WO2000032572A2 - Decouverte et essais combinatoires de liquides ioniques - Google Patents

Decouverte et essais combinatoires de liquides ioniques Download PDF

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WO2000032572A2
WO2000032572A2 PCT/US1999/028761 US9928761W WO0032572A2 WO 2000032572 A2 WO2000032572 A2 WO 2000032572A2 US 9928761 W US9928761 W US 9928761W WO 0032572 A2 WO0032572 A2 WO 0032572A2
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substituted
array
group
alkyl
aryl
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WO2000032572A3 (fr
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Vince Murphy
Alfred Hagemeyer
Damodara M. Poojary
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Symyx Technologies
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00047—Ionic liquids
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00281—Individual reactor vessels
    • B01J2219/00283—Reactor vessels with top opening
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement
    • B01J2219/00308—Reactor vessels in a multiple arrangement interchangeably mounted in racks or blocks
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    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
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    • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
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    • B01J2219/00277—Apparatus
    • B01J2219/00479—Means for mixing reactants or products in the reaction vessels
    • B01J2219/00481—Means for mixing reactants or products in the reaction vessels by the use of moving stirrers within the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/0068—Means for controlling the apparatus of the process
    • B01J2219/00702—Processes involving means for analysing and characterising the products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00718—Type of compounds synthesised
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    • B01J2219/00722—Nucleotides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00738—Organic catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
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    • B01J2219/00756—Compositions, e.g. coatings, crystals, formulations
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/04—Libraries containing only organic compounds
    • C40B40/14—Libraries containing macromolecular compounds and not covered by groups C40B40/06 - C40B40/12
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • the present invention relates to combinatorial materials science, specifically to libraries of ionic liquids and methods useful for the combinatorial research into the use and discovery of ionic liquids for a variety of reactions, including reactions where the ionic liquid acts as a part of the reaction medium for the reaction. Combinatorial techniques are employed to test the compositions and methods of this invention.
  • Combinatorial materials science generally refers to methods for creating a collection of diverse compounds or materials using a relatively small set of precursors and/or methods for rapidly testing or screening the collection of compounds or materials for desirable performance characteristics and properties.
  • combinatorial materials science permits scientists to systematically explore the influence of structural variations in candidates by dramatically accelerating the rates at which they are created and evaluated. Compared to traditional discovery methods, combinatorial methods sharply reduce the costs associated with preparing and screening each candidate.
  • Ionic liquids are known. Ionic liquids are ionic compositions that are molten at low temperature, which are sometimes referred to as molten salts. See Seddon, "Ionic Liquids for Clean Technology", J. Chem. Tech. Biotechnol., 68, pp. 351-356 (1997), incorporated herein by reference. Ionic liquids are known to form part of the reaction media for certain types of reactions. For example, Olivier and Chauvin, "Nonaqueous Room-Temperature Ionic Liquids: A New Class of Solvents for Catalytic Organic Reactions", Chem. Ind. (Dekker) (1996), 68, pp.
  • Ionic compounds are known, see for example Kawabata et al. Journal of Antibiotics, vol. 48, no. 9, pp. 1049-1051 (1995). Ionic liquids are commercially available, for example from Solvent Innovation GmbH, Cologne, Germany.
  • Cationic polymerizations are also well known and are described in numerous publications. See, for example G. Odian, Principles of Polymerization (Wiley & Sons, 1991). Cationic polymerization of isoolefins, in particular isobutylene is also well documented. See, for example R. Faust, T. D. Shaffer, Cationic Polymerization (American Chemical Society, 1997).
  • disadvantages associated with the known processes including the use of extremely low temperatures and the need to use polar, volatile solvents such as methyl chloride. There is clearly a need to develop new solvent systems and catalysts, which may be used at higher temperatures.
  • very low Mw polyisobutylenes (below about 3,000 Mw), low Mw polyisobutylenes (about 3,000-10,000 Mw), high Mw polyisobutylenes (between about 10,000-100,000 Mw) and very high Mw polyisobutylenes (above 100,000 Mw) is in the properties that such polymers may possess.
  • Very low Mw polyisobutylenes are typically useful in adhesives, lubricants, motor oil and transmission fluids.
  • Low Mw polyisobutylenes are useful in sealants and caulking applications.
  • High Mw polyisobutylenes are useful in rubber products or as impact modifiers of thermoplastics.
  • Very high Mw polyisobutylenes possess unique physical and chemical properties, such as low oxygen permeability and mechanical resilience, finding uses in the automobile industry as rubber products.
  • Patent 5,304,615 states that when using ionic liquids as the polymerization medium for isobutylene, either alone or with comonomers, "contrary to expectations, the molecular weight of the product does not increase with decreasing temperatures" (col. 4, lines 5-7). Finally, although U.S. Patent 5.304,615 states that polymers of Mw up to 100,000 can be formed (see Example 2), no one has demonstrated, until this invention, the ability to prepare very high Mw polyisobutylenes with an ionic liquid.
  • this invention provides arrays of ionic liquids where each member of the array may be characterized by the general formula A ⁇ B " where A + represents any stable organic or inorganic cation and B " represents any stable organic or inorganic anion.
  • Each member of the array differs from other members of the array by having a different chemical composition.
  • the array can be formed in plates that contain a plurality of vials, with each vial holding a member of the array of the ionic liquids, such that each member of the array cannot contact another member of the array.
  • this invention relates to a method of testing ionic liquids in particular reactions, comprising providing an array of ionic liquids and running the reaction of interest in parallel using the ionic liquids in the array as a component in the reaction, such as the solvent, catalyst, etc.
  • a component in the reaction such as the solvent, catalyst, etc.
  • Different ionic liquid compositions can be tested in the reaction of interest.
  • each member of the array can contain the same ionic liquid allowing for process conditions of the reaction to be varied within the array.
  • the reactions of interest including cross-coupling, Friedel-Crafts, dimerization, oligomerization, polymerization, hydrogenation, oxidation, dehydrogenation, aromatization, carbonylation, dehydrodimerization, hydrodehalogenation, hydrodesulfur
  • this invention relates to the combinatorial testing of ionic liquids for the polymerization of olefins or isoolefins or for the copolymerization of an olefin or isoolefin plus additional comonomer.
  • an array of ionic liquids is provided with an aliquot of each member of the array being dispensed into a reactor block containing a plurality of reaction vessels.
  • the other components of the polymerization reaction are added to the reactor vessels (e.g., monomer, catalyst, co-solvents, etc.) and the reaction is carried out in parallel at desired reaction conditions, which may be varied between two or more arrays or within a single array.
  • reaction components depends on the reaction being studied.
