Organic Catalysts for Non-Aqueous Aldol Condensation

Abstract

The present disclosure provides a process. In one embodiment, the process includes preparing a first blend consisting of nonanal, a C8 olefin, and a C7-C9 alkane. The process includes adding a component selected from a C4 aldehyde, a C5 aldehyde, and combinations thereof to the first blend to produce a nonaqueous reaction mixture having an initial water content of 0% to 10% by weight. The process includes introducing an organic base catalyst to the nonaqueous reaction mixture, heating the nonaqueous reaction mixture to a temperature of 30°C to 100°C, and subjecting the nonaqueous reaction mixture to a cross-aldol condensation. The process includes preparing a C8 enal, a C8 olefin, and a C7-C9 alkane. 10 Henard, C. 13 Henard, C. 14 Enal, and C 18 and producing cross-aldol products comprised of components selected from: enals, hydroxybenzoates ...

Description

Background Art

[0001] The regeneration of purged hydrocarbon species is one of the greatest challenges for large-scale polyolefin production. For example, the conversion rate of octene comonomer in the polymerization production of ethylene / octene copolymer is generally very low, for example, 10-20%. This means that 80-90% of the octene can pass through the reactor without being converted into polymer.

[0002] Hydroformylation of an industrial purge stream of octene / alkane using a hydroformylation catalyst produces a mixture of C9 aldehyde, unreacted C8 olefin, and hydrocarbon solvent. Then, by subjecting this hydroformylation product to a cross-aldol reaction with butyraldehyde and / or valeraldehyde, C8-C 18 aldehydes are produced. Subsequent hydrogenation then uses these C8-C 18 aldehydes to produce C8-C 18 alcohols. C8-C 18 alcohols are starting materials with high demand in end uses such as surfactants, for example.

[0003] Industrial-scale cross-aldol condensation reactions are typically carried out using an inorganic base catalyst such as sodium hydroxide (NaOH) dissolved, for example, in an aqueous solution. However, the use of an inorganic base catalyst in an aqueous solution becomes problematic when attempting to carry out a cross-aldol reaction between a hydroformylation product generated from a purge stream composed of octene isomers / alkanes and butyraldehyde or valeraldehyde. The presence of unreacted C8 olefins and hydrocarbon solvents (alkanes) in the hydroformylation product of the purge stream provides a non-aqueous and non-polar environment for the aldol reaction. C9 aldehydes and C4 aldehydes or C5 aldehydes have significantly different polarities. Their relative solubilities in water and in mixtures of alkanes and octenes are very different. C4 aldehydes or C5 aldehydes have a higher solubility in the aqueous phase than C9 aldehydes. In this situation, self-condensation of C4 aldehydes or C5 aldehydes becomes predominant over the desired cross-aldol condensation of C4 aldehydes or C5 aldehydes with C9 aldehydes in the reaction. The cross-condensation reaction can be promoted by adding a solvent, such as isopropanol, so that the aldehyde is miscible with the inorganic base catalyst. 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] Furthermore, using an inorganic base catalyst in the presence of a polar organic solvent requires a high concentration of the inorganic base catalyst to achieve a high conversion of the aldehyde reactants. However, a high concentration of the inorganic base catalyst typically results in unwanted side reactions and unwanted by-products. Side reactions not only reduce the yield of the desired product but also result in the formation of carboxylic acids, for example, by the Cannizzaro reaction. The presence of carboxylic acids and their salts (e.g., those present in the C9 aldehyde product derived from the purge stream of the polymerization unit) in the presence of unreacted olefins and hydrocarbons can lead to severe gelation. Gelation of the aldol reaction mixture is a problem because it makes the handling of the reaction mixture difficult, increases the cost of further processing of the aldol reaction product, and increases time and energy consumption.

[0005] Accordingly, there is a recognized need in the art for catalysts that can promote aldol reactions when hydrophobic hydroformylation reaction products (e.g., nonanal) are used as starting materials. Further, when non-aqueous alkene / alkane hydroformylation reaction products are used as starting materials, catalysts are desired that can produce aldol reaction products that contain little or no azeotropic mixture and result in a product that is fluid at room temperature. SUMMARY OF THE INVENTION

[0006] The present disclosure provides a process. In one embodiment, the process includes preparing a first blend composed of nonanal, C8 olefin, and C7-C9 alkanes. The process includes adding to the first blend a component selected from C4 aldehydes, C5 aldehydes, and combinations thereof to produce a non-aqueous reaction mixture having an initial water content of 0 wt% to 10 wt% water. The process includes introducing an organic base catalyst into the non-aqueous reaction mixture, heating the non-aqueous reaction mixture to a temperature of 30 °C to 100 °C, and cross-aldol condensing the non-aqueous reaction mixture. The process includes producing a cross-aldol product composed of a component selected from C8 enals, C 10 enal, C 13 enal, C 14 enal, C 18 enal, and combinations thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0007]

Figure 1

[0008]

Figure 2A

[0009]

Figure 2B

[0010]

Figure 3A

[0011]

Figure 3B

[0012]

Figure 4A

[0013]

Figure 4B

[0014] Definitions Any reference to the Periodic Table of the Elements is a reference to that published by CRC Press, Inc., 1990 - 1991. References to groups of elements in this table are by the new notation for numbering the groups.

