Novel substituted phosphite transition metal compound

Abstract

The present invention relates to a transition metal compound containing at least one phosphite compound of formula P(OR) 3 (I), where R represents an organic group, and where at least one R group is represented by formula (II) [Chemical formula 115] JPEG2025518040000128.jpg39160 The ring represented by A in the formula represents an aromatic group or a heteroaromatic group, which may have one or more additional substituents in addition to R 1 and R 2 and may have one or more additional substituents, the dotted line represents a single bond to the oxygen atom of the phosphite compound of formula (I), R 1 and R 2 each represent a substituent ortho to the oxygen atom of the phosphite compound of formula (I) in the above aromatic group or heteroaromatic group, and in the formula, the substituents R 1 and R 2 are each independently selected from the group consisting of an optionally substituted aliphatic group and an optionally substituted aliphatic bridging group that forms a fused ring system with another atom of the aromatic group or heteroaromatic group corresponding to the ring represented by A, and where at least two R groups are different from each other. The present invention further relates to the use of the transition metal compound of formula (I) as a curing catalyst for a curable polyorganosiloxane composition and / or a silane composition, a curable polyorganosiloxane composition and / or a silane composition containing one or more transition metal compounds of formula (I), its use for the production of a molded article, and a method for producing a curable polyorganosiloxane composition.

Description

Technical Field

[0001] This invention relates to novel substituted phosphite transition metal compounds, their use as curing catalysts for curable polyorganosiloxane compositions and / or silane compositions, curable polyorganosiloxane compositions and / or silane compositions containing one or more of the above-mentioned transition metal compounds, the use of one or more of the above-mentioned phosphites for the production of curable polyorganosiloxane and / or silane compositions, curable polyorganosiloxane and / or silane compositions containing one or more of the above-mentioned phosphites, cured polyorganosiloxane and / or silane compositions obtained by curing the above-mentioned curable polyorganosiloxane and / or silane compositions, the use of the above-mentioned curable polyorganosiloxane compositions and / or silane compositions for the production of molded articles, extruded articles, coatings, and sealants, and a method for the production of the above-mentioned curable polyorganosiloxane compositions.

Background Art

[0002] Platinum(0)-vinylsiloxane complexes, such as divinyltetramethyldisiloxane complex (Karstedt catalyst) or tetravinyltetramethylcyclotetrasiloxane complex, can catalyze hydrosilylation reactions at very high reaction rates. Therefore, these catalysts are currently used to crosslink, cure, or vulcanize silicone rubbers having alkenyl groups and SiH groups by hydrosilylation between 20 and 200 °C. However, according to Arrhenius' law, this reaction at room temperature may result in an unacceptably short pot life (usable time) or bath life (usable time in the tank) (1 to 10 minutes at 25 °C).

[0003] From the disclosure of the prior art, it is well known that the high reaction rate of platinum catalysts can be slowed down by inhibitors such as esters, for example maleic acid esters and fumaric acid esters, ketones, sulfoxides, phosphines, phosphites, nitrogen or sulfur-containing derivatives, hydroperoxides, and acetylene derivatives such as alkynols. When explaining the effect of such inhibitors by Arrhenius' law, generally, a shift in the line in the graph showing 1 / k (k = reaction constant [s -1 ) with respect to 1 / T (°K) on the x-axis can be observed, that is, when the pot life is extended, it can be observed that simultaneously, the reaction rate at high temperatures decreases.

[0004] Some prior art documents have attempted to decouple the effects of pot life and cure rate at high temperatures. For example, US3,188,300 discloses specific aliphatic, alicyclic, and aromatic phosphites to prevent early gelation at 20 - 30°C. EP948565A1 discloses a siloxane composition containing substituted aromatic phosphites, which shows that there is another relationship between the cure rate at 140°C and the pot life at room temperature. US2006 / 0135689 (Fehn) discloses a siloxane composition containing an olefin - nitrogen-containing ligand - platinum complex, which is said to increase the pot life at room temperature and the high reaction rate at high temperatures.

[0005] US2006 / 0128881A1 and US2004 / 0116561A1 disclose hydrosilylation polyorganosiloxane curing compositions containing phosphites, but do not disclose phosphites having aryloxy groups further substituted by alkenyl groups and / or aryl groups. Furthermore, these documents are not related to the technical problem of decoupling the effect of pot life and cure rate in hydrosilylation polyorganosiloxane curing compositions at high temperatures.

[0006] WO2010009755(A1) discloses a hydrosilylation-curing composition of a polyorganosiloxane and / or a silane, which comprises a specific phosphite and a transition metal compound containing at least one of the specific compounds. The phosphite described therein carries three identical aromatic groups substituted by either at least one aromatic group or at least three alkenyl groups.

[0007] US3,188,300A1 and US5,380,812 also disclose the use of phosphites as inhibitors in hydrosilylation silicone-curing compositions. As possible substituents, a monoalicyclic group, namely cyclohexyl and tris-phenyl phosphite, are also shown. However, the inventors have found that when using tris(cyclohexyl) phosphite or tris(phenyl) phosphite, although the pot life or storage stability is acceptable respectively, the curing rate is unacceptably low at high temperatures.

[0008] JP2007009041A discloses, in Examples 1 - 5, a curable composition comprising an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups, a compound containing at least two SiH groups in the molecule, and the presence of a platinum vinylsiloxane complex and a phosphite compound capable of forming a hydrosilylation catalyst. Further, JP2007009041A discloses the general structure of a phosphite which is a component of a curable composition comprising an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups, a compound containing at least two SiH groups in the molecule, and a hydrosilylation catalyst. The transition metal catalyst based on the phosphite of JP2007009041A is not included in the scope of the present invention, and JP2007009041A preferably states that a compound containing a carbon-carbon double bond does not contain a siloxane unit, whereas the present invention is completely different from the present invention in that a component having at least two alkenyl groups is required to be a polyorganosiloxane.

[0009] In the "Journal of Organometallic Chemistry", vol. 799, pp. 201 - 207, Grice et al. started from a platinum complex containing a phosphite with three identical aryl substituents and disclosed the structure of a Pt(II) metallacycle obtained via cyclometalation by C - H activation. In that, one of the arylalkyl substituents of the phosphite ligand in this complex discloses a divalent element of the metallacycle, but the disclosed structure is different from the structure of the transition metal compound of the present invention in which the phosphite bears three monovalent organic residues on the oxygen atom of the phosphite. In the "Polymer" journal, vol. 33, no. 1, pp. 161 - 165, Jongsma et al. disclosed coordinating an arylphosphite to a rhodium central metal atom to form a hydroformylation rhodium catalyst. This catalyst is formed in the context of the study of polymer - bound hydroformylation rhodium catalysts and is completely different from the technical field of the present invention.

[0010] In the "Journal of Molecular Catalysis A Chemical", vol. 259, no. 1 - 2, pp. 267 - 274, Gavrilov et al. disclosed rhodium, palladium, and platinum complexes prepared from iminoarylphosphites containing a ferrocenyl group or a cymantrenyl group. This document is directed towards the application of palladium complexes as catalysts for asymmetric allylation substitution reactions and is completely different from the technical field of the present invention.

[0011] DE223770, which is directed towards the development of a catalyst for the hydrocyanation of olefins, discloses a tris(2,5 - xylyl) - phosphite nickel complex. There is no disclosure in this document of transition metal compounds within the scope of the present invention or any phosphite compounds containing 2,6 - substituted aryl groups.

[0012] The present invention aims to provide a hydrosilylation polyorganosiloxane curing composition having a long pot life, i.e., storage stability, and at the same time having a high curing rate at high temperatures, and this property is not affected by long-term storage. In particular, it aims to provide "one-component type" and "two-component type" hydrosilylation polyorganosiloxane curing compositions. The inventors have surprisingly found that a specific phosphite having a substituted aromatic group with a specific residue is suitable for solving these problems and can provide good dispersibility due to its low melting point.

Summary of the Invention

[0013] Thus, the present invention relates to a transition metal compound containing at least one phosphite compound of the formula P(OR) 3 (I) wherein R represents an organic group, and here at least one R group is represented by formula (II)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0014] - rhodium complexes, palladium complexes, and platinum complexes containing a phosphite of the following general formula

Chemical formula

[0015] The present invention further relates to the use of a transition metal compound comprising a phosphite compound of formula (I) as a curing agent for a curable polyorganosiloxane composition and / or a silane composition, a curable polyorganosiloxane composition and / or a silane composition comprising one or more such transition metal compounds comprising a phosphite of formula (I), and the use of one or more phosphites of formula (I) for the production of a curable polyorganosiloxane and / or a silane composition, a curable polyorganosiloxane and / or a silane composition comprising one or more phosphites of formula (I), and a two-component curable polyorganosiloxane and / or a silane composition, a cured polyorganosiloxane and / or a silane composition obtained by curing the above-described curable polyorganosiloxane and / or a silane composition, and the use of the above-described curable polyorganosiloxane composition and / or a silane composition for the production of molded articles, extruded articles, coatings, and sealants, and a method for the production of the above-described curable polyorganosiloxane composition.

Embodiments for Carrying Out the Invention

[0016] In a first aspect, the present invention relates to a transition metal compound comprising at least one phosphite compound.

[0017] In particular, the present invention relates to a transition metal compound comprising at least one phosphite compound of the formula P(OR) 3 (I) wherein R represents an organic group, and wherein at least one R group is represented by formula (II)

Chemical formula

[0018] For a transition metal compound containing at least one phosphite compound, there is a condition that this compound is different from the following - a platinum complex containing a phosphite of the following formula;

Chemical formula

Chemical formula

Chemical formula

[0019] - a rhodium complex, a palladium complex, and a platinum complex containing a phosphite of the following general formula

Chemical formula

[0020] According to the present invention, compounds containing at least one atom or ion of an element in the d-block of the periodic table, including the f-block lanthanoid and actinoid series, are each regarded as transition metal compounds.

[0021] The transition metal in such transition metal compounds is preferably selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, and platinum is the most preferred transition metal.

[0022] It is possible to isolate the transition metal compounds of the present invention containing the specific phosphite ligand of formula (I), but in the actual polyorganosiloxane curing system by hydrosilylation, without separately forming a transition metal phosphite complex compound, certain general transition metal compounds are often added to the polyorganosiloxane together with the phosphite, or certain transition metal compounds are reacted with the phosphite so to speak in situ, and this reaction product is added to the polyorganosiloxane curing system by hydrosilylation.

[0023] Therefore, from a technical point of view, isolation of the transition metal phosphite complex compound is usually not necessary, and it is sufficient to determine the influence of phosphite addition on the pot life or storage stability and the curing rate at high temperature without accurately identifying the catalytically active transition metal species.

