WO2019045809A1 - Procédé de fabrication d'un alcool à ramification gamma - Google Patents

Procédé de fabrication d'un alcool à ramification gamma Download PDF

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WO2019045809A1
WO2019045809A1 PCT/US2018/034393 US2018034393W WO2019045809A1 WO 2019045809 A1 WO2019045809 A1 WO 2019045809A1 US 2018034393 W US2018034393 W US 2018034393W WO 2019045809 A1 WO2019045809 A1 WO 2019045809A1
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olefin
vinylidene
formula
phosphine
branched
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Patrick C. CHEN
Kyle G. LEWIS
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Exxonmobil Chemical Patents Inc.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • This disclosure relates to alcohols and processes for making the same.
  • this disclosure relates to gamma-branched alcohols and processes for making the same.
  • Branched aliphatic primary alcohols especially those having long carbon chains, have found use in many applications such as surfactants, solvents, wetting agents, solubilizing agents, emulsifiers, or as an intermediates for making derivatives such as esters and ethers that can be used as surfactants, solvents, wetting agents, solubilizing agents, emulsifiers, and lubricant base stocks or additives.
  • a specific type of branched aliphatic alcohols are Guerbet alcohols, which are beta-
  • branched primary alcohols having the following general structure: where R 1 and R 2 can be any hydrocarbyl group, preferably alkyl groups such as linear alkyl groups. Guerbet alcohols and derivatives thereof, such as esters thereof, have found use as lubricant base stocks. Guerbet alcohols can be produced by Guerbet reaction, in which two primary alcohol molecules condense to produce a beta-branched primary alcohol molecule and water.
  • R 1 and R 2 can be any hydrocarbyl group.
  • Such gamma-branched alcohols cannot be produced via two molecules of primary alcohols.
  • U.S. Patent No. 8,383,869 B2 discloses a process for making such gamma-branched alcohols from a terminal olefin including a first step of producing a vinylidene olefin dimer of the terminal olefin, followed by hydroformylation of the vinylidene olefin dimer.
  • this patent teaches that in the hydroformylation process, multiple alcohol isomers will be produced. Because the isomers have the same molecular weight and similar molecular structure, it would be very difficult to produce one gamma-branched alcohol at high purity.
  • JP2005-298443 A discloses a similar process for making gamma-branched alcohols from alpha- olefin.
  • a high-purity gamma-alcohol product can be far more useful than a mixture of multiple alcohols having different molecular structures. This is especially true where the gamma-branched alcohol is used as a feed to produce a derivative thereof, and a high purity of the derivative is desired for its end application.
  • This disclosure relates to a process for making an alcohol product comprising a
  • R 1 gamma-branched alcohol having a formula (F-I) below: H (F-I), where each R 1 group, the same or different, is independently a C2-C28 linear or branched alkyl group, the process comprising the following steps: (I) providing a vinylidene feed comprising
  • FIG. 1 is a 13C-NMR spectra of the C21-alcohol made in Example Bl in this disclosure.
  • FIG. 2 is a super-imposed diagram showing and comparing portions of the gas chromatography spectra of the C21-alcohol made in Example Bl and that of the alcohol product made in Example B2.
  • FIG. 3 is a super- imposed diagram showing and comparing portions of the 13C- NMR spectra of the C21 -alcohol made in Example Bl and that of the alcohol product made in Example B2.
  • alkyl group or “alkyl” interchangeably refers to a saturated hydrocarbyl group consisting of carbon and hydrogen atoms.
  • Linear alkyl group refers to a non-cyclic alkyl group in which all carbon atoms are covalently connected to no more than two carbon atoms.
  • Branched alkyl group refers to a non-cyclic alkyl group in which at least one carbon atom is covalently connected to more than two carbon atoms.
  • Cycloalkyl group refers to an alkyl group in which all carbon atoms form a ring structure comprising one or more rings.
  • aryl group refers to an unsaturated, cyclic hydrocarbyl group consisting of carbon and hydrogen atoms in which the carbon atoms join to form a conjugated ⁇ system.
  • aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 3-naphthyl, and the like.
  • arylalkyl group refers to an alkyl group substituted by an aryl group or alkylaryl group. None-limiting examples of arylalkyl group include benzyl, 2-phenylpropyl, 4- phenylbutyl, 3-(3-methylphenyl)propyl, 3-(/ tolyl)propyl, and the like.
  • alkylaryl group refers to an aryl group substituted by an alkyl group.
  • alkylaryl group include 2-methylphenyl, 3-methylphenyl, 4- methylphenyl, 2-methyl-l-naphtyl, 6-phenylhexyl, 5-pentylphenyl, 4-butylphenyl, 4- terterybutylphenyl, 7-phenylheptanyl, 4-octylphenyl, and the like.
  • cycloalkylalkyl group refers to an alkyl group substituted by a cycloalkyl group or an alkylcycloalkyl group. An example of cycloalkylalkyl group is cyclohexylmethyl.
  • alkylcycloalkyl group refers to a cycloalkyl group substituted by an alkyl group.
  • alkylcycloalkyl group include 2-methylcyclohexyl, 3- methylcyclohexyl, 4-methylcyclohexyl, 4-tertiary butyl cyclohexyl, 4-phenylcyclohexyl, cyclohexylpentyl, and the like.
  • Hydrocarbyl group or “hydrocarbyl” interchangeably refers to a group consisting of hydrogen and carbon atoms only.
  • a hydrocarbyl group can be saturated or unsaturated, linear or branched, cyclic or acyclic, containing a cyclic structure or free of cyclic structure, and aromatic or non-aromatic.
  • Cn group or compound refers to a group or a compound comprising carbon atoms at total number thereof of n.
  • Cm-Cn or Cm to Cn group or compound refers to a group or compound comprising carbon atoms at a total number thereof in the range from m to n.
  • a C1-C50 alkyl group refers to an alkyl group comprising carbon atoms at a total number thereof in the range from 1 to 50.
  • carbon backbone in an alkane or an alkyl group refers to the longest straight carbon chain in the molecule of the compound or the group in question.
  • olefin refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-to-carbon double bond in the structure thereof, wherein the carbon-to-carbon double bond does not constitute a part of an aromatic ring.
  • the olefin may be linear, branched linear, or cyclic.
  • a "linear terminal olefin” is a terminal olefin defined in this paragraph wherein R 1 is hydrogen, and R 2 is hydrogen or a linear alkyl group.
  • vinyl means an olefin having the following formula: wherein R is a hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group.
  • R 1 and R 2 are each independently a hydrocarbyl group, preferably a saturated hydrocarbyl group such as alkyl group.
  • R 1 and R 2 are each independently a hydrocarbyl group, preferably saturated hydrocarbyl group such as alkyl group.
  • tri-substituted vinylene means an olefin having the following formula:
  • R 1 , R 2 , and R 3 are each independently a hydrocarbyl group, preferably a saturated hydrocarbyl group such as alkyl group.
  • PAO(s) includes any oligomer(s) and polymer(s) of one or more terminal olefin monomer(s). PAOs are oligomeric or polymeric molecules produced from the polymerization reactions of terminal olefin monomer molecules in the presence of a catalyst system, optionally further hydrogenated to remove residual carbon- carbon double bonds therein.