[0015] For the purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent United States version is so incorporated by reference) with respect to the particular definition disclosure (to the extent not inconsistent with any definitions provided in this disclosure) and general knowledge in the art.

[0016] The numerical ranges disclosed in this specification include all values from the lower limit value and the upper limit value, including the lower limit value and the upper limit value. In the case of a range containing explicit values (for example, 1 or 2, or 3 to 5, or 6, or 7), any sub-range between any two explicit values is included (for example, in the range of 1 to 7 above, sub-ranges such as 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc. are included).

[0017] Unless otherwise stated to the contrary, implied from the context, or not the custom in the art, all parts and percentages are by weight, and all test methods are the latest at the filing date of this disclosure.

[0018] "Alcohol" refers to a compound having a hydroxyl group (-OH) bonded to a hydrocarbon group.

[0019] "Aldehyde" refers to a compound having a carbonyl functional group (C=O) bonded to one hydrocarbon group and a hydrogen atom.

[0020] "Alkene" refers to a hydrocarbon having a carbon-carbon double bond.

[0021] As used herein, the terms "blend" or "polymer blend" refer to a blend of two or more polymers. Such blends may or may not be miscible (not phase-separate at the molecular level). Such blends may or may not be phase-separated. Such blends may or may not include one or more domain configurations determined from transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art.

[0022] The term "composition" refers to a mixture of the materials that make up the composition, as well as reaction products and decomposition products produced from the materials of the composition.

[0023] 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 specifically disclosed. To avoid doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or not, unless the contrary is stated. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps, or procedures, except those that are not essential to the operability. The term "consisting of" excludes any component, step, or procedure not specifically depicted or enumerated. The term "or" refers to the listed members individually and in any combination, unless otherwise specified. The use of the singular includes the use of the plural and vice versa.

[0024] An "enal" is an aldehyde compound having a carbon-carbon double bond. An enal can be produced by dehydration of the intermediate compound obtained after aldol (or crossed aldol) condensation of an aldehyde. A non-limiting example of an enal is 2-ethylhexenal, which results from the self-condensation of C4 of the aldehyde as shown below. [Chemical formula]

[0025] An "enol" is an alcohol having a carbon-carbon double bond. An enol can be produced by partial hydrogenation of an enal.

[0026] "Ethylene polymer" is a polymer that contains more than 50 weight percent (wt%) of polymerized ethylene monomer (based on the total amount of polymerizable monomers) and may optionally contain at least one comonomer. Examples of ethylene polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene polymer" and "polyethylene" may be used interchangeably.

[0027] "Hydrocarbon" refers to a compound containing only hydrogen and carbon atoms. "Hydrocarbonyl" (or "hydrocarbonyl group") refers to a hydrocarbon having a valence (typically monovalent).

[0028] As used herein, the term "1-octene" is an unsaturated hydrocarbon alpha-olefin having the molecular formula C8H 16 and having the unsaturation at the alpha position. 1-octene has the molecular structure (A) as shown below. Structure (A)

Chemical formula

[0029] As used herein, the term "isomer of octene" is an unsaturated hydrocarbon having the molecular formula C8H 16 and having the unsaturation (double bond) not at the alpha position. In other words, the term "isomer of octene" refers to any octene excluding 1-octene. Non-limiting examples of isomers of octene 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.

[0030] As used herein, the term "linear internal octene isomer" refers to a straight-chain and unsaturated hydrocarbon composed of an 8-carbon chain, and the unsaturation (double bond) is not at the α-position. Examples of 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, "branched C8 olefin" refers to an unsaturated hydrocarbon having the molecular formula C8H 16 and having a main chain length of 7 carbon atoms or less. Relative to the linear nature of Structure A, a branched C8 olefin has at least one hydrocarbon group directly bonded to the main chain. Non-limiting examples of branched C8 olefins include methylheptenes such as 3-methyl-2-heptene, 3-methyl-3-heptene, 5-methyl-2-heptene, 5-methyl-3-heptene. Further non-limiting examples of branched C8 olefins include dimethylhexenes such as 3,4-dimethyl-2-hexene, 3,4-dimethyl-3-hexene, 2,3-dimethyl-3-hexene. Further non-limiting examples include ethyl ethylenes such as 2-ethyl-1-hexene.

[0031] "Olefin" refers to an unsaturated aliphatic hydrocarbon having a carbon-carbon double bond.

