CZ257695A3 - Ionic liquid, process of its preparation and conversion method of olefinic hydrocarbons - Google Patents

Ionic liquid, process of its preparation and conversion method of olefinic hydrocarbons Download PDF

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CZ257695A3
CZ257695A3 CZ952576A CZ257695A CZ257695A3 CZ 257695 A3 CZ257695 A3 CZ 257695A3 CZ 952576 A CZ952576 A CZ 952576A CZ 257695 A CZ257695 A CZ 257695A CZ 257695 A3 CZ257695 A3 CZ 257695A3
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ionic liquid
halide
carbon atoms
chloride
alkyl
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CZ952576A
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Czech (cs)
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Ala A K Abdul-Sada
Philip William Ambler
Philip Kenneth Gordon Hodgson
Kenneth Richard Seddon
Nevin John Stewart
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Bp Chem Int Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation 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
    • C07C2/06Preparation 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
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56Addition to acyclic hydrocarbons
    • C07C2/58Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron

Abstract

This invention relates to an ionic liquid comprising a dialkyl substituted imidazolium halide wherein at least one of the said alkyl substituents has 6 or more carbon atoms, a method of preparation of such imidazolium halides, and the use thereof for hydrocarbon conversion reactions such as oligomerization or polymerization of olefins and for the alkylation of paraffins, isoparaffins or aromatics with olefins. Polymerization of C4 raffinates using these ionic liquids as catalysts enables a much higher percentage of n-butenes to be incorporated in the product polymer than would be possible in conventional cationic polymerization processes.

Description

The invention relates to novel ionic liquids, to a process for their preparation and to their use as a reaction medium and catalyst for various chemical reactions such as oligomerization, polymerization and alkylation of olefinic hydrocarbons, for example the production of olefin polymers, in particular butene polymers from raffinate I and II from refining. which comprises inter alia a mixture of 1-butene, 2-butene and isobutene.

BACKGROUND OF THE INVENTION

Ionic liquids are predominantly mixtures of salts that melt below room temperature. These salt mixtures include aluminum halides in combination with one or more imidazolium halides, pyridinium halides or phosphonium halides, the latter being preferably substituted. Examples of the latter include one or more 1-methyl-3-butylimidazolium halides, 1-butylpyridinium halides and tetrabutylphosphonium halides.

These ionic liquids are known to be used as solvents and as catalysts, for example for dimerization and / or oligomerization of olefins such as ethylene, propylene, 1-butene and / or 2-butene, and for alkylation of benzene with alkyl halides. In this context, Jeffrey A. Boon et al. in an article in the Journal of Organic Chemistry, Vol. 51, 1986, pp. 480-483:

In organic reactions, ionic liquids are generally not used as solvents. Most ionic liquids are liquid only at high temperatures and are only slightly more preferred than commonly used aqueous or organic media. Most organic reactions in molten salts use eutectic mixtures, but these mixtures also require temperatures above 200 ° C.

Furthermore, this article states:

Numerous other substituted imidazolium chlorides and pyridinium chlorides form molten salts with aluminum chloride, but do not exhibit the favorable physical properties that have been sought in this research.

From the foregoing, it is apparent that not all ionic liquids possess the properties required for the specific reactions in which they are to be used, and that the choice of specific ionic liquids for a given reaction is not so simple.

This is also emphasized in another article by Yves Chouvin et al., J. Chem. Soc., Chem. Comm., 199, p. 1715 1716. In the research described in this article, the authors intended to catalyze the dimerization of alkenes using nickel complexes in organochloraluminate molten salts, excluding all other products. In this article, the authors also state:

However, no attempt appears to have been made to utilize the solubility of the organometallic catalyst and the insolubility of the reaction products of the catalytic reaction in these solvents.

The authors also add:

In the absence of any nickel complex, the acid melt catalyses the formation of oligomers whose molecular weight is characteristic of the cationic reaction.

To further illustrate the unpredictability of these reactions, FR-A-2611700 (Institut Francaise du Petrole) describes a process for oligomerizing olefins, including but not limited to 1-butene and 2-butene, using a liquid-phase nickel catalyst. Specifically, the catalyst used is a nickel complex dissolved in an ionic liquid that forms a liquid phase.

Later FR-A-2626572 describes an alkylation process using a catalyst in an ionic liquid comprising at least one aluminum or boron halide and at least one quaternary ammonium halide. The quaternary ammonium halide may be a dialkylimidazolium halide in which one of the alkyl. the radicals may be an amyl group, i.e. a group having 5 carbon atoms.

It is clear from the above that the action of ionic liquids in these reactions cannot be predicted at all. In addition, ionic liquids containing alkyl-substituted imidazolium halides in which any of the alkyl substituents would contain more than 5 carbon atoms have not been described in any of the above publications.

