WO2014004954A1 - Conversion d'oléfines internes linéaires en alpha oléfines linéaires - Google Patents

Conversion d'oléfines internes linéaires en alpha oléfines linéaires Download PDF

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Publication number
WO2014004954A1
WO2014004954A1 PCT/US2013/048431 US2013048431W WO2014004954A1 WO 2014004954 A1 WO2014004954 A1 WO 2014004954A1 US 2013048431 W US2013048431 W US 2013048431W WO 2014004954 A1 WO2014004954 A1 WO 2014004954A1
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WO
WIPO (PCT)
Prior art keywords
borane
adduct
scavenger
isomerization catalyst
alkyl group
Prior art date
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PCT/US2013/048431
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English (en)
Inventor
Timothy T. Wenzel
Thomas H. Peterson
Francis J. Timmers
Kevin A. Frazier
Thomas P. Clark
Robert FROESE
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Dow Global Technologies Llc
Priority date (The priority date 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 date listed.)
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Publication of WO2014004954A1 publication Critical patent/WO2014004954A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2562—Catalytic processes with hydrides or 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

Definitions

  • This disclosure relates to methods for converting linear internal olefins to linear alpha olefins.
  • LAOs Linear alpha olefins
  • LIOs linear internal olefins
  • conversion of LIOs to LAOs can be a challenging process due to the contrathermodynamic double bond isomerization involved in converting LIOs to LAOs.
  • This disclosure provides a method for converting LIOs to LAOs including contacting a LIO with a borane isomerization catalyst in a reaction vessel to form a mixture that includes an adduct formed from the LIO and the borane isomerization catalyst, the adduct having an alkyl group bonded to boron at a non-terminal position of the alkyl group, isomerizing the adduct to move the alkyl group bonded to boron to a terminal position of the alkyl group, and dehydroborating the adduct in the presence of a scavenger olefin to form a LAO and a scavenger adduct that is formed from the scavenger olefin and the borane isomerization catalyst.
  • the present disclosure does not employ a dehydroboration catalyst, such as cobalt or nickel, which are employed for some other processes.
  • LIOs are linear olefins having from four carbons to twelve carbons including a double bond between two non-terminal carbons.
  • LIOs include, but are not limited to, 2-butene, 2-methyl-2-butene, 2-pentene, 4-octene, 2-hexene, 3- hexene or a combination thereof.
  • a mixture including 4-octene and 2- butene may be employed.
  • the method includes employing a borane isomerization catalyst that is selected from a group consisting of bis (trifluoromethyl)borane [HB(CF 3 ) 2 ],
  • the borane isomerization catalyst can be part of an initial feedstock to the reaction vessel and/or can be recycled to the reaction vessel.
  • the borane isomerization catalyst has a thermodynamically calculated activation energy for isomerizing an alkyl group from a non-terminal position (e.g., a secondary carbon) to a terminal position (e.g., a primary carbon) when bonded to a boron of an adduct, as discussed herein, in the range of from 1 kilocalories (kcal)/mole (mol) to 40 kcal/mol.
  • the borane isomerization catalyst has a ratio of boron at the primary carbon compared to boron bonded at an adjacent secondary carbon for a given reaction at equilibrium of greater than substantially 5.
  • the method includes employing the LIO and the borane isomerization catalyst in a mole ratio in a range of from 1 : 1 to 50: 1.
  • the LIO and the borane isomerization catalyst can be added to the reaction vessel in a mole ratio in a range of from 1 :1 to 50:1 to form a mixture including the adduct from the LIO and the borane isomerization catalyst, the adduct having an alkyl group bonded to boron at a nonterminal position of the alkyl group.
  • the LIO and the borane isomerization catalyst can form the adduct at a temperature in a range of from 10 °C to 30 °C.
  • the mixture can include the LIO, the borane isomerization catalyst, and the adduct, among others for example.
  • the method can include removing excess LIO from the mixture.
  • Removing excess LIO can be accomplished by devolitization, among other processes. Removing excess LIO can occur in another vessel (e.g., other than the reaction vessel). Removed excess LIO can be recycled to the reaction vessel.