[0032] "Polymer" refers to a compound prepared by polymerizing monomers that give rise to multiple and / or repeating "units" or "~mer units" that constitute the polymer, whether of the same type or different types, in polymerized form. Thus, the term "polymer" in its broad sense encompasses the term "homopolymer" which is commonly used to refer to polymers prepared from only one type of monomer, and the term "copolymer" which is commonly used to refer to polymers prepared from at least two types of monomers. Polymers also include all forms of copolymers such as random, block, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" each mean the above-mentioned copolymers prepared by polymerizing ethylene or octene with one or more additional polymerizable α-olefin monomers. Polymers are often said to be "made of" one or more specific monomers, "based on" a specific monomer or monomer type, "containing" a specific monomer content, etc., but in this context, it should be noted that the term "monomer" is understood to refer to the polymerized residues of a specific monomer and not to non-polymerized species. Generally, polymers herein are referred to as being based on "units" which are the polymerized forms of the corresponding monomers.

[0033] Test Methods Gas Chromatography (GC)

[0034] The composition of the used solvent and the hydroformylation reaction product is determined by gas chromatography (GC) using the following conditions. [Table 1]

[0035] The quantification of this data in Section A of Table 1 and the Examples section is based on weight percent using response factors derived from standard solutions of known concentration.

[0036] The composition of the crossed aldol reaction product is determined by GC using the following conditions. [Table 2]

[0037] Quantification in the Examples section is based on GC area percent (alternatively referred to as "GC area" or "GC%") from the FID signal. Confirmation of peak identity / component structure is based on signals from an electron ionization mass selective detector that match the test library of the National Institute of Standards and Technology of the United States.

[0038] N:I ratio. The hydroformylation reaction of olefins having three or more carbon atoms yields a mixture of both linear and branched isomers. As used herein, the term "N:I ratio" is the ratio of linear or normal (N) aldehyde isomers to branched or isoaldehyde (I) isomers. The N:I ratio is calculated by dividing the concentration (wt%) of the normal aldehyde by the concentration (wt%) of the isoaldehyde. The weight percent concentration of each aldehyde isomer is measured by gas chromatography (GC).

[0039] Turbidity is measured using a Hach ratio turbidimeter in the range of 0 - 200 NTU. Measurements are taken at room temperature using an 8-drum sample cell. The calibration of the instrument was confirmed using a Gelex turbidity standard. Each sample was equilibrated for at least 15 seconds to allow the readings to stabilize. If the sample had phase separation, the organic phase was measured. Organic phase mixture. Results are reported in nephelometric turbidity units (NTU). **Modes for Carrying Out the Invention**

[0040] The present disclosure provides a process. The process includes preparing a first blend composed of nonanal, C8 olefin, and C7 - C9 alkanes, and adding a component selected from C4 aldehydes, C5 aldehydes, and combinations thereof to the first blend to produce a non - aqueous reaction mixture. The non - aqueous reaction mixture has an initial water content of 0 wt% to 10 wt% water. The process includes introducing an organic base catalyst into the non - aqueous reaction mixture. The process includes heating the non - aqueous reaction mixture to a temperature of 30°C to 100°C and cross - aldol condensing the non - aqueous reaction mixture. The process includes producing a cross - aldol product composed of components selected from C8 enal, C 10 enal, C 13 enal, C 14 enal, and C 18 enal, and combinations thereof.

[0041] The process includes preparing a first blend composed of or consisting of nonanal, C8 olefin, olefin C7 - C9 alkanes and containing 0 wt% or more than 0 wt% to 10 wt% water, or 0 wt% or more than 0 wt% to 8 wt% water. In one embodiment, the first blend is a reaction product of the hydroformylation of a purge stream. As used herein, a "purge stream" is one of several fractions separated from or otherwise recovered from the effluent exiting the polymerization reactor after the polymerization reaction has occurred. The liquid effluent exiting the polymerization reactor contains a solid (granular) polymer product, which is removed. A recycle stream is also removed from the effluent, which is further processed and returned to the polymerization reactor. The purge stream is the 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 utilized during the polymerization reaction. It will be understood that the purge stream does not contain or substantially does not contain solid polymer product therein.

[0042] In one embodiment, the purge stream is the effluent from the polymerization reactor where ethylene is copolymerized with octene. The purge stream contains unreacted octene isomers and other hydrocarbons.

[0043] In one embodiment, the purge stream is (i) 20 wt% to 55 wt%, or 25 wt% to 50 wt% of 1-octene, (ii) 20 wt% to 60 wt% of linear internal octene isomers, (iii) 2 wt% to 8 wt% of branched C8 olefins, and (iv) 5 wt% to 60 wt% of a hydrocarbon solvent, where the weight percentages are based on the total weight of the purge stream. It will be understood that the sum of components (i) to (iv) is 100 wt% of the purge stream.

[0044] The purge stream is fed to a hydroformylation reactor system. In the hydroformylation reactor system, a formyl group (-CH=O) and a hydrogen atom are bonded to the carbon-carbon double bond of an alkene (i.e., an olefin) by a hydroformylation reaction to produce an aldehyde. Since the purge stream contains octene isomers, when the purge stream is subjected to hydroformylation conditions, a reaction product composed of nonanal is produced. "Nonanal" is an aldehyde having 9 carbon atoms. The purge stream is a mixture of alkenes (mainly octene isomers) and alkanes, and as a result, the reaction product from the hydroformylation reaction contains components other than nonanal. Non-limiting examples of other components in the hydroformylation reaction product include C8 olefins, C7 - C9 alkanes, and combinations thereof.

