WO1993002993A1 - Procede d'oligomerisation de 1-butene - Google Patents

Procede d'oligomerisation de 1-butene Download PDF

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Publication number
WO1993002993A1
WO1993002993A1 PCT/FI1992/000199 FI9200199W WO9302993A1 WO 1993002993 A1 WO1993002993 A1 WO 1993002993A1 FI 9200199 W FI9200199 W FI 9200199W WO 9302993 A1 WO9302993 A1 WO 9302993A1
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Prior art keywords
butene
oligomerization
reaction
acid
mol
Prior art date
Application number
PCT/FI1992/000199
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English (en)
Inventor
Mika Kapanen
Mikko Aalto
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.)
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Publication date
Application filed by Neste Oy filed Critical Neste Oy
Priority to EP92912983A priority Critical patent/EP0641298A1/fr
Publication of WO1993002993A1 publication Critical patent/WO1993002993A1/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
    • C07C2/14—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
    • 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 invention is concerned with a method of oligomerization of 1-butene.
  • the butene used for preparation of oligomers of butene has conventionally been iso- or tert-butene, that has been oligomerized to an oligomer of a suitable molar mass.
  • These oligo- and polymers that are formed in the oligomerization of isobutene are called with a common name, poly-i-butenes or polybutylenes depending on the composition of the starting material.
  • the source of i-butene has mainly been the so called raffinate I flow. In this raffinate I flow there are 1- and 2-butenes as well as butanes in addition to the isobutene. Alternatively the starting material used has been purified isobutene.
  • cationic mechanism One of the most important mechanisms of polymerization of olefines are the cationic mechanism and the coordination polymerization. Of these mechanisms, coordination polymerization is primarily used for preparation of poly-1-butene plastics if the structure of the product to be formed is wished to define very exactly in forehand.
  • the cationic mechanism produces only oligomers or viscotic fluids, so called liquid polymers, in the polymerization of 1-butene.
  • the catalysts used in the cationic mechanism have been Lewis acids such as BF 3 , AlClo, AlBr «, TiCL, SnCL etc. It is known that Lewis acid catalysts cannot alone initiate a polymerization reaction but need a proton donor or a cocatalyst. Such cocatalysts are for example water, alcohols, carboxylic acids, inorganic acids, given alkyl halides or halogenes.
  • the oligomerization can be carried out in bulk, in other words without any auxiliary solvent or in the presence of an inert solvent.
  • Such inert solvents are for example alkanes such as hexane and heptane and cycloalkanes such as cyclohexane and cycloheptane.
  • Oligomers suitable for different applications have thus conventionally been prepared by oligomerization of isobutene or of the raffinate I flow.
  • the catalyst used has been for example BFg and AlClg.
  • water, short-chained alcohols and organic acids have been mentioned as cocatalysts.
  • 1-Butanol has generally been used together with BF « as cocatalyst when the intention has been to produce fractions suitable as lubricants and additives of those. These fractions have generally been produced by copolymerization.
  • Larkin et al. (US 4 417 082, 4395 578 and 4434309) used 1-butene as short chained define and Cg...C j g alkene as long chained define in the copolymerization.
  • the catalyst system was consisted of BFg and -1-butanol and possibly a transition metal cation.
  • Nipe et al. (US 4 225 739) also used BFg as 1-butanol catalyst for the copolymerization but the short chained olefine was propene instead of 1- butene.
  • Torck et al. for example used a BF -HF complex in tetra methylene sulphone solution as di- and trimerization catalyst.
  • Chen et al. US 4 849 572 used water and/or methanol as cocatalyst and thus the M of the product was 520....1500 g/mol. Halaska et al.
  • Carboxylic acid cocatalysts are very httle known for oligomerization of short- chained olefines. Sheng et al. (US 4 263 465) used a carboxylic acid with not more than five carbon atoms as cocatalyst. Their process was carried out in two steps. The first step comprised 1-butene as a fraction for oligomerization, the numerical average length of the carbon chain of which was 8...18, preferably 10...16 carbon atoms. In the second step the product fraction of the first step is cooligomerized together with Cg...C «g alfaolefines.
  • Carboxylic acids containing for example five carbon atoms have been used for oligomerization of long- chained olefines.
  • patent publication GB 1 378 449 there has for example been used n- and i-valerianic acid, methyl butanoic acid and mixtures of those to catalyst the oligomerization of Cg...C.p olefines together with BFg.
  • Poly-i butene and polybutylene have been produced already in many years even in an industrial scale, but the produc- tion of poly-n-butene by oligomerization of 1-butene is not known.
  • the oligomerization of 1-butene is carried out in a one step process by using a boron trifluoride cocatalyst complex as catalyst, wherein the cocatalyst is water, C 2 -CJ Q monoalcohol or C p -Cg monocarboxylic acid, prefer- ably valerianic acid.
  • a boron trifluoride cocatalyst complex as catalyst, wherein the cocatalyst is water, C 2 -CJ Q monoalcohol or C p -Cg monocarboxylic acid, prefer- ably valerianic acid.
  • the light fractions of poly-i-butene and poly ⁇ butylene can be substituted the numerical average molar mass being 110...ca 650 or even 850 g/mol.
  • the object of this invention is an oligomerization method of 1-butene by which poly-n-butenes can be produced, the numerical average molar mass being in the aforesaid range.
  • Oligomers of short-chained olefines are technically important intermediates which can be used for preparation of very different end products.
  • the most important of the short-chained olefines are propene and different isomers of butene and pentene.