  • the method includes isomerizing the adduct to move the alkyl group bonded to boron to a terminal position of the alkyl group.
  • the contents of the reaction vessel can be heated to a temperature in a range of from 25 °C to 140 °C to move the alkyl group bonded to the boron to a terminal position of the alkyl group.
  • the method includes dehydroborating the adduct in the presence of a scavenger olefin to form a LAO and a scavenger adduct that is formed from the scavenger olefin and the borane isomerization catalyst.
  • Dehydroborating the adduct can occur in the reaction vessel and/or another vessel such as a falling film evaporator, for example.
  • scavenger adducts are useful for separating LAOs from the borane isomerization catalyst, for example.
  • the scavenger olefin is any olefin capable of reacting with the adduct
  • the scavenger olefin may be selected from a group consisting of cyclododecene, limonene, pinene, carene or a combination thereof.
  • the reaction between the adduct and the scavenger olefin can be thermodynamically driven and/or driven by mass action (e.g., by selective removal of the LAO).
  • the scavenger olefin may be employed in mole ratio in a range of from 0.5:1 to 10: 1, where the mole ratio indicates the ratio of scavenger olefin to adduct, i.e. the adduct having the alkyl group bonded to boron to the terminal position of the alkyl group.
  • LAOs are linear alpha olefins having from four carbons to twelve carbons.
  • LAOs examples include, but are not limited, to 1-butene, 1-pentene, 1-octene, 1- hexene or a combination thereof.
  • the LAOs are formed as the alkyl group bonded to the boron at the terminal position of the alkyl group is separated from the adduct.
  • the scavenger adduct is formed by the scavenger olefin and the borane isomerization catalyst separated from the adduct.
  • the method can include regenerating the borane isomerization catalyst from the scavenger adduct.
  • the scavenger adduct can be heated to a temperature in a range of from 150 °C to 200 °C, to regenerate the borane isomerization catalyst (e.g., separate the borane isomerization catalyst and the scavenger olefin from the scavenger adduct).
  • the method can include recycling the borane isomerization catalyst to the reaction vessel.
  • the method can include removing a number of
  • the method can include dimerizing a portion of the LAO to form a LIO and adding the formed LIO to the reaction vessel.
  • the method can employ a solvent to form a solution including the LIO.
  • solvents include, but are not limited to, benzene, cyclohexane, toluene or a combination thereof.
  • the solvent may be employed in a range of from greater than 0 weight percent to 85 weight percent, where the weight percent is based upon weight of the LIO and the solvent.
  • the method can occur in one or more continuous flow reactors.
  • continuous flow reactors include, but are not limited to, plug-flow reactors and fluidized bed reactors.
  • portions and/or all of the method can occur in one or more batch reactors.
  • H-FAB 6w(pentafluorophenyl)borane
  • FAB triethylsilane
  • FAB tris(pentafluorophenyl)boron
  • Example (Ex) 1 Conversion of trans-4-octene to 1 -octene.
  • NMR indicates approximately an 80% yield of the adduct. Isomerize the adduct by heating the contents of the reaction vessel to 60 °C for 10 hrs to move the alkyl group bonded to boron to a terminal position of the alkyl group and form 1-octyl-FAB. NMR indicates
  • Ex 1 shows contacting a LIO with a borane isomerization catalyst in a reaction vessel forms 4-octyl-FAB, which isomerizes to 1-octyl-FAB.
  • 1-octene is produced via dehydroboration of 1-octyl FAB in the presence of limonene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention consiste à mettre en contact une OIL avec un catalyseur d'isomérisation au borane dans un récipient de réaction pour former un mélange qui contient un produit d'addition formé à partir de l'OIL et du catalyseur d'isomérisation au borane, le produit d'addition ayant un groupe alkyle lié au bore à une position non terminale du groupe alkyle, à isomériser le produit d'addition pour déplacer le groupe alkyle lié au bore sur une position terminale du groupe alkyle, et à deshydroborer le produit d'addition en présence d'un piège à oléfines pour former une AOL et un piège au produit d'addition qui est formé à partir du piège à oléfines et du catalyseur d'isomérisation au borane.
PCT/US2013/048431 2012-06-29 2013-06-28 Conversion d'oléfines internes linéaires en alpha oléfines linéaires WO2014004954A1 (fr)

