Composition containing a mixed C8 - C18 alcohol and its surfactant

Abstract

The present disclosure provides a composition, in one embodiment, comprising: 2-heptylundecanol, a member selected from the group consisting of 2-ethylhexanol and 2-propylheptanol; and a mixture of alcohol (1) and alcohol (2), wherein alcohol (1) has structure (1), where R1 is selected from the group consisting of ethyl and propyl groups, and R2 and R3 are each independently selected from the group consisting of hydrogen and alkyl groups, with the proviso that the total number of carbon atoms in R1 and R2 is 7; and alcohol (2) has structure (2), where R4 is selected from the group consisting of n-propyl, isopropyl, n-butyl, and isobutyl groups.

Description

Background Art

[0001] The recycling of purged hydrocarbon species is one of the greatest challenges faced by 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] Therefore, in the art, there is a continuing need for methods for utilizing hydrocarbon species in purge streams, particularly industrial purge streams of octene / alkane, that avoid mere disposal. There is a further need to utilize the octene monomer present in the purge stream. In addition, there is a need to develop cost-effective lightly branched detergent range alcohols that are readily biodegradable and produce high-performance surfactant materials.

Summary of the Invention

[0003] Applicants have found that hydroformylation of an industrial purge stream of octene / alkane produces a mixture of C9 aldehyde, unreacted C8 olefin, and a hydrocarbon solvent. This hydroformylation product is then cross-aldol reacted with butyraldehyde and / or valeraldehyde to produce C8-C 18 aldehydes. Subsequent hydrogenation allows these C8-C 18 aldehydes to be used to produce C8-C 18 alcohols. C8-C 18 alcohols are starting materials in high demand for end uses such as, for example, surfactants.

[0004] The present disclosure provides a composition. In one embodiment, the composition comprises 2-heptylundecanol, a member selected from the group consisting of 2-ethylhexanol and 2-propylheptanol, A mixture of alcohol (1) and alcohol (2), Alcohol (1) has structure (1),

[0005] [Chemical formula] In the formula, R1 is selected from the group consisting of an ethyl group and a propyl group, R2 and R3 are each independently selected from the group consisting of hydrogen and an alkyl group, provided that the total number of carbon atoms of R1 and R2 is 7, Alcohol (2) has structural formula (2),

[0006] [Chemical formula] In the formula, R4 is selected from the group consisting of an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. [Brief Description of the Drawings]

[0007]

Figure 1

Figure 2

Figure 3

[0008] 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.

[0009] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication is incorporated by reference in its entirety (or the equivalent U.S. version thereof is so incorporated by reference) with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0010] The numerical ranges disclosed herein include all values from the lower value to the upper value, including the lower and upper values. In the case of ranges containing explicit values (e.g., 1 or 2, or 3 to 5, or 6, or 7), any sub-range between any two of the explicit values is included (e.g., 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).

[0011] Unless otherwise stated to the contrary, implied by the context, or not a convention in the art, all parts and percentages are by weight and all test methods are the latest as of the filing date of this disclosure.

[0012] "Alcohol" is a compound having a hydroxyl group (-OH) bonded to a hydrocarbon group.

[0013] "Aldehyde" is a compound having a carbonyl functional group (C=O) bonded to one hydrocarbon group and a hydrogen atom.

[0014] "Alkene" is a hydrocarbon containing a carbon-carbon double bond.

[0015] 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-separating at the molecular level). Such blends may or may not be phase-separated. Such blends may or may not contain one or more domain configurations determined from transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art.

[0016] The term "composition" refers to a mixture of materials including the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0017] 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 any other components, steps, or procedures from the scope of any subsequent description, except for those that are not essential to the operation. The term "consisting of" excludes any component, step, or procedure not explicitly depicted or enumerated. The term "or" refers to the listed members individually and in any combination, unless otherwise specified. The use of the singular form includes the use of the plural form, and vice versa.

[0018] "Enal" is an aldehyde compound containing a carbon-carbon double bond. Enal can be formed by aldol (or crossed aldol) condensation of an aldehyde, followed by dehydration of the resulting intermediate compound. A non-limiting example of enal is 2-ethylhexenal, which results from the self-condensation of a C4 aldehyde as shown below.

