EP4472991A1 - Procede de préparation d'isocyanato-organosilanes - Google Patents

Procede de préparation d'isocyanato-organosilanes

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Publication number
EP4472991A1
EP4472991A1 EP22709592.4A EP22709592A EP4472991A1 EP 4472991 A1 EP4472991 A1 EP 4472991A1 EP 22709592 A EP22709592 A EP 22709592A EP 4472991 A1 EP4472991 A1 EP 4472991A1
Authority
EP
European Patent Office
Prior art keywords
alcohol
reaction
process step
reaction mixture
alkoxysilane
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.)
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Application number
EP22709592.4A
Other languages
German (de)
English (en)
Inventor
Volker Stanjek
Wolfgang DÖRING
Lars Zander
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.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP4472991A1 publication Critical patent/EP4472991A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the invention relates to a process for preparing isocyanate-functional organosilanes.
  • Organosilanes that have both an isocyanate function and a reactive alkoxysilyl group can be reacted with their isocyanate function with almost any hydroxyl-functional polyol.
  • alkoxysilane-functional polymers Because of this ability, they are important starting materials for the production of alkoxysilane-functional polymers.
  • the latter are products that can be cured via condensation reactions of their alkoxysilyl groups on contact with atmospheric moisture and are therefore ideal binders that are used in a large number of adhesives, sealants and coating materials.
  • alkoxysilane-terminated polypropylene glycols which can be obtained by reacting the above-mentioned isocyanate-functional alkoxysilanes with long-chain polypropylene glycols.
  • the name hybrid polymers has meanwhile become established for this product group.
  • ⁇ -isocyanatomethyl-alkoxysilanes ie compounds in which the reactive alkoxysilyl group is only separated from the isocyanate function by a methyl group, the corresponding ⁇ -alkoxysilane-terminated polymers are obtained.
  • These are characterized by an extremely high reactivity to atmospheric humidity and - unlike most conventional silane-functional polymers - do not require any tin catalysts for a rapid reaction Curing at room temperature.
  • the ⁇ -isocyanatomethyl-alkoxysilanes are therefore of particular importance.
  • the corresponding amine-functional alkoxysilanes of the formula (1) optionally with dialkyl carbonate (EP 3221324 & EP 3546465) or a mixture of urea and an alcohol (EP 3546468) to give the corresponding carbamate-functional silanes (2).
  • the respective isocyanate-functional silane (3) is then prepared from the latter in a second reaction step by thermolytic alcohol elimination.
  • a disadvantage of this process is the fact that the aminoalkyl alkoxysilanes required as starting materials are usually significantly more expensive than the corresponding chloroalkyl alkoxysilanes.
  • 3-aminopropyl-alkoxysilanes are commercially available in sufficiently large amounts, which limits the industrial applicability of these processes to isocyanate-functional silanes which also have a propyl spacer between the isocyanate and the alkoxysilyl function.
  • the first process step the production of carbamate-functional silanes starting from the corresponding chloroalkylsilanes, has already been described, for example in EP 2455385.
  • the chloroalkylalkoxysilanes are refluxed with potassium cyanate and an alcohol of the formula in a solvent.
  • Dimethylformamide is preferably used as the solvent.
  • the corresponding carbamatoalkyl alkoxysilanes and potassium chloride are formed as a co-product.
  • the solvent is then removed by distillation and the salt is filtered off.
  • a non-polar solvent is preferably used prior to the filtration step poor salt solubility, such as toluene, added, which is removed by distillation after the filtration step.
  • this process is used both for preparing 3-carbamatopropyl alkoxysilanes, ie compounds of the formula (2), and for preparing ⁇ -carbamatomethyl alkoxysilanes of the formula (4).
  • carbamatoalkyl-alkoxysilanes produced in this way are also further processed by the known processes for thermolytic alcohol elimination to give the corresponding isocyanate-functional alkoxysilanes.
