EP4069704A1 - Siliranverbindungen als stabile silylenvorstufen und deren verwendung in der katalysatorfreien herstellung von siloxanen - Google Patents

Siliranverbindungen als stabile silylenvorstufen und deren verwendung in der katalysatorfreien herstellung von siloxanen

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Publication number
EP4069704A1
EP4069704A1 EP19816646.4A EP19816646A EP4069704A1 EP 4069704 A1 EP4069704 A1 EP 4069704A1 EP 19816646 A EP19816646 A EP 19816646A EP 4069704 A1 EP4069704 A1 EP 4069704A1
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Prior art keywords
radical
radicals
group
silirane
hydrocarbon radical
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EP19816646.4A
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German (de)
English (en)
French (fr)
Inventor
Richard Weidner
Fabian Andreas David HERZ
Matthias Fabian NOBIS
Bernhard Rieger
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Wacker Chemie AG
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Wacker Chemie AG
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    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
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    • C07F7/02—Silicon compounds
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
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    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
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    • C07F7/02—Silicon compounds
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    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

Definitions

  • the invention describes silirane-functionalized compounds consisting of a substrate to which at least two
  • Si1irane groups of the formula (I) are covalently bonded, as well as a mixture containing the silirane-functionalized compounds according to the invention and a process for the preparation of siloxanes.
  • the crosslinking occurs through the thermal activation of multifunctional siliranes, which represent a stable precursor for highly reactive silylene species.
  • the network formation takes place here through the reaction of the silylenes with functionalized siloxanes or polysiloxanes, and enables the use of a wide range of common siloxane compounds.
  • Silicones are of great interest because of their excellent chemical and physical properties and are therefore used in a variety of ways.
  • the van der Waals forces between homopolymer chains in siloxanes are very weak.
  • this leads to flow behavior and very poor properties, even with very large molecular weights. For this reason, siloxanes are crosslinked and thus obtain their rubber-elastic state.
  • Tin-based added to accelerate the crosslinking reaction.
  • organic peroxides are used, which decompose into radicals when heated (HTV).
  • the reactive radicals crosslink e.g. vinyl methyl siloxanes.
  • silylenes are charge-free divalent silicon compounds and thus the heavier homologues of the carbenes. Due to their diverse reactivity, silylene compounds are suitable for crosslinking a wide variety of monomers. For example, silylenes react with Si-H compounds in an insertion reaction that produces a disilane. The reaction with nucleophiles such as silanoias or alcohols also takes place through insertion into the OH bond. When a silylene is inserted into the Si-O bond of an alkoxysilane, a disilane is formed. Silylenes react with alkenes and alkynes via a cycloaddition to form silacyclopropanes (silirane) or silacyclopropenes (silirene).
  • Scheme 1 Reactivities of silylene compounds.
  • Silylenes insert e.g. in Si-H, Si-OH and Si-OR compounds or react with double bonds in a cycloaddition
  • silylenes such as Me2Si: which are not stable and quickly dimerize. Since the production of the polysilanes is carried out under very harsh conditions, this synthesis method leaves little room for maneuver in the choice of the functional groups. More complex silylenes can be obtained by reducing dihalosilanes. Lithium or KC8, for example, can be used as reducing agents. There are known silylene compounds with thermodynamically and kinetically stabilizing groups which are absolutely stable at room temperature. Since the reactivity decreases with increasing stability of the silylenes, highly stabilized silylenes are less suitable as functional groups for the linkage of siloxanes.
  • sirane compounds are particularly suitable, which can be split into silylene and olefin by means of suitable activation, for example by thermolysis or photolysis.
  • suitable activation for example by thermolysis or photolysis.
  • the driving force behind the dissociation is the high ring tension of the siliranes.
  • Silirane compounds are significantly more stable than their silylene analogues and can be seen as masked silylenes.
  • the stability of the siliranes and the required decomposition temperature can be controlled by their functionalization.
  • Siliranes can also react with nucleophilic compounds such as alcohols in a ring-opening reaction. Since it is an addition reaction, there is no cleavage product. By using siliranes in the linkage of siloxanes, these are consequently compatible with a very broad spectrum of functional groups. Due to the high ring tension in the cycle, siliranes are generally very reactive.