[0019]

Chemical formula

[0020] "Enol" is an alcohol containing a carbon-carbon double bond. Enol can be formed by partial hydrogenation of enal.

[0021] "Ethylene-based 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 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-based polymer" and "polyethylene" may be used interchangeably.

[0022] "Hydrocarbon" is a compound that contains only hydrogen and carbon atoms. "Hydrocarbonyl" (or "hydrocarbonyl group") is a hydrocarbon having a valence (typically monovalent). The term "alkyl group" is used interchangeably with "hydrocarbonyl group".

[0023] As used herein, the term "1-octene" is an unsaturated hydrocarbon alpha-olefin having the molecular formula C8H 16 and having the unsaturation in the alpha position. 1-octene has a molecular structure (A) as shown below.

[0024] [Chemical formula]

[0025] 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 in the alpha position. In other words, the term "isomer of octene" is 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.

[0026] As used herein, the term "linear internal octene isomer" is a linear unsaturated hydrocarbon composed of a chain of 8 carbon atoms, and the unsaturation (double bond) is not in the alpha 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, the term "branched C8 olefin" is an unsaturated hydrocarbon having a main chain length of C8H 16 and up to 7 carbon atoms. In contrast to the linear nature of Structure A, branched C8 olefins contain 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. Additional 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 ethylhexenes such as 2-ethyl-1-hexene.

[0027] An "olefin" is an unsaturated aliphatic hydrocarbon having a carbon-carbon double bond.

[0028] "Polymer" is a compound prepared by polymerizing monomers that provide a plurality of and / or repeating "units" or "mer units" that constitute the polymer in a polymerized form, whether of the same type or different types. Thus, the general term "polymer" includes the term "homopolymer" which is usually used to refer to a polymer prepared from only one type of monomer, and the term "copolymer" which is usually used to refer to a polymer prepared from at least two types of monomers. Polymers also include all forms of copolymers such as, for example, random, block, etc. The terms "ethylene / α-olefin polymer" and "octene / α-olefin polymer" each mean the above-mentioned copolymers prepared from polymerizing ethylene or octene with one or more additional polymerizable α-olefin monomers. Polymers are often referred to as being "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 residue of a specific monomer and not to non-polymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomers.

[0029] Test Methods Gas Chromatography (GC).

[0030] The composition of the used solvent and the hydroformylation reaction product is determined by gas chromatography (GC) using the following conditions.

[0031] [Table 1]

[0032] The quantification of the data in Table 1 (in the following Examples section) and in section A of the Examples section is based on weight percent using a response factor derived from a standard solution at a known concentration.

[0033] The compositions of the cross-aldol reaction products and the crude alcohol products are determined by both GC and gas chromatography / mass spectrometry (GC / MS) using the following conditions.

[0034] [Table 2]

[0035] Quantification in Sections B - E of the Examples section is based on GC area percent (referred to interchangeably as "GC area" or "GC") from the FID signal. Confirmation of peak identity / component structure is based on electron ionization mass selective detector signals that match the National Institute of Standards and Testing library.

[0036] N:I ratio. The hydroformylation reaction of olefins having three or more carbon atoms produces 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 determined by gas chromatography (GC).

DETAILED DESCRIPTION OF THE INVENTION

[0037] The present disclosure provides a composition. The composition includes 2-heptylundecanol and a member selected from 2-ethylhexanol and 2-propylheptanol. The composition further includes a mixture of alcohol (1) and alcohol (2). Alcohol (1) has structure (1),

[0038] [Chemical formula] In the formula, R1 is selected from an ethyl group and a propyl group, R2 and R3 are each independently selected from hydrogen and an alkyl group, provided that the total number of carbon atoms of R2 and R3 is 7. Alcohol (2) has structure (2),

[0039] [Chemical formula] In the formula, R4 is selected from an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

[0040] In one embodiment, the composition is a reaction product of a purge stream composed of octene isomers or is otherwise derived from the purge stream. The purge stream is subjected to a series of chemical reactions, namely hydroformylation reaction, cross aldol condensation reaction, and hydrogenation, to produce the composition.