  • the PAO can be a dimer (resulting from two terminal olefin molecules), a trimer (resulting from three terminal olefin molecules), a tetramer (resulting from four terminal olefin molecules), or any other oligomer or polymer comprising two or more structure units derived from one or more terminal olefin monomer(s).
  • the PAO molecule can be highly regio-regular, such that the bulk material exhibits an isotacticity, or a syndiotacticity when measured by 13 C NMR.
  • the PAO molecule can be highly regio-irregular, such that the bulk material is substantially atactic when measured by 13 C NMR.
  • a PAO material made by using a metallocene -based catalyst system is typically called a metallocene-PAO ("mPAO")
  • a PAO material made by using traditional non-metallocene-based catalysts e.g., Lewis acids, supported chromium oxide, and the like
  • cPAO conventional PAO
  • uPAO unhydrogenated PAO
  • rhodium carbonyl compounds means compounds comprising rhodium covalently bonded to at least one carbonyl group.
  • Non-limiting examples of rhodium carbonyl compounds include: Rh 4 (CO) i2, Rli6(CO) i6, (acetylacetonato)dicarbonylrhodium(I), chlorodicarbonylrhodium dimer, and chlorobis(ethylene)rhodium dimer.
  • phosphine compound refers to a phosphorous-containing organic compound having the formula PR3, where R is a hydrocarbyl group, preferably an aryl group, an alkylaryl group, an alkyl group, or an arylalkyl group.
  • syngas means a mixture of carbon monoxide and hydrogen, preferably at a molar ratio of 1 : 1.
  • the term "selectivity" of a terminal olefin in a reaction toward a given product species means the percentage of the terminal olefin converted into the given product species on the basis of the all of the terminal olefin converted. Thus, if in a specific oligomerization reaction, 5% of the terminal olefin monomer is converted into trimer, then the selectivity of the terminal olefin toward trimer in the oligomerization reaction is 5%.
  • compositions of mixtures of olefins comprising terminal olefins (vinyls and vinylidenes) and internal olefins (1,2-di-substituted vinylenes and tri-substituted vinylenes) are determined by using ⁇ -NMR.
  • a NMR instrument of at least a 500 MHz is run under the following conditions: a 30° flip angle RF pulse, 120 scans, with a delay of 5 seconds between pulses; sample dissolved in CDCb (deuterated chloroform); and signal collection temperature at 25 °C.
  • CDCb deuterated chloroform
  • peaks corresponding to different types of hydrogen atoms in vinyls (Tl), vinylidenes (T2), 1,2-di-substituted vinylenes (T3), and tri-substituted vinylenes (T4) are identified at the peak regions in TABLE I below.
  • Second, areas of each of the above peaks (Al, A2, A3, and A4, respectively) are then integrated.
  • quantities of each type of olefins (Ql, Q2, Q3, and Q4, respectively) in moles are calculated (as Al/2, A2/2, A3/2, and A4, respectively).
  • an oligomerization product mixture consisting essentially of a dimer comprises dimer at a concentration by weight of at least 90 wt%, based on the total weight of the oligomerization product mixture.
  • KV100 Kinematic viscosity at 100°C
  • KV40 kinematic viscosity at 40°C
  • Unit of all KV100 and KV40 values herein is cSt unless otherwise specified.
  • the vinylidene olefin useful in the process of this disclosure for making the gamma- branched alcohol has a formula (F-II) below:
  • each R 1 can be independently any hydrocarbyl group, preferably an alkyl group, more preferably a linear or branched alkyl group, still more preferably a linear alkyl group.
  • each R 1 comprises even number of carbon atoms.
  • Particularly desirable examples of each R 1 include: ethyl, n-propyl, n- butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-icosyl, n- docosyl, n-tetracosyl, n-hexacosyl, and n-octacosyl.
  • R 1 are: n-butyl, n-hexyl, n- octyl, n-decyl, and n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.
  • Each R 1 can be a branched alkyl group, preferably a branched alkyl group having the followin (F-IV),
  • R 2 and R 3 are independently hydrocarbyl groups, preferably alkyl groups, more preferably linear or branched alkyl groups, still more preferably linear alkyl groups, m is an integer and m > 3, preferably m > 4, still more preferably m > 5, still more preferably m > 6, still more preferably m > 7.
  • the two R 1 are identical.
  • examples of preferred vinylidene olefin having a formula (F-II) useful in the process of this disclosure are: 3-methyleneheptane; 4-methylenenonane; 5-methyleneundecane; 7- methyleneheptadecane; 9-methylenenonadecane; 11-methylenetricosane; 13- methyleneheptacosane; and 15-methylenehentriacontane, and mixtures thereof.
  • the two R 1 groups in formula (F-II) differ, it is highly desirable that they differ in terms of molar mass thereof by no greater than 145 (or 130, 115, 100, 85, 70, 55, 45, 30, or even 15) grams per mole.
  • the two R 1 groups differ in terms of total number of carbon atoms contained therein by no greater than 10 (or 9, 8, 7, 6, 5, 4, 3, 2, or even 1).
  • the monomer feed may comprise multiple terminal olefins having differing formulas (F-III).
  • multiple vinylidene olefins having different formulas (F-II) may be produced in the dimerization reaction, which can be used together as the vinylidene olefin feed for making a gamma-branched alcohol product comprising multiple gamma-branched alcohol compounds.
  • the monomer feed comprises multiple terminal olefins, it is highly desirable that they differ in terms of molecular weight thereof by no greater than 145 (or 130, 115, 100, 85, 70, 55, 45, 30, or even 15) grams per mole.
  • the multiple terminal olefins contained in the monomer feed differ in terms of total number of carbon atoms contained therein by no greater than 10 (or 9, 8, 7, 6, 5, 4, 3, 2, or even 1).
  • Such dimerization can be carried out advantageously in the presence of a catalyst system comprising a metallocene compound.
  • U.S. Patent No. 4,658,078 discloses a process for making a vinylidene olefin dimer from a terminal olefin monomer, the content of which is incorporated herein by reference in its entirety.
  • the batch processes as disclosed in U.S. Patent No. 4,658,078 resulted in the production of trimers and higher oligomers at various levels along with the intended dimer, which can be removed by, e.g., distillation, to obtain a substantially pure dimer product.
  • 4,658,078 may contain 1,2-di-substituted vinylene(s) and tri-substituted vinylenes at various levels. To the extent the concentrations of the 1,2-di-substituted vinylene(s) and tri-substituted vinylenes are acceptable to the intended application of this disclosure, the batch processes as disclosed in U.S. Patent No. 4,658,078 may be used to produce the dimer having formula (F- II) above useful in the process for making the gamma-branched alcohol in tis disclosure. [0051] Such dimerization can also be carried out in the presence of trialkylaluminium such as tri(tert-butyl)aluminum as disclosed in U.S. Patent No. 4,987,788, the content of which is incorporated by reference in its entirety.