[0024] Nevertheless, it is possible to prepare and isolate the transition metal compounds that form the basis of the phosphites of the present invention by ligand exchange reactions that are generally known. For example, the well-known Karstedt catalyst can react with the phosphites of formula (I) of the present invention to give a transition metal compound according to the present invention: In the synthetic route it follows, for example, the well-known divinyltetramethyldisiloxane complex (DVTMDS) cross-linked dinuclear platinum complex (Karstedt catalyst) can be cleaved by any nucleophile (e.g., phosphite) to give a mononuclear platinum complex:

[0025] [Chemical formula]

[0026] The transition metal compound according to the present invention has the formula P(OR) 3 (I) and contains at least one phosphite compound, where R is an organic group.

[0027] Accordingly, the phosphite compounds of the present invention are organic phosphites, which may be considered esters of the unobserved tautomeric forms of phosphorous acid H 3 PO 3 .

[0028] According to the present invention, the organic group is any organic substituent having one free valence on a carbon atom, regardless of the type of functionality. Alternatively, the term organo group may be used.

[0029] According to the present invention, the R groups other than the R groups having formula (II) in the phosphites of formula (I) are preferably selected from optionally substituted aromatic groups and C1-C12 alkyl groups selected from optionally substituted linear, branched, or cyclic alkyl groups, and even more preferably selected from optionally substituted C1-C6 alkyl groups.

[0030] Here, the aromatic group and the C1-C12 alkyl group selected from linear, branched, or cyclic alkyl groups that constitute the group in the phosphite of formula (I) or the R group other than the R group having formula (II) may be substituted with an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group, or a Si-organic group, and the aromatic group may also be substituted with a linear, branched, or cyclic C1-C12 alkyl group.

[0031] In the phosphite compound of formula (I), at least one R group is represented by formula (II)

Chemical formula

[0032] The aromatic group according to the present invention is a hydrocarbon group containing at least one cyclic conjugated moiety, having significantly higher stability than a virtual localization structure that may carry substituents other than C and H, such as a halide group or a hydroxyl group. Preferred aromatic groups according to the present invention are a phenyl group, a benzyl group, a xylyl group, a tri-tert-butylated phenyl group, a di-tert-butylphenyl group, a di-tert-butylmethylphenyl group, a tert-butyldimethylphenyl group, and a naphthyl group.

[0033] According to the present invention, the heteroaromatic group is a heterocyclic group, which is derived from an aryl group in such a way that substitution of one or more methine groups and / or vinylene groups by trivalent or divalent heteroatoms such as S, O or N maintains the characteristics of an aromatic continuous π - electron system and a high degree of stability is observed, and the groups therein may be optionally substituted by groups other than H and C, such as a halide group or an amino group. Preferred heterocyclic groups are a furyl group, a thienyl group, a pyrrolyl group, an imidazolyl group, a pyridyl group, a triazolyl group, an isoquinolyl group, and a quinolyl group. The aromatic group and heteroaromatic group represented by formula (II) may carry a linear, branched, or cyclic C1 - C12 alkyl group, an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group or a Si - organic group as a substituent.

[0034] The dotted line in the structure of formula (II) represents a single bond to the oxygen atom of the phosphite compound of formula (I), which is ortho - position to each of the R 1 group and the R 2 group.

[0035] Regarding R groups in general, the group of formula (II) is an organic group having one free valence, whereby the structure is bonded to one of the oxygen atoms of the phosphite compound. The R group does not have an additional free valence or complex - forming site by which the R group can bind to another ligand of the transition metal atom or transition metal compound of the complex.

[0036] Thus, R 1 and R 2 in the structure of formula (II) each represent a substituent in the above - mentioned aromatic group or heteroaromatic group that is in the ortho - position to the oxygen atom of the phosphite compound of formula (I), and R 1 and R 2is independently selected from the group consisting of an optionally substituted aliphatic group, particularly an optionally substituted alkyl group and an optionally substituted alkenyl group, and an optionally substituted aliphatic bridging group, an alkoxy group, an alkoxycarbonyl group, and a Si-organic group that form a condensed ring system with another atom of an aromatic group or heteroaromatic group corresponding to the ring represented by A. R 1 or R 2 The aliphatic groups constituting, particularly the alkyl group, alkenyl group or the above-mentioned aliphatic bridging group may be substituted with an alkoxide group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group, or a Si-organic group.

[0037] According to the present invention, the alkoxy group constituting R 1 or R 2 is understood as an alkoxide group linked to the ring A via an oxygen atom, and a C1-C12 alkoxy group is preferred. More preferably, R 1 and R 2 may be selected from a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, an n-heptoxy group, an n-octoxy group, an n-nonoxy group, an n-decoxyl group, an isopropoxy group, an isobutoxy group, an isoamyloxy group, a cyclopentoxy group, and a cyclohexoxy group.

[0038] The alkoxycarbonyl group according to the present invention is understood as an ester functional group, where R 1 and R 2 selected from the alkoxycarbonyl group consist of a carbonyl group bonded to the ring A that also bears an alkoxide group. Preferably, R 1 and R 2It may be selected from a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an n-pentoxycarbonyl group, an n-hexoxycarbonyl group, an n-heptoxycarbonyl group, an n-octoxycarbonyl group, an n-nonoxycarbonyl group, an n-decoxylcarbonyl group, an isopropoxycarbonyl group, an isobutoxycarbonyl group, an isoamyloxycarbonyl group, a cyclopentoxycarbonyl group, and a cyclohexoxycarbonyl group.

[0039] According to the present invention, the term Si-organic group refers to an alkyl group carrying one or more Si-based functional groups, such as a trialkylsilyl group, a trialkoxysilyl group, and a polyorganosilane group, a carbosilane group and a carbosiloxane group, and another moiety, such as an Si-based functional group bonded to ring A via a silicon atom, such as a silyl group, particularly a trialkylsilyl group, a trialkoxysilyl group, and another moiety, such as an Si-based functional group bonded to ring A via an oxygen atom, particularly including a siloxy group.

[0040] Examples of the siloxy group are linear or branched oligosiloxy groups and polysiloxy groups, and are composed of 1 to 5000 siloxy units selected from dimethylsiloxy units, phenylmethylsiloxy units, diphenylsiloxy units, methylsiloxy units, phenylsiloxy units, or SiO units carrying a hydroxyl terminal group, a trimethylsilyl terminal group, a dimethylsilyl terminal group, or a vinyl terminal group. 4 / 2 Preferably, the Si-organic group is selected from a trialkylsilyl group and a trialkylsiloxy group, wherein the alkyl group is a C1-C6 alkyl group, or a siloxy group having up to 12 siloxy units, wherein the organic residue is preferably a methyl group, and most preferably the siloxy group contains a D2, D3, D4, D5 or D6 siloxane-based moiety.

[0041] Preferably, the groups R 1 and R 2independently selected from linear, branched, or cyclic alkyl groups of C1 - C20, preferably methyl, ethyl, n - propyl, isopropyl, cyclopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, cyclobutyl, n - pentyl, isopentyl, neopentyl, cyclopentyl, n - hexyl, cyclohexyl, n - heptyl, n - octyl, n - nonyl, n - decyl, n - undecyl, n - dodecyl, n - tridecyl, n - tetradecyl, n - pentadecyl, n - hexadecyl, n - heptadecyl, n - octadecyl, n - nonadecyl, or n - eicosyl, more preferably these groups are independently selected from methyl, ethyl, isopropyl, and tert - butyl, and most preferably from methyl and tert - butyl.

[0042] Also preferably, the group R in the structure of formula (II) 1 and R 2 are independently selected from alkyl groups bearing one or more trialkylsilyl groups or trialkoxysilyl groups, or Si - based functional groups bonded to ring A via a silicon atom, particularly trialkylsilyl groups and trialkoxysilyl groups, or Si - based functional groups bonded to ring A via an oxygen atom, particularly siloxy groups.

[0043] Substituent R 1 and R 2 One of being optionally selected from substituted aliphatic groups and the other substituent being selected from Si - organic groups, alkoxy groups or alkoxycarbonyl groups is within the scope of the present invention.

[0044] R 1 and R 2Alternatively, any optional one or more additional substituents of ring A in formula (II) may be independently selected from any organic group, wherein preferred organic groups are optionally substituted alkyl groups, optionally substituted alkenyl groups, alkoxy groups as defined above, and alkoxycarbonyl groups as defined above, halide groups, nitro groups, cyano groups, or Si-organic groups as defined above.

[0045] The alkyl and alkenyl groups that constitute any optional additional substituents of ring A may be substituted with alkoxy groups, alkoxycarbonyl groups, halide groups, nitro groups, cyano groups or Si-organic groups. Preferably, R 1 and R 2 Additional substituents of ring A in formula (II) other than are selected from C1-C12 alkyl substituents, more preferably methyl, ethyl, isopropyl, and tert-butyl groups, and most preferably selected from methyl and tert-butyl groups.

[0046] According to the definition of the phosphite of formula (I) and the group R having formula (II), the phosphite may contain up to 6 different ortho substituents R 1 and R 2 per phosphite compound. Preferably, one of the groups R of the phosphite of formula (I) is a C1-C12 alkyl group, especially a methyl, ethyl or isopropyl group, and two of the groups R of formula (I) are represented by formula (II), wherein ring A is a phenyl group, and one or two of each R 1 and R 2 groups are selected from tert-butyl substituents.

[0047] According to the present invention, at least two of the R groups of the phosphite compound of formula (I) containing a transition metal compound are different from each other. Preferably, one of the R groups is a C1-C12 alkyl group, and two further R groups are aryl groups, more preferably both of the two further R groups are represented by formula (II), wherein the ring represented by A is a phenyl group, and R 1 and R2 carrying a base and having or not having one further substituent, most preferably one of the R groups is a C1-C12 alkyl group and the other two R groups are both represented by formula (II), wherein the ring represented by A is independently selected from a methyl group and a tert-butyl group R 1 and R 2 a phenyl group carrying a group, and most preferably the above phenyl group is independently selected from a methyl group and a tert-butyl group R 1 and R 2 and further carries one substituent selected from a methyl group and a tert-butyl group in addition to the group, or has no further substituent.

[0048] Particularly preferred is that one group R of the phosphite of formula (I) is a methyl group, an ethyl group, or an isopropyl group, and the other two R groups of formula (I) are R groups represented by formula (II), which are the same phenyl group, and when present, R 1 group, R 2 group and, as a further substituent, carries a substituent selected from a methyl group, an ethyl group, and a tert-butyl group.

[0049] The transition metal compound of the present invention is different from the following - a platinum complex containing a phosphite of the following formula;

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0050] In an embodiment according to the present invention, the transition metal compound of the present invention contains at least one phosphite having the formula (III):

Chemical formula

Chemical formula

[0051] According to this embodiment, it is preferable that two of the groups R having the formula (II) are the same and the third group R having the formula (II) is different from the two identical groups R having the formula (II).

