EP4126890A1 - Composés organométalliques - Google Patents

Composés organométalliques

Info

Publication number
EP4126890A1
EP4126890A1 EP20717141.4A EP20717141A EP4126890A1 EP 4126890 A1 EP4126890 A1 EP 4126890A1 EP 20717141 A EP20717141 A EP 20717141A EP 4126890 A1 EP4126890 A1 EP 4126890A1
Authority
EP
European Patent Office
Prior art keywords
ether
glycol
reaction
propylene glycol
partially
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Withdrawn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
EP20717141.4A
Other languages
German (de)
English (en)
Inventor
Nicholas RAU
Annika Frey
Ralf Karch
Eileen Woerner
Angelino Doppiu
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.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
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 Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP4126890A1 publication Critical patent/EP4126890A1/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Withdrawn legal-status Critical Current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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • 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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage

Definitions

  • precursor compounds such as. B. [W (0) (0R) 4 ] suitable for processes for the production of a semiconductor element, a photo element, a photovoltaic cell or catalyst, ie a catalytically active organic or inorganic compound
  • compounds of the type [W (0) (OR) 4 ] are usually represented on the basis of WOCI 4 .
  • the target compounds [W (0) (OR) 4 ] are obtained by reaction with i) the free alcohol and ammonia or ii) the corresponding lithium alcoholate.
  • the introduction of NH 3 gas is essential necessary. This produces large amounts of NH 4 CI.
  • at least three times the amount of alcohol must be added than is necessary to replace the four chlorine atoms.
  • the problem with this route is, in particular, the use of the hydrolysis-sensitive starting material WOCI 4 , which has to be prepared, isolated and sublimatively purified in a previous reaction step before it can be used further.
  • the synthesis route ii) is described in WO 2016/006231 A1, inter alia, for [W (0) (0sBu) 4 ], sBuOH, nBuLi and WOCI 4 being used as starting materials. as
  • Solvents are tetrahydrofuran and toluene. After vacuum distillation, the product is a slightly yellow liquid. The yield is 73% (87 mmol).
  • a major disadvantage of the known process management for the production of compounds of the type [W (0) (OR) 4 ] consists in the use of the non-commercial available WOCI 4 .
  • the hydrolysis-sensitive starting material WOCI 4 has to be produced in an upstream synthesis, isolated and sublimatively purified before it can be used further. Its representation therefore not only represents an additional synthesis step, but is also complex and cost-intensive.
  • the use of nBuLi for the production of the lithium alcoholates LiOR is also preparatively complex and cost-intensive.
  • Another disadvantage is that large amounts of inorganic salts, such as. B. LiCI or NH 4 CI, are obtained, the separation of which is difficult in many cases. This is because the reactions are usually carried out in THF or alcohols as solvents. If lithium ions are present in the reaction mixture, it can also lead to the formation of lithium tungstate complex salts, such as. B. Li [W (0) (0R) 5 ], which are also difficult or impossible to separate.
  • the synthesis routes known from the literature are to be classified as unsatisfactory from an ecological and economic point of view.
  • the invention is therefore based on the object of overcoming these and other disadvantages of the prior art and of providing a method with which easily, inexpensively and reproducibly defined oxido (tetraalkoxido) tungsten compounds in high purity and good yields and low silicon content can be produced.
  • the purity of the oxido (tetraalkoxido) tungsten Compounds meet the requirements for precursors for the production of high quality substrates which have tungsten layers or layers containing tungsten.
  • the process should be distinguished by the fact that it can also be carried out on an industrial scale - with comparable yield and purity of the target compounds.
  • new oxido (tetraalkoxido) tungsten compounds are to be made available.
  • a substrate is to be made available which has a tungsten layer or a tungsten-containing layer on one surface, which can be produced using an oxido (tetraalkoxido) tungsten compound obtainable or obtained by the claimed method or using one of the new oxido (tetraalkoxido) tungsten compounds.
  • the object is achieved by a process for the preparation of oxido (tetraalkoxido) tungsten compounds according to the general formula
  • R is selected from the group consisting of a straight-chain, branched or cyclic alkyl radical (C5-C10), a straight-chain, branched or cyclic partially or fully halogenated alkyl radical (C5-C10), an alkylene alkyl ether radical
  • n -R F a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear aryl, a partially or fully substituted mononuclear or polynuclear aryl, a mononuclear or polynuclear heteroaryl and a partially or fully substituted mononuclear or polynuclear heteroaryl, where
  • - R E are independently selected from the group consisting of a straight-chain, branched or cyclic alkylene radical (C1-C6) and a straight-chain, branched or cyclic partially or fully halogenated alkylene radical (C1-C6)
  • - R F are independently selected from the group consisting of a straight-chain, branched or cyclic alkyl radical (C1-C10), a straight-chain, branched or cyclic partially or fully halogenated alkyl radical (C1-C10)
  • - n 1 to 5 or 1, 2 or 3 comprising the steps: a) reaction of WCI 6 with hexamethyldisiloxane in an aprotic solvent in a reaction vessel, b) distillative removal of by-products and solvents, c) addition of an alcohol ROH, where R is as defined above; and a molar ratio WCI 6 : ROH is at least 1: 4, and d) feeding in ammonia NH 3 or at
  • the general formula I here includes both the monomers and any oligomers.
  • [W (0) (0 / Pr) 4 ] is present in the solid state as a dimer.
