Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • 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
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • 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
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
• • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

• the present invention relates to the field of catalysis of dehydrogenocondensation reactions allowing the polymerization / crosslinking of silicone.
• the reactive species involved are monomers, oligomers, and / or polymers of polyorganosiloxane (POS) nature.
• the reactive units concerned in these species are on the one hand the SiH units and on the other hand the SiOH units.
• the applications more particularly targeted by the invention are crosslinked silicone elastomeric coatings useful as non-stick coatings on various solid supports, for example flexible supports (fibrous paper or fabric eg) or non-fibrous, such as polymer films (polyester or polyolefin eg), or alternatively supports made of aluminum or any other metal such as tinplate.
• Another application more specifically concerned with the invention relates to crosslinked silicone foams.
• the invention relates to siloxane compositions crosslinkable by dehydrogenocondensation of the type of those comprising: o -A- at least one monomer, oligomer and / or organosiloxane polymer having, per molecule, at least one reactive unit ⁇ SiH; o -B- at least one monomer, oligomer and / or organosiloxane polymer having, per molecule, at least one reactive unit ⁇ SiOH; o -C- at least one metallic catalyst; o -D- optionally at least one crosslinking inhibitor; o -E- optionally at least one polyorganosiloxane resin
• the invention also relates to the use of a new dehydrogenocondensation catalyst based on organometallic complexes (Ir, Ru, Mn) for the dehydrogenocondensation between silicone species (monomers / oligomers / polymers) intended to polymerize / crosslink between them.
• the invention also relates to the polymerization / crosslinking processes involving the abovementioned compositions including the catalyst more specially selected in accordance with the invention.
• the invention aims to obtain non-stick silicone coatings or crosslinked silicone foams using silicone compositions comprising a particular organometallic catalyst (based on iridium, ruthenium, or manganese).
• a silicone composition of polyorganosiloxane (POS) type comprising more precisely a polydimethyldisiloxane with silanol ends and a crosslinker constituted by a POS with ⁇ SiH units in the chain and at trimethylsilyl ends, a catalyst constituted by a rhodium complex (RhCl 3 [(C 8 H ⁇ ) 2 S] 3 ), as well as a crosslinking inhibitor (for example diethylmaleate, diethylacetylene dicarboxylate, triallylisocyanurate, vinyl acetate).
• This composition comprises 100 parts of POS with SiOH ends, one to 20 parts of POS SiH and 10 to 500 parts per million of the rhodium-based catalytic complex and finally 0 to 0.1 part by weight of inhibitor.
• This silicone composition crosslinkable by dehydrogenocondensation in the presence of a rhodium complex can be used for the production of non-stick coatings on flexible supports such as paper and plastic or metallic films. Crosslinking takes place at a temperature of 150 ° C.
• European patent application EP-A-1 167 424 describes the production of linear block silicone copolymers by dehydrogenocondensation of POS polymers with silanol ends and aromatic POS with ⁇ SiH ends in the presence of a metal catalyst.
• the POS with silanol ends is a polydimethylsiloxane
• the POS block with SiH motif is for example 1,4-bis (dimethylsilylbenzol
• the catalyst is for example a platinum complex such as the Karstedt catalyst.
• dehydrogenocondensation catalysts are metal catalysts based on. platinum, rhodium, palladium, plutonium and iridium, platinum being particularly preferred.
• the copolymer block or blocks with ⁇ SiH units have the particularity that they comprise a POS entity comprising a ⁇ SiAr-Si (R) 2 -O- unit.
• French patent application FR-A-2 806 930 relates to the use of boron derivatives of the Tris (pentafluorophenyl) borane type as heat-activated catalyst for the dehydrogenocondensation between a POS with SiH units, for example of formula:
• Such silicone compositions which can be crosslinked by dehydrogenocondensation in the presence of Lewis acids of the boron derivative type can be used for the production of non-stick coatings on flexible supports, in particular on paper, as well as in the manufacture of crosslinked silicone foams in which the hydrogen release and the quality of the crosslinking network are controlled.
• one of the essential objectives of the present invention is to provide a silicone composition ⁇ SiH / ⁇ SiOH polymerizable / crosslinkable by dehydrogenocondensation, in the presence of a catalyst judiciously selected to perfect at least one of the specifications set out above. .
• Another essential objective of the present invention is to provide a process for polymerizing and / or crosslinking a composition of the type of that mentioned in the statement of objectives above; this process should be quick economic and efficient in terms of quality of final product obtained.
• Another essential objective of the invention is to provide a process for producing at least one non-stick coating on a support (preferably flexible), consisting in using the crosslinking / polymerization process and / or the composition mentioned above, to improve profitability without prejudicing the qualities of the composite: coating / support obtained.