SUMMARY OF THE INVENTION

It has now surprisingly been found that ionic liquids containing alkylimidazolium compounds in which the alkyl substituent contains 6 or more hydrogen atoms have remarkable properties.

The present invention provides an ionic liquid comprising a dialkyl-substituted imidazolium halide wherein at least one of the alkyl substituents contains 6 or more carbon atoms.

When used in ionic liquids, the imidazolium compounds typically contain at least two alkyl groups substituted at the 1 and 3 positions of the imidazolium structure. The substituents at these two positions are generally interchangeable. Thus, in the imidazolium halides of the invention, at least one of the 1 or 3 substituents is an alkyl group with at least 6 carbon atoms. The exact position of each of these groups is indifferent because the 1,3-disubstituted imidazolium halides have a symmetric molecule. The alkyl substituent containing 6 or more carbon atoms may be a straight or branched chain alkyl group. Suitably, these alkyl groups contain 6 to 30, preferably 6 to 18, carbon atoms.

The halide group in the imidazolium compounds of the invention may be a chloride, bromide or iodide group.

Specific examples of imidazolium compounds that are contained in the ionic liquids of the invention include:

1-methyl-3-hexylimidazolium chloride, 1-methyl-3-octylimidazolium chloride,

1-methyl-3-decylimide hydrochloride, 1-methyl-3-dodecylimidazolium chloride, 1-methyl-3-hexadexylimidazolium chloride and 1-methyl-3-octadexylimidazolium chloride.

Obviously, in the above compounds, the 1-position methyl group could be replaced by any C 1 -C 4 alkyl group such as ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl and the same effect would be achieved. As explained above, it would also be possible to change the placement of substituents at the 1- and 3-positions or to have both substituents at the 1- and 3-positions with 5 or more carbon atoms in the alkyl group, since the 1,3-disubstituted imidazolium halide has a symmetric molecule. . Furthermore, it would also be possible to replace the chloride ion in the above compounds with a bromide or iodide ion, and to always produce compounds that are as effective as ionic liquids.

The imidazolium halides of the invention can be prepared as follows:

For example, a 1-methyl-3-alkylimidazolium halide having 6 or more carbon atoms in the alkyl moiety can be prepared by mixing dry 1-methylimidazole with 1-alkyl * haloalkane, wherein the alkyl group contains 6 or more carbon atoms (and optionally with a solvent such as acetonitrile if a homogeneous mixture is to be obtained) and the resulting mixture is placed, for example, in a Corius tube stored in a dry box. The Corio tube is then sealed with a super seal in a dry cabinet and sealed under vacuum. The two reactants form two layers in a Corio tube, and the resulting mixture is heated to about 90 ° C for about a week. The resulting product was cooled to room temperature to give a viscous product, which was transferred from a dry cabinet to a Schlenk round-bottomed flask and left under vacuum for several hours. The resulting viscous liquid is then purified by recrystallization from acetonitrile and analyzed to identify and characterize the 1-methyl-3-alkylimidazolium halide having 6 or more carbon atoms in the alkyl moiety.

It is a feature of the present invention that when the length of at least one of the alkyl chains in the dialkylimidazolium halide is greater than 5 carbon atoms, the catalytic efficiency of ionic liquids containing such halides increases in polymerization reactions compared to the ionic liquids containing halides with alkyl chains of 4 or less. carbon atoms. In particular, the efficiency of such ionic liquids is improved when raffinate I, raffinate II or isobutene is used as the polymerized feed.

It is a further feature of the invention that polymers produced using ionic liquids containing the dialkylimidazolium halides of the invention may have, if desired, a broader molecular weight distribution compared to polymers made using conventional imidazolium halides.

The ionic liquids according to the invention expediently contain, in addition to the imidazolium halides defined above, an aluminum compound, which is expediently an aluminum halide, such as aluminum chloride, or an alkyl aluminum halide, such as an alkyl aluminum dichloride, or a dialkyl aluminum halide. Ethylaluminum dichloride is preferably used as the aluminum compound.

As is well known in the art, the ratio of components in the ionic liquid to be used as the catalyst should be such that these components remain in the liquid state under the reaction conditions. Yet another feature of the present invention is that, in the manufacture of multicomponent ionic liquids, the presence of the dialkylimidazolium halides of the present invention allows the liquids to contain a greater proportion of the other components while remaining in a liquid state, in some cases at room temperature. uses conventional imidazolium halides.

The ionic liquids produced from the imidazolium halides of the invention can be used as catalysts for any reaction involving ionic liquids. These reactions include oligomerizations, alkylations, polymerizations and the like. The ionic liquids containing the dialkylimidazolium halides of the invention are particularly suitable for the oligomerization and polymerization of olefins, especially isobutene-containing feedstocks.