  • other compounds may be added to the ionic liquid to form a new catalyst composition, which polymerizes an isoolefin or copolymerizes the isoolefin plus additional comonomer.
  • this invention uses ionic liquids as a portion of the reaction medium for polymerizing of isoolefins into polyisoolefins in a combinatorial manner.
  • the ionic liquid is part of a two or more phase solvent system, with the other portions of the solvent system comprising non-ionic liquids, such as alkanes (e.g., hexane, heptane), cycloalkanes (e.g., cyclohexane, methyl(cyclohexane), aromatics), Isopar E®, etc.
  • alkanes e.g., hexane, heptane
  • cycloalkanes e.g., cyclohexane, methyl(cyclohexane), aromatics
  • Isopar E® etc.
  • the entire system is agitated to increase surface area between phases and where the system includes all solvents, catalysts, monomers, scavengers, etc.
  • the miscibility of the two or more solvents can be adjusted by changing the components of the ionic liquid, such as by varying the chain length of a hydrocarbon portion of the cation or anion in the ionic liquid.
  • aspects of this invention include methods of making arrays of ionic liquids using liquids handling robots or other methods and methods of running reactions in parallel with ionic liquids.
  • R groups e.g., R 1 , R 2 , and R 3
  • R 1 , R 2 and R 3 can be identical or different (e.g. R 1 , R 2 and R 3 may all be substituted alkyls or R 1 and R ⁇ may be a substituted alkyl and R 3 may be an aryl, etc.).
  • a named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name.
  • representative R groups as enumerated above are defined herein. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.
  • catalyst is used herein to include all forms of catalysis, including classic initiators, co-initiators, co-catalysts, activating techniques, etc.
  • an organometallic compound has a cationic charge, initiating a cationic polymerization in an ionic liquid, the organometallic will be referred to as a catalyst herein.
  • the organometallic compound or complex operates in a coordination mechanism, it will still be referred to herein as a catalyst.
  • hydrocarbyl is used herein to refer to a radical having only carbon and hydrogen atoms, including, e.g., alkyl and the like.
  • alkyl is used herein to refer to a branched or unbranched, saturated or unsaturated, monovalent hydrocarbon radical. When the alkyl group has from 1-6 carbon atoms, it is referred to as a "lower alkyl.” Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, 2-propenyl (or allyl), n-butyl, t-butyl, i- butyl (or 2-methylpropyl), etc. In particular embodiments, alkyls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
  • Substituted alkyl refers to alkyl as just described including one or more groups such as lower alkyl, aryl, acyl, halogen (i.e., alkylhalos, e.g., CF 3 ), hydroxy, amino, phosphido, alkoxy, alkylamino, acylamino, acyloxy, aryloxy, aryloxyalkyl, mercapto, both saturated and unsaturated cyclic hydrocarbons, heterocycles and the like. These groups may be attached to any carbon of the alkyl moiety.
  • groups such as lower alkyl, aryl, acyl, halogen (i.e., alkylhalos, e.g., CF 3 ), hydroxy, amino, phosphido, alkoxy, alkylamino, acylamino, acyloxy, aryloxy, aryloxyalkyl, mercapto, both saturated and unsaturated cyclic
  • aryl is used herein to refer to an aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety.
  • the common linking group may also be a carbonyl as in benzophenone.
  • the aromatic ring(s) may include substituted or unsubstituted phenyl, naphthyl, biphenyl, diphenylmethyl and benzophenone among others.
  • aryls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
  • Substituted aryl refers to aryl as just described including one or more groups such as alkyl, acyl, halogen, alkylhalos (e.g., CF 3 ), hydroxy, amino, phosphido, alkoxy, alkylamino, acylamino, acyloxy, mercapto and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety.
  • the linking group may also be a carbonyl such as in cyclohexyl phenyl ketone.
  • substituted aryl groups include -C 6 F 5 and -C 6 H (CF ) 2 .
  • acyl is used to describe a substituted carbonyl substituent, — C(O)J, where J is alkyl or substituted alkyl, aryl or substituted aryl as defined herein.
  • amino is used herein to refer to the group -NJJ', where J and J' may independently be hydrogen, alkyl, substituted alkyl, aryl, substituted aryl or acyl.
  • alkoxy is used herein to refer to the — OJ group, where J is an alkyl, substituted lower alkyl, aryl, substituted aryl, wherein the alkyl, substituted alkyl, aryl, and substituted aryl groups are as described herein.
  • Suitable alkoxy radicals include, for example, methoxy, ethoxy, phenoxy, substituted phenoxy, benzyloxy, phenethyloxy, t-butoxy, etc.
  • phosphino refers to the group -PIT, where J and J' may independently be hydrogen, alkyl, substituted alkyl, aryl, substituted aryl or acyl.
  • mercapto defines moieties of the general structure J — S — J' wherein J and J' are the same or different and are hydrogen, alkyl, aryl or unsubstituted or substituted heterocyclic as described herein.
  • saturated cyclic hydrocarbon denotes groups such as cyclopropyl, cyclobutyl, cyclopentyl, etc. and substituted analogues of these structures.
  • unsaturated cyclic hydrocarbon is used to describe a monovalent nonaromatic group with at least one double bond, such as cyclopentene, cyclohexene, etc. and substituted analogues thereof.
  • heteroaryl refers to aromatic rings in which one or more carbon atoms of the aromatic ring(s) are substituted by a heteroatom such as nitrogen, oxygen or sulfur.
  • Heteroaryl refers to structures that may be a single aromatic ring, multiple aromatic ring(s), or one or more aromatic rings coupled to one or more nonaromatic ring(s). In structures having multiple rings, the rings can be fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety.
  • the common linking g ⁇ oup may also be a carbonyl as in phenyl pyridyl ketone.
  • rings such as thiophene, pyridine, isoxazole, phthalimide, pyrazole, indole, furan, etc. or benzo-fused analogues of these rings are defined by the term "heteroaryl.”
  • Heteroarylalkyl defines a subset of “alkyl” wherein the heteroaryl group is attached through an alkyl group as defined herein. For example, if R 2 is a heteroarylalkyl, the alkyl portion will be bonded to the atom from which R 2 emanates and the heteroaryl portion will be a "substituent" on the alkyl.
  • Substituted heteroaryl refers to heteroaryl as just described wherein the heteroaryl nucleus is substituted with one or more groups such as alkyl, acyl, halogen, alkylhalos (e.g., CF 3 ), hydroxy, amino, alkoxy, alkylamino. acylamino, acyloxy, mercapto, etc.
  • substituted analogues of heteroaromatic rings such as thiophene, pyridine, isoxazole, phthalimide, pyrazole, indole, furan, etc. or benzo-fused analogues of these rings are defined by the term "substituted heteroaryl.”
