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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

• the present invention relates to a method for the oligomerization of olefins and olefin mixtures by using a boron trifluoride cocatalyst complex.
• oligomerization and polymerization of various olefins constitute commonly known technology. These reactions may occur thermally without a catalyst; as radical reactions over, for example, peroxide catalysts or coordination polymerization catalysts; by an anionic mechanism over basic catalysts; by a cationic mechanism over Friedel-Crafts catalysts; and by polymerization by using molecular sieves, for example zeolites.
• An anionic mechanism is used mainly for olefin dimerization reactions, for example, for the dimerization of propylene to 4-methyl-l-pentene.
• Coordination polymerization is used mainly for the preparation of various plastics, such as polyethylene, polypropylene, and poly-1-butene, in which it is desirable to determine in advance precisely the structure of the formed product.
• a cationic mechanism and polymerization by using molecular sieves produce in the polymerization of olefins only light oligomers or viscous liquids, so-called liquid polymers.
• the catalysts used in the cationic mechanism have been Lewis acids such as BF 3 , A1C1 3 , AlBr 3 , TiCl 4 , SnCl 4 , etc. It is known that Lewis-acid catalysts cannot alone initiate a polymerization reaction; they require a proton donor, i.e. a cocatalyst. Examples of such cocatalysts are water, alcohols, carboxylic acids, inorganic acids, certain alkyl halides, and halogens.
• the oligomerization can be carried out in bulk, i.e. without an auxiliary solvent, or in the presence of an inert solvent. Examples of such inert solvents are alkanes such as hexane and heptane, and cycloalkanes such as cyclohexane and cycloheptane.
• Oligomerization occurs in the presence of an active catalyst complex.
• a catalyst complex can be prepared through a reaction between BF 3 and a cocatalyst, separate from the oligomerization reactor or in situ in the reactor.
• Water, short-chain alcohols, and or ⁇ ganic acids are commonly mentioned as the cocatalysts used.
• a 1-butanol cocatalyst has commonly been used together with BF 3 when the object has been to produce fractions suitable for use as lubricants or their additives.
• the monomer has commonly been some long-chain alpha-olefm or internal olefin, or their mixture. In particular, 1-decene has been used as the monomer.
• cocatalysts used with BF 3 and decene include water (Bronstert, EP 271 034), alcohol alcoxylate (Theriot, EP 467 345), alcohol mixtures (Pratt, US 4 587 3- 68), an alcohol ester mixture (Brennan, US 3 997 621), and a mixture of butanol and ethyl glycol or of butanol, ethyl glycol and methylethyl ketone (Morgansson and Vayda, US 4 409 415, US 4 436 947, EP 77 113).
• Nipe et al. (US 4 225 739) also used a BF 3 - 1-butanol catalyst for copolymerization in which the short-chain olefin was propylene and the long-chain olefin was a mixture of C 15 - C 18 olefins.
• Larkin et al. (US 4 395 578, US 4 417 082, and US 4 434 309) used for copolymerization 1-butene or propylene as the short-chain olefin and from one to three C 6 -C lg alkenes of different lengths as the long-chain olefin.
• the catalyst system consisted of BF 3 and 1- butanol and possibly a transition-metal cation.
• Pasky used for co-oligomerization propylene oligomers having an average carbon chain length of 12-18 and C 5 -C 6 olefins, the catalyst complex comprising BF 3 and butanol.
• Nelson and Zuech (US 4 484 014) used a two-step method in which the first step was a coordination catalyzed reaction for the oligomerization of ethylene with TEA (triethyl aluminum) into C 6 -C 16 olefins.
• the reaction occurs at a higher temperature than does normal oligomerization of ethylene.
• the C 6 -C 16 fraction contained branched olefins 10 - 55 %, whereas under normal conditions nearly 100 % straight-chain alpha- olefins would have been produced with TEA.
• the produced mixture of ethylene oligomers was further oligomerized in a batch reaction into a lubricant fraction by using a BF 3 -propanol catalyst.
• the catalyst complex formed in situ through a reaction between BF 3 and propanol.
• Schick and Gemmil (US 4 182 922) used propylene or a mixture of ethylene and propyle ⁇ ne as the monomer feed in the first step.
