EP0866784A1 - Verfahren zur oligomerisierung von olefinen sowie katalysator - Google Patents

Verfahren zur oligomerisierung von olefinen sowie katalysator

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Publication number
EP0866784A1
EP0866784A1 EP96944392A EP96944392A EP0866784A1 EP 0866784 A1 EP0866784 A1 EP 0866784A1 EP 96944392 A EP96944392 A EP 96944392A EP 96944392 A EP96944392 A EP 96944392A EP 0866784 A1 EP0866784 A1 EP 0866784A1
Authority
EP
European Patent Office
Prior art keywords
olefin
oligomenzation
catalyst
boron
pendant
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.)
Withdrawn
Application number
EP96944392A
Other languages
English (en)
French (fr)
Inventor
Tze-Chiang Chung
Ruidong Ding
Ronald L. Shubkin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Corp North America Inc
Original Assignee
BP Corp North America Inc
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
Priority claimed from US08/572,224 external-priority patent/US5945574A/en
Priority claimed from US08/572,278 external-priority patent/US5811617A/en
Application filed by BP Corp North America Inc filed Critical BP Corp North America Inc
Publication of EP0866784A1 publication Critical patent/EP0866784A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • 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
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • 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
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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

Definitions

  • This invention relates generally to the preparation of alpha-olefin oligomers which are useful as synthetic lubricants and functional fluids and more particularly to a novel catalyst system and a novel catalytic process for conducting such oligome ⁇ zations
  • BACKGROUND Alpha-olefin oligomers and their use as synthetic lubricants are well-known
  • the oligomers are usually hydrogenated in order to improve their stability
  • Hydrogenated oligomers produced from 1-alkenes, especially linear 1-alkenes having in the range of about 8 to about 14 carbon atoms are generally deemed most suitable for use as synthetic lubricants and fluids
  • Hydrogenated oligomer oils with viscosities of about 2-10 cSt at 100°C are typically used for general lubricating oil applications
  • These materials are, in general mixtures of different percentages of dimer, trimer tetramer pentamer and, in the case of the higher viscosity products in this range, higher oligomers as well
  • hydrogenated oligomers with still higher viscosities are desired
  • U S Pat No 5,288,677 discloses immobilized Lewis acid catalysts and their use as catalysts for the polymerization of isobutylene, mixed butenes and copolymenzation of monomers including 1 -butene, ethylene and 1 - hexene
  • One of the catalysts used for polymerization of isobutylene is hydroxylated polybutene-1 copolymer which has been reacted with BF 3 in a manner to form a sigma ( ⁇ ) bond between the boron and oxygen atoms
  • this copolymer is depicted in simplified form in the patent as PB-O-BF 2 ("PB" referring to polybutene) Additional experiments have been conducted using PP-0-BF 2 catalyst systems, such as
  • PP-0-BF 2 /HCI PP-0-BF 2 /t-BuCI
  • PP-0BF 2 /BF 3 gaseous BF 3
  • PP refers to polypropylene
  • n-BuOH is n-butanol
  • CH 2 CI 2 is methylene chloride
  • t-BuCI is tertiary butyl chloride
  • a 1 -olefin having in the range of about 8 to about 20, and preferably about 8 to about 14 carbon atoms, or a mixture of two or more such 1 -olefins is oligomerized by contact with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron tnhalide, most preferably boron trifluoride, and, optionally, (iii) an organomagnesium halide Studies have indicated that the components (i) and (ii) form a complex under ordinary ambient temperature conditions The oligome ⁇ z
  • Another feature of this invention is the fact that by utilizing appropriate combinations of reaction time and temperature, oligomer product mixtures having different proportions of dimers, trimers, tetramers, etc , can be formed For example, by increasing the temperature products having higher proportions of dimer and trimer and smaller proportions of tetramer and higher oligomers can be formed Similarly, by keeping the temperature relatively low and increasing the reaction period the proportion of dimer in the product mixture can be decreased.
  • the olefins used in making the oligomers are predominately (at least 50 mole %) C 8 -C 20 and preferably predominately C 8 -C 14 straight chain (i e linear) monoolefmically unsaturated hydrocarbons in which the olefinic unsaturation exists in the 1- or alpha-position of the straight chain
  • alpha-olefins are available as articles of commerce, and can be made by thermal cracking of paraffinic hydrocarbons or by well-known Ziegler ethylene chain growth technology
  • Individual olefins can be used as well as mixtures of such olefins
  • Examples of olefins that can be used are 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-tr ⁇ decene, 1-tetradecene, 1- pentadecene, 1-hexadecene, 1-octadecene, 1-
  • oligome ⁇ zable olefins used in the practice of this invention can also be mixtures or combinations of olefins having an average in the range of about 8 to about 20 carbon atoms per molecule, such as mixtures of octenes, decenes and dodecenes having an average carbon content per molecule falling in this range
  • the olefin polymer having pendant omega-hydroxyalkyl groups can be prepared in a two-stage operation In the first stage a polymer having hydrocarbyl-borohydrocarbyl groups depending from the backbone is formed This involves either homopolyme ⁇ zmg or copolymenzing a hydrocarbyl borane monomer having an omega-alkenyl group (e g , B-(5-hexen-1-yl)-9- BBN, B-(7-octen-1-yl)-9-BBN, etc ) as described for example in U S Pat Nos 4,734,472 and 4,751 ,276