Thus, in another aspect, the present invention provides a process for the polymerization of an olefinic feed containing one or more C 2 -C 4 olefins by contacting the feed with an ionic liquid containing

(a) a compound of the formula RnMX 3 -n , wherein R is C 1 -C 6 alkyl, M is aluminum or gallium, X is halogen and n is 0, 1 or 2, and

b) a dialkyl-substituted imidazolium halide in which at least one of the alkyl substituents contains 6 or more carbon atoms, the melting point of the ionic liquid being lower than the reaction temperature.

The term “polymerisation products” in this description means the following substances:

i. oligomers, defined in accordance with conventional practice, as very low molecular weight polymers containing 2 to 10 repeating units (see

AND

Polymer Chemistry, An Introduction, R. B. Seymours and C. E. Carraher, 2nd Edition, 1988, p. 14, Marcel Dekker Inc., And ii. polymers containing at least 11 repeating units, i.e. polymers having an average molecular weight of 600 to 100,000.

As the hydrocarbon feed for the above process, ethylene, propylene, 1-butene, 2-butene and / or isobutene, preferably a raffinate from the refining process, which may be raffinate I or raffinate II, are expediently used.

The raffinate I is usually butadiene raffinate, which is a by-product of thermal or catalytic cracking (carried out by a fluid or other process) in a refinery. The raffinate I essentially comprises 4-carbon hydrocarbons, in particular a mixture of 1-butene, 2-butene and isobutene together with a certain amount of saturated hydrocarbons. More specifically, the raffinate I comprises at least 10% by weight of isobutene, 20 to 40% by weight of 1-butene and 2-butene and 10 to 20% by weight of butanes.

Raffinate II is composed of unpolymerized by-products obtained when raffinate I is polymerized using, for example, Lewis acids as catalyst. A similar product can be obtained in the form of a gaseous by-product from the production of methyl tert-butyl ether (MTBE), which is an unleaded compound used as an additive to remove engine knock. The by-products obtained in both of the above processes have substantially the same composition and are rich in n-butenes. These by-products are so-called raffinate II and usually contain 30 to 55% by weight of 1-butene, about 10% by weight of cis-2-butene, about 17% by weight of trans-2-butene, up to 6% by weight of isobutene and up to 30% by weight. % of saturated hydrocarbons having 4 carbon atoms, i.e. n-butane and isobutane. Since raffinate II, which is otherwise a waste material, can be cationically polymerized to polybutenes, its value as a raw material is obvious.

The ionic liquids which may be used include an aluminum or gallium compound, suitably a halide such as aluminum chloride or gallium chloride, or also an alkylaluminium / gallium halide such as an alkylaluminium / gal-; llium dichloride or dialkylaluminum / gallium chloride. It is preferably ethylaluminum / gallium dichloride. Component b) of the ionic liquid is a dialkyl-substituted imidazolium halide, especially a 1-alkyl-3-alkyl-imidazolium halide having 1 to 4 carbon atoms in the 1-alkyl group and 6 or more carbon atoms in the 3-alkyl group of the invention described above. Of the alkylimidazolium halides mentioned above, 1-methyl-3-octylimidazolium chloride is preferred.

The ratio of components a) and b) in the ionic liquid should be such that the mixture can remain in the liquid state under the reaction conditions. The usual relative molar ratio of the aluminum or gallium compound to the component b) of the ionic liquid is suitably in the range from 1: 2 to 3: 1, preferably from 1.5: 1 to 2: 1. If the ionic liquid is to be used as the reaction medium or solvent within this range, the amount of component (a) may be less than 50 mol% of the ionic liquid as a whole. However, if the ionic liquid is to be used as a catalyst, the amount of component a) is preferably greater than 50 mol%, based on the ionic liquid as a whole.

The polymerization reaction is conveniently carried out at a temperature ranging from -50 to + 100 ° C, preferably from -30 to + 70 ° C. The reaction can be carried out either by reacting

i) the olefinic hydrocarbon feed to be polymerized is bubbled through an ionic liquid, or ii) dispersing the ionic liquid at a suitable concentration in the olefinic hydrocarbon feed to be polymerized and the resulting dispersion polymerized.

In the case of alternative (i), the rate at which the olefinic hydrocarbon feed is to be bubbled, and in the case of alternative (ii), the amount of ionic liquid to be mixed into the feed and in both cases the reaction temperature will depend on the molecular weight of the desired product. In a reaction of this type, it would normally be expected that the higher the temperature used, the lower the molecular weight of the polymer.

It has now surprisingly been found that when using alternative (i), the relative product forms a separate layer floating on the surface of the ionic liquid. This product layer essentially contains no catalyst or contaminant ionic liquid. Thus, the polymer product can be easily removed from the surface of the ionic liquid, for example by pumping. This feature has several advantages:

A. The ease of separation of the polymer product from the catalyst component results in a further reaction of the olefinic end group of the polymer, such as isomerization, minimized and the polymer retains the originally produced structure. This means that subsequent undesired reactions can be avoided without the need for conventional stopping agents (for decomposition of the reaction mixtures) such as an alkali metal base.

