EP3687968A1 - Néo-acides et leur procédé de production - Google Patents

Néo-acides et leur procédé de production

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Publication number
EP3687968A1
EP3687968A1 EP18740989.1A EP18740989A EP3687968A1 EP 3687968 A1 EP3687968 A1 EP 3687968A1 EP 18740989 A EP18740989 A EP 18740989A EP 3687968 A1 EP3687968 A1 EP 3687968A1
Authority
EP
European Patent Office
Prior art keywords
acid
olefin
vinylidene
formula
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18740989.1A
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German (de)
English (en)
Inventor
Patrick C. CHEN
Kyle G. LEWIS
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Publication of EP3687968A1 publication Critical patent/EP3687968A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
    • 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
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • 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 carboxylic acids and processes for making the same.
  • this disclosure relates to neo-acid compounds and processes for making the same.
  • Neo-acids are carboxylic acids having the following general structure:
  • R a , R b , and R c are independently hydrocarbyl groups.
  • the quaternary carbon next to the carboxylic group makes it unique and interesting.
  • a specific neo-acid, 2,2- dimethylpropanoic acid (corresponding to the above formula where R a , R b , and R c are methyl), has found use in many applications. This neo-acid can be made by carboxylation of isobutene via Koch reaction:
  • Neo-acids with at least one long carbon chain may find use as intermediates for surfactants, lubricant base stocks, plasticizers, and the like.
  • neo-acids can be produced from reacting a vinylidene olefin with carbon monoxide in the presence of an acid catalyst.
  • Such neo-acids can have one or two long carbon chains comprising at least 6 carbon atoms.
  • a first aspect of this disclosure relates to a compound having a formula (F-I) below:
  • R 1 and R 2 are each independently a hydrocarbyl group comprising at least two carbon atoms, provided R 1 and R 2 are not simultaneously ethyl or n-butyl.
  • a second aspect of this disclosure relates to a process for making a neo-acid product comprising a neo-acid compound having a formula (F-I) below:
  • the Figure is a 13 C-NMR spectra of the neo-acid product made in Example B2 in this disclosure.
  • 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.
  • 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.
  • a "substituted” hydrocarbyl group is a hydrocarbyl group in which one or more hydrogen atom is substituted by any another group.
  • An “unsubstituted” hydrocarbyl group is a hydrocarbyl group.
  • 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.
  • 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
  • nucleic acid refers to a carboxylic acid having the following general
  • R a , R b , and R c are independently hydrocarbyl groups.
  • 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 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%.
  • NMR spectroscopy provides key structural information about the synthesized polymers.
  • Proton NMR ⁇ H-NMR analysis of the unsaturated PAO product gives a quantitative breakdown of the olefinic structure types (viz. vinyl, 1,2-di-substituted, tri- substituted, and vinylidene).
  • 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.
  • the following approach is taken in determining the concentrations of the various olefins among all of the olefins from an NMR spectrum.
  • 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.
  • 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.
  • R 1 and R 2 are each independently a hydrocarbyl group comprising at least two (2) carbon atoms (preferably a C2 to C60 hydrocarbyl group, more preferably a C2 to C60 alkyl group, still more preferably a C2 to C60 linear or branched alkyl group, and still more preferably a C2 to C30 linear or branched alkyl group), provided R 1 and R 2 are not both ethyl or n-butyl.
  • R 1 and R 2 each independently comprise cl to c2 carbon atoms, where cl and c2 can be, independently, any integer from 2 to 60, such as 2, 3, 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, or 60, as long as cl ⁇ c2.
  • R 1 and R 2 each independently comprise even number of carbon atoms.
  • At least one of R 1 and R 2 can be a up, preferably a branched alkyl group having the following formula (F-IV): (F-IV),
  • R a and R b are independently hydrocarbyl groups, preferably alkyl groups, more preferably linear or branched alkyl groups, still more preferably linear alkyl groups, m is a non- negative integer, preferably m > 2, more preferably m > 3, still more preferably m > 4, still more preferably m > 5, still more preferably m > 6, still more preferably m > 7.
  • R 1 and/or R 2 can be a group branched at the 1-location, i.e., the carbon directly connected to the quaternary carbon atom.
  • branched alkyls for R 1 and R 2 include: 2-ethylhexyl, 2-propylheptanyl, 2-butyloctyl, and 3,5- dimethyloctyl.