• Another essential objective of the invention is to provide a process for producing at least one article of cross-linked silicone foam, consisting in using the above-mentioned cross-linking / polymerization process and / or the composition mentioned above in the objectives, this process allowing control the volume of hydrogen gas released and the quality of the crosslink.
• POS o -F- optionally at least one charge; characterized in that the catalyst -C- is chosen from the group of organometallic complexes comprising at least one of the following metals: Ir, Ru, Mn.
• the siloxane composition is characterized in that the catalyst -C- corresponds to the following formula (I):
• o Ir is an Iridium atom of valence I or III
• o X represents a ligand with an electron, preferably chosen from the group comprising halogens, hydrogen, acetate, an aromatic or heteroaromatic group, substituted or no, CN, RO, RS, R 2 N, R 2 P with R corresponding to an alkyl, aryl or arylalkyl unit o L and L 'independently represent a ligand with two electrons, preferably chosen from the group comprising:
• hydrocarbon radicals comprising at least one unit:
• the catalyst (I ′) is also known under the name of Vaska complex, which had never been proposed in reactions between POS ⁇ SiH and POS ⁇ SiOH by dehydrogenocondensation.
• They are also interesting because at low concentration, they only require limited amounts of energy to activate the dehydrogenocondensation. In particular, they can in fact be activated at a temperature below 150 ° C, preferably below 100 ° C, or even equal to room temperature.
• the catalyst -C- based on Ruthenium, Manganese and preferably Iridium is advantageously present in an amount varying between 1.10 "6 and 5, preferably between 1.10 " and 1.10 " parts by weight of the dry matter in organosiloxane monomer, oligomer and / or polymer to be reacted.
• siloxane species -A- with reactive units ⁇ SiH is preferably chosen from those which have at least one unit of formula (II) and which are terminated by units of formula (III) or cyclic units consisting of units of formula (II) shown below:
• a linear or branched alkyl radical containing 1 to 8 carbon atoms optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3, 3, 3-trifluoropropyl,
• siloxane species -B- with reactive units ⁇ SiOH are retained within the framework of the invention, those having at least one unit of formula (IN) and terminated by units of formula (N) or cyclic consisting of patterns of formula (IN) shown below:
• R 2 are identical or different and represent: • a linear or branched alkyl radical containing 1 to 8 carbon atoms, optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3, 3, 3-trifluoropropyl,
• an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms, - the symbols Z 'are similar or different and represent:
• the species of type -A- and -B- can also include in their structure so-called (Q) or (T) motifs defined as indicated below: oo
• R 3 possibly representing one of the substituents proposed for R 1 or R 2 .
• the polyorganosiloxanes -A- used contain from 1 to 50 SiH units per molecule.
• the polyorganosiloxanes -B- used contain from 1 to 50 SiOH units per molecule.
• oligomers and polymers corresponding to the general formula (VI) are especially preferred as derivatives -A-:
• - x and y each represent a whole or fractional number varying between 0 and 200
• R ' 1 and R " 1 represent independently of each other:
• a linear or branched alkyl radical containing 1 to 8 carbon atoms optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3, 3, 3-trifluoropropyl,
• oligomers and polymers corresponding to the general formula (Nile) are especially preferred as derivatives -B-:
• R - R ' 2 and R " 2 represent independently of each other:
• a linear or branched alkyl radical containing 1 to 8 carbon atoms optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3, 3, 3-trifluoropropyl,
• an aralkyl part having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted
• 1 ⁇ b ⁇ 55 preferably 10 ⁇ b ⁇ 55 preferably 30 ⁇ b ⁇ 55
• siloxane species -A- and -B- are oligomers, polymers, they can be described as indicated below.
• POS -A- can be linear (eg (NI)), branched or cyclic.
• its viscosity is preferably less than 100 mPa.s; the identical or different organic radicals are preferably methyl, ethyl and / or phenyl.
• the hydrogen atoms of the ⁇ SiH functions are linked directly to the silicon atoms located at the chain end (s) and / or in the chain.
• linear constituent -A By way of example of a linear constituent -A, mention may be made of polymethylhydrogenosiloxanes with trimethylsiloxyl and / or hydrogenodimethylsiloxy ends.
• cyclic polymers those corresponding to the following formulas can be cited:
• branched polymers can be cited: CH 3 Si [CH 3 ) 3 ] [OSi (CH 3 ) 2 H] 2 ; If [OSi (CH 3 ) (C 2 H 5 ) H] [OSi (CH 3 ) 2 H] 3 , as well as those made up of SiOH 2 and H (CH 3 ) 2 SiOo > 5 units with a CH / Si ratio of 1 to 1.5.
