WO2009027541A2 - Composés d'oxygène comprenant des éléments qui appartiennent au groupe du bore - Google Patents

Composés d'oxygène comprenant des éléments qui appartiennent au groupe du bore Download PDF

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WO2009027541A2
WO2009027541A2 PCT/EP2008/061514 EP2008061514W WO2009027541A2 WO 2009027541 A2 WO2009027541 A2 WO 2009027541A2 EP 2008061514 W EP2008061514 W EP 2008061514W WO 2009027541 A2 WO2009027541 A2 WO 2009027541A2
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bis
borate
benzodiolato
boron group
compound
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PCT/EP2008/061514
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German (de)
English (en)
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WO2009027541A3 (fr
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Jens RÖDER
Ulrich Wietelmann
Hannes Vitze
Wolfram Lerner
Matthias Wagner
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Chemetall Gmbh
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    • 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 System
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • 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 System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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

Definitions

  • the present invention relates to oxygen compounds of elements of the boron group, the preparation of these compounds and their use as additives, stabilizers, catalysts, co-catalysts, activators for catalyst systems, conductivity improvers and electrolytes.
  • subject of the invention are oxygen compounds of boron and aluminum.
  • the activation of the cationic, catalytically active compound in the polymerisation of olefins and ⁇ -olefins with certain Bronsted and Lewis acids is well known.
  • Such systems are used in Ziegler and Ziegler-Natta olefin polymerizations, especially in catalyst and pre-catalyst systems of Group 3-10 metals, in catalyst and pre-catalyst systems based on Group 3 metal complexes. 10 with delocalized ⁇ -bound ligands or complexes of metals of groups 3-10 with delocalized ⁇ -bound ligands and other ligands with coordinating heteroatoms such as oxygen, sulfur, phosphorus or nitrogen.
  • suitable Bransted acids can transfer a proton to the pre-catalyst to form the cationic, catalytically active compound.
  • Suitable Lewis acids can 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.
  • aluminum alkyls or methylaluminoxane (MAO) mostly in toluene solution, are used.
  • MAO is a compound which is obtained by partial hydrolysis of trimethylaluminum and whose composition is generally not precisely determined. 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 F 5 ) 3 or Bronsted acids, for example ammonium cations with [B (C 6 F 5 ) 4 ] anions, are also used to activate such systems (WO-A-03 / G. Fink, R. Mülhaupt, HH Brintzinger, Ziegler Catalysts, Recent Scientific Innovations and Technological Improvements, Springer Heidelberg, 1995, J. Scheirs, W.
  • the described co-catalysts and activators for catalyst systems for olefin polymerisation are used in particular in high-pressure and / or low-pressure and / or in solution and / or suspension and / or gas-phase polymerisation processes, both in discontinuous and continuous processes.
  • the disclosure of WO-A-88/02009, US-A-5,084,534, US-A-5,405,922, US-A-4,588,790, US-A-5,032,652, US-A-4,543,399, US-A-4,564,647 and US-A -4,522,987 is fully incorporated herein by reference.
  • B (C 6 F 5 ) 3 is also used in organic synthesis as a catalyst and synthesis aid.
  • 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).
  • Salts of various boron compounds are also known for their good conductivity in solution.
  • Examples here are LiBF 4 but also organoborates such as Li [B (C 6 Fs) 4 ], NH 4 [B (C 6 F 5 ) 4 ] or other organoborates with perfluorinated or partially fluorinated alkyl or aryl substituents (I. Krossing , I. Raabe, Angew, Chem. 2004, 116, 21 16-2142).
  • Lithium trifluoromethanesulfonate Li triflate
  • lithium imides lithium bis (perfluoroalkylsulfonyl) imide
  • lithium methides lithium ths (perfluoroalkylsulfonyl) methide
  • All of these salts require relatively expensive manufacturing processes, are therefore relatively expensive and have other disadvantages such as corrosivity to aluminum or poor conductivity.
  • lithium-ion batteries with liquid electrolytes is almost exclusively lithium hexafluorophosphate (LiPF 6 ) used as conductive salt.