  • At least one of R 1 and R 2 can be linear alkyl groups such as: ethyl, n -propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n- decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n- pentacosyl, n-hexacosyl,
  • the total number of carbon atoms in linear R 1 and R 2 is an even number.
  • the total number of carbon atoms in the linear R 1 and/or R 2 combined is from al to a2, where al and a2 can be, independently, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96, or 100, as long as al ⁇ a2.
  • the total number of carbon atoms in the linear R 1 and R 2 combined is from 8 to 96, more preferably from 8 to 80, still more preferably from 8 to 64, still more preferably from 8 to 48, still more preferably from 8 to 40, still more preferably from 8 to 32, still more preferably from 8 to 28, still more preferably from 8 to 26, still more preferably from 8 to 24, still more preferably from 8 to 22, and still more preferably from 8 to 20.
  • the total number of carbon atoms in R 1 and R 2 combined is from bl to b2, where bl and b2 can be, independently, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96, or 100, as long as bl ⁇ b2.
  • the total number of carbon atoms in R 1 and R 2 is in a range from 8 to 96, more preferably from 8 to 80, still more preferably from 8 to 64, still more preferably from 8 to 48, still more preferably from 8 to 40, still more preferably from 8 to 32, still more preferably from 8 to 28, still more preferably from 8 to 26, still more preferably from 8 to 24, still more preferably from 8 to 22, and still more preferably from 8 to 20.
  • R 1 and R 2 are identical. In such case, it is particularly preferred that R 1 and R 2 contain even number of carbon atoms. It is also particularly preferred that R 1 and R 2 are identical linear alkyl groups. Where R 1 and R 2 in formula (F-I) 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. Preferably in such cases R 1 and R 2 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).
  • neo-acid compounds of this disclosure are as follows: 2-methyl-2-propylheptanoic acid; 2-butyl-2-methylhexanoic acid; 2-ethyl-2- methyloctanoic acid; 2-butyl-2-methyloctanoic acid; 2-butyl-2-methyldecanoic acid; 2-hexyl- 2-methyloctanoic acid; 2-hexyl-2-methyldecanoic acid; 2-methyl-2-octyldecanoic acid; 2- hexyl-2-methyldodecanoic acid; 2-methyl-2-octyldodecanoic acid; 2-decyl-2- methyldodecanoic acid; 2-decyl-2-methyltetradecanoic acid; 2-methyl-2-octyltetradecanoic acid; 2-dodecyl-2-methyltetradecanoic acid; 2-dodecyl-2-methyltetradecanoic acid; 2-
  • Another aspect of this disclosure relates to a process for making a neo-acid product comprising a neo-acid compound having a formula (F-I) below:
  • R 1 and R 2 are each independently a hydrocarbyl group comprising at least two (2) carbon atoms (preferably a C2-C60 hydrocarbyl group, more preferably a C2-C60 alkyl group, still more preferably a C2-C60 linear or branched alkyl group, still more preferably a C2 to C30 linear or branched alkyl group); preferably R 1 and R 2 are not both ethyl or n-butyl), the process comprising:
  • olefin feed comprising a vinylidene olefin having a formula (F-II), where R 1 and R 2 correspond to the R 1 and R 2 in formula (F-I) above, respectively;
  • R 1 and R 2 are each independently a hydrocarbyl group comprising at least two (2) carbon atoms (preferably a C2-C60 hydrocarbyl group, more preferably a C2-C60 alkyl group, still more preferably a C2-C60 linear or branched alkyl group, still more preferably a C2 to C30 linear or branched alkyl group).
  • this compound can be considered as a dimer derived from to molecules of terminal olefin(s), it will be referred to as a terminal olefin dimer or a vinylidene dimer of terminal olefin(s) in this disclosure.
  • R 1 and R 2 each independently comprise cl to c2 carbon atoms, where cl and c2 can be, independently, any integer from 2 to 60, such as 2, 3, 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, or 60, as long as cl ⁇ c2.
  • R 1 and R 2 each independently comprise even number of carbon atoms.
  • At least one of R 1 and R 2 can be a up, preferably a branched alkyl group having the following formula (F-IV): (F-IV),
  • R a and R b are independently hydrocarbyl groups, preferably alkyl groups, more preferably linear or branched alkyl groups, still more preferably linear alkyl groups, m is a non- negative integer, preferably m > 2, more preferably m > 3, still more preferably m > 4, still more preferably m > 5, still more preferably m > 6, still more preferably m > 7.
  • R 1 and/or R 2 can be a group branched at the 1-location, i.e., the carbon directly connected to the quaternary carbon atom.