[0052] More preferably, all groups R having the structure of formula (II) are based on a phenyl group, that is, ring A in formula (II) represents a phenyl ring, and each has an essential substituent R 1 and R 2 and carry two or three substituents including.

[0053] According to this embodiment, the substituents R 1 , R 2 and, when present, each of the third substituents having the structure of formula (II) is independently selected from a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group, and more preferably is selected from a methyl group and a tert-butyl group.

[0054] Even more preferably, in the phosphite having the formula (III), one or more groups R having the structure of formula (II) are di- or tri-tert-butylated phenyl groups, and more preferably two or more of the groups R having the structure of formula (II) in the phosphite having the formula (III) are di- or tri-tert-butylated phenyl groups.

[0055] In the phosphite having the formula (III), when one or more of the groups R having the structure of the formula (II) are di- or tri-tert-butylated, the substituent R 1 , R 2 and, when present, the further substituents on the ring A of one or two further groups R having the structure of the formula (II) are also preferably methyl groups.

[0056] In another embodiment according to the present invention, the transition metal compound according to the present invention comprises at least one phosphite compound of the formula (I), wherein in the formula (I) at least one group R is an organic group different from the group of the formula (II). The group R different from the organic group represented by the formula (II) in the group R or the phosphite of the formula (I) is an unsubstituted aromatic or heteroaromatic group, an aromatic or heteroaromatic group having only one substituent or no substituent at the ortho position with respect to the bond of the R group to the oxygen atom, or an aliphatic group, particularly selected from any of C1-C28 alkyl groups. Preferably, the phosphite compound of the formula (I) contains one group R different from the structure of the formula (II) and two groups R which may be the same or different represented by the formula (II).

[0057] According to this embodiment, it is preferable that the phosphite compound contains one group different from the structure of the formula (II), more preferably this group R different from the structure of the formula (II) is a C1-C28 alkyl group, more preferably a C1-C12 alkyl group, even more preferably a C1-C6 alkyl group, still more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, or a cyclohexyl group, and most preferably selected from a methyl group and an ethyl group. In addition, the two groups R represented by the formula (II) of the phosphite compound of the formula (I) according to this embodiment may be the same or different.

[0058] According to this embodiment, in the phosphite compound of formula (I), it is preferable that all groups R represented by formula (II) are based on phenyl groups, that is, ring A is a phenyl ring, and each of ring A has, including the essential substituents R 1 and R 2 carries two or three substituents. According to this embodiment, the substituent R 1 , R 2 and, when present, each of the third substituent is more preferably independently selected from a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group, and most preferably selected from a methyl group and a tert-butyl group.

[0059] Even more preferably, in the phosphite compound of formula (I), the group R having the structure of formula (II) is a di- or tri-tert-butylated phenyl group, more preferably two of the groups R in the phosphite compound of formula (I) have the structure of formula (II) and are di- or tri-tert-butylated phenyl groups. When one or more of the groups R having the structure of formula (II) are di- or tri-tert-butylated, it is also preferable that one of the other groups or another group R in the phosphite compound of formula (I) is a C1-C6 n-alkyl group, most preferably a methyl group or an ethyl group.

[0060] In yet another embodiment according to the present invention, the transition metal compound according to the present invention contains at least one phosphite selected from the group consisting of formula (IV) or formula (V):

Chemical formula

Chemical formula

Chemical formula

[0061] Preferably, one or more groups R in formula (IV) or formula (V) 6 is selected from C1-C28 alkyl groups, more preferably from C1-C12 alkyl groups, even more preferably from C1-C6 alkyl groups, still more preferably from methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, or cyclohexyl group, and most preferably from methyl group, ethyl group, n-propyl group or isopropyl group.

[0062] One or more groups R having formula (II) in formula (IV) or formula (V) are preferably selected from substituted phenyl groups, that is, ring A represents a phenyl group, where R 1 , R 2And, when present, each of the further substituents is independently selected from a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group, most preferably selected from a methyl group and a tert-butyl group, and even more preferably, in formula (IV) or formula (V), one or more of the groups R having the structure of formula (II) are di- or tri-tert-butylated phenyl groups, more preferably two or more of the groups R having the structure of formula (II) are di- or tri-tert-butylated phenyl groups.

[0063] In a further embodiment according to the present invention, the transition metal compound according to the present invention comprises at least one phosphite compound of formula (I), wherein in at least one group represented by formula (II), the ring represented by "A" is an aromatic group, which is optionally R 1 and R 2 and may have one or more further substituents apart from that.

[0064] Preferably, the aromatic ring A in at least one group represented by formula (II) is a phenyl group or a naphthyl group, more preferably a phenyl group.

[0065] Also preferred is that the ring A in at least one group represented by formula (II) is selected from the preferred aromatic groups listed above, and R 1 , R 2 and, when present, the further substituents are the same as or different from each other, and preferably R 1 and R 2 are selected from the group of C1-C6 alkyl groups, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a cyclopentane group, an isoamyl group, a neopentyl group, or a cyclohexyl group.

[0066] More preferably, R 1 , R 2and, when present, a further substituent attached to the phenyl ring forming ring A of the structure of formula (II) is selected from a methyl group and a tert-butyl group.

[0067] In a further preferred embodiment according to the invention, in the transition metal compound of the invention, in at least one group represented by formula (II), the ring denoted by "A" is a phenyl group, which is optionally R 1 and R 2 and may have one or more further substituents apart from.

[0068] As already described above, R 1 and R 2 are the same as or different from each other, and are preferably independently selected from the group of C1-C6 alkyl groups, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a cyclopentane group, an isoamyl group, a neopentyl group, or a cyclohexyl group. Even more preferably, the substituents R 1 and R 2 are the same and are selected from a tert-butyl group, or R 1 is a tert-butyl group and R 2 is selected from a methyl group or an ethyl group, most preferably R 1 is a tert-butyl group and R 2 is also a tert-butyl group or a methyl group.

[0069] More preferably, the phenyl ring A in at least one group represented by formula (II) bears one, two, or three further substituents apart from the above-mentioned R 1 and R 2 and they are selected from the group consisting of Si-organic groups, C1-C6 alkyl groups, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a cyclopentane group, an isoamyl group, a neopentyl group, or a cyclohexyl group.

[0070] According to this embodiment, when the phenyl ring A is R1 and R 2 also preferably bears, in the meta position relative to, a further substituent selected from an n-alkyl group, an n-alkenyl group, a halide group, a nitro group, a cyano group, an alkoxy group, an alkoxycarbonyl group or an organosilyl group, more preferably this further substituent is selected from a methyl group, an isobutyl group, a tert-butyl group, a vinyl group, an allyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, a trimethylsilyl group, a triethylsilyl group, or a triisopropylsilyl group, and even more preferably the further substituent in the meta position relative to R 1 , R 2 and R 1 and R 2 and the further substituent in the meta position relative to R 1 , R 2 and R 1 and R 2 and the further substituent in the meta position relative to R is the same type of substituent selected from a methyl group, an isobutyl group, a tert-butyl group or a trimethylsilyl group.

[0071] In another embodiment according to the invention, the transition metal compound according to the invention comprises at least one phosphite compound of formula (I), wherein the groups R in the group R represented by formula (II) 1 and R 2 are each independently an optionally substituted straight-chain, branched-chain, or cyclic alkyl group, preferably having up to 10 carbon atoms, more preferably having up to 6 carbon atoms.

[0072] According to this embodiment, the groups R 1 and R 2is preferably selected from an optionally substituted straight-chain alkyl group selected from a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or an n-octyl group, an optionally substituted branched-chain alkyl group selected from an isobutyl group, a tert-butyl group, an isoamyl group, a neopentyl group, an isohexyl group, or a neohexyl group, or an optionally substituted cyclic alkyl group selected from a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0073] The group R in the group represented by formula (II) 1 and R 2 The straight-chain, branched-chain, or cyclic alkyl group constituting may be substituted with an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group, or a Si-organic group.

[0074] In a further embodiment according to the invention, the phosphite of formula (I) composed of the transition metal compound according to the invention is selected from the compounds of formula (VI):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0075] R 1 and R 2 are as defined above, but R 3 -R 5 is preferably independently selected from hydrogen, a C1-C12 alkyl group, and an organosilyl group, and more preferably from hydrogen, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, and a trimethylsilyl group.

[0076] More preferably, one or more of the groups R of formula (II) composed of formula (VI) and (VII) are mono-, di- or tri-tert-butylated phenyl rings, and the total number of substituents other than hydrogen on the phenyl ring is 4 or less, and even more preferably 3 or 2. R 3 、R 4 、and R 5 The aliphatic groups constituting may be substituted with an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group or a Si-organic group.

[0077] In a further embodiment according to the invention, the phosphite of formula (I) composed of a transition metal compound is a monodentate ligand. Therefore, the phosphite of formula (I) has only one site for coordinating to the central metal atom of the transition metal compound. Similarly, one or more transition metal atoms of the transition metal compound constituting the phosphite of formula (I) are not part of a metallacycle.

[0078] In a further embodiment according to the invention, the group R of the phosphite of formula (I) composed of a transition metal compound contains no metal atoms. According to this embodiment, the fact that any of the groups R of the phosphite of formula (I) contains a metal atom is clearly excluded whether it would be as a component of a metallacycle, as a cation which is a counterion of an organic anion group, or as part of an organometallic residue such as, for example, a ferrocenyl group.

[0079] In another embodiment according to the invention, the group R of the phosphite of formula (I) composed of a transition metal compound contains no nitrogen atoms.

[0080] According to this embodiment, the group R of the phosphite of formula (I) contains no nitrogen atoms, and thus the presence of any nitrogen-containing residues and substituents such as amino groups, nitro groups, imino groups and amide groups is excluded from the group R.

[0081] In yet another embodiment according to the invention, the group R of the phosphite of formula (I) composed of a transition metal compound does not contain any group containing an N atom or a P atom, preferably does not contain any group containing an N atom, a P atom, an S atom or a Se atom, and most preferably does not contain any group containing an N atom, a P atom, an S atom, a Se atom or an O atom.

[0082] According to this embodiment, the absence of the above-mentioned heteroatoms is preferred because they are capable of coordinating to the central metal atom of the transition metal compound, and thus the presence of a heteroatom or a functional group containing a heteroatom can interfere in an undesirable manner with the coordination of the phosphorus atom of the phosphite of formula (I) to the central metal atom.

[0083] In a preferred embodiment according to the present invention, the group R of the phosphite of formula (I) can contain only C atoms, H atoms, O atoms and halogen atoms, where the O atom can only exist as an ether bond or an ester group, preferably the group R can contain only C atoms, H atoms and halogen atoms, and most preferably the group R in the phosphite of formula (I) consists of C atoms and H atoms.

