WO2022248067A1 - Composés à fonction silirène et leurs mélanges pour la préparation de siloxanes et leur conférant des propriétés favorisant l'adhérence - Google Patents

Composés à fonction silirène et leurs mélanges pour la préparation de siloxanes et leur conférant des propriétés favorisant l'adhérence Download PDF

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WO2022248067A1
WO2022248067A1 PCT/EP2021/064438 EP2021064438W WO2022248067A1 WO 2022248067 A1 WO2022248067 A1 WO 2022248067A1 EP 2021064438 W EP2021064438 W EP 2021064438W WO 2022248067 A1 WO2022248067 A1 WO 2022248067A1
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radical
group
sir
silirene
hydrogen
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PCT/EP2021/064438
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German (de)
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Maximilian MOXTER
Matthias Fabian NOBIS
Bernhard Rieger
Richard Weidner
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Wacker Chemie Ag
Technische Universität München
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the invention describes silirene-functionalized compounds consisting of a substrate to which at least two silirene groups of the formula (I) are covalently bonded. Also described is a process for preparing these compounds and mixtures for crosslinking and adhesion promotion, containing these compounds.
  • Silicones also called poly(organo)siloxanes or siloxanes for short
  • silicones can be used in a variety of ways due to their chemical and physical properties. Unlike carbon-based plastics, the van der Waals forces between siloxane polymer chains are weak, which is why high molecular weight siloxane polymers are still flowable.
  • the polymer components In order to obtain dimensionally stable, rubber-elastic silicones, the polymer components have to be crosslinked with one another.
  • addition crosslinking condensation crosslinking and free-radical crosslinking.
  • vinyl-functionalized polyorganosiloxanes react with hydridosiloxanes (hydrosilylation).
  • condensation-curing systems can be handled as one-component systems.
  • Radical crosslinking uses organic peroxides, for example, which decompose into highly reactive radicals through thermal or photolysis and link functional polyorganosiloxanes (eg vinyl-methyl-siloxanes) with one another in a free-radical manner.
  • catalyst-free crosslinking can also be done by silirane-containing compounds, as described in PCT/EP2019/083744.
  • the crosslinking is based on the reactivity of intermediately formed silylenes (cf.
  • Silylenes are highly reactive divalent silicon compounds and react with a large number of functional groups such as Si-H, Si-OH or CH with insertion. With unsaturated structural motifs such as alkenes, alkynes or carbonyl compounds, silylenes form cyclic secondary products by addition.
  • PCT/EP2019/083744 does not use the silylenes themselves, but silirane compounds as storage-stable and easy-to-handle precursors. These can be split into silylene and olefins in particular by thermal activation (thermolysis), with the driving force for dissociation being the ring strain of the siliranes. Photochemical activation of the siliranes to silylenes is also possible, but due to their weak absorption behavior, siliranes can only be converted into silylenes by UV-C light with wavelengths below ⁇ 300 nm at high intensity and long exposure times. Activation at wavelengths above 300 nm would be technically much easier to implement, but this would require compounds with better absorption bands in the UV-A range.
  • UV-active compounds e.g. platinum UV catalysts
  • siloxanes regardless of whether they are crosslinked to form elastomers or not, show only low adhesion properties on plastic surfaces made of polyolefins (e.g. polyethylene (PE) and polypropylene (PP)), polyethylene terephthalate (PET) or polycarbonate (PC), which is due to the slightly polar to non-polar nature of the plastics.
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PC polycarbonate
  • Adhesion to plastic substrates can often only be achieved by complex manipulations of the surface, e.g. by pre-treating with solvents, a multi-stage oxygen plasma treatment and/or by applying a primer (U. Stschreib, Vacuum in Research and Practice 2015, 27, 16-21).
  • US 2011/0105777 A1 discloses 1,4-disilacyclohexanes, which are formed from intermediately generated, halogenated silacyclopropenes, so-called silirenes.