  • R can not only be a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear aryl, a partially or fully substituted mononuclear or polynuclear aryl, a mononuclear or polynuclear heteroaryl and a partially or fully substituted mononuclear or polynuclear heteroaryl be a straight-chain, branched or cyclic alkyl radical with five to ten carbon atoms, which can not be, partially or fully halogenated, but R can also be of the formula ( R E -0) n -R F correspond.
  • n is an integer from 1 to 5, such as 4, in particular 1, 2 or 3.
  • R E corresponds to the formula (R E -0) n -R F , then, if n is greater than 1, that is to say 2, 3, 4 or 5, several R E radicals can be present. These can be the same or different and the radicals R E can be selected independently of one another from the group consisting of a straight-chain, branched or cyclic alkylene radical with one to six carbon atoms, a partially or completely straight-chain, branched or cyclic halogenated alkylene radical (C1 - C6 ) with one to six carbon atoms.
  • the radical R F can be selected independently of one another from the group consisting of a straight-chain, branched or cyclic alkyl radical with one to ten (C1-C10), in particular three to seven (C3-C7), a straight-chain, branched or cyclic, partially or fully halogenated alkyl radical with one to ten carbon atoms (C1-C10) can be selected.
  • the R F radicals can, however, also differ, just as the R E radicals differ and thus can lead to different R radicals. If different radicals R F and / or R E and thus different radicals R are present, as stated above, then the alcohols ROH used are mixtures.
  • the alcohol ROH is selected from the group consisting of sBuCH 2 OH, / BuCH 2 OH, (/ Pr) (Me) CHOH, (nPr) (Me) CHOH, (Et) 2 CHOH, (Et) (Me) 2 COH, CeHnOH, C 6 H 5 CH 2 OH, and C 6 H 5 OH.
  • the alcohol ROH is selected from the group consisting of 2-fluoroethanol, 2,2-dichloro-2-fluoroethanol, 2-chloroethanol,
  • the alcohol ROH is a glycol ether.
  • Polyethers are also understood as glycol ethers.
  • the glycol ether is selected from the group consisting of a monoethylene glycol monoalkyl ether, a diethylene glycol monoalkyl ether, a triethylene glycol monoalkyl ether, a monopropylene glycol monoalkyl ether, a dipropylene glycol monoalkyl ether, a tripropylene glycol monoalkyl ether, a tri-propylene glycol monoalkyl ether, a monomonoxomethylene monoalkyl ether, a monomonoxomethylene monoalkyl ether, a monomonoxomethylene monoalkyl ether, a monomonoxomethylene monoalkyl ether, a monomonoxomethylene monoalkyl ether, a monomonoxomethylene monoalkyl ether, a monomonoxomethylene monoalkyl ether,
  • the specified glycol ethers can also be used as isomer mixtures.
  • the aprotic solvent can also be a mixed solvent.
  • reaction container is not limited to a volume, a material quality, an equipment and / or a shape.
  • the completeness of the reaction or the end of the reaction in step d) can be determined by the fact that, for example, ammonia supplied in gaseous form is no longer captured by the reaction mixture, but flows through the reaction mixture, the drop in the temperature of the reaction mixture or a decay of the exotherm or combinations thereof .
  • a bubble counter, a pressure relief valve and / or a pressure sensor, mass flow meter or flow meter, temperature sensor or temperature switch can be used. If the completeness of the reaction is determined with a time delay, excess NH 3 gas can simply be removed from the reaction mixture by creating a negative pressure in the reaction vessel.
  • a similar procedure can be used if ammonia or amine are supplied in gaseous form under pressure, in a liquid state or as a solution.
  • the claimed process advantageously enables the preparation of the target compounds [W (0) (OR) 4 ] in a one-pot synthesis, that is, the intermediate product of step a), the reaction of WCI 6 with hexamethyldisiloxane, is not isolated, but is in step b) only by-products distilled off.
  • the inexpensive, commercially available WCI 6 is used as the starting material.
  • the hydrolysis-sensitive tungsten (VI) compound WOCL is produced by reaction with hexamethyldisiloxane (TMS 2 0) in an aprotic solvent. This is particularly advantageous because it eliminates the complex isolation and sublimative purification of WOCL, which here is only an intermediate product.
  • step c) By adding at least four molar equivalents of ROH - based on WCI 6 - the respective oxido (tetraalkoxido) tungsten complex is obtained in step c), only four molar equivalents of ROH being required for the preparation of the respective target compound.
  • the by-product trimethylsilyl chloride (TMSCI) obtained in step a) competes in step c) with the reaction to the desired end product with a side reaction in that it also reacts with ROH to form the defined compound TMSOR, which in the case of the R radicals used here is not only relatively poorly volatile but also require two additional equivalents of ROH to ensure that the WOCL is completely vented.
  • step c) The hydrogen chloride formed in step c) is captured by feeding in ammonia or an amine, for example by introducing NH 3 gas, in accordance with step d).
  • NH 4 CI in particular precipitates out quantitatively, while the target compound, e.g. B. [W (0) (0 / Pr) 4 ], remains in solution.
  • a contamination of the respective tungsten (VI) oxo-alkoxide by the accumulating NH 4 CI load is thus advantageously significantly reduced.
  • Another advantage is that it does not lead to the formation of indefinable by-products such as. B. comes from lithium tungstate complex salts, which can only be separated with difficulty or not at all.
  • the respective target compound in solution can be reacted directly with one or more other reactants.
  • the compound of the type [W (0) (OR) 4 ] can, for example, by means of a simple filtration, optionally with a filter aid, such as. B. activated carbon, an aluminosilicate or silica, followed by removal of all volatile constituents such as solvents, can be isolated.
  • a filter aid such as. B. activated carbon, an aluminosilicate or silica
  • NH 4 CI can be removed easily and approximately quantitatively, preferably quantitatively, by means of a filtration step.
  • the isolated compound advantageously has neither NH 3 nor silicon-containing impurities or residues of the solvent or solvent mixture used.
  • the end product can still contain residues of solvent, TMSOR, hexamethyldisiloxane or the defined, easily separable by-product from the reaction of amine or
  • Ammonia such as ammonium chloride NH 4 CI contain.