  • trialkylaluminium such as tri(tert-butyl)aluminum
  • the vinylidene olefin having formula (F-II) feed used in the process of this disclosure for making gamma-branched alcohol comprises a single vinylidene olefin having formula (F-II) having a purity thereof of at least 90 wt%, preferably at least 92 wt%, more preferably at least 94 wt%, still preferably at least 95 wt%, still more preferably 96 wt%, still more preferably at least 97 wt%, still more preferably at least 98 wt%, still more preferably at least 99 wt%, based on the total weight of the olefins contained in the feed.
  • the individual vinylidene olefins contained in the mixture have similar molecular weights, i.e., having molecular weights that differ by no more than, e.g., 145, 130, 115, 100, 85, 70, 55, 45, 30, or even 15 grams per mole.
  • the individual vinylidene olefins contained in the mixture differ in terms of total number of carbon atoms contained therein by no more than 10, 9, 8, 7, 6, 5, 4, 3, 2, or even 1.
  • the individual vinylidene olefins contained in the mixture can be structural isomers.
  • the vinylidene olefins having different chemical formulas and/or molecular weight can be converted into gamma-branched alcohol compounds having different chemical formulas and/or molecular weight under the same reaction conditions following the same reaction mechanism.
  • the corresponding mixture of vinylidene olefin can be used as the vinylidene olefin feed for making the gamma-branched alcohol product by using the process of this disclosure.
  • the vinylidene having formula (F-II) feed used in the process of this disclosure for making gamma-branched alcohol comprises 1,2-di-substituted vinylene(s) and tri- substituted vinylene(s) as impurities at a total concentration no greater than 5 wt%, preferably no greater than 4 wt%, still more preferably no greater than 3 wt%, still more preferably no greater than 2 wt%, still no greater than 1 wt%, based on the total weight of olefins contained in the feed.
  • a particularly desirable process for a vinylidene olefin dimer product from a terminal olefin feed for use in the process of this disclosure is continuous, as opposed to a batch process such as those disclosed in U.S. Patent No. 4,658,078.
  • the oligomerization (dimerization being one) reaction can therefore be carried out in a continuously operated reactor, such as a continuously stirred tank reactor, a plug flow reactor or a loop reactor.
  • a continuously operated reactor such as a continuously stirred tank reactor, a plug flow reactor or a loop reactor.
  • This continuous process represents a significant improvement to the processes disclosed in U.S. Patent No. 4,658,078, as it results in the production of a high-purity vinylidene olefin dimer of the terminal olefin dimer.
  • the oligomerization reaction pursuant to the continuous process features an exceedingly high selectivity toward dimer and exceedingly low selectivity toward trimers and higher oligomers and an exceedingly high selectivity toward vinylidene olefin dimer as opposed to 1,2-di-substituted vinylene and tri-substituted vinylene.
  • the oligomer mixture obtained from the oligomerization step upon removal of residual terminal olefin monomer and catalyst, can be used directly as a high-purity vinylidene olefin dimer for the process of making a gamma-branched alcohol of this disclosure.
  • the oligomerization reaction can be carried out with a high conversion of the terminal olefin monomer.
  • the oligomerization reaction of the continuous process results in little isomerization of the terminal olefin monomer, the dimer, and other oligomers. Therefore, the residual terminal olefin monomer contained in the oligomerization reaction mixture can be separated and recycled to the oligomerization reaction.
  • the oligomerization reaction in the continuous process is carried out under mild, steady conditions in a continuous fashion, resulting in a vinylidene olefin dimer intermediate with consistent composition and quality, which, in turn, can be used for making a gamma-alcohol product with high purity.
  • the terminal olefin monomer useful in the continuous process for making the vinylidene olefin having formula (F-II) can desirably comprise from nl to n2 carbon atoms per molecule, where nl and n2 can be, independently, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, as long as nl ⁇ n2.
  • the terminal olefin monomer useful in the continuous process for making the vinylidene olefin having formula (F-II) can be preferably a linear terminal olefin.
  • linear terminal olefins as the monomer for the process of this disclosure are: 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- octadecene, 1-nonadecene, 1-icosene, 1-henicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1- pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, and 1-triacontene.
  • linear terminal olefins as the monomer for the process of this disclosure are: 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- octadecene, 1-nonadecene, and 1-icosene.
  • Linear terminal olefins having even number of carbon atoms can be advantageously manufactured by the oligomerization of ethylene, as is typically done in the industry. Many of these linear terminal olefins with even number of carbon atoms are commercially available at large quantities.
  • Branched terminal olefins can be used as the monomer in the process as well.
  • Particularl useful branched terminal olefins are those represented by the following formula: , where R x and R y are independently any hydrocarbyl group, preferably any C1-C30 alkyl group, more preferably any C1-C30 linear alkyl group, n is an integer, and n > 2, preferably n > 4, more preferably n > 5.
  • R x and R y are independently any hydrocarbyl group, preferably any C1-C30 alkyl group, more preferably any C1-C30 linear alkyl group
  • n is an integer, and n > 2, preferably n > 4, more preferably n > 5.
  • the terminal olefin monomer may be fed as a pure material or as a solution in an inert solvent into the continuously operated oligomerization reactor.
  • the inert solvent include: benzene, toluene, any xylene, ethylbenzene, and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and saturated isomers thereof, and mixtures thereof; n-heptane and branched isomers thereof, and mixtures thereof; n-octane and branched isomers thereof, and mixtures thereof; n-nonane and branched isomers thereof, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and any mixture of the above; Isopar® solvent; and the like.
  • terminal olefins used herein can be produced directly from ethylene growth process as practiced by several commercial production processes, or they can be produced from Fischer-Tropsch hydrocarbon synthesis from CO/H2 syngas, or from metathesis of internal olefins with ethylene, or from cracking of petroleum or Fischer-Tropsch synthetic wax at high temperature, or any other terminal olefin synthesis routes.
  • a preferred feed for this invention is preferably at least 80 wt% terminal olefin (preferably linear alpha olefin), preferably at least 90 wt% terminal olefin (preferably linear alpha olefin), more preferably 100% terminal olefin (preferably linear alpha olefin).
  • the feed olefins can be the mixture of olefins produced from other linear terminal olefin process containing C4 to C20 terminal olefins as described in Chapter 3 "Routes to Alpha- Olefins" of the book Alpha Olefins Applications Handbook, Edited by G. R. Lappin and J. D. Sauer, published by Marcel Dekker, Inc. N.Y. 1989.
  • the terminal olefin feed and or solvents may be treated to remove catalyst poisons, such as peroxides, oxygen or nitrogen-containing organic compounds or acetylenic compounds before being supplied to the polymerization reactor.
  • catalyst poisons such as peroxides, oxygen or nitrogen-containing organic compounds or acetylenic compounds
  • the treatment of the linear terminal olefin with an activated 13 Angstrom molecular sieve and a de-oxygenate catalyst, i.e., a reduced copper catalyst can increase catalyst productivity (expressed in terms of quantity of PAO produced per micromole of the metallocene compound used) more than 10-fold.
  • the feed olefins and or solvents are treated with an activated molecular sieve, such as 3 Angstrom, 4 Angstrom, 8 Angstrom or 13 Angstrom molecular sieve, and/or in combination with an activated alumina or an activated de-oxygenated catalyst.
