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• • 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
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
  • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
• • 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
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
• • 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
  • 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
• • 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
• • 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
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
• • 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
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
• • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

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 organo-metallic complexes based on platinum useful in particular as crosslinking catalyst by hydrosilylation of polyorganosiloxanes A of Si-H type and of compounds B with aliphatic unsaturation and / or reactive function.
• the present invention also relates to a crosslinking process in which the above-mentioned catalyst is 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.
• cross-linking in situ by photoactivation e.g. by UV irradiation
• photoactivation e.g. by UV irradiation
• 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).
• US Pat. Nos. 4,510,094 and 4,600,484 thus disclose organometallic complexes of platinum, as well as catalysts and processes for hydrosilylation using them, constituted by a cyclopentadienyl group bonded in ⁇ to the atom of platinum and by three other aliphatic groups linked in ⁇ to Pt.
• the reactions catalyzed by these compounds involve polyorganosiloxanes comprising silicon atoms bound to hydrogen and polyorganosiloxanes comprising aliphatic unsaturations, e.g. alkylene, preferably ethylenic.
• Cp which is one of the starting products for the synthesis of this catalyst, can only be prepared from a dimer and by implementing drastic conditions: (- 40 ° C among others ).
• this ligand Cp can be considered as a particularly toxic product.
• Such a synthesis of Cp is disclosed in A. DAVIDSON and PE RAKITA, Inorg. Chem., 9 (1970), 289.
• one of the essential objectives of the present invention is to provide new platinum complexes which are useful, in particular, as hydrosilylation catalysts, of Si-H type polyorganosiloxanes and of aliphatic unsaturated compounds (preferably ethylenic, eg Si-Vi) and / or of compounds with reactive polar functions:
• Another objective of the invention is to provide a process for hydrosilylation by photoactivation of reactive products, and in particular of silicones, in which the abovementioned catalysts are used, said process having to be carried out easily, quickly. , and inexpensive.
• Another objective of the invention is to propose a composition of silicone oils crosslinkable by photoactivation:
• Such a system should thus be easily storable and usable, for example for paper anti-adhesion, dental impressions, sealing or jointing materials, adhesives, or for any other application in which it is advantageous to implement a in situ crosslinking of silicone elastomers.
• the present invention thus relates to new platinum complexes of the following formula:
• Cy is one of the two cyclic residues (a) and (b) following ⁇ (a)
• D C1-C12 alkyl and alkoxy, linear or branched, D trialkylsilyl, aryl, aralkyl, arylalkoxyl, the alkyl parts of which are linear or branched Ci-C ⁇ and the aryl parts of which comprise 1 or 2 aromatic cyles, D the above radicals being optionally substituted, in particular perhalogenated, - NR'R "with R 'and R" identical or different and representing hydrogen, a linear or branched C1-C4 alkyl or a substituted or unsubstituted phenyl, 0 R 4 H , alkyl, ⁇ (b)
• R 5 H, alkyl
• R, R, R are identical or different from each other and represent an aliphatic group having from 1 to 8 carbon atoms, the methyl, ethyl, propyl, pentyl, hexyl, allyl, acetyl, propionyl groups being preferred and the group methyl being very particularly preferred.
• the present invention also relates to a hydrosilylation catalyst between, on the one hand, polyorganosiloxanes A having, per molecule, at least one reactive radical Si-H and free of silicon atom bonded to more than two atoms of hydrogen, and, on the other hand, compounds B having at least one reactive unsaturated aliphatic group and / or at least one reactive function, said catalyst being (thermo) photoactivatable and comprising at least one platinum complex chosen by the complexes of formula (la) and (Ib) described above, but without excluding complexes (1) to (14) mentioned above.
• the polyorganosiloxane compounds considered are chemical substances having specific molecular identities or are formed by mixtures of these substances.
• the catalyst according to the invention is particularly advantageous in the context of in situ silicone crosslinking techniques, in which compositions are used comprising both polymers intended to react with each other and a photosensitive catalytic system, so that it does not It is not necessary to mix at the time of application.
• this catalyst meets the requirements for stability at room temperature and high reactivity under the effect of light radiation, in particular d JV. This catalyst is indeed very efficient in hydrosilylation.