[0041] The purge stream contains octene isomers. As used herein, "purge stream" is one of several fractions that is separated from the effluent exiting the polymerization reactor after the polymerization reaction has occurred or is otherwise recovered. 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 that remains 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 and other hydrocarbons, including octene isomers, that are utilized during the polymerization reaction. It will be understood that the purge stream does not contain or substantially does not contain a solid polymer product therein.

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

[0043] In one embodiment, the purge stream includes the following: (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)-(iv) is 100 weight percent of the purge stream.

[0044] In one embodiment, the purge stream is fed to a hydroformylation reactor system. In the hydroformylation reactor system, the hydroformylation reaction attaches a formyl group (-CH=O) and a hydrogen atom to the carbon-carbon double bond of an alkene (i.e., an olefin) to produce an aldehyde. Since the purge stream contains octene isomers, subjecting the purge stream to hydroformylation conditions forms a reaction product composed of nonanal. "Nonanal" is an aldehyde containing 9 carbon atoms. The purge stream is a mixture of an alkene (mainly octene isomers) and an alkane, and as a result, 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 C8 olefins, C7-C9 alkanes, and combinations thereof.

[0045] An aldehyde selected from C4 aldehydes, C5 aldehydes, and combinations thereof (hereinafter, "C4 / C5 aldehydes") is added to a reaction product composed of nonanal (hereinafter, "nonanal product") to form a mixture, mixture A. The crossed aldol condensation of mixture A forms a crossed aldol product. The crossed aldol product is an alcohol, a solvent, water, and C8 enal, C 10 enal, C 13 enal, C 14 enal, C 18It is composed of components selected from enals and combinations thereof.

[0046] In one embodiment, a C4 aldehyde is added to a reaction product composed of nonanal (hereinafter, "nonanal product") to form a mixture A4 which is a mixture. The cross-aldol condensation of mixture A4 forms a cross-aldol product. The cross-aldol product comprises alcohol, solvent, water, and a C8 enal, C 13 enal, C 18 It is composed of components selected from enals and combinations thereof.

[0047] In one embodiment, a C5 aldehyde is added to a reaction product composed of nonanal (hereinafter, "nonanal product") to form a mixture A5 which is a mixture. The cross-aldol condensation of mixture A5 forms a cross-aldol product. The cross-aldol product comprises alcohol, solvent, water, and a C 10 enal, C 14 enal, C 18 It is composed of components selected from enals and combinations thereof.

[0048] The cross-aldol product is hydrogenated. The cross-aldol product comprises a C8 enal, C 10 enal, C 13 enal, C 14 enal, C 18 enal, and combinations thereof. The hydrogenation of the cross-aldol product forms a crude alcohol product. The crude alcohol product comprises a C8 alcohol, C 10 alcohol, C 13 alcohol, C 14 alcohol, C 18 alcohol, alkane components, other species, and combinations thereof. As used herein, the term "species" is a mixture of alcohol, enal, enol, and aldehyde, where each alcohol, enal, enol, and aldehyde in the species has the same number of carbon atoms.

[0049] "C8 species" is a mixture of C8 alcohol, C8 enal, C8 enol, and C8 aldehyde. "C 10 species" is C 10 alcohol, C 10 enal, C 10 enol, and a mixture of C 10 aldehyde. "C 13 species" is C 13 alcohol, C 10 enal, C 13 enol, and a mixture of C 13 aldehyde. "C 14 species" is C 14 alcohol, C 14 enal, C 14 enol, and a mixture of C 14 aldehyde. "C 18 species" is C 18 alcohol, C 18 enal, C 18 enol, and a mixture of C 18 aldehyde.

[0050] In one embodiment, the cross - aldol product is composed of C8 enal, C 13 enal, C 18 enal, and combinations thereof. Hydrogenation of the cross - aldol product forms a crude alcohol product. The crude alcohol product is composed of C8 alcohol, C 13 alcohol, C 18 alcohol, an alkane component, other species, and combinations thereof. Separation of the alkane component from the crude alcohol product leaves a residual product composed of C8 alcohol, C 13 alcohol, C 18 alcohol, and combinations thereof.