  • the oligomers of butene, M of which is 110...2500 g/mol, is used for example as solvents, fuels, in preparation of chemicals and in prep- * aration of lubricants and additives for those.
  • properties of the oligomers there can be mentioned for example resistance against oxidation caused by heat, a low freezing point, low volatility, and a good temperature- viscosity relation. The aforesaid properties are important, especially when the oligomers are used for producing lubricants and additives for those. Because of the reactive double bond, the oligomers can be used as intermediates in the production of different chemical compounds.
  • oligomers of 1-butene are used for preparation of for example alkyl benzenes, alkyl phenols and alkyl succinic acid anhydride.
  • Surfactants are prepared from alkyl benzenes and phenols by sulphonation.
  • the oligomers of 1-butene can be used for example for preparing sulphonates, phenates, thiophosponates and ashless dispersants, alkenyl succinic imides.
  • the molar mass of the hydrocar ⁇ bon part in these compounds is ca 350...1200 g/mol, even 2500 g/mol in alkenyl succinic imide.
  • a steel reactor with the volume of 300 ml was internally cooled by a cooling coil and, when necessary, externally heated by a outer electric bath.
  • the reactor was equipped with a mixer.
  • 1-Butene and the catalyst were fed into the reactor via a valve to the liquid phase.
  • the temperature of the reaction mixture was studied by a thermocouple.
  • the temperature of the reaction mixture was tried to keep at the wished value with the precision of ⁇ 1°C from the desired value.
  • 100 ml n-heptane was added as solvent to the reactor in nitrogen atmosphere and also cocatalyst the amount of which is mentioned in the example.
  • the solvent had been dried with molecular sieves. Thereafter 60...70 g of liquid 1-butene was added to the reactor.
  • the reactor was pressurized with BFg gas and the catalyst complex was formed in situ and the reaction started immediately.
  • the pressure of the reactor was kept constant by means of BFg gas.
  • the reaction parameters were the following: the pressure 2.5...10 bar expressed as over pressure, the reaction temperature 10...70°C and the reaction time 1...121 minutes or 1...6 hours.
  • the reaction was finished by adding an excess of either NaOH solution or water to the reactor.
  • the product fraction was washed with NaOH solution and thereafter with water until the pH of the fraction was neutral.
  • the product distribution was analyzed by the GC method. Examples 1 and 2
  • the cocatalyst used was 14.2 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 4.0 bar and the temperature 20°C.
  • the reaction time in Example 1 was 9 minutes and in Example 2 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the numerical average molar mass of the product distributions of the Examples were 237 g/mol and 310 g/mol.
  • the cocatalyst used was 5.1 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 4.0 bar and the temperature 20°C.
  • the reaction time in Example 3 was 9 minutes and in Example 4 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the numerical average molar mass of the product distributions of the Examples were 268 g/mol and 383 g/mol.
  • the viscosity index 81 was defined for this unhydrated product, measured in 100°C, the kinematic viscosity being 4.3 cSt.
  • the cocatalyst used was 37.8 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 4.0 bar and the temperature 20°C.
  • the reaction time in Example 5 was 9 minutes and in Example 6 49 minutes. After the reaction times mentioned the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the numerical average molar mass of the product distributions of the Examples were 220 g/mol and 302 g/mol.
  • the cocatalyst used was 13.4 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 2.5 bar and the temperature 20°C.
  • the reaction time was in Example 7 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the cocatalyst used was 13.0 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 4.0 bar and the temperature 20°C.
  • the reaction time was 6 hours. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the numerical average molar mass of the product distributions of the Example were 386 g/mol.
  • the cocatalyst used was 4.8 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 10 bar and the temperature 10°C.
  • the reaction time in Example 9 was 9 minutes and in Example 10 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the cocatalyst used was 4.9 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 10 bar and the temperature 40°C.
  • the reaction time in Example 11 was 4 minutes and in Example 12 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the numerical average molar mass of the product distributions of the Examples were 275 g/mol and 371 g/mol.
  • the lower fractions (C.g_) were separated by vacuum distillation from the product of Example 6, whereby M - 429 g/mol.
  • the viscosity index 82 was defined for this unhydrated product measured in 100°C, the kinematic viscosity being 7.0 cSt.
  • the cocatalyst used was 5.0 mmol n-valerianic acid per one mole of 1-butene.
  • the pressure of the reactor was 10 bar and the temperature 70°C.
  • the reaction time in Example 13 was 9 minutes and in Example 14 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
  • the hydrogen carbon phases were analyzed and the results were the following:
  • the numerical average molar mass of the product distributions of the Examples were 219 g/mol.
  • 1-butene can be oligomerized also with other organic acid cocatalysts than n- valerianic acid, both with alcohols and water as Examples 15...21 show.
  • the pres ⁇ sure of the reactor was 4.0 bar and the temperature 20°C, the reaction time 5 being 36 minutes.
  • the cocatalysts were acetic acid (Ex. 15), n-octanoic acid (Ex. 16), ethanol (17), 1-pentanol (18), 1-octanol (19) and water (20).
  • the comparison examples is a reaction carried out in the same conditions with n-valerianic acid.
  • the cocatalyst used was 14.5...15.9 mmol cocatalyst per one mole as 1-butene.