  • branched alkyls for R 1 and R 2 include: 2-ethylhexyl, 2-propylheptanyl, 2-butyloctyl, and 3,5- dimethyloctyl.
  • At least one of R 1 and R 2 can be linear alkyl groups such as: ethyl, n -propyl, n -butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n- decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n- pentacosyl, n-hexacosyl,
  • the total number of carbon atoms in linear R 1 and R 2 is an even number.
  • the total number of carbon atoms in the linear R 1 and/or R 2 combined is from al to a2, where al and a2 can be, independently, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96, or 100, as long as al ⁇ a2.
  • the total number of carbon atoms in the linear R 1 and R 2 combined is from 8 to 96, more preferably from 8 to 80, still more preferably from 8 to 64, still more preferably from 8 to 48, still more preferably from 8 to 40, still more preferably from 8 to 32, still more preferably from 8 to 28, still more preferably from 8 to 26, still more preferably from 8 to 24, still more preferably from 8 to 22, and still more preferably from 8 to 20.
  • the total number of carbon atoms in R 1 and R 2 combined is from bl to b2, where bl and b2 can be, independently, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96, or 100, as long as bl ⁇ b2.
  • the total number of carbon atoms in R 1 and R 2 is in a range from 8 to 96, more preferably from 8 to 80, still more preferably from 8 to 64, still more preferably from 8 to 48, still more preferably from 8 to 40, still more preferably from 8 to 32, still more preferably from 8 to 28, still more preferably from 8 to 26, still more preferably from 8 to 24, still more preferably from 8 to 22, and still more preferably from 8 to 20.
  • R 1 and R 2 are identical. In such case, it is particularly preferred that R 1 and R 2 contain even number of carbon atoms. It is also particularly preferred that R 1 and R 2 are identical linear alkyl groups. Where R 1 and R 2 in formula (F-I) 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. Preferably in such cases R 1 and R 2 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).
  • a single vinylidene olefin having a formula (F-II) where R 1 and R 2 are identical can be advantageously made in the dimerization process, which can be used as the vinylidene olefin feed in step (I) of the process of this disclosure for making a neo-acid product.
  • 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 neo-acid product comprising multiple neo-acid 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 neo-acid product in tis disclosure.
  • Such dimerization can also be carried out in the presence of trialkylaluminum 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.
  • trialkylaluminum 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.
  • the vinylidene olefin having formula (F-II) feed used in the process of this disclosure for making neo-acid product 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 neo-acid 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 neo-acid product by using the process of this disclosure.
  • the vinylidene olefin feed used in the process of this disclosure for making neo-acid product 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.
  • Non-limiting, particularly desirable examples of vinylidene olefins for the process for making neo-acid products of this disclosure include: 3-methylenepentane; 4- methylenenonane; 3-methylenonane; 5-methyleneundecane; 5-methylenetridecane; 7- methylenetridecane; 7-methylenepentadecane; 9-methyleneheptadecane; 7- methyleneheptadecane; 9-methylenenonadecane; 11-methylenehenicosane; I lmethylenetricosane; 9-methylenehenicosane; 13-methylenepentacosane; 13- methyleneheptacosane; 11-methylenepentacosane; 15-methylenenonacosane; 15- methylenehentriacontane; 13-methylenenonacosane; 15-methylenetritriacontane; 17-
  • Preferred mixtures are those having total number of carbon atoms in the molecules thereof no greater than 8, preferably no greater than 6, still more preferably no greater than 4, still more preferably no greater than 2.
  • the following vinylidene olefins are preferred, especially as a high-purity, single vinylidene olefin feed: 4-methylenenonane; 5-methyleneundecane; 6- methylenetridecane; 7-methylenepentadecane; 8-methyleneheptadecane; 9- methylenenonadecane; 11-methylenetricosane; 13-methyleneheptacosane; 15- methylenehentriacontane; 17-methyleneheptatriacontane; and 19-methylenenonatriacontane.
  • 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 neo-acid product 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.
  • Particularly useful examples of 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 a non-negative integer, preferably n > 2, more preferably n > 4, and still 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 a non-negative integer, preferably n > 2, more preferably n > 4, and still more preferably n > 5.
  • the terminal olefin per se represents a vinylidene olefin, which can be a vinylidene olefin described above, and can be made from terminal olefins through dimerization of terminal olefin(s) monomer described here.
