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WO2000010945A1 - Fabrication d'alpha-olefines - Google Patents

Fabrication d'alpha-olefines Download PDF

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Publication number
WO2000010945A1
WO2000010945A1 PCT/US1999/018708 US9918708W WO0010945A1 WO 2000010945 A1 WO2000010945 A1 WO 2000010945A1 US 9918708 W US9918708 W US 9918708W WO 0010945 A1 WO0010945 A1 WO 0010945A1
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WO
WIPO (PCT)
Prior art keywords
recited
olefins
alkyl
hydrocarbyl
ethylene
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Application number
PCT/US1999/018708
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English (en)
Inventor
Steven Arthur Svejda
Original Assignee
E.I. Du Pont De Nemours And Company
University Of North Carolina At Chapel Hill
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.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company, University Of North Carolina At Chapel Hill filed Critical E.I. Du Pont De Nemours And Company
Priority to AU54900/99A priority Critical patent/AU5490099A/en
Publication of WO2000010945A1 publication Critical patent/WO2000010945A1/fr

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    • 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

Definitions

  • Linear ⁇ -olefins especially those containing about 6 to about 20 carbon atoms, are important items of commerce, with about 1.5 million tons reportedly being produced in 1992.
  • the ⁇ -olefins are used as intermediates in the manufacture of detergents, as monomers (especially in linear low density polyethylene) , and as intermediates for many other types of products. As a consequence, improved methods of making these compounds are of interest.
  • Most commercially produced ⁇ -olefins are made by the oligomerization of ethylene, catalyzed by various types of compounds, see for instance B. Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH, einheim, 1989, p.
  • World Patent Application 96/23010 describes the use of certain ⁇ -diimine nickel complexes, and cocatalysts such as alkyl aluminum compounds, for the oligomerization of ethylene to linear ⁇ -olefins.
  • the effect of dialkyl aluminum halides on the Schulz-Flory distribution of the resulting product is not disclosed.
  • This invention concerns a process for the production of ⁇ -olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: ethylene; a first compound W of the formula R R A1Y; and a second compound of the formula
  • R and R are each independently hydrocarbyl or substituted hydrocarbyl
  • R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
  • R and R are each independently alkyl; Y is chlorine or bromine; and Q and S are each independently an anion; and wherein an ⁇ -olefin containing 4 to 40 carbon atoms is produced.
  • hydrocarbyl group is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
  • substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are heteroaromatic rings .
  • alkyl aluminum compound a compound in which at least one alkyl group is bound to an aluminum atom.
  • Other groups such as alkoxide, oxygen, and halogen may also be bound to aluminum atoms in the compound.
  • hydrocarbylene herein is meant a divalent group containing only carbon and hydrogen. Typical hydrocarbylene groups are -(CH 2 ) -, -CH 2 CH(CH 2 CH 3 )CH 2 CH 2 - and
  • hydrocarbylene groups herein contain 1 to about 30 carbon atoms .
  • substituted hydrocarbylene herein is meant a hydrocarbylene group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbylene groups herein contain 1 to about 30 carbon atoms . Included within the meaning of "substituted” are heteroaromatic rings.
  • the product of the process described herein is an ⁇ -olefin. It is preferred that in the process a linear ⁇ -olefin is produced. It is also preferred that the ⁇ -olefin contain 4 to 32, preferably 6 to 20, carbon atoms .
  • (I) is used as a catalyst, and a neutral ' Lewis acid, which is an alkyl aluminum compound of the formula R R AIY is also present as part of the catalyst system (sometimes called a "first compound” in the claims) .
  • R AIY is also present as part of the catalyst system (sometimes called a "first compound” in the claims) .
  • Y is chlorine.