Applications Claiming Priority (2)

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US201261666373P 2012-06-29 2012-06-29
US61/666,373 2012-06-29

Publications (1)

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WO2014004954A1 true WO2014004954A1 (fr) 2014-01-03

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB874507A (en) * 1958-11-28 1961-08-10 Exxon Research Engineering Co Method for isomerizing olefins
US3063966A (en) 1958-02-05 1962-11-13 Du Pont Process of making wholly aromatic polyamides
US3227793A (en) 1961-01-23 1966-01-04 Celanese Corp Spinning of a poly(polymethylene) terephthalamide
US3414645A (en) 1964-06-19 1968-12-03 Monsanto Co Process for spinning wholly aromatic polyamide fibers
US3600350A (en) 1970-04-20 1971-08-17 Du Pont Poly(p-benzamide) composition,process and product
US3767756A (en) 1972-06-30 1973-10-23 Du Pont Dry jet wet spinning process
US4018735A (en) 1974-07-10 1977-04-19 Teijin Limited Anisotropic dopes of aromatic polyamides
JPS62223134A (ja) * 1979-03-28 1987-10-01 Kureha Chem Ind Co Ltd 高級α‐オレフインの製造方法
RU2045586C1 (ru) 1993-07-09 1995-10-10 Владимир Николаевич Сугак Анизотропный раствор для формования нити и нить, полученная из этого раствора
US5474842A (en) 1991-08-20 1995-12-12 Hoiness; David E. Aramid particles as wear additives
US5646234A (en) 1994-04-06 1997-07-08 Hoechst Ag Production of fibers or films using specific forming solutions and the fibers of films obtainable thereby
US5667743A (en) 1996-05-21 1997-09-16 E. I. Du Pont De Nemours And Company Wet spinning process for aramid polymer containing salts

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063966A (en) 1958-02-05 1962-11-13 Du Pont Process of making wholly aromatic polyamides
GB874507A (en) * 1958-11-28 1961-08-10 Exxon Research Engineering Co Method for isomerizing olefins
US3227793A (en) 1961-01-23 1966-01-04 Celanese Corp Spinning of a poly(polymethylene) terephthalamide
US3414645A (en) 1964-06-19 1968-12-03 Monsanto Co Process for spinning wholly aromatic polyamide fibers
US3600350A (en) 1970-04-20 1971-08-17 Du Pont Poly(p-benzamide) composition,process and product
US3767756A (en) 1972-06-30 1973-10-23 Du Pont Dry jet wet spinning process
US4018735A (en) 1974-07-10 1977-04-19 Teijin Limited Anisotropic dopes of aromatic polyamides
JPS62223134A (ja) * 1979-03-28 1987-10-01 Kureha Chem Ind Co Ltd 高級α‐オレフインの製造方法
US5474842A (en) 1991-08-20 1995-12-12 Hoiness; David E. Aramid particles as wear additives
US5811042A (en) 1991-08-20 1998-09-22 E. I. Du Pont De Nemours And Company Process for making aramid particles as wear additives
RU2045586C1 (ru) 1993-07-09 1995-10-10 Владимир Николаевич Сугак Анизотропный раствор для формования нити и нить, полученная из этого раствора
US5646234A (en) 1994-04-06 1997-07-08 Hoechst Ag Production of fibers or films using specific forming solutions and the fibers of films obtainable thereby
US5667743A (en) 1996-05-21 1997-09-16 E. I. Du Pont De Nemours And Company Wet spinning process for aramid polymer containing salts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DANIEL J. PARKS ET AL: "Synthesis, Properties, and Hydroboration Activity of the Highly Electrophilic Borane Bis(pentafluorophenyl)borane, HB(C 6 F 5 ) 2 1", ORGANOMETALLICS, vol. 17, no. 25, 1 December 1998 (1998-12-01), pages 5492 - 5503, XP055083837, ISSN: 0276-7333, DOI: 10.1021/om980673e *

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