  • the end product therefore has a purity of at least 97%, advantageously more than 97%, in particular more than 98% or 99%.
  • the target compound can therefore be used and / or stored after isolation without further purification.
  • the reproducible yield is depending on the choice of alcohol ROH and the solvent or
  • Solvent mixture also in the case of upscaling towards an industrial scale - usually> 80% or> 90%.
  • the claimed method overcomes the disadvantages of the prior art.
  • there are significantly lower levels of contamination due to salt loads that are difficult to separate such as.
  • the process is characterized by a particularly simple and inexpensive process management, because it is a one-pot synthesis.
  • few process steps that are easy to accomplish in terms of preparation and that are easily scalable are necessary.
  • commercially readily available and inexpensive starting materials are used.
  • Definable, easily and readily separable by-products are formed which can be separated off almost quantitatively, advantageously quantitatively.
  • there is no formation of non-separable lithium tungstate complex salts such as. B. Li [W (0) (OR) 5 ].
  • the desired oxido (tetraalkoxido) tungsten compound is obtained reproducibly without further distillative and / or sublimative purification in improved, high purity.
  • the oxido (tetraalkoxido) tungsten compounds that can be produced with the claimed method meet the purity requirements for precursors for the production of high quality substrates which have tungsten layers or layers containing tungsten.
  • the yields are good to very good, reproducible and exceed the yields of the synthesis methods known from the literature.
  • the process can also be carried out on an industrial scale, with comparable yields and purity of the target compounds being achieved.
  • the claimed method saves time, energy and costs. Overall, it can be classified as more economical in comparison.
  • the aprotic solvent is selected from the group consisting of aliphatic solvents, benzene derivatives and halogenated hydrocarbons.
  • the aprotic solvent is for example pentane, hexane, isohexane, heptane, octane, decane, toluene, xylene, dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, 1,1,1,1-trichloroethane, trichloroethene or tetrachloroethene. Mixtures of solvents can also be used.
  • the by-product NH 4 Cl can be separated off particularly easily and quickly when using one of these solvents or a mixture of one or more of these solvents.
  • the solvents pentane, isohexane, heptane, toluene, dichloromethane, trichloromethane, carbon tetrachloride, 1,2-dichloroethane and trichloroethene can advantageously be completely recycled without losses. This has a positive effect on the life cycle assessment of the process.
  • step a) the reaction of WCI 6 with hexamethyldisiloxane in the aprotic solvent in the reaction container comprises the following steps: i) providing a solution or a suspension of WCI 6 in the aprotic solvent, ii) adding hexamethyldisiloxane, wherein during the addition and / or after the addition of hexamethyldisiloxane, a reaction of WCI 6 with hexamethyldisiloxane takes place.
  • the aprotic solvent can also be a mixture of solvents or a mixture of isomers.
  • a molar ratio of WCI 6 : hexamethyldisiloxane is at least 1: 1.
  • step a) ii) the addition of hexamethyldisiloxane to the solution or the suspension of WCI 6 in the aprotic solvent takes place using a metering device. That can add take place, for example, by dropping or injecting.
  • a shut-off valve and / or a shut-off valve and / or a metering pump can be provided in a feed line of the reaction container.
  • Hexamethyldisiloxane in a solvent S is added to the solution or the suspension of WCI 6 in the aprotic solvent, the solvent S, in which hexamethyldisiloxane is dissolved, being miscible or identical to the aprotic solvent in which WCI 6 is dissolved or suspended.
  • this can be advantageous for better control of the course of the reaction or the exothermicity.
  • An internal temperature of the reaction container can be determined with the aid of a temperature sensor or a plurality of temperature sensors for an area or a plurality of areas of the reaction container. At least one temperature sensor is provided for determining the internal temperature Tu, which generally corresponds to an average temperature T Di of the reaction mixture.
  • the internal temperature Tu of the reaction vessel is between 0 ° C and 140 ° C or from 10 ° C to 140 ° C. In yet another embodiment of the process, the internal temperature Tu is des
  • Reaction container during the reaction of WCI 6 with hexamethyldisiloxane between 10 ° C and 100 ° C or from 20 ° C to 100 ° C.
  • the internal temperature Tu of the reaction vessel is regulated and / or controlled using a heat transfer medium Wu.
  • a cryostat can be used, for example, which contains a heat transfer medium, which ideally can function both as a coolant and as a heating medium.
  • the heat transfer medium Wu deviations in the internal temperature Tu from a setpoint T Si established for the conversion of WCI 6 with hexamethyldisiloxane can be largely intercepted or compensated for.
  • a constant internal temperature Tu can only be achieved with difficulty due to the usual device deviations.
  • the reaction of WCI 6 with hexamethyldisiloxane can, however, be carried out at least in a preselected temperature range or in several preselected temperature ranges.
  • a preselected temperature range or in several preselected temperature ranges can be advantageous to create a temperature program for even better control of the course of the reaction or the exothermicity.
  • a lower temperature or a lower temperature range can be selected than in one second phase of adding hexamethyldisiloxane.
  • more than two phases of the addition and thus more than two preselected temperatures or temperature ranges can be provided.
  • the WCI 6 concentration and the solvent or solvent mixture it can during the addition and / or after the addition of
  • Hexamethyldisiloxane be favorable to carry out an increase in the internal temperature Tu of the reaction vessel using the heat transfer medium Wu. This can, if necessary, ensure that the conversion of WCI 6 with hexamethyldisiloxane takes place quantitatively.