  • the monomeric silacyclopropenes for this are generated from hydride-containing halosilanes and acetylenes using quaternary organophosphonium salts, however, due to their high reactivity, the silacyclopropenes dimerize rapidly to form 1,4-disilacyclohexanes.
  • the compound class of 1,4-disilacyclohexanes is described as a starting material for the production of inorganic/organic hybrid materials.
  • JP53-059656 A2 discloses alkyl- and aryl-substituted silacylopropenes (monosilrenes) and their photochemical preparation from disilane- and phenyl-substituted acetylenes by using a mercury vapor or xenon gas discharge lamp.
  • compound-typical photochemical and thermal cyclization reactions with unsaturated carbon-carbon (eg alkynes) and Called carbon-element multiple bonds e.g. ketones
  • Semenov et al. (Russian Journal of Applied Chemistry 2012, 85, 2, 320-326) describe the functionalization of OH-terminated polyorganosiloxanes by reaction with silacyclopropenes produced as intermediates.
  • the silacyclopropene is generated by photolysis of phenylethynyl-substituted disilanes in OH-terminated polyorganosiloxane and reacts with this rapidly with nucleophilic ring opening through the OH function.
  • the previously OH-terminated siloxane now has vinyldimethylsilyl end caps and, for example, is converted to a silicone elastomer with hydridopolysiloxanes in the presence of the platinum-based Speyer catalyst.
  • the radicals R 2 , R 3 are independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 hydrocarbon radical, the silyl radical -SiR 4 R 5 R 6 and organopolysiloxane radical - (CH 2 ) y- [SiR 9 R 10 -O] x - [SiR 11 R 12 R 13 ] where R 9 through R 13 are independently selected from the group consisting of methyl, ethyl, phenyl, hydrogen, ethynyl and vinyl, where the index x is zero or an integer value of 1 to 200 and the index y is zero or is an integer from 1 to 10, and where R 2 and R 3 can also be part of a cyclic radical.
  • the silicone-functionalized compounds can be used both as crosslinkers for silicones (formation of elastomers) and as adhesion promoters for coating plastics with silicones, without having to resort to metal-containing catalysts. Their crosslinking or adhesion-promoting effect can be induced not only thermally but also photochemically.
  • the unsaturated structural motif of silacyclopropene, often also referred to as silirene, can be photochemically activated at wavelengths between 300 and 400 n because of its pseudo-aromatic character. This results in the advantage that the crosslinking/adhesion promotion can be stimulated in a more targeted manner with low-energy light. With particular advantage, an overlap with the absorption wavelengths of platinum UV catalysts often contained in existing products can be avoided in order to avoid competing absorption processes.
  • the substrate is preferably selected from the group consisting of silanes, organosilicon compounds, silicic acids, hydrocarbons, carbon-based oligomers and polymers.
  • the substrate is particularly preferably selected from the group consisting of siloxanes, precipitated silica, pyrogenic silica, polyolefins, acrylates, polyacrylates, polyvinyl acetates, poly urethanes and polyethers.
  • the polyethers can be, for example, polyethers made from propylene oxide and/or ethylene oxide units.
  • the substrate is an organosilicon compound of general formula (II)
  • R x is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C 1 -C 20 hydrocarbyl and unsubstituted or substituted C 1 -C 20 - hydrocarbyloxy radical, wherein the subscripts a, b, b', c, c', c'', d, d', d'', d''' indicate the number of the respective siloxane unit in the compound and are independently zero or one are integers from 1 to 100,000, with the proviso that the sum of a, b, b', c, s', c'', d, d', d'', d''' is at least 2 and at least one of the subscripts b', c', d' is h 2 or at least one of the subscripts c'', d'' or d'''
  • the radical R in the formula (I) is preferably a C 1 -C 3 - alkylene radical, particularly preferably an ethylene radical.
  • R 1 on the Si atom in the formula (I) can be used to exert a kinetic and thermodynamic influence on the reactivity and stability of the silirene-functionalized compounds.