[0045] The process includes adding to a first blend (a first blend containing nonanal, C8 olefin, and C7 - C9 alkanes) a component selected from C4 aldehydes, C5 aldehydes, and combinations thereof (hereinafter referred to as "C4 / C5 aldehyde") to produce a non-aqueous reaction mixture having an initial water content of 0 wt% to 8 wt%. The initial water content is 0 wt% or more than 0 wt% to 10 wt% water, or 0 wt% or more than 0 wt% to 8 wt% water, or 1 wt% to 8 wt% water, or more than 0 wt% to 6 wt% water, or 1 wt% to 4 wt% water. In one embodiment, the initial water content is 0 wt% or more than 0 wt% to 10 wt%, or 0 wt% or more than 0 wt% to 8 wt% water, or 0 wt% or more than 0 wt% to 6 wt% water, or 0 wt% or more than 0 wt% to 4 wt% water. The weight percent is based on the total weight of the non-aqueous reaction mixture.

[0046] The process includes introducing an organic base catalyst into the non-aqueous reaction mixture. As used herein, "organic base catalyst" is a compound composed of (i) an alkylammonium cation or an alkylphosphonium cation, where the alkyl moiety is a C 10 ~C 30 hydrocarbonyl group (or a C 10 ~C 20 hydrocarbonyl group), and the organic base catalyst also includes (ii) an anion that is a hydroxyl group (-OH) or a halo group (-Cl, -Br). The anion may be a hydroxyl group (-OH) bonded to the cation, or the 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.

[0047] In one embodiment, the 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 to 1:1. In other words, this process 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.

[0048] In one embodiment, the organic base is introduced into the reaction mixture until the inorganic base catalyst such as sodium hydroxide and / or potassium hydroxide is excluded. In other words, this process uses the organic base catalyst as the sole catalyst, thereby avoiding or otherwise eliminating the presence of inorganic bases (such as sodium hydroxide and / or potassium hydroxide) in the process.

[0049] After the organic base catalyst is introduced into the non-aqueous reaction mixture, the process includes heating the non-aqueous reaction mixture to a temperature of 30°C to 100°C, or a temperature of 40°C to 70°C, or a temperature of 50°C to 60°C, and subjecting the non-aqueous reaction mixture to a crossed aldol condensation. In the crossed aldol condensation step, the organic base catalyst catalyzes the condensation of an aldehyde and an alcohol to produce a crossed aldol product and a by-product of condensed water. The crossed aldol product is composed of enals selected from C8 enal, C 10 enal, C 13 enal, C 14 enal, C 18 enal, C 10 enal, C 13 enal, C 14 enal, C 18 species, and combinations thereof. In one embodiment, the crossed aldol product contains a majority of C8 enal, C 10 enal, C 13 enal, C 14 enal, C 18 enal (where "majority" means more than 50% of the total GC area of the crossed aldol reaction product).

[0050] As used herein, the term "species" is a mixture of alcohol, enal, enol, and aldehyde, and each alcohol, enal, enol, and aldehyde in the species has the same number of carbon atoms. "C8 species" is a mixture of C8 alcohol, C8 enal, C8 enol, and C8 aldehyde. "C 10 species" is a mixture of C 10 alcohol, C 10 enal, C 10 enol, and C 10 aldehyde. "C 13 species" is a mixture of C 13 alcohol, C 10 enal, C 13 enol, and C 13 aldehyde. "C 14 species" is a mixture of C 14 alcohol, C 14 enal, C 14 enol, and C 14 aldehyde. "C 18 species" is a mixture of C 18 alcohol, C 18 enal, C 18 enol, and C 18 aldehyde.

[0051] The process includes producing a cross - aldol product that is a fluid liquid at 23°C and has a turbidity value of less than 1.0 NTU, or 0 NTU or greater than 0 NTU to 1.0 NTU. By using (i) a low initial water content (0 - 10 wt% initial water), (ii) an olefin, and (iii) an inorganic base catalyst (e.g., NaOH) in the presence of an alkane, a cross - aldol product that is a non - fluid gel at 23°C and has a turbidity exceeding 200 NTU is produced. The applicant has unexpectedly found that by using an organic base catalyst in the presence of (i) a low initial water content (0 - 10 wt% initial water), (ii) an olefin, and (iii) an alkane, a cross - aldol product that is fluid at 23°C and has a turbidity of less than 1.0 NTU is produced. In one embodiment, the process includes producing a cross - aldol product that is a fluid liquid at 23°C and has a turbidity value of 0 NTU to 1.0 NTU, or greater than 0 NTU to 0.9 NTU, or 0.05 NTU to 0.5 NTU.