  • an activated molecular sieve such as 3 Angstrom, 4 Angstrom, 8 Angstrom or 13 Angstrom molecular sieve
  • Such treatment can desirably increase catalyst productivity 2- to 10-fold or more.
  • a pure 1-octene feed will result in a single C16 dimer vinylidene olefin (7-methylenepentadecane)
  • a pure 1-decene feed will result in a single C20 dimer vinylidene olefin (9- methylenenonadecane)
  • a pure 1-dodecene feed will result in a single C24 dimer vinylidene olefin (11-methylenetricosane)
  • a pure 1-tetradecene feed will result in a single C28 dimer vinylidene olefin (13-methyleneheptacosane).
  • the third category of dimers can have multiple isomers as shown.
  • a terminal olefin feed consisting of 1-decene and 1-dodecene in the continuous process for making the vinylidene olefin having formula (F-II) results in the production of a dimer mixture comprising 9-methylenenonadecane, 9-methylenehenicosane, 11-methylenehenicosane, and 11-methylenetricosane.
  • a dimer mixture of two (or even more) terminal olefin may be used as a terminal olefin feed into the oligomerization reactor.
  • a high-purity terminal olefin feed invariably contains impurities such as other terminal olefins at various concentrations in addition to the predominant terminal olefin.
  • impurities such as other terminal olefins at various concentrations in addition to the predominant terminal olefin.
  • various quantities of multiple minor vinylidene olefin dimer olefins may be produced in addition to the intended predominant dimer of the predominant terminal olefin.
  • such terminal olefin feed comprising minor quantities of other terminal olefin(s) than the predominant terminal olefin can be tolerated in the continuous process for making the vinylidene olefin having formula (F-II) .
  • the metallocene compound in the catalyst system useful in the continuous process for making the vinylidene olefin having formula (F-II) can be represented by the formula Cp(Bg) n MX2Cp' , where Cp and Cp', the same or different, represents a cyclopentadienyl, alkyl- substituted cyclopentadienyl, indenyl, alkyl-substituted indenyl, 4,5,6,7-tetrahydro-2H- indenyl, alkyl-substituted 4,5,6,7-tetrahydro-2H-indenyl, 9H-fluorenyl, and alkyl-substituted 9H-fluorenyl;
  • Bg represents a bridging group covalently linking Cp and Cp'
  • n is zero (0), one (1), or two (2), preferably zero (0) or one (1), more preferably zero (0, i.e., where
  • R 9 is independently a C1-C30 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl groups.
  • Preferred R 9 includes substituted or unsubstituted methyl, ethyl, n-propyl, phenyl, and benzyl.
  • Bg is category (i) or (ii) above. More preferably Bg is category (i) above.
  • all R 9 's are identical.
  • M represents Hf or Zr.
  • M is Zr.
  • X the same or different at each occurrence, independently represents a halogen such as CI or a hydrocarbyl such as: linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl and branched isomeric group thereof, n-pentyl and branched isomeric group thereof, n-hexyl and branched isomeric group thereof, n-heptyl and branched isomeric group thereof, n-octyl and branched isomeric group thereof, n-nonyl and branched isomeric group thereof, n-decyl and branched isomeric group thereof, and the like; a cycloalkyl group; a cycloalkylalkyl group; an alkylcycloalkyl group; an aryl group such as phenyl;
  • X is methyl or CI; more preferably X is CI.
  • metallocene compound results in the formation of vinylidene olefin in the oligomerization reaction.
  • a more preferred group of metallocene compound useful for the continuous process for making the vinylidene olefin used in the process for making gamma-branched alcohol product of this disclosure are those unbridged metallocene compounds having a general formula bisCpMX2, where bisCp represents two cyclopentadienyl rings, M is Zr or Hf (preferably Zr), and X is as defined above, but preferably selected from CI, C1-C10 linear or branched alkyl groups, phenyl, and benzyl.
  • the most preferred metallocene compound useful in the continuous process for making the vinylidene olefin having formula (F-II) is bisCpZrC , which is commercially available and can be represented by the following formula:
  • the terminal olefin monomer (or multiple co-monomers) are fed into the oligomerization reactor at a first feeding rate of R(to) moles per hour, and the metallocene compound is fed into the reactor at a second feeding rate of R(mc) moles per hour.
  • the ratio of the first feeding rate to the second feeding rate R(to)/R(mc) be in the range from xl to x2, where xl and x2 can be, independently, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1,000, as long as xl ⁇ x2.
  • the metallocene compound is dissolved or dispersed in an inert solvent and then fed into the reactor as a solution or a dispersion.
  • inert solvent for the metallocene compound can be, e.g., benzene, toluene, any xylene, ethylbenzene, and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and saturated isomers thereof, and mixtures thereof; n-heptane and branched isomers thereof, and mixtures thereof; n-octane and branched isomers thereof, and mixtures thereof; n-nonane and branched isomers thereof, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and any mixture of the above; Isopar® solvent
  • One or more metallocene compound(s) may be used in the continuous process for making the vinylidene olefin having formula (F-II).
  • the alumoxane used in the process of this disclosure functions as activator of the metallocene compound and scavenger for impurities (such as water).
  • Alumoxanes can be obtained by partial hydrolysis of alkyl aluminum compounds.
  • alumoxanes useful in the process of this disclosure include those made by partial hydrolysis of trimethyl aluminum, triethyl aluminum, tri(n-propyl)aluminum, tri(isopropyl)aluminum, tri(n- butyl)aluminum, tri(isobutyl)aluminum, tri-(tert-butyl)aluminum, tri(n-pentyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, and mixtures thereof.
  • Preferred alumoxane for the process of this disclosure is methylalumoxane ("MAO") made from partial hydrolysis of trimethyl aluminum.
  • the alumoxane feed supplied into the continuously operated oligomerization reactor is advantageously substantially free of metal elements other than aluminum, alkali metals, alkaline earth metals, and the metal(s) contained in the metallocene compound(s) described above.
  • the alumoxane feed used in the process of this disclosure comprises metal elements other than aluminum, alkali metals, alkaline earth metals, Zr, and Hf at a total concentration of no greater than xl ppm by mole, based on the total moles of all metal atoms in the alumoxane feed, where xl can be 50,000, 40,000, 30,000, 20,000, 10,000, 8,000, 6,000, 5,000, 4,000, 2,000, 1,000, 800, 600, 500, 400, 200, 100, 80, 60, 50, 40, 20, or even 10.
  • the alumoxane feed used in the process of this disclosure comprises metal elements other than aluminum, Zr, and Hf at a total concentration of no greater than x2 ppm by mole, based on the total moles of all metal atoms in the alumoxane feed, where x2 can be 50,000, 40,000, 30,000, 20,000, 10,000, 8,000, 6,000, 5,000, 4,000, 2,000, 1,000, 800, 600, 500, 400, 200, 100, 80, 60, 50, 40, 20, or even 10. Still more preferably, the alumoxane feed fed into the reactor is free of all metals other than aluminum and the metal(s) contained in the metallocene compound(s) described above.