• This mixture was oligomerized with a catalyst of VOCl 3 and ethyl aluminum chloride.
• the produced oligomer mixture was further co- oligomerized with a longer-chain olefin or a mixture of propylene and a longer-chain olefin by using a BF 3 -propanol complex formed in situ.
• the longer-chain olefin used was butene, hexene or decene.
• the longer-chain olefin or the mixture of propylene and a longer-chain olefin was fed into the second step in a Vi-batch manner.
• the viscosity index of the reaction products was dependent on the longer-chain olefin used. When butene was used, the viscosity index of the end product was 113 and, when decene was used, it was 133.
• Hsia Chen and Tabak (US 4 568 786) used as the feed in the first step a mixture of propylene and butene, which was oligomerized with an HZSM-5-zeolite catalyst. From the formed product there was separated a C 9 -C lg fraction, which was oligomerized in the second step with a zeolite or BF 3 catalyst. In a BF 3 -catalyzed batch reaction, butanol was used as a cocatalyst, and the complex was formed separate from the oligomerization reactor.
• Heckelsberg et al. (US 4 319 064, US 4 386 229) used as the 1st step a disproportionation reaction of 1-octene and/or 1-decene to produce a mixture of C 8 -C ⁇ 8 internal olefins.
• This mixture or a part of it was oligomerized in the 2nd step with a BF 3 -propanol or BF 3 - phosphoric acid catalyst complex formed in situ.
• the catalysts used for the oligomerization of the Raffinate I stream flow which contains n-butenes and inert butanes in addition to the principal component i-butene, depend in part on the desired product distribution.
• Torck et al. (GB 1 312 950) used as a di- and trimerization catalyst, for example, a BF 3 -HF complex in a tetramethylene sulfonic solution.
• Chen et al. US 4 849 572
• used water and/or methanol as a cocatalyst, in which case the product, poly-i-butene, had M Rico 520-1500 g/mol.
• Samson (EP 145 235) used a BF 3 -ethanol complex for the oligomerization of Raffinate I.
• Halaska et al. used BF 3 or alkyl aluminum chlorides having a general formula of R2A1C1 or RA1C1 2 , where R is a C,-C 8 alkyl.
• These catalyst systems are the same as the catalysts used in the patent of Loveless et al. (US 4 041 098) for the oligomerization of C 3 -C 14 olefins, preferably C 8 -C, 0 olefins.
• Carboxylic acid cocatalysts are little known in the oligomerization of short-chain olefins. Sheng and Arnold (US 4 263 465) used as a cocatalyst a carboxylic acid having at maximum five carbon atoms. Their process was a two-step process. The first step comprised the oligomerization of 1-butene into a fraction having a number-average carbon chain length of 8-18, preferably 10-16 carbon atoms. In the second step, the product fraction of the first step is co-oligomerized with C 8 -C, 8 alpha-olefin. In each step there was used in the batch reaction a catalyst complex which had been prepared by a reaction between BF 3 and a cocatalyst, separate from the oligomerization reactor.
• Carboxylic acids among them those containing five carbon atoms, have also been used for the oligomerization of longer-chain olefins.
• n- and i- valeric acid, methylbutanoic acid, or mixtures of these were used for catalyzing the oligomerization of C 6 -C 12 olefins, preferably 1-decene, together with BF 3 .
• the catalyst complex was formed separate from the oligomerization reactor.
• two different flows were fed into the reactor, in a Vi-batch manner. These flows consisted of a BF 3 -cocatalyst complex and a monomer saturated with BF 3 .
• the present invention relates to a method for the oligomerization of olefins and olefin mixtures in a one-step process by using a boron trifluoride cocatalyst complex.
• the oligomerization of olefins or olefin mixtures is carried out in a one-step process by using as the catalyst a boron trifluoride cocatalyst complex in which the cocatalyst is water, a C 2 -C, 0 monoalcohol, or a C 2 -C 8 monocarboxylic acid, preferably pentanol or valeric acid.
• the invention is characterized by the characteristics presented below in the patent claims.
• the olefin mixture is preferably the so-called Raffinate II stream, in which the principal components are 1- and 2-butenes and butanes, or a mixture of a longer-chain, C 6 -C 20 olefin and Raffinate II.