  • the corresponding ⁇ -isocyanatomethyl-alkoxysilanes of the formula (5) would also be accessible from the ⁇ -carbamatomethyl-alkoxysilanes of the formula (4).
  • the object of the present invention was therefore to develop a process for preparing isocyanate-functional organosilanes which no longer has the disadvantages of the prior art.
  • the invention relates to a process for the preparation of isocyanatoalkyl-alkoxysilanes (S-I) of the general formula (6),
  • R 1 , R 3 and R 4 are each independently an unsubstituted or halogen-substituted hydrocarbon radical having 1-10 carbon atoms,
  • R 2 is a divalent, unsubstituted or halogen-substituted hydrocarbon radical with 1-10 carbon atoms, which can be interrupted by non-adjacent oxygen atoms,
  • X is a halogen atom and x is 0, 1, 2 or 3.
  • Process steps 1 to 3 are carried out in the order given one after the other.
  • the process according to the invention can of course also include further process steps, for example further work-up steps of the silane (SC), which take place between process steps 1 and 2.
  • SC silane
  • the radicals R 1 , R 3 and R 4 can be the same or different.
  • the radicals R 1 in the alcohol (A) and R 4 in the haloalkyl-alkoxysilane (SH) of the general formula (7) are preferably identical, because otherwise the radicals R 4 on the silicon atom would be exchanged during the 1st process step can come. This would give a mixture of different silanes (SC) of the general formula (9) in which the individual silane molecules have different R 1 radicals and different R 4 radicals, which is possible but usually not desirable.
  • halogen substituents are present on the radicals R 1 , R 2 , R 3 and R 4 , these are preferably selected from fluorine and chlorine. However, the radicals R 1 , R 2 , R 3 and R 4 are preferably halogen-free.
  • R 3 preferably represents a methyl, ethyl, iso- or n-propyl radical, a methyl radical being particularly preferred.
  • R 4 is preferably a methyl, ethyl, iso- or n-propyl radical, a methyl or ethyl radical being particularly preferred.
  • R 2 is preferably a propylene or more preferably a methylene radical.
  • R 1 preferably represents a methyl, ethyl, iso- or n-propyl radical, with a methyl or ethyl radical being particularly preferred.
  • the variable x is preferably 2 or 3, and in the silanes (SH) of general formula (7) X is preferably a chlorine atom.
  • the component (K) used in the 1st process step is preferably a crown ether and/or what are known as phase transfer catalysts, the use of phase transfer catalysts being very particularly preferred.
  • the component (K) can consist of a single compound or of a plurality of individual compounds. All the individual compounds of component (K) are preferably crown ethers and/or phase transfer catalysts, in particular exclusively phase transfer catalysts.
  • Crown ethers are cyclic ethers whose schematic structure in the sequence of ethyleneoxy units (-CH 2 -CH 2 -O-) and/or cyclohexane-1,2-diol units is reminiscent of a crown.
  • Typical crown ethers consist of 4 ethyleneoxy units ([12]crown-4), 5 ethyleneoxy units ([15]crown-5) or 6 ethyleneoxy units ([18]crown-6).
  • Dicyclohexano-[18]crown-6 is a representative of a crown ether which, in addition to ethyleneoxy units, also has cyclohexane-1,2-diol units.
  • Crown ethers form very stable complexes with cations such as potassium or sodium, which are soluble in organic media, and when these complexes dissolve, the corresponding counteranions inevitably also dissolve from the organic matrix.
  • Phase transfer catalysts are salts whose cations have organic residues and therefore have good or at least moderate solubility in organic media. And due to the good solubility of the cation, an anion is also inevitably dissolved. The anion contained in the original salt can be exchanged for other anions.
  • phase-transfer catalysis describes a chemical process in which a reactant in an organic phase is allowed to react with an anion present as part of a salt in an organic-immiscible aqueous phase. The presence of the phase transfer catalyst enables the anion to pass through the phase boundary from the aqueous into the organic phase, where the actual chemical reaction then takes place.
