EP2097424A1 - Composés de coordination du groupe du bore - Google Patents

Composés de coordination du groupe du bore

Info

Publication number
EP2097424A1
EP2097424A1 EP07822703A EP07822703A EP2097424A1 EP 2097424 A1 EP2097424 A1 EP 2097424A1 EP 07822703 A EP07822703 A EP 07822703A EP 07822703 A EP07822703 A EP 07822703A EP 2097424 A1 EP2097424 A1 EP 2097424A1
Authority
EP
European Patent Office
Prior art keywords
borate
tetrakis
tris
borane
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07822703A
Other languages
German (de)
English (en)
Inventor
Wolfram Lerner
Jens RÖDER
Hannes Vitze
Matthias Wagner
Ulrich Wietelmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP2097424A1 publication Critical patent/EP2097424A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/062—Al linked exclusively to C
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to a coordination compound of an element of the boron group, the preparation of this compound and their use as an additive, stabilizer, catalyst, co-catalyst, activator for catalyst systems, conductivity improvers and electrolyte.
  • the subject of the invention is a coordination compound of boron.
  • boron compounds having one or more B-C atomic bonds are extremely labile compounds which spontaneously ignite upon contact with air or oxygen.
  • An example of this is triethylboron. This burns instantly with green flame on contact with air. Due to the danger of these substances, such compounds are not generally operational.
  • boron compounds with aryl radicals such as, for example, B (C 6 H 5 ) 3 .
  • aryl radicals such as, for example, B (C 6 H 5 ) 3
  • Alternative compounds contain fluorine-substituted groups such as B (C 6 F 5 ) 3 or salts such as Li [B (C 6 F 5 ) 4 ] or the corresponding ammonium salts of [B (C 6 Fs) 4 ].
  • the activation of the cationic, catalytically active compound in the polymerization of olefins and ⁇ -olefins with certain Br ⁇ nsted and Lewis acids is well known.
  • Such systems are used in Ziegler and Ziegler-Natta olefin polymerization, especially in Group 3-10 metal catalyst and pre-catalyst systems, in catalyst and pre-catalyst systems based on Group 3 metal complexes. 10 with delocalized ⁇ -bound ligands or in complexes of metals of group 3-10 with delocalized ⁇ -bound ligands and other ligands with coordinating heteroatoms such as oxygen, sulfur, phosphorus or nitrogen.
  • Suitable Bronsted acids can transfer a proton to the pre-catalyst to form the cationic, catalytically active compound.
  • suitable Lewis acids may also form the cationic, catalytically active compound, for example by abstraction of a negatively charged ligand.
  • the cationic, catalytically active compound is activated and stabilized by means of a weakly coordinating anion.
  • MAO aluminum alkyls or methylaluminoxane
  • toluene solution aluminum alkyls or methylaluminoxane (MAO)
  • MAO is generally a compound of unclear composition, which is obtained by hydrolysis of trimethylaluminum. When stored, the solution tends to polymerize and form a gel, and the activity of the solution is greatly inferior.
  • Lewis acids such as B (C 6 Fs) 3 or Bronsted acids, for example ammonium cations with, for example, [B (C 6 Fs) 4 ] anions, are also used to activate such systems (WO-A-03 / 010,171 G. Fink, R. Mülhaupt, H.
  • fluorine-substituted compounds such as B (C 6 F 5 ) 3 and [B (C 6 F 5 ) 4 ] salts are the fluorine substituents. These compounds are ecologically questionable. They are characterized by a high persistence in the environment and a severe biodegradability on the other hand, these substances and their degradation and combustion products are harmful to the ozone layer of the earth.
  • B (C 6 F 5 ) 3 is also used in organic synthesis as a catalyst and synthesis aid. Above all, B (C 6 F 5 ) 3 is suitable for the synthesis of oligo (ethylene oxide) -functionalized siloxanes (NAA Rossi, Z. Zhang, Q. Wang, K. Amine, R. West, Polymer Preprints 2005, 46, 723- 724).
  • EP-B-0097076 discloses solid solutions for ionic, in particular cationic. These solid solutions consist of macromolecular materials and Li, Na, K salts of trivalent elements of the boron group in quadruple coordination sphere.
  • LiPF 6 lithium hexafluorophosphate
