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WO1996026913A1 - Procede d'elaboration pour poly-n-butenes a grande viscosite - Google Patents

Procede d'elaboration pour poly-n-butenes a grande viscosite Download PDF

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Publication number
WO1996026913A1
WO1996026913A1 PCT/FI1995/000106 FI9500106W WO9626913A1 WO 1996026913 A1 WO1996026913 A1 WO 1996026913A1 FI 9500106 W FI9500106 W FI 9500106W WO 9626913 A1 WO9626913 A1 WO 9626913A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
cocatalyst
butene
oligomerization
olefin
Prior art date
Application number
PCT/FI1995/000106
Other languages
English (en)
Inventor
Mika Kapanen
Erkki Halme
Salme Koskimies
Original Assignee
Neste Oy
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 Neste Oy filed Critical Neste Oy
Priority to AU18133/95A priority Critical patent/AU1813395A/en
Priority to PCT/FI1995/000106 priority patent/WO1996026913A1/fr
Publication of WO1996026913A1 publication Critical patent/WO1996026913A1/fr

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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
    • 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
    • C07C2527/12—Fluorides
    • C07C2527/1213—Boron fluoride
    • 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
    • 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
    • C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts

Definitions

  • This patent application relates to the co-oligomerization of olefins or olefin blends with an aromatic or alicyclic hydro ⁇ carbon which contains a vinylic or olefinic pendant group.
  • a complex made up of a Friedel-Crafts catalyst and a cocatalyst is used for catalyzing the oligomerization reaction.
  • oligomerization and polymerization of various olefins is commonly known technology. These reactions can occur thermally without a catalyst, as a radical reaction with, for example, peroxide catalysts, coordination polymerization catalysts, through an anionic mechanism with basic catalysts, through a cationic mechanism with Friedel-Crafts catalysts, and through polymerization by using molecular sieves, e.g. zeolites.
  • the anionic mechanism is mainly used for olefin dimerization reactions, for example for the dimerization of propylene to 4- methyl-1-pentene.
  • Coordination polymerization is mainly used for the preparation of various plastics, such as polyethylene, polypropylene and poly-1-butene, in which it is desired to determine in advance very precisely the structure of the prod ⁇ uct to be formed.
  • the cationic mechanism and polymerization with molecular sieves in olefin polymerization produce only light oligomers or viscous liquids, so-called liquid polymers.
  • the catalysts used in the cationic mechanism have been Lewis acids such as BF3, AICI3, AlBr 3 , TiCl 4 , SnCl 4 , etc. It is known that Lewis acid catalysts cannot alone initiate a polymeriza ⁇ tion reaction but require a proton donor, i.e. a cocatalyst. Such cocatalysts include water, alcohols, carboxylic acids, inorganic acids, certain alkyl halides, and halogens.
  • the oli ⁇ gomerization can be performed in bulk, i.e. without an auxil ⁇ iary solvent, or in the presence of an inert solvent.
  • Such inert solvents include alkanes, such as hexane and heptane, and cycloalkanes, such as cyclohexane and cycloheptane.
  • Oligomerization takes place in the presence of an active cat ⁇ alyst complex.
  • a catalyst complex can be prepared through a reaction between BF 3 and a cocatalyst, separately from the oligomerization reactor or in the reactor in situ.
  • the cocat ⁇ alyst is in general said water, short-chain alcohols or organic acids.
  • the product distribution produced by using a BF 3 catalyst complex in many cases contains considerable amounts of light oligomers, i.e. dimers, trimers and tetramers.
  • the uses of these light fractions mainly include various solvents and fuels having a low degree of refinement.
  • the hydrocarbon component used in the preparation of various additives for lubricants and plastics consists of oligomers of iso-butene and Raffinate I stream, which contains, in addition to the main component i-butene, also n-butenes and inert butanes.
  • Nipe et al. (US 4 225 739) also used a BF 3 - 1-butanol catalyst for copolymerization in which the short-chain olefin was pro ⁇ pylene and the long-chain olefin was a blend of C ⁇ -C ⁇ g olefins.
  • Larkin et al. (US 4 395 578, US 4 417 082 and US 4 434 309) used in copolymerization 1-butene or propylene as the short- chain olefin and one to three Cg.-.C ⁇ g alkenes of different lengths as the long-chain olefin.
  • the catalyst system consisted of BF and 1-butanol, and possibly a transition-metal cation.
  • Pasky (US 4 451 684) used, for co-oligomerization, propylene oligomers having a mean carbon chain length of 12...18 and C5- Cg olefins, the catalyst complex being made up of BF3 and but- anol.
  • Halaska et al. used BF3 or alkyl aluminum chlor ⁇ ides having the general formula R2AICI or RAICI2, where R is a c l-8 a lk ⁇ l « As cocatalysts they used HF, HCl or compounds which contain a reactive chlorine or fluorine atom bound to a ter ⁇ tiary, benzylic or allylic carbon atom.
  • R is a c l-8 a lk ⁇ l «
  • These catalyst systems are the same as were the catalysts used by Loveless et al. (US 4 041 098) for the oligomerization of C3...C24 olefins, pref- erably Cg...C 10 olefins.