  • phase transfer catalysts examples are:
  • Ammonium salts such as tetrabutylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride, dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride, tribenzylmethylammonium chloride, benzyltriethylammonium chloride, alkylbenzyldimethylammonium chlorides or tricaprylylmethylammonium chloride, as well as the corresponding ammonium bromide iodides and hydroxides, and
  • Phosphonium salts such as tetrabutylphosphonium chloride or hexadecyltributylphosphonium bromide as well as the corresponding phosphonium bromides, iodides and hydroxides.
  • Component (K) is preferably present in the reaction mixture in a total amount of from 0.01 to 10% by weight, particularly preferably in a total amount of from 0.1 to 5% by weight, particularly preferably in a total amount of 0.3% up to 3% by weight added, in each case based on the total mass of the reaction mixture.
  • Component (K) can be added before or during the ongoing reaction, but it is preferably added from the beginning of the reaction.
  • phase transfer catalysts or/or one or more crown ethers is particularly preferred one or more phase transfer catalysts are added to the reaction mixture in the abovementioned preferred, particularly preferred total amounts.
  • the 1st process step according to the invention is preferably carried out in an anhydrous reaction system, ie a system which, unlike the usual implementation of a phase transfer catalysis, contains no aqueous salt phase.
  • the cyanates of all monovalent or divalent metal ions can be used as metal cyanates (MOCN), preference being given to the alkaline earth metal cyanates and in particular the alkali metal cyanates.
  • Sodium and in particular potassium cyanate is particularly preferably used.
  • At least 0.8 mol, particularly preferably at least 0.9 mol, in particular at least 1 mol, of cyanate ions and preferably at most 2 mol, particularly preferably at most 1.5 mol and in particular at most 1.2 mol of cyanate ion are used per mole of haloalkyl-alkoxysilane ( S-H) of the general formula (7) used.
  • Alcohols (A) used are preferably methanol, ethanol, isopropanol or n-propanol, particular preference being given to methanol and ethanol.
  • the 1st process step according to the invention is preferably carried out in the presence of at least one aprotic solvent (L).
  • the solvent (L) preferably has a boiling point of at least 140° C., particularly preferably at least 150° C., and preferably at most 240° C., particularly preferably at most 220° C., in each case at 0.1 MPa.
  • solvents (L) which can be used are dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-methylimidazole, sulfolane, diethylformamide, dimethylacetamide, diethylacetamide, acetylacetone, acetoacetic ester, hexamethylphosphoric triamide, nitriles such as acetonitrile or butyronitrile, and ethers and/or esters at least two ether or ester groups per molecule can be used.
  • Preferred solvents (L) are dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, sulfolane and diethylformamide, dimethylformamide being particularly preferred.
  • the solvent is preferably used in amounts such that at least 0.1 and at most 1.5 parts by weight of solvent (L) are used per part by weight of the total amount of starting material.
  • the total amount of educt is made up of the amount of silane (SH), metal cyanate (MOCN) and alcohol (A).
  • the solvent is preferably used in amounts such that at least 0.2 part by weight, particularly preferably at least 0.3 part by weight, of solvent (L) is used per part by weight of the total amount of starting material.
  • the solvent is preferably used in amounts such that a maximum of 1 part by weight, particularly preferably a maximum of 0.7 part by weight, of solvent (L) is used per part by weight of the total amount of starting material.
  • all the solids, including the metal cyanate (MOCN) and the component (K) are initially taken in a solvent (L), the haloalkyl-alkoxysilane (S-H) and the alcohol ( A), on the other hand, are metered in completely or at least partially only during the reaction.
  • the haloalkyl-alkoxysilane (S-H) is particularly preferably metered in at least 80% by weight in each case only during the reaction.