  • the invention relates to silirane-functionalized compounds consisting of a substrate to which at least two silirane groups of the formula (I) are covalently bonded, where in formula (I) the index n assumes the value 0 or 1; and in which the radical R a is a divalent C1-C20 hydrocarbon radical, and where the radical R 1 is selected from the group consisting of (i) Ci-C2o ⁇ hydrocarbon radical, (ii) C3.-C20 hydrocarbonoxy radical, (iii) silyl radical - SiR a R b R c , in which the radicals R a , R b , R ° are independently a C1-C6 hydrocarbon radical, (iv) amine radical - NR X 2, in which the radicals R x are independently selected from the group consisting of (iv.i) hydrogen, (iv.ii) C1-C20 hydrocarbon radical, and (iv.iii) silyl radical - SiR a R
  • the substrate is preferably selected from the group consisting of organosilicon compounds, hydrocarbons, silicas, glass, sand, stone, metals, semi-metals, metal oxides, mixed metal oxides, and carbon-based oligomers and polymers.
  • the substrate is particularly preferably selected from the group consisting of silanes, siloxanes, precipitated silica, fumed silica, glass, hydrocarbons,
  • a particular embodiment of the invention are silirane-functionalized organosilicon compounds of the general formula (II) wherein the radicals R x are independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C1-C20 hydrocarbon radical and (iv) unsubstituted or substituted Ci-C 2 o-hydrocarbonoxy radical; and in which the indices indicate the number of the respective siloxane unit in the compound and, independently of one another, mean an integer in the range from 0 to 100,000, with the proviso that the sum of together assumes at least the value 2 and at least one of the indices ⁇ Is 2 or at least one of the indices c is not equal to 0; and the radicals R 'represent a
  • the arrangement of the silicon atoms of the silirane-functionalized compounds is of elementary importance. It is imperative that the silicon atoms are connected to one another via a basic structure. In this way, after activation of the silirane-functionalized compound, a crosslinkable compound with several silylene groups is obtained. If the silicon atoms are not bridged, the activation of the siliranes generates free "monosilylenes" and multifunctional vinyl compounds. These free monosilylenes are not able to crosslink and react with the functional groups of the siloxanes (see Scheme 6).
  • the radical R a is preferably a C 1 -C 3 -alkylene radical.
  • the radical R a is particularly preferably an ethylene radical.
  • the radical R 1 is preferably selected from the group consisting of (i) C1-C6 hydrocarbon radical and (ii) amine radical - N (SiR a R b R c ) 2, in which the radicals R a , R b , R ° are independently a C1-C6 hydrocarbon radical.
  • the radical R 1 is particularly preferably selected from the group consisting of (i) C1-C6-alkyl radical and (ii) - N (SiMe3) 2.
  • the radicals R 2 , R 3 , R 4 , R 5 are preferably selected independently of one another from the group consisting of (i) hydrogen and (ii) C1-C6-alkyl radical, in which the radicals R 2 and R 4 can be part of a cyclic remainder.
  • the radicals R 2, R 3, R 4 z R 5 are independently selected from the group consisting of (i) hydrogen and (ii) C1-C6 alkyl, wherein the radicals R 2 and R 4 can be part of a hexenyl radical.
  • a preferred embodiment are silirane-functionalized compounds, where in formula (II) the indices c assume the value 0 and the index takes the value 2; and where in formula (IIa) the index n assumes the value 1; and the radical R a is a C1-C3-alkylene radical; and the radical R 1 is selected from the group consisting of (i) C1-C6 hydrocarbon radical and (ii) amine radical - N (SiR a R b R c ) 2, in which the radicals R a , R b , R ° are independent of one another a C1-C6 Are hydrocarbon radical; and the radicals R 2 , R 3 , R 4 , R 5 are independently selected from the group consisting of (i) hydrogen and (ii) C1-C6-alkyl radical, in which the radicals R 2 and R 4 are also part of a cyclic radical could be.
  • Another preferred embodiment are silirane-functionalized compounds, where in formula (II) the indices assume the value 0 and the index d 'assumes the value 2; and where in formula (IIa) the index n assumes the value 1; and R a is an ethylene radical; and the radical R 1 is selected from the group consisting of (i) C1-C6-alkyl radical and (ii) - N (SiMe3) 2; and the radicals R 2 , R 3 , R 4 , R 5 are selected independently of one another from the group consisting of (i) hydrogen and (ii) C1-C6-alkyl radical, in which the radicals R 2 and R 4 are also part of a hexenyl radical can.
  • silirane-functionalized compounds according to the invention are the compounds SV1, SV2 and SV3 shown in Scheme 5.
  • Organosilicon compounds take place, for example, by reducing dihalosilanes with reducing agents such as lithium or potassium graphite in polar, coordinating solvents (eg tetrahydrofuran).
  • reducing agents such as lithium or potassium graphite in polar, coordinating solvents (eg tetrahydrofuran).
  • polar, coordinating solvents eg tetrahydrofuran.
  • the reduction of the dihalosilane groups results in intermediate silylenes, which are trapped with olefin compounds and react to form a silirane.