  • This salt has the necessary conditions for use in high-energy cells, that is, it is readily soluble in aprotic solvents, it leads to electrolytes with high conductivities and it has a high degree on electrochemical stability. Oxidative decomposition occurs only at potentials greater than. 4.5V are.
  • LiPF 6 has serious disadvantages, which can be attributed mainly to its lack of thermal stability (decomposition above about 130 0 C).
  • thermal stability decomposition above about 130 0 C
  • corrosive and toxic hydrogen fluoride is released, which on the one hand complicates handling and, on the other hand, attacks and damages battery components, for example the cathode.
  • lithium salts with perfluorinated organic radicals were tested. These are the lithium trifluoromethanesulfonate (“Li triflate”), lithium imides (lithium bis (perfluoroalkylsulfonyl) imides) and lithium methides (lithium tris (perfluoroalkylsulfonyl) methides). All of these salts require relatively expensive preparation processes, are therefore relatively expensive and have other disadvantages such as corrosivity to aluminum or poor conductivity and the ecological disadvantages already described.
  • Alternative conducting salts and electrolytes based on boron salts which are virtually insoluble in hydrocarbons, are disclosed in DE-C-101 11410 and DE-A-10359604 A, which are fully incorporated herein by reference.
  • Lithiumorganoborate As another class of compounds for use as conductive salt in rechargeable lithium batteries Lithiumorganoborate were investigated. However, because of the already described low oxidation stability and safety concerns in the handling of triorganoboranes, they are ruled out for commercial systems.
  • the object of the present invention is to overcome the disadvantages of the prior art.
  • the object of the present invention is to provide a compound which is good in hydrocarbons and aprotic solvents is soluble and stable to oxygen, contains no fluorine substituents and has only a slight tendency to coordinate to metal centers.
  • R 8 and R 9 are each independently selected from H, functionalized and / or unfunctionalized branched and / or unbranched alkyl and / or cycloalkyl groups having 1 to 20 C atoms and / or functionalized and / or unfunctionalized aryl and / or hetaryl groups having 1 to 12 carbon atoms selected;
  • R 1 , R 2 , R 3 are independently of one another from functionalized and / or unfunctionalized branched and / or unbranched alkyl and / or cycloalkyl groups having 1 to 50 carbon atoms and / or functionalized and / or unfunctionalized aryl and / or hetaryl groups 1 to 12 carbon atoms selected;
  • X is a trivalent element of the boron group in a triple or quadruple coordination sphere
  • Y is a tetravalent element of carbon group C, Si, Ge, Sn, Pb;
  • M + alkali metal, Li, Na, K, Rb, Cs or [(R 4 R 5 R 6 R 7 JN] + or H + or [(C 6 H 5 ) 3 C] + or mixtures thereof;
  • R 4 , R 5 , R 6 , R 7 are each independently selected from H, functionalized and / or unfunctionalized branched and / or unbranched alkyl, Akenyl-, alkynyl, cycloalkyl group having 1 to 50 carbon atoms and / or aryl groups with 1 to 12 C atoms selected polymers;
  • Inventive coordination compounds according to formula 1 are tri-coordinated trivalent elements of the boron group or salts of tetracoordinated, trivalent elements of the boron group with substituents other than aryl or alkylaryl or fluoroaryl or fluoroalkylaryl on the element of the boron group.
  • the coordination compounds of the invention are readily soluble in hydrocarbons, show high stability to oxygen and have a low tendency to coordinate to metal centers.
  • R, R 1 , R 2 , R 3 are: methyl, ethyl, ethenyl, ethynyl, n-propyl, isopropyl, cyclopropyl, propen-3-yl, propyn-3-yl, n-butyl, cyclobutyl, 1-butene-4-yl, 1-butyne-4-yl, 2-buten-4-yl, crotyl, 2-butyne-4-yl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, cyclopentyl, cyclopentadienyl, iso-pentyl, neo-pentyl, tert-pentyl, cyclohexyl, hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, thexyl,
  • R 4 , R 5 , R 6 and R 7 are: H, methyl, ethyl, ethenyl, ethynyl, n-propyl, iso-propyl, cyclopropyl, propen-3-yl, propyn-3-yl, n-butyl , Cyclobutyl, 1-butene-4-yl, 1-butyne-4-yl, 2-buten-4-yl, crotyl, 2-butyne-4-yl, 2-butyl, iso-butyl, tert-butyl, n -Pentyl, cyclopentyl, cyclopentadienyl, iso-pentyl, neo-pentyl, tert-pentyl, cyclohexyl, hexyl, n -heptyl, iso-heptyl, n -octyl, isooct