  • the advantage of this particularly preferred variant lies in the improvement in the safety of the reaction, since the clearly exothermic reaction can thus be controlled and, if necessary, also stopped by regulating the metering of the silane (S-H).
  • Dosing the liquid silane (S-H) is usually much more convenient than dosing the solid metal cyanate (MOCN), which is also conceivable in principle.
  • the amount of alcohol (A) in the initial charge and the metering rate of the remaining amount of alcohol (A) are controlled via the boiling point of the reaction mixture. Preference is given to initially introducing enough alcohol for the reaction mixture to have a boiling point of >110° C. and more preferably >120° C. before the start of the alcohol metering.
  • the upper limit of the boiling point is preferably at least 5° C., particularly preferably at least 10° C., below the boiling point of the solvent (L).
  • the alcohol (A) is preferably metered in so quickly that the reaction mixture has a boiling point >110° C. and more preferably >120° C. throughout the entire reaction time.
  • the upper limit of the boiling point is preferably at least 5° C., particularly preferably at least 10° C., below the boiling point of the solvent (L) over the entire reaction time.
  • the first process step according to the invention is preferably carried out under reflux.
  • the preferred procedure described, in which the alcohol dosage during the process step according to the invention is controlled by the reaction temperature, is based on the surprising discovery that it is possible in this way to combine a high reaction rate with a high yield. Dosing the alcohol too quickly leads to this (A) to this, at which the boiling point of the reaction mixture falls below the preferred or particularly preferred limits, to a significant slowing down of the reaction. Conversely, if the temperature is too high or if the reaction is not carried out under reflux, more oligomeric and/or polymeric impurities are formed.
  • controlling the metering rate of the alcohol (A) via the reflux temperature of the reaction mixture offers the person skilled in the art an easily implementable option for keeping the alcohol concentration in the reaction mixture in an optimal range for the entire duration of the reaction, both in terms of the reaction rate as well as to achieve the best possible results in terms of yield.
  • a preferred example is the addition of a metal iodide, preferably an alkali metal iodide and particularly preferably potassium iodide.
  • At least 0.01 part by weight particularly preferably at least 0.1 part by weight, in particular at least 0.5 part by weight of metal iodide, and preferably at most 5 parts by weight, particularly preferably at most 3 parts by weight and in particular at most 2 parts by weight of metal iodide per 100 parts by weight of metal cyanate deployed.
  • the solids can easily be separated off after the first process step, which is preferably done by filtration.
  • the first process step which is preferably done by filtration.
  • at least 70% and particularly preferably at least 85% of the solvent (L) are removed by distillation before the metal halides formed as by-products and any metal cyanate residues that are still present are separated off.
  • At least one solvent (II) which has a lower dipole moment than the solvent (L) is added to the reaction mixture before the solids are separated off, which takes place in particular by filtering off the metal salts. If the solvent (II) has a higher boiling point than the solvent (L), the solvent (II) can be added before or after the inventive removal of the solvent (L) by distillation. However, the at least one solvent (L1) is preferably added only after the solvent (L) has been removed by distillation, irrespective of the respective boiling points of the solvents (L) and (L1).
  • the reaction mixture preferably contains at least 0.3, in particular at least 0.5, parts by weight and at most 3, in particular at most 1.5 parts by weight of one or more solvents (II) per previously removed part by weight of solvent (L) added.
  • the filter cake is preferably washed with the same solvent (II) which was added to the reaction mixture after the removal of the solvent (L).
  • the filtrates are then preferably combined and the solvent (II) is removed by distillation.
  • the solvent (LI) is preferably an aromatic and/or aliphatic hydrocarbon (e.g. the various stereoisomers of pentane, hexane, heptane, octane, etc., cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, etc. benzene, toluene, the various xylene types etc.), substituted aromatics (e.g.
  • chlorobenzene e.g. pyridine, furan etc.
  • ethers e.g. diethyl ether, methyl t-butyl ether, tetrahydrofuran, dibutyl ether, anisole etc.