  • R 1 is preferably a C 1 -C 6 hydrocarbon radical or amine radical -N(SiR 4 R 5 R 6 ) 2 , where R 4 , R 5 , R 6 are independent of one another are a C 1 -C 6 hydrocarbyl radical.
  • R 1 is particularly preferably a C 1 -C 6 -alkyl radical or -N(SiMe 3 ) 2 .
  • the indices a, b, b', c, c', c'', d, d'' and d''' preferably assume the value zero and the index d' the value 2; where in formula (I) the index n has the value 1, R is a C 1 -C 3 alkylene radical and R 1 is a C 1 -C 6 hydrocarbon radical, a silyl radical -SiR 4 R 5 R 6 or an amine radical -N is (SiR 4 R 5 R 6 ) 2 wherein R 4 , R 5 , R 6 are independently C 1 -C 6 hydrocarbon radicals.
  • the radicals R 2 , R 3 are independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 hydrocarbon radical, silyl radical --SiR 4 R 5 R 6 and organopolysiloxane radical
  • the indices a, b, b', c, c', c'', d, d'' and d''" take the value zero and the index d' the value 2, where in formula (I ) the index n has the value 1, R is an ethylene radical and R 1 is a C 1 -C 6 alkyl radical, an amine radical -N(SiMe 3 ) 2 or a silyl radical -SiR 4 R 5 R 6 , where R 4 , R 5 , R 6 are independently C 1 -C 6 hydrocarbon radicals, and where R 2 , R 3 are independently selected from the group with hydrogen, C 1 -C 20 hydrocarbon radical, silyl radical -SiR 4 R 5 R 6 and organopolysiloxane residue
  • R x in the formula (II) is preferably selected independently from the group consisting of methyl, ethyl, hydrido, vinyl and phenyl.
  • Another aspect of the invention relates to a method for preparing the silirene-functionalized compounds.
  • a silirane-containing precursor for example compounds as described in PCT/EP2019/083744, with an alkyne of the general formula R 2 -C CR 3 in an organic Solvent in the temperature range from 100 to 150 ° C or implemented with the addition of silver triflate in the temperature range from 50 to 120 ° C.
  • the radicals R 2 , R 3 are selected independently of one another the group with hydrogen, halogen, C1-C 20 hydrocarbon residue, silyl residue -SiR 4 R 5 R 6 , in which R 4 , R 5 , R 6 are independently a C 1 -C 6 hydrocarbon residue, and organopolysiloxane residue - (CH 2 ) y - [ SiR 9 R 10 -O] x - t SiR 11 R 12 R 13 ] where R 9 to R 13 are independently selected from the group consisting of methyl, ethyl, phenyl, ethynyl and vinyl, where the index x Zero or an integer from 1 to 200 and the index y is zero or an integer from 1 to 10, and where R 2 and R 3 can be part of a cyclic radical.
  • the organic solvent is preferably an ether and/or an aromatic solvent. Diethyl ether, THF, benzene and toluene are particularly preferred.
  • Another subject of the invention is a mixture containing a) at least one of the silirene-functionalized compounds described and b) at least one compound A which has at least two radicals R 14 , the radicals R 14 being selected independently of one another are from the group with (i) -Si-H, (ii) -OH, (iii) -C x H 2 x-OH, where x is an integer ranging from 1 to 20,
  • compound A can be a polyether with at least one OH terminus.
  • the compound A is preferably selected from siloxanes of the general formula (III)
  • R x is independently selected from the group consisting of halogen, an unsubstituted C 1 -C 20 hydrocarbon radical and a substituted C 1 -C 20 hydrocarbon radical.
  • the indices a, b, b', c, c', c'', d, d', d'', d'''' indicate the number of the respective siloxane unit in the compound and independently mean an integer in the range from 0 to 100,000, with the proviso that the sum of a , b , b ' , c, c', c'', d, d', d'', d''' has at least the value 2 and at least one of the indices b', c', d' is ⁇ 2 or at least one of the indices c'',d'' or d'" is not equal to 0.