[0084] In a specific embodiment according to the present invention, the transition metal compound according to the present invention contains at least one phosphite of formula (I) selected from the following:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0085] The compounds according to this embodiment have been found to give particularly excellent results with respect to pot life, i.e., storage stability, and at the same time, when used as a curing catalyst for curable polyorganosiloxane and / or silane compositions, have been found to have a high curing rate at high temperatures. Achieving a high rate of effect is not affected by the long-term storage of the transition metal compounds according to this embodiment.

[0086] In a more preferred embodiment according to this embodiment, the phosphite compound of formula (I) of the transition metal compound is selected from the following:

Chemical formula

Chemical formula

Chemical formula

[0087] Here, even more preferably, the phosphite of formula (I) is

Chemical formula

[0088] In a further embodiment according to the present invention, the transition metal of the transition metal compound according to the present invention is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.

[0089] The selection of the transition metal from those listed above, i.e., the selection of a suitable precursor compound containing such a transition metal for the preparation of the transition metal compound according to the present invention, is made in each case based on the temperature and the required time desired for carrying out the hydrosilylation reaction that is being considered in the presence of all the other components of the reaction composition, especially when curing the silicone composition.

[0090] The selection of the central atom(s) of the catalyst complex is generally made based on the nature of the transition metal compound and the ease of preparing such complexes from the transition metal-containing precursor compound and the corresponding phosphite, either in advance or in situ.

[0091] According to this embodiment, the most preferred transition metal compound is platinum.

[0092] In a further preferred embodiment according to the present invention, the transition metal of the transition metal compound according to the present invention is platinum.

[0093] As already mentioned, platinum is the most preferred transition metal for the formation of the transition metal complex. The platinum-based transition metal compound according to the present invention, i.e., a compound containing at least one phosphite compound of formula (I) containing at least one group R represented by formula (II), may be formed starting from a platinum compound such as hexachloroplatinic acid, Speier catalyst, Ashby catalyst, or Karstedt catalyst.

[0094] In a further embodiment according to the present invention, the transition metal compound is a transition metal complex compound, wherein the transition metal has an oxidation state of zero (0), and preferably the transition metal complex compound is a Pt(0) compound.

[0095] Complexes in the oxidized state (0), especially Pt(0) complexes, can catalyze hydrosilylation reactions with very high reaction rates. The compounds according to this embodiment contain at least one phosphite compound described in the previous embodiment, exhibit a desired high reaction rate at high temperatures, and enable the provision of a curable composition having an unusually long pot life and a high reaction rate at high temperatures.

[0096] In another embodiment according to the present invention, the transition metal compound according to the present invention contains one or more alkenyl ligands.

[0097] This one or more alkenyl ligands can be any compound having at least one C-C double bond, where the C-C double bond therein can be an internal C-C bond or a terminal C-C bond of the carbon scaffold of the ligand compound.

[0098] Preferably, at least one of the one or more C-C double bonds of the alkenyl ligand is in a terminal position.

[0099] Typically, the alkenyl ligands according to this embodiment are selected from monoalkenes, dienes, trienes, polyenes or ketoalkenes, preferably selected from monoalkenes, dienes, and trienes.

[0100] Examples of monoalkenes, which are compounds containing one C-C double bond acting as an alkenyl ligand according to this embodiment, are ethene, isobutene, cyclohexene, cyclooctene, tetrafluoroethylene, maleic anhydride, and fumaric acid esters such as dimethyl fumarate, diethyl fumarate, or diisopropyl fumarate.

[0101] Examples of dienes, which are compounds containing two C-C double bonds acting as alkenyl ligands according to this embodiment, are butadiene, isoprene, cyclohexadiene, cyclooctadiene, norbornadiene, and C5-C10 alkadienes terminated with C-C double bonds, such as 1,7-octadiene.

[0102] Examples of trienes and tetraenes, which are compounds containing three or four C-C double bonds acting as alkenyl ligands according to this embodiment, are cycloheptatriene and cyclooctatetraene.

[0103] The alkenyl ligand may also be selected from polyenes containing more than four C-C double bonds or ketoalkenes.

[0104] A more preferred alkenyl ligand selected from the group described above is an alkenylsiloxane ligand, which is characterized according to the present invention by the presence of at least one organosiloxane group and at least one alkenyl group.

[0105] In a more preferred embodiment according to the present invention, the transition metal compound according to the present invention contains one or more alkenylsiloxane ligands.

[0106] According to the present invention, any ligand containing one or more C-C double bonds and one or more organosiloxane units is considered an alkenylsiloxane ligand. Preferably, the alkenylsiloxane ligand contains two or more C-C double bonds, where more preferably this siloxane ligand contains two terminal C-C double bonds, particularly two C-C double bonds provided by a terminal vinylsiloxane moiety. In addition, it is preferred that the alkenylsiloxane ligand contains two or more siloxane groups, preferably 2 to 100 adjacent siloxane groups, where it is particularly preferred that the adjacent siloxane groups form an unbranched linear structure or an unbranched cyclic structure.

[0107] Examples of preferred alkenylsiloxane ligands are 1,3-divinyltetramethyldisiloxane (Vinyl-M2, for example used as a ligand in Karstedt catalysts), and tetravinyltetramethyl-tetracyclosiloxane (Vinyl-D4).

[0108] In a further preferred embodiment according to the invention, the transition metal compound according to the invention is represented by the following formula:

Chemical formula

[0109] The transition metal compound according to this embodiment can be obtained by adding the phosphite of formula (I) described above to a solution of a platinum-based Karstedt catalyst, or to a curable composition containing a platinum-based Karstedt catalyst or a part of a curable composition. In general, it is noted that the embodiments of the transition metal compound containing the phosphite of formula (I) described above can be combined independently, except when it is impossible for merely logical reasons.

[0110] Another embodiment of the invention relates to the use of the transition metal compound of formula (I) defined in any of the above embodiments as a curing catalyst for curable polyorganosiloxane compositions and / or silane compositions.

[0111] The above-mentioned transition metal compounds according to the invention can be advantageously used as curing catalysts for curable polyorganosiloxane and / or silane compositions, because these transition metal compounds catalyze the hydrosilylation reaction necessary for these compositions to cure at high temperature with a high reaction rate, and on the other hand, it is also possible to provide a composition with a long pot life when compared with curing catalysts of the prior art.

[0112] Here, the transition metal compounds according to the invention used for curing the curable polyorganosiloxane composition and / or the silane composition can be prepared prior to their use for curing the above-described compositions and, if desired, may optionally be isolated, or this transition metal compound may be formed in the composition to be cured by the addition of a suitable precursor compound, for example a transition metal salt or complex as described above and a phosphite of formula (I).

[0113] The use of the transition metal compounds containing a phosphite of formula (I) according to the invention as a curing catalyst for all kinds of curable polyorganosiloxane compositions and / or silane compositions is described in detail above and is included within the scope of the invention. However, the invention basically relates to hydrosilylation-curable polyorganosiloxane compositions and / or silane compositions, i.e., compositions in which the curing of the composition takes place by a hydrosilylation reaction via an addition reaction of these groups between at least one compound containing one or more Si-H groups and at least one compound containing one or more unsaturated C-C bonds.

[0114] In particular, the transition metal compounds containing a phosphite of formula (I) as defined above are used for curing the curable polyorganosiloxane compositions and / or silane compositions described in another embodiment of the invention below:

[0115] Another embodiment of the invention relates to curable polyorganosiloxane compositions and / or silane compositions containing one or more transition metal compounds containing a phosphite of formula (I) as defined above.

[0116] This embodiment of the invention relates to all kinds of curable polyorganosiloxane compositions and / or silane compositions containing phosphites of formula (I), which are basically hydrosilylation-curable polyorganosiloxane compositions and / or silane compositions, i.e., compositions in which the curing of the composition takes place by a hydrosilylation reaction via an addition reaction of these groups between a compound containing one or more Si-H groups and a compound containing one or more unsaturated C-C bonds.

[0117] Such curable polyorganosiloxane compositions and / or silane compositions according to the invention contain one or more compounds containing one or more unsaturated C-C bonds and one or more compounds containing one or more Si-H moieties.

[0118] The transition metal compounds containing phosphites of formula (I) described above can be advantageously used as curing catalysts for curable polyorganosiloxane and / or silane compositions because these transition metal compounds catalyze the hydrosilylation reaction necessary for these compositions to cure at high temperature with a high reaction rate and, on the other hand, also make it possible to provide compositions with a long pot life when compared with the curing catalysts of the prior art.

[0119] The transition metal compounds containing phosphites of formula (I) constituting the curable polyorganosiloxane compositions and / or silane compositions according to the invention may be added as isolated compounds, or a transition metal-containing precursor compound and one or more phosphites of formula (I) may be preferably mixed in a solvent and added in situ as a solution in a solvent, for example, without isolating the transition metal compound of the invention and without further processing, or by adding a suitable transition metal-containing precursor compound, such as a transition metal salt or complex like Karstedt catalyst or Ashby catalyst, and one or more phosphites of formula (I) as described above to the curable polyorganosiloxane and / or silane compositions, they may be formed in situ in the curable composition.

[0120] Thus, the curable polyorganosiloxane composition and / or silane composition according to the present invention typically contains one or more compounds containing two or more unsaturated C-C bonds, one or more compounds containing two or more Si-H moieties, and one or more transition metal compounds containing a phosphite of formula (I).

[0121] It is noted that usually an excess amount of the phosphite of formula (I) is present in the curable composition according to the present invention. This is because when forming a transition metal compound containing the phosphite of formula (I), the phosphite of formula (I) is applied in excess with respect to the transition metal-containing precursor compound in order to achieve complete conversion of the transition metal-containing precursor compound.

[0122] Therefore, the curable composition preferably contains one or more phosphites of formula (I) in addition to the phosphite of formula (I) contained in one or more transition metal compounds containing the phosphite of formula (I) contained in the curable composition.

[0123] According to the present invention, the curable polyorganosiloxane composition and / or silane composition preferably comprises (A) one or more polyorganosiloxanes and / or silanes having on average at least two alkenyl groups, and (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups, (C) one or more transition metal compounds, wherein the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, (D) optionally, one or more phosphites of formula (I) as defined in any of the above embodiments, and (E) optionally one or more auxiliary agents.

[0124] The curable polyorganosiloxane composition and / or silane composition containing the phosphite of formula (I) may be dissolved, dispersed, suspended, or emulsified in a liquid if necessary. All viscosities shown in this application were determined according to DIN53019, and unless otherwise specified, they are at 25 °C and a shear rate D = 10 s -1 therein.