  • esters e.g Ethyl acetate, methyl acetate, butyl acetate, alkyl benzoates, dialkyl maleates, dialkyl phthalates, etc.
  • ketones e.g. acetone, butanone, etc.
  • alcohols e.g. t-butanol
  • Aromatic and/or aliphatic hydrocarbons such as the various cyclic or non-cyclic pentane, hexane, heptane or octane isomers, and toluene or xylene, are particularly preferred.
  • the filterability of the suspension formed in the 1st process step according to the invention can be significantly improved by the preferred use of a second solvent (LI).
  • the amount of salt remaining in dissolved form in the filtrate is significantly reduced, which is advantageous for the subsequent 2nd process step, since less or ideally no more salt can precipitate in the bottom of the distillation according to the invention.
  • the evaporator unit (VD) used in the second process step according to the invention can be any previously known evaporator unit, such as a thin-film, falling-film or short-path evaporator, with the three types of evaporator mentioned being preferred.
  • the preferred layer thickness of the reaction mixture is preferably Form of a liquid film in the evaporator unit (VD) preferably at a maximum of 2 cm, particularly preferably at a maximum of 1 cm, in particular at a maximum of 0.5 cm, very particularly preferably at a maximum of 0.3 cm.
  • VD evaporator unit
  • the 2nd process step according to the invention is preferably carried out in the evaporator unit (VD) at a pressure of at most 20 mbar, particularly preferably at most 10 mbar, in particular at most 5 mbar.
  • the 2nd process step according to the invention is preferably carried out in the evaporator unit (VD) at a temperature of not more than 180.degree. C., particularly preferably not more than 160.degree. C., in particular not more than 140.degree.
  • the 2nd process step according to the invention is preferably carried out in such a way that the reaction mixture in the evaporation unit (VD) has an average residence time of not more than 20 minutes, particularly preferably not more than 10 minutes, particularly preferably not more than 5 minutes.
  • All process steps according to the invention are preferably carried out in a protective gas atmosphere, preferably argon or nitrogen.
  • the second process step according to the invention is based on several discoveries.
  • component (K) which increases the solubility of anions in the organic reaction mixture, cannot be separated off by a filtration carried out after the 1st process step, was foreseeable.
  • anion whose solubility in organic media is improved by component (K).
  • SC carbamatoalkyl alkoxysilane
  • the carbamatoalkyl-alkoxysilanes (S-C) produced according to the invention preferably have a purity of >90%, particularly preferably >95%, in particular >98%.
  • the thermolytic elimination of alcohol from the carbamatoalkyl alkoxysilane (SC), which takes place in the third process step according to the invention, can be carried out in various ways.
  • the carbamatoalkyl alkoxysilanes (SC) are preferably heated to high temperatures >200° C., particularly preferably >250° C., if appropriate even >280° C., with an alcohol molecule being split off from the carbamate function and the formation of the Isocyanatoalkyl alkoxysilane (SI) comes.
  • SI Isocyanatoalkyl alkoxysilane
  • the cleavage can of course be carried out comparatively simply in a flask or kettle, with the more volatile reaction products being removed by distillation. However, more complex processes such as those described in EP 3221324 or EP 3546465 are usually more efficient.
  • the catalyst (K) is preferably added to the carbamatoalkyl-alkoxysilane (SC) before the start of the reaction.
  • the catalyst (K) is particularly preferably liquid or soluble in the carbamatoalkylalkoxysilane (SC).
  • Preferred catalysts (K) are all compounds which are used in polyurethane chemistry for catalyzing condensation reactions of isocyanates and alcohols.
  • Divalent tin catalysts such as tin diacetate or tin dilaurate can also be used.