  • the polymerization is effected using a suitable Ziegler-Natta catalyst system such as T ⁇ CI 3 AA/AIEt 2 CI (where "AA" means aluminum activated) Procedures for producing the hydrocarbylborane monomers are also described in these two patents When forming the copolymers, the hydrocarbyl borane having an omega-alkenyl
  • Suitable olefin polymers having pendant omega-hydroxyalkyl groups comprise poly(1-alken- ⁇ _-ol) polymers in which the 1-alken- ⁇ -ol units contain 6 to about 12 carbon atoms each, and poly(1-alkene-co-1-alken-__-ol) polymers in which the alkene units contain 3 to about 10 carbon atoms each and the l-alken-ra-ol units contain 6 to about 12 carbon atoms each
  • the homopolymers are typified by poly(1-hexen-6-ol) and poly(1-octen-8-ol)
  • the copolymers include poly(1-butene-co-1-alken- ⁇ -ol) polymers, such as poly(1- butene-co-1-hexen-6-ol) and poly(1-butene-co-1-octen-8-ol), poly(1-pentene- co- 1-alken- ⁇ -ol) polymers, such as poly
  • Poly(propylene-co-1-hexen-6-ol) is a particularly preferred hydroxyalkyl olefin polymer for use in the practice of this invention
  • the olefin polymer having pendant omega-hydroxyalkyl groups is first reacted with an organomagnesium compound, preferably an organomagnesium halide, commonly known as a Grignard reagent
  • an organomagnesium compound preferably an organomagnesium halide, commonly known as a Grignard reagent
  • the olefin polymer is preferably treated in a particulate or finely-divided state while suspended in an anhydrous inert medium such as paraffinic, cycloparaffinic or aromatic hydrocarbon, and under an inert atmosphere
  • the treatment is normally conducted at ordinary room temperatures Reaction periods of up to 8 hours or more at room temperature can be used
  • Suitable hydrocarbylmagnesium halides include alkylmagnesium chlorides and bromides, such as ethylmagnesium chloride, propylmagnesiurp chloride, butylmagnesium chloride, butylmagnesium bromide isobutylmagnesium chloride, pentylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, and the like Cycloalkyl and aryl Grignard reagents such as phenylmagnesium chloride can also be used Alkylmagnesium chlorides are preferred Grignard reagents are often regarded as containing a complex of RMgX or a complex of R 2 Mg and MgX 2 in equilibrium with R 2 Mg and MgX 2 Thus the terms organomagnesium halide and the terms of like import (e g , hydrocarbylmagnesium halide alkylmagnesium halide, etc ) are intended to
  • the product can be dried under vacuum at room temperature or slightly elevated temperature (e.g., up to 65°C) and stored under anhydrous oxygen-free conditions such as under a vacuum or under a dry inert gas such as nitrogen or argon.
  • the product may be kept in an anhydrous, inert liquid such as a paraffinic or cycloparaffinic hydrocarbon (e.g., hydrogenated alpha-olefin oligomer) which can be used as a medium in which the oligomenzation reaction is to be conducted.
  • anhydrous, inert liquid such as a paraffinic or cycloparaffinic hydrocarbon (e.g., hydrogenated alpha-olefin oligomer) which can be used as a medium in which the oligomenzation reaction is to be conducted.
  • the complex of this invention as formed will typically have a magnesium:boron:halide:oxygen atom ratio of 1 :1 :4:1 , respectively.
  • the polymer contains at least one and preferably a plurality of pendant groups containing a moiety composed of one atom of magnesium, one atom of boron, four atoms of halide and one atom of oxygen -- a moiety which for convenience may be depicted as -0-Mg-X-BX 3 — such polymer constitutes a composition of this invention
  • oligomenzation is effected by contacting the monomer(s) with a catalytic amount of the catalyst system Typical catalytic amounts fall in the range of about 0.5% to about 30% of the weight of the monomer to be ohgomerized
  • the catalyst system is used in the range of about 1 % to about 15% of the weight of the 1 -olefin monomer with about 5% to about 10% being most preferred when using catalyst formed without use of organomagnesium halide component, for example formed from olefin polymer with pendant omega-hydroxyalkyl groups and boron tnhalide
  • Oligomenzation temperatures are typically in the range of about 0 to about 80°C, and preferably are in the range of about 20 to about 60°C
  • protic catalyst promoters are not required, but can be used if desired Among promoters that can be used are water, carboxylic acids, mineral acids, alcohols, phenols, carboxylic acid esters and anhydrides, ketones, aldehydes, hydroxy ketones, hydroxy aldehydes, alcohol alkoxylates, and mixtures of any two or more of the foregoing If and when used, the amount of such promoter is typically from about 0 001 to about 0 04 moles per mole of 1 -olefin monomer(s)
  • the promoter can be mixed with the olefin feed or the promoter can be charged separately to the reactor, either entirely at the outset or portionwise as the oligomenzation proceeds
  • the 1 -olefin or mixture of 1 -olefins, boron tnhalide, and polymer having pendant omega-hydroxyalkyl groups can be charged to the reactor in any suitable sequence
  • the boron trihalide is introduced directly into a heterogeneous mixture of the 1 -olefin and the solid polymer having pendant omega-hydroxyalkyl groups
  • the catalyst complex or system formed from polymer having pendant omega-hydroxyalkyl groups organomagnesium halide and boron tnhalide is contacted with the 1 -olefin or mixture of 1 -olefins
  • boron trifluoride is the preferred boron tnhalide for use in forming the catalyst system