  • Sheng and Arnold used as the cocatalyst a car- boxylic acid having at least five carbon atoms. Their process was a two-step process. The first step comprised the oligomer ⁇ ization of 1-butene to a fraction in which the number-average carbon chain length is 8...18, preferably 10...16 carbon atoms. In the second step, the product fraction of the first step was co-oligomerized with a C ...C ⁇ -olefin. In each step, a cat ⁇ alyst complex prepared through a reaction between BF3 and a cocatalyst, separately from the oligomerization reactor, was used in the batch reaction.
  • the present invention relates to the oligomerization of olefins and blends thereof with alicyclic or aromatic compounds which contain a vinylic or olefinic pendant group by using as the catalyst Friedel-Crafts catalysts, preferably boron tri- fluoride.
  • the olefin is preferably 1-butene and the olefin blend is a so-called Raffinate II stream, which has 1- and 2-butenes and inert butanes as the principal com ⁇ ponents.
  • the alicyclic compound which con ⁇ tains a vinylic or olefinic pendant group is preferably vinyl cyclohexane, vinyl cyclohexene and its various isomers, allyl cyclohexane, or allyl cyclohexene and its various isomers.
  • the aromatic compound which contains a vinylic or olefinic pendant group is preferably styrene or ⁇ -methyl styrene.
  • the catalyst system comprises a complex made up of a Friedel-Crafts catalyst and a cocatalyst, which may be an alcohol, a carboxylic acid, water or an inorganic acid.
  • the Friedel-Crafts cat ⁇ alyst is boron trifluoride.
  • the cocatalyst is preferably a carboxylic acid or alcohol.
  • oligomers of olefins and olefin blends are technologically important intermediates, which can be used for the preparation of highly varied end products.
  • the oligomers prepared according to the present invention con ⁇ tain in the polymer chain an olefinic double bond with in ⁇ creased reactivity.
  • the oligomer properties to be mentioned include resistance to oxidation under the effect of heat, a low pour point, a low volatility, and a good temperature-viscosity dependence. The said properties are important especially if the oligomers are used for the production of lubricants and their additives.
  • the process according to the invention can also be used for producing oligomers having a low viscosity index. These oligomers and their derivatives are used mainly for applications other than lubricants and their additives.
  • the oligomers can be used as intermediates in the production of various chemical com ⁇ pounds.
  • the oligomers are used, for example, for the preparation of alkyl benzenes, alkyl phenols, and alkyl succinic acid anhydride.
  • Alkyl benzenes and alkyl phenols are used for preparing surfactants by sulfona- tion.
  • the oligomers can be used, for example, in the preparation of sulfonates, phenates, thiophosphonates, and ash-free dispersing agents, alkenyl suc- cinimides.
  • the molar mass of the hydrocarbon component is approx. 350...1200 g/mol, in alkenyl succinimide as high as 2500 g/mol.
  • Other uses include lubricants in two- stroke spark-ignition engines, machining oil in the rolling and drawing of metallurgical materials, in the leather and rubber industries, and in rendering various surfaces hydrophobic.
  • the oligomerization reactions were performed, unless otherwise stated, in a steel reactor which had a volume of 300 ml and which was cooled internally by using a cooling coil and was, when necessary, heated by using an electric bath.
  • the reactor was equipped with a mixer.
  • the temperature of the reaction mixture was monitored by using a thermocouple.
  • the aim was to maintain the temperature of the reaction mixture at the set value with a precision of ⁇ 1 °C.
  • the reagents used and their amounts are given in the examples.
  • the reactor was first charged with the solvent, if necessary, and the cocatalyst, and with the aromatic or cyclic hydrocarbon containing a vinylic or olefinic pendant group, indicated in the examples.
  • the olefin or the olefin blend and the catalyst were batched into the liquid phase in the reactor.
  • Liquid ole ⁇ fin was fed in the desired amount into the reactor.
  • the reactor was pressurized with BF 3 gas, whereupon the catalyst complex formed in situ and the reaction started immediately.
  • the reactor pressure was maintained constant by means of BF3 gas. The pressure was sufficient to keep the monomers in the liquid phase.
  • reaction parameters used were as follows: pressure 0...10 bar, indicated as overpressure, reaction tem ⁇ perature 10...70 °C, and reaction time 1...4 hours.
  • the reac ⁇ tion was terminated by adding into the reactor an excess of either an NaOH solution or water.
  • the product fraction was washed with an NaOH solution and was neutralized with water after the wash.
  • the examples depict the various possibilities of the process to produce oligomer fractions with different monomer blends.
  • the control examples are Examples 1...6, the examples illustrating the present invention are Examples 7...14. It should be borne in mind that by the use of the process being disclosed it is possible to produce highly different product fractions, and so the examples are only indicative of the possibilities of the process.
  • Example 16 Solvent, toluene, was used in Example 16 (22.7 % by weight of the feed) and in Example 18 (22.9 % by weight of the feed).
  • KV Q and V 10 kinematic viscosities measured at 40 °C and 100 °C, respectively; result indicated in cSt

