CURABLE SILICONE COMPOSITION IN THE PRESENCE OF WATER OR HUMIDITY IN THE AIR

专利摘要:
The invention relates to curable compositions in the presence of water or moisture of the air comprising at least one polyorganosiloxane having one or more condensable or hydrolyzable and condensable group (s) and at least one a compound capable of catalyzing the condensation reaction of the condensable or hydrolyzable and condensable groups of the polyorganosiloxane. This compound is a heterometallic complex whose chemical formula comprises at least two different metal atoms M and M ', M being an atom selected from the group consisting of the atoms of columns 2 and 13 of the periodic table of the elements and M being an atom selected from the group consisting of the atoms of column 4 of the periodic table of the elements, and at least one alkoxide or chelating ligand.
公开号:FR3014106A1
申请号:FR1362008
申请日:2013-12-03
公开日:2015-06-05
发明作者:Vincent Monteil；Roger Spitz；Aurelie Mondiere；Tania Ireland；Anne Seggio
申请人:Centre National de la Recherche Scientifique CNRS；Universite Claude Bernard Lyon 1 UCBL；Bluestar Silicones France SAS；
IPC主号:

专利说明:

[0001] TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel curable composition in the presence of water or moisture of the air, preferably at room temperature, commonly called RTV silicone (for "Room Temperature Vulcanizable"). More specifically, the invention relates to a curable composition in the presence of water or moisture of air comprising at least one polyorganosiloxane A having one or more condensable group (s) or hydrolyzable (s) and condensable (s) ) and at least one compound C which is a heterometallic complex, making it possible to dispense with the use of tin catalyst. BACKGROUND ART Curable silicone formulations preferably at room temperature (or RTV silicones) are manufactured in large tonnages and are used for the production of sealants, gaskets, moldings, adhesives, foams. Typically, these formulations contain a hydroxyl terminated silicone oil, for example an α, - (hydroxydimethylsilyl) -polydimethylsiloxane, optionally prefunctionalized with a silane to have hydrolysable and condensable ends, a crosslinking agent, a polycondensation catalyst, conventionally a tin salt or an alkyl titanate, and optionally various fillers and additives according to the intended end application. These silicone compositions which harden by polymerization and / or crosslinking from room temperature (which may vary between regions between 5 ° and 30 ° C) are well known to those skilled in the art and are classified into two distinct groups: compositions packaged in the form of a "single component" composition (RTV-1), which are in the form of a single part (or component) whose packaging is airtight, and - the packaged compositions in the form of a "two-component" (RTV-2) composition which is in the form of two distinct parts (hence the name "two-component") and whose packaging containing the catalyst is airtight . Airtight packagings are intended to avoid contacting the silicone compositions containing the catalyst with the moisture of the air during storage before use. During the curing which occurs by polymerization and / or crosslinking of these silicone compositions, water is provided by the atmospheric moisture in the case of RTV-1. In the case of RTV-2, dimethyl tin dicarboxylates are commonly used as catalysts, but may require the addition of a quantity of water in one of the parts in order to activate the catalyst and allow the reaction of polycondensation when the contents of the two parts are mixed with the ambient air so as to form the elastomeric network which results in a hardening of the composition. For example, single-component silicone compositions (RTV-1) used as mastics or adhesives cold crosslink according to a mechanism involving a number of reactions that may be successive or simultaneous: A functionalization reaction that results from the presence of a silicone oil having silanol functions, for example a hydroxyl-terminated silicone oil, such as a , - (hydroxydimethylsilyl) -polydimethylsiloxane, with a crosslinking agent, such as an SiX4-type silane (for example a silicate) or a compound having the following function -SiX3 with X being most often an alkoxy, acyloxy, amino, amido, enoxy, aminoxy, cetiminoxy or oxime function. These functions are well known to be reactive with the silanol functions. The resulting product is most often referred to as "functionalized oil". This reaction may be desired directly during the preparation of the composition (in situ functionalization) or possibly as a pre-step before the addition of the other components of the composition. In this pre-step, it is common to use a functionalization catalyst such as lithium hydroxide (lithium hydroxide) or potassium hydroxide to give the one-component composition good storage stability. To do this, the skilled person may choose specific functionalization catalysts and adjust the amount of the reagents so as to be in molar excess of crosslinking relative to silanol functions to be functionalized. - Crosslinking by means of hydrolysis of the functionalized oil generally carried out by virtue of the water vapor diffusing into the material from the surface exposed to the atmosphere, and of a condensation between the silanol groups formed and other residual reactive functions.
[0002] As for the compositions packaged in the form of a two-component composition (RTV-2), the first component (or part) comprises the polyorganosiloxanes capable of polycondensing and the second component, which is airtight, contains the catalyst and one or more crosslinking agents. (s). The two components (or parts) are mixed during use and the mixture cures by crosslinking reactions in the form of a relatively hard elastomer, especially when the composition comprises reinforcing fillers. These compositions packaged in two-component systems are well known and are described in particular in Walter Noll's "Chemistry and Technology of Silicones" 1968, 2nd edition on pages 395 to 398. These compositions most often comprise the following ingredients: a polyorganosiloxane reactive with silanol groups at the end of the chain (for example an α,--di (hydroxydimethylsilyl) (polydimethylsiloxane), in the chain, or both at the end of the chain and in the chain; a crosslinking agent; a condensation catalyst, and optionally water, often present when a dialkyltin dicarboxylate is used as a catalyst, the water acting as an activator for said catalyst, the most well-known catalysts used for decades as well; in the one-component, two-component compositions are tin derivatives, for example alkyltin compounds, such as dilaurate, ibutyltin (DBTDL), which are known for their good efficiency to catalyze crosslinking while being liquid, soluble in silicone and colorless oils. However, they have the disadvantage of being toxic and classified CMR II, toxic for reproduction. The replacement of tin catalysts currently represents a major challenge for the players in this technical field.
[0003] Alternative catalysts have already been proposed in the prior art, including titanium-based catalysts (see, for example, International Patent Application WO 2013/036546). Many other catalysts have been mentioned, for example catalysts based on zinc, scandium, ytterbium, copper, silver, cerium, molybdenum, bismuth, hafnium or guanidine derivatives. The use of zirconium or titanium chelates has been described in particular in the international patent application WO 01/49789. Furthermore, it has been proposed in patent application FR 2 856 694 the use of mixed catalysts consisting of the combination of at least two metal derivatives, the first being a derivative of titanium or zirconium, and the second being a derivative of zinc, aluminum, boron or bismuth. Mixed catalysts are obtained by simply combining several monometallic catalysts at the time of formulation. Even if interesting effects are obtained, in particular in terms of yellowing and adhesion, these metal catalysts do not make it possible to achieve the crosslinking kinetics and the hardnesses of the elastomers obtained with tin catalysts. In this context, one of the objectives of the present invention is to provide novel non-toxic condensation catalysts for replacing tin catalysts.
[0004] These catalysts may advantageously have one or more of the following properties: - be equivalent or more kinetically efficient than tin-based catalysts; allow the elastomers to be cured equivalent or better than that obtained with tin catalysts; - lead to translucent materials, not yellowing over time; - maintain performance in the absence or presence of adhesion promoters.
[0005] BRIEF DESCRIPTION OF THE INVENTION The inventors have discovered that these objectives can be achieved by using heterometallic complexes as catalysts for the condensation reaction of polyorganosiloxanes having condensable or hydrolyzable and condensable groups.
[0006] According to a first aspect, the subject of the invention is a curable composition in the presence of water or moisture of air comprising: (A) at least one polyorganosiloxane A having one or more condensable group (s) or hydrolyzable (s) and condensable (s), and (B) at least one compound C, capable of catalyzing the condensation reaction of the condensable or hydrolyzable and condensable groups of the polyorganosiloxane A, and which is a heterometallic complex whose chemical formula comprises: at least two different metal atoms M and M ', M being an atom selected from the group consisting of the atoms of columns 2 and 13 of the periodic table of elements and M' being an atom selected from the group consisting of the atoms of the column 4 of the periodic table of the elements, and - at least one alkoxide or chelating ligand. According to another aspect, the invention relates to the use of a compound C as defined above and in the present description, as a catalyst for a condensation reaction of a polyorganosiloxane having one or more condensable group (s). (s) or hydrolyzable (s) and condensable (s).
[0007] In particular, the invention also relates to the use of a heterometallic complex according to the invention and as described in the present description as a polycondensation catalyst of polyorganosiloxane capable of curing by polycondensation reaction in a silicone elastomer. Furthermore, it is also an object of the present invention a heterometallic chelate complex whose chemical formula comprises: at least two different metal atoms M and M ', M being an atom selected from the group consisting of the atoms of the columns 2 and 13 of the periodic table of the elements and M being an atom selected from the group consisting of the atoms of column 4 of the periodic table of elements, and 25 - at least one chelating ligand. DETAILED DESCRIPTION OF THE INVENTION It is understood that in the context of this description, the term "between" should be interpreted to include the indicated boundaries.
[0008] The composition according to the invention is a curable composition (also called "vulcanizable") in the presence of water or moisture of the air, commonly called RTV silicone. It comprises, in a conventional manner: at least one polyorganosiloxane A having one or more condensable or hydrolyzable and condensable groups, and at least one compound C according to the invention capable of catalyzing the condensation reaction of the condensable or hydrolysable and condensable groups of the polyorganosiloxane A. Said composition is curable in the presence of water or humidity of the air preferably at room temperature. By "ambient temperature" is preferably meant about 20 ° C. Said compound C is a heterometallic complex whose chemical formula comprises: at least two different metal atoms M and M ', M being an atom selected from the group consisting of the atoms of columns 2 and 13 of the periodic table of elements and M' being an atom selected from the group consisting of the atoms of column 4 of the periodic table of elements, and - at least one alkoxide or chelating ligand. In the present invention, the atoms of columns 2 and 13 of the periodic table of elements are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), boron (B), aluminum (Al), gallium (Ga), indium (In) and thallium (Tl). Preferably, M is a magnesium or aluminum atom. The atoms of column 4 of the periodic table of the elements are titanium (Ti), zirconium (Zr), hafnium (Hf) and rutherfordium (Rf). Preferably, M 'is a titanium or zirconium atom.
[0009] The term "heterometallic complex" refers in the present invention to a polynuclear complex whose chemical formula comprises at least two different metal atoms. According to a preferred embodiment, the compound C is a heterometallic complex whose chemical formula comprises: at least two different metal atoms M and M ', M being a magnesium (Mg) or aluminum (Al) atom, and preferably an aluminum atom (Al), and Me being a titanium atom (Ti) or zirconium (Zr), and - at least one alkoxide or chelating ligand.
[0010] It can therefore preferably be chosen from the group consisting of heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M 'chosen from the following pairs: M is an atom of magnesium (Mg) and M 'is a titanium atom (Ti), - M is a magnesium atom (Mg) and M' is a zirconium atom (Zr), - M is an aluminum atom (Al) and M 'is a titanium atom (Ti), or - M is an aluminum atom (Al) and M' is a zirconium atom (Zr). It is even more preferably selected from the group consisting of heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M 'chosen from the following pairs: M is an atom of aluminum (Al) and M 'is a titanium atom (Ti), or - M is an aluminum atom (Al) and M' is a zirconium atom (Zr). Even more preferably, the compound C according to the invention is chosen from the group consisting of heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two metal atoms M and M ', M being an atom of aluminum (Al) and M 'is a zirconium atom (Zr). The molar ratio of the metal M to the metal M 'can be between 0.1 and 10, and preferably between 0.25 and 4.
[0011] According to a very preferred embodiment, the compound C according to the invention is chosen from the group consisting of: heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M ' M being an aluminum atom and M 'being a zirconium atom and in which the molar ratio Al / Zr is 1; heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M ', M being an aluminum atom and M' being a zirconium atom and in which the Al molar ratio is Zr is 2; heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M ', M being an aluminum atom and M' being a titanium atom and in which the Al molar ratio is / Ti is 1; heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M ', M being an aluminum atom and M' being a titanium atom and in which the Al molar ratio is / Ti is 2; heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M ', M being a magnesium atom and M' being a zirconium atom and in which the molar ratio Mg / Zr is 1; heterometallic complexes whose chemical formula comprises at least one alkoxide or chelating ligand and at least two different metal atoms M and M ', M being a magnesium atom and M' being a titanium atom and in which the molar ratio Mg / Ti is 1. According to a still more preferred embodiment, the compound C is chosen from the group consisting of: heterometallic complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being the aluminum and M 'being zirconium and in which the molar ratio Al / Zr = 0.5, 1 or 2; and at least one alkoxide or chelating ligand; and heterometallic complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being titanium and in which the molar ratio Al / Ti = 1 or 2, and at least one alkoxide or chelating ligand.