  • 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 substantially pure dimer compound ( - n 2'- n 2 - , i.e., a vinylidene olefin having a formula (F-II) where R 1 and R 2 are identically R) is desirable
  • 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)nMX 2 Cp' , 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', and n is zero (0), one (1), or two (2), preferably zero (0) or one (1), more preferably zero (0, i.e., where the metal
  • 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.
  • Preferably 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 neo-acid 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 bisCpZrCh, 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, CO2, and mixtures thereof.
  • a particularly desirable quenching agent is water.
  • the metal elements contained in the oligomerization mixture 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 neo-acid product in this disclosure.
  • Koch chemistry is employed to make neo-acids from the vinylidene olefins described above.
  • the Koch chemistry involves a step (called “carboxylation” herein) of reacting the olefin with carbon monoxide in the presence of a strong acid at effective reaction temperature and an effective partial pressure of CO.
  • carboxylation Typically in a subsequent step the reaction mixture from the carboxylation step of reacting with CO is allowed to contact with water to produce a carboxylic acid.
  • the step of reacting the vinylidene olefin with CO is carried out in a batch reactor due to the pressurized nature.
  • the reactions can be schematically illustrated as follows:
  • the acid catalyst used in the carboxylation step can be any strong organic or inorganic acids.
  • Non-limiting examples are: (i) Br(
  • the amount of the acid catalyst used expressed in terms of molar ratio of the catalyst to the vinylidene olefin can range from rl to r2, where rl and r2 can be, independently, 0.01, 0.02, 0.04, .0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1, 2, 4, 5, 6, 8, 10, 20, 40, or 50, as long as rl ⁇ r2.
  • the quantity of the catalyst by mole means the quantity by mole of molecules, ions, or functional groups that provide the catalytic effect in the carboxylation reaction between the vinylidene olefin and CO in the catalyst material.
  • the quantity by mole of a BF3 catalyst means the quantity by mole of BF3- I.IH2O.
  • BF3 2H2O is believed to be not catalytically effective for the reaction between the vinylidene olefin and CO.
  • subsequent addition of anhydrous BF3 into the reaction system can convert BF3 2H2O into catalytically active form BF3- I.IH2O.
  • BF3 2H2O and anhydrous BF3 are introduced into the reaction system separately at stoichiometric quantities to form BF3- 1.1 H2O
  • all BF3 is present in the reaction system in the form of BF3- I.
  • IH2O for the purpose of calculating the molar quantity of the BF3 catalyst, and the acid catalyst is only added at the time when anhydrous BF3 is introduced into the reaction system.
  • the quantity of a HF catalyst by mole means the quantity by mole of protons provided by the catalyst (considered as equal to the quantity of HF because of the strong acidity of HF).
  • the quantity by mole means the quantity by mole of the functional groups or ions provided by the catalyst material.
  • the active acid catalyst is not allowed to contact the olefin until after the olefin has already formed a mixture with CO at a high CO partial pressure in the reaction mixture.
  • the active acid catalyst is added to the reaction system only after the partial pressure of CO in the reaction system has reached 2.0 mega Pascal ("MPa"), preferably 2.5 MPa, more preferably 3.0 MPa, still more preferably 3.5 kPa, still ore preferably 5.0 MPa, still more preferably 7.0 MPa.
  • BF3 is used as an acid catalyst for the reaction between the vinylidene olefin and CO
  • the BF3 2H2O is not catalytically effective for the oligomerization of the vinylidene olefin or the carboxylation reaction between the vinylidene olefin and CO.
  • BF3 is introduced into the reactor to effect the carboxylation reaction between the vinylidene olefin and CO.
  • the temperature elevation process starts after at least a portion of the active catalyst is introduced into the reactor.
  • the catalyst can be added to the reaction system as a solution in an inert solvent, as a substantially pure material, or as a dispersion in an inert dispersant.
  • the inert solvent and/or dispersant 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;
  • the carboxylation reaction of the vinylidene olefin with CO is desirably conducted in the presence of an atmosphere comprising CO at an absolute partial pressure of CO in a range from pi to p2 MPa, where pa and p2 can be 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, or 14.0, as long as pi ⁇ p2.
  • a high total partial pressure of CO is conducive to a high conversion of the vinylidene.
  • the conversion of vinylidene in the carboxylation reaction is at least 70%, preferably at least 75%, more preferably at least 80%, more preferably at least 85%, more preferably at least 90%, still more preferably at least 95%.