[0051] In one embodiment, the cross - aldol product is C 10 enal, C 14 enal, C 18It is composed of enals and their combinations. Hydrogenation of the cross-aldol product forms a crude alcohol product. The crude alcohol product comprises C 10 alcohol, C 14 alcohol, C 18 alcohol, an alkane component, other species, and their combinations. Separation of the alkane component from the crude alcohol product yields a residual product comprising C 10 alcohol, C 14 alcohol, C 18 alcohol, and their combinations.

[0052] 1. Mixed Alcohol Composition This composition comprises 2-heptylundecanol and a member selected from 2-ethylhexanol and 2-propylheptanol. The composition further comprises a mixture of alcohol (1) and alcohol (2). Alcohol (1) has structure (1),

[0053]

Chemical formula

[0054]

Chemical formula

[0055] In one embodiment, the composition comprises a C8 alcohol, C 13 alcohol, C 18Derived from or otherwise obtained from residual products composed of alcohols and combinations thereof. The composition includes 2-heptylundecanol and 2-ethylhexanol. The composition further includes a mixture of alcohol (1) and alcohol (2). Alcohol (1) has structure (1),

[0056] [Chemical formula] wherein R1 is an ethyl group, R2 and R3 are each independently selected from hydrogen and an alkyl group, provided that the total number of carbon atoms of R2 and R3 is 7. Alcohol (2) has structure (2),

[0057] [Chemical formula] wherein R4 is selected from an n-propyl group and an isopropyl group. In one embodiment, the composition includes 5 mol% to 40 mol% of 2-heptylundecanol, 5 mol% to 40 mol% of 2-ethylhexanol, 10 mol% to 40 mol% of alcohol (1), and 10 mol% to 40 mol% of alcohol (2).

[0058] In one embodiment, the composition is C 10 alcohol, C 14 alcohol, C 18 Derived from or otherwise obtained from residual products composed of alcohols and combinations thereof. The composition includes 2-heptylundecanol and 2-propylheptanol. The composition further includes a mixture of alcohol (1) and alcohol (2). Alcohol (1) has structure (1),

[0059] [Chemical formula] wherein R1 is a propyl group, R2 and R3 are each independently selected from hydrogen and alkyl groups, provided that the total number of carbon atoms of R2 and R3 is 7. Alcohol (2) has structure (2),

[0060]

Chemical formula

[0061] 2. Surfactant composition The present disclosure provides another composition, namely a surfactant. As used herein, a "surfactant" is a compound containing both a hydrophobic group (tail) and a hydrophilic group (head). Thus, a surfactant is a compound containing both a water-insoluble component and a water-soluble component. The composition includes a component having structure (3),

[0062]

Chemical formula

[0063] In one embodiment, the composition having structure (3) contains R which is a 2-ethylhexyl group. The 2-ethylhexyl group is present in an amount of 5 mol% to 40 mol%.

[0064] In one embodiment, the composition having structure (3) contains R which is a 2-propylheptyl group. The 2-propylheptyl group is present in an amount of 5 mol% to 40 mol%.

[0065] In one embodiment, the composition having structure (3) contains R which is a 2-ethylundecanyl group. The 2-ethylundecanyl group is present in an amount of 5 mol% to 40 mol%.

[0066] In one embodiment, the composition having structure (3) contains R which is a 2-propylundecanyl group. The 2-propylundecanyl group is present in an amount of 5 mol% to 40 mol%.

[0067] In one embodiment, the composition having structure (3) contains R which is a 2-butylnonanyl group. The 2-butylnonanyl group is present in an amount of 5 mol% to 40 mol%.

[0068] In one embodiment, the composition having structure (3) contains R which is a 2-pentylnonanyl group. The 2-pentylnonanyl group is present in an amount of 5 mol% to 40 mol%.

[0069] In one embodiment, the composition having structure (3) contains R which is a 2-heptylundecanyl group. The 2-heptylundecanyl group is present in an amount of 5 mol% to 40 mol%.

[0070] In one embodiment, the composition having structure (3) contains R selected from 5 mol% to 40 mol% of 2-ethylhexyl group, 10 mol% to 40 mol% of 2-ethylundecanyl group, 10 mol% to 40 mol% of 2-butylnonanyl group, 5 mol% to 40 mol% of 2-heptylundecanyl group, and combinations thereof, M is hydrogen, m is 0, n is an integer from 1 to 70.