  • the silirene-functionalized compounds are stable precursors of highly reactive silylenes. After activation, a silylene residue is formed from the silirene group.
  • the silirene-functionalized compounds must have at least two silirene groups in order to function as crosslinkers and adhesion promoters. It is imperative that the Si atoms of the silirene groups are bridged to one another via a basic structure (cf. Scheme 2) in order to link polymers that are otherwise functional to one another.
  • Scheme 2 Top: The Si atoms of the silirene-functionalized compound are bridged through a backbone, resulting in a crosslinkable, reactive bis-silylene species upon activation. Bottom: The silirene groups are not bridged via the Si atoms, resulting in non-crosslinking cleavage products upon activation.
  • the molar ratio of silirene groups to functional groups in the siloxane of the general formula (III) is preferably in a range from 5:1 to 1:5.
  • Another subject of the invention are mixtures containing a) at least one of the silicone compounds described and b) at least one natural or synthetic polymer selected from the group consisting of addition-crosslinking silicone compositions, condensation-crosslinking silicone compositions, hybrid materials/STP, inorganic polymers and organic polymers.
  • addition-crosslinking silicone compositions generally refers to hydrosilylatable mixtures containing hydridopolysiloxanes, alkenyl-containing polyorganosiloxanes and fillers (e.g. silicas). These mixtures can only be crosslinked thermally or photochemically to form elastomeric silicones in the presence of catalysts (e.g. the platinum-based Karstedt catalyst) and inhibitors. Such mixtures are described, for example, in EP 0651 019 A1 or EP 0 444 960 A2.
  • the addition-crosslinking silicone compositions therefore contain metal catalysts.
  • the condensation-crosslinking silicone masses contain metal catalysts.
  • Hybrid materials/STP are generally reactive silane-terminated within the meaning of the invention organic polymers (e.g. polyether) which are used, for example, as adhesives, sealants and coating materials. Such materials are described, for example, in WO 2017/137281 A1.
  • inorganic polymers are generally natural and synthetic inorganic polymers (e.g. silicic acids, silicate structures, polysilanes and polysiloxanes).
  • organic polymers are generally natural and synthetic organic polymers suitable for producing moldings, coatings or laminates. Examples of such polymers can be found, for example, in U.S. 5,792,812; US 2007/0141250 A1 and US 4,686,124.
  • the silirene-functionalized compounds, or the reactive silylenes produced from them are suitable for otherwise crosslinkable siloxanes (technology basis: hydrosilylation or condensation crosslinking) on unreactive polymer substrates such as PE, PP, to bring PET and PC to liability.
  • the Siliren-functionalized compounds act as adhesion promoters between the inert polymer carrier body and the applied crosslinkable siloxane mixture by forming covalent bonds.
  • the mixture according to the invention is therefore, with particular advantage, a self-adhesive mixture.
  • moldings containing the mixture described and a slightly polar to non-polar carrier material.
  • the molding is preferably selected from the group consisting of extrusion or injection molding, single-layer or multi-layer laminates (e.g. produced by spin coating, Calendering or dipping processes), encapsable shaped bodies (e.g. produced in electrocasting by filling, dipping or plasticizing), bondable or sealable shaped bodies (reactive adhesives) and transitions between identical or different shaped bodies of the same or different carrier materials.
  • the latter means in particular jointing compounds for bonding several dissimilar materials.
  • the shaped body can contain the carrier material in the form of a coating.
  • the shaped body can consist of the carrier material to which the mixture is applied.
  • the carrier material preferably comprises at least one synthetic hydrocarbon polymer selected from the group consisting of polyolefins made from mono- or polyenes, polyhalogen olefin, polyether, polyvinyl chloride, polyvinylidene difluoride, polytetrafluoroethene, polycarbonate, polyester and copolymers thereof.
  • the carrier material can consist of or comprise polymer blends of the hydrocarbon polymers mentioned.