  • hydrocarbyl-substituted ammonium salts such as trimethylammonium, triethylammonium, tripropylammonium, tri / sopropylammonium, tri (n-butyl) ammonium, N, N-Dimethylphenylammonium, N 1 N- dimethylbenzylammonium, N, N-Diethylphenylammonium, N, N-Diethylbenzyl- are ammonium , N, N-dimethyl (2,4,6-trimethylphenyl) ammonium, N, N-dimethyl (2,4,6-triethylphenyl) ammonium, N, N-dimethyl (2,4,6-trimethylbenzyl) ammonium, N 1 N-dimethyl (2,4,6-triethylbenzyl) ammonium, N, N-di (tetradecyl) phenylammonium, N, N-di (tetradecyl)
  • N N-dimethylphenylammonium, methylbis (octadecyl) ammonium, dimethyloctadecylammonium, methylbis (tetradecyl) ammonium, N, N-bis (octadecyl) phenylammonium and N, N-bis (octadecyl) (3,5- dimethylphenyl) ammonium.
  • mixtures of different substituted ammonium ions are preferred according to the invention. Examples include the commercially available amines containing mixtures of two CH, C 16 or Ci 8 alkyl groups and a methyl group. Such amines are available from Chemtura under the trade name Kemamine TM T9701 and from Akzo-Nobel under the trade name Armeen TM M2HT.
  • Also preferred according to the invention is the trityl cation [(C 6 Hs) 3 C] + , the triphenylcarbonium ion.
  • Examples of X are: boron, aluminum, gallium, indium and thallium. Boron and aluminum are particularly preferred according to the invention.
  • Coordination compounds according to formula 1 which are particularly preferred according to the invention are: tris (trimethylsilylmethyl) borane, tris (triisopropylsilylmethyl) borane, tris (trieth-butylsilylmethyl) borane, tris (trimethylsilylethynyl) borane, tris (triisopropylsilylethynyl) borane, tris (triisopropylethynyl) aluminum , tris (tritert-butylsilylethynyl) borane, Tripropinylboran, Triisopropinylboran, Tributinylboran as well as the lithium, N 1 N- Dimethylphenylammonium-, tetra (alkyl) ammonium, tetra (n-butyl) ammonium salts of the anions and Triphenylcarboniumsalze tetrakis (trimethylsilylmethyl) borate,
  • the coordination compound according to the invention is characterized by a high solubility in hydrocarbons.
  • the coordination compound according to the invention is characterized by a low tendency to coordinate to metal centers.
  • the coordination compound according to the invention is characterized by a high stability to oxygen.
  • the coordination compound according to the invention is characterized by a high thermal stability.
  • the coordination compound according to the invention contains no fluorine atoms and is therefore more environmentally friendly compared to the prior art.
  • the conductivity of the coordination compound according to the invention is just as good or better in comparison to commercially available conductive salts.
  • Another object of the invention is the preparation of the coordination compound according to the invention.
  • Another object of the invention is the use of the coordination compound according to the invention as a co-catalyst and activator for catalyst systems, in particular co-catalyst and activator for catalyst systems in olefin polymerization.
  • Monomers which are polymerized with the aid of catalysts which use a coordination compound according to the invention or a plurality of coordination compounds according to the invention include ethylenically unsaturated monomers, acetylenes, conjugated and / or unconjugated dienes and polyenes.
  • the monomers include olefins, for example ⁇ -olefins having 2 to 20,000, preferably 2 to 20 and particularly preferably 2 to 8 C atoms or combinations of two and / or more of such ⁇ -olefins.
  • ⁇ -olefins examples include ethylene, propene, 1-butene, 1, 4-butadiene, 1-pentene, 4-methylpent-1-ene, isoprene, 1-hexene, 1-heptene, 1-octene, 1 -none, 1-decene, 1-undencene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene or combinations thereof, as well as long-chain oligomeric or polymeric vinyl-terminated reaction products and 10 to 30 carbon alpha-olefins, those of the reaction mixture be added for a long time Branches within the polymer to obtain.