  • the oligomenzation reaction is typically conducted at about atmospheric pressure, but super-atmospheric pressures can be used, if desired Normally it is unnecessary to exceed pressures of about 100 psig If it is desired to monitor the progress of the reaction, samples of the oligomenzation mixtures can be taken at suitable periods during the course of the reaction and subjected to gas chromatographic (GC) analysis
  • GC gas chromatographic
  • the reaction can be conducted in a single stirred reactor or in a series of reactors Alternatively, the reactor may contain a bed of the catalyst through which the liquid phase is continuously passed or circulated in a closed loop
  • reaction mixture is simply separated from the heterogeneous catalyst for further processing such as distillation and/or hydrogenation Unreacted olefin can be recovered and recycled
  • this invention provides a process which comprises a) conducting a first or initial reaction of a series of separate oligomenzation reactions by contacting at least one oligome ⁇ zable 1 -olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (u) a boron tnhalide, and, optionally, (iii) an organomagnesium halide, whereby the oligomenzation results in a reaction mixture comprising a liquid alpha-
  • Solvents or reaction diluents such as suitable paraffinic or naphthenic oils or paraffinic, cycloparaffinic or aromatic hydrocarbons such as hexane heptane, octane, decane, cyclohexane, toluene, xylene, etc can be employed if desired Excess unreacted olefin can also serve as a diluent Whenever deemed necessary or desirable, the oligomer can be recovered from the liquid phase in which it is formed by conventional procedures such as distillation
  • a preferred catalyst system of this invention namely a system formed from poly(propylene-co-1-hexen-6-ol) ("PP-OH"), boron trifluoride and, in some cases, a hydrocarbon-soluble alkylmagnesium chloride
  • PP-OH poly(propylene-co-1-hexen-6-ol)
  • boron trifluoride and, in some cases, a hydrocarbon-soluble alkylmagnesium chloride
  • a typical procedure for producing PP-OH involves a) forming B-(5-hexen-1-yl)-9-borobicyclo[3.3.1]nonane ("hexenyl- 9-BBN”), b) copolymenzing the hexenyl-9-BBN with propylene to form poly(propylene-co-1 -hexen-6-yl-9-BBN), and c) oxidizing this boron-containing polyolefin polymer to PP-OH by use of sodium hydroxide and
  • a dry 2-liter flask is equipped with a magnetic stirring bar and a connecting tuoe leading to a nitrogen source
  • the flask is thoroughly flushed with nitrogen before the injection inlet is capped with a rubber serum stopple
  • a slight positive pressure of nitrogen is maintained in the flask thereafter
  • the flask is charged via syringe with 190 mL (1.6 mole) of 1 ,5-hexadiene
  • To the stirred diene solution is then added (via syringe) 800 mL of a 0.5 molar 9- BBN-THF solution
  • the reaction is effected with constant stirring at room temperature After a period of three hours, excess 1 ,5-hexadiene and THF solvent are stripped by distillation at reduced pressure. Pure hexenyl-9-BBN is obtained at 130°C and 10 ⁇ m.
  • Copolymenzation of Pro py lene and Hexenyl-9-BBN in a Continuous Reaction 15 477 g of hexenyl-9-BBN and 200 mL of hexane are placed in an argon filled Parr stirred pressure reactor and sealed Then 12 g of propylene are added under N 2 pressure A slurry of 1 027 g of T ⁇ CI 3 and 4 705 g of AIEt 2 CI in 80 mL of toluene are then added under N 2 pressure to catalyze the copolymenzation Additional propylene is added at 30-m ⁇ nute intervals with 10, 8, 6 and 5 g of propylene added, respectively After the last monomer charge, the reaction is run for an additional hour before terminating the reaction by injection of 100 mL of isopropyl alcohol The reaction mixture is stirred for an additional 1/2 hour before venting the excess pressure and flushing the polymeric product with additional isopropyl alcohol Some typical results for copolymenz
  • Propylene/hexenyl-9-BBN copolymer and 700 mL of THF are placed in a 2-liter round bottom flask equipped with septum and stirrer
  • To the resultant non-homogenous slurry is added dropwise a solution of 19 g of NaOH in 100 mL of degassed water.
  • the flask is then cooled to 0°C before slowly adding 87.6 g of degassed 30% H 2 0 2 solution via a double tipped needle.
  • the reaction mixture is allowed to slowly come to room temperature before heating up to 55°C for 6 hours.
  • the PP-OH polymer poly(propylene- co-1-hexen-6-ol), is then precipitated in water, squeeze dried, and placed in a slurry 500 mL of methanol After 3 hours of vigorous stirring , approximately 75 mL of MeOH is distilled off under N 2 to remove boric acid-methanol azeotrope. The polymer is again precipitated in water , squeeze dried , washed with acetone, and dried under high vacuum at 45°C. Typical properties of the PP-OH polymer formed in this manner and of polypropylene homopolymer made by the same polymerization method (Run No 5) are summarized in Table 2. The PP-OH polymers of Run Nos .
  • Poly(propylene-co-1-hexen-6-ol (PP-OH polymer)) containing 3 mole % of hexenol groups, prepared as in Example 3, is ground to a fine powder and vacuum dried for two hours
  • the dried PP- OH polymer (6 grams) is suspended in 40 mL of anhydrous, oxygen-free hexane, and then 50 mmol of butylmagnesium chloride is introduced into the slurry
  • the mixture is kept at room temperature for five hours
  • the resultant complex (PP-OH-Mg-CI) is in the form of powdery solids, and is separated from the liquid phase by filtration through a glass frit and washed three times with anhydrous, oxygen-free hexane
  • the PP-O-Mg-CI powder is then resuspended in 40 mL of dry, oxygen-free hexane, and while continuously stirring the mixture, boron trifluoride is introduced at atmospheric pressure over a three-hour period