• a method for the oligomerization of such mixtures is not previously known in the literature.
• the products formed are co-oligomers and not, for example, mixtures of oligomers of butene and oligomers of longer-chain olefin (homo-oligomers).
• the olefins may randomly link with a hydrocarbon chain, and this can be demonstrated with the appended mass spectrometric analyses (the experiments corresponding to the chromatograms presented are Examples 63-66).
• the analyses were performed by direct inlet mass spectrometry by using as the apparatus a VG Trio-2-quadrupole mass spectrometer (VG Masslab, Manchester, U.K.).
• Oligomers prepared according to the present invention contain in the polymer chain an olefinic double bond having increased reactivity.
• the properties of the oligomers include resistance to oxidation under the effect of heat, a low pour point, low volatility, and a good temperature-viscosity dependence. The above properties are important, especially if the oligomers are used for the production of lubricants and their additives.
• the method according to the invention can also be used for producing oligomers having a low viscosity index. These oligomers and their derivatives are used in the main for applications other than lubricants and their additives.
• oligomers can be used as intermediates in the production of various chemical compounds.
• oligomers are used for the preparation of, for example, alkyl benzenes, alkyl phenols, and alkyl succinic acid anhydride.
• surface active agents are prepared by sulfonation.
• oligomers can be used, for example, in the preparation of sulfonates, phenates, thiophosphonates, and ash-free dispersing agents, alkenyl succinimides. In these compounds the molecular mass of the hydrocarbon fraction is approx.
• alkenyl succinimide as high as 2500 g/mol.
• Other uses include the use as a lubricant in two-stroke spark-ignition engines, as the processing oil in the rolling and drawing of metallurgic materials, in the leather and rubber industries, and in making various surfaces hydrophobic.
• the oligomerization reactions of olefins and olefin mixtures were performed in a steel reactor the volume of which was 300 ml and which was cooled internally by means of a cooling coil and was heated, when necessary, externally in an electric mantle.
• the reactor was equipped with a stirrer.
• the temperature of the reaction mixture was monitored by means of a thermocouple.
• the temperature of the reaction mixture was maintained at the set value with a precision of ⁇ 1 °C.
• the reagents used and their amounts are mentioned in the examples.
• the reactor was first charged with a solvent, if necessary, and with the cocatalyst mentioned in the examples. Liquid monomer was fed into the reactor in the desired amount. After the adding of the monomer, the reactor was pressurized by means of BF 3 gas, whereupon the catalyst complex formed in situ and the reaction started immediately. The monomer or the monomer mixture and the catalyst were fed into the liquid phase of the reactor. The reactor pressure was maintained constant by means of BF 3 gas. The pressure was sufficient to keep the monomers in the liquid phase.
• the reaction parameters used were as follows: pressure 0-10 bar, expressed as overpressure; reaction temperature 10-70 °C; and reaction time 1-120 minutes or 1-8 hours. The reaction was halted 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 product distribution was analyzed by the GC method.
• the examples illustrate the various possibilities of the process for producing oligomer fractions with different monomers and catalyst systems.
• the reference examples are Examples 1-15.
• the present invention is illustrated by Examples 16-66. It should be borne in mind that by the process being disclosed it is possible to produce highly different product distributions, so the examples only suggest the possibilities offered by the process.
• the cocatalyst used was n-valeric acid at 5.1 mmol per one mole of 1-butene.
• the reactor pressure was 4.0 bar and temperature 20 °C.
• the reaction time was 9 min ⁇ utes and in Example 2 it was 49 minutes. After the said reaction times, the reactions were halted by means of an NaOH solution.
• the hydrocarbon phases were analyzed, the results being as follows.
• the cocatalyst used was n-valeric acid at 13.4 mmol per one mole of 1-butene.
• the reactor pressure was 2.5 bar and temperature 20 °C.
• the reaction time was 49 minutes. After the said reaction time, the reaction was halted by means of an NaOH solution.
• the hydrocarbon phase was analyzed, the result being as follows:
• the number-average molecular mass of the product distribution according to the example was 202 g/mol.
• the cocatalyst used was n-valeric acid at 13.0 mmol per one mole of 1-butene.