  • the carboxylation reaction of the vinylidene olefin with CO is desirably conducted at a temperature in a range from tl°C to t2°C, where tl and t2 can be, independently, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, or 120, as long as tl ⁇ t2.
  • 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 carboxylation between the vinylidene olefin and CO is conducted in a batch reactor that can withstand a high internal pressure.
  • the reactor is cooled down and depressurized, and the carboxylation product mixture, comprising unreacted vinylidene olefin, catalyst, the desired neo-acid product, and other undesired by-products, can be advantageously separated to obtain the neo-acid product.
  • the carboxylation reaction between the vinylidene olefin and CO may be conducted with or without the presence of an inert solvent.
  • 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.
  • water may be included in the reactants at a small quantity, to the extent the presence of water does not reduce the activity of the catalyst.
  • the reaction mixture is typically allowed to contact with water to complete the carboxylation of the vinylidene olefin to produce the desired neo-acid product.
  • the contact with water can result in the formation of a mixture including an aqueous phase and an organic phase.
  • the acid is typically preferentially distributed in the organic phase, and any acid catalyst soluble in water or reactive with water can be preferentially distributed in the aqueous phase.
  • a solid catalyst such as solid zeolites, solid acids, and acid resin
  • the catalyst can be convenient filtered from the liquid, dried and reused as appropriate in the carboxylation reaction.
  • the neo-acid product in the organic phase may be further purified to obtain a product comprising primarily the intended acid having a formula (F-I) with desired purity. Purification can be done via one or more of water washing, solvent extraction, distillation, liquid or gas chromatography, or by using a sorbent.
  • a high selectivity of the vinylidene olefin toward the desired neo-acid can be achieved in the carboxylation process if the catalyst is not added to the reaction until a high CO partial pressure (e.g., a partial pressure of at least 5.0, 5.5, 6.0, 6.5, or 7.0 MPa) in the reaction system has been established, resulting in a neo-acid product having a purity of the desired neo-acid after removal of the vinylidene and heavy components of at least 95 wt%, 96 wt%, at least 97 wt%, at least 98 wt%, or even at least 99 wt%, based on the total weight of the neo-acid product.
  • a high CO partial pressure e.g., a partial pressure of at least 5.0, 5.5, 6.0, 6.5, or 7.0 MPa
  • a high CO partial pressure e.g., a partial pressure of at least 5.0, 5.5
  • 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, 1-icosene, and the like can be conveniently used to fabricate neo-acids 2-ethyl-2-methylhexanoic acid, 2-methyl-2-propylheptanoic acid,
  • 2- butyl-2-methyloctanoic acid 2-hexyl-2-methyldecanoic acid, 2-methyl-2-octyldodecanoic acid, 2-decyl-2-methyltetradecanoic acid, 2-dodecyl-2-methylhexadecanoic acid, 2-methyl-2- tetradecyloctadecanoic acid, 2-hexadecyl-2-methylicosanoic acid, and 2-methyl-2- octadecyldocosanoic acid, respectively.
  • neo-acids that can be made by the process of this disclosure include the following: 2-ethyl-2-methylhexanoic acid, 2-methyl-2-propylheptanoic acid, 2-butyl-2-methyloctanoic acid, 2-hexyl-2-methyldecanoic acid, 2-methyl-2- octyldodecanoic acid, 2-decyl-2-methyltetradecanoic acid, and 2-dodecyl-2- methylhexadecanoic acid.
  • the feed may comprise two or more of the following vinylidene olefins such as 4-methylenenonane; 3-methylenenonane; 5-methyleneundecane; 5- methylenetridecane; 7-methylenetridecane; 7-methylenepentadecane; 9- methyleneheptadecane; 7-methyleneheptadecane; 9-methylenenonadecane; 11- methylenehenicosane; 11-methylenetricosane; 9-methylenehenicosane; 13- methylenepentacosane; 13-methyleneheptacosane; 11-methylenepentacosane; 15- methylenenonacosane; 15-methylenehentriacontane; 13-methylenenonacosane; 15- methylenetritritritritri
  • the above vinylidene olefin feed can be used to make a neo-acid product comprising two or more of the following neo-acid compounds: 2-methyl-2-propylheptanoic acid; 2-butyl-2-methylhexanoic acid; 2-ethyl-2-methyloctanoic acid; 2-butyl-2-methyloctanoic acid; 2-butyl-2-methyldecanoic acid; 2-hexyl-2-methyloctanoic acid; 2-hexyl-2- methyldecanoic acid; 2-methyl-2-octyldecanoic acid; 2-hexyl-2-methyldodecanoic acid; 2- methyl-2-octyldodecanoic acid; 2-decyl-2-methyldodecanoic acid; 2-decyl-2-methyltetradecanoic acid; 2-methyl-2-octyltetradecanoic acid; 2-dodec
  • the neo-acid product comprises mixtures of two or more of the foregoing differing in number of carbon atoms contained therein no greater than 8, more preferably no greater than 6, still more preferably no greater than 4, and still more preferably no greater than 2.