  • 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 of electrochemical stability. Oxidative decomposition occurs only at potentials greater than. 4.5V are.
  • LiPF 6 has serious drawbacks, mainly due to its lack of thermal stability (decomposition above about 130 ° C) can be attributed.
  • 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.
  • fluorine-substituted compounds such as B (C 6 F 5 ) 3 , [B (C 6 F 5 ) 4 ] salts and LiPF 6 always has the fluorine substituents.
  • Compounds containing fluorine substituents 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 - A -
  • DE-C-198 29 030 and DE-C-101 08 592 discloses lithium bis (oxalato) borate (LiBOB), the first boron-centered complex salt described for use as an electrolyte, which uses a dicarboxylic acid (in this case oxalic acid) as the chelating component.
  • DE-C-101 08 592 discloses unsymmetrical boron chelate complexes which are well suited as additives in conductive salts.
  • Dicate cholate borates are known to be very low in solubility, especially in nonpolar solvents.
  • oxygen atoms of dicatecholato borates coordinate to metal ions.
  • Dicate cholatoborates-based noncoalescing or weakly coordinating anions are not previously known (J. Barthel et al., J. Electrochem, Soc., 1995, 142, 2527-2531, Y. Sasaki et al., J.
  • the object of the present invention is to overcome the disadvantages of the prior art.
  • the object of the present invention is to provide compounds which are readily soluble in hydrocarbons and aprotic solvents, have little or no toxicity, contain no fluorine substituents and have only a slight tendency to coordinate to metal centers.
  • the compounds should also have a high thermal stability and electrical conductivity.
  • the compounds are intended as additives, Stabilizers, catalysts, co-catalysts, activators for catalyst systems, conductivity improvers, for example, to reduce the electrostatic charge of plastics, and / or electrolytes usable.
  • the object is surprisingly achieved by the oxygen compounds according to the invention of elements of the boron group (in short: oxygen compounds of the boron group).
  • the oxygen-containing substituents according to the invention are substituted 1,2-aryl-dioxy substituents with large groups in positions 3 and 6 or a mixture of at least two of these substituents.
  • X is a trivalent element of the boron group connected to four
  • G 1 , G 2 are independently of one another substituents in positions 3 and 6 of a 1, 2-aryloxy compound, wherein G 1 , G 2 are independently functionalized or unfunctionalized branched or unbranched
  • M y + is an alkali metal cation, Li + , Na + , K + , Rb + , Cs + , or [(R 1 R 2 R 3 R 4 ) N] + or H + or [(C 6 Hs) 3 C] + or a main group metal or a
  • R 1 , R 2 , R 3 , R 4 are each independently selected from H, functionalized and / or unfunctionalized branched and / or unbranched alkyl, alkenyl, alkynyl, cycloalkyl group having 1 to 50 carbon atoms and / or aryl groups with 1 up to 12 C atoms or a polymer selected;
  • R 1 , R 2 , R 3 and R 4 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 -
  • Cations of the anionic oxygen compounds of the boron group which are preferred according to the invention are triple-hydrocarbon-substituted ammoniumates such as trimethylammonium, triethylammonium, tripropylammonium,
  • N-dimethyl (2,4,6-thymethylphenyl) ammonium N, N-dimethyl (2,4,6-methylphenyl) ammonium, N, N-dimethyl (2,4,6-thymethylbenzyl) ammonium, N, N-dimethyl (2,4,6-methylbenzyl) ammonium, N, N-di (tetradecyl) phenylammonium, N, N-di (tetradecyl) (2,4,6-thmethylphenyl) ammonium, N, N-di (octadecyl) phenylammonium, N, N-di (octadecyl) (2,4,6-thmethylphenyl) ammonium, methyldicyclohexylammonium, tetra (n-butyl) ammonium, triphenylammonium.
  • Particularly preferred according to the invention are N, N-di
  • mixtures of different substituted ammonium ions are preferred according to the invention.
  • these amines are the commercially available mixtures of two C 4 -, C 6 - or C 8 -alkyl groups and contain 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.
  • G 1 and G 2 are: ethynyl, n-propyl, iso-propyl, cyclopropyl, propen-3-yl, propyn-3-yl, n-butyl, cyclobutyl, i-but-4-yl, 1-butyne 4-yl, 2-buten-4-yl, crotyl, 2
  • Tritertbutylsilylethynyl dimethylthexylsilylethynyl.
  • substituted and unsubstituted aromatics such as fluorene, indene, indane.
  • particularly preferred according to the invention are trimethylsilyl, triisopropylsilyl, tritert-butylsilyl, dimethylthexylsilyl, trimethylsilylethynyl, triisopropylsilylethynyl, tri-tert-butylsilylethynyl, dimethylthexylsilylethynyl, isopropyl, tert-butyl, thexyl, phenyl and benzyl.
