Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2291—Olefins
• • 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
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0086—Platinum compounds
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/828—Platinum
• • 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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
• • 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
  • 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
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing 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

Definitions

• the present invention relates to the field of catalysis of crosslinking reactions between polymer chains, e.g. silicones, comprising reactive radicals capable of forming interchain bridging, so as to obtain a crosslinked material having a certain hardness and a certain mechanical strength.
• polymer chains e.g. silicones
• reactive radicals capable of forming interchain bridging
• substrates A are intended to react with substrates of type B having, per molecule, at least one reactive unsaturated aliphatic group and / or at least one reactive function, eg epoxide, in the presence of a catalyst comprising at least one platinum complex, such a reaction being initiated or activated by light rays, of wavelength, chosen, preferably, in the field of ultraviolet (UV).
• UV ultraviolet
• the present invention relates, first of all, to new catalytic systems formed by photoactive organoplatinic complexes in the crosslinking by hydrosilylation of polyorganosiloxanes A of Si-H type and of compounds B with aliphatic unsaturation and / or with reactive function. .
• the present invention also relates to a hydrosilylation process in which the above-mentioned catalytic systems are used, as well as compositions which can be crosslinked by photoactivation and which contain, inter alia, the substrates A and B and the above-mentioned catalyst.
• coatings formed from a mixture of silicone oils which can be crosslinked together and which are intended to form non-stick layers on fibrous supports such as paper, dental impressions, adhesives, sealants, jointing materials, etc.
• non-stick paper application among others, cross-linking in situ by photoactivation, eg by UV irradiation, is particularly advantageous insofar as it allows high coating speeds.
• this in situ crosslinking can take place easily at room temperature. It also avoids the use of solvents, the elimination of which is costly and difficult.
• these catalysts are in the form of organometallic complexes (platinum or the like).
• platinum has proven to be the most suitable metal for entering into the composition of these organometallic complexes.
• the source of the platinum in this solution is formed by the catalyst of SPEIER or hexachloroplatinic acid.
• This KARSTEDT catalyst has the drawback of not being part of the photoactivatable hydrosilylation catalysts.
• the activation adapted to this KARSTEDT catalyst is thermoactivation, which is, all the same, much more restrictive and expensive than a simple UV activation, of the type of that targeted by the invention.
• Another major defect of the catalyst of the KARSTEDT solution is that it has a relatively poor storage stability (gel time at 25 ° C less than or equal to 1 min).
• Another objective of the invention is to provide a hydrosilylation process by photoactivation of reactive products, and in particular of silicones, in which the abovementioned catalytic systems are used, said process having to be easy to carry out, fast, and inexpensive.
• Another objective of the invention is to propose compositions of silicone oils crosslinkable by photoactivation:
• compositions stable in storage, can be used, for example, for paper anti-adhesion, dental impressions, sealing or jointing materials, adhesives, or for any other application in which it is advantageous to use performs cross-linking in situ of silicone elastomers.
• R 1 , R 2 , R 3 , R 4 are different or similar to each other and represent an alkyl and / or acyl group, preferably an alkyl having from 1 to 18 carbon atoms, methyl, ethyl, propyl, pentyl groups , hexyl, allyl, acetyl, propionyl being particularly preferred and especially methyl, ⁇ L 1 being a ligand of the following formula:
• ⁇ Z 1 , Z 2 are identical or different and:
• alkyl and alkenyl residues considered above being linear or branched and containing from 1 to 6 carbon atoms
• ⁇ either are two atoms linked to each other and belonging to a preferably aromatic ring.