  • the copolymers can be, for example, ethylene propylene diene monomer rubber (EPDM) or acrylonitrile butadiene styrene (ABS).
  • EPDM ethylene propylene diene monomer rubber
  • ABS acrylonitrile butadiene styrene
  • the mixture according to the invention can be cured by a process for curing by means of thermal and/or photochemical activation.
  • the mixture is first brought into contact with the carrier material.
  • Photochemical activation in a wavelength range from 300 to 400 n is particularly preferred. Also included in the invention is a process for preparing siloxanes (siloxane elastomers), comprising the steps
  • the thermal activation preferably takes place in a temperature range from 0.degree. C. to 200.degree. C., preferably from 10 to 180.degree. C., particularly preferably from 15 to 150.degree.
  • Thermal activation can also be done in two stages and include the following steps:
  • the photochemical activation is preferably carried out with actinic radiation in a wavelength range from 300 to 800 nm, preferably from 300 to 500 nm, particularly preferably from 300 to 400 nm.
  • catalysts can also be used to accelerate adhesion promotion.
  • Compounds that destabilize silirenes and thus cause cleavage into silylene and olefin are suitable as catalysts.
  • examples for such catalysts are AgOTf and Cu(OTf),Cu(OTf) 2 or Zn(OTf) 2
  • FIG. 1 shows 29 Si NMR spectra of a reaction mixture of triethylsilane and silacyclopropene 7c after activation.
  • FIG. 2 shows 1 H-NMR spectra of a reaction mixture of triethylsilane and silacyclopropene 7c after activation.
  • FIG. 3 shows a 1 H- 29 Si HMBC NMR spectrum of a reaction mixture of triethylsilane and silacyclopropene 7c after activation.
  • FIG. 4 shows 29 Si NMR spectra of a reaction mixture of triethylsilane and silacyclopropene 7d after activation.
  • FIG. 5 shows 1 H-NMR spectra of a reaction mixture of triethylsilane and silacyclopropene 7d after activation.
  • FIG. 6 shows a 29 Si-NMR and a 1 H-NMR spectrum of a reaction mixture of pentamethyldisiloxane and silacyclopropene 7d after photochemical activation.
  • Mass spectrometry was carried out using a LIFDI-MS 700 with an ion source from Linden CMS.
  • Elemental analyzes were carried out by the microanalytical laboratory of the Faculty of Chemistry at the Technical University of Kunststoff using a Vario EL from Elementar.
  • the mixtures were thermally cured in a "LHT6/30" drying cabinet from Carbolite-Gero.
  • UV/vis spectra were measured in acetonitrile (concentrations: 0.1-0.3 mmol/L) at room temperature using a Varian "Cary 50 Scan UV-Vis” spectrophotometer.
  • Synthesis examples Synthesis Example 1 Preparation of monofunctional 1,1-di-tert-butyl-2,3-substituted silirenes 7a to 7e (scheme 3)
  • Scheme 3 Representation of the silacyclopropenes 7a to 7e.
  • Bis-silacyclopropane (PI, 200 mg, 424 ⁇ mol, 1 eq.) is mixed with bis(trimethylsilyl)-acetylene (181 mg, 1.06 mmol, 2.5 eq.) and 5 mL toluene in a 25 mL Schlenk flask at 110° C and refluxed for 72 h. The solvent and excess acetylene are then removed at 2*10 -2 mbar and 50°C. 196 mg (66%, 280 ⁇ mol) of the Siliren crosslinker V1 are obtained as a colorless oil.
  • 1H NMR: (294 K, 500 MHz, C 6 D 6 ) d 0.15 (s, 12 H, OSi-CH 3 ),
  • Bis-silacyclopropane (P2, 50.0 mg, 73.8 ⁇ mol, 1 eq.) is treated with bis(trimethylsilyl)-acetylene (31.4 mg, 184 ⁇ mol, 2.5 eq.) and 5 mL toluene in a 25 mL Schlenk flasks, heated to 110°C and refluxed for 72 h. Then the solvent and excess acetylene are removed at 2*10 -2 mbar and 50°C. 501 mg (75%, 55.3 ⁇ mol) of the Siliren crosslinker V2 are obtained as a colorless oil.