  • the duration of the increase in the internal temperature Tu of the reaction vessel using the heat transfer medium Wu can be, for example, between 10 minutes and 6 hours.
  • the molar ratio WCI 6 : ROH is at least 1: 4 or is between 1: 4 and 1:40 or 1: 6.1 and 1:40 or 1: 4 and 1: 6.1.
  • the molar ratio is selected as a function of the particular reactant ROH and the particular aprotic solvent or solvent mixture.
  • step b) the solvent and / or solvent and the TMSCI formed as a by-product in step a) are removed by distillation.
  • a distillation bridge is set up on a laboratory scale after the reaction of WCI 6 with hexamethyldisiloxane has ended. Suitable industrial systems are usually already designed accordingly and provided with appropriate facilities.
  • the distillation can advantageously be carried out gently under reduced pressure. In this case, pressures of about 50 mbar to about 250 mbar, in particular 120 mbar to about 220 mbar, have proven useful.
  • Suitable temperatures are usually around 30 ° C. to around 50 ° C. in order to bring about a gentle distillation, for example by distillation at 40 ° C. and a pressure of 170 mbar. If no more distillate is collected (the head temperature of the distillation bridge used also falls), the pressure can be increased gradually, for example in Steps of 10 mbar each are further reduced until the distillate distills over again and the distillation stops again. If the pressure is about 50 mbar below the pressure at the start of the distillation, a drag distillation can be carried out and about 10% to about 50%, in particular about 20% to about 40%.
  • the alcohol ROH is added using a metering device. The addition can take place, for example, by dropping or injecting.
  • a shut-off valve and / or a shut-off valve or a metering pump can be provided in a feed line of the reaction container
  • a solution of the alcohol ROH in a solvent M is added to the reaction mixture from step b), the solvent M in which the alcohol ROH is dissolved being miscible or identical with the aprotic solvent from step a) .
  • this can be advantageous for better control of the course of the reaction or the exothermicity.
  • an internal temperature T c of the reaction vessel is between -30 ° C. and 50 ° C. during the addition and / or after the addition of the alcohol ROH.
  • the internal temperature T c of the reaction vessel is between -25 ° C. and 30 ° C. during the addition and / or after the addition of the alcohol ROH.
  • the internal temperature T c of the reaction vessel during the addition and / or after the addition of the alcohol ROH is between -15.degree. C. and 20.degree.
  • At least one temperature sensor is provided for determining the internal temperature T c , which generally corresponds to an average temperature T D 2 of the reaction mixture.
  • the temperature sensor can be identical to the one used to determine the internal temperature Tu.
  • the internal temperature T c of the reaction vessel is regulated and / or controlled using a heat transfer medium W c.
  • a cryostat can be used, for example, which contains a heat transfer medium, which ideally can function both as a coolant and as a heating medium.
  • Heat transfer medium W c the reaction of the WOCI 4 generated in step a) with ROH can, however, be carried out at least in a preselected temperature range or in a plurality of preselected temperature ranges.
  • a preselected temperature range or in a plurality of preselected temperature ranges can be advantageous to create a temperature program for even better control of the course of the reaction or the exothermicity.
  • a lower temperature or a lower temperature range can be selected during a first phase of adding the alcohol ROH than in a second phase of adding the alcohol ROH. It is also possible for more than two phases of the addition and thus more than two preselected temperatures or temperature ranges to be provided.
  • an internal temperature T N of the reaction vessel during step d) and / or thereafter is between -30 ° C. and 100 ° C. or between -25 ° C. and 80 ° C. or between -20 ° C. and 60 ° C.
  • ammonia or amine is fed in, which can be done by introducing gaseous or liquid amine or ammonia, a solution of ammonia or amine or by applying pressure to amine or NH 3 gas. When pressure is applied, a pressure of 1 mbar to 6 bar, in particular 100 mbar to 4.5 bar, can be selected.
  • There is at least one temperature sensor for determining the internal temperature T N provided, which generally corresponds to an average temperature T D 3 of the reaction mixture. The temperature sensor can be identical to the one for determining the internal temperature Tu and / or the internal temperature T c .
  • amine is used, it is generally possible to use different amines, also as a mixture, such as primary, secondary or tertiary amines.
  • amines also as a mixture, such as primary, secondary or tertiary amines.
  • Alkylamines are advantageously used. These can be methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-tert. -Butylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, tri-tert-butylamine, tricyclohexylamine or mixtures thereof.
  • DIPEA diisopropylethylamine
  • Urotropine acetamidine, ethylenediamine, triethylenetetramine, morpholine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-en (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO®) , L /, L /, L / ', L /' - Tetramethylethylenediamine (TMEDA), pyridine, pyrazole, pyrimidine, imidazole, guanidine, hexamethyldisilazane or combinations thereof can be used.
  • DIPEA diisopropylethylamine
  • the internal temperature T N of the reaction vessel is regulated and / or controlled using a heat transfer medium W N.
  • a cryostat can be used, for example, which contains a heat transfer medium, which ideally can function both as a coolant and as a heating medium.
  • step d) can be carried out at least in a preselected temperature range or in a plurality of preselected temperature ranges.
  • a preselected temperature range or in a plurality of preselected temperature ranges.
  • it can be used for even better control of the The course of the reaction or the exotherm may be advantageous to create a temperature program.
  • an internal temperature T Ni of the reaction vessel during a first phase of feeding in the ammonia or amine by introducing it in a liquid or gaseous state or as a solution or by applying pressure is between -30 ° C and 20 ° C and an internal temperature T N 2 of the reaction vessel during a second phase and / or after the second phase of supplying or introducing or pressurizing amine or NH 3 gas between 21 ° C and 100 ° C.