  • Substituted heteroarylalkyl refers to a subset of "substituted alkyls” as described above in which an alkyl group, as defined herein, links the heteroaryl group to the bonding point on the ligand.
  • heterocyclic is used herein to describe a monovalent saturated or unsaturated nonaromatic group having a single ring or multiple condensed rings from
  • heterocycles 1-12 carbon atoms and from 1-4 heteroatoms selected from nitrogen, phosphorous sulfur or oxygen within the ring.
  • heterocycles are, for example, tetrahydrofuran, morpholine, piperidine, pyrrolidine, etc.
  • substituted heterocyclic as used herein describes a subset of “heterocyclics” wherein the heterocycle nucleus is substituted with one or more functional groups such as alkyl, acyl, halogen, alkylhalos (e.g., CF ), hydroxy, amino, alkoxy, alkylamino, acylamino, acyloxy, mercapto, etc.
  • functional groups such as alkyl, acyl, halogen, alkylhalos (e.g., CF ), hydroxy, amino, alkoxy, alkylamino, acylamino, acyloxy, mercapto, etc.
  • heterocyclicalkyl defines a subset of “alkyls” wherein an alkyl group, as defined herein, links the heterocyclic group to the bonding point on the molecule.
  • substituted heterocyclicalkyl defines a subset of "heterocyclic alkyl” wherein the heterocyclic nucleus is substituted with one or more groups such as alkyl, acyl, halogen, alkylhalos (e.g., CF ), hydroxy, amino, alkoxy, alkylamino, acylamino, acyloxy, mercapto, etc.
  • scavenger is used herein to mean a compound that does not substantially interfere with the reaction, but reacts with impurities or undesired species that may be present in the system.
  • a “scavenger” is intended to refer to a compound that increases catalyst activity presumably by reacting with impurities or undesired species.
  • polyisobutylenes is used herein to refer to either homopolymers of isobutylene or copolymers of isobutylene and a suitable comonomer, which include acrylates, methacrylates, acrylonitriles, C -C 20 butadienes, C -C 7 isoolefins, C 4 -C ⁇ diolefins, C 4 - conjugated diolefins, cationically polymerizable aromatics (such as indene and fulvenes) and styrene (each of which can be substituted or unsubstituted).
  • acrylates methacrylates, acrylonitriles
  • C -C 20 butadienes C -C 7 isoolefins
  • C 4 -C ⁇ diolefins C 4 - conjugated diolefins
  • cationically polymerizable aromatics such as indene and fulvenes
  • styrene
  • More specific comonomers included within the definition of polyisobutylenes include those selected from the group consisting of piperylene, 2,3-dimethylbutadiene, 2,4- dimethyl- 1,3-pentadiene, cyclopentadiene, methylcyclopentadiene, limonene, 1 ,3- cyclohexadiene, norbornadiene, isoprene, 1-butene, 2-butene, norbornene and combinations thereof.
  • the ionic liquids in the array(s) of this invention may be characterized by the general formula A + B " where A + is a cationic organic or inorganic molecule and B " is an anionic organic or inorganic molecule. In some embodiments, A + can be linked to
  • Mole fractions of A + and B " in the ionic liquid are one variable that may be changed between members of the array of ionic liquids.
  • acyclic organic systems are also suitable and may be converted into stable organic cations A + in a similar manner.
  • examples include, but are not limited to amines (including amidines, imines, guanidines and the like), phosphines (including phosphinimines and the like), arsines, stibines, ethers, thioethers, selenoethers and the like.
  • a + can be characterized by the general formula:
  • R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; and a is 0, 1, 2 or 3 signifying the number of R 3 groups attached to a carbon atom of the ring.
  • R 1 is ethyl and R " is methyl.
  • a + can be characterized by the general formula:
  • R 1 and R 3 are as defined above and b is 0, 1, 2, 3, 4 or 5 signifying the number of R 3 groups attached to a carbon atom of the ring.
  • a + can be characterized by the general formula:
  • R 1 , R 2 , R 3 and a are as defined above.
  • a + can be characterized by the either of the general formulas: R'R ⁇ R 4 ⁇ or R'R R 4 ?* where each of R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl. heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino. thio, seleno, and combinations thereof.
  • B " may be represented by the general formula
  • Z X Z " where R is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl. substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; X is selected from the group of halogens (e.g., Cl, F, I and Br); and z is 0, 1, 2, 3 or 4.
  • R is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl. substituted heteroaryl, alkoxy, aryloxy, acyl,
  • B " may be selected from the group consisting of halogens, JX 4 " , PF 6 “ , AsF “ , SbF 6 ⁇ NO “ , NO-, “ , S0 2” , JR4 * (where R is as defined above, X is as defined above and J is boron), substituted or unsubstituted carboranes , substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometallates, substituted or unsubstituted carboxylates and triflates.
  • B " may also be a non-coordinating anion; see U.S. Patent 5,599,761, incorporated herein by reference.
  • B " is an inorganic anion, such as A1 2 C1 7 ⁇ Cl “ , JF “ (where J is boron), PF 6 “ , A1C1 " or a metal-organic anion.
  • an ionic liquid may comprise multiply charged cations or multiply charged anions, or both.
  • a n+ B n" A n+ nB " nA + B n" where n is any positive integer greater than 1.
  • An ionic liquid using a multiply charged ion is one that uses an imidazolium cation that may be represented by the following general formula:
  • R, R , R ⁇ , R and a are as defined above, and m is an integer from 1-50.
  • This example is depicted with an alkyl chain connecting the two-imidazolium moieties, but other connecting chains may also be used, such as substituted alkyls, substituted aryls and the like.
  • Ionic liquids containing other multiply charged systems can also be used, including multiply charged cations prepared from the other unsubstituted or substituted heterocyclic ring systems or acyclic systems described above.
  • Ionic liquids containing multiply charged ions may be mixed with ionic liquids containing singly charged ions to form useful catalyst combinations.
  • the ionic liquids used in this invention may be combined with reagents that may initiate cationic polymerizations, such as, but not limited to JR 3 . y X y , AlR 3 . y X y , alkylaluminoxanes, GaR 3 . y X y , InR 3 . y X y , TiR ⁇ X z , In(triflate) , Ge[NR 2 ] 2 , SnR_ t . z X z , VC1 3 . VC1 4 .
  • reagents that may initiate cationic polymerizations, such as, but not limited to JR 3 . y X y , AlR 3 . y X y , alkylaluminoxanes, GaR 3 . y X y , InR 3 . y X y , TiR ⁇ X z , In(triflate) , Ge[NR
  • R is defined as above; J is boron; y is a number 0, 1 , 2 or 3; z is a number 0. 1 , 2, 3 or 4; Cp is an unsubstituted or substituted cyclopentadienyl ring, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl and the like such as bridging version of cyclopentadienyl, idenyl and fluorenyl complexes; X is a halogen, such as Cl, Br, I or F. Other initiators known to those skilled in the art may also be suitable.