  • organic bismuth and/or zinc compounds for example the various catalysts from Borcherts such as Borchi-Kat 22, Borchi-Kat 24 or Borchi-Kat 0244, organic titanium compounds such as titanates, eg titanium(IV) isopropylate or titanium(IV) acetylacetonate, organic iron compounds, eg iron(III) acetylacetonate, iron(II) acetylacetonate or other metal compounds such as zirconium(IV) acetylacetonate, cobalt(III) acetylacetonate or manganese acetylacetonate can be used.
  • catalysts (K) Preference is given to using non-volatile or only slightly volatile catalysts, in particular the abovementioned metal complexes, particular preference being given to tin(IV), tin(II) and iron(III) complexes.
  • the catalyst (K') is preferably used in concentrations of 1-10000 ppm, with concentrations of 10-5000 ppm or 100-2000 ppm being particularly preferred.
  • an inert gas flow e.g. made of argon, hydrogen or nitrogen, is passed through this evaporation unit during the evaporation process.
  • This is preferably heated before being introduced into the evaporation unit, particularly in the industrial process.
  • the hot stream of carrier gas supports the heating and vaporization of the reaction mixture. Nitrogen is preferred as the gas.
  • the evaporated reaction products are then preferably fractionally condensed, with the alcohol eliminated preferably being separated off in gaseous form and the isocyanatoalkylalkoxysilane (SI) and the carbamatoalkylalkoxysilane (SC) which may have also been partially evaporated being condensed together or, if appropriate, also separately in succession. Separating the alcohol prevents a reverse reaction of the isocyanatoalkyl-alkoxysilane (SI) formed.
  • the separation of the alcohol preferably takes place in a cooler or a simple separation column, in which the alcohol is removed in gaseous form and silanes (SI) and (SC) are condensed out together.
  • the isocyanatoalkyl-alkoxysilane (S-I) is then preferably purified by distillation, which can be done either continuously or batchwise, the former being preferred.
  • the carbamatoalkyl alkoxysilane (S-C) separated off in the process is preferably returned to the thermolytic production process.
  • the process according to the invention has the advantage that it is suitable for preparing all isocyanatoalkyl-alkoxysilanes (S-I) for which the corresponding haloalkyl-alkoxysilanes (S-H) are available. This applies in particular to the ⁇ -isocyanatomethyl-alkoxysilanes, which are of particular interest because of their high reactivity.
  • the method according to the invention has the advantage that it provides very good yields and is therefore comparatively inexpensive.
  • the process according to the invention has the advantage that in the carbamatoalkyl-alkoxysilane (S-C) produced according to the invention as an intermediate after the 2nd process step only a small amount of by-products are present, which can lead to disturbances in the 3rd process step, e.g. due to the formation of deposits .
  • the method according to the invention has the advantage of being very simple and robust. All of the above symbols of the above formulas each have their meanings independently of one another. In all formulas the silicon atom is tetravalent.
  • reaction mixture is cooled to about 30.degree.
  • 1000 g of toluene are added and the mixture is stirred at room temperature for 30 min. All solids are then filtered off via a pressure filter with a Seitz K900 filter at an overpressure of 0.2 bar. The filtration is possible without any problems and is completed within approx. 20 minutes.
  • the filter cake is regrown twice with 500 g of toluene, which is also completed within approx. 20 minutes.
  • the filtrates are combined.
  • the toluene is removed by distillation at a pressure of about 30 mbar and a bottom temperature which increases from 30 to 70° C. in the course of the distillation. About 95% of the used amount of toluene recovered in a purity> 95%.
  • the toluene distilled off can be reused without any problems.
  • This crude product is analyzed by 1 H NMR.
  • the product purity can be checked, for example, by integrating the CH 3 O—CO—NH—CH 2 —Si(CH 3 )(OCH 3 ) 2 signal and comparing this integral value with the signal integrals of an added internal standard such as benzenetricar - bonic acid trimethyl ester can be determined.
  • the crude product analyzed using this method has a purity of 92.8%.
  • the crude product is a light yellow, clear liquid.