  • the reaction vessel is between -30 ° C and 20 ° C and an internal temperature T N 2 of the reaction vessel during a second phase and / or after the second phase of supplying or introducing or pressurizing amine or NH 3 gas between 21 ° C and 100 ° C.
  • Another modification of this embodiment provides that the internal temperature T N 2 of the reaction vessel during the second phase and / or after the second phase of supplying or introducing or pressurizing amine or NH 3 gas between 23 ° C and 60 ° C amounts to.
  • At least one temperature sensor is provided for determining the internal temperatures T Ni and T N 2, the internal temperatures T Ni and T N 2 generally corresponding to an average temperature T D 4 and TD 5 of the reaction mixture.
  • the temperature sensor for determining the internal temperature T Ni can be identical with that for determining the internal temperature T N 2 and / or with that for determining the internal temperature Tu and / or with that for determining the internal temperature T c .
  • Such a temperature program for supplying or introducing or pressurizing NH 3 gas enables - depending on the choice of the other reaction parameters - an even better control of the exothermicity or the course of the reaction.
  • the duration of the supply or introduction or pressurization of amine or NH 3 gas and the choice of the internal temperature T N or T Ni and T N 2 of the reaction vessel depend, among other things, on the batch size, the choice of the ROH reactant and the choice of solvent or solvent mixture dependent.
  • the two phases can differ in terms of their duration.
  • the first phase can comprise a longer period of time than the second phase at the comparatively higher internal temperature T N 2 of the reaction vessel.
  • the first phase of supplying or introducing or pressurizing amine or NH 3 gas z. B. include one hour, where T Ni ⁇ 20 ° C, and the second phase of supplying or introducing or pressurizing amine or NH 3 gas can include 30 min, where T N 2 ⁇ 21 ° C.
  • the first phase of supplying or introducing or pressurizing amine or NH 3 gas and the second phase of supplying or introducing or pressurizing amine or NH 3 gas comprise identical periods of time. This makes it comparatively easier to carry out the process.
  • step e) is carried out after step d) which comprises a separation of precipitated by-products or impurities.
  • the separation can comprise one or more steps.
  • by-products that have arisen are removed.
  • the chloride captured by reaction with amine or ammonia can primarily be separated off as precipitated ammonium chloride or ammonium salt (such as diethylammonium chloride). In principle, this can be done by any suitable method.
  • Filtration for example, is suitable for this, in which case the filter cake can advantageously be washed with the solvent used.
  • the precipitated by-products can also be sedimented or centrifuged and the solution of the product [W (0) (OR) 4 ] can be separated off by decanting.
  • the separation takes place by filtration; in a second stage, remaining, insoluble by-products or impurities are also separated off by centrifugation and subsequent decanting.
  • the isolation comprises a filtration step.
  • Several filtration steps can also be provided, optionally also one or more filtrations over a cleaning medium, such as, for. B. activated carbon, an aluminosilicate or silica, so that even soluble impurities and fines can be removed.
  • the filter cake which can also include the NH 4 CI load, for example, can be mixed with a small amount of a highly volatile solvent, such as. B. CH 2 CI 2 , are washed in order to extract any product contained in the NH 4 CI load. In a specific embodiment, washing is carried out with the solvent used as the reaction medium.
  • a highly volatile solvent such as. B. CH 2 CI 2
  • a step f) can then be carried out which comprises an isolation of [W (0) (OR) 4 ].
  • the isolation can include further procedural measures, such as. B. reducing the volume of the Mother liquor, ie concentration, e.g. B. by means of "bulb-to-bulb", the addition of a solvent and / or a solvent exchange in order to achieve crystallization or precipitation of the product from the mother liquor and / or to remove impurities and / or starting materials, washing and drying of the product, recrystallization, distillation and / or sublimation.
  • the solvent used is separated off by distillation (in vacuo) in step f).
  • R is selected from the group consisting of a straight-chain, branched or cyclic alkyl radical (C5-C10), a straight-chain, branched or cyclic partially or fully halogenated alkyl radical (C5-C10), an alkyl ether radical (R E -0) n -R F , a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear aryl, a partially or fully substituted mononuclear or polynuclear aryl, a mononuclear or polynuclear heteroaryl and a partially or fully substituted mononuclear or polynuclear heteroaryl, wherein
  • - R E are independently selected from the group consisting of a straight-chain, branched or cyclic alkylene radical (C1-C6) and a straight-chain, branched or cyclic partially or fully halogenated alkylene radical (C1-C6)
  • - R F are independently selected from the group consisting of a straight-chain, branched or cyclic alkyl radical (C1-C10), a straight-chain, branched or cyclic partially or fully halogenated alkyl radical (C1-C10)
  • n 1 to 5 or 1, 2, or 3, in particular obtainable by a process for the production of oxido (tetraalkoxido) tungsten compounds according to one of the exemplary embodiments described above.
  • the tungsten (VI) oxo-alkoxides of the type [W (0) (OR) 4 ] can advantageously be prepared particularly simply and inexpensively in a one-pot synthesis.
  • the oxido (tetraalkoxido) tungsten compounds can be reproducibly produced in high purity without further distillative and / or sublimative purification. In particular, they meet the purity requirements for precursors for the production of high quality substrates which have tungsten layers or layers containing tungsten. The yields are good to very good and reproducible.
  • the oxido (tetraalkoxido) tungsten compounds can also be produced on an industrial scale, with comparable yields and purity of the target compounds being achieved.