[0071] In one embodiment, the composition having structure (3) contains R selected from 5 mol% to 40 mol% of 2-ethylhexyl groups, 10 mol% to 40 mol% of 2-ethylundecanyl groups, 10 mol% to 40 mol% of 2-butylnonanyl groups, 5 mol% to 40 mol% of 2-heptylundecanyl groups, and combinations thereof, M is SO3 - and m is 0, n is an integer from 0 to 20.

[0072] In one embodiment, the composition having structure (3) contains R selected from 5 mol% to 40 mol% of 2-propylheptyl groups, 10 mol% to 40 mol% of 2-propylundecanyl groups, 10 mol% to 40 mol% of 2-pentylnonanyl groups, 5 mol% to 40 mol% of 2-heptylundecanyl groups, and combinations thereof, M is SO3 - and m is 0, n is an integer from 0 to 20.

[0073] 3. Ethoxylate Composition The present disclosure provides another aqueous composition. In one embodiment, the composition contains an ethoxylate having structure (4),

[0074] [Chemical formula] wherein R is selected from 2-ethylhexyl groups, 2-ethylundecanyl groups, 2-butylnonanyl groups, 2-heptylundecanyl groups, and combinations thereof, n is an integer from 1 to 70, or from 3 to 40, or from 3 to 15.

[0075] In one embodiment, the composition having structure (4) contains R which is a 2-ethylhexyl group. The 2-ethylhexyl group is present in an amount of 5 mol% to 40 mol%.

[0076] In one embodiment, the composition having structure (4) contains R which is a 2-ethylundecanyl group. The 2-ethylundecanyl group is present in an amount of 10 mol% to 40 mol%.

[0077] In one embodiment, the composition having structure (4) contains R which is a 2-butylnonanyl group. The 2-butylnonanyl group is present in an amount of 10 mol% to 40 mol%.

[0078] In one embodiment, the composition having structure (4) contains R which is a 2-heptylundecanyl group. The 2-heptylundecanyl group is present in an amount of 5 mol% to 40 mol%.

[0079] In one embodiment, the composition contains an ethoxylate having structure (4),

[0080]

Chemical formula

[0081] In one embodiment, the composition having structure (4) contains R which is a 2-propylheptyl group. The 2-propylheptyl group is present in an amount of 5 mol% to 40 mol%.

[0082] In one embodiment, the composition having structure (4) contains R which is a 2-propylundecanyl group. The 2-propylundecanyl group is present in an amount of 10 mol% to 40 mol%.

[0083] In one embodiment, the composition having structure (4) contains R which is a 2-pentylnonanyl group. The 2-pentylnonanyl group is present in an amount of 10 mol% to 40 mol%.

[0084] In one embodiment, the composition having structure (4) contains R which is a 2-heptylundecanyl group. The 2-heptylundecanyl group is present in an amount of 5 mol% to 40 mol%.

[0085] 4. Alkyl Sulfate Composition The present disclosure provides another aqueous composition. In one embodiment, the composition contains an alkyl ether sulfate or an alkyl sulfate having structure (5).

[0086]

Chemical formula

[0087] In one embodiment, the composition having structure (5) contains R which is a 2-ethylhexyl group. The 2-ethylhexyl group is present in an amount of 5 mol% to 40 mol%.

[0088] In one embodiment, the composition having structure (5) contains R which is a 2-ethylundecanyl group. The 2-ethylundecanyl group is present in an amount of 10 mol% to 40 mol%.

[0089] In one embodiment, the composition having structure (5) contains R which is a 2-butylnonanyl group. The 2-butylnonanyl group is present in an amount of 10 mol% to 40 mol%.

[0090] In one embodiment, the composition having structure (5) contains R which is a 2-heptylundecanyl group. The 2-heptylundecanyl group is present in an amount of 5 mol% to 40 mol%.

[0091] In one embodiment, the composition is

[0092]

Chemical formula

[0093] In one embodiment, the composition having structure (5) includes R which is a 2-propylheptyl group. The 2-propylheptyl group is present in an amount of 5 mol% to 40 mol%.