[0052] In one embodiment, the process includes adding a C4 aldehyde to a first blend to produce a non - aqueous reaction mixture (0 - 10 wt% initial water content). The process includes introducing an organic base catalyst (TBAH) at a molar ratio of organic base catalyst to total aldehyde of 0.0036 - 0.0286:1 and producing a cross - aldol product composed of an enal selected from C8 enal, C 13 enal, C 18 enal, and combinations thereof. The cross - aldol product may further include an alcohol solvent, water, unreacted aldehyde, other C8, C 13 , and C 18 species (other than the aforementioned enals). The cross - aldol product includes a majority of C8 enal, C 13 enal, and C 18 enal (where "majority" means more than 50% of the total GC area of the cross - aldol reaction product). The cross - aldol product is fluid at 23°C and has a turbidity value of 0 NTU to 1.0 NTU, or greater than 0 NTU to 0.9 NTU, or 0.05 NTU to 0.5 NTU. The C8 / C 13 / C 18 The conversion rate to the species is 90% - 99%, or 92% - 98%, or 93% - 97%.

[0053] In one embodiment, the process includes adding a C5 aldehyde to a first blend to produce a non-aqueous reaction mixture (0 - 8 wt% initial water). The process includes introducing an organic base catalyst (TBAH) at a molar ratio of organic base to total aldehyde of 0.0036 - 0.0286:1, and C 10 enal, C 14 enal, C 18 enal, and producing a cross-aldol product composed of an enal selected from these and combinations thereof. The cross-aldol product may further include an alcohol solvent, water, unreacted aldehyde, other C 10 , C 14 , C 18 species (other than the above-mentioned enals). The cross-aldol product includes a majority of C 10 enal, C 14 enal, and C 18 enal (wherein "majority" means more than 50% of the total GC area of the cross-aldol reaction product). The cross-aldol product is fluid at 23°C and has a turbidity value of 0 NTU - 1.0 NTU, or greater than 0 NTU - 0.9 NTU, or 0.05 NTU - 0.5 NTU. The C 10 / C 14 / C 18 The conversion rate to the species is 90% - 99%, or 92% - 98%, or 93% - 97%.

[0054] By way of illustration and not limitation, some embodiments of the present disclosure are described in detail in the following examples.

Examples

[0055] The composition of the purge stream recovered from the ethylene / octene polymerization production process is shown in Table 1 below.

Table 3

[0056] The ligands of the hydroformylation catalysts used in the inventive examples (IE) of the present invention are shown in Table 2 below.

Table 4

[0057] The hydroformylation conditions are provided in a reactor system as shown in FIG. 1. The reactor system consists of three 1-liter stainless steel stirred tank reactors (Rx1, Rx2, Rx3) connected in series. Each reactor is equipped with a vertically mounted stirrer and a tubular sparger near the bottom for supplying olefin and / or synthesis gas to the reactor. The sparger has a plurality of holes large enough to supply a desired gas flow to the main liquid portion. Each reactor has a silicone oil shell as a means for controlling the reactor temperature. Reactors 1 and 2 and reactors 2 and 3 are further connected via lines to transfer any unreacted gas and to flow a portion of the solution containing the aldehyde product and the catalyst from reactor 1 to reactor 2 and further from reactor 2 to reactor 3 (e.g., by pressure difference or pumping). Thereby, the unreacted olefin in reactor 1 is further hydroformylated in reactor 2 and then in reactor 3. In an alternative configuration, reactor 3 (Rx3) may be bypassed so that only two reactors are used.

[0058] Each reactor also has a pneumatic level controller for maintaining the desired liquid level in the reactor. Reactor 1 further has a line for introducing olefin, carbon monoxide, and hydrogen through a sparger, whereas makeup carbon monoxide and hydrogen are sent to Reactors 2 and 3 via a transfer line that also transfers unreacted gas from Reactor 1 to Reactor 2 and further from Reactor 2 to Reactor 3. Each reactor also has a blow-off vent for removing unreacted gas while controlling it as needed. A portion of the liquid reaction solution is continuously pumped sequentially from the final reactor to a vaporizer consisting of a heating zone, and a portion of the volatile components is swept to a water-cooled condenser using a flowing gas (stripping gas) stream, where it can be recovered as a liquid in a product receiver (crude product). The non-volatile substances are passed through an aqueous extraction zone consisting of a contact region and a separation zone. As described in US5741944, the purpose of the aqueous extraction is to prevent further hydrolysis of the phosphite ligand by extracting acidic by-products. After the aqueous extraction, the organic non-volatile substances are returned to Reactor 1 through a recirculation line.

[0059] A purge stream is introduced into Reactor 1 (where "olefin" in Figure 1 represents the purge stream). The purge stream is from an ethylene-octene polymerization production process. The composition of the purge stream is shown in Table 1 above.