• ⁇ Y 1 , Y 2 are identical or different and representing an alkyl, aryl radical preferably phenyl, alkyloxy, oryloxy, hydrogen or halogen,
• ⁇ L 2 being a ligand consisting of one of the following two residues (2 1 ), (2 2 ):
• Y 3 to Y 6 on the one hand and E 3 , E 4 on the other hand are identical or different and correspond to the same definition as that given above for Y 1 , Y 2 and E 1 , E 2 respectively,
• Y 3 and Y 4 and / or Y 5 and Y 6 can also together form a cyclic group, preferably an aromatic group comprising one or more aromatic rings having from 6 to 8 members, being in ortho or pericondensed form, and optionally substituted by monovalent radicals corresponding to the definition given above for Y 3 to Y 6 ;
• Z 3 , Z 5 are identical or different and correspond to:
• CR 13 with R 13 H or lower alkyl C 1 , C 6 , N;
• Z 4 is a residue comprising from 2 to 5 phenylene radicals linked together by:
• the ligand L is advantageously a chromophore. It can be varied in nature. This ligand L is also decisive with regard to the definition of two preferred species C 1 and C 2 in accordance with the invention.
• the first species C 1 is that in which there is only one platinum atom of real and formal degree of oxidation 0, complexed with the siloxane residue and the ligand L 1 , via the ⁇ double bonds.
• the second species C 2 has two platinum atoms, also of real and formal oxidation state 0 and complexed each with a siloxane residue and the ligand L 2 : (2 1 ), (2 2 ).
• the subject of the invention is also a new photoactivatable catalytic system - possibly thermoactivable - based on platinum and useful in particular in the hydrosilylation between, on the one hand, polyorganosiloxanes A having, per molecule, at least one reactive radical Si- H and free of silicon atom linked to more than two hydrogen atoms and, on the other hand, of compounds B having at least one reactive group and / or at least one reactive polar function,
• Such catalytic systems are particularly advantageous in the context of in situ crosslinking techniques, for example of silicones, in which “ready-to-use” compositions are used and comprising both polymers intended for react between them and a photosensitive catalytic system, so that this considerably simplifies their application.
• These compositions are known to those skilled in the art under the name "single-component".
• the photoactivatable catalytic systems according to the invention make it possible to control the crosslinking conditions and therefore the final mechanical properties targeted for the crosslinked elastomeric compositions. It is thus possible to adapt these to the intended application (e.g. non-stick, paper).
• the catalytic system of which it is a question in the present presentation can consist of a mixture of complexes C 1 , C 2 with ligands of formulas (1) and / or (2 1 ) and / or (2 2 ).
• the complexes C 1 are chosen from the following compounds, taken alone or as a mixture:
• the C 2 complexes are selected from the following compounds, taken alone or as a mixture
• the catalytic system contains, in the free state, at least one stabilizing agent formed by at least one ligand Ls of formula L 1 or L 2 as defined above.
• the ligand Ls forming the stabilizing agent can be identical or different to the ligands (L 1 , L 2 ) of the complexes (I): C 1 , C 2 .
• the compound Ls in the catalytic system in an excess of 1 to 30, preferably 10 to 20 molar equivalents relative to the platinum present.
• This Ls compound can in fact be considered as a catalyst inhibitor. It is moreover possible to use in combination or as a replacement for Ls other conventional inhibitors of hydrosilylation catalysts. These inhibitors also known under the name of thermal blockers make it possible to increase the "pot life" of the compositions considered (stabilities greater than 3-5 days) without harming the kinetics of hydrosililation.
• R is a linear or branched alkyl radical, or a phenyl radical
• R ' is H or a linear or branched alkyl radical, or a phenyl radical
• the total number of carbon atoms contained in R and R 1 being at least 5, preferably from 9 to 20.
• Said alcohols are preferably chosen from those having a boiling point above 250 ° C. Mention may be made, by way of examples:
• the synthesis of the platinum complexes (I) according to the invention consists in reacting a ligand L with products of average formula [Pt 2 ] [ViMe 2 Si - O - Si Me 2 Vi] 3 . These products are preferably formed by a KARSTEDT catalyst solution.
• This reaction can be carried out in bulk or in a solvent, such as toluene, ethanol or isopropanol.
• the catalytic system can comprise a precursor of the complexes (I), eg C 1 or C 2 .
• a precursor of the complexes (I) eg C 1 or C 2 .
• Such a precursor is advantageously constituted by a composition of the starting materials for the synthesis of the complexes
• the formation of the platinum complexes takes place in situ, before and / or during the use of the crosslinkable composition containing the precursor composition. This greatly simplifies the preparation.