  • R are each independently alkyl containing 2 to 6 carbon atoms, and more preferred that R and R are both ethyl.
  • R R AIY abstracts Q or S, a f ⁇ 7 — relatively noncoordinating anion, such as R R A1YS is formed. It will be understood that the formulas such as R R A1YS also includes variation in which the various groups bound to aluminum may be redistributed.
  • Relatively noncoordinating anions are known in the art, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al . , Chem. Rev., vol. 88 p. 1405- 1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference .
  • the temperature at which the process is carried out is about -100°C to about +200°C, preferably about 0°C to about 150°C, more preferably about 25 C to about 100°C. It is believed that at higher temperatures, lower molecular weight ⁇ -olefins are produced, all other factors being equal.
  • the pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. It is also believed that increasing the pressure increases the relative amount of ⁇ -olefin (as opposed to internal olefin) produced.
  • the process to make ⁇ -olefins may be run in a solvent (liquid), and that is preferred.
  • the solvent may in fact be the ⁇ -olefin produced.
  • Such a process may be started by using a deliberately added solvent which is gradually displaced as the reaction proceeds.
  • solvent it is not necessarily meant that any or all of the starting materials and/or products are soluble in the (liquid) solvent.
  • R and R are each independently hydrogen, hydrocarbyl, or R and R taken together are hydrocarbylene to form a ring; and more preferred that R 3 and R4 are both hydrogen or methyl or R and R taken together are
  • R 2 and R5 are hydrocarbyl or substituted hydrocarbyl. What these groups are greatly determines whether the ⁇ -olefins of this process are made, or whether higher polymeric materials, i.e., materials containing over 25 ethylene units, are coproduced or produced almost exclusively. If R 2 and R5 are highly sterically hindered about the nickel atom, the tendency is to produce higher polymeric material. For instance, when R and R are both 2 , 6-diisopropylphenyl mostly higher polymeric material is produced. However, when R 2 and R are both phenyl, mostly the ⁇ -olefins of this process are produced. Of course this will also be influenced by other reaction conditions such as temperature and pressure, as noted above.
  • R and R are phenyl unsubstituted in the ortho positions
  • preferred groups for R 2 and R5 are phenyl, p-methoxyphenyl, p-trifluoromethylphenyl, and p-methylphenyl
  • Q and S are both independently anions, and both are preferably monoanions . However, Q and S taken together may also be a dianion, i.e., an anion having 2 negative charges.
  • Useful anions for Q and/or S are chloride, bromide, alkyl, carboxylate anions, and sulfonates. Preferred anions are chloride, bromide and alkyl.
  • ⁇ -olefins in oligomerization reactions of ethylene to produce ⁇ -olefins, usually a mixture of such ⁇ -olefins is obtained containing a series of such ⁇ -olefins differing from one another by two carbon atoms (an ethylene unit) .
  • the process for preparing ⁇ -olefins described herein produces products with a high percentage, preferably at least about 80 mole percent, more preferably at least about 90 mole percent, of terminal olefinic groups (as opposed to internal olefinic groups).
  • the product mixture also contains a relatively high percentage, preferably at least about 80 mole percent, more preferably at least about 90 mole percent, of molecules which are linear.
  • K n (C n+2 olefin) /n (C n olefin) wherein n(C n olefin) is the number of moles of olefin containing n carbon atoms, and n(C n+2 olefin) is the number of moles of olefin containing n+2 carbon atoms, or in other words the next higher oligomer of C n olefin.
  • the K factor is preferred to be in the range of about 0.6 to about 0.8 to make the ⁇ -olefins of the most commercial interest. It is also important to be able to vary this factor, so as to produce those olefins which are in demand at the moment. It has surprisingly been found that fi 7 cocatalysts of the formula R R AIY give product mixtures with higher Schulz-Flory constants than alkyl aluminum compounds previously used, such as methyl alumoxane .