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé qui consiste à utiliser du trifluorure de bore et un co-catalyseur pour oligomériser des oléfines, celles-ci consistant de préférence en un mélange d'hydrocarbures qui contient des 1-butènes et/ou des 2-butènes, par exemple sous la forme du courant dit des produits raffinés II et d'hydrocarbures cycliques aromatiques ou bien alicycliques. De préférence, on peut choisir pour les hydrocarbures aromatiques un styrène, un alpha-méthylstyrène, un alkylstirène, ou bien un mélange de ces stirènes, et, pour les hydrocarbures alicycliques, le vinyl cyclohexane, le vinyl cyclohexène, ou bien un mélange des deux. Le co-catalyseur est un alcool aliphatique, un acide carboxylique ou un acide inorganique. L'oligomérisation peut être effectuée avec ou sans support, à une température qui excède 0 °C, la pression étant comprise entre 1 et 10 bar sous l'effet du trifluorure de bore. Il est possible d'utiliser l'oligomère obtenu au moyen d'un tel procédé comme solvant ou bien comme additif dans les combustibles ou les lubrifiants, les tensioactifs, les huiles blanches et les huiles utilisées en cosmétique qui nécessitent une très grande pureté, ainsi que dans les matières plastiques en polychlorure de vinyle (PVC) et à base de polyoléfine. S'agissant des résines à base de polyester et d'ester vinylique, on peut utiliser l'oligomère obtenu pour remplacer en partie le monomère (par exemple, styrène), ce qui permet de réduire l'évaporation des monomères et d'empêcher le retrait en phase de durcissement, et aussi d'améliorer les propriétés optiques des résines en question.
PCT/FI1995/000106 1995-02-27 1995-02-27 Procede d'elaboration pour poly-n-butenes a grande viscosite WO1996026913A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU18133/95A AU1813395A (en) 1995-02-27 1995-02-27 Process for preparation of poly-n-butenes having high viscosity
PCT/FI1995/000106 WO1996026913A1 (fr) 1995-02-27 1995-02-27 Procede d'elaboration pour poly-n-butenes a grande viscosite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FI1995/000106 WO1996026913A1 (fr) 1995-02-27 1995-02-27 Procede d'elaboration pour poly-n-butenes a grande viscosite

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WO1996026913A1 true WO1996026913A1 (fr) 1996-09-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6872692B2 (en) 2001-09-21 2005-03-29 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4967029A (en) * 1989-09-07 1990-10-30 Mobil Oil Corporation Liquid lubricants from alpha-olefin and styrene copolymers
EP0506310A1 (fr) * 1991-03-28 1992-09-30 Texaco Chemical Company Procédé de préparation de bases pour lubrifiants synthétiques par oligomérisation d'oléfines à longue chaîne avec le vinylcyclohexene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4967029A (en) * 1989-09-07 1990-10-30 Mobil Oil Corporation Liquid lubricants from alpha-olefin and styrene copolymers
EP0506310A1 (fr) * 1991-03-28 1992-09-30 Texaco Chemical Company Procédé de préparation de bases pour lubrifiants synthétiques par oligomérisation d'oléfines à longue chaîne avec le vinylcyclohexene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6872692B2 (en) 2001-09-21 2005-03-29 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluid

Also Published As

Publication number Publication date
AU1813395A (en) 1996-09-18

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