[0012] One or more ligands complex the metal atoms. The heterometallic complex according to the invention comprises at least one ligand chosen from an alkoxide ligand or a chelating ligand. The term "alkoxide ligand" refers to a ligand of the chemical formula OR, where R is a C1-C24 alkyl group. Preferably, the alkoxide ligand is a ligand of chemical formula OR, where R is C2-C12 alkyl, and more preferably, R is selected from the group consisting of ethyl, isopropyl, n-propyl n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylhexyl and 2-butyloctyl. The term "chelating ligand" refers to a ligand bound at least two times to one or more metal atoms. The chelating ligand may be selected from bidentate, tridentate or tetradentate chelating ligands, preferably bidentate. A large number of chelating ligands are known to those skilled in the art. In what follows, the chelating ligands are described in their free and neutral form. When they are associated with a central element in a complex, it is possible that these chelating ligands have lost a proton or are in a tautomeric form. Preferably, the chelating ligand is a ligand of general formula (I): (I) in which: each X represents, independently of one another, an oxygen atom or an NR 'group, R' representing a C1 to C8 alkyl group optionally substituted one or more times by a halogen atom and / or an aryl group; R 1 and R 2, independently of one another, represent: a C 1 to C 8 alkyl or cycloalkyl group, optionally substituted one or more times with a halogen atom and / or an aryl group; aryl, optionally substituted one or more times with a halogen atom, - a C1-C8 alkoxide group, optionally substituted one or more times with a halogen atom and / or with an aryl group, - -OH, - - NR "2, each R" representing, independently of one another, a hydrogen atom or a C1-C8 alkyl group optionally substituted one or more times with a halogen atom and / or with an aryl group; R3 represents a monovalent group, preferably a hydrogen atom or a C1-C4 alkyl group.
[0013] Preferably, the chelating ligand is selected from the group consisting of a ligand of the type (3-ketoester, a ligand of the type (3-diester, a ligand of the type (3-diketone, a ligand of the type (3-diacid , a ligand of the type (3-ketoamide and a ligand of the type (3-diimide.) Even more preferably, the chelating ligand is chosen from the group consisting of ethyl acetoacetate, ethyl ethyl acetate, propionyl ethyl acetate, ethyl 2-ethyl acetoacetate, ethyl trifluoro acetoacetate, ethyl t-butyl acetatoacetate, ethyl cyclopropyl acetoacetate, propyl acetoacetonate, acetoketone, ethyl acetate and the like. hexafluoroacetylacetone, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, diisopropylmalonate, acetoacetamide, bis-N, N '- (2-phenylethyl) -2,4-diiminopentane, methyl acrylate, 1,8-diazabicyclo (5.4.0) undec-7-ene and pivaloyl methyl acetate. The heterometallic complex may comprise a single ligand or several ligands. The number and nature of the ligands is adapted to the coordination number of the metal atoms. When the heterometallic complex comprises only a single ligand, it is chosen from an alkoxide ligand and a chelating ligand as defined above.
[0014] When the heterometallic complex comprises several ligands, these may be the same or different. It may be for example several identical or different alkoxide ligands, several identical or different chelating ligands, or a mixture of ligand (s) alkoxide (s) and ligand (s) chelating (s). In addition, other types of ligands may be present.
[0015] Most preferably, the heterometallic complex may comprise one or more oxo (O) ligands, one or more hydroxyl (OH) ligands and / or one or more alcohol ligands. These ligands are likely to be present in particular because of the oligomerization and hydrolysis phenomena of metal complexes with alkoxide ligands. The term "alcohol ligand" refers to a ligand of the chemical formula (C1-C24 alkyl) -OH.
[0016] On the other hand, the heterometallic complex may comprise other neutral ligands. The term "neutral ligand" refers in the present invention to a ligand that coordinates the metal by providing a pair of electrons to the metal. Those skilled in the art will use any type of neutral ligand suitable for the metal concerned. The neutral ligand may be chosen from neutral ligands carrying at least one pair of free electrons such as amines, phosphines, ethers and water, the ligands coordinating via one or more n bonds such as ethylene, and the ligands coordinating via a bond such as H 2. Preferably, the heterometallic complex according to the invention does not comprise any other neutral ligand. Compound C according to the invention may be a heterometallic complex of general formula (II): [M ', M' (Lig1) '(Lig2) y (Lig3) z] (II) in which: the symbol M represents an Mg magnesium atom or Al aluminum; the symbol M 'represents a titanium atom Ti or zirconium Zr; the symbol Lig1 represents an alkoxide ligand; the symbol Lig2 represents a chelating ligand; the symbol Lig3 represents a ligand chosen from the group consisting of: an oxo ligand, a hydroxide ligand, an alcohol ligand and a neutral ligand; and - m, n, x, y and z are numbers such that m> 0, n> 0, x> 0, y> 0, z> 0 and (x + y)> O. In the notation above , the numbers m, n, x, y and z can be integers or not. When dealing with non-integer numbers, it will be understood by those skilled in the art that formula (II) is a general formula based on the composition of the complex and on the molar ratios between the different atoms or atomic groups. Moreover, it is understood in this formula that if x is other than zero, then one or more identical or different LigI ligands may be present, if y is different from zero, then one or more identical or different Lig2 ligands to each other. can be present, and if z is different from zero, then one or more ligands Lig3 identical or different from each other may be present. The numbers m and n may be independently selected from 0 to 20, zero being excluded, and the m / n ratio may be from 0.1 to 10. Preferably, m and n may be independently 1, 2, 3 or 4. In addition, the m / n ratio is preferably between 0.25 and 4. The compound C according to the invention may in particular be chosen from the group consisting of the heterometallic complexes of formulas (IIa) to (IIf ): [Al Zr (Lig1) '(Lig2) y (Lig3) z] (IIa) [Al2 Zr (Lig1)' (Lig2) y (Lig3) z] (IIb) [Al Ti (Lig1) '(Lig2) y (Lig3) z] (IIc) [Al2 Ti (Lig1) '(Lig2) y (Lig3) z] (IId) [Mg Zr (Lig1)' (Lig2) y (Lig3) z] (11e) [Mg Ti] (Lig1) '(Lig2) y (Lig3) z] (IIf) in which Lig1, Lig2, Lig3, x, y and z are as defined above. The heterometallic complex according to the invention comprises at least one Ligl alkoxide ligand or a Lig2 chelating ligand. In the general formula (II), x, y and z are numbers such that x> 0, y> 0, z> 0 and (x + y)> 0. x and y can not therefore be equal to zero in same time. x may be preferably between 0 and 20, and more preferably between 0.1 and 12. y may be preferably between 0 and 20, and more preferably between 2 and 10. z may be included most preferably between 0 and 2. Lig1 is an alkoxide ligand preferably as described above, Lig2 is a chelating ligand preferably as described above and Lig3 is a neutral ligand preferably as described above. Two particularly preferred embodiments are presented below. According to a first particularly preferred embodiment of the present invention, the compound C is a heterometallic alkoxide complex whose chemical formula comprises at least two different metal atoms M and M ', M being a magnesium or aluminum atom and M' being an atom of titanium or zirconium. This complex comprises at least one alkoxide ligand as defined above. The ligands of this complex may be only alkoxides, identical or different from each other, optionally in admixture with one or more ligands chosen from the group consisting of an oxo ligand, a hydroxide ligand and an alcohol ligand. Compound C according to this embodiment may be a heterometallic complex of general formula (II) in which "y" is zero and "x" is other than zero. It is preferably a heterometallic alkoxide complex of general formula (III): [M ', M' (Lig1) '(Lig3) 2] (III) in which: the symbol M represents a magnesium atom Mg or d Al aluminum; the symbol M 'represents a titanium atom Ti or zirconium Zr; the symbol Lig1 represents an alkoxide ligand; the symbol Lig3 represents a ligand chosen from the group consisting of an oxo ligand, a hydroxide ligand and an alcohol ligand; m, n, x, y and z are numbers such that m> 0, n> 0, x> 0 and z> 0. In particular, compound C is a heterometallic alkoxide complex whose chemical formula comprises: minus two different metal atoms M and M ', M being magnesium or aluminum and M being titanium or zirconium, and - at least one alkoxide ligand; and preferably said heterometallic alkoxide complex is selected from the group consisting of: - heterometallic alkoxide complexes whose chemical formula comprises: - at least two different metal atoms M and M ', M being aluminum and M being zirconium, at least one alkoxide ligand of chemical formula 0- (linear or branched C 3 to C 12 alkyl), and in which the molar ratio Al / Zr is equal to 0.5, 1 or 2; the heterometallic alkoxide complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium and M being zirconium, at least one alkoxide ligand of chemical formula O- (linear or branched alkyl) C2 to C12), and - in which the molar ratio Mg / Zr is 0.5, 1, 2, 3 or 4; and heterometallic alkoxide complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being titanium, at least one alkoxide ligand of chemical formula O- linear alkyl or - branched C3 to C12), and - in which the molar ratio Al / Ti is 1 or 2; and even more preferably, said heterometallic alkoxide complex is selected from the group consisting of AlZr (OBu) 4 (OsBu) 3, Al2Zr (OnBu) 4 (OsBu) 6, AlZr 2 (OnBu) 1, AlTi (OsBu) 3 ( 0nBu) 4 and Al2Ti (OnBu) io.
[0017] Certain heterometallic alkoxide complexes according to this embodiment are commercially available. For example, Gelest provides aluminum-titanium, aluminum-zirconium and magnesium-zirconium heterometallic alkoxide complexes. In addition, the heterometallic alkoxide complexes according to this embodiment can be prepared from the corresponding monometallic alkoxides. One possible route of synthesis is to react the monometallic alkoxides together with stirring, preferably without solvent and preferably at room temperature, for a time sufficient for the association reaction to take place. Generally, this reaction is exothermic.
[0018] The desired heterometallic alkoxide complexes can be obtained conventionally by ligand exchange. The exchange of alkoxide ligands can conventionally be carried out by reaction of a first complex with the alcohol corresponding to the desired alkoxide ligand, this alcohol being less volatile than the alcohol corresponding to the ligand of the first complex, optionally in a suitable solvent, with heating and preferably under reduced pressure. According to a second particularly preferred embodiment of the present invention, the compound C is a heterometallic chelate complex whose chemical formula comprises at least two different metal atoms M and M ', M being a magnesium or aluminum atom and M' being an atom of titanium or zirconium. This complex comprises at least one chelating ligand as defined above. The ligands of this complex may be only chelates, identical or different from each other, or one or more chelates mixed with one or more ligands selected from the group consisting of an alkoxide ligand, an oxo ligand, a hydroxide ligand and a ligand alcohol. Compound C according to this embodiment may be a heterometallic complex of general formula (II) in which "y" is other than zero. It is preferably a heterometallic chelate complex of general formula (IV): [M ', M' (Lig1) '(Lig2) y (Lig3) z] (IV) in which: the symbol M represents an Mg magnesium atom or Al aluminum; the symbol M 'represents a titanium atom Ti or zirconium Zr; the symbol Lig1 represents an alkoxide ligand; the symbol Lig2 represents a chelating ligand; the symbol Lig3 represents a ligand chosen from the group consisting of an oxo ligand, a hydroxide ligand and an alcohol ligand; - m, n, x, y and z are numbers such that m> 0, n> 0, x> 0, y> 0 and z> O.
[0019] In particular, compound C is a heterometallic chelate complex whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium or aluminum and M' being titanium or zirconium, and minus a chelate ligand; said heterometallic chelate complex being preferably selected from the group consisting of: - heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being zirconium, at least one chelating ligand, preferably selected from the group consisting of ethyl acetoacetate, propyl acetoacetate and diisopropyl malonate; optionally at least one alkoxide ligand of the chemical formula O- (linear or branched alkyl); C3 or C4), and - having a molar ratio Al / Zr = 1 or 2; heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being zirconium, at least one chelating ligand, preferably chosen from the group consisting of ethyl acetoacetate, propyl acetoacetate and diisopropyl malonate, having a molar ratio Al / Zr = 1 or 2, and not comprising an alkoxide ligand; heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium and M' being zirconium, at least one chelating ligand, preferably ethyl acetoacetate, and having a molar ratio Mg / Zr = 1; heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being titanium, at least one chelating ligand, preferably chosen from the group consisting of ethyl acetoacetate and propyl acetoacetate, optionally at least one alkoxide ligand of chemical formula 0- (linear or branched C 3 or C 4 alkyl), and having a molar ratio Al / Ti = 1; and heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium and M' being titanium, at least one chelating ligand, preferably ethyl acetoacetate, - optionally at least one alkoxide ligand of chemical formula 0- (linear or branched C3 alkyl), and - having a molar ratio Mg / Ti = 1; and even more preferably said heterometallic chelate complex being selected from the group consisting of AlZr (EAA) 3 (OnPr) 4, Al2Zr (EAA) 6 (OnPr) 4, AlZr (EAA) 7, Al2Zr (EAA) io and AlTi (EAA) 3 (0nBu) 4. Some monometallic chelate complexes are commercially available. For example, DuPont Company offers chelated complexes of titanium or zirconium under the name Tyzore. Other monometallic chelate complexes having the desired ligands can be obtained conventionally by ligand exchange. The ligand exchange can conventionally be carried out by reacting a first complex with the precursor corresponding to the desired ligand, optionally in a suitable solvent, with heating and preferably under reduced pressure. The synthesis of the heterometallic chelate complexes can be carried out according to three methods: by a Lewis acid-base reaction by bringing into contact one or more monometallic alkoxide complexes and / or chelates, preferably at ambient temperature and without solvent, during a sufficient time for the association reaction to take place, for example, according to the following reaction scheme: ## EQU1 ## (Lig1) '(Lig2) y (Lig3) z + mM' (Lig1 M'M '', (Lig1) ' (Ligl ')', (Lig2) y (Lig3) z in which M, M ', Lig1, Lig2, Lig3, n, m, x, y and z have the meanings given above, Lig1' represents the alkoxide ligand identical or different from Lig1, x 'is a number such that x'> 0; - By substitution of one or more alkoxide ligands on a heterometallic alkoxide complex with a chelate ligand, for example according to the following reaction scheme: M'M ' (Lig1) (Lig3) z + y Lig2 M'M '', (Lig1) y (Lig2) y (Lig3) z + y Lig1 in which M, M ', Lig1, Lig2, Lig3, n, m, x, y and z on t the meanings given above; - By synthesis in two steps: a) synthesis of a monometallic chelate complex from a monometallic alkoxide complex by ligand exchange with a chelate, for example according to the following reaction scheme: Mn (Lig1) '(Lig3), + ## STR1 ## then the combination of the monometallic chelate complex with a monometallic alkoxide complex based on a different metal, for example according to the following reaction scheme: Mn (Lig1) ', y (Lig2) y (Lig3), + y Lig1b) (Lig1) '(Lig2) y (Lig3), + m IVF (Lig1') ', M'M' ', (Lig1)' (Lig1 ')', (Lig2) y (Lig3), This route of synthesis in two steps can advantageously be monotope ("one-pot"), without isolation of intermediate products. To the inventors' knowledge, no heterometallic chelate complex as described in the present invention has been proposed in the past.