  • Oxido (tetraalkoxido) tungsten compounds such.
  • B. [W (0) (/ Pr) 4 ] and [W (0) (sBu) 4 ] are known in principle.
  • Compounds of the type [W (0) (OR) 4 ] obtainable by a process for the preparation of oxido (tetraalkoxido) tungsten compounds according to one of the exemplary embodiments described above, differ significantly in terms of their properties from those obtained by means of a process from the State of the art can be produced.
  • the isolated target compounds have at least as high a purity as compounds of the type [W (0) (OR) 4 ], which are prepared according to methods from the prior art and - as is customary in the literature - by means of a fractional distillation, without costly purification and / or a sublimation have been purified.
  • the tungsten (VI) -oxido-alkoxides obtainable according to an exemplary embodiment of the method described above have demonstrably no analytically detectable contamination by solvents or NH 3 .
  • the isolated product [W (0) (0sBu) 4 ] which was only recondensed but not fractionally distilled, is at least as pure as a distilled comparison product, produced according to WO 2016/006231 (cf.
  • R is selected from the group consisting of CH 2 sBu, CH 2 / Bu, CH (Me) (/ Pr), CH (Me) (nPr), CH (Et) 2 , C (Me) 2 (Et), C 6 Hn, CH 2 C 6 H 5 and C 6 H 5 .
  • OR is a corresponding base of a glycol ether.
  • the glycol ether is selected, for example, from the group consisting of a monoethylene glycol monoether, a diethylene glycol monoether, a triethylene glycol monoether, a monopropylene glycol monoether, a dipropylene glycol monoether, a tripropylene glycol monoether, a monooxomethylene monoether, a dioxomethylene monoether and a dioxomethylene monoether.
  • OR is selected from the group consisting of O-CH 2 CH 2 -O-CH 3 , O-CH 2 CH 2 -O-CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O- CH (CH 3 ) 2 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -
  • the term layer is synonymous with the term film and does not make any statement about the layer thickness or the film thickness.
  • a substrate for. B. corundum foils, silicon wafers or metallic or ceramic carriers can be used for catalytic converters.
  • the substrate can itself be part of a component, such as a semiconductor element, photovoltaic element or a car catalytic converter or exhaust gas purification system.
  • the tungsten layer or the tungsten-containing layer can be deposited by means of a gas phase deposition method, e.g. B. Atomic Layer Deposition (ALD) or Chemical Vapor Deposition (CVD).
  • ALD Atomic Layer Deposition
  • CVD Chemical Vapor Deposition
  • the oxido (tetraalkoxido) tungsten compounds used are particularly suitable as precursors for the production of high-quality tungsten layers and layers containing tungsten on a surface of a substrate.
  • they are free from contamination by solvents and NH 3 , which are disadvantageous for the coating process and thus for the performance of the coated substrates.
  • tungsten compounds according to the general formula [W (0) (OR) 4 ] (I), where the four radicals R are independently selected from the group consisting of from a straight-chain, branched or cyclic alkyl radical C6 - C8.
  • the tungsten (VI) oxo-alkoxides of the type [W (0) (OR) 4 ] can advantageously be prepared particularly simply and inexpensively in a one-pot synthesis.
  • the oxido (tetraalkoxido) tungsten compounds can be reproducibly produced in high purity without further distillative and / or sublimative purification. In particular, they meet the purity requirements for precursors for the production of high quality substrates which have tungsten layers or layers containing tungsten. The yields are good to very good and reproducible.
  • the oxido (tetraalkoxido) tungsten compounds can also be produced on an industrial scale, with comparable yields and purity of the target compounds being achieved.
  • R is selected from the group consisting of C5H11, C5H9, C9H19, C10H21 and O q H d .
  • R is selected from the group consisting of 2-fluoroethyl, 2,2-dichloro-2-fluoroethyl , 2-chloroethyl, 2-bromoethyl, 2,2-dibromoethyl, 2,2,2-tribromoethyl, hexafluoroisopropyl, (2,2-dichlorocyclopropyl) methyl and (2,2-dichloro-1-phenylcyclopropyl) methyl.
  • OR is a corresponding base of a glycol ether.
  • the glycol ether is selected from the group consisting of a monoethylene glycol monoether, a diethylene glycol monoether, a triethylene glycol monoether, a
  • OR is selected from the group consisting of O-CH 2 CH 2 -O-CH 3 , O -CH 2 CH 2 -O-CH 2 CH 3, O-CH 2 CH 2 -O-CH 2 CH 2 CH 3, O-CH 2 CH 2 -O- CH (CH 3) 2, O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 2 CH 3 , O-CH 2 CH 2 -OC 6 H 5 , O-CH 2 CH 2 -OC 6 H 5 , O-CH 2 CH 2 -OC 6 H 5 , O-CH 2 CH 2 -OC 6 H 5 , O-CH 2 CH 2 -OC 6 H 5 , O-CH 2 CH 2 -
  • Some of the aforementioned compounds of the type [W (0) (OR) 4 ] have comparatively low melting points due to the nature of the radical R or the ligand OR. Some representatives of these oxido (tetraalkoxido) tungsten compounds are in liquid form at or slightly above room temperature. Comparatively low-melting compounds of the general formula [W (0) (OR) 4 ] are particularly suitable as precursors for producing a high-quality tungsten layer or a layer containing tungsten on a surface of a substrate. Due to their high purity, the oxido (tetraalkoxido) tungsten compounds used are particularly suitable for the deposition of high-quality tungsten layers and layers of tungsten compounds, semiconductor applications, photovoltaics and catalysts or their precursors. In particular, they are free from contamination by solvents and NH 3 , which are disadvantageous for the performance in these applications.
  • the object is also achieved by the use of an oxido (tetraalkoxido) tungsten compound according to the general formula [W (0) (OR) 4 ] (I), obtained or obtainable by a process for the preparation of oxido (tetraalkoxido) tungsten compounds according to one of the embodiments described above, for the production of a semiconductor element, a photo element, a photovoltaic cell or catalyst, ie a catalytically active organic or inorganic compound or a support coated with at least one catalytically active layer for a car exhaust gas catalyst.