• catalytic system according to the invention is sufficiently reactive and efficient to dispense with the use of photosensitizers, it is entirely possible, for the sake of optimization, to use such products.
• At least one photosensitizer having a triplet energy greater than or equal to 31 Kcal / mole and selected from (poly) aromatic (optionally metallic) and heterocyclic products, preferably in the following list of products: toluene, pyridine, ferrocene, benzene, thioxanthone, anthracene, benzophenone, this selection being made so that the triplet lifetimes of the platinum complexes and of the photosensitizer (s) are preferably of the same order.
• these photosensitizers are used at a rate of 5 ⁇ 10 -3 to
• the photosensitive catalytic system according to the invention is non-reducible, so that it does not tend to react with the reactive Si-Hs of type A polyorganosiloxanes.
• the present invention relates to a hydrosilylation process between, on the one hand, polyorganosiloxanes A having, per molecule, at least one reactive radical Si-H and free of silicon atoms bound to more than two hydrogen atoms, and on the other hand, compounds B preferably chosen from polyorganosiloxanes and having, per molecule, at least one unsaturated aliphatic reactive group and / or at least one reactive function, process in which one implements at least one platinum complex as a catalyst.
• This process differs from its similar in that it consists essentially in reacting compounds A and B in the presence of a catalytic system of the type of that according to the invention described above, and / or by using simultaneously a synthesis of complexes (I) in which a precursor is formed, as described above, formed by a composition of the starting materials (excess ligand + KARSTEDT catalyst) and possibly using at least the constituents of the above catalytic system, the initiation of the reaction being at least partly carried out by photoactivation.
• the compounds A are chosen from polyorganohydrogensiloxanes comprising:
• the symbols W are similar or different and representing a monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst and preferably chosen from (cyclo) alkyl groups having from 1 to 18 carbon atoms included, and, advantageously, among the methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl groups and also among the C 6 -C 12 aryl or aralkyl groups and, advantageously, among the xylyl and totyl and phenyl radicals,
• Organopolysiloxane A can only be formed of units of formula (1) or additionally comprise units of formula (2).
• Organopolysiloxane A can have a linear, branched or unbranched, cyclic or network structure. The degree of polymerization is greater than or equal to 2. More generally, it is less than 5,000.
• linear polymers When linear polymers are involved, these essentially consist of "D" W 2 SiO 2/2 , WHSiO 2/2 , and “M” W 3 SiO 1/2 or W 2 HSiO 1/2 units. , WH 2 SiO 1/2 ; the blocking terminal "M” units can be trialkylsiloxy, dialkylarylsiloxy groups.
• terminal "M” units mention may be made of trimethylsiloxy, dimethylphenylsiloxy, dimethylethoxysiloxy, dimethylethyltriethoxysilylsiloxy groups, etc.
• units "D” mention may be made of dimethylsiloxy, methylphenylsiloxy groups.
• Said linear polyorganosiloxanes A can be oils of dynamic viscosity at 25 ° C of the order of 1 to 100,000 mPa.s at 25oC, generally of the order of 10 to 5,000 mPa.s at 25 ° C, or gums having a molecular weight of the order of 1,000,000.
• cyclic polyorganosiloxanes consist of "D" W 2 SiO 2/2 , and WHSiO 2/2 units , which may be of the dialkylsiloxy or alkylarylsiloxy type.
• Said cyclic polyorganosiloxanes have a viscosity of the order of 1 to 5000 mPa.s.
• the dynamic viscosity at 25 ° C all the silicone polymers considered in this presentation can be measured using a BROOKFIELD viscometer, according to AFNOR NFT 76 102 standard of February 1972.
• the viscosity in question in this presentation is the dynamic viscosity at 25 ° C called “Newtonian”, that is to say the dynamic viscosity which is measured, in a manner known per se, at a shear rate gradient sufficiently low so that the viscosity measured is independent of the speed gradient.