[0020] This is why the present invention also relates to a heterometallic chelate complex comprising: at least two different metal atoms M and M ', M being a magnesium or aluminum atom and M' being a titanium or zirconium atom and - at least one chelate ligand.
[0021] The inventors have discovered that, quite unexpectedly, the heterometallic complexes according to the invention were better catalysts for the condensation reaction of the condensable or hydrolyzable and condensable groups of a polyorganosiloxane, and in particular of the polycondensation reaction of the silicones, than the simple mixture of the corresponding monometallic complexes.
[0022] Compound C as catalyst is present in the curable composition in the presence of water or air humidity according to the invention in catalytic amount. The catalyst concentration in the composition according to the invention may be between 0.1% and 6%, preferably between 1% and 3%, by weight, relative to the total weight of the composition.
[0023] Preferably, the polyorganosiloxane A according to the invention carries at least two groups selected from the group consisting of hydroxy, alkoxy, alkoxy-alkyleneoxy, amino, amido, acylamino, aminoxy, iminoxy, cetiminoxy and acyloxy groups. enoxy. According to a preferred embodiment, the polyorganosiloxane A comprises: (i) at least two siloxyl units of the following formula (V): Râ Zb SiO 4 - (a + b) (V) 2 in which: the symbols R 4, which are identical or different, represent monovalent hydrocarbon radicals C1 to C30, - the symbols Z, identical or different, each represent a hydrolyzable and condensable group or a hydroxyl group, and preferably are selected from the group consisting of hydroxy, alkoxy, alkoxyalkylene groups; -oxy, amino, amido, acylamino, aminoxy, iminoxy, cetiminoxy, acyloxy, iminoxy, cetiminoxy and enoxy, - a is 0, 1 or 2, b is 1, 2 or 3, the sum a + b is equal to 1, 2 or 3, and (ii) optionally one or more siloxyl units of the following formula (VI): SiO 4 -C (VI) 2 in which: the symbols R 5, which are identical or different, represent monovalent hydrocarbon radicals C1 to C30 optionally substituted with one or several halogen atoms or with amino, ether, ester, epoxy, mercapto or cyano groups, and the symbol c is equal to 0, 1, 2 or 3. Preferably, the polyorganosiloxane A has the general formula (VII): ZdR63_d Si -O- (SiR62-0) p-SiR63-dZd (VII) in which: the symbols Z, which are identical or different, each represent a hydrolyzable and condensable group or a hydroxyl group, and preferably are chosen from the group consisting of hydroxy, alkoxy, alkoxy-alkyleneoxy, amino, amido, acylamino, aminoxy, iminoxy, cetiminoxy, acyloxy and enoxy, the symbols R6, which are identical or different, represent optionally substituted monovalent C1 to C30 hydrocarbon radicals. by one or more halogen atoms or by amino, ether, ester, epoxy, mercapto or cyano groups, the symbol d is equal to 1, 2 or 3, preferably equal to 2 or 3, and when Z is a hydroxy group then d = 1, - when the polyor ganosiloxane A is a silicone oil, the symbol p is between 1 and 2000, preferably between 1 and 1000, and when the polyorganosiloxane A is a silicone gum, the symbol p is preferably greater than 2000 and its value is determined from so that the consistency of the gum is between 200 and 2000 according to the standard (es) cited in the present description. In the formulas (V), (VI) and (VII), the symbols R4, R5 and R6 are preferably: alkyl radicals having from 1 to 20 carbon atoms, optionally substituted with one or more aryl or cycloalkyl groups, by one or more halogen atoms or with amino, ether, ester, epoxy, mercapto, cyano or (poly) glycol groups. Mention may be made, for example, of methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, pentafluoro- 4,4,4,3,3 butyl; cycloalkyl and halocycloalkyl radicals having 5 to 13 carbon atoms such as cyclopentyl, cyclohexyl, methylcyclohexyl, propylcyclohexyl, 2,3-difluorocyclobutyl, 3,4-difluoro-5-methylcycloheptyl radicals; mononuclear aryl and haloaryl radicals having from 6 to 13 carbon atoms such as the radicals: phenyl, tolyl, xylyl, chlorophenyl, dichlorophenyl, trichlorophenyl; or alkenyl radicals having from 2 to 8 carbon atoms such as the radicals: vinyl, allyl and butene-2-yl. The viscosity of the polyorganosiloxane A is generally between 50 mPa.s and 1,000,000 mPa.s at 25 ° C. In the case of a silicone rubber, the viscosity of the polyorganosiloxane A is then greater than 1,000,000 mPa.s at 25 ° C. and the consistency of the gum is preferably between 200 and 2,000. the consistency can be made by measuring the penetrability using a penetrometer for example according to AFNOR standards NFT 60 119 or NFT 60 123. The NFT standard 60 123 is particularly suitable for the present description. In the particular case where the polyorganosiloxane A is a polyorganosiloxane of general formula (VII) with hydroxyl-type symbols Z, then the symbol d will preferably be equal to 1. In this case, it is preferred to use poly (dimethylsiloxane) having terminal silanol functions (also called "alpha-omega" positions) and which are generally oils whose viscosity varies, for example, for molding application between 100 mPa.s at 25 ° C. and 20 000 mPa.s at 25 ° C. . It is advantageous to use those in which at least 60% of the radicals R4 and R5 (in the formulas (V) and (VI)) or of the radical R6 (in the formula (VII)) are methyl radicals, the other radicals being generally phenyl and / or vinyl radicals. According to the invention, the symbols Z each represent a hydroxyl group or a hydrolyzable and condensable group which are preferably chosen from the group consisting of alkoxy, alkoxy-alkyleneoxy, amino, amido, acylamino, aminoxy, iminoxy and cetiminoxy groups. , acyloxy and enoxy. When the polyorganosiloxane A has hydrolyzable and condensable Z groups according to the invention and is a polyorganosiloxane, preferably a polydimethylsiloxane with hydrolyzable and condensable Z groups, it is most often described as a functionalised polymer and it corresponds to a stable form. the absence of moisture which can be used in a one-component composition and thus be packaged in hermetically sealed cartridges which will be opened by the operator during use to form after curing a cured elastomer.
[0024] Examples of hydrolyzable and condensable Z groups of alkoxy type include groups having from 1 to 8 carbon atoms such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec- butoxy, tert-butoxy, 2-methoxyethoxy, hexyloxy or octyloxy. As an example of hydrolyzable and condensable groups Z of the alkoxyalkyleneoxy type, mention may be made of the methoxy-ethyleneoxy group. Examples of amino-type hydrolyzable and condensable Z groups that may be mentioned include methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, sec-butylamino or cyclohexylamino groups. As an example of hydrolyzable and condensable groups Z of amido type, mention may be made of the N-methyl-acetamido group.
[0025] As an example of hydrolyzable and condensable groups Z of the acylamino type, mention may be made of the benzoyl-amino group. As examples of aminoxy hydrolyzable and condensable Z groups, mention may be made of dimethylaminoxy, diethylaminoxy, dioctylaminoxy or diphenylaminoxy groups. Examples of hydrolysable and condensable groups Z of the iminoxy type, and in particular cetiminoxy, include the groups derived from the following oximes: acetophenone oxime, acetone oxime, benzophenone oxime, methyl ethyl ketoxime, diisopropyl ketoxy or methyl isobutyl -cétoxime.
[0026] As an example of hydrolyzable and condensable groups Z of the acyloxy type, mention may be made of the acetoxy group. As an example of hydrolyzable and condensable Z groups of enoxy type, mention may be made of the 2-propenoxy group. When the polyorganosiloxane A has hydroxyl-type Z groups, they can then be functionalized in-situ in the one-component compositions, via a functionalization catalyst, so that they can be stored and packaged in hermetically sealed cartridges. Preferably, the functionalization catalyst is lithium hydroxide (lithium hydroxide) or potassium hydroxide. Lithium is largely in commerce. Preferably, it is used in solution in an alcohol, for example methanol or ethanol. The preparation of the polyorganosiloxane A comprising alkoxylated groups by functionalization is described, for example, in the French patent application FR 2,638,752. Preferably, the polyorganosiloxane A has the formula (VIII): (Ra) eROCH2CH2) fOR9b_eSiO R7 Si (Ra) eROCH2CH2) fOR9] 3-e Si 0 R7 (VIII) in which: the substituents R7, which may be identical or different, each represent a substituted or unsubstituted, aliphatic, cyclanic or aromatic saturated monovalent hydrocarbon radical C1 to C13; the substituents R8, which may be identical or different, each represent a substituted or unsubstituted, aliphatic, cyclanic or aromatic, saturated or unsubstituted monovalent hydrocarbon radical C1 to C13; the substituents R 9, which are identical or different, each represent a linear or branched C 1 to C 6 alkyl radical; it has a value sufficient to give the polyorganosiloxane A a dynamic viscosity at 25 ° C ranging from 50 mPa.s to 1,000,000 mPa.s when it is a silicone oil or greater than 1,000,000 mPa.s when it is an eraser, and preferably when it is a silicone oil, the symbol q is between 1 and 2000, and preferably between 1 and 1000, and when it is is a silicone gum, q is preferably greater than 2000 and its value will be determined so that the consistency of the gum is between 200 and 2000 according to the standard (s) cited (s) in the present description; and the index e is equal to zero or 1 and the index f is equal to zero or 1. According to another preferred embodiment, the polyorganosiloxane A comprising at least one alkoxylated group is obtained by reacting, optionally in the presence of a catalytically effective amount of at least one functionalization catalyst: a) at least one polyorganosiloxane A 'comprising siloxyl units of formula (IX): OH SiO4- (9 + h) (IX) 2 Wherein: - x + y = 0, 1, 2 or 3; the substituents R.sup.1, identical or different, each represent a monovalent hydrocarbon radical C1 to C.sub.30 and preferably chosen from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals, and at least two siloxyl units comprising a group = SiOH are present in the polyorganosiloxane A ', with b) at least one polyalkoxylated silane H of formula (X): (R11). If (OR12) (4_ (X) in which: - i = 0 or I, - the symbol RH represents a monovalent hydrocarbon radical C1 to C, 3, and - the symbols R12, which are identical or different, each represent a monovalent radical; C1-C6 hydrocarbon radical or an alkoxyalkyl radical optionally having an ester function As a preferred component, the polyorganosiloxane A comprises the following siloxyl units: M = ROH (R13) 2 SiO 1/2] and D = [R14 R15 SiO2 / 2]; formulas in which RH, R14 and R15 are radicals, which may be identical or different, chosen from the group consisting of linear or branched C 1 -C 6 alkyl radicals (such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl); butyl, n-pentyl, n-hexyl), C3-C5 cycloalkyl radicals (such as cyclopentyl, cyclohexyl), C6-C10 aryl radicals (such as phenyl, naphthyl) and C6-C15 alkylaryl radicals (such as as tolyles, xylyl).