  • 1H NMR: (294 K, 500 MHz, C 6 D 6 ) d 0.15 (s, 12 H, OSi-CH 3 ),
  • Bis-silacyclopropane (PI, 200 mg, 424 ⁇ mol, 1 eq.) is treated with l-phenyl-2-trimethylsilyl-acetylene (185 mg, 1.06 mmol,
  • Synthesis Example 5 Preparation of bis-functional 1,1'-((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(ethane-2,1-diyl))bis(2-phenyl-27, 27,3-tris(trimethylsilyl)-silren-1-amine) V4 (Scheme 7).
  • Bis-silacyclopropane (P2, 150 mg, 221.4 ⁇ mol, 1 eq.) is treated with l-phenyl-2-trimethylsilyl-acetylene (96.5 mg, 553.4 ⁇ mol,
  • Synthesis example 6.0 Preparation of the precursor Px2 of trifunctional silirene crosslinker V5 (scheme 8).
  • Tris-vinylsiloxane (Pxl, 20.0 g, 57.7 mmol, 1 eq.), trichlorosilane (35.2 g, 260 mmol, 4.5 eq.) and 100 mL toluene are mixed in a 500 mL Schlenk flask .
  • 0.05 mL Karstedt catalyst (2.1 to 2.4% Pt in xylene) is added to this mixture and the mixture is stirred at room temperature for 18 h. The mixture is then heated at 80° C. for 1 h. The mixture is filtered over dried neutral aluminum oxide and the remaining solvent is removed in vacuo. 40.2 g (92%) of the precursor Px2 are obtained as a clear, colorless liquid.
  • Synthesis example 6.2 Preparation of the precursor P3 of trifunctional silirene crosslinker V5 (scheme 10).
  • Scheme 10 Representation of the precursor P3.
  • Tris-dichlorosilane (Px3, 9.5 g, 11.6 mmol, 1 eq.) is dissolved in 20 mL THF, cooled to -30 °C, followed by trans-but-2-ene (19.5 g, 348 mmol, 30 eq.) to condense the reaction.
  • Synthesis example 6.3 Preparation of the precursor Px4 of trifunctional silirene crosslinker V5 (scheme 11).
  • Tris-trichlorosilane (Px2, 10.0 g, 13.3 mmol, 1 eq.) is mixed with 50 mL of THF in a 250 mL Schlenk flask.
  • KHMDS potassium hexamethyldisilazide
  • Synthesis example 6.4 Preparation of the precursor P4 of trifunctional silirene crosslinker V5 (scheme 12).
  • Tris-dichlorosilane (Px4, 5.0 g, 4.43 mmol, 1 eq.) is dissolved in 10 mL THF, cooled to -30 °C, followed by trans-but-2-ene (7.46 g, 133 mmol, 30 eq.) to condense the reaction. Crushed Li pieces (460 mg,
  • Synthesis example 6.5 Preparation of the tri-functional silirene crosslinker V5 (scheme 13).
  • Tris-silacyclopropane (P4, 150 mg, 138 ⁇ mol, 1 eq.) is mixed with l-phenyl-2-trimethylsilyl-acetylene (84 mg, 484 ⁇ mol, 3.5 eq.) and 5 mL toluene in a 25 mL Schlenk flask . The mixture is then heated to 110° C. and refluxed for 72 h. The solvent and excess acetylene are then removed in vacuo (2*10 ⁇ 2 mbar, 80° C.), with 213 mg (71%, 301 ⁇ mol) of the Siliren crosslinker V6 being obtained as a yellowish oil.
  • Scheme 16 Representation of precursor P7 from P6.
