the weight percent of initial water and the results are provided in Table 4.

[0088] ii. Comparison sample B, Comparison sample C

[0089] Isopropanol (21 g) and a certain amount of NaOH specified in Table 4 were charged into a 300 mL Parr reactor, purged with nitrogen three times, and sealed. The solution was heated to 60° C. with vigorous stirring. Preparation C 4 A mixture of aldehyde (0.175 mol, 12.6 g) and the nonanal reaction product from hydroformylation reaction 1 (Table 3 above) (0.0875 mol, 22.2 g) was analyzed using GC and introduced into the reactor at a feed rate of 40 mL / min using a small laboratory pump. After addition, the temperature was maintained at 60° C. reaction temperature for 1 hour under stirring. The reaction mixture was then cooled to 40° C. and immediately analyzed using GC. After cooling to room temperature, the turbidity of the reaction mixture was analyzed and photographs were taken to illustrate liquid or gel properties.

[0090] In Comparative Sample B, a slightly turbid liquid reaction mixture was obtained. For Comparative Sample B, gelation was visually observed, such as Figure 2A As shown in the photograph in FIG. 1 , Comparative Sample B is a gel. Even when the container is turned upside down (subjected to inversion), Comparative Sample B cannot flow, as shown in FIG. Figure 2B As shown in the photo in. The turbidity of comparative sample B was measured to be over 200 NTU.

[0091] Comparative sample C was not a gel and the mixture was able to flow. However, the product yield was low: C 4 The conversion rate was 21%, C 9 The conversion rate was 33%. Comparative Sample C also had high turbidity (greater than 1 NTU), with Comparative Sample C having a turbidity of 36 NTU.

[0092] (iii) Inventive Examples (IE) 2a-2d: Nonanal Reaction Products from Hydroformylation Reaction 1 with Different Amounts of Homogeneous cross-aldol condensation reaction catalyzed by TBAH

[0093] A mixture of butyraldehyde (25.3 g; 0.350 mol) and the nonanal reaction product (Table 3 above) (38.2 g; 0.175 mol of n-nonanal) from hydroformylation reaction 1 was prepared and loaded into a 300 mL Parr reactor, purged three times with nitrogen, and sealed under nitrogen. A 40 wt % TBAH aqueous solution (amount specified in Table 4) was prepared and added to the Parr reactor at a feed rate of 20 mL / min using a Gilson pump at 30 ° C. After addition, the reaction mixture was heated to 60 ° C under vigorous stirring, and the temperature was maintained at 60 ° C for 60 minutes. The reaction mixture was cooled to 40 ° C and quenched with 0.9 equivalents of acetic acid. The neutralized reaction mixture was transferred to a separatory funnel, and the organic phase was collected. The conversion of butyraldehyde and nonanal and C were calculated according to gas chromatography. 8 , C 13 and C 18 The product yield of enal was calculated as the weight % of initial water and the results are summarized in Table 4. Inventive Examples 2a-2d were each able to flow without any gelling occurring. Figure 4A is a photo showing IE 2d in a container in a vertical position. When the container containing IE 2d is inverted, as shown in the photo and Figure 4B As shown in , IE 2d flows downward to cover the container lid of the upside-down container. Inventive Examples 2a-2d each have a low turbidity (less than 1.0 NTU), IE 2a has a turbidity value of 0.14 NTU, IE 2b has a turbidity value of 0.12 NTU, IE 2c has a turbidity value of 0.13 NTU, and IE 2d has a turbidity value of 0.12 NTU.

[0094] (iv) Example 3 of the present invention: Nonanal reaction product from hydroformylation reaction 1 and tetrabutylammonium bromide + Homogeneous Cross-Aldol Condensation Reaction Catalyzed by NaOH

[0095] A mixture of butyraldehyde (25.3 g; 0.350 mol) and the nonanal reaction product (Table 3 above) (38.2 g; 0.175 mol of n-nonanal) from hydroformylation reaction 1 was prepared and loaded into a 300 mL Parr reactor, purged three times with nitrogen, and sealed under nitrogen. A mixed catalyst solution of tetrabutylammonium bromide (3.8 mmol, 1.21 g) and NaOH (3.8 mmol, 0.15 g) dissolved in water (3 g) was prepared and added to the Parr reactor at a feed rate of 20 mL / min using a Gilson pump at 30 ° C. After addition, the reaction mixture was heated to 60 ° C under vigorous stirring, and the temperature was maintained at 60 ° C for 60 minutes. The reaction mixture was cooled to 40 ° C and quenched with 0.9 equivalents of acetic acid. The neutralized reaction mixture was transferred to a separatory funnel, and the organic phase was collected. The conversion of butyraldehyde and nonanal and C were calculated according to gas chromatography. 8 , C 13and C 18 The product yield of enal was calculated as the weight % of initial water and the results are provided in Table 4. Inventive Example 3 was able to flow without any gelling. IE3 had a low turbidity (less than 1.0 NTU), with the turbidity value of IE3 being 0.15 NTU.