[0027] The polyorganosiloxane A may be a linear polydiorganosiloxane having at least two SiOH silanol groups per molecule and whose dynamic viscosity at 25 ° C is between 50 mPa.s and 50 x 106 mPa.s, preferably between 50 mPa.s and 106 mPa.s in the case of silicone oils, or greater than 106 mPa.s in the case of silicone gums. All the viscosities referred to in the present description correspond to a dynamic viscosity quantity which is measured, in a manner known per se, at 25.degree. When it comes to silicone gums, it is possible to choose those whose consistency is between 200 and 2000. Preferably, the polyorganosiloxane A is chosen from the group consisting of the polyorganosiloxanes of formula (XI): R 17 Si 0 H R 18 r (XI) in which: - a value sufficient to give the polyorganosiloxane of formula (XI) a dynamic viscosity at 25 ° C ranging from 50 mPa.s to 1 000 000 mPa.s when HO25 is concerned; a silicone oil or greater than 1 000 000 mPa.s when it is a silicone rubber, and preferably when it is a silicone oil the symbol r is between 1 and 2000, and preferably between 1 and 1000, and when it is a silicone gum, r is preferably greater than 2000 and its value will be determined so that the consistency of the gum is between 200 and 2000 according to the or the standard (s) cited in this description; R'7 and R'8, which may be identical or different, represent an alkyl having from 1 to 6 carbon atoms, a cycloalkyl having from 3 to 8 carbon atoms, an aryl, an alkylarylene or an arylalkylene.
[0028] Examples of the most useful polyorganosiloxane A, because of their industrial availability, are those for which R '7 and R' 8 are independently selected from the group of radicals consisting of a methyl, an ethyl, a propyl, an isopropyl, a cyclohexyl, phenyl, and 3,3,3-trifluoropropyl. In a very preferred manner, at least about 80% by number of these radicals are methyl radicals.
[0029] Even more preferably, the polyorganosiloxane A is the polyorganosiloxane of formula (XII): CH 3 CH 3 CH 3 (XII) HO-Si-O Si SiCH 3 OH CH 3 C H 3 with 1 s 4200 and preferably 2 s 1500. The Identical or different organic groups generally present in the structure of the polyorganosiloxane A are methyl, ethyl, phenyl or trifluoropropyl radicals. Preferably, at least 80% by number of said organic groups are methyl groups directly attached to the silicon atoms. In the context of the present invention, more particularly α,--bis (dimethylhydroxysilyl) polydimethylsiloxanes are preferred.
[0030] In the context of the present invention, it is especially possible to use the α,--bis (dimethylhydroxysilyl) polydimethylsiloxanes prepared by the anionic polymerization process described in US Pat. Nos. 2,891,920 and 3,294,725.
[0031] The polyorganosiloxane A may also be chosen from organosilicon resins bearing at least one hydroxyl or alkoxy group, groups which are either condensable or hydrolysable, or condensable, which comprise at least two different siloxyl units chosen from those of formula M, D, T and Q with: - the siloxyl unit M = (R °) 3SiO1 / 2, - the siloxyl unit D = (R °) 2SiO2 / 2, - the siloxyl unit T = R ° SiO3 / 2, and - the siloxyl unit Q = SiO4 / 2; formulas in which R ° represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms, and preferably from 1 to 20 carbon atoms, or a ',', -OR group with R = H or an alkyl radical having from 1 to at 40 carbon atoms, and preferably from 1 to 20 carbon atoms; with the proviso that the resins comprise at least one T or Q unit. Said resin preferably has a weight content of hydroxy or alkoxy substituents of between 0.1 and 10% by weight relative to the weight of the resin, and preferably a weight content of hydroxy or alkoxy substituents of between 0.2 and 5% by weight relative to the weight of the resin. The organosilicon resins generally have about 0.001 to 1.5 OH and / or alkoxyl groups per silicon atom. These organosilicon resins are generally prepared by co-hydrolysis and co-condensation of chlorosilanes such as those of formulas (R19) 3SiCl, (R19) 2Si (C1) 2, R19Si (C1) 3 or Si (Cl) 4, radicals R19 being identical or different and generally chosen from linear or branched C1-C6 alkyl, phenyl and 3,3,3-trifluoropropyl radicals. Examples of alkyl radicals R19 include methyl, ethyl, isopropyl, tert-butyl and n-hexyl. As an example of a resin, mention may be made of T (OH), Dem, Dem, mem, mDem, mDem type silicic resins or mixtures thereof. The composition according to the invention may further contain a crosslinking agent B. The crosslinking agent is preferably an organosilicon compound carrying, by molecule, more than two hydrolyzable groups bonded to the silicon atoms. Such crosslinking agents are well known to those skilled in the art and are commercially available.
[0032] The crosslinking agent B is preferably a silicon compound in which each molecule comprises at least three hydrolyzable and condensable Y groups, said crosslinking agent B having the following formula (XIII): R20 (4_i) Siyi (XIII) in which - the symbol R2 ° is a monovalent hydrocarbon radical comprising from 1 to 30 carbon atoms, the symbols Y, which are identical or different, are chosen from the group consisting of the alkoxy, alkoxyalkyleneoxy, amino, amido and acylamino groups; aminoxy, iminoxy, cetiminoxy, acyloxy or enoxy, and preferably Y is an alkoxy, acyloxy, enoxy, cetiminoxy or oxime group, - the symbol j = 2, 3 or 4, and preferably j = 3 or 4. Examples of groups Y are the same as those mentioned above when the symbol Z is a hydrolyzable and condensable group, that is to say different from a hydroxyl group. The crosslinking agents B are products that are accessible on the silicone market. In addition, their use in compositions curing at room temperature is known. It appears in particular in the French patents FR 1 126 411, FR 1 179 969, FR 1 189 216, FR 1 198 749, FR 1 248 826, FR 1 314 649, FR 1 423 477, FR 1 432 799 and FR 2 067. 636. The crosslinking agent B has at least one hydrolyzable group such as: acyloxy of formula -O-CO-R ", alkoxy of formula -O-R ', amino of formula -NR21R22, amido of formula -NR21COR22, alkenyloxy of formula -O-CR21 = CHR22, aminoxy of formula -O-NR21R22, -O-N = CT - cetiminoxy of formula -O-N = CR21R 22 or in which R "" represents an alkyl or aryl radical having from 1 to 15 carbon atoms, R21 and R22, which may be identical or different, represent alkyl or aryl radicals containing from 1 to 8 carbon atoms and T represents an alkylene radical containing from 4 to 8 carbon atoms, among the radicals R ', Ril and R22, Mention may in particular be made of methyl, ethyl, cyclohexyl and phenyl radicals. Among the radicals T, mention may be made especially of those of formula: - (CH 2) 4 -, - (CH 2) 5- and - (CH 2) 6 -.
[0033] By way of other examples of crosslinking agent B, mention may be made of the alkoxysilanes and the partial hydrolysis products of this silane of the following general formula (XIV): R23k si (oR24) (4_k) (XIV) in which: the symbols R 23, which are identical or different, represent alkyl radicals having from 1 to 8 carbon atoms, such as the methyl, ethyl, propyl, butyl, pentyl, ethyl-2-hexyl, octyl and decyl radicals, and the C 3 oxyalkylene radicals; -C6, - the symbol R24 represents a linear or branched, saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated and / or aromatic, monocyclic or polycyclic carbocyclic group, and - k is equal to 0, 1 or 2. As an example C3-C6 oxyalkylene radicals include the following radicals: - CH3OCH2CH2- CH3OCH2CH (CH3) - CH3OCH (CH3) CH2- - CH2 -CH2- -2-2- _2- The acyloxysilane crosslinking agents have been well known for a long time. They are described in particular in patents US 3,077,465, US 3,382,205, US 3,701,753, US 3,957,714, US 4,115,356, US 4,273,698, FR 2,429,811 and FR 2,459,820. Examples of alkoxysilanes include those of the formula: Si (OCH 3) 4 Si (OCH 2 CH 3) 4 Si (OCH 2 CH 2 CH 3) 4 (CH 3 O) 3 SiCH 3 (C 2 H 5 O) 3 SiCH 3 (CH 3 O) 3 Si (CH = CH 2) (C 2 H 5 O) 3 Si ( CH = CH2) (CH3O) 3 Si (CH2-CH = CH2) (CH3O) 3Si [CH2- (CH3) C = CH2] (C2H50) 3 Si (OCH3) Si (OCH2-CH2-OCH3) 4 CH3Si (OCH2) -CH2-OCH3) 3 (CH2 = CH) Si (OCH2CH2OCH3) 3 C6H5Si (OCH3) 3 C6H5Si (OCH2-CH2-OCH3) 3. Cetiminoxysilane crosslinking agents have been well known for a long time. They are described, for example, in French patents FR 1,314,649, FR 1,371,250, US Pat. No. 3,678,003 and US Pat. No. 3,986,999, British Patent GB 1,468,467, Belgian Patent BE 901,479, and US Pat. EP 157 580. By way of example of cetiminoxysilanes, mention may be made of those of formula: ## STR5 ## C (CH3) C2H5] 3 C6H5S4O-N = C (CH3) 213 CH3Si [-ON = C (C2H5) (CH2) 3CH3] 3 [(CH3) 2C = N-O-] Si [-ON = C (CH3) C2H5] 3 CH3Si [-ON = C (CH3CH (C2H5) (CH2) 3CH3] 3 CH3Si [-ON = C (CH3CH (C2H5) (CH2) 3CH3] 3 H3C-Si N = C (CH2) 4 ## STR2 ## By way of example of acyloxysilanes, mention may be made of those of formula: ## STR2 ## C6H5Si (OCOCH3) 3 CH3Si [OCOCH (C2H5) - (CH2) 3-CH3] 3 3 CF3CH2CH2Si (OCOC6H5) 3 CH3 Si (OCOCH3) 2 [OCOH (C2H5) - (CH2) 3 -CH3] CH3COOSi [OCOCH ( C2H5) - (CH2) 3 -CH3] Other examples of crosslinking agent B include ethyl polysilicate, or n-propyl polysilicate. crosslinking B, alkoxysilanes, cetiminoxysilanes, alkyl silicates and alkyl polysilicates are more particularly preferred, in which the organic radicals are alkyl radicals having from 1 to 4 carbon atoms. Preferably, the following crosslinking agents B are preferred, which may be used alone or in admixture: ethyl polysilicate and n-propyl polysilicate; alkoxysilanes such as dialkoxysilanes, for example dialkyldialkoxysilanes, trialkoxysilanes, for example alkyltrialkoxysilanes, and tetraalkoxysilanes, and preferably propyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane and isobutyltriethoxysilane; propyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, tetraisopropoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and those of the following formulas: ## STR2 ## than the following acetoxysilanes: tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinylt riacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane, octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane and tetraacetoxysilane; silanes comprising alkoxy and acetoxy groups such as: methyl diacetoxymethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane and methylacetoxydiethoxysilane, methyltris (methylethylketoximo) silane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3- (glycidyloxy) propyltriethoxysilane, vinyltris (methylethylketoximo) silane, tetra-kis (methyl ethyl ketoximino) silane. From 0.1 to 60 parts by weight of crosslinking agent B is generally used per 100 parts by weight of polyorganosiloxane A. Preferably from 0.5 to 15 parts by weight are used per 100 parts by weight of polyorganosiloxane A. The composition according to the invention may also comprise at least one charge D. The charges that may be provided are preferably mineral. They can be especially siliceous. As for siliceous materials, they can act as reinforcing or semi-reinforcing filler. The reinforcing siliceous fillers are chosen from colloidal silicas, silica powders for combustion and precipitation, or mixtures thereof. These powders have an average particle size generally less than 0.1 μm (micrometers) and a BET specific surface area greater than 30 m 2 / g, preferably between 30 and 350 m 2 / g. Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used. In the case of non-siliceous mineral materials, they can be used as semi-reinforcing mineral filler or stuffing. Examples of these non-siliceous fillers that may be used alone or in admixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, unexpanded vermiculite, calcium carbonate, calcium carbonate and the like. zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime. These fillers have a particle size generally of between 0.001 and 300 μm (micrometers) and a BET surface area of less than 100 m 2 / g. In a practical but nonlimiting manner, the fillers used may be a mixture of quartz and silica. Charges can be processed by any suitable product. In terms of weight, it is preferred to use a filler quantity of between 1% and 50% by weight, preferably between 1% and 40% by weight relative to all the constituents of the composition. In the case of calcium carbonate, this filler may be a chemically obtained synthetic calcium carbonate better known as "precipitated calcium carbonate" or a ground natural calcium carbonate prepared, for example, from chalk , calcite, marble or from their mixture. These two families of calcium carbonate may have undergone a nonreactive surface treatment. This type of treatment involves covering the surface of the charges with an organic substance. Among such useful organic compounds, fatty acids and especially stearic acid or a salt thereof are preferred. A useful calcium carbonate may also result from a reactive surface treatment carried out by means of coupling agents such as organotrialkoxysilanes which are very widely used as coupling agents. Preferably, the ground natural calcium carbonate has a specific surface area strictly less than 3 m 2 / g, measured according to the BET method and has been surface-treated with at least one fatty acid containing from 10 to 24 carbon atoms or its respective salt. selected from calcium, magnesium, zinc salts or their mixture and preferably has been surface-treated with a stearic acid or its respective salt of calcium, magnesium or zinc. Preferably, the amount of crushed natural calcium carbonate added to the composition is between 1 and 100 parts by weight relative to the total weight of the composition according to the invention. In combination with these fillers can be used inorganic and / or organic pigments as well as agents improving the thermal resistance (salts and oxides of rare earths such as ceric oxides and hydroxides) and / or the flame resistance of the elastomers. For example, the oxide cocktails disclosed in International Application WO 98/29488 may be used. Among the agents improving the flame resistance can be mentioned halogenated organic derivatives, organic phosphorus derivatives, platinum derivatives such as chloroplatinic acid (its reaction products with alkanols, ether-oxides), complexes platinum chloride-olefins. These pigments and agents together represent at most 20% of the weight of the charges. The composition according to the invention may also comprise at least one adhesion promoter E such as, for example, organosilicon compounds bearing both: one or more hydrolysable groups bonded to the silicon atom, and one or more organic groups substituted by radicals comprising a nitrogen atom or chosen from the group of (meth) acrylate, epoxy and alkenyl radicals, and even more preferably from the group consisting of the following compounds taken alone or as a mixture: vinyltrimethoxysilane (VTMO), 3-glycidoxypropyltrimethoxysilane (GLYMO), methacryloxypropyltrimethoxysilane (MEMO), [H2N (CH2) 3] Si (OCH2CH2CH3) 3, [H2N (CH2) 3] Si (OCH3) 3 [H2N (CH2) 3] Si (OC2H5) 3 [H2N (CH2) 4] Si (OCH3) 3 [H2NCH2CH (CH3) CH2CH2] SiCH3 (OCH3) 2 [H2NCH2] Si (OCE13) 3 [n-C4H9-HN-CH2] Si (OCH3) 3 [H2N CH2) 2NH (CH2) 3] Si (OCE13) 3 [H2N (CH2) 2NH (CH2) 3] Si (OCH2CH2OCH3) 3 [CH3NH (CH2) 2NH (CH2) 3] Si (OCE13) 3 [H2N (NHCH2CH2) 2NH (CH2) 3] If (OCE13) 3H2N- (CH2) -NH- (CH2) 3-Si- (OCH3) 2 O-CH (CH2) CHOCH3 F-12N- (C1- 12) -N1-1- (C1-12) 3-SI- (OC1-13) 2 CH = C1-12 The adhesion promoter E may be present in the silicone composition according to the invention in an amount of between 0% and 20% by weight, preferably between 1% and 20% by weight, relative to the weight of the polyorganosiloxane A. In addition to the main constituents, linear non-reactive polyorganosiloxane polymers F can be introduced with the intention of acting on the physical characteristics of the compositions in accordance with the invention and / or the mechanical properties