  • Ions or compounds of metal elements other than aluminum, alkali metals and alkaline earth metals can be Lewis acids capable of catalyzing undesired polymerization of the terminal olefin monomer, the dimer and higher oligomers, resulting in the production of undesired 1,2-di-substituted vinylenes and tri-substituted vinylenes.
  • Lewis acids such as metal ions can also catalyze the isomerization of the terminal olefin monomer and the isomerization of the vinylidene olefin dimer and higher oligomers, resulting in the production of internal olefin isomers of the terminal olefin monomer, 1,2-di- substituted vinylene and tri-substituted vinylene dimers and higher oligomers, which is undesirable for many applications of the oligomer product, including but not limited to the dimer product.
  • the alumoxane used in the continuous process for making the vinylidene olefin having formula (F-II) is substantially free of any Lewis acid capable of catalyzing the isomerization of the terminal olefin monomer, isomerization of a vinylidene olefin dimer, and polymerization of the terminal olefin monomer via mechanism differing from the oligomerization catalyzed by the metallocene compound used herein.
  • the metallocene compound per se, the alumoxane per se, and any variations and derivatives thereof during the oligomerization reaction are not considered as Lewis acids.
  • a portion or the entirety of the alumoxane fed into the continuously operated oligomer reactor may be mixed with a portion or the entirety of the metallocene compound(s) described above, preferably dissolved and/or dispersed into an inert solvent, before it is fed into the reactor.
  • the stream carrying a portion or the entirety of alumoxane fed into the reactor may contain the metal element(s) contained in the metallocene compound(s).
  • the alumoxane may be supplied into the reactor as a stream separate from the terminal olefin monomer stream and the metallocene compound stream. Alternatively or in addition, at least a portion of the alumoxane may be combined with the terminal olefin monomer and supplied into the reactor together. Mixing alumoxane with the olefin monomer before being supplied into the reactor can result in the scavenging of catalyst poisons contained in the monomer feed before such poisons have a chance to contact the metallocene compound inside the reactor. It is also possible to combine at least a portion of the alumoxane with at least a portion of the metallocene compound in a mixture, and supply the mixture as a catalyst stream into the reactor.
  • the alumoxane is desirably dissolved or dispersed in an inert solvent before being fed into the reactor or before being combined with the monomer feed and/or the metallocene compound.
  • inert solvent can be made of the following: benzene, toluene, any xylene, ethylbenzene, and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and saturated isomers thereof, and mixtures thereof; n-heptane and branched isomers thereof, and mixtures thereof; n-octane and branched isomers thereof, and mixtures thereof; n-nonane and branched isomers thereof, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and any mixture of the inert solvent.
  • the terminal olefin monomer (or multiple co-monomers) is fed into the oligomerization reactor at a first feeding rate of R(to) moles per hour, and the metallocene compound is fed into the reactor at a second feeding rate of R(mc) moles per hour, and the alumoxane is fed into the reactor at a third feeding rate corresponding to R(A1) moles of aluminum atoms per hour.
  • the ratio of the third feeding rate to the second feeding rate R(A1)/R(mc) be in the range from yl to y2, where yl and y2 can be, independently, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, as long as yl ⁇ y2.
  • the oligomerization reaction in the process of this disclosure advantageously is carried out at a mild temperature in the range from tl to t2°C, where tl and t2 can be, independently, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90, as long as tl ⁇ t2.
  • the oligomerization reaction may be carried out at a residence time in the range from rtl to rt2 hours, where rtl and rt2 can be, independently, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.0, 10, 12, 15, 18, 24, 30, 36, 42, or 48, as long as rtl ⁇ rt2.
  • the oligomerization reaction is preferably carried out in the presence of mechanical stirring of the reaction mixture such that a substantially homogeneous reaction mixture with a steady composition is withdrawn from the reactor once the reactor reaches steady state.
  • the oligomerization reaction of the process of this disclosure is carried out under mild pressure. Because the oligomerization reaction is sensitive to water and oxygen, the reactor is typically protected by an inert gas atmosphere such as nitrogen. To prevent air leakage into the reactor, it is desirable that the total pressure inside the reactor is slightly higher than the ambient pressure.
  • the oligomerization reaction can be carried out in the presence of a quantity of inner solvent.
  • solvent include: benzene, toluene, any xylene, ethylbenzene, and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and saturated isomers thereof, and mixtures thereof; n-heptane and branched isomers thereof, and mixtures thereof; n-octane and branched isomers thereof, and mixtures thereof; n-nonane and branched isomers thereof, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and any mixture of the above; Isopar® solvent; and the like.
  • a high selectivity of the terminal olefin toward vinylidenes olefins e.g., at least 95%, 96%, 97%, 98%, or even 99%
  • a low selectivity of the terminal olefin toward internal olefins including 1,2-di-substituted vinylenes and tri-substituted vinylenes e.g., at most 5%, 4%, 3%, 2%, or even 1%)
  • the oligomers thus made, especially the dimer tend to be predominantly vinylidene and can be advantageously used as a vinylidene without further purification in applications where vinylidenes are desired.
  • selectivity of the terminal olefin toward trimer can reach no greater than 4%, no greater than 3%, no greater than 2%, or even no greater than 1%.
  • selectivity of the terminal olefin toward tetramer and even higher oligomers are even lower and in many embodiments negligible.
  • the selectivity of the terminal olefin toward tetramer and higher oligomers is typically no greater than 2%, or no greater than 1%, or no greater than 0.5%, or even no greater than 0.1%.
  • the selectivity of the terminal olefin toward dimer can be at least 90% (or > 91%, > 92%, > 93%, > 94%, > 95%, > 96%, > 97%, > 98%, or even > 99%).
  • the process of this disclosure also exhibits a high conversion of the terminal olefin monomer, e.g., a conversion of at least 40%, 45%, 50%, 55%, 60%, 65%, or 70%, can be achieved in a single pass oligomerization reaction. With recycling of unreacted monomer separated from the oligomerization reaction mixture to the oligomerization reactor, the overall conversion can be even higher, making the process of this disclosure particular economic.
  • the alumoxane introduced into the reaction system in the process of this disclosure is substantially free of metals other than aluminum, metals contained in the metallocene compound, alkali metals, and alkaline earth metals, the terminal olefin monomer does not undergo significant isomerization reaction. Likewise, the isomerization of the vinylidene dimers and higher oligomers to form 1,2-di-substituted vinylene and tri- substituted vinylene is substantially avoided as well.
  • the oligomerization reaction mixture stream withdrawn from the reactor typically comprises the unreacted terminal olefin monomer, the intended dimer, trimer, tetramer and higher oligomers, the metallocene compound, the alumoxane, and optional solvent.
  • a stream of quenching agent is injected into the stream to terminate the oligomerization reactions.
  • quenching agents include: water, methanol, ethanol, C02, and mixtures thereof.
  • a particularly desirable quenching agent is water.
  • the metal elements contained in the oligomerization mixture including aluminum and Zr or Hf, needs to be removed from the mixture. Removal thereof can be achieved through mechanical filtration using a filtration aid such as Celite. Presence of aluminum in the liquid mixture can cause isomerization of the monomer and dimer during subsequently processing steps, such as distillation to remove the unreacted monomers and the optional distillation to remove higher oligomers such as trimers and tetramers in rare cases where the purity requirement for the dimer is so high that even the small quantity of trimer and higher oligomers produced in the continuous process for making the vinylidene olefin having formula (F-II) is considered excessive.