[0094] In one embodiment, the composition having structure (5) includes R which is a 2-propylundecanyl group. The 2-propylundecanyl group is present in an amount of 10 mol% to 40 mol%.

[0095] In one embodiment, the composition having structure (5) includes R which is a 2-pentylnonanyl group. The 2-pentylnonanyl group is present in an amount of 10 mol% to 40 mol%.

[0096] In one embodiment, the composition having structure (5) includes R which is a 2-heptyldecanyl group. The 2-heptyldecanyl group is present in an amount of 5 mol% to 40 mol%.

[0097] By way of example and not limitation, some embodiments of the present disclosure will be described in detail in the following examples.

Examples

[0098] The composition of the purge stream recovered from the ethylene / octene polymerization production process is provided in Table 1 below. The weight percentages are based on the total weight of the purge stream.

[0099]

Table 3

[0100] The ligands of the hydroformylation catalysts used in the inventive examples (IE) of the present invention are provided in Table 2 below.

[0101]

Table 4

[0102] A. Subject the purge stream to hydroformylation conditions 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 cylindrical sparger near the bottom for supplying olefin and / or synthesis gas to the reactor. The sparger contains a plurality of holes large enough to provide the desired gas flow to the liquid body. Each reactor has a silicone oil shell as a means for controlling the reactor temperature. Reactors 1-2 and reactors 2-3 are further connected via lines such that unreacted gas is transferred and a portion of the liquid solution containing the aldehyde product and catalyst flows from reactor 1 to reactor 2 and from reactor 2 to reactor 3 (e.g., by pressure difference or pump). Thus, the unreacted olefin in reactor 1 is further hydroformylated in reactor 2 and subsequently in reactor 3. In an alternative configuration, reactor 3 (Rx3) can be bypassed such that only two reactors are used.

[0103] Each reactor also contains a pneumatic level controller for maintaining a desired liquid level within the reactor. Reactor 1 further contains lines for introducing olefins, carbon monoxide, and hydrogen through a sparger, and at the same time, the formed carbon monoxide and hydrogen are sent to Reactors 2 and 3 via transfer lines that also carry unreacted gas from Reactor 1 to Reactor 2 and from Reactor 2 to Reactor 3. Each reactor also includes, as needed, a blow-off port for the controlled removal of unreacted gas. A portion of the liquid reaction solution is continuously pumped from the final reactor in series to a vaporizer, which consists of a heating zone where a stream of flowing gas (stripping gas) is used to sweep a portion of the volatile components to a water-cooled condenser where they can be collected as a liquid in a product receiver (crude product). The non-volatile material passes through an aqueous extraction zone consisting of a contact region and a separation zone. The purpose of the aqueous extraction is to extract acidic by-products and thereby prevent additional hydrolysis of the phosphite ligand as described in U.S. Patent No. 5,741,944. After aqueous extraction, the organic non-volatile material is pumped back to Reactor 1 through a recycle line.

[0104] A purge stream is introduced into Reactor 1 (the "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 provided in Table 1 above.

[0105] The hydroformylation reaction (i.e., exposure of the purge stream to hydroformylation conditions) is carried out using two reactors (Rx1 and Rx2, Rx3 is bypassed). A 2-liter 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 iso-butyl aldehyde of about 30:1 based on the total weight of C4 aldehydes) is charged to the reactor system shown in Figure 1. The reactors are then heated to 70 °C under flowing synthesis gas (H2:CO ratio = 1:1). The pressures in reactor 1 and reactor 2 are maintained at 244 psig 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 with a strip gas composed of 1:1 synthesis gas at a flow rate of 790 sLph, and the vaporizer pressure is maintained at 7 psig at a catalyst temperature of 101 °C.

[0106] After several days of continuous operation, butyl aldehyde and tetraethylene glycol dimethyl ether are removed overhead, leaving a reaction process fluid composed of nonanal, aldehyde heavy ends (by-products of in-situ aldol condensation), unreacted olefins, and hydrocarbon solvent (continuously introduced as part of the spent solvent). The reaction product composed of nonanal (nonanal reaction product) is collected at a rate of 155 grams per hour. The composition of the purge stream hydroformylation reaction product (referred to interchangeably as the "nonanal product") is shown in Table 3 below.