[0125] The above components (A) to (E) are defined as follows:

[0126] Component (A) The composition of the present invention contains one or more polyorganosiloxanes and / or silanes (A) having on average at least two alkenyl groups, such as those disclosed in US3,096,303, US5,500,148A (Examples). Suitable component (A) can be described by the general formula (III'), [M a D b T c Q d m (III') where formula (III') represents the ratio of the siloxy units M, D, T, and Q, and these units can be in blocks or randomly dispersed in the polymer chain. Inside the polysiloxane chain, each siloxane unit can be the same or different, and preferably, a = 1 to 10, preferably 2 to 8, more preferably 2 to 7, even more preferably 2 to 6, b = 0 to 12000, preferably 1 to 10000, more preferably 2 to 8000, even more preferably 5 to 6000, still more preferably 20 to 4000, c = 0 to 50, preferably 0 to 25, more preferably 0 to 8, and also preferably 1 to 48, more preferably 2 to 45, even more preferably 3 to 40, still more preferably 5 to 30, d = 0 to 1, m = 1 to 5000, preferably 1 to 4800, more preferably 1 to 4200, even more preferably 1 to 3500, still more preferably 1 to 2500.​

[0127] These indices represent the average degree of polymerization Pn based on the number average molecular weight Mn.

[0128] Polymer (A) is selected from the group of alkenyl-containing polyorganosiloxanes and undergoes a hydrosilylation reaction with hydrogen siloxane to form a silicon-carbon bond.

[0129] Polymer (A) or a mixture thereof contains a group selected from the following: M = R' 3 SiO 1 / 2 or M * D = R' 2 SiO 2 / 2 or D * T = R'SiO 3 / 2 or T * Q = SiO 4 / 2 , divalent R 2 '-group, where M * = R 1 ' p R' 3-p SiO 1 / 2 , D * = R 1 ' q R' 2-q SiO 2 / 2 , T * = R 1 'SiO 3 / 2 , wherein p = 1 to 3, q = 1 to 2.

[0130] R' is preferably a normal, iso, or tert-C 1 ~C 30 alkyl group, alkoxyalkyl group, C 5 ~C 30 cyclic alkyl group, or C 6 ~C 30Selected from aryl groups, alkylaryl groups, these groups having one or more O-atoms, N-atoms, S-atoms or F-atoms, such as ethers or amides or poly(C 2 ~C 4 ) alkylene ethers are substitutable.

[0131] Examples of the above-mentioned monovalent residue R' in component (A) include hydrocarbon groups and halogenated hydrocarbon groups.

[0132] Examples of suitable monovalent hydrocarbon radicals preferably include alkyl radicals such as CH 3 -, CH 3 CH 2 -, (CH 3 ) 2 CH-, C 8 H 17 - and C 10 H 21 -, alicyclic radicals such as cyclohexylethyl, aryl radicals such as phenyl, tolyl, xylyl, aralkyl radicals such as benzyl and 2-phenylethyl. Preferred monovalent halogenated hydrocarbon radicals have the formula C n F 2n+1 CH 2 CH 2 -, where n has a value from 1 to 10, for example, CF 3 CH 2 CH 2 -, C 4 F 9 CH 2 CH 2 -, C 6 F 13 CH 2 CH 2 -, C 2 F 5 -O(CF 2 -CF 2 -O) 1~10 CF 2 -, F[CF(CF 3 )-CF 2 -O] 1~5 -(CF 2 ) 0~2 -, C 3 F7 -OCF(CF 3 )- and C 3 F 7 -OCF(CF 3 )-CF 2 -OCF(CF 3 )- and the like.

[0133] Preferred groups for R' are a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group.

[0134] R 1 ' is selected from unsaturated groups containing a C=C-group (alkenyl group), for example: normal-, iso-, tert- or cyclic-C 2 ~C 30 -alkenyl group, C 6 ~C 30 -cycloalkenyl group, C 8 ~C 30 -alkenylaryl group, cycloalkenylalkyl group, vinyl group, allyl group, methallyl group, 3-butenyl group, 5-hexenyl group, 7-octenyl group, ethylidene-norbornanyl group, styryl group, vinylphenylethyl group, norbornenyl-ethyl group, limonenyl group, and these groups can be substituted with one or more O-atoms or F-atoms, for example, ethers or amides or poly-C 2 ~C 4 polyethers having up to 1000 polyether units. The alkenyl radical is preferably bonded to the terminal silicon atom, and the olefin functionality is in the terminal alkenyl group of the higher-order alkenyl radical, because the α,ω-dienes used to prepare alkenylsiloxanes are readily available.

[0135] R 1 's preferred groups are a vinyl group and a 5-hexenyl group.

[0136] R 2 ' is, for example, a divalent aliphatic or aromatic, normal-, iso-, tert- or cyclic-C 1 ~C 14- It contains an alkylene group, an arylene group or an alkylene aryl group and crosslinks the siloxy units. Its content does not exceed 30 mol% of all the siloxy units. Suitable divalent hydrocarbon group R 2 Preferred examples of include any alkylene residue, preferably, for example, -CH 2 -, -CH 2 CH 2 -, -CH 2 (CH 3 )CH-, -(CH 2 ) 4 -, -CH 2 CH(CH 3 )CH 2 -, -(CH 2 ) 6 -, -(CH 2 ) 8 - and -(CH 2 ) 18 -; cycloalkylene radicals such as cyclohexylene; arylene radicals such as phenylene, xylylene and combinations of hydrocarbon radicals such as benzylene, i.e., -CH 2 CH 2 -C 6 H 4 -CH 2 CH 2 -,-C 6 H 4 CH 2 - are included. Preferred groups are α,ω-ethylene, α,ω-hexylene or 1,4-phenylene.

[0137] Suitable divalent halogenated hydrocarbon radicals R 2' Examples of include any divalent hydrocarbon group in which one or more hydrogen atoms are replaced by halogen atoms such as fluorine, chlorine or boron. Preferred divalent halogenated hydrocarbon residues have the formula -CH 2 CH 2 (CF 2 ) 1~10 CH 2 CH 2 -, which is, for example, -CH 2 CH 2 CF 2 CF 2 CH 2CH 2 - and, further, other examples of suitable divalent hydrocarbon ether radicals and halogenated hydrocarbon ether radicals include -CH 2 CH 2 OCH 2 CH 2 -, -C 6 H 4 -0-C 6 H 4 -, -CH 2 CH 2 CF 2 OCF 2 CH 2 CH 2 -, and -CH 2 CH 2 OCH 2 CH 2 CH 2 - are included.

[0138] R', R 1 ' and / or R 2 ' radicals are such polymers containing polyorganosiloxanes, such as alkenyl-dimethylsiloxy or trimethylsiloxy terminated polydimethylsiloxanes, and may contain other siloxane units other than alkenylmethylsiloxy groups and dimethylsiloxy groups, such as poly-(dimethyl-co-diphenyl)siloxane.

[0139] The widely described component (A) of the composition of the present invention can be any polyorganosiloxane compound containing two or more silicon atoms linked by oxygen and / or a divalent group R 2 ', where silicon is bonded to 0 to 3 monovalent groups per silicon atom, provided that the organosilicon compound contains at least two unsaturated hydrocarbon residues bonded to silicon. This component can be solid or liquid and can have a measurable viscosity of less than 100 kPa.s at 25 °C at a shear rate D = 1 s -1 .

[0140] The polyorganosilicon compound (A) containing an unsaturated hydrocarbon residue bonded to at least two silicons preferably has a viscosity in the range of 10 to 100,000,000 mPa·s at a shear rate D = 10 s -1 at 25°C. The preferred range is about 100 to 10,000,000 mPa·s, more preferably the viscosity is in the range of 200 to 1,000,000 mPa·s, even more preferably in the range of 200 to 500,000 mPa·s, and most preferably in the range of 200 to 200,000 mPa·s (according to DIN 53019).

[0141] The siloxane units with radicals R' and / or R 1 ' can be the same or different for each silicon atom. In a preferred embodiment, the structure is represented by the general formulas (III'a) to (III'b) shown below.

[0142] A preferred polyorganosiloxane component (A) for the composition of this invention is a substantially linear polyorganosiloxane (A) having the formula (III'a) or (III'e) to (III'i). The expression "substantially linear" includes polyorganosiloxanes containing no more than 0.2 mol% (trace amounts) of T-type or Q-type siloxy units. This means that the polymer (A) is preferably a linear, fluid liquid or rubber (A1) having a Newtonian fluid-like viscosity and not a solid at 25°C.

[0143] R 1 ' p R' 3-p SiO(R' 2 SiO) b SiR' 3-p R' p 1 (III'a)(A1) R 1 ' p R' 3-p (R' 2 SiO) b1 (R 1 ' q R' 2-q SiO)b1x SiR' 3-p R p 1 ' (III'b) b => 0 to 12000, more preferably 10 to 9000, even more preferably 50 to 5000, and even more preferably 50 to 1000, b1 => 0 to 12000, more preferably 10 to 9000, even more preferably 50 to 5000, and even more preferably 50 to 1000, b1x = 0 to 1000, more preferably 1 to 500, even more preferably 10 to 200, and even more preferably 10 to 100, b1 + b1x => 0 to 12000, more preferably 10 to 9000, even more preferably 50 to 5000, and even more preferably 60 to 1000, p = 0 to 3, q = 1 to 2, However, there are at least two alkenyl groups per molecule.

[0144] Preferred groups for R' are a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group.

[0145] R 1 Preferred groups for R' are a vinyl group, a hexa-5-enyl group, and a cyclohexenyl-2-ethyl group.

[0146] The average degree of polymerization Pn or "b" etc. is based on M as the number average molar mass in the range up to 12000 n and the preferred range is 400 to 5000.

[0147] The polyorganosilicon compound (A) containing at least two unsaturated hydrocarbon residues bonded to silicon preferably has a shear rate D = 10 s at 25°C -1has a viscosity in the range of 10 to 100,000,000 mPa·s, preferably in the range of about 100 to 10,000,000 mPa·s, more preferably the viscosity is in the range of 200 to 1,000,000 mPa·s, even more preferably in the range of 200 to 500,000 mPa·s, and most preferably in the range of 200 to 200,000 mPa·s.

[0148] Such viscosities at 25 °C for component (A) are suitable for the production of a wide range of various products, such as molded or extruded rubber parts using liquid silicone rubber and high-viscosity rubber, curable "in-situ formed" seals, and coatings for substrates.

[0149] In the group of alkenyl-containing siloxanes (A), the addition of other so-called vinyl-rich polymers (A2) is preferred to modify the mechanical properties.

[0150] This polymer (A2) is selected from the group consisting of polymers of formula (III'b) to (III'd) or formula (III'h) to (III'i), i.e., linear polyorganosiloxanes with additional alkenyl side chains, or branched polyorganosiloxanes having T units and Q units at higher concentrations than the types described above: Me 3 SiO(Me 2 SiO) b1 (MeViSiO) b1x SiMe 3 (III'c), and ViMe 2 SiO(Me 2 SiO) b1 (MeViSiO) b1x SiMe 2 Vi (III'd), where Vi = vinyl.