[0060] The hydroformylation reaction is carried out using two reactors (Rx1 and Rx2. Rx3 is bypassed). 2 L of a catalyst solution composed 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 C4 aldehydes (about 85 wt%, ratio of n-butyl aldehyde to isobutyl aldehyde = about 30:1) is placed into the reactor system shown in Figure 1. The reactors are then heated to 70 °C under flowing synthesis gas (CO:H2 ratio = 1:1). The pressures in reactors 1 and 2 are maintained at 244 and 220 psig, respectively. The spent solvent is fed to reactor 1 at a rate of 138 grams per hour. The vaporizer system is operated using a strip gas consisting of 1:1 synthesis gas at a flow rate of 790 sLph, and the pressure in the vaporizer is maintained at 7 psig at a catalyst temperature of 101 °C.

[0061] After several days of continuous operation, when butyl aldehyde and tetraethylene glycol dimethyl ether are removed overhead, a reactor process fluid composed of nonanal, heavy aldehydes (by-products of in-situ aldol condensation), unreacted olefins, and hydrocarbon solvent (continuously introduced as part of the spent solvent) remains. The reaction product composed of nonanal (nonanal reaction product) is recovered at a rate of 155 grams per hour. The composition of the nonanal reaction product is shown in Table 3 below. B. Supply a purge stream to the hydroformylation conditions (hydroformylation 2).

[0062] The hydroformylation conditions are provided in the two-reactor system as shown in Figure 1 and described in the above hydroformylation 1. 2 L of a catalyst solution composed of rhodium dicarbonyl acetylacetonate (150 ppm rhodium), ligand B (0.75 wt%, 7.0 molar equivalents per mole of rhodium), and the C9 aldehyde product from Example 1A is placed in a miniplant. The reactor is then heated to 90 °C under flowing synthesis gas (CO:H2 ratio = 1:1). The pressures in reactors 1 and 2 are maintained at 472 and 438 psig, respectively. The spent solvent is fed to reactor 1 at a rate of 175 grams per hour. The vaporizer system is operated using a stripping gas consisting of 1:1 synthesis gas at a flow rate of 790 sLph, and the pressure in the vaporizer is maintained at 7 psig at a catalyst temperature of 100 - 105 °C. The C9 aldehyde product is recovered at a rate of 212 grams per hour. The composition is shown in Table 3.

Table 5

[0063] The C4 and C9 conversion rates are calculated using 1-dodecane as the internal standard for GC. A master batch of butyraldehyde containing 1 mol% of the internal standard is prepared using a mixture of 1-dodecane (17 g, 0.1 mol) and butyraldehyde (720 g, 10.0 mol). This master batch of butyraldehyde is used for subsequent cross aldol chemistry. The C4 and C9 aldehyde conversion rates are calculated between the feed amounts of the raw material mixtures of C4 and C9 and the product mixture using the GC method. The product yield is evaluated using GC area integration / 1-dodecane. For example, the area ratio of C8 / 1-dodecane represents the yield of the C8 product, the area ratio of C 13 / 1-dodecane represents the yield of the C 13 product, the area ratio of C 18 / 1-dodecane represents the yield of the C 18 product, and the total (C8 + C 13 + C 18 ) / 1-dodecane represents the yields of the C8, C 13 and C 18 products. i. Comparative Sample (CS) A

[0064] Comparative Sample A is a NaOH (aqueous solution) - catalyzed cross - aldol condensation reaction between the nonanal reaction product obtained from Hydroformylation 1 (Table 3 above) and butyraldehyde. A mixture of butyraldehyde (25.3 g, 0.350 mol) and the nonanal reaction product obtained from Hydroformylation 1 (38.2 g, 0.175 mol of n - nonanal) is prepared, 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) is prepared and added to the Parr reactor using a Gilson pump at a feed rate of 20 mL / min at 30 °C. After addition, the reaction mixture is heated to 60 °C with vigorous stirring and the temperature is maintained at 60 °C for 60 minutes. The reaction mixture is cooled to 40 °C and quenched with 0.9 equivalent of acetic acid. The neutralized reaction mixture is transferred to a separatory funnel and the organic phase is recovered. The conversion rates of butyraldehyde and nonanal, and the product yields of C8, C13, and C18 enals are calculated from gas chromatography, the initial weight % of water is calculated, and the results are shown in Table 5. ii. Comparative Sample B, Comparative Sample C

[0065] Isopropanol (21 g) and the amount of NaOH shown in Table 5 are placed in a 300 mL Parr reactor, purged three times with nitrogen, and sealed. The solution is heated to 60 °C with vigorous stirring. A mixture of C4 aldehyde (0.175 mol, 12.6 g) and the nonanal reaction product obtained from Hydroformylation 1 (Table 3 above) (0.0875 mol, 22.2 g) is prepared, analyzed using GC, and introduced into the reactor at a feed rate of 40 mL / min using a small lab pump. After addition, the temperature is maintained at the reaction temperature of 60 °C with stirring for 1 hour. Then, the reaction mixture is cooled to 40 °C and analyzed immediately using GC. After cooling to room temperature, the turbidity of the reaction mixture is analyzed and photographed to show liquid or gel behavior.