  • oxido (tetraalkoxido) tungsten compound according to the general formula [W (0) (OR) 4 ] (I) obtained or obtainable by a process for the preparation of oxido (tetraalkoxido) tungsten compounds according to one of the embodiments described above, for the production of a semiconductor element, a photo element, a photovoltaic cell or catalyst, ie a catalytically active organic
  • R E are independently selected from the group consisting of a straight-chain, branched or cyclic alkylene radical (C1-C6) and a straight-chain, branched or cyclic partially or fully halogenated alkylene radical (C1-C6),
  • defined oxido (tetraalkoxido) tungsten compounds can be prepared in a simple, inexpensive and reproducible manner in high purity and good to very good yields.
  • the compounds which can be prepared in a one-pot reaction have no contamination from starting materials, by-products, decomposition products, solvents or the like after their isolation. This does not require any complex purification of the crude product isolated in each case by fractional distillation and / or sublimation. Rather, no purification is necessary, ie the isolated crude product and the end product are identical, or, for example, a simple recondensation of the respective is sufficient
  • the compounds that can be produced with the claimed method are suitable for use as precursors for the production of high-quality substrates which have tungsten layers or layers containing tungsten.
  • the claimed method is characterized in that it - with comparable yield and purity of
  • Target connections - can also be carried out on an industrial scale. Overall, the claimed process can be assessed as satisfactory from an ecological and economic point of view. Further features, details and advantages of the invention emerge from the wording of the claims and from the following description of exemplary embodiments. Examples
  • WCI 6 (50.832 g; 128.17 mmol) is weighed into a flask and dissolved / suspended in 300 ml of heptane (abs. Or EMSURE). In a separate dropping funnel, 20.875 g (128.17 mmol, stoichiometric) hexamethyldisiloxane are weighed out and diluted with heptane to a 50% by volume solution. The hexamethyldisiloxane solution is slowly metered in over 30 minutes with stirring at an internal temperature of 19-30 ° C. After complete
  • the reaction mixture is metered in and stirred for 3 h.
  • the color of the reaction solution changes from dark red-violet to orange-yellow.
  • reaction solution After the end of the metering, the reaction solution is cooled to 15 ° C and the flow temperature is set to 0 ° C.
  • a gas inlet tube is placed on the apparatus and the gas path is first flushed with argon or nitrogen. Inert gas is then passed through the reaction solution for 10 min in order to displace excess HCl. After 10 minutes, ammonia is slowly passed in at a temperature of 10-15 ° C. The gas flow is initially so strong that the ammonia introduced is completely absorbed by the reaction solution. The temperature should be in the range of 0-40 ° C during initiation. The introduction of gas is ended as soon as the temperature of the reaction mixture falls and gas is blown off through the pressure relief valve. Then inert gas is passed through the reaction mixture again for 10 min.
  • Embodiment 1-3 Analytical data
  • ICP-OES Metals analysis
  • Embodiment 4-7 General implementation
  • WCI 6 (50.832 g; 128.17 mmol) is weighed into a flask and dissolved / suspended in 300 ml of heptane (abs. Or EMSURE).
  • heptane abs. Or EMSURE
  • 20.875 g (128.17 mmol, stoichiometric) hexamethyldisiloxane are weighed out and diluted with heptane to a 50% by volume solution.
  • the hexamethyldisiloxane solution is slowly metered in over 30 minutes with stirring at an internal temperature of 19-30 ° C.
  • the reaction mixture is stirred for 3 h.
  • the color of the reaction solution changes from dark red-violet to orange-yellow.
  • a distillation bridge with a scaled 250 ml Schlenk tube is put on.
  • the pressure is carefully reduced to 170 mbar and the temperature of the reaction mixture is slowly increased to 40.degree.
  • the first distillate is obtained from a head temperature of 34-36 ° C.
  • the distillation at 170 mbar / 40 ° C is continued until no more distillate is collected in the Schlenk flask and the head temperature of the distillation apparatus falls from 38 ° C to below 34 ° C.
  • the pressure is then slowly reduced to 160 mbar, 150 mbar and 140 mbar in 10 mbar steps and distilled in each case until no more distillate is collected and the head temperature falls below 34.degree.
  • the pressure is reduced to 120 mbar (boiling point heptane at 40 ° C.) and a drag distillation is carried out. Twice the volume of the heptane collected so far is also distilled off. After the distillation has ended, the distillation apparatus is removed again and exchanged for a dropping funnel. The distillate is discarded.
  • Reaction solution passed to displace excess HCl. After 10 minutes, ammonia is slowly passed in at a temperature of 10-15 ° C. The gas flow is initially so strong that the ammonia introduced is completely absorbed by the reaction solution. The temperature should be in the range of 0-40 ° C during initiation. The gas introduction is terminated as soon as the
  • NH3 ammonia
  • DA diethylamine
  • no . number of the example
  • the silicon contents were always in the range from 180 to 280 ppm. Without a distillation step, the silicon contents were between 800 and 5000 ppm with comparable yields.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé monotope de production de composés oxydo(tétraalcoxydo)tungstène selon la formule générale [W(O)(OR)4] (I), à partir de WCl6, d'hexaméthyldisiloxane, d'un alcool ROH et d'une amine ou d'un gaz NH3. L'invention concerne en outre l'utilisation d'un composé [W(O)(OR)4] (I) et d'un substrat, qui présente sur une surface une couche de tungstène ou une couche contenant du tungstène, qui sont appropriés pour la production d'éléments photovoltaïques, d'éléments semi-conducteurs ou de catalyseurs de gaz d'échappement de véhicule. Le procédé permet la production de produits définis d'une manière simple, économique et reproductible avec une pureté élevée et de bons à très bons rendements.
EP20717141.4A 2020-04-01 2020-04-01 Composés organométalliques Withdrawn EP4126890A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/059264 WO2021197598A1 (fr) 2020-04-01 2020-04-01 Composés organométalliques