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP96944392A 1995-12-13 1996-12-13 Verfahren zur oligomerisierung von olefinen sowie katalysator Withdrawn EP0866784A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US08/572,224 US5945574A (en) 1995-12-13 1995-12-13 Olefin oligomerization process and catalysts therefor
US572224 1995-12-13
US572278 1995-12-13
US08/572,278 US5811617A (en) 1995-12-13 1995-12-13 Olefin oligomerization process
PCT/US1996/019988 WO1997021651A1 (en) 1995-12-13 1996-12-13 Olefin oligomerization process and catalyst

Publications (1)

Publication Number Publication Date
EP0866784A1 true EP0866784A1 (de) 1998-09-30

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ID=27075784

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96944392A Withdrawn EP0866784A1 (de) 1995-12-13 1996-12-13 Verfahren zur oligomerisierung von olefinen sowie katalysator

Country Status (4)

Country Link
EP (1) EP0866784A1 (de)
JP (1) JP2000502084A (de)
CA (1) CA2239182A1 (de)
WO (1) WO1997021651A1 (de)

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Publication number Priority date Publication date Assignee Title
JPWO2010117028A1 (ja) * 2009-04-10 2012-10-18 出光興産株式会社 αオレフィンオリゴマーおよびその製造方法

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Publication number Priority date Publication date Assignee Title
US5288677A (en) * 1991-06-28 1994-02-22 Exxon Chemical Patents Inc. Immobilized Lewis acid catalysts

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* Cited by examiner, † Cited by third party
Title
See references of WO9721651A1 *

Also Published As

Publication number Publication date
CA2239182A1 (en) 1997-06-19
WO1997021651A1 (en) 1997-06-19
JP2000502084A (ja) 2000-02-22

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