• organopolysiloxanes A are:
• compounds B they are selected from polyorganosiloxanes comprising similar or different units of formula:
• the symbols X are similar or different and represent a hydrogen atom or a reactive function, preferably epoxyfunctional, linked to silicon by a divalent radical eg C 1 -C 20 optionally comprising at least one heteroatom, the radicals X more particularly preferred being: 3-glycidoxypropyl, 4-ethanediyl (1,2-epoxycylohexyl) ...,
• Y are similar or different and represent a linear or branched C 1 -C 12 alkenyl residue, and having at least one ethylenic unsaturation at the chain end and / or in the chain and optionally at least one heteroatom;
• ⁇ d, e and f are 0, 1, 2 or 3;
• Y residues they are advantageously chosen from the following list: vinyl, propenyl, 3-butenyl, 5-hexenyl, 9 decenyl, 10-undecenyl, 5.9 -decadienyl, 6-11-dodecadienyl.
• Organopolysiloxanes B can have a linear structure (branched or not) cyclic or network. Their degree of polymerization is preferably between 2 and 5000.
• the terminal blocking "M” units can be trialkylsiloxy, dialkylarylsiloxy, dialkylvinylsiloxy, dialkylalkenylsiloxy groups.
• terminal "M” units examples include trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy, dimethylhexenylsiloxy, dimethylethoxysiloxy, dimethylethyltriethoxysilylsiloxy groups, etc.
• units "D” mention may be made of dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylesiloxy, methyldecadienylsiloxy, methyl-3-hydroxypropylsiloxy, methylpropyl-3-glycidoxy-methyl-3-propoxy , 4'-epoxycyclohexyl) ethylsiloxy, methylbutoxysiloxy, methyl- ⁇ -trimethoxysilylethylsiloxy, methyl- ⁇ -triethoxysilylethylsiloxy.
• Said linear polyorganosiloxanes B can be oils of dynamic viscosity at 25 ° C of the order of 1 to 100,000 mPa.s at 25 ° C, generally of the order of
• cyclic polyorganosiloxanes B consist of "D" units W 2 SiO 2/2 , WSiO 2/2 , WYSiO 2/2 , which may be of the dialkylsiloxy, alkylarylsiloxy, alkylvinylsiloxy, alkylYsiloxy type. , alkylXsiloxy; examples of such patterns have already been cited above.
• Said cyclic polyorganosiloxanes B have a viscosity of the order of 1 to 5000 mPa.s.
• the compounds B with aliphatic unsaturation useful in the context of the process according to the invention are, for example, those with olefinic or acetylene unsaturation well known in the technical field considered.
• Si-H / unsaturated groups and / or reactive function e.g. epoxy either between 0.4 and 10 preferably between 1 and 4 and, more preferably still, is of the order of
• the catalyst being present in an amount from 1 to 400, preferably from 10 to 300 and, more preferably, from 20 to 200 ppm of platinum metal, expressed by weight relative to the compounds A and B present.
• the technical literature of the field considered gives all the other useful information, as for the reaction conditions of hydrosilylation by photoactivation (A / B mixture and UV irradiation at 25 ° C).
• crosslinking reactions of silicone oils in particular hydrosilylation (e. G: Si-H / Si-Vi), catalyzed by photosensitive complexes of platinum, such as those according to the invention, pass through the formation of particles. colloids, useful as a support for platinum, according to a heterogeneous catalysis process.
• photoactivation preferably takes place in the ultraviolet range.
• thermoactivation is preferably carried out using infrared radiation and it advantageously takes place after the photoactivation.
• a last aspect of the invention which is mentioned in a nonlimiting manner in the present description, relates to a crosslinkable and in particular photocrosslinkable composition, characterized in that it comprises the compounds A and B, and a catalyst as defined above.
• the above composition can also comprise at least one photosensitizer having a triplet energy greater than or equal to 31 Kcal / mole and selected from (poly) aromatic (optionally metallic) and heterocyclic products, and preferably from the following list of products: toluene, pyridine, ferrocene, benzene, thioxanthone, anthracene, benzophenone, this selection being made so that the triplet lifetimes of the platinum complexes and (of ) photosensitizer (s) are, advantageously, of the same order.