  • the ionic liquid of this invention may contain a functional group, for example, that can act as a catalyst or scavenger.
  • the functional group may be attached directly to the cationic portion of the ionic liquid, such as is represented by the following general formula:
  • R, R , R , a and m are as defined above, and Y is any functional group.
  • Y is capable of binding the catalyst or scavenger to a component of the ionic liquid.
  • the catalyst or scavenger may be joined to the anion
  • R, R 1 , R 3 a and m are as defined above; and R 4 and R" ⁇ are defined as R 1 is defined above and D may be any halogen, SCN, CN, OH, OR. OCOR, COOR, O 2 SR.
  • This ionic liquid may be combined with a catalyst (and/or optionally a scavenger) such as those listed above to form useful catalyst compositions capable of preparing very high molecular weight polyisobutylenes.
  • ionic liquids of this invention may be made by methods known to those of skill in the art. See for example, U.S. Patent No. 5,731,101 and WO 95/21871 , both of which are incorporated herein by reference.
  • the ionic liquids of this invention can be catalysts alone, or may be combined with other compounds to form new catalytic compositions.
  • Organometallic complexes may be added to the ionic liquids, with such complexes being any of those disclosed in commonly owned U.S. patent application no. 08/898,715, filed July 22, 1997, inco ⁇ orated herein by reference.
  • the catalysts useful with the ionic liquids are those that initiate a cationic polymerization reaction, including those listed above. See also WO 95/29940, inco ⁇ orated herein by reference.
  • Other mechanisms besides cationic polymerization may be at work in the presence of an organometallic complex, which may or may not have a charge. This specification is not limited to a cationic mechanism in conjunction with polymerization reactions.
  • the presence of the ionic liquid will have an effect on the polarity of polymerization mixture.
  • the structure, yield, selectivity, molecular weight, etc. of the polymer product formed can vary.
  • the ionic liquid can solubilize compounds that are ordinarily insoluble in organic solvents (e.g., metal complexes), the products can be readily separated from the ionic liquid, for example by decanting.
  • this invention provides an easy method for removing product polymers from unwanted catalyst and avoiding additional ashing procedures for the removal of catalysts from polymer products.
  • this invention anticipates that novel polymers, copolymers or inte ⁇ olymers may be formed as a result of the processes of this invention, including polymers having unique physical and melt flow properties.
  • Such polymers can be employed alone or with other polymers in a blend to form products that may be molded, cast, extruded or spun.
  • Polymerization can be carried out in a cationic process or in the Ziegler-Natta or Kaminsky-Sinn methodology, including temperatures of from -100°C to 400°C and pressures from atmospheric to 3000 atmospheres.
  • the ionic liquids may serve only as the solvent for an organometallic compound or complex, which acts as the catalyst.
  • organometallic complexes such as mono-cyclopentadienyl or bis-cyclopentadienyl complexes.
  • the organometallic compounds may be active catalysts or may be combined with an activator.
  • an activator or activating technique those of skill in the art may use alumoxanes, strong Lewis acids, compatible noninterfering activators and combinations of the foregoing. See U.S. Patents 5,599,761 , 5,616,664, 5,453,410, 5,153,157 and 5,064,802.
  • Suspension, solution, slurry, gas phase or high-pressure polymerization processes may be employed with the catalysts and compounds of this invention.
  • Such processes can be run in a batch, semi-batch or continuous mode. Examples of such processes are well known in the art.
  • a support for the catalyst may be employed, which may be alumina, silica or a polymers support. Methods for the preparation of supported catalysts are known in the art. Slurry, suspension, solution and high- pressure processes use a suitable solvent as known to those skilled in the art.
  • the ionic liquids of this invention form a portion of the reaction medium by mixing the ionic liquid with one or more co-solvents.
  • the miscibility of the ionic liquid with the one or more co- solvents may result in a solvent system that does not appear to be a two phase solvent system.
  • the miscibility of the ionic liquid with the co-solvent(s) can be adjusted by changing R, R 1 , R 2 or R 3 in the above formulas for the ionic liquids to be more compatible with the co-solvent.
  • R is a long chain alkane
  • the ionic liquid will be more miscible with a hexane co-solvent.
  • a long chain alkane is considered to be a Cio-Cioo alkyl, for example.
  • Co-solvents can be selected from the group consisting of alkanes, substituted alkanes, aromatics and substituted aromatics.
  • a mixed solvent system i.e., ionic liquid and co-solvent
  • ionic liquid and co-solvent may increase the solubility of certain organometallic complexes. See, Chauvin et al., bid. Eng. Chem.
  • Reactions useful to this invention include but are not limited to certain other organic transformations, such as cross-coupling reactions (e.g., Suzuki, Heck, aminations, Negishi, Meyers, Stille etc.), Friedel-Crafts, dimerization, oligomerization and polymerization reactions (e.g., Ziegler-Natta catalysts and other single-site coordination catalysts such as metallocenes may be used in the presence of an ionic liquids) as well as the other reactions listed herein.
  • cross-coupling reactions e.g., Suzuki, Heck, aminations, Negishi, Meyers, Stille etc.
  • Friedel-Crafts e.g., dimerization
  • oligomerization and polymerization reactions e.g., Ziegler-Natta catalysts and other single-site coordination catalysts such as metallocenes may be used in the presence of an ionic liquids
  • ionic liquids can be used to form two phases, leading to a large number of organic product mixtures useful in heterogeneous catalysis. In many cases this leads to a bi-phasic system which allows easy product separation and catalyst recycling.
  • the lack of vapor pressure allows convenient removal of products through distillation.
  • metal catalyzed reactions either by oxidized metals (e.g. Pd 2+ ) or by reduced metals (e.g. Pd (0) ). These metals could be in homogeneous solution or immobilized/heterogenized onto a support.
  • Reduced metals can be unsupported (e.g., Pd black, nanoparticles, clusters, colloids) or supported (e.g., Pd/C).
  • Metal ions can be reduced or activated in-situ in the ionic liquid (e.g., by contacting with a gaseous reducing agent).
  • a gaseous reducing agent By proper choice (or high throughput screening of arrays of ionic liquids) of cations and anions the catalyst performance can be improved.
  • the selection of anions ranges from basic, coordinating anions like Cl ⁇ to acidic, non-coordinating anions like A1 2 C1 ⁇ (as discussed above).
  • the anions may have a significant role in the reactivity of the metal catalyst.