of the elastomers resulting from the hardening of these compositions. These non-reactive linear polyorganosiloxane polymers F are well known; they more particularly comprise: α, β-bis (triorganosiloxy) diorganopolysiloxane polymers having viscosities of at least 10 mPa.s at 25 ° C., formed essentially of diorganosiloxy units and at most 1% of monoorganosiloxy and / or siloxy units; , the organic radicals bonded to the silicon atoms being chosen from methyl, vinyl and phenyl radicals. Preferably, at least 60% of these organic radicals are methyl radicals and 10% at most are vinyl radicals. The viscosity of these polymers can be between 10 mPa.s and 106 mPa.s at 25 ° C; it is then more or less viscous silicone oils (silicone oils). When the viscosity is greater than 106 mPa.s, they are described as silicone gums. It is preferable to choose those whose consistency is between 200 and 2000. They therefore include viscous to viscous oils and hard soft gums. They are prepared according to the usual techniques described more precisely in the French patents FR 978 058, FR 1 025 150, FR 1 108 764, FR 1 370 884. It is preferable to use α, β-bis (trimethylsiloxy) dimethylpolysiloxane viscosity oils. ranging from 10 mPa.s to 1000 mPa.s at 25 ° C. These polymers that act as plasticizers can be introduced in a proportion of at most 70 parts by weight, preferably 5 to 20 parts by weight per 100 parts by weight of the polyorganosiloxane A. Other auxiliary agents and customary additives can be used. incorporated in the composition according to the invention. These are chosen according to the applications in which said compositions are used. The composition according to the invention may comprise the following amounts: - per 100 parts by weight of at least one polyorganosiloxane A as described above, - from 0.1 to 60 parts by weight, preferably from 1 to 15 parts by weight of at least one crosslinking agent B, - a catalytically effective amount of at least one compound C according to the invention and as described above, - from 0 to 150 parts by weight of at least one filler D, and preferably from 0.1 to 150 parts by weight, from 0 to 20 parts by weight of at least one adhesion promoter E, and preferably from 0.1 to 20 parts by weight, and 0 to 150 parts by weight of at least one non-reactive linear polyorganosiloxane polymer F, and preferably from 1 to 150 parts by weight.
[0034] The compositions of the invention may further comprise conventional functional additives. As families of usual functional additives, mention may be made of: - adhesion modulators, - additives for increasing the consistency, - pigments, - additives for heat resistance, oil resistance or fire resistance, for example metal oxides.
[0035] More generally, in terms of quantity, the compositions according to the invention may have standard proportions in the technical field considered, knowing that one must also take into account the intended application. According to another embodiment, the composition according to the invention does not contain a catalyst having in its structure at least one tin atom. According to another variant of the invention, compound C is the only polycondensation catalyst present in said composition which may optionally contain at least one functionalization catalyst. According to another embodiment, the invention relates to a single-component composition RTV-1 in a single airtight package P comprising: a) at least one polyorganosiloxane A as defined above, b) at minus a crosslinking agent B as defined above, c) a catalytically effective amount of at least one compound C as defined above, and d) optionally at least one D load. The one-component RTV-1 composition is in one part. It is storage stable in the absence of water and hardens in the presence of water to form an elastomer. It can be manufactured by mixing the various components away from moisture, with or without heating. The catalyst is preferably incorporated at the end. Preferably, the mixture is carried out under reduced pressure to promote the departure of volatile materials. Thus stored in a confined environment and protected from the presence of water and moisture in the air, the one-component RTV-1 composition is stable for storage for several months. The single component compositions RTV-1 according to the invention are used as such, that is to say undiluted, or in the form of dispersions in diluents, and are storage stable in the absence of moisture. or water and harden at low temperatures (after leaving solvents in the case of dispersions) in the presence of water to form elastomers. One-component RTV-1 compositions are described in detail in, for example, EP 141,685, EP 147,323, EP 102,268, EP 21,859, FR 2,121,289 and FR 2,121,631.
[0036] After the deposition of the compositions according to the invention, prepared from a single-component RTV-1 composition, on solid substrates in a humid atmosphere, it is found that an elastomeric hardening process is used. It is carried out from the outside inside the deposited mass. A skin is first formed on the surface and then crosslinking continues in depth and results in a hardening of the silicone elastomer. The complete formation of the skin, which results in a non-sticky touch of the surface, requires a period of time of a few minutes, this period depending on the relative humidity of the atmosphere surrounding the compositions and the ability of crosslinking of these. The deposited layer may have a variable thickness, generally between 0.15 mm and several centimeters, preferably between 1 mm and 1 cm. Furthermore, the deep curing of the deposited layers, which must be sufficient to allow the demolding and handling of elastomers formed, requires a longer period of time. Indeed, this period depends not only on the factors mentioned above for the formation of non-sticky touch but also on the thickness of the deposited layers, which thickness generally ranges between 0.5 mm and several centimeters. Single-component compositions can be used for multiple applications such as grouting in the building industry, assembly of various materials (metals, plastics, natural and synthetic rubbers, wood, cardboard, earthenware, brick, ceramic, glass , stone, concrete, masonry), insulation of electrical conductors, encapsulation of electronic circuits, preparation of molds for the manufacture of resins or synthetic foams. Another subject of the invention relates to a two-component RTV-2 composition, a precursor of the composition according to the invention and as defined above, in two separate packages P1 and P2, characterized in that: a) packaging P1 is airtight and comprises: a catalytically effective amount of at least one compound C according to the invention and as defined above, and at least one crosslinking agent B as defined above, and b) the package P2 contains neither said compound C nor said crosslinking agent B and comprises: per 100 parts by weight of at least one polyorganosiloxane A as defined above, and - from 0 to 10 parts (s) ) by weight of water. A two-component RTV-2 composition is in two separate packages: Pl which contains the catalyst and is airtight and P2. They are conditioned after incorporation of the catalyst into two separate fractions, one of the fractions being able to contain, for example, only the catalyst according to the invention or a mixture with the crosslinking agent. The RTV-2 bicomponent compositions according to the invention are also produced by mixing the various constituents in suitable apparatus. RTV-2 bicomponent compositions are described in detail, for example, in patents EP 118,325, EP 117,772, EP 10,478, EP 50,358, EP 184,966, US 3,801,572 and US 3,888,815, cited as references. The two-component RTV-2 composition makes it possible, after mixing the two parts P1 and P2, to obtain the composition according to the invention. This is a "precursor" composition of the composition according to the invention. Each part of the two-component RTV-2 composition can be manufactured by mixing the various constituents. Both parts can be stored and marketed as a kit. In use, the two parts are mixed, and this mixture can be deposited on a solid substrate. The deposited layer may have a variable thickness, generally between 0.15 mm and several centimeters, preferably between 1 mm and 1 cm. The placing in contact with the polyorganosiloxane A, with water and with the compound C which acts as catalyst triggers the reactions leading to the hardening of the composition until an entirely hard elastomer is obtained. The composition according to the invention advantageously has a kinetics of hardening comparable to that of the compositions currently available on the market containing a tin-based catalyst, both in terms of speed of skin formation and rate of hardening in depth. In addition, advantageously, the performance of this composition is not modified by the presence of adhesion promoter. The compositions according to the invention are particularly useful for molding applications, particularly when in the form of two-component RTV-2.
[0037] For the implementation of the compositions according to the invention in this application, the techniques of casting or application via a spatula, a brush or by spraying are useful.
[0038] As an example of a molding technique, mention may be made of: the "boat molding" which is intended for the manufacture of self-supporting molds, in one or more pieces, by simple casting of the composition after mixing the two parts of the RTV-2 with the liquid state on the initial model. This method is preferred for relatively simple forms and without large spoils; - "one- or two-part" screeding, and - "stamping-molding" which is preferred for taking impressions of inclined, vertical or overhanging patterns, usually of large dimensions or where it is impossible to move the model.
[0039] Another object of the invention relates to a silicone elastomer obtained: after allowing to cure in the presence of water or moisture of the air the composition according to the invention and as described above; or - after having brought into contact with the humidity of the air the contents of the package P of the one-component composition RTV-1 according to the invention and as described above and allowed to harden said content; or - after mixing the contents of the packaging P1 and P2 of the two-component RTV-2 composition according to the invention and as described above and let the mixture harden. The silicone elastomer obtained advantageously has a hardness at least equivalent to that of the elastomers obtained from compositions containing a tin-based catalyst. They can also be translucent and not yellow over time. Another subject of the invention relates to a method of coating the composition according to the invention and as defined above on a flexible support S comprising the following steps a), b) and c): a) preparing a composition according to the invention and as defined above, b) then is deposited continuously or discontinuously said composition on said flexible support S, and c) is allowed to cure said silicone composition according to the invention in the presence of moisture provided by ambient air or by the addition of water so as to form a silicone elastomer. According to a variant of the process according to the invention, the composition in step a) is prepared after mixing the contents of the packages P1 and P2 of the two-component RTV-2 composition according to the invention and as defined above. or from the contents of the package P of the one-component composition RTV-1 according to the invention and as defined above. The coating of silicone compositions according to the invention on flexible supports has many applications. For example, when the flexible support is a textile, waterproofing properties are targeted or when the support is a paper or a polymer type PVC, PET ..., anti-adhesion properties are most often sought. Thus, once applied on a support, the silicone composition according to the invention cures thanks to the humidity of the air and / or by the presence of water in the composition to form a solid silicone elastomer coating. In these liquid silicone coating compositions, the silicone phase can be diluted in a solvent. The flexible supports S coated with a silicone film or a silicone layer cured by non-adhering crosslinking are preferably chosen from the group consisting of the supports made of textile, paper, polyvinyl chloride, polyester, polypropylene, polyamide, polyethylene, polyurethane or polyethylene terephthalate. For the purposes of the invention, the term "textile" means a generic term encompassing all textile structures. The textiles may be made of yarns, fibers, filaments and / or other materials. They include soft fabrics, whether woven, glued, knitted, braided, felt, needled, sewn, or made by another method of manufacture. These textiles can be openwork, that is to say include free spaces not made of textile. In order for the coating of the silicone composition of the invention to be effective, it is preferable for the smallest dimension of these free spaces to be less than 5 mm, especially less than 1 mm. According to the invention, any type of flexible support S textile can be used. As an indication, mention may be made of: natural textiles, such as textiles of plant origin, such as cotton, linen, hemp, jute, coconut, cellulosic fibers of paper; and textiles of animal origin, such as wool, hair, leather and silks; - artificial textiles, such as cellulosic textiles, such as cellulose or its derivatives; and protein textiles of animal or vegetable origin; and synthetic textiles, such as polyester, polyamide, polymallic alcohols, polyvinyl chloride, polyacrylonitrile, polyolefins, acrylonitrile, (meth) acrylate-butadiene-styrene copolymers and polyurethane. Synthetic textiles obtained by polymerization or polycondensation can include in their matrices in particular different types of additives, such as pigments, delusterants, mattifying agents, catalysts, thermal and / or light stabilizers, anti-static agents, flame retardants antibacterial, antifungal and / or anti-mite agents. As a type of flexible supports in textile, mention may be made in particular of the supports obtained by rectilinear intertwining of the yarns or fabrics, the supports obtained by curvilinear interweaving of the yarns or knits, the mixed or tilted surfaces, the nonwoven supports and the composite supports. Among the multitude of possible textile supports used in the process of the invention may be mentioned: felts, denims, jacquard weaves, needles, sewn, crocheted, grenadines, lace and serrated, damask, sails, alpacas, baratheas, basins, buckles, brocades, calico, velvet, canvas, rags, flocked, glue, stamens, braids, faults, scarves, gauzes, geotextiles, jaspés, quilts, tufted, organzas, pleats, ribbons and canvases. The textile flexible support S used in the process of the present invention may consist of one or more identical or different textiles assembled in various ways. The textile can be mono- or multilayer (s). The textile support may for example consist of a multilayer structure that can be produced by various assembly means, such as mechanical means such as sewing, welding, or spot or continuous bonding. The flexible support S of textile may, in addition to the coating process according to the present invention, undergo one or more other treatments, also called finishing or finishing treatment. These other treatments can be carried out before, after and / or during said coating process of the invention. Other treatments that may be mentioned include: dyeing, printing, counter-gluing, coating, assembly with other textile materials or surfaces, washing, degreasing, preforming or fixing. According to a preferred embodiment of the invention, the flexible support S textile is a lace or an elastic band.