[0096] (v) Example 4 of the present invention: with C 4 Aldehydes and branched C 9 Cross-aldol condensation of the isomers to produce C 8 -C 18 Hydroxyaldehyde product

[0097] A mixture of butyraldehyde (25.3 g; 0.350 mol) and the nonanal reaction product (Table 3 above) (38.2 g; 0.175 mol of n-nonanal) from hydroformylation reaction 2 was prepared and loaded into a 300 mL Parr reactor, purged three times with nitrogen, and sealed under nitrogen. A 40 wt % aqueous solution of TBAH (15 mmol, 9.73 g) was added to the Parr reactor at a feed rate of 20 mL / min using a Gilson pump at 30 ° C. After addition, the reaction mixture was heated to 60 ° C under vigorous stirring, and the temperature was maintained at 60 ° C for 60 minutes. The reaction mixture was cooled to 40 ° C and quenched with 0.9 equivalents of acetic acid. The neutralized reaction mixture was transferred to a separatory funnel, and the organic phase was collected. Butyraldehyde, nonanal, branched C 9 The conversion rate of aldehyde and C 8 , C 13 and C 18 The product yield of enal was calculated as the weight % of initial water and the results are provided in Table 4. Inventive Example 4 was able to flow without any gelling. IE4 had a low turbidity (less than 1.0 NTU), with the turbidity value of IE4 being 0.09 NTU.

[0098] IE4 showed that TBAH catalyst not only 4 Aldehyde and C 9 The aldehyde conversion was greater than 98% (99%), and the branched C 9 Aldehyde conversion was greater than 60% (62%).

[0099] Table 4. Cross-aldol reaction process, products and characteristics

[0100]

[0101] *Branch C 9 Conversion rate: 62%

[0102] It is particularly intended that the present disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments including parts of the embodiments and combinations of elements of different embodiments as appear within the scope of the following claims.

Claims

1. A method, comprising: providing a first blend comprising nonanal, C8 olefins, and C7-C9 alkanes; adding a component selected from the group consisting of C4 aldehydes, C5 aldehydes, and combinations thereof to the first blend to form a non-aqueous reaction mixture having an initial water content of 0 wt % to 10 wt % water; introducing an organic base catalyst into the non-aqueous reaction mixture, wherein the organic base catalyst is selected from tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), tetrabutylphosphonium hydroxide (TBPH), tetrabutylammonium bromide, and combinations thereof; heating the non-aqueous reaction mixture to a temperature of from 30°C to 100°C and subjecting the non-aqueous reaction mixture to a cross-aldol condensation reaction; and Formed from a group consisting of C8 olefinic aldehyde, C 10 Alkenal, C 13 Alkenal, C 14 Alkenal and C 18 The components of enals and their combinations constitute the cross-aldol products.

2. The method of claim 1, comprising forming a cross-aldol product having a turbidity value from 0 NTU to less than 1.0 NTU.

3. A process according to any one of claims 1 to 2, comprising forming a cross-aldol product which is mobile at 23°C.

4. The method of any one of claims 1 to 2, comprising introducing the organic base catalyst at a molar ratio of organic base catalyst to total aldehyde of 0.0036:1 to 0.0286:

1.

5. The process of any one of claims 1 to 2, comprising forming the crossed aldol product in the absence of an inorganic base.

6. The method according to any one of claims 1 to 2, comprising: adding a C4 aldehyde to the first blend to form the non-aqueous reaction mixture; introducing the organic base catalyst at a molar ratio of organic base catalyst to total aldehyde of 0.0036:1 to 0.0286:1; and Formed from a group consisting of C8 olefinic aldehyde, C 13 Alkenal and C 18 The components of enals and their combinations constitute the cross-aldol products.

7. The method according to any one of claims 1 to 2, comprising: adding a C5 aldehyde to the first blend to form the non-aqueous reaction mixture; introducing the organic base catalyst at a molar ratio of organic base catalyst to total aldehyde of 0.0036:1 to 0.0286:1; and Formed by selecting C 10 Alkenal, C 14 Alkenal and C 18 The components of enals and their combinations constitute the cross-aldol products.

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