Publications (1)

Publication Number Publication Date
EP4126890A1 true EP4126890A1 (fr) 2023-02-08

Family

ID=70189934

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20717141.4A Withdrawn EP4126890A1 (fr) 2020-04-01 2020-04-01 Composés organométalliques

Country Status (7)

Country Link
US (1) US20230192736A1 (fr)
EP (1) EP4126890A1 (fr)
JP (1) JP2023527507A (fr)
KR (1) KR20220161464A (fr)
CN (1) CN115244062A (fr)
TW (1) TW202146423A (fr)
WO (1) WO2021197598A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPP027497A0 (en) * 1997-11-07 1997-12-04 Sustainable Technologies Australia Limited Preparation of metal alkoxides
TW201606115A (zh) 2014-07-07 2016-02-16 液態空氣喬治斯克勞帝方法研究開發股份有限公司 用於薄膜沉積之含鉬及鎢之前驅物

Also Published As

Publication number Publication date
JP2023527507A (ja) 2023-06-29
CN115244062A (zh) 2022-10-25
WO2021197598A1 (fr) 2021-10-07
US20230192736A1 (en) 2023-06-22
KR20220161464A (ko) 2022-12-06
TW202146423A (zh) 2021-12-16

Similar Documents

Publication Publication Date Title
DE602004005505T2 (de) Verfahren zur Herstellung und Reinigung von Bis(tertiärbutylamino)silan
EP1689756B1 (fr) Procede pour preparer des sels d'anions faiblement coordonnees, sels correspondants et leur utilisation
WO1997034875A1 (fr) Procede de preparation de carbenes heterocycliques
EP2285813B1 (fr) Procédé de retraitement de résidus contenant des sels, issus de la préparation d'organosilanes à fonction amino
DE69504526T2 (de) Herstellung von metallorganischen verbindungen
EP2291385A1 (fr) Procédé de traitement en phase aqueuse d'un organosilane à fonction amino contenant des halogénures d'ammonium et/ou des aminhydrohalogénures organiques
EP3847126B1 (fr) Procédé de fabrication de composés de dialkylamido-éléments
EP4126890A1 (fr) Composés organométalliques
WO2020120150A1 (fr) Composés organométalliques
EP1519914A1 (fr) Nouveaux complexes de metaux alcalino-terreux et leur utilisation
EP3724204B1 (fr) Complexes métalliques comportant des triazénidoligandes et leurs utilisations permettant la séparation de métaux de la phase gazeuse
WO2021186087A1 (fr) Iodure de triméthylplatine(iv)
WO2018138150A1 (fr) Procédé de réduction d'halogénures métalliques
EP3653577B1 (fr) Tris-(trichlorosilyl)-dichloro-gallyl-germane, son procédé de production et son utilisation
EP1824864B1 (fr) Procede continu de decomposition de silazane
WO2020120148A1 (fr) Alkylaluminates de lithium utilisés en tant que réactifs de transfert d'alkyle
DE69110734T2 (de) Verfahren zur Herstellung von hexamethylcyclotrisilazan.
EP3908589A1 (fr) Composés organométalliques
EP3166953B1 (fr) Procédé de préparation d'un hydridocarbonyltris(triphénylphosphine)rhodium (i)
EP4098643A1 (fr) Complexes de métaux nobles avec des ligands dihydroguajazuléniques et leur utilisation
WO2021197597A1 (fr) Composés organométalliques
WO2013139332A1 (fr) Réactif de transition à base de carbènes
EP3428123A1 (fr) Procédé de réduction de halogénures métalliques
DE69724143T2 (de) Herstellung von bis-trialkylsilylamiden, und diese verbindungen enthaltende zusammensetzungen
DE102012013941A1 (de) Verfahren zur Herstellung von Galliumtrialkylverbindungen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20221102

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20231106

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UMICORE AG & CO. KG

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: 20240307