• the catalyst according to the invention is also advantageous in that it makes it possible to obtain crosslinked elastomeric compositions with modular properties, eg: giving anti-adhesion to surfaces of substrates such as metal, glass, plastics and paper.
• the catalyst of which it is a question in the present description may consist of a mixture of complexes of formula (I), each contributing obtaining advantageous results specific to the invention.
• the synthesis of the platinum complexes according to the invention, which had hitherto never been used as photosensitive catalysts for hydrosilylation reactions could in no way be called complexity.
• this synthesis consists in reacting, e.g., the anion of ⁇ -diketoesters or of ⁇ -diketones on [I.Pt Me3] 4 as described by BRICE J.E. and Coll. in "J. S. Inorg. Chem., 28 (1989), 1".
• the compounds (Ib) are prepared according to the procedure described above for (la), by reacting the anion (eg lithiated, potassium, sodium or thallic) of ⁇ -diketoesters or of ⁇ -diketones of tropolone on [I. Pt.Me3] 4, constituting the ligand Cy.
• anion eg lithiated, potassium, sodium or thallic
• the photosensitive catalyst 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 counterparts in that it consists essentially in reacting compounds A and B in the presence of a catalyst of the type of that in accordance with the invention described above, the initiation of the reaction being carried out by photoactivation.
• the compounds A are chosen from polyorganohydrogensiloxanes comprising: * units of the following formula: H a W b SiO 4 - a + b) (1)
• the symbols W are similar or different and representing a monovalent hydrocarbon group, free of 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, from methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl groups and also among the C6-C12 aryl or aralkyl groups and, advantageously, among the xylyl and totyl and phenyl radicals, all of these groups being optionally halogenated (eg fluorine) and / or hydroxylated and / or alkoxylated.
• - a is 1 or 2
• b is 0, 1 or 2
• the sum (a + b) has a value between 1 and 3
• 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.
• 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 25 ° C, generally of the order from 10 to 5,000 mPa.s at 25 ° C, or gums having a molecular mass of the order of 1,000,000.
• cyclic polyorganosiloxanes consist of "D" units W2Si ⁇ 2 / 2, and WHSi ⁇ 2 / 2, which can 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 of all the silicone polymers mentioned in this presentation can be measured using a BROOKFIELD viscometer, according to AFNOR NFT 76 102 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 W correspond to the same definition as that given above for W
• ⁇ 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 in C1-C20 optionally comprising at least one heteroatom, the more particularly preferred X radicals being: 3-glycidoxy ⁇ ropyl, 4-ethanediyl (1,2-epoxyclohexyl), ...
• ⁇ the symbols Y are similar or different and represent a linear or branched alkenyl residue in Ci -Ci 2 and having at least one ethylenic unsaturation at the end of chain and / or in the chain and optionally at least one heteroatom;
• the reactive polar functions are chosen from the following residues: hydrogen, epoxide, radicals in
• 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.
• linear polymers When linear polymers are involved, these essentially consist of units "D" W2Si ⁇ 2 / 2, Si ⁇ 2 / 2, YSi ⁇ 2 / 2, and "M" W3SiO ⁇ / 2, w “ 2YSiO ⁇ / 2, " 2XSiO ⁇ / 2, 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, methyl-
• 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 10 to 5,000 mPa.s at 25 ° C, or gums having a molecular mass of the order of 1,000,000.
• cyclic polyorganosiloxanes B these consist of units "D" W2Si ⁇ 2 / 2, WSi ⁇ 2 / 2, WYSi ⁇ 2 / 2. which may be of the dialkylsiloxy, alkylarylsiloxy, alkylvinylsiloxy, alkylYsiloxy, alkylXsiloxy type; 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 reaction mixture comprises compounds A and compounds B in an amount such that the Si-H molar ratio / unsaturated groups and / or reactive polar function is between 0.4 and 10, preferably between 1 and 4 and, more preferably still, of the order of 2.5 ⁇ 0.5, the catalyst being present in an amount of 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 catalyst 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 to 5%, preferably 0.5 to 1.5 and, more preferably still, approximately 1% by weight relative to the weight of the compounds A and B used.
• 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.