  • co-solvents or modifiers the reactivity of the catalytic metal can be further enhanced. For example, transferring its coordinating Cl ⁇ ligands to a Lewis acid can activate Pd ions.
  • each of the candidate materials e.g., catalysts
  • a capability to enhance a chemical process of interest e.g., a chemical reaction
  • the candidate materials can be in a gaseous, liquid or solid phase. Solid-phase materials are preferred for some applications.
  • the particular elements, compounds or compositions to be included in a library of candidate materials will depend upon the particulars of the chemical process being investigated. However, the particular chemical process being investigated is not critical, and can include chemical reactions and chemical separations, among others.
  • the chemical process is preferably a chemical reaction, which for pu ⁇ oses hereof, means a process in which at least one covalent bond of a molecule or compound is formed or broken.
  • immunoreactions in which immunoaffinity is based solely on hydrogen bonding or other forces - while chemical processes - are not considered to be chemical reactions.
  • CO/alkene, CO/alkyne co-polymerization
  • co-polymerization e.g. CO/alkene, CO/alkyne
  • insertion reaction aziridation, metathesis (including olefin metathesis), carbon-hydrogen activation, cross coupling, Friedel-Crafts acylation and alkylation, Diels-AIder reactions, C-C coupling, Heck reactions, arylations, Fries rearrangement, vinylation, acetoxylation, aldol-type condensations, aminations, reductive aminations, hydrodechlorinations, hydrodesulfurations and Fischer-Tropsch reactions, asymmetric versions of any of the aforementioned reactions, and combinations of any of the aforementioned reactions in a complex reaction sequence of consecutive reactions.
  • the candidate materials can be generally classified as those materials which are chemically altered or consumed during the course of the reaction (e.g., co-reactant materials, cataloreactants) and those materials which are not chemically altered or consumed during the course of the reaction (e.g., catalysts, selective blocking moieties).
  • the candidate materials are catalysts.
  • the term catalyst is intended to include a material that enhances the reaction rate of a chemical reaction of interest or that allows a chemical reaction of interest to proceed where such reaction would not substantially proceed in the absence of the catalyst.
  • the candidate materials preferably comprise elements or compounds selected from the group consisting of inorganic materials, metal-ligands and non-biological organic materials.
  • the candidate materials will consist essentially of inorganic materials, consist essentially of metal-ligand materials, or consist essentially of non-biological organic materials.
  • the candidate materials will be compositions comprising mixtures of inorganic materials, metal-ligand materials, and/or non-biological organic materials in the various possible combinations.
  • Inorganic materials include elements (including carbon in its atomic or molecular forms), compounds that do not include covalent carbon-carbon bonds (but which could include carbon covalently bonded to other elements, e.g., CO ), and compositions including elements and/or such compounds.
  • Inorganic candidate materials that could be investigated according to the approaches described herein include, for example: noble metals such as Au, Ag, Pt, Ru, Rh, Pd, Ag, Os and Ir; transition metals such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Hf, Nb, Mo, Ta, W and Re; rare-earth metals such as La, Ce, Pr, Nd, Sm, Eu, Tb, Th, Dy and U; alloys of noble metals, transition metals and or rare-earth metals; metal oxides such as CuO, NiO and Co 3 0 ; noble-metal-doped metal oxides such as noble-metal-doped CuO, NiO and Co 3 0 4 ; multi-metal oxides such as binary oxides of Cu-Cr, Cu-Mn, Cr-Mn, Ni-Cr, Ni-Mn, Ni-Cu, Ni-Mo, Cu-Mo, Ni-Co, Co-Mo,
  • metal carbides such as MoC, WC, PdC
  • metal sulfates metal sulfides, metal nitrides, metal carbonates, metal chlorides, metal acetates, polyoxometallates (POM); metal phosphates such as vanadylpyrophosphates (VPO); Bronstead acids such as HF; Lewis Acids such as A1C1 3 ; and mixtures of any of the aforementioned inorganic materials, among others.
  • Exemplary inorganic material libraries could include, for example, a triangular-shaped array of ternary metal oxides (e.g. such as oxides of the ternary metal partners described above) with single metal oxide compounds at each corners, binary metal oxide compositions along each of the sides with varying ratios of constituents, and ternary metal oxide compositions in the interior regions of the triangular array with varying ratios of constituents.
  • ternary metal oxides e.g. such as oxides of the ternary metal partners described above
  • Quaternary rectangle-shaped arrays of metal oxides having 4 metals in each well and ternaries as the edges can be used.
  • the inorganic materials do not have to be in the solid state to be catalytically active, although in many embodiments the materials will be in the solid state.
  • Homogeneous solutions of atomically dispersed metal ions with inorganic, simple substituents (as opposed to complex ligands) and anionic counterions are one embodiment of the invention.
  • the precursor can be a soluble solid salt of the metal or a stock solution. Examples are Pd(OAc) 2 , Pd(NO 3 ) 2 , PdCl 2 , and PdSO 4 .
  • Redox active metals like the soluble salts of V, Cr, Mn, Fe, Co, Ni, Cu, Pd, Pt, Os, Rh, Re, Ru, Ce and Lewis acidic metals, like Al, B, Ga, Ge, Sn, Sb, Ir, Re, the rare earths, Ti, Zr, Zn, Fe, W, Mo are most common.
  • Anions are simple and available like acetate, nitrate, sulfate, chloride, and oxalate. Libraries of inorganic candidate materials can be prepared, for example, according to the methods disclosed in U.S. Patent No. 5,776,359 to Schultz et al.
  • Metal-ligands comprise a central metal atom or ion surrounded by, associated with and/or bonded to other atoms, ions, molecules or compounds - collectively referred to as "ligands" - typically through a carbon (to form, e.g., an organometallic), nitrogen, phosphorous, sulfur or oxygen atom and/or one or more linker moieties.
  • the one or more ligands typically bind to one or more metal center and/or remain associated therewith, and by such association, modify the shape, electronic and/or chemical properties of the active metal center(s) of the metal-ligand complex.
  • the ligands can be organic (e.g., • '-aryl, alkenyl, alkynyl, cyclopentadienyl, CO, alkylidene, carbene) or inorganic (e.g., Br “ , Cl “ , OH “ , NO 2" , etc.), and can be charged or neutral.
  • the ligand can be an ancilliary ligand, which remains associated with the metal center(s) as an integral constituent of the catalyst or compound, or can be a leaving group ligand, which may be replaced with an ancillary ligand or an activator component.
  • Exemplary metals / metal ions include ions derived from, for example, simple salts (e.g., A1C1 3 , NiCl 2 , etc.), complex or mixed salts comprising both organic and inorganic ligands (e.g., [(• 5-C 5 Me 5 )IrCl ] 2 , etc.) and metal complexes (e.g., Gd(NTA) 2 , CuEDTA, etc.), and can generally include, for example, main group metal ions, transition metal ions, lanthanide ions, etc.