  • a filtration aid such as Celite
  • the liquid mixture contains aluminum at a concentration no higher than 50 ppm by weight (preferably no higher than 30 ppm, still more preferably no higher than 20 ppm, still more preferably no higher than 10, still preferably no higher than 5 ppm), based on the total weight of the liquid mixture.
  • a mixture comprising monomer, the desired dimer, the trimer and higher oligomers and the optional solvent is obtained.
  • the monomer and solvent can be removed by flashing or distillation at an elevated temperature and/or optionally under vacuum. Because isomerization of the monomer is avoided in (i) in the oligomerization reaction due to the lack of Lewis acid capable of catalyzing isomerization reaction and (ii) in the flashing/distillation step due to the removal of aluminum and other metal elements from the liquid mixture at the earlier filtration step, the monomer reclaimed form the mixture consists essentially of the terminal olefin monomer as introduced into the reactor.
  • the reclaimed monomer can be recycled to the oligomerization reactor as a portion of the monomer stream.
  • the thus obtained oligomer mixture absent monomer and solvent may be used as a vinylidene dimer olefin product as is due to the low percentage of trimer and higher oligomers.
  • the dimer product as a result of the continuous process for making the vinylidene olefin having formula (F-II) advantageous comprises dimer(s) of the monomer(s) as the predominant component, and trimers at a concentration no higher than 5 wt% (preferably ⁇ 4 wt%, ⁇ 3 wt%, ⁇ 2 wt%, ⁇ 1 wt%, or even ⁇ 0.5 wt%), based on the total weight of the dimer product.
  • the dimer product comprises dimer at a concentration of at least 90% (or > 91%, > 92%, > 93%, > 94%, > 95%, > 96%, > 97%, > 98%, or even > 99%), based on the total weight of the dimer product.
  • the dimer product as a result of the continuous process for making the vinylidene olefin having formula (F-II) can advantageous comprise vinylidene(s) at a total concentration of at least 95 wt% (preferably > 96 wt%, > 97 wt%, > 98%, or even > 99 wt%), based on the total weight of the dimer product.
  • the vinylidene dimer product obtainable from the process of this disclosure can advantageously comprise one of the following compounds at a concentration of at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or even at least 99 wt%, based on the total weight of the dimer product, if a substantially pure terminal olefin (with a concentration of at least 95 wt%, 96 wt%, 97 wt%, 98 wt%, or 99 wt% of the terminal olefin, based on the total weight of the terminal olefins included in the monomer feed) is utilized as the monomer feed: 3-methylenepentane (from 1-butene); 4-methylenenonane (from 1-pentene); 5- methyleneundecane (from 1-hexene); 6-methylenetridecane (from 1-heptene); 7- methylenepentadecane (from
  • the high-purity, predominantly dimer, predominantly vinylidene product resulting from the continuous process for making the vinylidene olefin having formula (F-II) can then be advantageously used as is as a high-purity organic compound in many applications, including in the hydroformylation reaction to make the gamma-branched alcohol in this disclosure.
  • U.S. Patent No. 8,383,869 B2 discloses a process for making gamma-branched alcohols from a terminal olefin including a first step of producing a vinylidene dimer of the terminal olefin, followed by hydroformylation of the vinylidene dimer.
  • This patent teaches that in the hydroformylation process, multiple alcohol isomers will be produced (lines 30-36, column 4). Because the isomers have the same molecular weight and similar molecular structure, it follows from the teaching in U.S. Patent No. 8,383,869 that it would be very difficult to produce one gamma-branched alcohol at high purity by hydroformylation of a vinylidene olefin.
  • JP2005 -298443 A discloses a similar process for making gamma-branched alcohols from alpha-olefin. While a high purity of a gamma-branched alcohol was reportedly produced in an example in this patent publication by using a cobalt-containing carbonylation catalyst, the purity still has room for improvement. In addition, the overall yield of the gamma- branched alcohol product from the terminal olefin as disclosed in JP2005-298443A has room for improvement as well.
  • the present inventors have surprisingly found that by using a Rh-containing carbonylation catalyst in combination with a phosphine compound, one can produce gamma- branched alcohols having formula (F-I) at an exceedingly high selectivity, significantly higher than that disclosed in JP2005-298443A, and contrary to the teaching in U.S. Patent No. 8,383,869.
  • the vinylidene olefin molecule reacts with CO and H2 to product a carbonylated derivative of the vinylidene. Without intending to be bound by a particular theory, it is believed that an aldehyde is formed as a result.
  • Rh-containing compound examples include the following of rhodium at any oxidative state (e.g., (I), (II) or (III)) and mixtures thereof: oxides; inorganic salts such as rhodium fluoride, rhodium chloride, rhodium bromide, rhodium iodide, rhodium nitrate, and rhodium sulfate; rhodium salts of carboxylic acids such as rhodium acetate, di-rhodium tetracetate, rhodium acetylacetonate, rhodium(II) isobutyrate, rhodium(II) 2-ethylhexanoate; rhodium carbonyl compounds such as Rh 4 (CO) i2, Rli6(CO) i6, (acetylacetonato)dicarbonylrhodium(I) ,
  • Exemplary catalytically effective amount of the Rh-containing compound can range from nl to n2 micromoles of the Rh-containing compound per mole of the vinylidene olefin to be converted, where nl and n2 can be, independently, 200, 250, 300, 350, 400, 450, 500, 550, 650, 700, 750, 800, 850, 900, 950, 1,000, 1, 100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800,
  • a portion of the Rh-containing compound can be solubilized in an inert solvent, or dispersed in an inert liquid medium and then introduced into the reaction system.
  • a portion of the Rh-containing compound can be dispersed in the vinylidene olefin to be converted as a suspension to effect the catalytic effect.
  • the reactor is equipped with a mechanical stirrer, such that the reaction is conducted with continuous stirring to achieve a uniform distribution of the Rh-containing compound in the reaction media.
  • Cobalt-containing compounds were used previously to catalyze the carbonylation of olefin compounds. However, in the process of this disclosure, in order to achieve a high selectivity of the vinylidene olefin toward the desired carbonylation conducive for the production of a gamma-branched alcohol, an Rh-containing compound is used instead.
  • Presence of a phosphine compound in the reaction system is important for a high selectivity toward the desired carbonylation reaction leading to a high-purity gamma-branched alcohol product having formula (F-I).
  • a phosphine compound in the reaction system without the presence of a phosphine compound in the reaction system, a plurality of alcohols can be produced; and on the other hand, when a phosphine compound is included, the hydroformylation is highly selective toward the desired gamma-branched alcohol having formula (F-I).
  • Non-limiting examples of useful phosphine compounds in the hydroformylation of vinylidene olefin in the process of this disclosure include: triphenyl phosphine; tri-(n-butyl) phosphine; tri-(tert-butyl) phosphine; tri-(n-pentyl) phosphine; tri-(n-hexyl) phosphine; tri(n- heptyl) phosphine; tri-(n-octyl) phosphine; tri(n-nonyl) phosphine; tri-(n-decyl) phosphine; and any mixture of two or more thereof, and the like.