  • all compounds with a double bond can be used as olefin compounds for scavenging the silylenes.
  • the choice of olefin can also influence the behavior of the silirane-functionalized organosilicon compound.
  • Organosilicon compounds split the siliranes back into silyls and olefins. It is therefore advantageous to choose an olefinic compound which is gaseous under the reaction conditions of a conversion reaction and can volatilize.
  • the silirane-functionalized compounds can also be produced via a Wurtz coupling in which the C-C bond of the silirane ring is made.
  • the silirane-functionalized compounds according to the invention are stable precursors of the highly reactive silylenes. Each silirane group does not form a silylene group until the crosslinker has been activated. The silirane-functionalized compounds according to the invention must therefore have at least two silirane groups in order to be able to function as crosslinkers.
  • Scheme 6 Schematic comparison of two different bis-silirane structures. Above: silicon atoms of the silirane-functionalized compound bridged by a structural framework, results in a crosslinkable reactive bis-silylene species when activated. Bottom: Silirane groups not bridged by silicon atoms, disintegrate into non-crosslinking cleavage products when activated.
  • the invention further provides a process for the production of siloxanes comprising the following steps: (i) providing a mixture according to the invention in accordance with the particular embodiment, and (ii) converting the mixture by thermal, photochemical or catalytic activation.
  • the linking of a mixture of functionalized siloxane of the formula (III) and a silirane-functionalized compound according to the invention can be achieved by thermal, photochemical or catalytic activation.
  • the silirane units of the organosilicon compound react to form silylenes, which then react with functional groups of the siloxane and crosslink them.
  • the thermal activation requires a temperature above the decomposition temperature of the silirane compound.
  • silirane compounds can be converted into silylenes by photochemical activation. The wavelength required for this is in the UV range. The reactivity of the siliranes is identical for both activation methods.
  • catalysts can also be used to accelerate the linking reaction or for room temperature crosslinking. Suitable catalysts are compounds that destabilize siliranes and thus cause cleavage into silyls and olefins. Examples of such catalysts are AgOTf and Cu (OTf) 2. In general, the activation of the siliranes also gives rise to olefinic compounds (eg 2-butene).
  • the activated silirane-functionalized compounds can react with a wide range of functional groups due to their high reactivity. Possible reaction partners are, for example, Si-H, Si-OR, Si-OH, C-OH, -NH2, SH and vinyl. This supports all common functional groups of industrial siloxanes.
  • the Functionalized siloxanes must have at least two of the functional groups mentioned for the formation of a network.
  • the crosslinking of a difunctional siloxane with a silirane compound works in that a new vulnerable group and thus a node is formed with each insertion of the silylene formed.
  • Vinyl-substituted (poly) siloxanes must have at least three vinyl groups due to their different reactivity (cycloaddition).
  • the properties of the crosslinked polymer can be changed through the length or the molecular mass of the functionalized siloxanes.
  • the silylene linkage method can be carried out with both low-molecular and high-molecular, functionalized siloxanes. Examples of functionalized siloxane compounds are shown in Scheme 7.
  • Disilane bonds between the silirane-functionalized compound and siloxane These disilanes have newly formed Si-H or Si-OR groups, which represent a further point of attack for silylenes. Each time a silylene reacts with the siloxane, another vulnerable functional group is created. Nucleophilic functional groups such as silanes, alcohols and amines also react with silylenes by inserting the silylene into the functional group. No disilanes are formed here, but rather siloxanes and silazanes, which also have a newly formed Si-H functionality for further crosslinking. By creating new points of attack during the reaction, it is also possible to use siloxanes with only two functional groups.
  • Scheme 8 Overview of the possible crosslinking strategies for the formation of siloxane networks with hydridosiloxanes (left), siloxanes (middle) and vinylsiloxanes (right).
  • the silirane-functionalized compound according to the invention and the functionalized siloxane of the formula (III) are mixed until homogeneous mixing is ensured.
  • the link is only made when the mixture is activated using one of the three methods mentioned above.
  • the mixture is activated until the silirane-functionalized compound according to the invention has reacted completely or until the desired properties have been achieved.
  • a successive networking process is also possible.
  • contact with oxygen and water must be prevented by means of inert gas or other suitable measures.
  • the temperature during the reaction is chosen so that it is above the decomposition temperature of the silirane-functionalized compound, that is, silylenes are formed by thermolysis.
  • the temperature is usually in a range from 60-200.degree. C., preferably in a range from 80-150.degree. C., particularly preferably in a range from 130-150.degree.
  • the silirane-functionalized compound is mixed with the functionalized siloxane of the formula (III) in a suitable molar ratio.