  • simple salts e.g., A1C1 3 , NiCl 2 , etc.
  • complex or mixed salts comprising both organic and inorganic ligands
  • metal complexes e.g., Gd(NTA) 2 , CuEDTA, etc.
  • main group metal ions e.g., transition metal ions, lanthanide ions, etc.
  • metal-ligand candidate materials can be prepared, for example, according to the methods disclosed in PCT Patent Application WO 98/03521 of Weinberg et al. Briefly, a desired ligand can be combined with a metal atom, ion, compound or other metal precursor compound. In many applications, the ligands will be combined with such a metal compound or precursor and the product of such combination is not determined, if a product forms. For example, the ligand may be added to a reaction vessel at the same time as the metal or metal precursor compound along with the reactants.
  • the metal precursor compounds may be characterized by the general formula M(L) rule (also referred to as ML n or M-Ln) where M is a metal and can include metals selected from the group consisting of Groups 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements.
  • M can be selected from the group consisting of Ni, Pd, Fe, Pt, Ru, Rh, Co and Ir.
  • L is a ligand and can be selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, hydrido, thio, seleno, phosphino, amino, and combinations thereof, among others.
  • L When L is a charged ligand, L can be selected from the group consisting of hydrogen, halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof .
  • L When L is a neutral ligand, L can be selected from the group consisting of carbon monoxide, isocyanide, nitrous oxide, PA 3 , NA 3 , OA 2 , SA 2 ,
  • SeA SeA , and combinations thereof, wherein each A is independently selected from a group consisting of alkyl, substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.
  • the ligand to metal precursor compound ratio is in the range of about 0.01 : 1 to about 100: 1, more preferably in the range of about 0.5: 1 to about 20: 1.
  • the metal atom, ion or metal precursor may be supported or not. Supports may be organic or inorganic. Similar to the ligands, the support may be an L. In other embodiments, the support will not form part of the metal precursor and suitable supports include silicas, aluminas, zeolites, polyethyleneglycols, polystyrenes, polyesters, polyamides, peptides and the like.
  • Pd supported metals include Pd/C, Pd/Si0 2 , Pd/CaC0 3 , Pd/BaC0 3 , Pd/aluminate, Pd/aluminum oxide, Pd/polystyrene, although any of the metals listed above could replace Pd in this list, e.g., Ni/C, etc.
  • the ligand will be mixed with a suitable metal precursor compound prior to or simultaneous with allowing the mixture to be contacted to the reactants. When the ligand is mixed with the metal precursor compound, a metal-ligand complex may be formed, which may be employed as a candidate material.
  • Non-biological organic materials include organic materials other than biological materials.
  • Organic materials are considered to include compounds having covalent carbon-carbon bonds.
  • Biological materials are considered to include nucleic acid polymers (e.g., DNA, RNA) amino acid polymers (e.g., enzymes) and small organic compounds (e.g., steroids, hormones) where the small organic compounds have biological activity, especially biological activity for humans or commercially significant animals such as pets and livestock, and where the small organic compounds are used primarily for therapeutic or diagnostic pu ⁇ oses.
  • nucleic acid polymers e.g., DNA, RNA
  • amino acid polymers e.g., enzymes
  • small organic compounds e.g., steroids, hormones
  • candidate materials being screened are preferably not, themselves, biological organic materials
  • the candidate materials of the invention can be employed to enhance reactions directed to producing a biological organic material as the product of a chemical reaction (e.g., materials that enhance chemical-based, non-enyzmatic DNA synthesis, or materials that enhance a synthetic, non-enyzmatic route to a particular hormone or steroid).
  • the candidate materials are catalysts being screened for catalytic activity and/or for catalytic selectivity for a chemical reaction of interest.
  • the candidate catalysts can be homogeneous catalysts or heterogeneous catalysts.
  • the candidate materials are preferably solids or liquids which are soluble or miscible in the reaction medium under the reaction conditions, but can also include gasses.
  • the candidate materials are preferably solids.
  • homogeneous candidate catalyst materials and heterogeneous candidate catalyst materials can include organic, inorganic and metal- ligand catalysts such as are described above.
  • Suzuki biaryl cross-coupling Pd-ligand e.g., phosphine
  • Rh- ligand e.g., phosphine, phosphite
  • hydrocarboxylation Mo-, Pd-, Rh-, Co-, ligand e.g., phosphine
  • Ni-, Pd- ligand e.g., bis-imine
  • olefin metathesis Ru- e.g., Mo- ligand
  • Ir methanol carbonylation
  • Rh with halides e.g., Mel, HI
  • epoxide ring opening Cu-ligand (e.g., alkoxide, amide, amine) halogen exchange reaction R4P + X "
  • X halide
  • Ar-Br -» Ar-F hydrolysis H + source (e.g., H 2 S0 )
  • Metal ions e.g., Zn, Cu, Pb, Mn, Cd,
  • the ionic liquids, catalysts, compositions and processes of this invention can ared and/or tested for in a combinatorial fashion.
  • the ionic liquids, complexes or processes may be prepared and/or tested in rapid serial and/or parallel fashion, e.g., in a library or array format.
  • the ionic liquids may take the form of one or more arrays comprising a plurality of compositions wherein each composition can be characterized by the general formula A + B " with the definitions above applying to this formula.
  • each of the plurality of compositions is somehow different from the other compositions in the array.
  • differences can be compositional (such as composition of ionic liquid or ratio of ionic liquid to other reaction media or catalyst composition or metal complex to activator ratio or volume of solvent, etc.), processing parameters (such as temperature, pressure, atmosphere composition, etc.) or other differences that those of skill in the art will recognize from a review of this specification.
  • each composition in the array is at a selected region on a substrate such that each composition is isolated from the other compositions. This isolation can take many forms, typically depending on the substrate used. If a flat substrate is used, there may simply be sufficient space between regions so that there cannot be interdiffusion between compositions.
  • the substrate can be a microtiter or similar plate having wells so that each composition is in a region separated from other compositions in other regions by a physical barrier.
  • the array typically comprises at least 10 different compositions, e.g., 10 different ionic liquids or 10 different mixed solvent systems including an ionic liquid or etc. In other embodiments, there are at least 25 compositions on or in the substrate each having a different chemical formula. In still other embodiments, there are at least 50 or 96 or 124 or more compositions on or in the substrate. Because of the manner of forming combinatorial arrays, it may be that each compound, material or composition is not pure. Typically, each compound, material or composition in the plurality is at least 50% pure within its region.