[0151] The preferred value of b1x is less than 0.5 × b1 or zero. If b1x is not zero, it is preferably between 0.0003 × b1 and 0.25 × b1, preferably between 0.0015 × b1 and 0.15 × b1.

[0152] Other preferred structures from formula (III'e) to (III'i) achieve an appropriate viscosity, which will be defined later, and describe polymers that are applicable without any solvent for viscosity adjustment. The range of the subscript defines the range of the possible average degree of polymerization P n .

[0153] Vi p Me 3-p SiO(Me 2 SiO) 10~12000 SiMe 3-p Vi p (III'e), PhMeViSiO(Me 2 SiO) 10~12000 SiPhMeVi (III'f), Vi p Me 3-p SiO(Me 2 SiO) 10~12000 (MeViSiO) 1~2500 SiMe 3-p Vi p (III'g), Me 3 SiO(Me 2 SiO) 10~12000 (MeViSiO) 1~2500 SiMe 3 (III'h), PhMeViSiO(Me 2 SiO) 10~12000 (MePhSiO) 1~1000 SiPhMeVi (III'i) and where Ph = phenyl, p = 0 to 3, preferably p = 1.

[0154] In a preferred embodiment, the polymer component (A) is a mixture of a polymer of formula (Ill'a) and a polymer of formula (Ill'b) or (Ill'h), whereby (III'b) has an alkenyl content ratio of 1 to 50 mol%, and the alkenyl content of the mixture of (A1) and (A2) is less than 2 mol%.

[0155] Another type of preferred polymer is a high concentration of SiMe with a defined curing rate (3-p) (alkenyl) p branched polyorganosiloxane (A2) having a group. Such structures are used particularly in release coating applications. Branched polymers are described, for example, in US5,616,672 and are preferably selected from branched polymers of formula (III'), where the polyorganosiloxane (A2) containing an alkenyl group has more than 0.2 mol% of T units = R'SiO 3 / 2 or Q units = SiO 4 / 2 having.

[0156] Preferably, the range of D:T of the branched vinyl-rich polymer is >10:1, preferably >33:1, and / or for each, (M アルケニル :Q) = 0.6 to 4:1.

[0157] All of these polymers can be prepared by any of the conventional methods for preparing triorganosiloxane-terminated polydiorganosiloxanes. For example, appropriate ratios of suitable hydrolyzable silanes, such as vinyldimethylchlorosilane and dimethyldichlorosilane, may be co-hydrolyzed and condensed, or alternatively a suitable 1,3-divinyltetraorganodisiloxane, such as a symmetrical divinyldimethyldiphenylsiloxane or divinyltetramethylsiloxane that supplies the end groups of the polydiorganosiloxane, may be equilibrated with a suitable dipolydiorganosiloxane, such as octamethylcyclotetrasiloxane, in the presence of an acidic or basic catalyst. Regardless of the method for preparing the polydiorganosiloxane (A), various amounts of volatile cyclic polydiorganosiloxanes are usually produced together.

[0158] Regarding the viscosity of the polydiorganosiloxane (A) defined above with respect to the object of the present invention, it refers to the part of the polyorganosiloxane, preferably essentially free of cyclic polydiorganosiloxanes (less than 1% by weight, preferably less than 0.5% by weight, measured at 150 °C and 20 mbar for 1 hour). This essentially cyclic-free part can be prepared by stripping the polydiorganosiloxane at 150 °C for at least 1 hour to produce this kind of polymer residue. This residue is essentially free of cyclic substances except for trace amounts of large cyclic polydiorganosiloxanes (molecular weight > 518 g / mol) that are not volatile as described above.

[0159] The average degree of polymerization P of the polymer (A) n is measured by GPC measurement against polystyrene standards based on the number average molar weight M n and is preferably in the range of > 10 to 12000, more preferably in the range of 40 to 6000, even more preferably in the range of 60 to 3000, and even more preferably in the range of 70 to 1500. The viscosity of such polymers is at 25 °C and shear rate D = 10 s -1 and is in the range of 10 to 50,000,000 mPa·s. The value of P n or the index "b" in the above formula (III'a) is such that the linear polyorganosiloxane (A) has a viscosity of at least 10 mPa·s at 25 °C. Preferably the viscosity range is about 40 mPa·s to 35,000,000 mPa·s, more preferably 100 mPa·s to 25,000,000 mPa·s, even more preferably 500 to 1,000,000 mPa·s, even more preferably 800 to 500,000 mPa·s, and even more preferably 2,000 to 200,000 mPa·s, and most preferably 2000 to 100,000 mPa·s. This viscosity approximately corresponds to the value of the average P n indicated by "b" or "b1 + b1x".

[0160] The concentration of the functional unsaturated group is in the range of 50 mol% to 0.033 mol% (mol% of the functionalized Si atoms relative to the total Si atoms), that is, in the case of polydimethylsiloxane, it is generally preferably 0.002 to 12 mmol / g, more preferably 0.004 to 3 mmol / g. The aforementioned siloxane units can be combined in any molecular arrangement such as linear, branched, cyclic, and combinations thereof, resulting in polyorganosiloxanes (A1) and (A2) useful as component (A). In a preferred embodiment, the hydrosilylation curable composition is solvent-free (volatile matter less than 1 wt%).

[0161] In the present application, the alkenyl content of component (A) 1 can be determined by 1H-NMR. See A.L. Smith (ed.): The Analytical Chemistry of Silicones, pp. 356 et seq., Vol. 112, J. Wiley & Sons, 1991, in Chemical Analysis edited by J.D. Winefordner.

[0162] Component (A) can also be selected from the group of silanes having the following general formula: R' e R 1 ' f Si(OR 9 ') (4-e-f) R' e R 1 ' f Si(NR 9 ' 2 ) (4-e-f) where R', R 1 ' are as defined above, R 9 ' is as defined below, and e = 0 to 3, f = 1 to 4, and e + f = 4; (R 9 'O) (3-g-h) (R 1 ' g )(R' h )Si-R2 '-Si(R' h )(R 1 ' g )(OR 9 ') (3-h-g) 、 (R 9 ' 2 N) (3-g-h) (R 1 ' g )(R' h )Si-R 2 '-Si(R' h )(R 1 ' g )(NR 9 ' 2 ) (3-h-g) 、 wherein R', R 1 ' and R 2 ' are as defined above, R 9 ' is as defined below, and g = 1 to 3, h = 0 to 2, and g + h = 3.

[0163] According to the present invention, particularly preferred polyorganosiloxanes having on average at least two alkenyl groups are -dimethylvinylsilyl-terminated polydimethylsiloxane having a general average composition MVi 2 D m wherein m is in the range of 50 to 1500, preferably 60 to 1400, more preferably 70 to 1400, and even more preferably 70 to 1000 -dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane) having a general average composition MVi 2 D n DVi o wherein n is in the range of 100 to 1000, preferably 200 to 900, more preferably 300 to 800, and even more preferably 400 to 700, and o is independently in the range of 10 to 120, preferably in the range of 15 to 90, more preferably in the range of 20 to 70, and even more preferably in the range of 25 to 50, for example, having an average composition of MVi 2 D 560DVi 36 is dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane).

[0164] Component (B) - (Crosslinking agent) The curable composition of the present invention contains, as component (B), a crosslinking agent and / or a chain extender for the polymer defined as (A). This component (B) is obtained from the group consisting of silanes and polyorganosiloxanes having on average at least two SiH groups, and can react with the alkenyl groups of the polymer (A) to crosslink two polymers to form an elastomeric network structure. In order to obtain more elastomeric behavior rather than a gel, it is preferable that at least 30 mol% of component (A) or (B) has three or more functional reactive groups (for (A), the number of Si-alkenyl groups relative to the total number of silicon atoms; for (B), the number of SiH-groups relative to the total number of silicon atoms).

[0165] Component (B) is preferably selected from the group of SiH-containing polyorganosiloxanes and SiH-containing organosilanes, which are each hydrogen silyl-modified hydrocarbons. Suitable is when component (B) is M = R' 3 SiO 1 / 2 、M H =R'YSiO 1 / 2 、D = R' 2 SiO 2 / 2 、D H =R'YSiO 2 / 2 、T = R'SiO 3 / 2 、T H =YSiO 3 / 2 、and SiO 4 / 2 and is composed of siloxane units selected from the group, where R' is as defined above, Y = R 1 ' and / or H, provided that there are on average at least two SiH-groups per molecule.

[0166] For example, they include the following: R' e H f Si(OR 9 ')(4-e-f) R' e H f Si(NR 9 ' 2 ) (4-e-f) Here, R' is as defined above, and R 9 ' is as defined below, and e = 0 to 3, f = 1 to 4, and e + f = 4.

[0167] Furthermore (R 9 'O) (3-g-h) (H g )(R' h )Si-R 2 '-Si(R' h )(H g )(OR 9 ') (3-h-g) , (R 9 ' 2 N) (3-g-h) (H g )(R' h )Si-R 2 '-Si(R' h )(H g )(NR 9 ' 2 ) (3-h-g) Here, g, h, R', R 2 ', R 9 ' are as defined above or as defined below.

[0168] This means that the polymer (B) can be formally described by the ratios in the general formula (IV'). [M a2 D b2 T c2 Q d2 m2 (IV') ​In the formula, the siloxy units M, D, T, and Q are as defined above, including the possibility of being SiH-containing M groups, D groups, and T groups. Also, as a possibility, as long as there are at least two SiH groups on average per molecule, a part of the siloxy groups may be alkenylsiloxy groups. The siloxy units may be dispersed in blocks or randomly in the polymer chain. Inside the polysiloxane chain, each siloxane unit can be the same or different, and preferably, a2 = 1 to 100, preferably 1 to 40, more preferably 1 to 10, even more preferably 2 to 5, b2 = 0 to 1000, preferably 2 to 500, more preferably 5 to 250, c2 = 0 to 50, preferably 0 to 45, more preferably 0 to 40, even more preferably 0 to 30, even more preferably 0 to 20, still more preferably 1 to 20, d2 = 0 to 1, m2 = 1 to 2000, preferably 1 to 1500, more preferably 1 to 120, even more preferably 1 to 100, still more preferably 1 to 80.

[0169] The above indexes represent the average degree of polymerization Pn based on the number average molecular weight Mn.