[0040] The textiles thus obtained, as such, or transformed into textile articles, can be used in many applications, such as, for example, in the field of clothing, in particular lingerie such as lace up stockings or bra , and hygiene items, such as bandages or bandages. These textile articles can be repositioned at different locations of the body or a garment for example thanks to the adhesion provided by the silicone elastomer. In practice, the deposition rate of the composition according to the invention on the flexible support S is between 0.1 g / m 2 and 1 g / m 2, preferably 0.3 g / m 2 and 0.5 g / m 2, which corresponds to thicknesses of the order of a micrometer. Other objects, features and advantages of the invention will become apparent from the following examples, which are given purely by way of illustration and in no way limitative. EXAMPLES Notation: OsBu: sec-butanolate OnBu: n-butanolate OtBu: tert-butanolate OBO: 2-butyloctanolate 0C4H9: butanolate (mixture of linear and branched compounds) OEH: 2-ethylhexanolate OEt: ethanolate OiPr: iso-propanolate OnPr: n -propanolate OPr2Me: 2-methylpropan-1-olate EAA: ethyl acetoacetate EEA: ethyl ethyl acetate EPA: propionyl ethyl acetate E2EA: ethyl 2-ethyl acetoacetate F.EEA: ethyl trifluoroacetoacetate t AEA: ethyl t-butyl acetatoacetate C4EA: ethyl cyclopropyl acetoacetate PrOH: propanol PAA: propyl acetoacetonate EPAA: ethyl propionyl acetoacetate acac: acetylacetone F.acac.F: hexafluoroacetylacetone Ph.acac.F: 4, 4,4-Trifluoro-1-phenyl-1,3-butanedione Ph.acac.Ph: 1,3-diphenyl-1,3-propanedione t.acac: 2,2,6,6-tetramethyl-3,5- heptanedione diPrm: diisopropylmalonate Aamid: acetoacetamide NacNac: bis-N, N '- (2-phenylethyl) -2,4-diiminopentane MA: methyl acrylate DBU: 1,8-diazabicyclo (5.4.0) undec-7-ene Example 1: Synthesis and analysis of the heterometallic alkoxide complex A1Ti (OsBu) 3 (InBu) 4 Al (OsBu) 3 and Ti (OnBu) 4 monometallic alkoxides have were ordered from Sigma-Aldrich and were used upon receipt. Al (OsBu) 3 and Ti (OnBu) 4 were mixed in the molar proportions of 1 mole per 1 mole and stirred for 2 hours at room temperature. The oil obtained quantitatively was then characterized by infrared. In the spectrum of the heterometallic complex, two very intense new bands were found at 1035.8 cm-1 and 996.2 cm-1, which correspond to the vibrations of the C-O bonds with an aluminum atom and a titanium atom in their chemical environment. The 611.7 cm-1 and 515.2 cm-1 bands, also very intense, correspond to the vibrations of the metal-O bonds in the sequence A1-0-Ti. The other bands of medium or low intensity correspond to the bands visible in the starting products, but with different resonance frequencies. These modifications show a new chemical environment around Al and Ti metals, and thus the creation of a new chemical species. EXAMPLE 2 Synthesis of Heterometallic Alkoxide Complexes A series of heterometallic alkoxide complexes was prepared according to the following method: Al (AlBu) 3, Al (OsBu) 3, Al (OBO) 3 Al (OiPr) Al monometallic alkoxides 3, Al (OEH) 3, magnesium Mg (0EO2, Mg (OBO) 2, zirconium Zr (OnBu) 4, Zr (OBO) 4, Zr (OnBu) 4, Zr (OnPr) 4, Zr (OEH) 4, Zr (OEt) 4 and titanium Ti (OBO) 4, Ti (OnBu) 4, Ti (OiPr) 4 and Ti (OEH) 4, are from Sigma-Aldrich and were used upon receipt or concentrated under reduced pressure. The monometallic alkoxide species selected according to the desired complex were mixed in the desired molar proportions and stirred for 2 hours at room temperature An oil was obtained quantitatively.
[0041] Below is the list of synthetized heterometallic complexes. The general formulas indicated represent the composition of the complex and the molar ratios between the different atoms or atomic groups as they should be according to the composition of the reaction medium and assuming that the reactions are total. One skilled in the art will of course understand that the reaction products obtained can deviate from these general formulas. Aluminum-zirconium complexes A1Zr (OnBu) 7 A1Zr (OBO) 7 A1Zr (OsBu) 3 (OnBu) 4 A10,7Zr (OsBu) 2,1 (InBu) 4 A10,8Zr (OsBu) 2,4 (OnBu) 4 A10 , 9Zr (OsBu) 2.7 (OnBu) 4 Al jZr (OsBu) 3.3 (OnBu) 4 A10.1Zr (OsBu) 0.3 (InBu) 4 35 A11.2Zr (OsBu) 3.6 (0nBu) 4 A10.2Zr (OsBu) 0.6 (0nBu) 4 A10.3Zr (OsBu) 0.9 (0nBu) 4 A10.4Zr (OsBu) 1.2 (0nBu) 4 Alo, 5Zr (OsBu) i, 5 ( OnBu) 4 A11.3Zr (OsBu) 3.9 (InBu) 4 A11.4Zr (OsBu) 4.2 (InBu) 4 A11.5Zr (OsBu) 4.5 (InBu) 4 A11.6Zr (OsBu) 4, 8 (InBu) 4 A10.6Zr (OsBu) 1.8 (InBu) 4 10 15 45 50 55 AluZr (OsBu) 5.1 (InBu) 4 A11.8Zr (OsBu) 5.4 (InBu) 4 A11.9Zr (OsBu) 5.7 (0nBu) 4 AlZro, i (OsBu) 3 (OnBu) o, 4 AlZr0.2 (0sBu) 3 (0nBu) o, 8 AlZr0.3 (0sBu) 3 (0nBu) 1.2 AlZr0 , 4 (0sBu) 3 (0nBu) 1.6 AlZr0.5 (0sBu) 3 (0nBu) 2 AlZr0.6 (0sBu) 3 (0nBu) 2.4 Magnesium-zirconium complexes: MgZr (OEt) 6 20 MgZr (OBO) ) Mg2Zr (0E08 Mg3Zr (0E010 Mg4Zr (OE-012 MgZr2 (OEt) ii Aluminum-titanium complexes: AlTi (OB0) 7 AlTi (OsBu) 3 (0nBu) 4 Alo, iTi (0 sBu) 0.3 (OnBu) ) 4 A10.2Ti (OsBu) 0.6 (InBu) 4 30 A1o, 3Ti (OsBu) o, 9 (InBu) 4 A10.4Ti (OsBu) 1.2 (InBu) 4 A10.5Ti (OsBu) 1, 5 (0nBu) 4 A10.6Ti (OsBu) 1.8 (0nBu) 4 A10.7Ti (OsBu) 2.1 (0n Bu) 4 Alo, 8Ti (OsBu) 2.4 (OnBu) 4 Alo, 9Ti (OsBu) 2.7 (OnBu) 4 Ali jTi (OsBu) 3.3 (OnBu) 4 Al 1-2Ti (OSBU) 3, 6 (0nBu) 4 Al1,3rri (OSBU) 3.9 (0nBu) 4 40 A11.4Ti (OsBu) 4.2 (0nBu) 4 A11.5 Ti (OSBU) 4.5 (0nB11) 4 A1Zr0.7 ( 0sBu) 3 (0nBu) 2.8 A1Zr0.8 (0sBu) 3 (0nBu) 3.2 A1Zr0.9 (0sBu) 3 (0nBu) 3.6 Al2Zr (OnPr) 4 (0iPr) 6 Al2Zr (OnBu) io Al2Zr (OnBu) 4 (0sBu) 6 Al2Zr (OEH) 10 A1Zr2 (0nBu) ii A11.6Ti (OsBu) 4.8 (0nBu) 4 Alurri (OSBU) 5.1 (0nBu) 4 AluTi (OsBu) 5.4 ( 0nBu) 4 A11.9 Ti (OSBU) 5.7 (0nB11) 4 A1Tio, 1 (OsBu) 3 (OnBu) o, 4 AlTi0.2 (0sBu) 3 (0nBu) D, s A1Ti0.3 (0sBu) 3 (InBu) 1.2 AlTi0.4 (OsBu) 3 (InBu) 1.6 Al TiO, 5 (OSBU) 3 (OnB11) 2.0 Al TiO, 6 (OSBU) 3 (OnB11) 2.4 Al TiO, 7 (OSBU) 3 (OnB11) 2.8 Al TiO, g (OSBU) 3 (OnB11) 3, 2 AlTi0.9 (0sBu) 3 (InBu) 3.6 Al2Ti (OiPr) io Al2Ti (OnBu) io Al2Ti ( In addition, the following commercial complexes were used: - Aluminum-zirconium complex: Al2Zr (OC4H9) Magnesium-zirconium complex: MgZr (OC4H9) 6 - Aluminum-titanium complex: Al2Ti (OC4H9) io Magnesium complex -titanium: MgTi (OC4H9) 6 Example 3: Synthesis of chelated complexes The monometallic alkoxides Mg (OEt), Al (OiPr) 3, Al (OsBu) 3, Zr (OnPr) 4, Zr (OnBu) 4, Zr (OnBu) 2 (acac) 2, Zr (acac) 4, Ti (OiPr) 4, Ti (OnBu) 4 and Ti (EAA) 2 (0Pr2Me) 2 are from Sigma-Aldrich and have been used upon reception or concentrated under reduced pressure.