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

Abstract

L'invention se rapporte à un procédé d'oligomérisation de 1-butène en un carbone d'hydrogène contenant en moyenne de 12 à 48 atomes de carbone ainsi qu'une liaison double insaturée, la température de reaction étant comprise entre -30 et 90 °C environ, la pression totale entre 1 et 15 bar environ, et le temps de retenue dans la réaction étant compris entre 5 minutes à 10 heures environ, le procédé consistant à utiliser, comme catalyseur, un complexe de BF3 et d'eau, un monoalcool C2-C10 ou un acide monocarboxylique C2-C8. Le produit obtenu peut être utilisé comme solvant ou lubrifiant, et comme un intermédiaire au cours de la préparation de différents produits chimiques tels que des lubrifiants ou des additifs de ceux-ci.
PCT/FI1992/000199 1991-08-02 1992-06-26 Procede d'oligomerisation de 1-butene WO1993002993A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP92912983A EP0641298A1 (fr) 1991-08-02 1992-06-26 Procede d'oligomerisation de 1-butene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI913690A FI90231C (fi) 1991-08-02 1991-08-02 Menetelmä 1-buteenin oligomeroimiseksi
FI913690 1991-08-02

Publications (1)

Publication Number Publication Date
WO1993002993A1 true WO1993002993A1 (fr) 1993-02-18

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PCT/FI1992/000199 WO1993002993A1 (fr) 1991-08-02 1992-06-26 Procede d'oligomerisation de 1-butene

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EP (1) EP0641298A1 (fr)
FI (1) FI90231C (fr)
WO (1) WO1993002993A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI93828C (fi) * 1992-12-31 1995-06-12 Neste Oy Menetelmä olefiiniseoksien oligomeroimiseksi, menetelmällä valmistettu oligomeeri ja sen käyttö

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263465A (en) * 1979-09-10 1981-04-21 Atlantic Richfield Company Synthetic lubricant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263465A (en) * 1979-09-10 1981-04-21 Atlantic Richfield Company Synthetic lubricant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Makromol. Chem., Vol. 191, 1990, ALDO PRIOLA: "Presence of Fragmentation Products in the Cationic Oligomerization of 1-Butene", pp 725-730. *

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Publication number Publication date
EP0641298A1 (fr) 1995-03-08
FI913690A0 (fi) 1991-08-02
FI90231C (fi) 1994-01-10
FI913690A (fi) 1993-02-03
FI90231B (fi) 1993-09-30

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