  • Preferred ⁇ -olefins therefor are ethylene, propene, 1-butene, 1, 4-butadiene, 1-pentene, 4-methylpent-1-ene, isoprene, 1-hexene, 1-heptene, 1-octene and combinations of ethylene and / or propenes with another ⁇ -olefin.
  • Other preferred monomers include styrene, halo- or alkyl-substituted styrene derivatives, vinylbenzocyclobutene, 1,4-butadiene, 1,4-hexadiene, dicyclopentadienes, ethylidenenorbornenes, and 1,7-octadiene. Mixtures of the mentioned monomers can also be used.
  • Another object of the invention is the use of the coordination compound according to the invention as a co-catalyst and activator for catalyst systems in olefin polymerization, in particular as a co-catalyst and activator for Ziegler and / or Ziegler-Natta and / or single-site and / or metallocene and / or half-sandwich and / or constrained-geometry and / or beyond-metallocene catalysts.
  • Suitable catalysts for the reaction with the coordination compound according to the invention are all compounds or complexes of metals of group 3-10 of the periodic table, which can be activated and have the capability of unsaturated compounds, for example olefins, ⁇ -olefins, ethylene, propene and compounds having ethylene groups to polymerize.
  • catalysts for the reaction with the coordination compound according to the invention are all compounds or complexes and mixtures of compounds or complexes of scandium in the oxidation states +2 and / or +3, titanium and / or zirconium and / or hafnium in the oxidation states +2, + 3 and / or +4, and / or manganese and / or iron in the oxidation states -2, -1, 0, +2, +3, +4, +5, +6 and / or +7 and / or nickel and / or palladium and / or platinum in the oxidation states -2, -1, 0, +2, +3 and / or +4 and / or lanthanum and / or neodymium in the oxidation states +1, +2 and / or +3, which can be activated and have the ability to polymerize unsaturated compounds, olefins, ⁇ -olefins, ethylene, propene and compounds having ethylene groups.
  • the invention further relates to the use of the coordination compound according to the invention as a cocatalyst and activator for catalyst systems in olefin polymerization in high and / or low pressure and / or solution and / or suspension and / or gas phase polymerization processes both in US Pat discontinuous as well as continuous processes.
  • the disclosure of VVO-A-88/02009, U.S. Patent Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647 and US-A -4,522,987 is fully incorporated herein by reference.
  • Suitable polymerization processes include solution processes, preferably continuous solution processes in the presence of an aliphatic and / or alicyclic and / or aromatic solvent or mixtures thereof.
  • the term aliphatic and alicyclic solvents includes straight-chain, branched and cyclic C 2 to C 20 alkanes, cyclohexane, cycloheptane, methylcyclohexane and
  • Methylcycloheptane is also suitable.
  • aromatic solvents such as toluene, xylene (all isomers), cumene or ethylbenzene. Also suitable as solvents
  • Monomers such as ethylene, propene, butadiene, isoprene, cyclopentene, 1-hexene, 3-methyl
  • Another object of the invention is the use of the coordination compound of the invention as a co-catalyst and activator for catalyst systems in olefin polymerization in heterogeneous and / or homogeneous processes.
  • Another object of the invention is the support of the coordination compound according to the invention on a solid support material.
  • the support can be made by impregnation, deposition on the surface, physisorption or by means of a chemical reaction on the surface to a heterogeneous Catalyst component which can be used to polymerize said monomers.
  • the molar ratio of the coordination compound of the invention to the catalyst material is 1000: 1 to 1: 1, preferably 200: 1 to 1: 1, more preferably 20: 1 to 1: 1.
  • the addition of the coordination compound of the invention to the catalyst material can be carried out at any point in the polymerization reaction.
  • the addition may be carried out prior to the start of the polymerization reaction and / or during the polymerization reaction, or also continuously or discontinuously from before the beginning of the polymerization reaction to any time during the polymerization reaction.