  • the library formed depends on how the desired reaction will be tested.
  • the libraries of this invention can be one or more arrays of ionic liquids, monomers and/or comonomers, solvents, catalysts, metal- ligand complexes or activators.
  • an array of ionic liquids having different compositions in the plurality can be formed and then used keeping all other conditions of the reaction constant.
  • reaction conditions, processes, reactants, catalysts or solvents can be varied in a known manner using one or more arrays of the present invention.
  • this invention provides arrays of ionic liquids where each member of the array may be characterized by the general formula A " ⁇ " where A + represents any stable organic or inorganic cation and B " represents any stable organic or inorganic anion. More specific definitions of A + and B " are discussed above.
  • the array can be formed in a plate that contain a plurality of vials, with each vial holding a member of the array of the ionic liquids, such that each member of the array cannot contact another member of the array.
  • the arrays can be in titer plate format, such as in a microtiter plate so that one member of the array cannot contact another member of the array.
  • One combinatorial research application is a method of discovering ionic liquids useful for particular reactions with the steps of the method comprising: providing an array of ionic liquids and running the reaction of interest in parallel using the ionic liquids in the array as a component in the reaction.
  • the ionic liquid can be functioning in any of the capacities discussed above, such as the solvent, initiator, etc. Different ionic liquid compositions can be tested in the reaction of interest.
  • each member of the array can contain the same ionic liquid allowing for process conditions of the reaction to be varied within the array. An example of this is shown in Example 1 where different members in the array contain the same ionic liquid, but are tested in a polymerization reaction carried out at different temperatures.
  • ionic liquids for the polymerization of isoolefins or for the copolymerization of an isoolefin plus additional comonomer can be tested in a combinatorial manner.
  • an array of ionic liquids is provided with an aliquot of each member of the array being dispensed into a reactor block containing an array of reaction vessels.
  • the reactor blocks discussed in the other inco ⁇ orated patent applications and patents below can be used in this embodiment.
  • the common theme among them is a plurality of reaction vessels for temperature or pressure controlled experiments.
  • the other components of the polymerization reaction are added to the reactor vessels (e.g., monomer, initiators, co-initiators, co-solvents, etc.) and the reaction is carried out at desired reaction conditions, which may be varied between two or more arrays or within a single array.
  • the order of addition of reaction components depends on the reaction being studied.
  • other compounds may be added to the ionic liquid to form a new catalyst composition, which polymerizes an isoolefin or copolymerizes the isoolefin plus additional comonomer.
  • the preferred isoolefins are isobutylenes for creating polyisobutylenes.
  • the catalytic performance (activity and/or selectivity) of the compositions of this invention can be tested in a combinatorial or high throughput fashion.
  • thin layer chromatography in combination with imaging technology may be employed or accelerated liquid chromatographic techniques or accelerated characterization techniques may be used.
  • TLC is well known in the art, see for example Vol. 1 , Thin-Layer Chromatography, Reagents & Detection Methods, Jork et al. (VCH Publishers, New York, New York 1990), inco ⁇ orated herein by reference.
  • accelerated liquid chromatographic, gel permeation chromatography and other techniques see provisional U.S. patent application no.
  • High throughput screening can also be performed rapidly and/or optically and/or in parallel, for example, as disclosed in commonly owned U.S. Patent Applications 09/067,448, filed April 2, 1998, 08/947,085, filed October 8, 1997, 09/113,171, filed August 12, 1998, and 08/946,135, filed October 7, 1997, each of which is inco ⁇ orated by reference.
  • Example 1/Library 1 an ionic liquid was used as a catalyst for the polymerization of isobutylene.
  • the ionic liquid chosen for this library was l-methyl-3-ethylimidazolium aluminum tetrachloride.
  • the reaction temperature was set to -30 °C by setting the cryogenic reactor. After this setup, (i.e., following the addition of the isobutylene), the reaction was stirred for 1 hour whereupon the reaction was quenched with 30 microliters of ethanol. The reactor was opened up and the polymer from each library element was analyzed by rapid molecular weight gel permeation chromatography described in provisional U.S. patent application no. 60/080,652, filed April 3, 1998, inco ⁇ orated herein by reference. The polymer yields and molecular weights are given below in Tables 3 and 4, respectively. Table 3: Approximate Polymer Yields (given as percentages)
  • Example 2/Librarv 2 The following example represents the case where a catalyst was added to an ionic liquid to produce a new catalyst composition for the polymerization of isobutylene.
  • the catalyst chosen for this library was ethylaluminumdichloride dispensed as a 1M solution in hexane. The polymerization was performed in hexane.
  • the ionic liquid chosen for this library was l-methyl-3-ethylimidazolium aluminum tetrachloride.
  • the following 12 x 8 library was created by dispensing the following volumes of ionic liquid (Table 5), ethylaluminumdichloride (Table 6), hexane (Table 5).
  • the reaction temperature was set to -30 °C by setting the cryogenic reactor. After this setup, (i.e., following the addition of the isobutylene), the reaction was stirred for 1 hour whereupon the reaction was quenched with 30 microliters of ethanol. The reactor was opened up and the polymer from each library element was analyzed as in Example 1. The polymer yields and molecular weights are given below in Tables 9 and 10, respectively.

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Abstract

La présente invention concerne des ensembles de liquides ioniques pour la recherche scientifique dans le domaine des matériaux combinatoires. Ces liquides non ioniques. Ces liquides ioniques peuvent être caractérisés par la formule générale A+B- dans laquelle A+ représente un quelconque cation inorganique ou organique stable, et B- un quelconque anion organique ou inorganique stable. Ces ensembles peuvent être utilisés comme co-solvants dans diverses réactions chimiques.