B. The polymer product formed does not need to be washed with water, since it contains a relatively low concentration of catalytic ionic liquid, which saves one processing step.

If alternative (ii) is used, it may be necessary to add a stopping agent, for example aqueous ammonia, to terminate the reaction and / or neutralize all the catalyst components. The products can then be washed with water and the polymer product produced can be separated. In this case, the unreacted substance can be allowed to evaporate and the dried product isolated.

It is a further feature of the present invention that the process makes it possible to introduce a much higher percentage of n-butenes into the polymer product than would otherwise be possible using conventional cationic polymerization processes such as aluminum chloride or boron trifluoride.

Yet another surprising feature of the invention is that, contrary to expectation, the molecular weight of the product does not increase with decreasing reaction temperature. Although reaction temperatures that are substantially higher than those used in the prior art are used, polymers of higher molecular weight than oligomers produced by known methods are obtained by the process of the invention.

These surprising features represent a highly desirable profile for the processing of low value feedstocks such as raffinate I and raffinate II while maximizing the utilization of the reactive carbon content of these feedstocks. This reduces the amount of hydrocarbon waste from the feedstock being processed.

The polymer products produced by the process of the invention can be used in the industry without any further processing as lubricants or cutting fluids. Alternatively, these polymers can be maleinized or converted to the corresponding succinic anhydride derivatives, which can then be further converted to the corresponding imides. The latter serve as detergents for lubricating oils and fuels.

As mentioned above, the ionic liquids according to the invention can also be used, for example, in alkylation reactions.

When used as catalysts for alkylation reactions, these ionic liquids may be alkylations of isoparaffins, such as isobutane, with a C 2 -C 4 olefin, such as ethylene. Alkylates are formed which increase the octane number of the fuels. Also suitable are alkylation of aromatic hydrocarbons with olefins, such as the conversion of benzene to ethylbenzene, a reaction precursor which is involved in the production of styrene. This alkylation reaction is conveniently carried out at a temperature of, for example, less than 100 ° C, conveniently at a temperature in the range of -30 to + 50 ° C. The ratio of the catalytic ionic liquid phase to the hydrocarbon phase during the alkylation will largely depend on the olefin reactivity and the acidity of the particular ionic liquid chosen. As a general guide, the molar ratio of catalyst to olefins is in the range of 1000: 1 to 1: 1000. If this ratio is to be expressed as the volume ratio of the catalyst phase to the hydrocarbon phase, the number range is 100: 1 to 1: 100. especially 20: 1 to 1:20.

Suitably, in the olefin alkylation of isoparaffins, the ratio of isoparaffin to olefin is in the range of 1000: 1 to 1: 1000.

The invention is illustrated by the following examples. These examples are illustrative only and are not to be construed as limiting the scope of the invention in any way. In all examples, the 1-methylimidazole used is distilled over sodium hydroxide and is always handled under a nitrogen atmosphere. All alkyl halides used are dried over calcium hydride for 1 week and distilled before use. It is not considered necessary to carry out detailed analyzes of the compounds obtained in order to determine their structure, since the reactions are stoichiometric, do not evolve any gases and do not precipitate any solids during the course of the reactions. However, in order to confirm this, in some examples NMR analyzes of the resulting products are given, and on the basis of these analyzes a structure has been ascribed to products that have not been subjected to NMR analysis.

In the tables below, the intensity values represent peak heights corresponding to the number of protons in a given position.

In this context, the designations very strong, strong, medium, weak and very weak are used for the following maximum intensity range (I / I o )

very strong - 80 to 100 ALIGN! strong - 60 to 80 medium - 40 to 60 weak - 20 May to 40 very weak - under 20 May

The symbol 6 (ppm) indicates the chemical shift in parts per million parts.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Production of 1-hexyl-3-methylimidazolium chloride

Dry 1-methylimidazole (9.03 g, 0.11 mol) was mixed with 1-chlorohexane (12.06 g, 0.1 mol) and placed in a Corio tube stored in a dry box. The Corio tube is then sealed with a super seal in a dry cabinet and sealed under vacuum. The two reactants form two layers in a Corio tube, and the resulting mixture is heated at about 100 ° C for a week. The resulting product was cooled to room temperature to give a viscous product, which was transferred from a dry box to a round bottom Schlenk flask and left under vacuum for 4 hours. The resulting viscous liquid is 1-hexyl-3-methylimidazolium chloride, which forms an ionic liquid at room temperature. 12.23 g (92.2%) of m / z 369 are obtained.