  • the formation of the catalytically active component consisting of the coordination compound according to the invention and the catalyst can take place outside and / or inside the reactor in which the polymerization is carried out.
  • the catalysts prepared using the coordination compounds of this invention may be used with at least one or more further catalysts together in the same reactor or in separate but connected reactors to produce polymer blends having the desired properties.
  • the coordination compound according to the invention can be used together with a reagent for controlling the molecular weight.
  • a reagent for controlling the molecular weight In addition to hydrogen and trialkylaluminum compounds, these are also other substances for polymer chain transfer.
  • the coordination compound of the invention is preferably used together with an oligomeric or polymeric aluminoxane compound and / or a tri (hydrocarbon) aluminum and / or a di (hydrocarbon) - aluminum chloride and / or a KohlenwasserstoffaluminiumdichloridISS used.
  • Such aluminum compounds are mostly added as "scavengers" to remove impurities.
  • the aluminum compounds which are preferred for this purpose comprise C1 to C20 trialkylaluminum compounds, in particular those containing methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl groups, and
  • Atoms in the alkyl groups and 6 to 18 C atoms in the aryl group preferably
  • the coordination compounds according to the invention are suitable for the production of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene (PP).
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LLDPE linear low density polyethylene
  • PP polypropylene
  • Another object of the invention are bottles, films, films, fibers, moldings, shoe soles, foams, polymers with vitreous appearance, car tires, rubbers, paints, powder coatings, pipelines, drinking water pipes, sewage pipes, profiles, window profiles, food packaging, blister packs and engineering plastics manufactured from polymers using the coordination compound according to the invention.
  • Another object of the invention is the use of the coordination compound of the invention as a catalyst and / or synthesis aid in organic synthesis.
  • Another object of the invention is the use of the coordination compound of the invention in organic synthesis as a catalyst and / or synthesis aid for the synthesis of oligo (ethylene oxide) functionalized siloxanes.
  • Another object of the invention is the use of the coordination compound according to the invention as electrolyte and conductive salt.
  • Another object of the invention is the use of the coordination compound of the invention for the production of electrolytes and conductive salts.
  • Another object of the invention is the use of the coordination compounds of the invention as an electrolyte in galvanic cells.
  • Another object of the invention is the use of the coordination compound according to the invention for the production of electrolytes for galvanic cells.
  • Another object of the invention is the use of the coordination compound of the invention as an electrolyte in lithium batteries, preferably in lithium ion batteries.
  • Another object of the invention is the use of the coordination compounds of the invention as an electrolyte in electrolytic
  • Double-layer capacitors are Double-layer capacitors.
  • the use of the coordination compound according to the invention as electrolyte is possible in all common solvents.
  • Preferred are alicyclic ethers, aliphatic and aliphatic difunctional ethers, esters, carbonates, nitriles, amines, acid amides, ionic liquids, hydrocarbons, halogenated hydrocarbons, heterocycles and heteroaromatics.
  • diethyl ether tetrahydrofuran, tetrahydro-2-methylfuran, tetrahydro-3-methylfuran, tetrahydro-2,5-dimethylfuran, tetrahydro-3,4-dimethylfuran, tetrahydropyran, cyclopentyl methyl ether, dimethoxyethane, diethoxymethane, diethoxyethane, polyethylene glycols, methyl formate , Ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, methoxyethyl acetate, ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, (2-methoxyethyl) methyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl
  • the Elekrolytalten prepared using the coordination compounds of the invention further additives may be added.
  • the appropriately substituted and metallated compound MZA is reacted in a suitable solvent with a compound of an element of the boron group (boron group element compound), preferably with a boron compound.
  • a compound of an element of the boron group boron group element compound
  • the ratio of the metalated compound to the boron group element compound is preferably 3 to 6 equivalents of the metalated compound to one equivalent of the appropriate boron group element compound.
  • Suitable solvents for carrying out the reaction are, for example, hydrocarbons or ethers.
  • Boron group element compounds suitable for preparation are preferably boron or aluminum Halogen compounds, for example BF 3 , BCI 3 or AICI 3 , or boric acid ester.
  • the boron-halogen compound can be used neat or as a complex with diethyl ether or tetrahydrofuran or tetrahydro-2-methylfuran.
  • boric acid esters such as trimethyl borate, triethyl borate and triisopropyl borate are suitable.
  • Particularly preferred according to the invention are BF 3 , BCI 3 and B (OMe) 3 .
  • the reaction temperature is from -100 0 C to 200 ° C. Preferred is a temperature range of -78 ° C to the boiling point of the solvent used, more preferably from -20 0 C to the boiling point of the solvent used.
  • the compound according to the invention of formula 1 can be isolated.
  • the reaction induced cation M + may be exchanged for other cations, M +, for example by means of ion exchangers or salt exchange or recrystallization.
  • Suitable solvents for exchanging the cation are hydrocarbons or ethers or aprotic organic solvents or protic organic solvents or alcohols or esters or water or mixtures of at least two of these solvents.
  • Preferred are hexane or heptane or toluene or diethyl ether or dibutyl ether or methyl tert-butyl ether or tetrahydrofuran or tetrahydro-2-methylfuran or methanol or ethanol or / soPropanol or acetonitrile or dimethyl sulfoxide or dimethylacetamide or poly (propylene) oxide or poly (ethylene) oxide or ethyl acetate or diethoxymethane or dimethoxyethane or propylene carbonate or water or or mixtures of at least two of these solvents.
  • Trimethylsilylethyne is reacted in tetrahydrofuran with n-butyllithium.
  • the resulting trimethylsilylethynyl lithium is reacted with BCI 3 .
  • From the LiCl is filtered off and the solvent removed in vacuo.
  • Example 3 Preparation of tris (trimethylsilylethynyl) borane
  • Trimethylsilylethyne is reacted in tetrahydrofuran with methylmagnesium chloride.
  • the resulting trimethylsilylethynylmagnesium chloride is reacted with BCI 3 .
  • From MgCl 2 is filtered off and the solvent removed in vacuo.
  • Triisopropylsilylethine is reacted in toluene with tert-butyllithium.
  • the resulting lithium triisopropylacetylide is reacted with BCI 3 in tetrahydrofuran. From the LiCl is filtered off and the solvent removed in vacuo.
  • tertButylsilylethyne is reacted in toluene with tert-butyllithium.
  • the obtained Lithiumtritertbutylacetylid is brought in tetrahydrofuran with BF 3 to the reaction. From the LiF is filtered off and the solvent removed in vacuo.
  • Lithium tetrakis (tritertbutylsilylethynyl) borate is dissolved in toluene and treated with one equivalent of N, N-dimethylphenylammonium chloride. From the precipitated LiCl is filtered off. N, N-Dimethylphenylammoniumtetrakis (tritertbutylsilylethinyl) borate is obtained after removal of the toluene in vacuo.
  • Lithium tetrakis (triisopropylsilylethynyl) borate is dissolved in toluene and treated with one equivalent of N, N-dimethylphenylammonium chloride. From the precipitated LiCl is filtered off. N, N-Dimethylphenylammoniumtetrakis (triisopropylsilylethynyl) borate is obtained after removal of the toluene in vacuo.
  • Example 8 Preparation of triphenylcarbonium tetrakis (triisopropylsilylethynyl) borate
  • Lithium tetrakis (triisopropylsilylethynyl) borate is dissolved in toluene and treated with one equivalent of chlorotriphenylmethane. From the precipitated LiCl is filtered off. Triphenylcarbonium tetrakis (triisopropylsilylethynyl) borate is obtained after removal of the toluene in vacuo.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)