[0066] In Comparative Sample B, a slightly turbid liquid reaction mixture is obtained. As shown in the photograph of FIG. 2A, gelation is visually observed in Comparative Sample B, and Comparative Sample B is a gel. As shown in the photograph of FIG. 2B, Comparative Sample B is not fluid even when the container is inverted (even when inverted). The turbidity of Comparative Sample B is measured as a value exceeding 200 NTU.

[0067] Comparative Sample C is not a gel, and the mixture is fluid. However, the product yield is low, with a C4 conversion rate of 21% and a C9 conversion rate of 33%. Comparative Sample C has a high turbidity (greater than 1 NTU), and Comparative Sample C has a turbidity of 36 NTU. (iii) Inventive Examples (IE) 2a to 2d of the present invention: Homogeneous cross-aldol condensation reaction of the nonanal reaction product obtained from hydroformylation 1 using various amounts of TBAH catalyst

[0068] A mixture of butyraldehyde (25.3 g, 0.350 mol) and the nonanal reaction product obtained from hydroformylation 1 (Table 3 above) (38.2 g, 0.175 mol of n-nonanal) was prepared, loaded into a 300 mL Parr reactor, purged three times with nitrogen, and sealed under nitrogen. A 40 wt% aqueous solution of TBAH (the amount shown in Table 5) was prepared and added to the Parr reactor using a Gilson pump at a feed rate of 20 mL / min 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 equivalent of acetic acid. The neutralized reaction mixture was transferred to a separatory funnel and the organic phase was recovered. The conversion rates of butyraldehyde and nonanal, as well as the product yields of C8, C13, and C18 enals, were calculated from gas chromatography, the initial wt% of water was calculated, and the results were summarized in Table 5. Examples 2a - 2d of the present invention each showed no gelation and were fluid. Figure 4A is a photograph showing IE 2d in a container in an upright position. As shown in the photograph and Figure 4B, when the container containing IE 2d was inverted, IE 2d flowed downward and covered the container cap of the inverted container. Examples 2a - 2d of the present invention each had a low turbidity (less than 1.0 NTU), the turbidity value of IE 2a was 0.14 NTU, the turbidity value of IE 2b was 0.12 NTU, the turbidity value of IE 2c was 0.13 NTU, and the turbidity value of IE 2d was 0.12 NTU. (iii) Example 3 of the present invention: Homogeneous cross-aldol condensation reaction of the nonanal reaction product obtained from hydroformylation 1 using tetrabutylammonium bromide + NaOH catalyst

[0069] A mixture of butyraldehyde (25.3 g, 0.350 mol) and the nonanal reaction product obtained from hydroformylation 1 (Table 3 above) (38.2 g, 0.175 mol of n-nonanal) is prepared, 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) is prepared and added to the Parr reactor at 30 °C using a Gilson pump at a feed rate of 20 mL / min. After addition, the reaction mixture is heated to 60 °C with vigorous stirring and the temperature is maintained at 60 °C for 60 minutes. The reaction mixture is cooled to 40 °C and quenched with 0.9 equivalent of acetic acid. The neutralized reaction mixture is transferred to a separatory funnel and the organic phase is recovered. The conversion rates of butyraldehyde and nonanal, as well as the product yields of C8, C 13 , and C 18 enal are calculated from gas chromatography, the initial weight % of water is calculated, and the results are shown in Table 5. Examples 3 of the present invention each show no gelation and are fluid. IE3 has a low turbidity (less than 1.0 NTU), and the turbidity value of IE3 is 0.15 NTU. (v) Example 4 of the present invention: Cross-aldol condensation reaction of a C4 aldehyde and a branched C9 isomer to produce a C8-C 18 aldol product

[0070] A mixture of butyraldehyde (25.3 g, 0.350 mol) and the nonanal reaction product from hydroformylation 2 (Table 3 above) (38.2 g, 0.175 mol of n-nonanal) is prepared, 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) is added to the Parr reactor at 30 °C using a Gilson pump at a feed rate of 20 mL / min. After addition, the reaction mixture is heated to 60 °C with vigorous stirring and the temperature is maintained at 60 °C for 60 minutes. The reaction mixture is cooled to 40 °C and quenched with 0.9 equivalent of acetic acid. The neutralized reaction mixture is transferred to a separatory funnel and the organic phase is recovered. The conversion rates of butyraldehyde, nonanal, and branched C9 aldehyde, as well as C8, C 13, and C 18 The product yield of enal was calculated from gas chromatography, the initial weight percentage of water was calculated, and the results are shown in Table 5. In each of Examples 4 of the present invention, gelation was not observed and the fluidity was present. IE4 has a low turbidity (less than 1.0 NTU), and the turbidity value of IE4 is 0.09 NTU.

[0071] IE4 shows that the TBAH catalyst not only converts linear C4 aldehyde and C9 aldehyde with a conversion rate exceeding 98% (99%), but also converts branched C9 aldehyde with a conversion rate exceeding 60% (62%).