[0042] Mg (EAA) 2, Al (OsBu) 2 (EAA) 2, Al (EAA) 3, Zr (OnPr) 2 (EAA) 2, Zr (OnPr) 2 (EEA) 2, Al (OnPr) chelated monometallic complexes 2 (EEA) 2, Al (OnPr) 2 (EPA) 2, Zr (OnPr) 2 (E2EA) 2, Zr (OnPr) 2 (F.EEA) 2, Zr (OnPr) 2 (t.EAA) 2, Zr (OnPr) 2 (C4EA) 2, Zr (OnPr) (EAA) 3, Zr (OnPr) (EPAA) 3, Zr (EAA) 4.PrOH, Zr (PAA) 4.PrOH, Zr (EPAA) 4. EPAA, Zr (OnPr) 2 (acac) 2, Zr (OnPr) 2 (F.acac.F) 2, Zr (OnPr) 2 (Ph.acac.F) 2, Zr (OnPr) 2 (Ph.acac. Ph) 2, Zr (OnPr) 2 (t.acac) 2, Zr (OnPr) 2 (diPrm) 2, Zr (diPrm) 4, Zr (OnPr) 2 (Aamid) 2, Zr (OnPr) 2 (NacNac) 2, Zr (OnPr) 2 (MA) 2, Zr (OnPr) 2 (DBU) 2.PrOH and Ti (EAA) 2 (OiPr) 2 were prepared according to the following method: 1 equivalent of the corresponding monometallic alkoxide complex was diluted in toluene. Then 1, 2, 3 or 4 equivalents of corresponding ligand were added to the previous mixture. The solution is then heated to 140 ° C to then distill the azeotropic mixture formed by the alcohol released and toluene. The residual solvent was evaporated. The heterometallic chelate complexes were prepared according to 3 synthetic routes. Lane 1: Combination of a monometallic alkoxide complex with a monometallic chelate complex A1Ti (EAA) 3 (InBu) 4 was prepared by mixing 1 mole of Al (EAA) 3 with 1 mole of Ti (OnBu) 4. The mixture was stirred for 2 hours at room temperature. When solubility difficulties persisted, the mixture was heated to 65 ° C. The complexes A1Zr (EAA) 3 (InPr) 4, AlZr (EAA) 7, AlZr0.5 (EAA) 5, Al2Zr (EAA) io, AlZr (OsBu) 3 (O nPr) 4 (diPrm) 2, MgZr (EAA) 6, MgTi (EAA) 4 (OiPr) 2 were prepared in the same way with the corresponding starting complexes in the corresponding proportions. Lane 2: AlZr ligand exchange (EAA) 7 was prepared from 4 g of AlZr (OnBu) 7 diluted in 15 mL of toluene. 7 equivalents of ethyl acetoacetonate were then added to the above mixture which was heated to 130 ° C. Then the azeotropic mixture formed by the liberated butanol and toluene was distilled off and the residual solvent was evaporated. Lane 3: One-pot synthesis A1Zr (EAA) 3 (OnPr) 4, AlZr (EAA) 3 (OnBu) 4, AlZr (OiPr) 5 (PAA) 2, AlTi (EAA) 3 (OnBu) 4 and A1Ti (PAA) 2 (OiPr) 5 and Al2Zr (EAA) 6 (0nPr) 4 were synthesized in a single pot. For this, 2 or 3 equivalents of ethyl acetoacetonate or propyl acetoacetonate were added to one equivalent of Zr (OnBu) 4, Ti (OnBu) 4 or Al (OiPr) 3. The mixture was immediately heated to 70 ° C until a homogeneous mixture was obtained which was concentrated under reduced pressure to liberate n-butanol or iso-propanol. After that, an equivalent of Al (OiPr) 3, Zr (OnBu) 4, Ti (OnBu) 4 or Zr (OnPr) 4 was added directly and, after stirring for 2 hours at room temperature, the Heterometallic complexes desired were obtained as a light yellow oil. EXAMPLE 4 Catalytic Properties of the Heterometallic Complexes To test the catalytic properties of the metal complexes, pasting compositions were prepared. For this, 3464 g of an α,--hydroxypolydimethylsiloxane oil with a viscosity of 20,000 mPa.s were mixed with 120 g of vinyltrimethoxysilane (VTMO). 16 g of lithiline diluted to 0.4% by weight in methanol were then added to the mixture formed. After stirring for 5 minutes, 400 g of pyrogenic silica AE55 were added. The mixture was concentrated under reduced pressure and then stored in a closed cartridge protected from moisture. For each test, 25 g of this mash and a quantity of catalyst were mixed using a speed mixer (2 times 20 seconds at 2000 rpm). The catalytic activity of each composition was then evaluated by taking several measurements under conditions of constant temperature and hygrometry (23 ° C to 50%): Skin formation time (TFP): time to finish which is observed a surface crosslinking. It is made with a beech stick on a film of 2 mm thickness. - The hardness (in shore A): it reflects the formation of the three-dimensional network. It was measured on the one hand on the superposition of 3 cords 2 mm thick, and on the other hand on a single bead of 6 mm thick, over increasing times (5h, 1 and 7 days). On the 6 mm thick cord, two measurements were taken: ">" corresponds to the hardness on the upper part of the cord and "<" corresponds to the lower or confined portion of the cord. "NR" means uncrosslinked, "ND" means non-demoldable, "D" means demoldable and "C" means tacky. These letters were used when the hardness was less than 5. The undetermined data are noted "n.d". The tests were carried out on heterometallic catalysts according to the invention and on catalysts of the prior art: - dibutyltin dilaurate (DBTDL) - tetrabutoxytitanium Ti (OnBu) 4 - tri (sec-butoxy) aluminum Al (OsBu) 3 - tetrapropoxyzirconium Zr (OnPr) 4 The results of catalysts of the alkoxide type in equimolar amounts are shown in Table 1: Catalysts mmol /% TFP DSA DSA S. D A7j OH wt 5h ld 2 mm 3 x 2 mm 6 mm <> DLDBE catalysts 2.1 2.7% 8 min D 26 33 Reference Ti (OnBu) 4 2.1 1.4% 15 min 20 29 30 25 Al (OsBu) 3 2.1 1 , 0% NR NR NR NR Zr (OnPr) 4 2.1 1.4% n / a ND N / A 18 19 Ex. 1 A1Zr (OsBu) 3 (0Bu) 4 2.1 2.6% n / a 26 27 30 25 Ex. 2 Alt4Zr (OsBu) 4.2 (OnBu) 4 2.1 2.9% 5 min 10 23 30 25 Ex. 3 Al2Zr (OC4HOlo 2.1 3.3% 5 min 19 29 29 24 Ex. 4 A1Ti (OsBu) ) 3 (0nBu) 4 2.1 2.5% n / a 28 33 33 28 Ex. 5 A10.5Ti (OsBu) 1.5 (OnBu) 4 2.1 1.9% 8 min 22 28 32 26 Ex. 6 Al2Ti (OC4H9) 10 2.1 3.2% 10 min 25 28 31 26 Ex. 7 A1Ti0.2 (0sBu) 3 (0nBu) 0.8 2.1 1.3% 8 min 14 TABLE 1 The results of mixed chelate catalysts in equimolar amounts are shown in Table 2: Catalysts mmol / OH% in TFP DSA DSA S. D A7 5 mm 2 mm 3 x 2 mm 6 mm catalysts DLDBE 2.1 2.7% 8 min D 26 33 Reference Ti (OnBu) 4 2.1 1.4% 15 min 20 29 30 25 Al (OsBu) 3 2.1 1.0% NR NR NR NR Zr (OnPr) 4 2.1 1.4% n / a ND N / A 18 19 Ex. 8 A1Zr (EAA) 7 2.1 4.3% 6 min 25 31 31 29 Ex. 9 A1Zr (OsBu) 3 (NPPr) 4 (diPrm) 2 2.1 3.7% 10 min 16 29 30 26 Ex. 10 A1Ti (OiPr) 5 (PAA) 2 2.1 2.0% 6 min 26 26 32 24 Table 2 Heterometallic complexes conduct rapidly, in less than 15 minutes, elastomers as hard as those obtained with reference catalysts such as dibutyltin dilaurate (DBTDL) and tetrabutoxytitanium Ti (OnBu) 4. EXAMPLE 5 Comparative Monometallic / Heterometallic Complexes The catalytic activity of the heterometallic complexes according to the invention was compared to the catalytic activity of the mixtures of the monometallic complexes. For this, pastes were prepared as described in Example 4, then mixed on the one hand with a heterometallic complex according to the invention and on the other hand with the corresponding in situ mixture of two monometallic complexes. The results are shown in Table 3: Catalysts mmol / OH% TFP DSA DSA DSA ds 5h ld 7j 2 mm 3 x 2 mm 6 mm <> Ex. 11 A1Zr (OsBu) 3 (0nBu) 4 1.6 2 Comparative A1 (OsBu) 3 1.6 1.2% 12 min 5 7 20 15 Zr (OnBu) 4 1.6 0.8% Ex. 12 A1Ti (OsBu) 3 (0nBu) 4 1.7 2.0% 10 min 17 27 31 25 Comparative Al (OsBu) 3 1.7 1.2% 7 min 16 27 30 22 Ti (OnBu) 4 1.7 0.8% Ex. 13 A1Zr (EAA) 3 (NPPr) 4 1.3 2.0% 8 min 14 27 32 27 Comparative A1 (EAA) 3 1.3 1.1% 24 min ND ND 17 15 Zr (OnPr) 4 1 3 0 9% Ex. 14 A1Ti (EAA) 3 (InBu) 4 1.3 2.0% 7 min 21 29 34 28 Comparative Al (EAA) 3 1.3 1.1% 20 min 5 20 29 26 Ti (OnBu) 4 1 Table 3 A better reactivity of the preformed heterometallic catalysts compared to monometallic alkoxides added in situ during the test is observed. It is believed that when placing the complexes in situ in contact, no association reaction of the complexes is possible since they are present in a highly diluted medium. The difference in hardness is also explained by the formation of new species leading to a new reactivity compared to monometallic species. Thus, it is necessary to preform the heterometallic complex before it is added to the silicone composition. It is furthermore noted that the compositions containing a zirconium-based catalyst, especially the Al-Zr complexes, remain translucent even after accelerated aging (2 mm films placed at 100 ° C. for 7 days). It is also noted that the compositions containing a heterometallic chelate catalyst are more stable after accelerated aging (cartridges placed at 50 ° C. for 3 weeks) than those containing a heterometallic alkoxide catalyst.
[0043] Example 6: Behavior in the presence of an adhesion promoter Pastes were prepared as described in Example 4 with additionally 1% by weight of an amino silane (3- (2-aminoethylamino) propyl-dimethoxymethylsilane) conventionally used as an adhesion promoter. These pastes were mixed with a catalyst and the catalytic activity of each composition was then evaluated as in Example 3. The results of the tests of the alkoxide catalysts in the presence of adhesion promoter are shown in Table 4: Catalysts mmol /% of TFP DSA DSA DSA OH wt. 5h ld 7d 2 mm 3 x 2 mm 6 mm <> Catalysts DLDBE 0.7 0.9% 5 min 25 29 31 29 references Ti (OnBu) 4 2.1 1.4 % 20 min NR NR NR A1 (OsBu) 3 2.1 1.0% 25 min NR NR NR Zr (OnPr) 4 2.1 1.4% 20 min NR NR NR Ex. 15 A1Zr (OsBu) 3 (0nB1 ) 4 2.1 2.6% n / a 8 9 13 28 Comparative 1 A (OsBu) 3 2.1 1.0% 10 min CDD Zr (OnBu) 4 2.1 1.6% Ex. 16 Al2Zr (OC4H9) io 2.1 3.3% 25 min n / a 26 32 28 Ex 17 A1Ti (OsBu) 3 (0nB1) 4 2.1 2.4% n / a C 9 C 19 Comparative 1 A (OsBu) 3 2.1 1, 4% 6 min C 3 6 21 Ti (OnBu) 4 2.1 1.0% Ex 18 Al2Ti (0E1-1) io 2.1 5.9% ndnd 22 36 31 Comparative Al (EO) 3 4.2 3.5% 20 min CCC Ti (OEH) 4 2.1 2.4% Ex. 19 Al2Ti (OC4H9) io 2.1 3.2% 20 min na 19 31 31 Table 4 The results of the tests Combined chelate catalysts in the presence of adhesion promoters are shown in Table 5: Catalysts mmol /% of TFP DSA DSA DSA OH wt 5h lj 7j 2 mm 3 x 2 mm 6 mm <> catalysts DLDBE 0.7 0, 9% 5 min 25 29 31 Reference Ti (OiPr) 2 (EAA) 2 1.8 1.5% 20 min D 15c 28 25 Al (EAA) 3 2.1 1.0% 10 min CDC Ex. 20 A1Zr (EAA) 3 (NPPr) 4 1.3 2.0% 5 min CD 11 23 Comparative 1 A (EAA) 3 1.3 1.1% 17 min CCC Zr (OnPr) 4 1.3 0.9% Ex. 21 Al2Zr (EAA) 6 (OnPr) 4 1.3 3.0% 12 min n / a 17 30 30 Ex. 22 A1Ti (EAA) 3 (0nBu) 4 1.5 2.0% 5 min C 2 16 23 Comparative Al (EAA) 3 1.5 1.1% 18 min CDD Ti (OnBu) 4 1.5 0.9% Table 5 In the presence of the adhesion promoter, it is possible to carry out the polycondensation with the catalyst. tin (DLDBE). On the other hand, the presence of the amino silane completely inhibits the reactivity of the catalysts of the prior art without tin.
[0044] The heterometallic complexes according to the invention, which do not contain tin, have a catalytic activity even in the presence of the adhesion promoter. The catalyzed reaction was found to be faster when the Al / Zr or Al / Ti molar ratio was 2. Example 7: Adhesion tests To carry out qualitative adhesion tests, a bead of product prepared from the The formulation described in Example 4 and the catalyst to be tested was deposited on glass plates, concrete (rough side) and anodized aluminum previously cleaned and brushed. After a cure time of 7 days (at 23 ° C. and 50% RH), a manual peel was made after having made a detachment primer at the support / seal interface. The results are expressed as a function of the type of rupture of the product bead: - RA: adhesive rupture (the bead is detached from the support); - RA +: break with adhesive tendency, but requiring the application of a force to take off the cord; - RA ++: breaking with adhesive tendency, but requiring the application of a strong force to take off the cord; - RC: cohesive type failure (the cord breaks under the application of a very high force, without having detached from the support, even partially); in this case the adhesion on the support is optimal. The results are shown in Table 6: Catalysts Adhesion to a support: aluminum concrete glass DLDBE RA RA RA catalysts of Zr references (OnPr) 4 RC RA RC Ti (OnBu) 4 RA RA + RA + Ti (EAA) 2 (OiPr) 2 RC RC RC Ex. 23 A1Zr (OsBu) 3 (OnBu) 4 RC RC RC Ex. 24 A1Ti (OsBu) 3 (OnBu) 4 RC RA RC Comparative A1 (OsBu) 3 + Ti (OnBu) 4 RC RA RA + Ex. A1Zr (EAA) 3 (0nPr) 4 RC RC RC Ex. 26 AlTi (EAA) 3 (0nBu) 4 RC RC Comparative Al (EAA) 3 + Ti (OnBu) 4 RA + RC RA ++ Table 6 Zirconium alkoxide allows to obtain cohesive breaks on glass and aluminum and adhesives on concrete. Only the titanium chelate reference catalyst allows adhesion to the three supports. Regardless of the content of alkoxide catalysts, aluminum and zirconium catalysts allow cohesive failure on glass and aluminum and adhesive failure on concrete. Catalysts comprising chelate groups make it possible to obtain cohesive breaks on the three supports. Adhesion is lost when the monometallic catalyst mixture is made during formulation. The presence of the chelate group brings the adhesion of the elastomer to the supports. It is therefore not necessary to add an adhesion promoter as with the reference tin. The preforming of the catalyst is once again essential for an optimal result.