Abstract

L'invention a pour objet un composé de coordination d'un élément du groupe du bore, la production de ce composé et son utilisation comme adjuvant, stabilisant, catalyseur, co-catalyseur, activateur pour systèmes catalyseurs, agent améliorant la conductivité et électrolyte.
EP07822703A 2006-11-17 2007-11-19 Composés de coordination du groupe du bore Withdrawn EP2097424A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006054649 2006-11-17
PCT/EP2007/062499 WO2008059065A1 (fr) 2006-11-17 2007-11-19 Composés de coordination du groupe du bore

Publications (1)

Publication Number Publication Date
EP2097424A1 true EP2097424A1 (fr) 2009-09-09

Family

ID=38973150

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07822703A Withdrawn EP2097424A1 (fr) 2006-11-17 2007-11-19 Composés de coordination du groupe du bore

Country Status (3)

Country Link
US (1) US8222457B2 (fr)
EP (1) EP2097424A1 (fr)
WO (1) WO2008059065A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10118976B2 (en) * 2016-01-04 2018-11-06 California Institute Of Technology Anion-coordinating polymer electrolytes and related compositions, methods and systems

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060674A (en) * 1976-12-14 1977-11-29 Exxon Research And Engineering Company Alkali metal anode-containing cells having electrolytes of organometallic-alkali metal salts and organic solvents
US4148756A (en) * 1977-04-25 1979-04-10 Exxon Research & Engineering Co. Novel trialkyl aluminum cocatalyst
US4543399A (en) * 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4588790A (en) * 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
FR2527610B1 (fr) * 1982-06-01 1987-08-14 Anvar Tetra-alkynyl borates ou -aluminates de metaux alcalins, leurs solutions solides avec des matieres plastiques et leur application a la constitution d'elements conducteurs pour des generateurs electrochimiques
FR2528556B1 (fr) 1982-06-10 1988-01-29 Ertt Sarl Procede et appareil d'echange direct de chaleur a demultiplication multiple entre fluides gazeux et liquides
US4522987A (en) * 1982-07-09 1985-06-11 Phillips Petroleum Company Low density polyethylene
US4564647A (en) * 1983-11-14 1986-01-14 Idemitsu Kosan Company Limited Process for the production of polyethylene compositions
US5084534A (en) * 1987-06-04 1992-01-28 Exxon Chemical Patents, Inc. High pressure, high temperature polymerization of ethylene
CA1338046C (fr) 1986-09-19 1996-02-06 Howard Curtis Welborn Jr. Polymerisation de l'ethylene a hautes temperature et pression
US4904631A (en) * 1988-11-08 1990-02-27 Exxon Chemical Patents, Inc. Supported vanadium catalyst for polymerization of olefins and a process of preparing and using the same
JP3077940B2 (ja) * 1993-04-26 2000-08-21 エクソン・ケミカル・パテンツ・インク 流動層重合法のための安定な操作条件を決定する方法
AU717137B2 (en) * 1995-11-24 2000-03-16 Ciba Specialty Chemicals Holding Inc. Borate coinitiators for photopolymerization
GB9609439D0 (en) * 1996-05-04 1996-07-10 Zeneca Ltd Polymerisable composition
US6534613B2 (en) * 1998-02-18 2003-03-18 Eastman Chemical Company Process for producing polyethylene
AU751049B2 (en) * 1998-04-15 2002-08-08 Shell Internationale Research Maatschappij B.V. Catalyst system for alpha-olefin oligomerization
JP4014737B2 (ja) * 1998-09-17 2007-11-28 昭和電工株式会社 熱重合性組成物及びその用途
US6777510B1 (en) * 2000-09-12 2004-08-17 California Institute Of Technology Internal Lewis acid single site catalyst family for polymerization of polar monomers
EP1334139A2 (fr) * 2000-11-07 2003-08-13 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
DE10111410C1 (de) * 2001-03-08 2002-07-25 Chemetall Gmbh Elektrolyt, enthaltend Lithium-bis(oxalato)borat und dessen Verwendung
WO2003010171A1 (fr) 2001-07-23 2003-02-06 Dow Global Technologies, Inc. Sel d'acide de lewis/d'adduits acides et activateurs de catalyseur correspondants
DE10139409A1 (de) * 2001-08-17 2003-02-27 Merck Patent Gmbh Polymerelektrolyte und deren Verwendung in galvanischen Zellen
US6794514B2 (en) * 2002-04-12 2004-09-21 Symyx Technologies, Inc. Ethylene-styrene copolymers and phenol-triazole type complexes, catalysts, and processes for polymerizing
JP2004149673A (ja) * 2002-10-30 2004-05-27 Mitsui Chemicals Inc エチレン系ワックスの製造方法
US6864210B2 (en) * 2003-02-06 2005-03-08 Equistar Chemicals, Lp Bimetallic olefin polymerization catalysts containing indigoid ligands
JP4139724B2 (ja) * 2003-04-10 2008-08-27 富士フイルム株式会社 平版印刷版原版
DE10359604A1 (de) 2003-12-18 2005-07-14 Dilo Trading Ag Elektrolyt zur Verwendung in einer elektrochemischen Zelle und elektrochemische Zelle mit dem Elektrolyt
EP1934235A1 (fr) * 2005-10-07 2008-06-25 Chemetall GmbH Sels de borate, procede de production et d'utilisation desdits sels