[0107] Table 3. Composition of the nonanal product. The weight percentages in Table 3 are based on the total weight of the nonanal product.

[0108]

Table 5

[0109] B. Cross Aldol Condensation A solution of isopropanol (IPA: 37.5 g), water (4.7 g), and NaOH (1.2 g) is charged into a 300 mL Parr reactor, purged three times with nitrogen, and sealed. The solution is heated to 60 °C while stirring vigorously. A mixture of (i) C4 aldehyde (25.2 g, 0.35 mol) and (ii) nonanal product (Table 3 above) (38.2 g, 0.175 mol of n-nonanal) is introduced into the Parr reactor with a small lab pump at a feed rate of 40 mL / min. After addition, the temperature is maintained at 60 °C for 1 hour with stirring to complete the cross-aldol condensation reaction, forming a cross-aldol product composed of C8 enal, C 13 enal, C 18 enal, and other species. The cross-aldol product is then cooled to 40 °C and quenched with 0.9 equivalent of acetic acid.

[0110] The cross-aldol product is transferred to a separatory funnel and separated for 30 minutes. A small amount of the aqueous phase (bottom phase) is removed. The cross-aldol condensation reaction (described in the above paragraph) is repeated three times, and the combined organic phase (320.5 g) is concentrated on a rotary evaporator at 50 °C and 146 mbar. The residue (208 g) is washed with water (104 g), leaving the organic phase with a water content of 3.58 wt%. To facilitate the azeotropic removal of water, additional IPA (60 g) is added to the organic phase. The mixture is concentrated twice on a rotary evaporator at 50 °C and 146 mbar to obtain the cross-aldol product (187.8 g). The composition of the cross-aldol product is shown in Table 4 below.

[0111]

Table 6

[0112] The conversion rates of C4 aldehyde and the crude C9 aldehyde product are 97.2 and 93.5%, respectively.

[0113] C. Hydrogenation of Cross-Aldol Product (Continuous) The hydrogenation reaction is carried out in a tubular reactor containing an 8-inch portion of a 3 / 8-inch stainless steel tube filled with 8 ml of Ni-3288 activated with hydrogen. Ni-3288 is a hydrogenation fixed-bed catalyst composed of 60 wt% nickel-containing trilobe extrudates available from BASF. The cross-aldol product (Table 4) is mixed with hydrogen and pumped through the Ni-3288 catalyst bed as a hydrogen-saturated liquid phase. The hydrogenation reaction is carried out at 140 °C, 500 psig, a liquid hourly space velocity (LHSV) of 2.2 hr -1 and a gas hourly space velocity (GHSV) of 600 hr -1 to produce a mixed alcohol / alkane product. The crude mixed alcohol / alkane product is collected in a cooled catch pot. The feed and mixed alcohol / alkane product compositions are shown in Table 5 below.

[0114] Table 5. Cross-aldol product (feed) and crude alcohol product from continuous hydrogenation. The data in Table 5 show the effective single-pass conversion of aldehydes to alcohols in the continuous hydrogenation process.

[0115]

Table 7

[0116] D.C8 - C 18 Separation of the alcohol mixture The crude alcohol product (700 g) from Table 5 is charged into a 1 L round-bottom distillation reactor equipped with a heating mantle and connected to a spinning band distillation column. A magnetic stir bar is used to achieve good mixing and uniform boiling. To remove the light fraction (where "light" interchangeably refers to C1 - C7 species) from the mixed alcohol / alkane product, the column pressure is set to 100 mmHg and a reflux ratio of 8:1 is established. The temperature of the liquid in the reactor ranges from 59.7 °C (start of distillation) to 154.9 °C (completion of light fraction removal). The overhead vapor temperature ranges from 34.4 °C to 56.4 °C during this same period. The light fraction (78.2 g) is collected as the overhead distillate, and a C8 - C 18 alcohol mixture (621.0 g) remains. The composition of the light fraction and the C8 - C 18 alcohol mixture is shown in Table 6 below.