• Component -B- can have a viscosity of up to 200,000 mPa.s. For economic reasons, a constituent is chosen whose viscosity is generally of the order of 20 to 10,000 mPa.s.
• the identical or different organic groups generally present in ⁇ , ⁇ -hydroxylated oils or gums are the methyl, ethyl, phenyl, trifluoropropyl radicals.
• at least 80% by number of said organic groups are methyl groups linked directly to the silicon atoms.
• the ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxanes are more particularly preferred.
• Resins -B- with silanol functions present per molecule at least one of the units
• the radicals R ′ generally present are methyl, ethyl, isopropyl, tert-butyl and n-hexyl.
• resins that may be mentioned include MQ (OH), MDQ (OH), TD (OH) and MDT (OH) resins.
• solvents of POS -A- or -B- so as to adjust the viscosity of the composition.
• conventional solvents of silicone polymers mention may be made of aromatic solvents such as xylene and toluene, saturated alphatic solvents such as hexane, heptane, white-spirit®, tetrahydrofuran and diethyl ether, chlorinated solvents such as than methylene chloride and perchlorethylene. In the context of the present invention, it will however be preferred not to use a solvent.
• siloxane species -A- and -B- are also decisive for the proper conduct of the dehydrogenocondensation of the composition according to the invention.
• the ratio ⁇ SiH / ⁇ SiOH is advantageously between 1 and 100, preferably between 10 and 50 and, more preferably still between 15 and 45.
• the composition according to the invention can also comprise at least one cross-linking inhibitor -D-.
• the latter is preferably chosen from acetylenic alcohols (ethynylcyclohexanol: ECH) and / or diallylmaleates and / or triallylisocyanurates and / or dialkylmaleates (diethylmaleates and / or dialkylalkinyledicarboxylates) or diethyleacylenes dicyleacethylene dicareayl ethylene dicarboxylates); polyorganosiloxanes, advantageously cyclic and substituted with at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred, - pyridine, phosphines and organic phosphites, unsaturated amides,
• R 1 is a linear or branched alkyl radical, or a phenyl radical
• R 2 is H or a linear or branched alkyl radical, or a phenyl radical
• the radicals R, R and the carbon atom located have triple bonds which can optionally form a ring; the total number of carbon atoms contained in R and R being at least 5, preferably from 9 to 20.
• Said alcohols are preferably chosen from those having a boiling point above 250 ° C. As examples, we can cite:
• 3-methyl-pentadecy-1 ol-3 are commercial products.
• Such a retarder is present at a maximum of 3000 ppm, preferably at a rate of 100 to 2000 ppm relative to the total weight of the organopolysiloxanes -A- and -B-.
• composition according to the invention can also comprise one or more POS -E- resins.
• These resins are well known and commercially available branched POS oligomers or polymers. They are present in the form of solutions, preferably siloxane. They have, in their structure, at least two different units chosen from those of formula R ' 3 Si ⁇ Q 5 (unit M), R' 2 SiO (unit D), R'SiOi 5 (unit T) and Si ⁇ 2 (unit Q) , at least one of these patterns being a T or Q pattern.
• radicals R ' are identical or different and are chosen from linear or branched alkyl radicals in C ⁇ -C 6 , alkenyl radicals in C 2 -C 4 phenyl, trifluoro-
• oligomers or branched organopolysiloxane polymers -E- mention may be made of MQ resins, MDQ resins, TD resins and MDT resins, the alkenyl functions being able to be carried by the M, D and / or T units.
• resins -E- which are particularly suitable, mention may be made of vinylized MDQ or MQ resins having a weight content of vinyl groups of between 0.2 and 10% by weight, these vinyl groups being carried by the units M and / or D.
• This resin -E- of structure is advantageously present in a concentration of between 10 and 70% by weight relative to all the constituents of the composition, preferably between 30 and 60% by weight and, more preferably still, between 40 and 60% by weight.
• composition according to the invention may also contain a filler -F-, preferably mineral and chosen from siliceous materials or not. When it comes to siliceous materials, they can play the role of reinforcing or semi-reinforcing filler.
• the reinforcing siliceous fillers are chosen from colloidal silicas, combustion and precipitation silica powders or a mixture thereof.
• These powders have an average particle size generally less than 0.1 ⁇ m and a BET specific surface greater than 50 m 2 / g, preferably between 100 and 300 m 2 / g.
• Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used.
• non-siliceous mineral materials can act as a semi-reinforcing or tamping mineral filler.