Example 2

Production of 1-octyl-3-methylimidazolium chloride

The process described in Example 1 was repeated except that 1-chloro-hexane (14.9 g, 0.1 mol) was used instead of 1-chlorohexane. The product 1-octyl-3-methylimidazolium chloride is obtained, which forms an ionic liquid at room temperature. 15.8 g of product are obtained (yield 96.6%) with an m / z value of 425.

Example 3

Preparation of 1-nonyl-3-methyliroidazolium chloride

The procedure of Example 1 was repeated except that 1-chloro-hexane (16.3 g, 0.1 mol) was used instead of 1-chlorohexane. The product is 1-nonyl-3-methylimidazolium chloride, which forms an ionic liquid at room temperature. 16.1 g of product are obtained (yield 90.0%) with an m / z value of 453.

Example 4

Production of 1-decyl-3-methylimidazolium chloride

The procedure described in Example 1 was repeated except that 1-chlorodecane (17.7 g, 0.1 mol) was used instead of 1-chlorohexane. The product 1-decyl-3-methylimidazolium chloride is obtained which forms an ionic liquid at room temperature. 18.3 g of product are obtained (yield 94.2%) with an m / z value of 481.

Example 5

Production of 1-dodecyl-3-methylimidazolium chloride

The procedure described in Example 1 was repeated except that 1-chlorododecane (20.48 g, 0.1 mol) was used instead of 1-chlorohexane. After heating to 100 ' C, the product is waxy and recrystallized from acetonitrile (50 mL) at -13 [deg.] C. for one week in a round bottom Schlenk flask. The crystals were isolated by Schlenk filtration and dried under vacuum for 48 hours. NMR analysis of the crystals obtained is shown in the table

1. Crystals have a melting point of 52.5 ° C. 19.4 g of product are obtained (yield 86.1%) with an m / z value of 537.

Table

C-NMR / 12 C product melt containing 40 mol% of aluminum chloride (Example 5)

(ppm) Intensity (I / O ) Type 0.5 weak singlet 0.9 very strong doublet 1.5 very weak singlet

Table I - continued

(ppm) Intensity (I / I Q ) TYPE 3.5 weak singlet 3.8 very weak singlet 4.6 very weak singlet 5.3 very weak singlet 7.0 very weak singlet 8.0 very weak singlet Example 6

Preparation of 1-tetradecyl-3-methylimide zolium chloride

The procedure described in Example 5 was repeated except that 1-chlorotetradecane (23.3 g, 0.1 mol) was used instead of 1-chlorododecane. The crystals formed were not analyzed by NMR, but were attributed to the structure of 1-tetradecyl-3-methylimidazolium chloride by analogy to Example 5. The crystals obtained had a melting point of 56.89%, obtained in an amount of 23.9 g (yield 93.3%). ) and their m / z value is 593.

Example 7

Preparation of 1-hexadecyl-3-methylimidazolium chloride

The procedure described in Example 5 was repeated except that 1-chloro hexadecane (26.09 g, 0.1 mol) was used instead of 1-chlorododecane. The resulting crystals were not analyzed by @ 1 H-NMR, but were attributed to the structure of 1-hexadecyl-3-methylimidazolium chloride by analogy to Example 5. The crystals obtained had a melting point of 61.6 DEG C., obtained in an amount of 25.7 g (yield 89). , 6%) and their m / z value is 649.

Example

Preparation of 1-octadecyl-3-methylimidazolium chloride

The procedure described in Example 5 was repeated except that 1-chloro octadecane (28.9 g, 0.1 mol) was used instead of 1-chlorododecane. The crystals formed were not analyzed by NMR, but attributed the structure of 1-octadecyl-3-methylimidazolium chloride by analogy to Example 5. The crystals obtained had a melting point of 71.07 ° C, obtained in an amount of 31.77 g (yield 93.3%). ) and their m / z value is 705.

Example9

An ionic liquid was prepared using 1-methyl-3-octylimidazolium chloride and aluminum chloride in a 2: 1 molar ratio (see Example 2). 5 ml of the resulting ionic liquid is dispersed in 200 g of raffinate II (having an olefin content of 62% by weight of the composition given in Table 2), as a raw material, in 750 ml of heptane. The dispersion is carried out by stirring at atmospheric pressure at 10 ° C for 180 minutes. The reaction is exothermic, but no temperature increase greater than 10 ° C is observed during the reaction time. The yield of the polymer product is 76.8% by weight based on the weight of the olefin present, i.e. 95.3 g of the polymer product is obtained from 124.0 g of olefin, the number average molecular weight of the obtained polymer (Mn) being 1,042.