  • the ⁇ -olefins made herein may be further polymerized with other olefins to form polyolefins, especially linear low density polyethylenes, which are copolymers containing ethylene. They may also be homopolymerized.
  • polyolefins especially linear low density polyethylenes, which are copolymers containing ethylene. They may also be homopolymerized.
  • These polymers may be made by a number of known methods, such as Ziegler-Natta-type polymerization, metallocene catalyzed polymerization, and other methods, see for instance World Patent Application 96/23010, see for instance Angew. Chem., Int. Ed. Engl . , vol. 34, p. 1143-1170 (1995), European Patent Application 416,815 and U.S. Patent 5,198,401 for information about metallocene-type catalysts, and J.
  • the ⁇ -olefins made herein may be converted to alcohols by known processes, these alcohols being useful for a variety of applications such as intermediates for detergents or plasticizers .
  • the ⁇ -olefins may be converted to alcohols by a variety of processes, such as the oxo process followed by hydrogenation, or by a modified single step oxo process (the ⁇ modified Shell process' ) , see for instance B. Elvers, et al . , Ed., Ullmann' s Encyclopedia of Chemical Technology, 5 th Ed., Vol. A18, VCH Verlagsgesellschaft mbH, Weinheim, 1991, p. 321-327, which is hereby included by reference.
  • the ethylene olig ' omerizations herein may also initially be carried out in the solid state by, for instance, supporting an active catalyst or catalyst precursor on a substrate such as silica or alumina.
  • a solution of the catalyst precursor may be exposed to a support having an alkylaluminum compound on its surface.
  • the support may also be able to take the place of the Lewis or Bronsted acid, for instance an acidic clay such as montmorillonite .
  • Another method of making a supported catalyst is to start a polymerization or at least make a nickel complex of another olefin or oligomer of an olefin such as cyclopentene on a support such as silica or alumina. All of these "heterogeneous" catalysts may be used to catalyze oligomerization in the gas phase or the liquid phase.
  • gas phase is meant that the ethylene is transported to contact with the catalyst particle while the ethylene is in the gas phase.
  • Example 1 and Comparative Examples A-G Ethylene oligomerizations were run with a nickel compound of the formula
  • the ethylene pressure was then released, and a suspension of the nickel dibromide complex was added to the autoclave via cannula .
  • the reactor was then sealed and pressurized with ethylene to 2.8 MPa.
  • the reaction was stirred under constant ethylene pressure for 30 min, after which time the pressure was released and the catalyst quenched with acetone and water.
  • An aliquot of the reaction mixture was analyzed by GLC to determine the Schulz-Flory K constant.
  • the integrated areas of the C i2 and C 1 oligomers were used to calculate the Schulz-Flory K constant.
  • the GLC conditions used are as follows: injector and detector temperatures, 250°C; oven temperature program, 100°C/4 min, 8°C/min ramp, 250°C/70 min.
  • Example 1 The solvents were removed on a rotary evaporator, and the residual toluene was removed in vacuo overnight, leaving 4.08 g ethylene oligomers. Lower olefins lost during workup were calculated using the Schulz-Flory K constant determined from a gas chromatograph taken of the olefin products following workup which was calculated as 3.12 g in Example 1. The total oligomer mass produced for Example 1 was 7.20 g (51,000 turnovers). The olefin mixture consisted of 90% ⁇ -olefins as measured by H NMR, and greater than 98 mole percent linear olefins as measured by GLC. Details of the Example and Comparative Examples are given in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Dans l'oligomérisation d'éthylène en α-oléfines linéaires au moyen de complexes de nickel sélectionnés d'α-diimines, l'utilisation de chlorures de dialkylaluminium comme cocatalyseurs permet d'obtenir une répartition présentant une plus grande proportion d'α-oléfines supérieures (constante de Schulz-Flory plus élevée).
PCT/US1999/018708 1998-08-18 1999-08-18 Fabrication d'alpha-olefines WO2000010945A1 (fr)