  • reaction is carried out under reflux and the metering rate is controlled by the boiling temperature of the reaction mixture, so that this temperature is constantly within the same temperature window of 123.degree. C. to 127.degree.
  • the dosing time is 105 min.
  • the mixture is stirred under reflux at 125-130° C. for a further 120 min.
  • the reaction mixture is also worked up exactly as described in Example la. The results are identical to those of example la within the scope of measurement accuracy.
  • Example 1a The procedure is as in Example 1a, except that exactly the same weight of tetrabutylphosphonium bromide is used instead of 30 g of tetrabutylammonium bromide. All other process parameters remain unchanged.
  • the reaction is carried out under reflux and the metering rate is controlled by the boiling temperature of the reaction mixture, so that this temperature is constantly within the same temperature window of 123 °C to 127 °C.
  • the dosing time is 95 minutes.
  • the mixture is stirred under reflux at 125-130° C. for only 60 minutes.
  • reaction mixture is also worked up exactly as described in Example la. Within the scope of measurement accuracy, the results are largely identical to those of example 1a, but the purity of the crude product is slightly lower at about 91.9%.
  • Example 1a The procedure is as in Example 1a, except that exactly the same weight amount of triphenylmethylammonium chloride is used instead of 30 g of tetrabutylammonium bromide. All other process parameters remain unchanged.
  • the reaction is carried out under reflux and the metering rate is controlled by the boiling temperature of the reaction mixture, so that this temperature is constantly within the same temperature window of 123.degree. C. to 127.degree.
  • the dosing time is 140 min.
  • the mixture is stirred under reflux at 125-130° C. for a further 120 min.
  • reaction mixture is also worked up exactly as described in Example la. Within the scope of measurement accuracy, the results are largely identical to those of example 1a, but the purity of the crude product is slightly lower at about 91.1%.
  • the reaction is carried out under reflux and the metering rate is controlled by the boiling temperature of the reaction mixture, so that this temperature is constantly within the same temperature window of 123 °C to 127 °C.
  • the dosing time is 350 min.
  • the mixture is stirred under reflux for a further 120 min, during which the temperature rises from an initial 123° C. to 125° C.
  • This reaction is then also carried out under reflux and the metering rate is controlled by the boiling point of the reaction mixture. However, it is dosed at such a speed that this temperature is constantly within a temperature window of 135 to 140 °C.
  • the metering time is 230 minutes. After the end of the addition, the mixture is stirred under reflux at 130° C. for a further 120 minutes.
  • the reaction mixture is also worked up exactly as described in Example la. However, at 81%, the purity of the end product is significantly lower than in the previous examples.
  • the purity of the product is determined by GC and is 96.3%, with dimethylformamide at 2.0%, methyl trimethoxysilane at 0.2%, methanol at 0.3% and toluene at 0.2% - represent the most serious contaminants.
  • GC-MS a targeted search is made for possible decomposition products of the phase transfer catalyst. 0.003% tributylamine is found.
  • the bromine content is determined by means of an elemental analysis. It is at 2 ppm.
  • Example 1b 400 g of N-(methyldimethoxysilylmethyl)-O-methylcarbamate, prepared according to Example 1b, are distilled in the same way as described in Example 2a.
  • the wall temperature of the short-path evaporator is again 125 °C and the applied pressure is 1 mbar.
  • the sump is a yellow liquid that becomes very viscous at room temperature but contains no precipitated solids.
  • the end product is collected in the distillate outlet of the short-path evaporator. It is a colorless liquid.
  • the yield is 92.5% at 370 g.
  • the purity of the product is 97.2%, with dimethylformamide at 1.8%, methyltrimethoxysilane at 0.2%, methanol at 0.1% and toluene at 0.2% representing the most important impurities.
  • the phosphorus content was determined by means of an elemental analysis. It is at 130 ppm.