  • Examples of X are: boron, aluminum, gallium, indium and thallium. Boron and aluminum are preferred according to the invention. Particularly preferred according to the invention is boron.
  • oxygen compounds of the boron group according to the invention are salts of tetracoordinated, trivalent elements of the boron group with substituents other than aryl or alkylaryl or fluoroaryl or fluoroalkylaryl or carboxy substituents on the element of the boron group.
  • Particularly preferred oxygen compounds according to the invention are:
  • the oxygen compounds of the boron group according to the invention are characterized by a high solubility in hydrocarbons.
  • the oxygen compounds of the boron group of the invention are characterized by a high stability to oxygen.
  • the oxygen compounds of the boron group according to the invention are characterized by a low tendency to coordinate to metal centers.
  • the oxygen compounds of the boron group according to the invention are characterized by a high thermal stability.
  • the conductivity of the oxygen compounds of the boron group according to the invention is just as good or better in comparison with commercially available conductive salts.
  • the compounds are useful as additives, stabilizers, catalysts, cocatalysts, activators for catalyst systems, conductivity improvers and / or electrolytes.
  • the oxygen compounds of the boron group according to the invention contain no fluorine atoms and are therefore more environmentally friendly compared to the prior art.
  • Another object of the invention is the preparation of the oxygen compounds of the boron group according to the invention.
  • the invention further relates to the use of the boron group oxygen compounds according to the invention as co-catalysts and activators for catalyst systems, in particular co-catalysts and activators for catalyst systems in olefin polymerisation.
  • Monomers polymerized by catalysts using an oxygen compound of the boron group of the present invention or a plurality of boron group oxygen compounds of the present 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, A-methylpent-1-ene, isoprene, 1-hexene, 1-heptene, 1-octene, 1 -none, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene or combinations as well as long-chain oligomeric or polymeric vinyl terminated reaction products and 10 to 30 carbon alpha-olefins added to the reaction mixture to obtain long branching within the polymer.
  • 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.
  • the invention further relates to the use of the boron group oxygen compounds according to the invention as co-catalysts and activators for catalyst systems in olefin polymerisation, in particular as co-catalysts and activators for Ziegler and / or Ziegler-Natta and / or single-site and / or or metallocene and / or half-sandwich and / or constrained-geometry and / or beyond-metallocene catalysts.
  • Suitable catalysts for the reaction with the boron group-containing oxygen compound of the invention are all compounds or complexes of metals of Groups 3-10 of the Periodic Table which can be activated and have the ability to form unsaturated compounds, for example olefins, ⁇ -olefins, ethylene, propene and compounds polymethylated with ethylene groups.
  • catalysts for the reaction with the oxygen compounds of the boron group 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, zirconium and / or hafnium in the oxidation states +2, + 3 and / or +4, manganese and / or iron in the oxidation states -2, -1, 0, +2, +3, +4, +5, +6 and / or +7, nickel, 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 are activated can be and have the ability to polymerize unsaturated compounds, olefins, ⁇ -olefins, ethylene, propene and compounds with ethylene groups.
  • 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.
  • aliphatic and alicyclic solvents includes straight-chain, branched and cyclic C 2 to C 2 o-alkanes, cyclohexane, cycloheptane, methylcyclohexane and methylcycloheptane.
  • aromatic solvents such as toluene, xylene (all isomers), cumene or ethylbenzene.
  • solvents are monomers such as ethylene, propene, butadiene, isoprene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1, 4-hexadiene, 1-octene, 1-decene , Styrene, divinylbenzene, allylbenzene and vinyltoluene. Included are all isomers of the compounds and mixtures of monomers.
  • the activation of the catalyst with the oxygen compound of the boron group according to the invention can also be carried out in the listed solvents.