• at least one photosensitizer having a triplet energy greater than or equal to 31 Kcal / mole and selected from (poly) aromatic (optionally metallic) and heterocyclic products, and preferably from the following list of products: toluene, pyridine, ferrocene, benzene, thioxanthone, anthracene, benzophenone, this selection being made so that the triplet lifetimes of the platinum complexe
• compositions in accordance with the invention are prepared either before (or even long before) or even immediately before the implementation of the hydrosilylation process. It should be noted that these compositions are particularly stable on storage and that, in accordance with the process of the invention, they offer rapid crosslinking kinetics. In addition, their uncrosslinked state, before exposure to the activation light radiation, offers great ease of handling, application or placement on different supports or other shaping molds.
• compositions and / or the method according to the invention can incorporate different additives, chosen according to the intended final application. It can be, for example, mineral or non-mineral fillers and / or pigments such as synthetic or natural fibers (polymers) ground calcium carbonate, talc, clay, titanium dioxide or silica smoke. This can improve e.g. the mechanical characteristics of the final materials.
• Soluble dyes, oxidation inhibitors and / or any other material which does not interfere with the catalytic activity of the platinum complex and does not absorb in the wavelength range chosen for photoactivation, can also be added. to the composition or used in the context of the process according to the invention.
• the composition can be applied, for various purposes, to the surface of any solid substrate.
• solid supports can be paper, cardboard, wood, plastic (e.g. polyester, nylon, polycarbonate), fibrous supports woven or not made of cotton, polyester, nylon etc, or a metal, glass or ceramic.
• the applications, more particularly, targeted by the catalyst, the process and the compositions according to the invention are, in particular, those of cross-linkable silicone oils "in situ", useful for the preparation of non-stick coatings on fibrous supports of any kind and in particular on paper.
• the above compositions make it possible to achieve very high coating speeds, due to their very rapid crosslinking kinetics.
• dental impression materials adhesives, sealants, sealants, adhesion primers.
• the operating method used consists in reacting a ligand of type ⁇ (maleic anhydride, Benzoquinone, maleimide, etc.) on the KARSTEDT complex of ideal formula: Pt 2 (ViMe 2 Si-O-SiMe 2 Vi) 3 .
• This reaction can be carried out in bulk or in a solvent such as toluene, ethanol or isopropanol, according to the following sequences:
• Fig. 1 attached represents the kinetics of hydrosilylation of silicone oils with Si-H and Si-Vi units.
• the silicone oils used have the following structures: - Oils with Si-H units: Me 3 SiO - (- SiMe 2 O) 15.6 (-SiMeHO) 8] -SiMe 3
• the catalytic systems to be tested and an excess of ligand are introduced into the Si-Vi pattern oil. Then add this mixture to the Si-H pattern oil.
• the platinum level is 200 ppm relative to the total mass.
• the Si-H / Si-Vi molar ratio is 1.7. 20 molar equivalents of ligand are used.
• the irradiation is carried out using an HPK 125 lamp with a power: 120 mJ / cm 2 .mn.
• the thickness of the film studied is 24 ⁇ m.
• the kinetics of disappearance of the Si-H patterns is carried out by FTIR by measuring the decrease in the vibration band v Si-H. The tests are carried out at 25 ° C. TABLE 2 below brings together the main systems used.
• Fig. 2 attached represents the kinetics of hydrosilylation of a mixture of silicone oils with Si-H / Si-Vi units described in Example 2, catalyzed by the following complex:
• Fig. 3 attached represents the comparison of the kinetics observed for the hydrosilylation of silicone oils with Si-H / Si-Vi units (identical to those of Example 2) with the two catalytic systems:
• Fig. 4 represents the various kinetics observed using the catalytic system of the following formula:
• the catalytic mixture is introduced into an oil with Si-Vi units (idem example NO 2) and then into a silicone oil with Si-H units.
• the Si-H / Si-Vi molar ratio 1.7.
• a film with a thickness of 24 ⁇ m is produced.
• the platinum concentration is 200 ppm. 6.3 DETERMINATION OF THE FREEZE TIME AT 250 ° C
• Figure 5 attached shows the hydrosilylation kinetics observed for O, P and Q.
• Figure 6 attached shows the hydrosilylation kinetics observed for R and S.
• the silicone oil with Si-alkenyl patterns is as follows:
• Figure 7 shows the hydrosilylation kinetics obtained.

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