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AU54900/99A AU5490099A (en) 1998-08-18 1999-08-18 Manufacture of alpha-olefins

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US9694298P 1998-08-18 1998-08-18
US60/096,942 1998-08-18

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003102006A1 (fr) * 2002-05-30 2003-12-11 Exxonmobil Chemical Patents Inc. Catalyseurs a base de metaux de transition tardifs solubles pour oligomerisations iii d'olefines
WO2004007509A1 (fr) * 2002-07-17 2004-01-22 Exxonmobil Chemical Patents Inc. Catalyseurs metalliques a transition tardive destines a la polymerisation et a l'oligomerisation d'olefines
US6733851B2 (en) 2001-11-06 2004-05-11 Cryovac, Inc. Packaging article having heat seal layer containing blend of hyperbranched and semicrystalline olefin polymers
US6737130B2 (en) 2001-11-06 2004-05-18 Cryovac, Inc. Hermetically heat-sealable, pressure-reclosable packaging article containing substantially spherical homogeneous polyolefin
US6761965B2 (en) 2001-11-06 2004-07-13 Cryovac, Inc. Irradiated multilayer film having seal layer containing hyperbranched polymer
US7160834B2 (en) 2003-03-18 2007-01-09 Exxonmobil Chemical Patents Inc. Soluble group-10 α-diimine catalyst precursors, catalysts and methods for dimerizing and oligomerizing olefins
WO2011045701A1 (fr) 2009-10-16 2011-04-21 Sasol Technology (Proprietary) Limited Séparation de composants d'un courant d'hydrocarbures multi-composants qui comprend de l'éthylène
WO2013168098A1 (fr) 2012-05-09 2013-11-14 Sasol Technology (Proprietary) Limited Séparation de composants d'un courant d'hydrocarbure à plusieurs composants
WO2013168099A1 (fr) 2012-05-09 2013-11-14 Sasol Technology (Proprietary) Limited Procédé pour l'oligomérisation d'un hydrocarbure pour former au moins un produit comonomère

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023010A2 (fr) * 1995-01-24 1996-08-01 E.I. Du Pont De Nemours And Company POLYMERES D'OLEFINES ET DE α-OLEFINES ET PROCEDES DE POLYMERISATION

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023010A2 (fr) * 1995-01-24 1996-08-01 E.I. Du Pont De Nemours And Company POLYMERES D'OLEFINES ET DE α-OLEFINES ET PROCEDES DE POLYMERISATION

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6737130B2 (en) 2001-11-06 2004-05-18 Cryovac, Inc. Hermetically heat-sealable, pressure-reclosable packaging article containing substantially spherical homogeneous polyolefin
US6761965B2 (en) 2001-11-06 2004-07-13 Cryovac, Inc. Irradiated multilayer film having seal layer containing hyperbranched polymer
US6733851B2 (en) 2001-11-06 2004-05-11 Cryovac, Inc. Packaging article having heat seal layer containing blend of hyperbranched and semicrystalline olefin polymers
US7161018B2 (en) 2002-05-30 2007-01-09 Exxonmobil Chemical Patents Inc. Soluble late transition metal catalysts for olefin oligomerizations II
US7067450B2 (en) 2002-05-30 2006-06-27 Exxonmobil Chemical Patents Inc. Soluble late transition metal catalysts for olefin oligomerizations III
WO2003102006A1 (fr) * 2002-05-30 2003-12-11 Exxonmobil Chemical Patents Inc. Catalyseurs a base de metaux de transition tardifs solubles pour oligomerisations iii d'olefines
US7429548B2 (en) 2002-05-30 2008-09-30 Exxonmobil Chemical Patents Inc. Soluble late transition metal catalysts for olefin oligomerizations III
WO2004007509A1 (fr) * 2002-07-17 2004-01-22 Exxonmobil Chemical Patents Inc. Catalyseurs metalliques a transition tardive destines a la polymerisation et a l'oligomerisation d'olefines
US7247687B2 (en) 2002-07-17 2007-07-24 Exxonmobil Chemical Patents Inc. Late transition metal catalysts for olefin polymerization and oligomerization
US7160834B2 (en) 2003-03-18 2007-01-09 Exxonmobil Chemical Patents Inc. Soluble group-10 α-diimine catalyst precursors, catalysts and methods for dimerizing and oligomerizing olefins
WO2011045701A1 (fr) 2009-10-16 2011-04-21 Sasol Technology (Proprietary) Limited Séparation de composants d'un courant d'hydrocarbures multi-composants qui comprend de l'éthylène
WO2013168098A1 (fr) 2012-05-09 2013-11-14 Sasol Technology (Proprietary) Limited Séparation de composants d'un courant d'hydrocarbure à plusieurs composants
WO2013168099A1 (fr) 2012-05-09 2013-11-14 Sasol Technology (Proprietary) Limited Procédé pour l'oligomérisation d'un hydrocarbure pour former au moins un produit comonomère

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