Table 6

[0072] The present disclosure is not limited to the embodiments and examples included in this specification, and it is particularly intended to include modified forms of those embodiments including a part of the embodiments and combinations of elements of different embodiments to the extent that they fall within the scope of the following claims. (Aspect) (Aspect 1) Nonanal, C 8 Olefin, and C 7 ~C 9 Preparing a first blend comprising an alkane, and Adding to the first blend a component selected from the group consisting of C 4 Aldehydes, C 5 Aldehydes, and combinations thereof to produce 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; Heating the non-aqueous reaction mixture to a temperature of 30°C to 100°C and subjecting the non-aqueous reaction mixture to a crossed aldol condensation; C 8 Enal, C 10 Enal, C 13 Enal, C 14 Enal, and C 18 Producing a crossed aldol product composed of a component selected from the group consisting of enal, and combinations thereof. A process comprising: (Aspect 2) The process according to Aspect 1, comprising producing a crossed aldol product having a turbidity value of less than 0 NTU to 1.0 NTU. (Aspect 3) The process according to Aspect 1 or 2, comprising producing a flowable crossed aldol product at 23°C. (Aspect 4) The process according to any one of Aspects 1 to 3, comprising introducing the organic base catalyst in a molar ratio of organic base catalyst to total aldehyde of 0.0036 to 0.0286:1. (Aspect 5) The process according to any one of Aspects 1 to 4, comprising introducing an organic base catalyst selected from the group consisting of tetrabutylammonium hydroxide, tributylmethylammonium hydroxide, tetrabutylphosphonium hydroxide, tetrabutylammonium bromide, and combinations thereof. (Aspect 6) The process according to any one of Aspects 1 to 5, comprising producing the crossed aldol product in the absence of an inorganic base. (Aspect 7) The process according to any one of Aspects 1 to 6, wherein Adding C 4 Aldehydes to the first blend to produce the non-aqueous reaction mixture; Introducing the organic base catalyst in a molar ratio of organic base catalyst to total aldehyde of 0.0036 to 0.0286:1; C 8 Enal, C 13 Enal, and C 18 Producing a crossed aldol product composed of a component selected from the group consisting of enal, and combinations thereof. A process comprising: (Aspect 8) The process according to any one of Aspects 1 to 6, wherein Adding C 5 Aldehydes to the first blend to produce the non-aqueous reaction mixture; introducing the organic base catalyst in a molar ratio of the organic base catalyst to the total aldehyde of 0.0036 to 0.0286:1; C 10 enal, C 14 enal, and C 18 producing a cross-aldol product composed of a component selected from the group consisting of enal and combinations thereof. A process comprising the above.

Claims

1. Nonanal, C ８ olefin, and C ７ ~C ９ Preparing a first blend containing alkanes, and To the first blend, add a component selected from the group consisting of C ４ aldehyde, C ５ aldehyde, and combinations thereof to produce 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; heating the non-aqueous reaction mixture to a temperature of 30°C to 100°C to perform cross-aldol condensation on the non-aqueous reaction mixture; C ８ Enal, C １０ Enal, C １３ Enal, C １４ Enal, and C １８ producing a cross-aldol product composed of a component selected from the group consisting of enal, and C, and combinations thereof. the organic base catalyst is (i) a compound composed of an alkylammonium cation or an alkylphosphonium cation, wherein the alkyl moiety is a C10-C30 hydrocarbyl group, and (ii) an anion that is a hydroxyl group (-OH) or a halo group (-Cl, -Br), a process.

2. The process according to claim 1, comprising producing a cross-aldol product having a turbidity value of 0 NTU to less than 1.0 NTU.

3. The process according to claim 1 or 2, comprising producing a cross-aldol product that is fluid at 23°C.

4. The process according to any one of claims 1 to 3, comprising introducing the organic base catalyst at a molar ratio of the organic base catalyst to the total aldehyde of 0.0036 to 0.0286:

1.

5. The process according to any one of claims 1 to 4, comprising introducing an organic base catalyst selected from the group consisting of tetrabutylammonium hydroxide, tributylmethylammonium hydroxide, tetrabutylphosphonium hydroxide, tetrabutylammonium bromide, and combinations thereof.

6. The process according to any one of claims 1 to 5, comprising producing the cross-aldol product in the absence of an inorganic base.

7. The process according to any one of claims 1 to 6, wherein Add C to the first blend ４ adding an aldehyde to produce the non-aqueous reaction mixture, the organic base catalyst is introduced at a molar ratio of the organic base catalyst to the total aldehyde of 0.0036 to 0.0286:1; C ８ enal, C １３ enal, and C １８ producing a cross - aldol product composed of components selected from the group consisting of enal, and combinations thereof. A process comprising this is provided.

8. The process according to any one of claims 1 to 6, wherein Add C to the first blend ５ adding an aldehyde to form the non-aqueous reaction mixture, the organic base catalyst is introduced at a molar ratio of the organic base catalyst to the total aldehyde of 0.0036 to 0.0286:1; C １０ enal, C １４ enal, and C １８ generating a cross - aldol product composed of a component selected from the group consisting of enal, and combinations thereof; a process comprising the above.

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