  • Another object of the invention is the use of the oxygen compounds of the invention boron group as co-catalysts and activators for catalyst systems in the olefin polymer in heterogeneous and / or homogeneous processes.
  • Another object of the invention is the support of the oxygen compounds of the invention boron group on a solid support material.
  • the support may be by impregnation, surface deposition, physisorption, or by chemical reaction at the surface to form a heterogeneous catalyst component which may be used to polymerize said monomers.
  • the molar ratio of the oxygen compounds according to the invention of the boron group to the catalyst material is 1000: 1 to 1: 1, preferably 200: 1 to 1: 1, particularly preferably 20: 1 to 1: 1.
  • the addition of the oxygen compounds of the boron group according to the invention to the catalyst material can be carried out at any time during the polymerisation 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 start of the polymerization reaction to any time during the polymerization reaction.
  • the formation of the catalytically active component consisting of the oxygen compounds according to the invention of the boron group and the catalyst can take place outside and / or inside the reactor in which the polymerization is carried out.
  • the catalysts prepared using the boron group oxygen compounds of the present 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.
  • oxygen compounds of the boron group 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 oxygen compounds of the boron group of the invention are preferably used together with an oligomeric or polymeric aluminoxane compound and / or a th (hydrocarbon) aluminum and / or a di (hydrocarbon) - aluminum chloride and / or a Kohlenwasserstoffaluminiumdichloridharm.
  • Such aluminum compounds are mostly added as "scavengers" to remove impurities.
  • the preferred aluminum compounds for this purpose include Cr to C 20 - ThalkylaluminiumENSen, in particular those with methyl, ethyl, propyl, isoPropyl, n-butyl, isoButyl, pentyl, neopentyl, or isoPentyl groups, and Diethylaluminum chloride and dialkyl (aryloxy) aluminum compounds having 1 to 6 carbon atoms in the alkyl groups and 6 to 18 carbon atoms in the aryl group, preferably 3,5-di (t-butyl) -4-methylphenoxy) diisobutylaluminum), methylaluminoxanes Methaluminoxanes, preferably isobutyl-modified methalumoxanes, and tri (ethylaluminum), tris (pentafluorophenyl) boranes, or tris (pentafluorophenyl) aluminum modified methaluminoxanes or supported derivatives thereof
  • the boron-group oxygen 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). From these polyolefins, prepared using the boron group oxygen compounds according to the invention, articles such as bottles, films, films, fibers, moldings, shoe soles, foams, polymers with glassy appearance, car tires, rubbers, paints, powder coatings, pipelines, drinking water pipes, sewage pipes, Profiles, window profiles, food packaging, blister packaging and engineering plastics.
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LLDPE linear low density polyethylene
  • PP polypropylene
  • Another object of the invention is the use of the oxygen compound of the invention boron group as a catalyst and / or synthesis aid in organic synthesis.
  • Another object of the invention is the use of the oxygen compounds of the invention boron group 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 oxygen compound of the invention the boron group as electrolytes, conductive salts and conductivity improvers
  • Another object of the invention is the use of the oxygen compound of the boron group according to the invention for the preparation of electrolytes and conductivity improvers.
  • Another object of the invention is the use of the oxygen compounds of the boron group according to the invention as electrolytes in galvanic cells.
  • Another object of the invention is the use of the oxygen compounds of the invention boron group for the production of electrolytes for galvanic cells.
  • Another object of the invention is the use of the oxygen compound of the boron group according to the invention as electrolytes in lithium batteries, preferably in lithium ion batteries.
  • Another object of the invention is the use of the oxygen compounds of the invention boron group as electrolytes in electrolytic double-layer capacitors.
  • oxygen compounds of the boron group 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, cyclopentylmethyl 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 carbon