• the reactor pressure was 4.0 bar and temperature 20 °C.
• the reaction time was 6 hours. After the said reaction time, the reaction was halted by means of an NaOH solution.
• the hydrocarbon phase was analyzed, the result being as follows:
• the number-average molecular mass of the product distribution according to Example 4 was 386 g/mol.
• the cocatalyst used was n-valeric acid at 4.9 mmol per one mole of 1-butene.
• the reactor pressure was 10 bar and temperature 40 °C.
• the reaction time was 4 min ⁇ utes and in Example 6 it was 121 minutes. After the said reaction times the reactions were halted by means of an NaOH solution.
• the hydrocarbon phases were analyzed, the results being as follows:
• the number-average molecular masses of the product distributions according to the examples were 275 g/mol and 371 g/mol.
• the cocatalyst used was n-valeric acid at 5.0 mmol per one mole of 1-butene.
• the reactor pressure was 10 bar and temperature 70 °C.
• the reaction time was 9 min ⁇ utes and in Example 8 it was 121 minutes. After the said reaction times the reactions were halted by means of an NaOH solution.
• the hydrocarbon phases were analyzed, the results being as follows:
• 1 -Butene can also be oligomerized with organic acid catalysts other than n-valeric acid, for example, with alcohols and water, as shown by Examples 9-15.
• the reactor pressure used was 4.0 bar and temperature 20 °C, the reaction time being 36 minutes.
• the cocatalysts used were acetic acid (Example 9), n-octanoic acid (10), ethanol (11), 1- pentanol (12), 1-octanol (13), and water (14).
• the reference example (15) is a reaction performed with n-valeric acid under the same conditions.
• Cocatalyst was used at a ratio of 14.5-15.9 mmol of cocatalyst per one mole of 1-butene.
• the results are shown in the following table, where n ⁇ stands for mmol of cocatalyst per one mole of butene.
• Raffinate II i.e. a mixture of butene and butane 30-50 Raffinate II + alpha-olefin 51-62 long-chain alpha-olefin
• the cocatalyst used was n-valeric acid at 32 mmol per one mole of the butene mixture.
• the reactor pressure was 4.0 bar and temperature 20 °C.
• the reaction time was 75 minutes. After the said reaction time the reaction was halted by means of an NaOH solution.
• the hydrocarbon phase was analyzed, the result being as follows:
• the cocatalyst used was n-valeric acid at 52 mmol per one mole of the butene mixture.
• the reactor pressure was 5.7 bar and temperature 30 °C.
• the reactor pressure was 4.5 bar and temperature 10 °C.
• the reaction time was 120 minutes in both examples. After the said reaction times the reactions were halted by means of an NaOH solution.
• the hydrocarbon phases were analyzed, the results being as follows:
• the cocatalyst used was n-valeric acid at 10 mmol per one mole of the butene mixture.
• the reactor pressure was 4.7 bar and temperature 10 °C.
• the reactor pressure was 5.1 bar and temperature 30 °C.
• the reaction time in both examples was 30 minutes. After the said reaction times the reactions were halted by means of an NaOH solution.
• the hydrocarbon phases were analyzed, the results being as follows:
• Example 21 the cocatalyst used was n-valeric acid at 51 mmol per one mole of the butene mixture.
• the reactor pressure was 3.1 bar and temperature 10 °C.
• Example 22 the cocatalyst used was n-valeric acid at 53.5 mmol per one mole of the butene mixture.
• the reactor pressure was 3.8 bar and temperature 30 °C.
• the reaction time in both ex- amples was 30 minutes. After the said reaction times the reactions were halted by means of an NaOH solution.
• the hydrocarbon phases were analyzed, the results being as follows:
• the monomer was Raffinate II, i.e. a mixture of butene and butane.
• Raffinate II can also be oligomerized with organic acid catalysts other than n-valeric acid, for example, with alcohols and water, as shown by Examples 23-29.
• the reactor pressure was 6-7 bar and temperature 20 °C, the reaction time being 120 minutes.
• the cocatalysts used were acetic acid (Example 23), n-octanoic acid (Example 24), ethanol (Example 25), 1 -pentanol (Example 26), 1-octanol (Example 27), and water (Example 28).