• these non-siliceous fillers which can be used alone or as a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, zirconia, a zirconate, unexpanded vermiculite, calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime.
• These fillers have a particle size generally between 0.001 and 300 ⁇ m and a BET surface area of less than 100 m 2 / g.
• the filler used is silica.
• the load can be treated using any suitable compatibilizing agent and in particular hexamethyldisilazane. For more details in this regard, reference may be made, for example, to patent FR-B-2,764,894.
• an amount of filler of between 5 and 30, preferably between 7 and 20% by weight relative to all of the constituents of the preparation.
• composition can be enriched using all kinds of additives according to the intended end applications.
• the composition may comprise an adhesion modulating system selected from known systems. These may be those described in French patent FR-B-2 450 642, US-B-3,772,247 or European patent application EP-A-0 601 938. By way of examples, mention may be made modulators based on: o from 96 to 85 parts by weight of at least one reactive polyorganosiloxane resin (A) of the type: MD vi Q, MMViQ, MD Vi T, MM Héxén y le Q or
• MM A11 y lo ⁇ yp ro Py le Q o from 4 to 15 parts by weight of at least one non-reactive resin (B) of type: MD'Q, MDD'Q, MDT ', MQ or MDQ.
• stabilization additives such as for example amino agents of tertiary or secondary amine type (cf. WO-A-98/07798; EP-A-162 524; EP -A-0 263 561).
• compositions can be bactericides, photosensitizers, fungicides, corrosion inhibitors, antifreeze agents, wetting agents, defoamers, synthetic latexes, dyes or acidifiers.
• the promoters of adherents such as for example those comprising at least one alkoxylated organosilane, at least one epoxidized organosilicon compound, and at least one metal chelate and / or a metal alkoxide for example (Vinyl TriMethoxySilane) / (GLYcidoxypropyltriMethOxysilane) / (tert-butyl titanate).
• This composition can be a solution or an emulsion. In the latter case, it can then comprise at least one surfactant and optionally at least one pH-fixing agent such as HCO 3 7CO 3 2 " and / or H 2 PO 4 " / HPO 4 2 " .
• Another means of defining the invention consists in understanding it from the angle of use as a heat-activatable catalyst for dehydrogenocondensation between, on the one hand, at least one monomer, oligomer and / or organosiloxane polymer having, through molecule, at least one motifSiH reactive unit and, on the other hand, at least one monomer, oligomer and / or organosiloxane polymer having, per molecule, at least one ⁇ SiOH reactive unit to obtain a product further comprising, optionally at least a crosslinking inhibitor, optionally at least one polyorganosiloxane resin (POS), and optionally at least one charge, of at least one catalyst -C- chosen from the group of organometallic complexes comprising at least one of the following metals: Ir, Ru, Mn, this catalyst -C- being as defined above.
• the present invention relates to a process for polymerizing and / or crosslinking a composition as defined above.
• This process is characterized in that a dehydrogenocondensation is carried out between said compounds - A- and -B- and in that said dehydrogenocondensation is initiated by thermoactivation of the catalyst -C-.
• Two embodiments are possible for adding the catalyst according to the invention.
• This can either be added to the mixture of compounds A and B, for example polymers of type SI or S2 or S3 with a polymer of type S4, or, preferably, be mixed beforehand with compound B, for example polymer of type S4, before being brought into the presence of compound A, for example the polymer SI or S2 or S3.
• the catalyst can be used as it is or in solution in a solvent.
• the mixtures are produced with stirring at room temperature.
• the catalyst solution may for example be used to prepare a bath with the monomer (s), oligomers and / or polymers to be polymerized and / or crosslink by dehydrogenocondensation, so that the concentration of the catalyst (s) present is between 0, 01 and 5% by weight in said bath, and preferably between
• the solvents which can be used for the catalysts are very numerous and varied and are chosen according to the catalyst used and the other constituents of the composition thus prepared.
• the solvents can be alcohols, esters, ethers, ketones, trace water and carbonates.
• the alcohols commonly used are para-tolyl-ethanol, isopropyl-benzyl alcohol, benzyl alcohol, methanol, ethanol, propanol, isopropanol and butanol.
• the ethers commonly used are methoxy-2-ethanol, ethoxy-2-ethanol, diethylene glycol, di-n-butyl ether.
• the usual esters are dibutylmaleate, dimethylethylmalonate, methyl salicylate, dioctyladipate, butyl tartrate, ethyl lactate, n-butyl lactate, isopropyl lactate.
• solvents usable for the bath of catalyst and entering into the other categories of solvents mentioned above are acetonitrile, benzonitrile, acetone, cyclohexanone, toluene and tetrahydrofuran.