  • Scheme 17 Representation of crosslinker V7 from precursor P7.
  • the precursor P7 (200 mg, 349 ⁇ mol, 1 eq.) is heated to 110°C with bis(trimethylsilyl)-acetylene (149 mg, 872 ⁇ mol, 2.5 eq.) and 5 ml toluene in a 25 ml Schlenk flask and left for 72 h refluxed. The solvent and excess acetylene are then removed at 2*10 -2 mbar and 50°C. 156 mg (56%, 195 ⁇ mol) of the Siliren crosslinker V7 are obtained as a colorless oil.
  • Application example 1 Crosslinking of hydridomethylsiloxane-dimethylsiloxane copolymer with Siliren crosslinkers C1 to C4 (diagram 18)
  • the silacyclopropene crosslinker Vx (representing V1 to V4) and the silicone oil are mixed in different ratios and homogenized in a vessel that is sufficiently permeable in the intended wavelength range.
  • the photochemical crosslinking takes place by irradiation at 350 nm under a fluorescent tube for 1 hour.
  • thermal crosslinking the mixture was stored at 140° C. for 1-2 hours.
  • Application example 2 Crosslinking of H-terminated polydimethylsiloxane with Siliren crosslinkers V1 to V4 (Scheme 19)
  • Crosslinking takes place by irradiation at 350 nm under a fluorescent tube for 2 hours.
  • the mixture was stored at 140° C. for 1-2 hours.
  • Scheme 24 Model reaction of silacyclopropene 7c with triethylsilane.
  • Triethylsilane acts as a scavenger for the silylene formed by the irradiation.
  • NMR spectra before and after irradiation as well as by a thermal control reaction, it can be shown that the reaction takes place according to Scheme 23.
  • a rearrangement reaction of silirene which is known from the literature, occurs as a side reaction. This can be greatly reduced by modifying the substituents (cf. analysis example 2).
  • Figure 1 shows 29 Si NMR spectra (in C 6 D 12 ) of the reaction mixture of triethylsilane and the silacyclopropene 7c after thermal treatment (diagram a (top)) and after photochemical irradiation (diagram b (middle)) .
  • the spectrum of the cleavage product bis-(TMS)-acetylene 9c (diagram c (bottom)) is also shown.
  • the lower diagram c shows the NMR spectrum of bis (TMS) - acetylene.
  • the remaining three signals at -14.6, -18.7, and -19.8 ppm in diagram b belong to the rearrangement product 9c mentioned.
  • the signal at 0.0 ppm is due to triethylsilane, since this was added in excess (4 eq.).
  • Scheme 25 Model reaction of silacyclopropene 7d with triethylsilane.
  • This second analytical example confirms the proposed reaction pathway based on the reaction of silacyclopropene 7d in combination with 4 eq. triethylsilane.
  • the implementation takes place in analogy to analysis example 2.
  • the same insertion product 8a is formed, since the elimination of the corresponding acetylene results in the same silylene fragment.
  • the rearrangement product 9a differs structurally, since a TMS functionality is replaced by phenyl.
  • the selectivity can be controlled by the choice of acetylene used.
  • the insertion reaction with a relative proportion of 71%, is clearly preferred to the rearrangement reaction.
  • the products can again be compared very clearly using their 29 Si NMR spectra.
  • FIG. 4 shows the 29 Si NMR spectra of the reaction mixture of triethylsilane and the silacyclopropene 7d after thermal treatment (top diagram) and after photochemical irradiation (bottom diagram).
  • thermal treatment 3 h at 140° C.
  • photoreaction 350 nm for 1 h
  • the insertion product 8a can be recognized by the signals at -8.1 and -6.2 ppm, the acetylene (l-phenyl-2-triethylsilyl-acetylene) by a shift of -18.4 ppm.
  • FIG. 5 shows the 1 H NMR spectrum of the thermal control reaction (top) and the 1 H NMR spectrum of the photoreaction (bottom).