  • Elekrolytallen containing the oxygen compounds of the boron group according to the invention can be added.
  • the corresponding substituted oxygen-containing substituent ie a substituted 1,2-aryl-dioxy substituent according to the invention, is reacted in a suitable solvent with a compound of an element of the boron group (boron group element compound), preferably with a boron or an aluminum compound.
  • a compound of an element of the boron group boron group element compound
  • the ratio of the 1,2-aryl dioxy substituent to the boron group element compound is preferably 1 to 4, more preferably 2 equivalents of the substituent to one equivalent of the suitable boron group element compound.
  • Suitable solvents for carrying out the reaction are, for example, hydrocarbons or ethers or halogenated hydrocarbons.
  • 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, or boric acid esters, or aluminum alkyls.
  • 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 trimethylborate, thethylborate and thisopropylborate are suitable.
  • aluminum hydroxide and aluminum carbonate and complex aluminum hydrides, borohydrides and aluminum amides are also suitable.
  • AIEt 3 , AIBu 3 , Li [AlH 4 ], Na [AlH 4 ], Mg [AlH 4 ] 2 , AICl 3 , Na [BH 4 ], BF 3 , BCI 3 , H 3 BO 3 and B are particularly preferred according to the invention (OMe) 3 .
  • the reaction temperature is from -100 ° C to 200 ° C. Preferred is a temperature range from -78 ° C to the boiling point of the solvent used, more preferably from -20 ° C to the boiling point of the solvent used.
  • water may be added.
  • the reaction mixture may be added with a basic salt. Basic salts of the formula M 2 CO 3 are preferred according to the invention, Li 2 CO 3 being particularly preferred.
  • the reaction mixture may be added with a base, which may be an amine. Up to 5 equivalents of base can be added to the reaction mixture. Preferred are one to 5 equivalents.
  • the compound according to the invention can be isolated according to formula 1.
  • the reaction induced cation M y + can be replaced by other cations M y +, for example by means of ion exchangers or salt exchange or recrystallization. A salination is also possible in a two- or multi-phase, liquid system.
  • Suitable solvents for exchanging the cation are hydrocarbons or ethers or esters or aprotic organic solvents or mixtures of at least two of these solvents.
  • Example 2 Preparation of lithium bis (3,6-di-tert-butylcatechol) borate
  • boric acid two equivalents of 3,6-di-tert-butyl catechol and 0.5 equivalent of Li 2 CO 3 are introduced into xylene and the suspension is heated to reflux on a water separator. Once the evolution of water is complete, the solvent is removed in vacuo.
  • Lithium bis (3,6-diisopropylcatechol) 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 7 Preparation of Thphenylcarbonium bis (3,6-di-tert-butylcatechol) borate
  • Lithium bis (3,6-ditertbutylcatechol) borate is dissolved in toluene and treated with one equivalent of chlorotriphenylmethane. From the precipitated LiCl is filtered off. Thphenylcarbonium tetrakis (isopropylsilylethynyl) borate is obtained after removal of the toluene in vacuo.

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Abstract

La présente invention concerne des composés d'oxygène comprenant des éléments qui appartiennent au groupe du bore, la préparation de ces composés et leur utilisation comme additifs, stabiliseurs, catalyseurs, co-catalyseurs, activateurs pour systèmes catalytiques, agents d'amélioration de la conductivité et électrolytes.
PCT/EP2008/061514 2007-08-30 2008-09-01 Composés d'oxygène comprenant des éléments qui appartiennent au groupe du bore WO2009027541A2 (fr)

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Publication number Priority date Publication date Assignee Title
WO2011032681A1 (fr) 2009-09-17 2011-03-24 Universität Heidelberg Métallates lipophiles
DE102009041864A1 (de) 2009-09-17 2011-03-31 Universität Heidelberg Lipophile Metallate
DE102013004943A1 (de) 2013-03-21 2014-09-25 Universität Heidelberg Lipophile Metallate

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WO2000034344A1 (fr) * 1998-12-09 2000-06-15 The B.F.Goodrich Company Polymerisation par ajout dans le moule de monomeres du type norbonene au moyen de complexes de metaux du groupe 10
US20040007693A1 (en) * 2002-07-03 2004-01-15 Roger Moulton Ionic liquids containing borate or phosphate anions

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