• the Applicant has had the merit of demonstrating that the addition of at least one surfactant in the reaction medium allows stabilization of the above-mentioned colloidal particles and therefore an optimization of the catalysis of the crosslinking reaction by the complex according to the invention.
• the surfactant is preferably a quaternary ammonium salt, such as tetraoctylammonium bromide, which is an example of a particularly preferred compound.
• this surfactant is present in the reaction medium in a proportion 2 to 15 times, preferably from 5 to 10 times the molar amount of platinum-metal.
• photoactivation preferably takes place in the ultraviolet range.
• thermoactivation is preferably carried out using infrared radiation and it takes place advantageously 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 an energy of triplet greater than or equal to 31 Kcal / mole and selected from (poly) aromatic (possibly 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 lifetime in triplet state of the organometallic complexes of platinum and of the photosensitizer (s) are advantageously of the same order.
• at least one photosensitizer having an energy of triplet greater than or equal to 31 Kcal / mole and selected from (poly) aromatic (possibly 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 lifetime in triplet state
• this composition includes among these constituents at least one surfactant, said agent preferably being a quaternary ammonium salt, tetraoctylammonium bromide being particularly preferred, knowing that the surfactant is present in the medium reaction at a rate of 2 to 15 times, preferably 5 to 10 times the molar amount of platinum-metal.
• surfactant preferably being a quaternary ammonium salt, tetraoctylammonium bromide being particularly preferred, knowing that the surfactant is present in the medium reaction at a rate of 2 to 15 times, preferably 5 to 10 times the molar amount of platinum-metal.
• 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 they offer, in accordance with the process of the invention, 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.
• the 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, minimum or non-filler and / or pigments such as ground synthetic or natural fibers (polymers), calcium carbonate, talc, clay, titanium dioxide or silica. 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.
• catalyst inhibitors such as for example certain polyolefinic siloxanes, pyridine, organic phosphites and phosphines, unsaturated amides, alkylated maleates, acetylenic alcohols (cf. FR-Bl 528 464 and FR-A-2372874).
• acetylenic alcohols inhibiting hydrosilylation reaction can have the formula:
• R is a linear or branched alkyl radical, or a phenyl radical; .
• R 8 is H or a linear or branched alkyl radical, or a phenyl radical; the radicals R 7, R 8 and the carbon atom located at ⁇ of the triple bond which can optionally form a ring; the total number of carbon atoms contained in R 7 and R 8 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 example:
• ⁇ -acetylenic alcohols are commercial products. These inhibitors, also known as 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 hydrosilylation.
• 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.
• 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 allow very high coating speeds to be achieved, due to their very rapid crosslinking kinetics.
• dental impression materials adhesives, sealants, sealants, adhesion primers.
• EXAMPLE 2 KINETICS OF HYDROSILYLATION OF Si-H AND Si-Vi OILS UNDER UV IRRADIATION.
• Silicone oil with Si-H units Me3Si- (SiMe2 ⁇ ) i5 j 6- (SiMeHO) 82-SiMe3, 3 mol% of Si-H units.
• Fig. 1 represents the different kinetics observed for different Pt (IV) catalysts.
• duration of irradiation on the ordinate: variation of the Si-H patterns, arbitrary units.
• the various catalysts tested are of the type (la): [(Z-CO-CH-CO-Z) PtMe3] 2:
• EXAMPLE 3 MEASUREMENT OF THE THERMAL GEL TIME.
• the thermal gel time is determined at 25 ° C.
• the platinum complex to be studied is introduced into the silicone oil with Si-Vi units, then the oil with Si-H units is added.
• the silicone oils used are those described in Example 1.
• the Si-H / Si-Vi molar ratio is 1.7.
• the measurement is carried out protected from light. Table II below collates our results obtained with 100 ppm of Platinum relative to the total mass. TABLE ⁇
• Fig. 2 brings together the results obtained with regard to the kinetics of hydrosilylation of a mixture of silicone oil Si-H / Si-Vi.
• the silicone oils used are identical to those described in Example 1.
• the Si-H / Si-Vi molar ratio is 1.7.
• the tests are carried out at 25 ° C under UV irradiation (medium pressure mercury lamp with a power of 80 W / cm).