• the preparation of the silicone composition according to the invention which can be used in particular as a coating base for the production of water-repellent non-stick coatings, is carried out using means and according to mixing methodologies well known to man. of art, whether compositions with or without solvents or emulsions.
• the invention also relates to a process for producing at least one non-stick coating on a support - preferably flexible -, characterized in that it consists essentially in applying to this support a composition as defined above, in preferably using POS -A- and -B- as defined above, and then ensuring that crosslinking occurs.
• the compositions can be applied using devices used on industrial paper coating machines such as a five-roller coating head, air knife systems or with an equalizing bar, on flexible supports or materials, then hardened by circulation in tunnel ovens heated to 70-200 ° C; the passage time in these ovens is a function of the temperature; this is generally on the order of 5 to 15 seconds at a temperature on the order of 100 ° C. and on the order of 1.5 to 3 seconds at a temperature on the order of 180 ° C.
• compositions can be deposited on any flexible material or substrate such as papers of various types (supercalendered, coated, glassine), cardboards, cellulose sheets, metal sheets, plastic films (polyester, polyethylene, polypropylene ).
• the quantities of compositions deposited are of the order of 0.5 to 2 g per m 2 of surface to be treated, which corresponds to the deposition of layers of the order of 0.5 to 2 ⁇ m.
• the materials or supports thus coated can subsequently be brought into contact with any adhesive materials, rubber, acrylic or other, sensitive to pressure.
• the adhesive material is then easily detachable from said support or material.
• the flexible supports coated with a non-stick silicone film can for example be:
• Another object of the invention relates to a process for producing at least one article of crosslinked silicone foam, characterized in that it essentially consists in crosslinking a composition as defined above, preferably using POS A and B as defined above, ensuring that at least part of the hydrogen gas formed is not removed from the reaction medium.
• compositions according to the invention are useful in the field of non-stick coatings on paints, the encapsulation of electrical and electronic components, coatings for textiles, as well as in the field of sheathing of optical fibers.
• the subject of the invention is also all coatings obtained by crosslinking a composition comprising siloxane species -A- with reactive SiH units of type SI, S2, S3 as defined above to siloxane species -B- of type S4 as defined above.
• These coatings can be of varnish, adhesive coating, non-stick coating and / or ink type.
• the invention also relates to: - all articles made of a solid material of which at least one surface is coated with the above-mentioned composition crosslinked and / or thermally polymerized; as well as the crosslinked silicone foam obtained by crosslinking a composition comprising the species SI and / or S2 and / or S3 as components -A- is the species of type S4 as components -B- and production of hydrogen gas by dehydrogenocondensation.
• the present invention also relates to the resins or polymers capable of being obtained from the compositions described above.
• the polyorganosiloxane polymers used are the following:
• the iridium concentration is calculated relative to the total mass of the mixture of SiH and SiOH oils.
• the iridium catalyst used is the Naska complex in solution in desulfurized toluene.
• This ink is supplied with a small application brush (if using another type of ink, specify it) (ink used daily: DLU 3 months).
• a score of 0 to 10 will be given corresponding to the time elapsed in seconds before the observation of the dewetting phenomenon.
• Examples 1, 2 and 3 demonstrate the effectiveness of the Naska catalyst for the dehydrogenocondensation reaction and the role of ethynylcyclohexanol (ECH) as a reaction retarder.
• Examples 4 and 5 demonstrate the activity of other complexes based on iridium and ruthenium.
• SiH / SiOH is 1.8 and the iridium concentration is 100 ppm.
• the setting time is measured; in this case, the gel time is less than 3 minutes at room temperature.
• the rapportSiH / ⁇ SiOH ratio is 1.8, the iridium concentration is 100 ppm and the ECH / Ir ratio is 20. After stirring, the gel time is greater than 2 hours at room temperature and is equal to 30 minutes at 80 ° C.
• Example 3 highlights the effectiveness of the Naska complex, at different ratios
• SiH / SiOH and at different concentrations of iridium.
• Naska IrCl (CO) (TPP) 2 is diluted in desulfurized toluene.
• a preformed mixture of POS S4 oil with ⁇ SiOH units and POS SI oil with ⁇ SiH units is added (the ⁇ SiH / ⁇ SiOH ratio and the iridium concentration are variable and are grouped in the table below). -Dessous). After stirring, the setting time at room temperature is measured:
• SiOH and POS SI oil with patterns ⁇ SiH The ⁇ SiH / ⁇ SiOH ratio is 1.8 and the ratio
• Ru / ⁇ SiOH is equal to 4.2x10 " (about 50 ppm ruthenium). After stirring, the setting time is measured at room temperature or at 80 ° C.

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