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008059065A1 *

Also Published As

Publication number Publication date
WO2008059065A1 (fr) 2008-05-22
US20100029875A1 (en) 2010-02-04
US8222457B2 (en) 2012-07-17

Similar Documents

Publication Publication Date Title
JP5990262B2 (ja) ヒドリド−トリシアノ−ボラートアニオンを含む化合物
JP5994779B2 (ja) 電気化学デバイス用電解液
WO2010139684A1 (fr) Composé constitué d'un groupe aromatique protoné et d'un anion faiblement coordonnant comme catalyseur de polymérisation pour l'isobutène ou un mélange de monomères contenant de l'isobutène
KR20140050058A (ko) 알킬-시아노-보레이트 또는 알킬-시아노-플루오로보레이트 음이온을 포함하는 화합물
JP5793509B2 (ja) パーフルオロアルキル−シアノ−アルコキシ−ボレートアニオンまたはパーフルオロアルキル−シアノ−アルコキシ−フルオロ−ボレートアニオンを含有する化合物
CA2552189A1 (fr) Synthese de liquides ioniques
DE112011100521T5 (de) Katalysator für ethylenische Polymerisation und Verfahren zur Herstellung von ethylenischem Polymer
DD299442A5 (de) Chromverbindungen, verfahren zu ihrer herstellung und ihre verwendung
DE602004006965T2 (de) Polymerisationskatalysatoren, organische übergangsmetallverbindungen, verfahren zur herstellung von polyolefinen
WO2007057406A1 (fr) Procede pour produire des homopolymeres ou copolymeres d'isobutene tres reactifs a partir de flux d'hydrocarbures c4 techniques au moyen de complexes catalytiques acides protoniques
JP2024054160A (ja) オレフィン重合活性化剤
WO2007057405A1 (fr) Procede pour produire des homopolymeres ou copolymeres d'isobutene tres reactifs au moyen de complexes catalytiques contenant du metal
WO2009027541A2 (fr) Composés d'oxygène comprenant des éléments qui appartiennent au groupe du bore
EP4182366A1 (fr) Cocatalyseurs de méthylaluminoxane modifiés par hydrocarbyle pour des complexes métal-ligand bis-phénylphénoxy
EP2097424A1 (fr) Composés de coordination du groupe du bore
DE69412275T2 (de) Verfahren zur olefinpolymerisation in gegenwart eines halogenierten metallocene enthaltendes katalysatorsystem
DE102007047812A1 (de) Koordinationsverbindungen der Borgruppe
Yinghuai et al. Syntheses and catalytic activities of single-wall carbon nanotubes-supported nickel (II) metallacarboranes for olefin polymerization
WO2010125035A1 (fr) Complexe métallique comportant un contrion coordinateur faible servant de catalyseur de polymérisation pour l'isobutène ou un mélange de monomères contenant de l'isobutène
KR101594682B1 (ko) 촉매 조성물 및 알파-올레핀의 제조 방법
Ramos et al. Titanium ferrocenyl-phosphinimide complexes
DE102004032581A1 (de) Polymerisationskatalysatoren, Hauptgruppenkoordinationsverbindungen, Verfahren zur Herstellung von Polyolefinen und Polyolefine
KR20230009908A (ko) 올레핀 중합 바이메탈 활성화제
KR20250154777A (ko) 입체 효과를 갖는 용매의 도입 및 전해질 제어를 이용한 전기화학적 암모니아 생산성 증대방법
DE10305227A1 (de) Polymerisationskatalysatoren, Organoübergangsmetallverbindungen, Verfahren zur Herstellung von Polyolefinen und Polyolefine

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090617

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20110331

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140603