[0045] Example 8: Colorimetric Tests To perform qualitative colorimetric tests, a product film 2 mm thick was prepared from the previous formulation and the catalyst to be tested. After a cure time of 7 days (at 23 ° C. and 50% RH), the opacity and the yellow color of the film through a white sheet were evaluated qualitatively. The qualitative results are given according to the catalysts of references: - corresponds to elastomers transparent and without color, - corresponds to film with opaque tendency, + corresponds to a film a little yellow, ++ corresponds to a yellow film. NH will be noted when the elastomer is not homogeneous with the appearance of insoluble catalyst parts in the oil. The results are shown in Table 7: Catalysts colorimetry Yellow opacity DLDBE catalysts - - Zr references (OnPr) 4 - - Ti (OnBu) 4 - + Ti (EAA) 2 (OiPr) 2 - ++ Ex .
[0046] 27 A1Zr (OsBu) 3 (0nBu) 4 - - Comparative Al (OsBu) 3 + Zr (OnBu) 4 - - Ex.
[0047] 28 A1Ti (OsBu) 3 (0nBu) 4 - + Comparative Al (OsBu) 3 + Ti (OnBu) 4 - + Ex.
[0048] AlZr (EAA) 3 (0nPr) 4 - Comparative Al (EAA) 3 + Zr (OnBu) 4 NH NH and - Ex.
[0049] Al (EAA) 3 (0nBu) 4 - ++ Comparative Al (EAA) 3 + Ti (OnBu) 4 NH NH and + Table 7 The films containing titanium catalysts are a little, if not completely yellow. Those catalyzed by mixtures of monometallic species are not homogeneous. On the other hand, elastomers based on aluminum and zirconium are perfectly translucent.

权利要求:
Claims (15)
[0001]
REVENDICATIONS1. A curable composition in the presence of water or moisture of air comprising: (A) at least one polyorganosiloxane A having one or more condensable or hydrolyzable and condensable group (s), and B) at least one compound C, capable of catalyzing the condensation reaction of the condensable or hydrolyzable and condensable groups of the polyorganosiloxane A, and which is a heterometallic complex whose chemical formula comprises: at least two different metal atoms M and M ', M being an atom selected from the group consisting of the atoms of columns 2 and 13 of the periodic table of elements and M 'being an atom selected from the group consisting of the atoms of column 4 of the periodic table of elements, and - at least an alkoxide or chelating ligand. 15
[0002]
2. Composition according to claim 1, characterized in that the compound C is a heterometallic complex whose chemical formula comprises: at least two different metal atoms M and M ', M being a magnesium (Mg) or aluminum atom (A1), and preferably an aluminum atom (Al), and Me being a titanium (Ti) or zirconium (Zr) atom, and - at least one alkoxide or chelating ligand.
[0003]
3. Composition according to claim 2, characterized in that the compound C is chosen from the group consisting of: heterometallic complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M 'being zirconium and wherein the molar ratio Al / Zr = 0.5, 1 or 2; and at least one alkoxide or chelating ligand; and heterometallic complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being titanium and in which the molar ratio Al / Ti = 1 or 2, and at least one alkoxide or chelating ligand.
[0004]
4. Composition according to any one of claims 1 to 3, characterized in that the compound C is a heterometallic alkoxide complex whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium or aluminum and Me being titanium or zirconium, and - at least one alkoxide ligand; and preferably said heterometallic alkoxide complex is selected from the group consisting of: - heterometallic alkoxide complexes whose chemical formula comprises: - at least two different metal atoms M and M ', M being aluminum and M being zirconium, at least one alkoxide ligand of chemical formula 0- (linear or branched C 3 to C 12 alkyl), and in which the molar ratio Al / Zr is equal to 0.5, 1 or 2; the heterometallic alkoxide complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium and M being zirconium, at least one alkoxide ligand of chemical formula O- (linear or branched alkyl) C2 to C12), and - in which the molar ratio Mg / Zr is 0.5, 1, 2, 3 or 4; and heterometallic alkoxide complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being titanium, at least one alkoxide ligand of chemical formula O- linear alkyl or - branched C3 to C12), and - in which the molar ratio Al / Ti is 1 or 2; and even more preferably, said heterometallic alkoxide complex is selected from the group consisting of AlZr (OBu) 4 (OsBu) 3, Al2Zr (OnBu) 4 (OsBu) 6, AlZr2 (OnBu) f 1, AlTi (OsBu) 3 (0nBu) 4 and Al2Ti (OnBu) io.
[0005]
5. Composition according to any one of claims 1 to 3, characterized in that compound C is a heterometallic chelate complex whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium or aluminum and M 'being titanium or zirconium, and - at least one chelate ligand; said heterometallic chelate complex being preferably selected from the group consisting of: - heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being zirconium, at least one chelating ligand, preferably selected from the group consisting of ethyl acetoacetate, propyl acetoacetate and diisopropyl malonate, optionally at least one alkoxide ligand of chemical formula 0- (linear or branched alkyl) C3 or C4), and - having a molar ratio Al / Zr = 1 or 2; heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being zirconium, at least one chelating ligand, preferably chosen from the group consisting of ethyl acetoacetate, propyl acetoacetate and diisopropyl malonate, having a molar ratio Al / Zr = 1 or 2, and not comprising an alkoxide ligand; heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium and M' being zirconium, at least one chelating ligand, preferably ethyl acetoacetate, and having a molar ratio Mg / Zr = 1; heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being aluminum and M' being titanium, at least one chelating ligand, preferably chosen from the group consisting of ethyl acetoacetate and propyl acetoacetate; optionally at least one alkoxide ligand of chemical formula 0- (linear or branched C 3 or C 4 alkyl) and having a molar ratio Al / Ti = 1; and heterometallic chelate complexes whose chemical formula comprises: at least two different metal atoms M and M ', M being magnesium and M' being titanium, at least one chelating ligand, preferably ethyl acetoacetate, - optionally at least one alkoxide ligand of chemical formula 0- (linear or branched C3 alkyl), and - having a molar ratio Mg / Ti = 1; and even more preferably said heterometallic chelate complex being selected from the group consisting of AlZr (EAA) 3 (O nPr) 4, Al 2 Zr (EAA) 6 (O nPr) 4, AlZr (EAA) 7, Al 2 Zr (EAA) 10 and A1Ti (EAA) 3 (0nBu) 4.
[0006]
The composition according to any one of claims 1 to 5, wherein the polyorganosiloxane A comprises: (i) at least two siloxyl units of the following formula (V): Ra Zb SiO4- (a + b) (V) 2 in which: the symbols R4, which may be identical or different, represent monovalent C1 to C30 hydrocarbon radicals, the Z symbols, which are identical or different, each represent a hydrolyzable and condensable group or a hydroxyl group, and preferably are chosen from the group consisting of hydroxy, alkoxy, alkoxyalkyleneoxy, amino, amido, acylamino, aminoxy, iminoxy, cetiminoxy, acyloxy, iminoxy, cetiminoxy and enoxy, 25 - a is 0, 1 or 2, b is equal to 1, 2 or 3, the sum a + b is equal to 1, 2 or 3, and (ii) optionally one or more siloxyl unit (s) of the following formula (VI): SiO 4 -C (VI) 2 in which - the symbols R5, which may be identical or different, represent monovalent hydrocarbon radicals in C1 to C30 optionally substituted by one or more halogen atoms or by amino, ether, ester, epoxy, mercapto or cyano groups, and - the symbol c is equal to 0, 1, 2 or 3.
[0007]
7. Composition according to any one of claims 1 to 6 further comprising a crosslinking agent B.
[0008]
8. Composition according to claim 7 wherein the crosslinking agent B is a silicon compound in which each molecule comprises at least three hydrolyzable and condensable Y groups, said crosslinking agent B having the following formula (XIII): R20 (4_i) Siyi (XIII) in which: the symbol R2 ° is a monovalent hydrocarbon radical comprising from 1 to 30 carbon atoms, the symbols Y, which are identical or different, are chosen from the group constituted by the alkoxy, alkoxyalkylene and oxy, amino, amido, acylamino, aminoxy, iminoxy, cetiminoxy, acyloxy or enoxy, and preferably Y is an alkoxy, acyloxy, enoxy, cetiminoxy or oxime group, the symbol j = 2, 3 or 4, and preferably = 3 or 4.
[0009]
9. Composition according to any one of claims 1 to 8, characterized in that it further contains an adhesion promoter E.
[0010]
10. A one-component RTV-1 composition in a single airtight package comprising: a) at least one polyorganosiloxane A as defined in claim 1 or claim 6, b) at least one crosslinking agent B , preferably as defined in claim 8, c) a catalytically effective amount of at least one compound C as defined in any one of claims 1 to 5, and d) optionally at least one charge D.
[0011]
11. RTV-2 bicomponent composition, precursor of the composition according to any one of claims 1 to 9, being in two separate packages P1 and P2, characterized in that: c) the packaging Pl is airtight and comprises: - a catalytically effective amount of at least one compound C as defined in any one of claims 1 to 5, and - at least one crosslinking agent B, preferably as defined in claim 8, and d) the package P2 contains neither said compound C nor said crosslinking agent B and comprises: per 100 parts by weight of at least one polyorganosiloxane A as defined in claim 1 or claim 6, and - from 0 to 10 part (s) by weight of water. 15
[0012]
12. Silicone elastomer obtained: after allowing to cure in the presence of water or moisture of air the composition as defined in any one of claims 1 to 9; or - after contacting with air moisture the contents of package P of the one-component RTV-1 composition as defined in claim 10 and allowing said contents to cure; or - after mixing the contents of the packages P1 and P2 of the two-component RTV-2 composition as defined in claim 11 and allowing the mixture to set. 25
[0013]
13. Use of a compound C as defined in any one of claims 1 to 5 as a catalyst for a condensation reaction of a polyorganosiloxane having one or more condensable or hydrolyzable group (s). ) and condensable (s). 30
[0014]
14. Heterometallic chelate complex whose chemical formula comprises: at least two different metal atoms M and M ', M being an atom selected from the group consisting of the atoms of columns 2 and 13 of the periodic table of the elements and M being an atom selected from the group consisting of the atoms of column 4 of the periodic table of elements, and - at least one chelating ligand.
[0015]
15. A method of coating the composition according to the invention and as defined above on a flexible support S comprising the following steps a), b) and c): a) a composition is prepared as defined in any one of claims 1 to 9, b) and then continuously or discontinuously deposited said composition on said flexible support S, and c) it is allowed to harden said silicone composition in the presence of moisture brought by the ambient air or by prior addition of water to form a silicone elastomer.

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2021-11-09| PLFP| Fee payment|Year of fee payment: 9 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1362008A|FR3014106B1|2013-12-03|2013-12-03|CURABLE SILICONE COMPOSITION IN THE PRESENCE OF WATER OR HUMIDITY IN THE AIR|FR1362008A| FR3014106B1|2013-12-03|2013-12-03|CURABLE SILICONE COMPOSITION IN THE PRESENCE OF WATER OR HUMIDITY IN THE AIR|

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US15/039,646| US9828470B2|2013-12-03|2014-12-03|Silicone composition that can be cured in the presence of water or atmospheric moisture|

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EP14825403.0A| EP3077460B1|2013-12-03|2014-12-03|Silicone composition that can be cured in the presence of water or atmospheric moisture|

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KR1020167017631A| KR101918374B1|2013-12-03|2014-12-03|Silicone composition that can be cured in the presence of water or atmospheric moisture|

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CN201480073623.XA| CN105934482B|2013-12-03|2014-12-03|In water or atmospheric moisture, there are the silicon compositions of curable|

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PCT/FR2014/053141| WO2015082837A1|2013-12-03|2014-12-03|Silicone composition that can be cured in the presence of water or atmospheric moisture|

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JP2016536120A| JP6588435B2|2013-12-03|2014-12-03|Silicone composition that can be cured in the presence of water or atmospheric moisture|

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JP2018060615A| JP2018150535A|2013-12-03|2018-03-27|Silicone composition that can be cured in the presence of water or atmospheric moisture|