• the catalyst used is [(EtO-CO-CH-CO-OEt) PtMe3] 2 (350 ppm platinum / total mass).
• the photosensitizers are introduced into the reaction mass at a rate of 1000 ppm / total mass.
• the film thickness is 24 ⁇ m.
• Fig. 3 shows the influence of adding an amount of aromatic solvent such as toluene or pyridine for the hydrosilytation reaction of silicone oils Si-H / Si-Vi.
• aromatic solvent such as toluene or pyridine
• the Si- H / Si- Vi molar ratio is 1.7.
• the tests are carried out at 25 ° C under UV irradiation (medium pressure mercury lamp with a power of 80 W / cm).
• the catalyst used is [(EtO-CO-CH-CO-OEt) PtMe3] 2 (350 ppm platinum / total mass).
• the film thickness is 24 ⁇ m.
• the solvents tested are: x toluene * pyridine;
• EXAMPLE 6 INFLUENCE OF THE QUANTITY OF CATALYST.
• Fig. 4 represents the influence of the amount of catalyst.
• the catalyst used is [(EtO-CO-CH-CO-OEt) PtMe3] 2 (200-500 ppm platinum / total mass).
• the film thickness is 24 ⁇ m.
• the tests are carried out at 25 ° C under UV irradiation (medium pressure mercury lamp with a power of 80 W / cm).
• the platinum complex is dissolved in a minimum of toluene and this solution is added to a silicone oil with Si-Vi patterns. This mixture is added to a silicone oil with an Si-H motif.
• the Si-H / Si-Vi molar ratio is 1.7.
• EXAMPLE 7 INFLUENCE OF THE NATURE OF SILICON OILS.
• Fig. 5 represents the kinetics of hydrosilylation of a mixture consisting of a silicone oil with Si-H units and a silicone oil with alkenyl units, catalyzed by the [(ETO-CO-CH-CO-OEt) PtMe3 complex ] 2 (350 ppm platinum / total mass).
• the Si-H / Si-Alkenyl molar ratio is 1.7.
• the alkenyl patterned silicone oil has the following formula:
• Fig. 6 represents the kinetics of hydrosilylation of a mixture consisting of a silicone oil with Si-H units and a silicone oil with epoxy units, catalyzed by the PtMe3 complex [(EtO-CO-CH-CO-OEt) ] 2 (350 ppm platinum / total mass).
• the Si-H / Si-Alkenyl molar ratio is 1.7.
• the silicone oil with epoxy patterns has the following formula:
• Fig. 7 shows the influence of the addition of oxygen on the rate of hydrosilylation of a mixture of Si-H / Si-Vi silicone oils, catalyzed by the following platinum complex: [(EtO-CO -CH-CO-OEt) PtMe3] 2 (200 ppm platinum / total mass).
• the silicone oils used are those described in Example 1 in a Si-H / Si-Vi molar ratio of 1.7.
• the catalyst is dissolved in a minimum of dry toluene and added to the silicone oil with Si-Vi units. Oxygen is then bubbled through this mixture (1 min, 25 ° C.) and the silicone oil with Si-H units is then introduced. The test is carried out at 25 ° C under UV irradiation (medium pressure mercury lamp with a power of 80 W / cm). The film thickness is 24 ⁇ m.
• Curve Ci corresponds to the test with O2 and curve C2 constitutes the negative control without O2-
• Fig. 8 represents the influence of the addition of an ammonium salt, for example BrN (n-Octyl) 4 (2000 ppm / total mass), in the reaction medium for hydrosilylation of silicone oils Si- H / Si- Vi.
• the silicone oils used are those described in Example 1.
• the catalyst used is the complex ((EtO-CO-CH-CO-OEt) PtMe3] 2 (350 ppm of platinum / total mass).
• the Si-H / SiVi molar ratio is 1.7.
• the test is carried out at 25 ° C under UV irradiation (medium pressure mercury lamp with a power of 80 W / cm).
• the film thickness is 24 ⁇ m.
• o with (nBu) 4 N® Br®

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• 1994
  • 1994-03-18 FR FR9403440A patent/FR2717481B1/fr not_active Expired - Fee Related
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