  • the molar ratio of silirane groups: functional groups in the siloxane is usually in a range of 4: 1 1: 4, preferably in a range of 1: 1 1: 4. Examples
  • Lithium with 2.5% sodium content was obtained by melting elemental lithium (Sigma-Aldrich, 99%, trace metal basis) and sodium (Sigma-Aldrich, 99.8%, sodium basis) at 200 ° C in a nickel crucible under an argon atmosphere . Before use, the Li / Na alloy was cut into as small pieces as possible in order to increase the surface area. Al2O3 (neutral) and activated charcoal were dried for 72 hours at 150 ° C in a high vacuum.
  • the bis-silirane SV1 is synthesized via a three-stage reaction path, starting with the starting compound divinyltetramethyldisiloxane. In the first synthesis step, this is done via a
  • the following synthesis step takes place via the substitution of the hexachlorosilane with tert-butyllithium.
  • 30.0 g (65.6 mmol, 1.0 equivalent) (Cl 3 SiCH 2 CH 2 SiMe 2 ) 2 O are dissolved in 75 ml of pentane and cooled to -10 ° C.
  • 8.40 g (131 mmol, 2.0 equivalents) of 1.7 M tert-butyllithium solution are slowly added dropwise via a dropping funnel. The reaction is then warmed to 0 ° C. and stirred for 8 hours. Lithium chloride formed is filtered off and the filtrate is separated off from the solvent in vacuo.
  • the last stage in the synthesis of the bis-silirane involves the reduction of the tetrachlorosilane using a lithium-sodium alloy (2.5% Na).
  • a lithium-sodium alloy (2.5% Na).
  • 10.0 g (20.0 mmol, 1.0 equivalent) of tetrachlorosilane (Cl 2 tBuSiCH 2 CH 2 SiMe 2 ) 2 O are dissolved in 50 mL of THE.
  • the reaction solution is cooled to -30 ° C, then 33.6 g (600 mmol, 30.0 equivalents) of cis-butene to be condensed.
  • the bis-silirane SV3 is prepared via a two-stage synthesis from the corresponding hexachlorosilane.
  • 10.0 g (21.9 mmol, 1.0 equivalent) (Cl3SiCH 2 CH 2 SiMe 2 ) 2O are initially charged in 40 ml of THF and cooled to 0 ° C.
  • a solution of 8.72 g (43.7 mmol, 2.0 equivalents) of potassium hexamethyldisilazane (KHMDS) in 30 ml of THF is then slowly added dropwise over a period of 30 minutes.
  • the resulting suspension is stirred for 6 hours at room temperature.
  • the solvent is then removed in vacuo.
  • the residue is taken up in 40 mL pentane and then filtered.
  • 12.5 g (81%, 17.7 mmol) (TMS 2 NCl 2 SiCH 2 CH 2 SiMe 2 ) 2O are obtained as a yellowish, clear liquid.
  • TMS2NCl 2 SiCH2CH2SiMe 2 Dissolve (TMS2NCl 2 SiCH2CH2SiMe 2 ) 2O in 50 mL THF and heat the reaction mixture to -30 ° C. Then 23.10 g (424 mmol, 30.0 equivalents) of cis-butene are condensed into the reaction vessel and 1.47 g (212 mmol,
  • the material is due to the short chain length of the siloxane is quite brittle and tears under tensile load.
  • the polymer swells a lot in benzene and does not dissolve. Soluble constituents could not be detected by NMR spectroscopy.
  • the butene formed during crosslinking can be perceived through the characteristic odor.
  • TCTS Tetramethylcyclotetrasiloxane
  • Tetramethylcyclotetrasiloxane in a molar ratio of 1: 0.9 (silirane groups: Si-H groups) weighed in under protective gas. The mixture is stirred with a magnetic stir bar until homogeneous mixing is ensured. The subsequent crosslinking takes place at 140 ° C for 24 hours under protective gas in a closed system. The resulting product is a solid, transparent and non-sticky polymer with slightly elastic properties. The polymer swells a lot in benzene without dissolving. No soluble components could be detected by NMR spectroscopy.
  • molar mixing ratios of 0.5: 1 (silirane groups: Si-OH groups) and 2: 1 (silirane groups: Si-OH groups) are used in an analogous procedure.
  • colorless, clear, very soft and sticky elastomers are obtained.
  • crosslinker is added in excess of stoichiometric, a colorless, cloudy polymer with elastic properties is obtained.
  • the polymer obtained is softer compared to the 1: 1 mixture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)
EP19816646.4A 2019-12-04 2019-12-04 Siliranverbindungen als stabile silylenvorstufen und deren verwendung in der katalysatorfreien herstellung von siloxanen Withdrawn EP4069704A1 (de)

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CN114746429A (zh) 2022-07-12

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