  • the comparison of the 1 H-NMR spectra shows that a new Si-H signal is formed at 3.68 ppm (photo reaction below).
  • Analysis Example 3 Detection of the reaction products from silirene compound 7d and siloxane model compound pentamethyldisiloxane by means of 1 H, 29 Si NMR (scheme 26).
  • FIG. 6 shows the 29 Si NMR spectrum (top) and the 1 H NMR spectrum (in C 6 D 12 , bottom) of the reaction mixture of pentamethyldisiloxane and the silacyclopropene 7d after photochemical irradiation.
  • the expected insertion product 8b was formed after irradiating the reaction mixture at 350 nm for one hour.
  • the chemical shift in the 29 Si NMR at 8.4, 5.5 and -6.6 ppm for the insertion product 8b matches the values known from the literature.
  • the formation of l-phenyl-2-trimethyl-sily-acetylene at -18.4 ppm and the corresponding rearrangement product 9d (cf. also analysis example 2) can also be seen.
  • the proton signal in the 1 H-NMR is slightly upfield at 3.59 ppm shifted compared to the Si-H signal of the insertion product 8a (3.68 ppm).
  • reaction according to Scheme 26 represents an even better model due to the chemical similarity of the pentamethyldisiloxane used to a polysiloxane. On the basis of this model reaction, the reaction mechanism can very probably also be transferred to long-chain hydridomethylpolysiloxanes.
  • the respective components are mixed together in the following mass ratios (e.g. with a "DAC-150.1" speed mixer from Hausschild):
  • a UV chamber "UVA cube” from Dr. Hönle (illuminance: 200 mW/cm 2 ) was used to activate adhesion promoter and/or RTV2 mass.
  • the mixtures were thermally cured in an "LHT6/30" drying cabinet. from Carbolite-Gero.

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Abstract

L'invention concerne des composés à fonction silirène, constitués d'un substrat auquel sont liés de façon covalente au moins deux groupes silirène de formule (I), n = 0 ou 1 ; R étant un groupe hydrocarboné divalent en C1-C20 ; R1 étant sélectionné dans le groupe comprenant (i) un groupe hydrocarboné en C1-C20, (ii) un groupe hydrocarbonoxy en C1-C20, (iii) un groupe silyl-SiR4R5R6, R4, R5, R6 représentant indépendamment les uns des autres un groupe hydrocarboné en C1-C6, (iv) un groupe amino-NRy2, Ry étant indépendamment les uns des autres sélectionnés dans le groupe comprenant (iv.i) un hydrogène, (iv.ii) un groupe hydrocarboné en C1-C20 et (iv.iii) un groupe silyl-SiR4R5R6, et (v) un groupe imino- N=CR7R8, R7, R8 étant indépendamment l'un de l'autre sélectionnés dans le groupe comprenant un hydrogène, un groupe hydrocarboné en C1-C20 et un groupe silyl-SiR4R5R6 ; R2, R3 étant indépendamment l'un de l'autre sélectionnés dans le groupe comprenant un hydrogène, un halogène, un groupe hydrocarboné en C1-C20, un groupe silyl-SiR4R5R6 et un groupe organopolysiloxane-(CH2)y-[SiR9R10-O]χ-[SiR11R12R13], R9 à R13 étant indépendamment l'un de l'autre sélectionnés dans le groupe comprenant un méthyle, un éthyle, un phényle, un éthinyle et un vinyle, l'indice x étant zéro ou un nombre entier de 1 à 200 et l'indice y étant zéro ou un nombre entier de 1 à 10, et R2 et R3 pouvant faire partie d'un groupe cyclique. L'invention concerne en outre des procédés de préparation de ces composés et de mélanges pour la promotion de la réticulation et de l'adhérence contenant ces composés.
PCT/EP2021/064438 2021-05-28 2021-05-28 Composés à fonction silirène et leurs mélanges pour la préparation de siloxanes et leur conférant des propriétés favorisant l'adhérence WO2022248067A1 (fr)

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