[0170] The ranges of M units, D units, T units, and Q units present in the molecule can cover almost all values representing fluids, flowable polymers, liquid and solid resins. Optionally, C remaining from synthesis 1 ~C 3 -alkoxy groups or Si-hydroxy groups-containing liquid silanes or liquid linear, cyclic, or branched siloxanes are preferably used. These compounds can have a low molecular weight or be condensation products, can be partially hydrolyzed, and the siloxanes are polymerized through equilibration or condensation under the action of an acidic catalyst.

[0171] The siloxane units having radical R' or Y can be the same or different for each silicon atom.

[0172] The preferred structure of the reactive polyorganosiloxane for component (B) in the composition of the present invention is a silane or a condensed silane / siloxane of formulas (IV'a) to (IV'd).

[0173] The preferred structure composed of the above units is selected from the following Y r R' 3-r SiO(R' 2 SiO) z (R'YSiO) v SiR' 3-r Y r (IV'a) Y r Me 3-r SiO(Me 2 SiO) z (MeYSiO) v SiMe 3-r Y r (IV'b) Me 3 SiO(MeYSiO) v SiMe 3 (IV'c) [YR'SiO] w (IV'd) z = 0 to 1000, preferably 1 to 250, more preferably 5 to 150, even more preferably 10 to 50, v = 0 to 100, preferably 2 to 80, more preferably 4 to 60, even more preferably 6 to 40, z + v = 1 to 1000, preferably 2 to 300, more preferably 5 to 250, even more preferably 10 to 80, w = 3 to 9, r = 0 or 1, and is also selected from the structures of the following formulas {[YSiO 3 / 2 [R 9 'O 1 / 2 n2} m2 (IV'e) {[SiO 4 / 2} [R 9 'O 1 / 2 n2 [R' 2 ​​YSiO 1 / 2 0,01~10 [YSiO 3 / 2 0~50 [R'YSiO 2 / 2 0~1000} m2 (IV'f) Here R 9 'O 1 / 2 is an alkoxy residue on a silicon atom, R' is as defined above, n2 = 0.001 to 3, a2 = 0.01 to 10, b2 = 0 to 1000, c2 = 0 to 50, m2 = 1 to 2000, Y = hydrogen or R 1 ', R 9 ' is hydrogen, normal-, iso-, tert- or cyclic-C 1 ~C 25 -alkyl group, such as an alkanoyl group like a methyl group, an ethyl group, a propyl group, an acyl group, an aryl group, -N=CHR like butanone oxime, an alkenyl group like a propenyl group, and this group R 9 ' may be substituted by one or more halogen atoms, pseudohalogen groups such as a cyano group.

[0174] A preferred group for Y is hydrogen.

[0175] One preferred embodiment of the compounds of types (IV'e) and (IV'f) is exemplified by a polymer compound from monomer compounds describable through the formula [(Me 2 HSiO 0.5 ) k SiO 4 / 2 m2 where the index k can have an integer or decimal value from 0.01 to (2 × m 2 +2). Such liquid molecules or resinous molecules have a significant concentration of SiOH- and / or (C 1 ~C 6 ​​​​)-It can contain an alkoxy-Si group.

[0176] For other types of preferred compounds having formulas (IV'a) to (IV'c), the indices z and v are the average P measured by GPC relative to polystyrene standards based on the number-average molar mass M n and are in the range of 0 to 1000 as defined. n

[0177] Other examples of suitable compounds preferred for component (B) in the composition of this invention include HMe 2 SiO(Me 2 SiO) z SiMe 2 H, HMe 2 SiO(HMeSiO) w (Me 2 SiO) z SiMe 2 H, Me 3 SiO-(MeHSiO) v -SiMe 3 , Me 3 SiO(HMeSiO) w (Me 2 SiO) z SiMe 3 , (MeHSiO) 3~6 , Si(OSiMe 2 H) 4 , Si x (OSiMe 2 H) 1,7x , MeSi(OSiMe 2 H) 3 , HMe 2 SiO-(Me 2 SiO) z1 (MePhSiO) z2 (MeHSiO) v SiMe 2 , H, Me 3 SiO-(Me 2 SiO) z1 (MePhSiO) z2 (MeHSiO) v SiMe 3 , HMe 2 SiO-(Me 2 SiO)​z1 (Ph 2 SiO) z2 (MeHSiO) v SiMe 2 H, Me 3 SiO-(Me 2 SiO) z1 (Ph 2 SiO) z2 (MeHSiO) v SiMe 3 is included, where z1 + z2 = z.

[0178] Component (B) can be used as a single component of one polyorganosiloxane polymer or a mixture thereof. In another embodiment, it is preferred to use a mixture of formula (IV'b) and formula (IV'c). If it is necessary to increase the curing rate, it is preferred to use an organopolysiloxane (B) of the type having HMe 2 SiO 0,5 -units to adjust the curing rate to a shorter time.

[0179] The molecular weight of component (B) is smaller; the number of functional groups per molecule in component (B) is larger than that in component (A).

[0180] If it is necessary to further increase the curing rate, it can be achieved, for example, by increasing the molar ratio of SiH to Si-alkenyl, or by increasing the amount of catalyst (C), or by increasing the proportion of polyorganosiloxane (B) containing HMe 2 SiO 0.5 units. Thus, in order to bring about a faster curing rate, a preferred component (B) contains HMe 2 SiO 0.5 (MH groups).

[0181] In a further preferred embodiment of component (B), this component is YR' 2 SiO(R' 2 SiO) z (R'YSiO) v SiR' 2A group according to formula (IV'a) consisting of a component (B1) such as Y or a group according to formula (IV'c) in which there are three or more functional groups Y, and YR' in which the average number of functional groups Y is 2 2 SiO(R' 2 SiO) z SiR' 2 Selected from components (B2) such as Y, where Y, R' and z are as defined above.

[0182] When (B1) and (B2) are used together, the preferred ratio of (B1) to (B2) of the functional group SiH is, based on (B1) and (B2), more than 0 to 70 mol% of (B2), and more preferably 30 to 100 mol%.

[0183] The molecular weight of component (B) is not critical; however, when the polyorganosiloxane component (B) has R' = methyl group, at 25 °C and shear rate D = 10 s -1 it preferably has a viscosity of 3 to 10,000 mPa·s, preferably 5 to 3,000 mPa·s, more preferably 8 to 2,500 mPa·s, and even more preferably 10 to 1,500 mPa·s. The viscosities described above are also preferred for polyorganosiloxane component (B) in general. This viscosity depends on the type of R' substituent and Y substituent, as well as the ratio and molar weight of the units M, D, T and Q. For polyorganosiloxanes containing only methyl groups as R' groups, the molar weight range represented as M n is between 136 and 100,000 g / mol, preferably between 250 and 50,000, more preferably between 400 and 25,000, and even more preferably between 1,000 and

[0184] The siloxane units with radicals R' or Y may be the same or different for each silicon atom. Each molecule can independently carry one or more groups.

[0185] The crosslinking agent (B) must have at least two or more reactive groups Y per molecule, while the chain extender (B2) has an average of two or three functional groups Y per molecule.

[0186] The concentration of the reactive group Y is 0.2 to 100 mol% of the Y group with respect to the silicon atom, that is, for polydimethyl-methylhydrogensiloxane, preferably SiY is about 0.1 to 17 mmol / g, and the preferred range is 0.15 to 16 mmol / g.

[0187] In one preferred embodiment, a mixture of compounds having the formula (IV'c) or formula (IV'd) is used together with a compound having the formula (IV'a) and / or formula (IV'b), where z = 0, R' is a methyl group, the SiH concentration is preferably SiH > 7 to 17 mmol / g, and in the second compound (B) the index z > 0, where the SiH concentration preferably has a value of 0.2 to 7 mmol / g.

[0188] When adhesion to other substrates, such as thermoplastic substrates, has to be achieved, it is preferred to use a compound of the formula (IV'a) and / or formula (IV'b) where R' = aryl, especially phenyl.

[0189] The SiH content in the present invention 1 can be determined by H-NMR. See A.L. Smith (ed.): The Analytical Chemistry of Silicones, pages 356 et seq. of volume 112 of J. Wiley & Sons, 1991, in Chemical Analysis edited by J.D. Winefordner.

[0190] The ratio of the crosslinking agent (B) to the polymer (A) required to obtain an elastomeric network structure, i.e., a non-sticky surface, can be calculated by the ratio of the reactive groups in (B) and (A). To ensure a predetermined level of multifunctional structure in the cured elastomeric network structure, it is preferred that the ratio of reactive groups (B):reactive groups (A) is in the range of 0.7 to 20:1, preferably 1.2 to 6:1, more preferably 1.5 to 4:1 and in excess.

[0191] According to the present invention, particularly preferred polyorganosiloxanes having on average at least two SiH groups are - a hydride-terminated poly(dimethylsiloxane) of general average composition MH 2 D a where a is in the range of 5 to 100, preferably 8 to 80, more preferably 10 to 50, even more preferably 12 to 40, even more preferably 13 to 25, for example a hydride-terminated poly(dimethylsiloxane) of general average composition MH 2 D 17 ; - a trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane) of general average composition M 2 D b DH c where b is in the range of 10 to 50, preferably 12 to 40, more preferably 14 to 40, even more preferably 15 to 30, and c is independently in the range of 2 to 50, preferably 4 to 40, more preferably 6 to 40, even more preferably 8 to 30, for example a trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane) of average composition M 2 D 20 DH 20 or of average composition M 2 D 20 DH 10 ; - a resin type of general average composition MH dx Q x where d is in the range of 1.1 to 2.5, preferably 1.2 to 2.2, more preferably 1.3 to 2.1, and even more preferably 1.5 to 2.0, for example of average composition MH1.7x Q x is; - general average composition M 2 DH e trimethylsilyl-terminated polymethylhydrogensiloxane of, where e is in the range of 5 to 100, preferably 10 to 80, more preferably 15 to 60, even more preferably 20 to 40, for example the average composition M 2 DH 30 trimethylsilyl-terminated polymethylhydrogensiloxane; or - general average composition M 2 D(Ph 2 ) f DH g D h trimethylsilyl-terminated poly(dimethylsiloxane - co - diphenylsiloxane - co - methylhydrogensiloxane) of, where f is in the range of 1 to 50, preferably 2 to 40, more preferably 3 to 25, even more preferably 5 to 15, g is independently in the range of 2 to 50, preferably 6 to 40, more preferably 12 to 30, and h is in the range of 1 to 50, preferably 2 to 40, more preferably 3 to 25, even more preferably 5 to 15, for example the average composition M 2 D(Ph 2 ) 2 DH 24 D 2 is trimethylsilyl-terminated poly(dimethylsiloxane - co - diphenylsiloxane - co - methylhydrogensiloxane).

[0192] Component (C) - (Transition metal compound) The curable composition of the present invention contains at least one transition metal compound containing the phosphite of formula (I) described above that acts as a hydrosilylation catalyst, where the transition metal is selected from the group consisting of compounds of Ni, Ir, Rh, Ru, Os, Pd and Pt as taught in US3,159,601; US3,159,662; US3,419,593; US3,715,334; US3,775,452 and US3,814,730.