Claims (25)

1. An ionic liquid containing a dialkyl substituent.
An imidazolium halide in which at least one of the alkyl substituents contains 6 or more carbon atoms. V Ί, h
The ionic liquid of claim 1, wherein the alkyl substituent of 6 or more carbon atoms is a straight or branched chain alkyl-S group. AND
The ionic liquid according to claim 1 or 2, wherein the alkyl substituent of 6 or more carbon atoms is an alkjyl group of 6 to 30 carbon atoms. and__
6 .X W 0 οι -oa
Ú g O 9:
•[•O
The ionic liquid according to any one of the preceding claims, wherein the halide group of the imidazolium halide is a chloride, bromide or iodide group.
5. An ionic liquid according to any of the preceding; wherein the imidazolium halide is selected from the group; including 1-methyl-3-hexylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-methyl-3-decylimidazolium chloride, 1-methyl-3-dodecylimidazolium chloride, 1-methyl-3-hexadexylimidazolium chloride and 1-methyl-3-octadexylimidazolium chloride.
The ionic liquid of claim 5, wherein the 1-methyl group of each of said compounds is replaced with a C 2 -C 4 alkyl group.
The ionic liquid of claim 6 wherein the C 2 -C 4 alkyl is selected from the group consisting of ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
The ionic liquid of any one of claims 5 to 7, wherein the chloride ion of each of said compounds is replaced with a bromide or iodide ion.
9. The process for producing an ionic liquid according to claim 1, wherein the dialkylimidazolium halide is prepared by mixing dry 1 to 4 carbon atoms in the alkyl group with 1-alkylhaloalkane wherein the alkyl group contains 6 or more carbon atoms. and optionally with a non-aqueous solvent, raise the temperature of the resulting mixture and maintain the mixture at such an elevated temperature for a period of time, then cool and recover the desired ionic liquid as such, or optionally purify by recrystallization.
An ionic liquid according to any one of claims 1 to 8 comprising, in addition to a dialkylimidazolium halide, an aluminum compound selected from the group consisting of aluminum halide, alkyl aluminum halide and dialkylaluminum halide.
The ionic liquid of claim 10, wherein the ratio of dialkylimidazolium halide to aluminum compound is such that when the ionic liquid is used as a catalyst, its components remain in a liquid state under the reaction conditions under which the catalyst is used.
A process for the conversion of olefinic hydrocarbons selected from the group consisting of oligomerization, alkylation and polymerization, characterized in that the conversion is carried out in the presence of an ionic liquid containing a dialkylimidazolium halide according to any one of claims 1 to 8 and 10 to 11.
The process according to claim 12, wherein the olefinic hydrocarbons comprise one or more olefins having 2 to 4 carbon atoms.
Process according to Claim 12 or 13, characterized in that the olefinic hydrocarbon feed used comprises ethylene, propylene, 1-butene, 2-butene and / or isobutene.
Process according to claim 12 or 13, characterized in that a raffinate from a refining process is used as the olefinic hydrocarbon feed, which raffinate is raffinate I or raffinate II.
Process according to any one of claims 12 to 15, characterized in that it comprises the polymerization of an olefinic hydrocarbon feed containing an olefinic hydrocarbon, in which the feed is contacted with an ionic liquid comprising
(a) a compound of the formula Rn MX 3 -n , wherein R represents an alkyl group having 1 to 6 carbon atoms, M represents aluminum or gallium, X represents a halogen atom and n represents 0, 1 or 2, and
b) a dialkyl-substituted imidazolium halide in which at least one of the alkyl substituents contains 6 or more carbon atoms, the melting point of the ionic liquid being lower than the reaction temperature.
17. The method of claim 16 wherein the ratio of components a) and b) in the ionic liquid is in the range of 1: 2 to 3: 1.
Process according to claim 16 or 17, characterized in that the polymerization products comprise
i. oligomers, defined in accordance with conventional practice, as very low molecular weight polymers containing from 2 to 10 repeating units; and *
* ii. polymers containing at least 11 repeating units, i.e. polymers having an average molecular weight of 600 to 100,000.
Process according to any one of claims 12 to 18, characterized in that the polymerization is carried out at a temperature in the range of -50 to 100 ° C.
Process according to any one of claims 12 to 19, characterized in that the polymerization is carried out by carrying out the polymerization