  • Exemplary catalytically effective amount of the phosphine compound can range from nl to n2 micromoles of the phosphine compound per mole of the vinylidene olefin to be converted, where nl and n2 can be, independently, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, and 6,000, as long as nl ⁇ n2.
  • the phosphine compound introduced into the carbonylation reaction mixture functions as a ligand to the Rh atom contained in the Rh-containing compound during reaction, which favorably catalyzes the desired carbonylation conducive to the formation of the gamma-branched alcohol of this disclosure when the carbonylated product from the vinylidene is reduced to produce an alcohol.
  • the phosphine compound may be introduced into the carbonylation reactor separately from the Rh-containing compound. Alternatively or additionally, a portion of the phosphine compound may be combined with a portion of the Rh-containing compound to form a mixture comprising a rhodium-phosphine compound complex and then the mixture is introduced in to the carbonylation reactor.
  • the carbonylation reaction of the vinylidene olefin is desirably conducted in the presence of an atmosphere comprising CO and hydrogen preferably at a molar ration of 1 : 1 at an absolute total partial pressure of CO and 3 ⁇ 4 in a range from pi to p2 MPa (million Pascal), where pi and p2 can be, independently, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10, as long as pi ⁇ p2.
  • a high total partial pressure of CO/H2 is conducive to a high conversion of the vinylidene.
  • the conversion of vinylidene in the carbonylation reaction is at least 70%, preferably at least 80%, more preferably at least 90%, still more preferably at least 95%.
  • the carbonylation reaction of the vinylidene olefin is desirably conducted at a relatively mild temperature in a range from tl °C to t2°C, where tl and t2 can be, independently, 40, 45, 50, 55, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or 180, as long as tl ⁇ t2.
  • a higher temperature is conductive to a higher conversion and a higher reaction rate, but at the expense of selectivity toward the desired carbonylated compound derived from the vinylidene olefin.
  • Reaction time can range from 0.5 hour to 96 hours, preferably 1 hour to 60 hours, more preferably no longer than 48 hours, still more preferably no longer than 36 hours, still more preferably no longer than 24 hours, still more preferably no longer than 12 hours, still more preferably no longer than 6 hours.
  • the carbonylation is conducted in a batch reactor that can withstand a high internal pressure.
  • the reactor is cooled down and depressurized, and the carbonylation product mixture, comprising unreacted vinylidene olefin, catalyst, the desired carbonylated product, and other undesired by-products, can be advantageously reduced in the next step without the need of purification.
  • the carbonylation reaction of the vinylidene can be advantageously conducted with or without an inert solvent.
  • Inert solvent useful in this step include but are not limited to: n- pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and saturated isomers thereof, and mixtures thereof; n-heptane and branched isomers thereof, and mixtures thereof; n-octane and branched isomers thereof, and mixtures thereof; n-nonane and branched isomers thereof, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and any mixture of the above, and the like.
  • Such reduction can be effected by combining the carbonylation product mixture (after removal of solid materials by, e.g., filtration) with a reducing agent under reducing conditions.
  • a reducing agent include: NaHB 4 , NaAlH 4 , and LiAlH 4 .
  • a preferred reducing agent useful in the process of this disclosure is molecular hydrogen.
  • Reduction by contacting hydrogen can be effected in the presence of a hydrogenation catalyst under hydrogenation conditions.
  • the hydrogenation catalyst can advantageously comprises a hydrogenation metal such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and combinations thereof preferably supported on an inorganic substrate such as activated carbon, silica, alumina, and the like.
  • Hydrogenation conditions can include a hydrogen partial pressure in a range from p3 to p4 MPa, where p3 and p4 can be, independently, 5.0, 6.0, 7.0,
  • Hydrogenation conditions can further include a hydrogenation temperature in the range from t3 to t4 °C, where t3 and t4 can be, independently, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200, as long as t3 ⁇ t4.
  • the hydrogenation reaction may be conducted with or without the presence of an inert solvent.
  • inert solvent useful for this step include: n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and saturated isomers thereof, and mixtures thereof; n- heptane and branched isomers thereof, and mixtures thereof; n-octane and branched isomers thereof, and mixtures thereof; n-nonane and branched isomers thereof, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and any mixture of the above, and the like.
  • the hydrogenation product mixture can be separated to remove the light components such as alkane of the vinylidene olefin to obtain an alcohol product comprising primarily the intended gamma-branched alcohol.
  • a high selectivity of the desired gamma-branched alcohol can be achieved in the hydroformylation process, resulting in an alcohol product having a purity of the desired gamma-branched alcohol after removal of the alkane but before the removal of components heavier than the gamma-branched alcohol of at least 96 wt%, or at least 97 wt% or at least 98 wt%, or even at least 99 wt%, based on the total weight of the alcohol product.
  • terminal olefins useful in the process of this disclosure include but are not limited to: 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and the like.
  • Preferred examples of gamma-branched alcohols that can be made by the process of this disclosure include the following: 3-ethylheptan-l-ol; 3-propyloctan-l-ol, 3-butylnonan- l-ol; 3-hexylundecan-l-ol; 3-octyltridecan-l-ol; 3-decylpentadecan-l-ol; and 3- dodecylheptadecan- 1 -ol.
  • Part A Dimerization of Terminal Olefins to Make Vinylidene Olefins
  • Example Al Dimerization of 1-Tetradecene in a Continuous Reactor
  • the product mixture effluent exiting the reactor was immediately quenched by injecting room-temperature water at a feeding rate of 2 milliliter per hour. Filter aid was then added into the quenched product mixture. The resultant mixture was then filtered to remove solids to obtain a liquid. The liquid was then measured by gas chromatography to show a conversion of 1-tetradecene in the reaction of 71%. The liquid was then vacuum distilled at an absolute pressure of 4 mmHg (533 Pascal) to obtain a clear residual liquid as the final product. The final product was then characterized by gas chromatography to show the following composition, with total concentration of dimers at 98.84
  • the final product was then characterized by 3 ⁇ 4 NMR. Data show that the final product was predominantly 13-methyleneheptacosane. Data showed the presence of vinyls, vinylidenes, 1,2-di-substituted vinylenes, and tri-substituted vinylenes. The vinyls are attributed to residual 1-tetradecene monomer. The remaining olefin types (1,2-di-substituted vinylenes, tri-substituted vinylenes, and vinylidenes) were normalized to sum up to 100%. Their respective distributions are given below:
  • the reactor was then operated at a constant reaction temperature of 70°C for a batch reaction period of 6.0 hours.
  • the product mixture at the end of the reaction period was immediately quenched by injecting 3 grams of water. Filter aid was then added into the quenched product mixture.
  • the resultant mixture was then filtered to remove solids to obtain a liquid.
  • the liquid was then measured by gas chromatography to show a conversion of 1-tetradecene in the reaction to oligomers of 37%.
  • the liquid was then vacuum distilled at an absolute pressure of 10 rnmHg (1333 Pascal) to remove residual monomer and to obtain a clear residual liquid as the final product.