PCT/US1999/028761 1998-12-04 1999-12-03 Decouverte et essais combinatoires de liquides ioniques WO2000032572A2 (fr)

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Cited By (20)

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EP1104751A1 (fr) * 1999-12-03 2001-06-06 Bayer Ag Procédé de production d'un mélange d'isomères de dinitronaphthalène à proportion élevée en 1,5-dinitronaphthalène
WO2001081436A1 (fr) * 2000-04-25 2001-11-01 Equistar Chemicals, L.P. Polymerisations d'olefines a l'aide de liquides ioniques utilises comme solvants
WO2002030862A1 (fr) * 2000-10-10 2002-04-18 The Queen's University Of Belfast Oxydation de composes alkyl-aromatiques
US6531241B1 (en) 1999-07-08 2003-03-11 Covalent Associates, Inc. Cyclic delocalized cations connected by spacer groups
FR2829763A1 (fr) * 2001-09-18 2003-03-21 Rhodia Polyamide Intermediates Procede de fabrication de composes nitriles
WO2003028882A1 (fr) 2001-10-02 2003-04-10 The Queen's University Of Belfast Procedes utilisant des zeolites en tant que catalyseurs/precurseurs de catalyseur
US6552232B2 (en) * 2001-06-26 2003-04-22 Exxonmobil Research And Engineering Company Process for conducting aldol condensation reactions in ionic liquid media
US6673737B2 (en) 2001-05-30 2004-01-06 Exxonmobil Research And Engineering Company Ionic liquid compositions
WO2007029929A1 (fr) 2005-09-07 2007-03-15 Lg Chem, Ltd. Procede de preparation d'acides organiques a partir de composes d'aldehyde au moyen d'une reaction d'oxydation a phase liquide
WO2009024312A2 (fr) * 2007-08-17 2009-02-26 Albert-Ludwigs-Universität Freiburg Procédé de production et de stabilisation de nanoparticules métalliques fonctionnelles dans des liquides ioniques
JP2009102385A (ja) * 2001-05-18 2009-05-14 Queen's Univ Of Belfast 水素化法
DE102008058448A1 (de) 2007-11-23 2009-06-25 Basf Se Polyisobutylderivate als Polymerisationskatalysatoren
US8143467B2 (en) 2007-12-18 2012-03-27 Exxonmobil Research And Engineering Company Process for synthetic lubricant production
CN103275014A (zh) * 2013-06-13 2013-09-04 盐城工学院 含五元唑环双偶氮结构的化合物、其制备方法及用途
US9073950B2 (en) 2011-12-01 2015-07-07 Dow Corning Corporation Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use
US9139699B2 (en) 2012-10-04 2015-09-22 Dow Corning Corporation Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9156948B2 (en) 2011-10-04 2015-10-13 Dow Corning Corporation Iron(II) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9221041B2 (en) 2011-09-20 2015-12-29 Dow Corning Corporation Iridium containing hydrosilylation catalysts and compositions containing the catalysts
US9480977B2 (en) 2011-09-20 2016-11-01 Dow Corning Corporation Ruthenium containing hydrosilylation catalysts and compositions containing the catalysts
US9545624B2 (en) 2011-09-20 2017-01-17 Dow Corning Corporation Nickel containing hydrosilylation catalysts and compositions containing the catalysts

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US6531241B1 (en) 1999-07-08 2003-03-11 Covalent Associates, Inc. Cyclic delocalized cations connected by spacer groups
US6420616B1 (en) 1999-12-03 2002-07-16 Bayer Aktiengesellschaft Process for preparing a dinitronaphthalene isomer mixture having an increased proportion of 1,5- dinitronaphthalene
EP1104751A1 (fr) * 1999-12-03 2001-06-06 Bayer Ag Procédé de production d'un mélange d'isomères de dinitronaphthalène à proportion élevée en 1,5-dinitronaphthalène
WO2001081436A1 (fr) * 2000-04-25 2001-11-01 Equistar Chemicals, L.P. Polymerisations d'olefines a l'aide de liquides ioniques utilises comme solvants
WO2002030862A1 (fr) * 2000-10-10 2002-04-18 The Queen's University Of Belfast Oxydation de composes alkyl-aromatiques
US7094925B2 (en) 2000-10-10 2006-08-22 The Queen's University Of Belfast Oxidation of alkyl-aromatic compounds
JP2009102385A (ja) * 2001-05-18 2009-05-14 Queen's Univ Of Belfast 水素化法
US6673737B2 (en) 2001-05-30 2004-01-06 Exxonmobil Research And Engineering Company Ionic liquid compositions
US6552232B2 (en) * 2001-06-26 2003-04-22 Exxonmobil Research And Engineering Company Process for conducting aldol condensation reactions in ionic liquid media
FR2829763A1 (fr) * 2001-09-18 2003-03-21 Rhodia Polyamide Intermediates Procede de fabrication de composes nitriles
WO2003024919A1 (fr) * 2001-09-18 2003-03-27 Rhodia Polyamide Intermediates Procede de fabrication de composes nitriles
US8039660B2 (en) 2001-09-18 2011-10-18 Rhodia Polyamide Intermediates Method of producing nitrile compounds
WO2003028882A1 (fr) 2001-10-02 2003-04-10 The Queen's University Of Belfast Procedes utilisant des zeolites en tant que catalyseurs/precurseurs de catalyseur
US7119235B2 (en) 2001-10-02 2006-10-10 The Queen's University Of Belfast Process utilizing zeolites as catalysts/catalyst precursors
WO2007029929A1 (fr) 2005-09-07 2007-03-15 Lg Chem, Ltd. Procede de preparation d'acides organiques a partir de composes d'aldehyde au moyen d'une reaction d'oxydation a phase liquide
WO2009024312A3 (fr) * 2007-08-17 2009-12-23 Albert-Ludwigs-Universität Freiburg Procédé de production et de stabilisation de nanoparticules métalliques fonctionnelles dans des liquides ioniques
WO2009024312A2 (fr) * 2007-08-17 2009-02-26 Albert-Ludwigs-Universität Freiburg Procédé de production et de stabilisation de nanoparticules métalliques fonctionnelles dans des liquides ioniques
DE102008058448A1 (de) 2007-11-23 2009-06-25 Basf Se Polyisobutylderivate als Polymerisationskatalysatoren
US8143467B2 (en) 2007-12-18 2012-03-27 Exxonmobil Research And Engineering Company Process for synthetic lubricant production
US9221041B2 (en) 2011-09-20 2015-12-29 Dow Corning Corporation Iridium containing hydrosilylation catalysts and compositions containing the catalysts
US9545624B2 (en) 2011-09-20 2017-01-17 Dow Corning Corporation Nickel containing hydrosilylation catalysts and compositions containing the catalysts
US9480977B2 (en) 2011-09-20 2016-11-01 Dow Corning Corporation Ruthenium containing hydrosilylation catalysts and compositions containing the catalysts
US9328205B2 (en) 2011-10-04 2016-05-03 Dow Corning Corporation Iron(III) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9156948B2 (en) 2011-10-04 2015-10-13 Dow Corning Corporation Iron(II) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9469799B2 (en) 2011-10-04 2016-10-18 Dow Corning Corporation Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
US9073950B2 (en) 2011-12-01 2015-07-07 Dow Corning Corporation Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use
US9139699B2 (en) 2012-10-04 2015-09-22 Dow Corning Corporation Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
CN103275014B (zh) * 2013-06-13 2015-09-23 盐城工学院 含五元唑环双偶氮结构的化合物、其制备方法及用途
CN103275014A (zh) * 2013-06-13 2013-09-04 盐城工学院 含五元唑环双偶氮结构的化合物、其制备方法及用途

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