i) the olefinic hydrocarbon feed to be polymerized is bubbled through an ionic liquid, or ii) dispersing the ionic liquid at a suitable concentration in the olefinic hydrocarbon feed to be polymerized and the resulting dispersion polymerized.
21. The method according to claim 12, characterized in that the olefinic hydrocarbon used for alkylation * paraffins, isoparaffins and aromatic hydrocarbons t hydrogen to form alkylate.
with"
A process according to claim 21, characterized in that the alkylation is an alkylation of aromatics carried out at a temperature of, for example, less than 100 ° C, suitably in the range of -30 to 50 ° C.
The method of claim 21 or 22, wherein the molar ratio of ionic liquid to olefinic hydrocarbon used for alkylation is in the range of 1000: 1 to 1: 1000.
Process according to one of Claims 21 to 23, characterized in that benzene or toluene is used as the aromatic hydrocarbon for the alkylation.
25. The process of claim 21 wherein the isoparaffin is alkylated, wherein the isoparaffin to olefin molar ratio is in the range of 1000: 1 to
1: 1000.
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Families Citing this family (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9603754D0 (en) 1996-02-22 1996-04-24 Bp Chem Int Ltd Lubricating oils
US5731101A (en) * 1996-07-22 1998-03-24 Akzo Nobel Nv Low temperature ionic liquids
US5824832A (en) * 1996-07-22 1998-10-20 Akzo Nobel Nv Linear alxylbenzene formation using low temperature ionic liquid
GB9616264D0 (en) 1996-08-02 1996-09-11 British Nuclear Fuels Plc Reprocessing irradiated fuel
GB9719551D0 (en) 1997-09-16 1997-11-19 British Nuclear Fuels Plc Treatment of molten salt reprocessing wastes
EP0989134A1 (en) * 1998-09-11 2000-03-29 Akzo Nobel N.V. Process for the in situ preparation of an ionic liquid
GB9823853D0 (en) 1998-10-30 1998-12-23 Bp Chem Int Ltd A process for making n-butyl esters from butadiene
US6037442A (en) * 1998-12-10 2000-03-14 E. I. Du Pont De Nemours And Company Preparation of olefin copolymers of sulfur dioxide or carbon monoxide
GB9827766D0 (en) * 1998-12-18 1999-02-10 Ici Plc Hologenation
DE60013832T2 (en) 1999-05-26 2005-09-29 Biotage Ab Preparation and Use of Ionic Liquids in Microwave Assisted Chemical Transformations
CN1409694A (en) * 1999-11-26 2003-04-09 沙索尔技术股份有限公司 Hydrocarbon conversion process
GB9928290D0 (en) 1999-12-01 2000-01-26 Univ Belfast Process for preparing ambient temperature ionic liquids
US6998152B2 (en) 1999-12-20 2006-02-14 Micron Technology, Inc. Chemical vapor deposition methods utilizing ionic liquids
FR2808268B1 (en) * 2000-04-26 2002-08-30 Atofina Ionic liquids derived from titanium, niobium, tantalum, tin or antimony lewis acids and their applications
US7259284B2 (en) 2000-05-31 2007-08-21 Chevron Phillips Chemical Company, Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
DE60010472T2 (en) * 2000-10-27 2005-05-19 Centre National De La Recherche Scientifique (C.N.R.S.) Imidazolium salts and the use of these ionic liquids as a solvent and as a catalyst
JP4641646B2 (en) * 2001-04-06 2011-03-02 株式会社トクヤマ Electrolyte for non-aqueous electrolyte
FR2829132B1 (en) * 2001-08-31 2004-06-18 Inst Francais Du Petrole Process for the oligomerization of olefins
FR2829133B1 (en) * 2001-08-31 2004-12-10 Inst Francais Du Petrole Process for the alkylation of olefins by isoparaffins
US6991718B2 (en) 2001-11-21 2006-01-31 Sachem, Inc. Electrochemical process for producing ionic liquids
AU2003237797B2 (en) 2002-04-05 2009-02-26 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
JP2005528195A (en) 2002-04-22 2005-09-22 シェブロン フィリップス ケミカル カンパニー エルピー Method for producing ionic liquid catalyst
CA2482896A1 (en) 2002-04-22 2003-10-30 Chevron Phillips Chemical Company Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
FR2843111B1 (en) * 2002-08-05 2004-09-24 Inst Francais Du Petrole Process for the purification of linear olefins
WO2004016571A2 (en) 2002-08-16 2004-02-26 Sachem, Inc. Lewis acid ionic liquids
CN100424259C (en) * 2002-12-12 2008-10-08 中国科学院化学研究所 Room temperature ionic liquid containing unsaturated double bond and its prepn and application
WO2004080974A1 (en) * 2003-03-12 2004-09-23 Chemtech Research Incorporation A purification method of ionic liquids to obtain their high purity
CA2543018C (en) 2003-10-31 2012-07-24 Chevron Phillips Chemical Company Lp Method and system to contact an ionic liquid catalyst with oxygen to improve a chemical reaction
AU2004285044B2 (en) 2003-10-31 2010-07-01 Chevron Phillips Chemical Company, Lp Method and system to add high shear to improve an ionic liquid catalyzed chemical reaction