  • the final product was then characterized by gas chromatography to show the following composition, with a total concentration of dimers at 95.42 wt%:
  • Example A3 (Comparative): Dimerization of 1-tetradecene in a batch reactor
  • Example A4 (Comparative): Dimerization of 1-Decene in a Batch Reactor
  • the product mixture at the end of the reaction period was immediately quenched by injection of 10 grams of water. Filter aid was then added into the quenched product mixture. The resultant mixture was then filtered to remove solids to obtain a liquid. The liquid was then measured by gas chromatography to show a conversion of monomers in the reaction to oligomers of 77%. The liquid was then distilled under a vacuum of an absolute pressure of 10 mmHg (1333 Pascal) to remove residual monomer and to obtain a clear residual liquid as an intermediate product. The intermediate product was then characterized by gas chromatography to show the following composition:
  • a further step of distillation of the intermediate product was then performed to remove the heavy trimer and tetramer to obtain a final product of C20 dimer having the following composition as measured by gas chromatography:
  • the final product in this example was characterized by 1H-NMR to determine the distribution of olefin types. Vinyls were quantified from the NMR spectra but assumed to be from residual monomer. The distribution of vinylidenes, 1,2-di-substituted vinylenes and tri- substituted vinylenes in the oligomers are as follows:
  • U.S. Patent No. 4,658,708 disclosed multiple examples in which a 1-olefin (such as propylene, 1-hexene, and 1-octene) was oligomerized in the presence of bisCpZrC and MAO to produce a dimer product with impressive selectivity toward dimers. Many examples in this patent reference showed significant isomerization of the 1-olefin to produce its isomer 2-olefin. No distribution data of the vinylidenes, 1,2-di-substituted vinylenes and tri-substituted vinylenes in the final product were given in the examples in this patent.
  • a 1-olefin such as propylene, 1-hexene, and 1-octene
  • the high level of isomerization of the 1 -olefin indicates that there is a high likelihood that the vinylidene olefin dimer and higher oligomers isomerized to form 1,2-di-substituted vinylenes and tri-substituted vinylenes at significant quantities.
  • the cause of the isomerization is highly likely the presence of CuS0 4 in the reaction systems, which was derived from the CuS0 4 - 5H20 used for making the MAO.
  • Syngas pressure inside the autoclave was then raised to 700 psig (4826 kPa, gauge pressure) at this temperature and held under constant pressure and temperature for 18 hours before it was depressurized.
  • the reaction product mixture a dark liquid, was then discharged and filtered to remove solid particles and obtain a carbonyl product mixture.
  • Olefin conversion in this step was measured to be 92.1% with selectivity to C21 carbonyl product estimated at 99%.
  • Infrared absorption spectra of the carbonyl product mixture with an overlay of that of the 9-methylenenonadecane- containing dimer product made in step Bla showed the formation of a peak at 1729.83 cm 1 , indicating the formation of an aldehyde.
  • step B lb-II The crude alcohol mixture produced from step B lb-II above was distilled to remove light fractions (fractions having normal boiling points lower than that of 3-octyltridecan-l-ol, such as 9-methylnonadecane) and undesired heavy fractions from the hydrogenated alcohol product to produce a high-purity fraction of 3-octyltridecan-l-ol (the "C21-alcohol").
  • the C21-alcohol purity was measured to be 98.2 wt%, with the balance being predominantly 9- methylnonadecane resulting from the hydrogenation in step B lb-II of the residual 9- methylenenonadecane from step B lb-I.
  • the C21-alcohol was measured to have the following properties: a KV100 of 4.18 cSt, a KV40 of 31.4 cSt, a viscosity index of -60.4, a flash point determined pursuant to ASTM D93 of 193°C, a density determined pursuant to ASTM D-4052 of 0.84 gram-cm 3 , and a refractive index determined pursuant to ASTM D-1218 of 1.453.
  • Example B2 (Comparative): Synthesis of 3-Octyltridecan-l-ol by hydroformylation in the presence of a Rh-containing compound and in the absence of triphenyl phosphine
  • Step B2a Carbonylation of 9-methylenenonadecane in the presence of a Rh-containing compound and in the absence of triphenyl phosphine
  • Step B2b Hydro genation of the Carbonylation Product Mixture
  • Step B2c Distillation to Obtain an Alcohol Product
  • a batch distillation was used to remove light components and undesired heavy components to produce an alcohol product overhead.
  • the alcohol product was measured to have a KV100 of 4.35 cSt, a KV40 of 34.2 cSt, and a viscosity index of -60.7, which are slightly different from those of the C21 -alcohol in Example Bl.
  • Example B Gas chromatography of the alcohol product in this Example B is also provided in FIG. 2, super-imposed to the gas chromatography of the C21 -alcohol product from Example B 1 above.
  • the alcohol product from this Example B2 comprises multiple compounds having similar structures and molecular weights. Without intending to be bound by a particular theory, the alcohol product from this Example B2 may comprise 3-octyltridecan-l-ol and multiple isomers thereof.
  • inclusion of a phosphine compound in the catalyst system in the carbonylation step of the vinylidene olefin is important for the production of a high-purity gamma-branched alcohol.

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Abstract

La présente invention concerne un procédé de fabrication d'un produit alcoolique comprenant un alcool à ramification gamma à partir d'une oléfine de vinylidène par hydroformylation.
PCT/US2018/034393 2017-08-28 2018-05-24 Procédé de fabrication d'un alcool à ramification gamma WO2019045809A1 (fr)

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WO2020257100A1 (fr) * 2019-06-20 2020-12-24 Exxonmobil Chemical Patents Inc. Alcools ramifiés formés à partir d'oléfines de vinylidène par hydroformylation et leurs procédés de production

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JP2005298443A (ja) 2004-04-15 2005-10-27 Idemitsu Kosan Co Ltd 長鎖分岐アルコールとその製造方法
EP1710225A1 (fr) * 2004-01-28 2006-10-11 Idemitsu Kosan Co., Ltd. Compose carbonyle contenant un groupe alkyle ramifie longue chaine
US8383869B2 (en) 2009-09-01 2013-02-26 Shell Oil Company Olefin oligomer composition

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US4658708A (en) * 1985-01-09 1987-04-21 Transitube Projet Machine for continuously and uniformly coating confectionery products
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US4987788A (en) 1988-10-25 1991-01-29 General Motors Corporation Electric motor-driven positioning element
EP1710225A1 (fr) * 2004-01-28 2006-10-11 Idemitsu Kosan Co., Ltd. Compose carbonyle contenant un groupe alkyle ramifie longue chaine
JP2005298443A (ja) 2004-04-15 2005-10-27 Idemitsu Kosan Co Ltd 長鎖分岐アルコールとその製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020257100A1 (fr) * 2019-06-20 2020-12-24 Exxonmobil Chemical Patents Inc. Alcools ramifiés formés à partir d'oléfines de vinylidène par hydroformylation et leurs procédés de production
CN114258389A (zh) * 2019-06-20 2022-03-29 埃克森美孚化学专利公司 由乙烯叉基烯烃通过加氢甲酰基化形成的支化醇及其制备方法

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