[0117]

Table 8

[0118] E. Ethoxylation reaction of 2EH, C8, C 13 , C 18 from the mixed alcohol / alkane product The ethoxylation reaction was carried out in a jacketed baffled 9 L stainless steel (SS) autoclave reactor equipped with a magnetic-driven impeller. Prior to each feed, ethylene oxide was charged into a designated feed (DF) tank positioned on a metering cell. Ethylene oxide (EO) was transferred from the DF tank to the reactor through a flow meter at a reaction temperature of 130 °C. Potassium hydroxide (85%) in solid pellet form was used as a catalyst, and a dehydration step was carried out until the water level measured by subsequent Karl Fischer titration was less than 1000 ppm.

[0119] 2-Ethylhexanol, 2-ethylundecanol, 2-butylnonanol, and 2-heptylundecanol are in a ratio of approximately 2.4 / 2.1 / 1.7 / 1 (by the integrated peak area of the gas chromatograph spectrum) of the residual mixture of Table 6 (above) of mixed C8 - C 18 Alcohol (209.2 g) and potassium hydroxide pellets (1.24 g, minimum purity 85%) were charged into a pre-nitrogen purged 9 L reactor. The mixture was heated to 100 °C with stirring and nitrogen sparging. The reactor was pressurized, then purged 7 times to remove atmospheric oxygen, and then pressurized with nitrogen to 16 - 20 psia at ambient temperature. The catalytically dehydrated alcohol was heated to 130 °C with stirring, and then ethylene oxide (total 325.6 g) was metered into the reactor at 130 °C over about 4 hours. After the EO supply was complete, the contents of the reactor were stirred at the reaction temperature for an additional 2 hours to consume unreacted oxide (digestate), and then cooled to 60 °C. A portion (50 grams) of the reactor contents was removed for neutralization with acetic acid for cloud point measurement. The cloud point (measured in a 1 wt% aqueous solution) was less than 25 °C. The reactor was heated to 130 °C with stirring. Ethylene oxide (total 93.0 g) was metered into the reactor at 130 °C over about 4 hours. After the EO supply was complete, the contents of the reactor were stirred at the reaction temperature for an additional 2 hours to consume unreacted oxide (digestate), and then cooled to 60 °C. 1.14 g of acetic acid was added to neutralize the reaction to obtain the final ethoxylated surfactant product. The cloud point (in a 1 wt% aqueous solution) was measured to be 82 °C.

[0120] This disclosure is not limited to the embodiments and examples contained herein, and is particularly intended to include modified forms of those embodiments, including portions of embodiments and combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims. (Aspect) (Aspect 1) A composition comprising: 2-heptylundecanol; a member selected from the group consisting of 2-ethylhexanol and 2-propylheptanol; a mixture of alcohol (1) and alcohol (2), wherein alcohol (1) has structure (1):

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Claims

**Claim 1** A composition comprising: A) 5 mol% to 40 mol% of 2-heptylundecanol, 5 mol% to 40 mol% of 2-ethylhexanol, 10 mol% to 40 mol% of alcohol (1) having structure (1), 【Chemical 1】 wherein, R １ is an ethyl group, R ２ and R ３ are each independently selected from the group consisting of hydrogen and alkyl groups, provided that the total number of carbon atoms of R ２ and R ３ is 7, an alcohol (1), and 10 mol% to 40 mol% of alcohol (2) having structure (2), 【Chemical 2】 wherein R ４ is selected from the group consisting of an n-propyl group and an isopropyl group, and contains alcohol (2), or B) 5 mol% to 40 mol% of 2-heptylundecanol, 5 mol% to 40 mol% of 2-propylheptanol, 10 mol% to 40 mol% of alcohol (1) having structure (1), [Chemical Formula 3] In the formula, R １ is a propyl group, R ２ and R ３ are each independently selected from the group consisting of hydrogen and an alkyl group, provided that the total number of carbon atoms of R ２ and R ３ is 7, an alcohol (1), and 10 mol% to 40 mol% of alcohol (2) having structure (2), 【Chemical Formula 4】 In the formula, R ４ is a composition comprising an alcohol (2) selected from the group consisting of an n-butyl group and an isobutyl group.

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