  • the purity of the product is 96.2%, with dimethylformamide at 2.1%, methyltrimethoxysilane at 0.1%, methanol at 0.1% and toluene at 0.2% representing the most important impurities.
  • Non-inventive implementation of the 2nd process step Distillation of N-(methyldimethoxysilylmethyl)-O-methylcarba- mate using a conventional distillation apparatus 400 g of N-(methyldimethoxysilylmethyl)-O-methylcarbamate prepared according to example la are placed in a 1 liter flask with a Claisen - Distilled top without a column at a pressure of 1 mbar. The bottom temperature rises from 115°C, initially slowly to 145°C and then suddenly to 180°C after about 2/3 of the contents of the flask have distilled off.
  • the temperature at the top is initially largely constant at 100° C., after the distillation of about 1/2 the contents of the flask, it begins to rise slowly to 103° C.
  • the head temperature initially rises to 110 °C until hardly any more distillate goes over and the head temperature begins to fall. The distillation is then terminated.
  • the distillate yield is around 295 g.
  • An analysis of the bottom by means of 1 H-NMR shows that the bottom contains hardly any ( ⁇ 1%) N-(methyldimethoxysilylmethyl)-O-methylcarbamate.
  • the N-(methyldimethoxysilylmethyl)-O-methylcarbamate is split into isocyanatomethylmethyldimethoxysilane and methanol in a thin-film evaporator with a length of 25 cm, an internal diameter of 8 cm and a wall temperature of 300.degree.
  • Example 2a 0.21 g of dioctyltin dilaurate are added to 300 g of the N-(3-trimethoxysilylpropyl)-O-methylcarbamate distilled in Example 2a. Dosing takes place at a rate of 165 ml/h at the upper end of the thin film evaporator.
  • a nitrogen stream of 65 l/h is passed from bottom to top, i.e. against the direction of flow of the reaction mixture. Under these conditions, the sump discharge is approx. 10% of the amount of silane metered in.
  • the evaporated product mixture is passed together with the stream of nitrogen through a Vigreux column which is 10 cm long and insulated by means of an aluminum foil jacket, the liquid column reflux being fed back into the thin-film evaporator.
  • the top temperature of the Vigreux column is constantly within a temperature window of 203-250 °C.
  • the mixture of starting material and product silane is selectively condensed using a conventional glass condenser at a temperature of 54 °C.
  • the methanol is then condensed out at a temperature of 0 °C before the stream of nitrogen is fed through a cold trap into the air extraction of the laboratory fume hood, in which the entire system is located. 238 g of condensed silane mixture are obtained.
  • the colorless liquid is analyzed by means of 1 H-NMR and gas chromatography. It contains 33.5% ⁇ -isocyanatomethyl-methyldimethoxysilane and 63.9% N-(3-trimethoxysilylpropyl)-O-methylcarbamate.

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Abstract

L'invention concerne un procédé de préparation d'organosilanes à fonction isocyanate.
EP22709592.4A 2022-01-31 2022-01-31 Procede de préparation d'isocyanato-organosilanes Withdrawn EP4472991A1 (fr)

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DE102010061816A1 (de) 2010-11-23 2012-05-24 Wacker Chemie Ag Verfahren zur Herstellung von Carbamatoorganosilanen
DE102014223823A1 (de) 2014-11-21 2016-05-25 Wacker Chemie Ag Herstellung von isocyanatfunktionellen Organosilanen
ES2820247T3 (es) * 2018-03-28 2021-04-20 Evonik Degussa Gmbh Procedimiento para la producción de isocianatos que contienen grupos alcoxisilano
ES2820280T3 (es) 2018-03-28 2021-04-20 Evonik Operations Gmbh Procedimiento para la producción de isocianatos que contienen grupos alcoxisilano
EP3546465B1 (fr) 2018-03-28 2020-09-09 Evonik Operations GmbH Procédé de production d'isocyanates contenant des groupes alcoxysilane
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