  • 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 wt%.
  • 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.
  • Example A2 (Comparative): Dimerization of 1-Tetradecene in a Batch Reactor
  • 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.
  • 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.
  • reaction mixture was then pressured into a 12-liter flask containing 4 liters of water. Nitrogen gas was bubbled through the mixture for 3 hours to remove residual BF3. Excess water was then drained off. The resultant mixture was then water washed seven (7) times, each time using one (1) liter of deionized water to remove the residual catalyst. Residual water in the resultant mixture was subsequently removed from with a rotary evaporator to obtain a crude product.
  • the total conversion of the vinylidene olefin in the carboxylation step was measured (by gas chromatography) to be 90.7%, with a yield to heavy dimer species of the vinylidene olefin measured to be 6.6%, and thus a yield to the desired neo-acid product at 84.1%.
  • the crude product was then batch distilled to remove lights (unreacted vinylidene olefin) and heavies to obtain a final neo-acid product.
  • Gas chromatography of the final neo- acid product showed a concentration of neo-acid of about 98% and a concentration of heavy components of about 2%.
  • the final neo-acid product was measured to have a KV100 of 8.51 cSt, and a KV40 of 64.0 cSt. 13 C-NMR spectra, included in FIG. 1, indicates that the final neo-acid product contained 2-methyl-2-octyldodecanoic acid at a purity of 98.1 wt%.
  • the resultant mixture was then pressured into a 12-liter flask containing 4 liters of water. Nitrogen gas was bubbled through the mixture for 3 hours to remove residual BF3. Excess water was then drained off. The resultant reaction mixture was water washed seven (7) times using one (1) liter of deionized water each time to remove residual BF3. Residual water was removed from the washed mixture with a rotary evaporator to obtain a crude product.
  • reaction mixture was then pressured into a 12-liter flask containing 4 liters of water. Nitrogen gas was bubbled through the mixture for 3 hours to remove residual BF3. Excess water was then drained off. The resultant mixture was then water washed seven (7) times using one (1) liter of deionized water each time in order to remove the residual BF3 catalyst. Residual water was removed from the reactor effluent with a rotary evaporator to obtain a crude product.
  • the preferred loading procedure involves adding CO to the reactor until a high partial pressure thereof of at least 400 psig (2.76 MPa, gauge pressure) total pressure in the reactor is achieved prior to adding gaseous BF3, which resulted in much higher conversion of the vinylidene and a much higher yield to the desired neo-acid product.
  • a high partial pressure thereof of at least 400 psig (2.76 MPa, gauge pressure) total pressure in the reactor is achieved prior to adding gaseous BF3, which resulted in much higher conversion of the vinylidene and a much higher yield to the desired neo-acid product.
  • raising the partial pressure of CO in the reaction system to a high level e.g., of at least 500 psig (3.45 MPa, gauge pressure), 600 psig (4.14 MPa, gauge pressure), 800 psig (5.12 MPa, gauge pressure), 1000 psig (6.89 MPa, gauge pressure), 1200 psig (8.27 MPa, gauge pressure), 1400 psig (9.65 MPa, gauge pressure), 1500 psig (10.34 MPa, gauge pressure), 1600 psig (11.03 MPa, gauge pressure), 1800 psig (12.41 MPa, gauge pressure), and 2000 psig (13.79 MPa, gauge pressure) before the introduction of BF3 into the reaction system lead to the preferred reaction between the vinylidene olefin and CO once BF3 is introduced, resulting in a much higher conversion of the vinylidene and a much higher selectivity toward the desired neo-acid product.
  • a high level e.g., of at least 500 psig (3.45 MPa, gauge pressure

Abstract

L'invention concerne des néo-acides de formule (F-1) et des procédés de préparation de ceux-ci à partir d'une oléfine de vinylidène par la chimie de Koch.
EP18740989.1A 2017-09-29 2018-07-12 Néo-acides et leur procédé de production Pending EP3687968A1 (fr)

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US4658078A (en) 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
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