• the reference example (29) was a reaction performed under the same conditions by using n-valeric acid. Cocatalyst was used at a ratio of 2.8-3.7 mmol of cocatalyst per one mole of the butane mixture.
• the table shows the alpha-olefin used as the comonomer, the cocatalyst used, and the product distributions as yields.
• the reaction conditions used were: temperature 40 °C; pressure 7-8 bar; and reaction time 120 minutes.
• the cocatalyst used was n-valeric acid (C 5 acid) or 1-pentanol (C 5 alcohol); the amounts are mentioned in the examples (kk, g).
• the product properties were determined on products from which the C 16 fraction and fractions lighter than this had been removed by vacuum distillation. Kinematic viscosity (KVlOO, cSt), viscosity index (VI,-) and pour point (PP, °C) were determined on these unhydrogenated products.
• KVlOO, cSt Kinematic viscosity
• VI,- viscosity index
• PP, °C pour point
• Examples 37-50 show the monomer feed compositions, the reaction times, and the product distributions.
• Raffinate II and alpha-olefin were fed into the reactor in the amounts mentioned in the examples.
• the reaction conditions were: temperature 30 °C and pressure 4-8 bar, i.e. sufficient to maintain Raffinate II in liquid state in each experiment.
• the cocatalyst used was n-valeric acid in an amount of 2.85 grams. After the said reaction times, the reactions were halted by means of an NaOH solution. The hydrocarbon phases were analyzed, the results are shown in the tables.
• feed materials were 1-dodecene (60 g) and Raffinate II (42 g).
• the alpha-olefin was 1-hexadecene (71 g) and the feed was Raffinate II (38 g).
• Example 63 the reaction conditions were: reaction temperature 30 °C; pressure 3 bar expressed as BF 3 overpressure; and reaction time 4 hours.
• Raffinate II was fed in as the monomer in an amount of 100 g and n-valeric acid as the cocatalyst in an amount of 2.86 g.
• the obtained product was analyzed mass spectrometrically.
• Example 64 The product in Example 64 was a product prepared according to Example 58, which was analyzed mass spectrometrically.
• Example 65 The product in Example 65 was a product prepared according to Example 46, which was analyzed mass spectrometrically.
• Example 66 The product in Example 66 had been prepared by mixing in mass proportions 50:50 the products of Example 63 and Example 58. This mixture was analyzed mass spectrometri- cally.
• the appended mass spectrometric analyses depict the analyses of four different experi ⁇ ments graphically, showing the absolute intensities of corresponding peaks of whole molecules (the molecular mass of which corresponds to the molecular mass of the alkene having a certain carbon number) with different molecular mass values.
• the peaks corresponding to fragmented products have been omitted from these alkene graphs; the be ⁇ havior of these peaks with different values of molecular mass, however, corresponds to the peaks of whole molecules.
• the following observations can be made from the graphs:
• the dominating alkene peaks are observable at carbon numbers 16, 20, 24, 28, 32, etc., i.e. at carbon numbers corresponding multiples, oligomers, of the carbon number of butene.
• the absolute intensities of the alkene peaks corresponding to butene oligomers decrease as the carbon number increases steadily.
• the alkene peaks dominating in the alkene graph of dodecene oligo ⁇ mers are at carbon numbers 24, 36, 48, etc., i.e. at carbon numbers corresponding to multiples, oligomers, of the carbon number of dodecene.
• the absolute intensities of the alkene peaks corresponding to dodecene oligomers decrease as the carbon number increases steadily.
• alkene peaks dominating in the alkene graph of products produced in the co- oligomerization between butenes and dodecene are at carbon numbers 16, 20, 24, 28, 36, etc.
• the alkene peaks dominating in the alkene graph of a blend of butene oligomers and dodecene oligomers are at carbon numbers 16, 24, 36 and 48.
• the peak at carbon number 16 is due to butene oligomers, but at carbon numbers 24, 36 and 48 the peaks are mainly due to dodecene oligomers.
• These graphs show clearly that olefin mixtures oligomerized by the method accor ⁇ ding to the invention do not produce mixtures of homo-oligomers but produce co- oligomers during the reaction when olefins may link randomly to the carbon chain.

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