US7888412B2 (en) 2004-03-26 2011-02-15 Board Of Trustees Of The University Of Alabama Polymer dissolution and blend formation in ionic liquids
CN1294300C (en) * 2004-06-07 2007-01-10 东华大学 Ion liquid and prepn process of synthetic aromatic fiber with the ion liquid
WO2006033990A2 (en) 2004-09-17 2006-03-30 California Institute Of Technology Use of ionic liquids as coordination ligands for organometallic catalysts
JP4719080B2 (en) * 2005-05-20 2011-07-06 新光硝子工業株式会社 Method for producing vinyl polymer
US7550520B2 (en) 2005-05-31 2009-06-23 The University Of Alabama Method of preparing high orientation nanoparticle-containing sheets or films using ionic liquids, and the sheets or films produced thereby
US8883193B2 (en) 2005-06-29 2014-11-11 The University Of Alabama Cellulosic biocomposites as molecular scaffolds for nano-architectures
MX343314B (en) 2005-10-07 2016-11-01 The Univ Of Alabama Multi-functional ionic liquid compositions.
US20070100181A1 (en) * 2005-10-27 2007-05-03 Harmer Mark A Olefin isomerization
GB0525251D0 (en) * 2005-12-12 2006-01-18 Univ Belfast Oligomerisation
US7572943B2 (en) * 2005-12-20 2009-08-11 Chevron U.S.A. Inc. Alkylation of oligomers to make superior lubricant or fuel blendstock
JP4719076B2 (en) * 2006-05-10 2011-07-06 新光硝子工業株式会社 Method for producing vinyl polymer
US7732651B2 (en) 2006-06-01 2010-06-08 Chevron Oronite Company, Llc Method of making an alkylated aromoatic using acidic ionic liquid catalyst
EP1900763A1 (en) * 2006-09-15 2008-03-19 Rütgers Chemicals GmbH process to prepare a hydrocarbon resin
CN100443157C (en) * 2006-11-16 2008-12-17 中国科学院长春应用化学研究所 Application of continuous microwave reactor
DE102008058448A1 (en) 2007-11-23 2009-06-25 Basf Se New polyisobutyl derivatives with ammonio, phosphonio, oxonio, sulfonio or selenio groups, are useful as catalysts for polymerizing cationically polymerizable monomers, e.g. isobutene
US8143467B2 (en) 2007-12-18 2012-03-27 Exxonmobil Research And Engineering Company Process for synthetic lubricant production
US8668807B2 (en) 2008-02-19 2014-03-11 Board Of Trustees Of The University Of Alabama Ionic liquid systems for the processing of biomass, their components and/or derivatives, and mixtures thereof
US7847030B2 (en) * 2008-02-29 2010-12-07 Exxonmobil Research And Engineering Company Diphenylamine functionalization of poly-α-olefins
US20100152518A1 (en) * 2008-12-15 2010-06-17 Chevron U.S.A., Inc. Process to make a liquid catalyst having a high molar ratio of aluminum to nitrogen
US20100152027A1 (en) * 2008-12-15 2010-06-17 Chevron U.S.A., Inc. Ionic liquid catalyst having a high molar ratio of aluminum to nitrogen
US8889934B2 (en) * 2008-12-15 2014-11-18 Chevron U.S.A. Inc. Process for hydrocarbon conversion using, a method to make, and compositions of, an acid catalyst
WO2010078300A1 (en) 2008-12-29 2010-07-08 The Board Of Trustees Of The University Of Alabama Dual functioning ionic liquids and salts thereof
US9096743B2 (en) 2009-06-01 2015-08-04 The Board Of Trustees Of The University Of Alabama Process for forming films, fibers, and beads from chitinous biomass
WO2011011322A1 (en) 2009-07-24 2011-01-27 The Board Of Trustees Of The University Of Alabama Conductive composites prepared using ionic liquids
US9394375B2 (en) 2011-03-25 2016-07-19 Board Of Trustees Of The University Of Alabama Compositions containing recyclable ionic liquids for use in biomass processing
US9328037B2 (en) 2014-07-09 2016-05-03 Uop Llc Benzene alkylation using acidic ionic liquids
US10100131B2 (en) 2014-08-27 2018-10-16 The Board Of Trustees Of The University Of Alabama Chemical pulping of chitinous biomass for chitin
US10011931B2 (en) 2014-10-06 2018-07-03 Natural Fiber Welding, Inc. Methods, processes, and apparatuses for producing dyed and welded substrates
US10435491B2 (en) 2015-08-19 2019-10-08 Chevron Phillips Chemical Company Lp Method for making polyalphaolefins using ionic liquid catalyzed oligomerization of olefins
CN108484353A (en) * 2018-04-12 2018-09-04 常州大学 A kind of synthetic method of bis- chloro- 5- fluorine (trichloromethyl) benzene of 2,4-

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2829137C2 (en) * 1978-07-03 1982-09-16 Th. Goldschmidt Ag, 4300 Essen, De
FR2611700B1 (en) * 1987-03-05 1989-07-07 Inst Francais Du Petrole Method for dimerization or codimerization of olefins
FR2626572B1 (en) * 1988-02-02 1990-05-18 Inst Francais Du Petrole Process for the alkylation of aliphatic hydrocarbons
EP0558187B1 (en) * 1992-02-19 1996-04-10 BP Chemicals Limited Butene polymers

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