[0193] Component (C) for the hydrosilylation reaction of the composition according to the present invention is a catalyst compound, which promotes the reaction between the hydrogen atom bonded to silicon of component (B) and the olefinic hydrocarbon substituent bonded to silicon of component (A). This transition metal compound can be any catalytically active component containing a transition metal and a phosphite of formula (I). Catalyst (C) includes a complex with σ-bonded and π-bonded carbon ligands and S, N, or P atom ligands, a metal colloid or salt of the above-mentioned metal. This catalyst can be present on a support such as silica gel or powdered charcoal, can support the metal, or can be a compound or complex of that metal. Preferably, the metal of component (C) can be any platinum complex compound.

[0194] Typical platinum-containing catalyst components in the polyorganosiloxane composition of the present invention are any form of platinum(0), (II), or (IV) compounds containing a phosphite of formula (I). Preferred complexes are Pt(0)-alkenyl complexes, such as alkenylsiloxane complexes like alkenyl, cycloalkenyl, vinylsiloxane, because of the ease of dispersion in the polyorganosiloxane system.

[0195] A particularly useful form of the platinum complex is a Pt(0) complex with an aliphatic unsaturated organosilicon compound. For example, 1,3-divinyltetramethyldisiloxane (derived from vinyl-M2 or Karstedt catalyst) as disclosed in US3,419,593 incorporated herein by reference is particularly preferred, and there are cyclohexane-Pt, cyclooctadiene-Pt, and tetravinyltetramethyl-tetracyclosiloxane (vinyl-D4).

[0196] Pt 0 -olefin complexes are, for example, 1,3-divinyltetramethyldisiloxane (M Vi 2) It is prepared by reduction of hexachloroplatinic acid or other platinum chlorides with an alcohol in the presence of a basic compound such as an alkali carbonate or alkali hydroxide. The transition metal compound containing the phosphite of formula (I) is formed by reacting the phosphite of formula (I) with a corresponding precursor compound, e.g., Pt 0 -olefin compound, in the curable composition or separately.

[0197] The amount of the platinum-containing catalyst component used in the composition of the present invention is not narrowly limited as long as it is an amount sufficient to promote hydrosilylation between component (A) and component (B) at a desired temperature within a required time in the presence of all other components of the composition of the present invention. The exact required amount of this catalyst component depends on the specific catalyst, the amount of other inhibitor compounds, and the ratio of SiH to olefin and is not easily predictable. This is equally true for all transition metal-containing catalysts. However, for the platinum catalyst, the above amount can be as small as possible for cost reasons. Preferably, platinum in an amount exceeding 1 part by weight is added per 1 million parts by weight of the organosilicon components (A) and (B) to ensure curing in the presence of other unspecified trace amounts of inhibitors. For the composition of the present invention, the amount of the platinum-containing catalyst component applied is preferably sufficient to provide from 1 to 200 ppm, preferably from 2 to 100 ppm, particularly preferably from 4 to 60 ppm by weight of platinum per part by weight of the polyorganosiloxane components (A) and (B).

[0198] Preferably, the above amount is at least 4 ppm per total weight of components (A) and (B).

[0199] Other platinum catalysts that may be used as precursor compounds are mentioned, for example, in US 3,715,334 or US 3,419,593, EP 1672031 A1, and Organometallics 1995, 14, 2202-2213 by Lewis, Colborn, Grade, Bryant, Sumpter, and Scott, all of which are incorporated herein by reference.

[0200] As already explained above, the specific phosphites of formula (I) used according to the invention interact with conventional transition metal compounds through ligand exchange reactions, thereby forming transition metal compounds containing the phosphites of formula (I) and influencing the hydrosilylation activity of the catalyst, while providing a surprisingly excellent balance between storage stability on the one hand and reactivity at elevated temperatures during curing on the other hand.

[0201] According to what has been described above regarding the formation of the transition metal compound containing the phosphite of formula (I), the presence of the phosphite of formula (I) and a transition metal-containing precursor compound, for example a conventional transition metal-based hydrosilylation catalyst, in the curable composition is equivalent to the presence of the transition metal compound containing the phosphite of formula (I) (C).

[0202] According to the invention, particularly preferred transition metal compounds (C) are {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{bis(2-tert-butyl-6-methyl-phenyl)ethylphosphite}platinum, {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{bis(2-tert-butyl-6-methyl-phenyl)methylphosphite}platinum, {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{bis(2,4-di-tert-butyl-6-methyl-phenyl)ethylphosphite}platinum, and {η 4 -(H 2 C=CHSiMe 2) 2 It is ethylbis(2,4,6-tri-tert-butylphenyl)phosphite platinum.

[0203] Component (D): Optionally, one or more phosphites (D) of formula (I) further constitute the curable polyorganosiloxane and / or silane composition according to the invention. One or more phosphites of formula (I) that exceed the amount of phosphite present in complex form in component (C) are either used in excess of the transition metal-containing precursor compound by the phosphite of formula (I) to ensure complete conversion of the transition metal-based precursor compound when preparing compound (C), or it is added in an amount sufficient to further delay the hydrosilylation reaction at room temperature to enable the mixing from component (A) to component (C) and the dispensing and coating processes without pre-curing.

[0204] Regarding component (D), it has the formula as defined above: P(OR) 3 (I) and can be referred to as a phosphite having it.

[0205] One or more phosphites (D) of formula (I) may preferably be added in a small amount, for example, less than 2% by weight (20,000 ppm) based on the total weight of (A) and (B).

[0206] A particularly preferred range is that component (D) is 0.2 - 12,000 ppm with respect to (A) and (B).

[0207] Furthermore, preferably, the molar ratio of the transition metal platinum derived from component (C) to the phosphite (D) containing the phosphite complexed with component (C) is 1:1 - 1:6, preferably 1:1.1 - 1:5, more preferably 1:1.2 - 1:4.

[0208] Based on the interaction with the transition metal hydrosilylation catalyst compound, component (D) acts as an inhibitor for the hydrosilylation reaction, thereby increasing the storage stability, i.e., increasing the pot life, and at the same time not exerting its inhibitory effect during the curing reaction.

[0209] According to the present invention, particularly preferred phosphites of formula (I) constituting component (D) are bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite, bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methyl-phenyl)ethyl phosphite, and ethyl bis(2,4,6-tri-tert-butylphenyl) phosphite.

[0210] Component (E): The polyorganosiloxane and / or silane composition according to the present invention may further contain an additional component (E) as an auxiliary additive. The siloxane composition according to the present invention may also contain additional components (E), such as conventional inhibitors, stabilizers, solvents, fillers, pigments, or processing aids, in order to achieve better processing characteristics of the polymer compositions (A) to (C) or (A) to (D) of the present invention.

[0211] Generally, the auxiliary additives may be for adjusting the processing time, onset behavior, and curing rate of the curable composition.

[0212] In some cases, it may be desirable to further add other conventional inhibitors, i.e., to further adjust the hydrosilylation activity by combining the phosphite of the present invention of component (D) with other conventional inhibitors.

[0213] Thus, the composition of the present invention may contain a predetermined amount of one or more additional conventional inhibitors. However, preferably, the composition of the present invention does not contain other phosphorus inhibitor compounds other than the phosphorus inhibitor compound of formula (I).

[0214] Conventional inhibitors for platinum group metal catalysts are well known in the art of organosilicon. Examples of various classes of such metal catalyst inhibitors include unsaturated organic compounds such as ethylenically or aromatically unsaturated amides, US 4,337,332; acetylenic compounds, US 3,445,420 and US 4,347,346; ethylenically unsaturated isocyanates, US 3,882,083; olefinic siloxanes, US 3,989,667; unsaturated hydrocarbon diesters, US 4,256,870, US 4,476,166 and US 4,562,096, and conjugated enynes. US 4,465,818 and US 4,472,563; other organic compounds such as hydroperoxides, US 4,061,609; ketones, US 3,418,731; sulfoxides, amines, nitriles, US 3,344,111; diaziridines, US 4,043,977; and various salts such as US 3,461,185, phosphorus compounds are preferably excluded. Examples thereof include the acetylenic alcohols of US 3,445,420 such as ethynylcyclohexanol and methylbutynol, 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1-dodecyn-3-ol, the unsaturated carboxylic acid esters of US 4,256,870 such as diallyl maleate and dimethyl maleate; and the maleic and fumaric esters of US 4,562,096 and US 4,774,111 such as diethyl fumarate, diallyl fumarate, and bis-(methoxyisopropyl) maleate. The half esters and amides of US 4,533,575; and the inhibitor mixtures of US 4,476,166 are also expected to behave similarly. Further classes of inhibitors are trialkyl thiolates, organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and pinane hydroperoxide, organic peroxides, organic sulfoxides, phosphines, triazoles and oximes. The above patents regarding inhibitors for conventional platinum group metal-containing catalysts are incorporated herein by reference.

[0215] When the compositions of the present invention optionally contain a solvent, these solvents are conventional organic solvents and are in the range of 20% by weight, preferably less than 10% by weight, and most preferably less than 5% by weight with respect to (A) to (C) or (A) to (D). From the group of olefinic hydrocarbons such as α-olefins, for example C 8 ~C 25 α-olefins, preferably C 14 ~C 20 α-olefins, or from the group of volatile siloxanes having a molecular weight of less than 518 g / mol and containing no alkenyl or SiH groups, a suitable reactive solvent can be selected. Mixtures of α-olefins can also be used.

[0216] Other additives included in the definition of component (E) are heat stabilizers, coloring compounds or pigments, antioxidants, biocides, antibacterial agents, for example Preventol 登録商標 、Katon 登録商標 、Dowicil 登録商標 、fillers, especially spherical silsesquioxanes to obtain additional anti-blocking properties in the release layer, anti-fogging additives as disclosed in US 6,586,535 or US 2003 / 0134043, anchorage additives, lubricants as disclosed in EP 819735 A1, and further auxiliary components typical of silicone release compositions. These other components may be contained in the reactive silicon-based composition described above in a total amount of up to 20% by weight.

[0217] When a filler is used in the composition of the present invention, the amount of the filler is between 1 and 300 parts by weight, preferably between 15 and 80 parts by weight, per 100 parts by weight of component (A). The filler is preferably selected from the group of hydrophilic or hydrophobic, preferably surface-treated fillers. The filler may act as a reinforcing filler, a thickener, an anti-blocking agent, or an anti-friction or matting additive.

[0218] The filler includes, for example, all particulate fillers, i.e., fillers having particles smaller than 100 μm (sieve residue), i.e., preferably fillers composed of particles smaller than this value. The filler may generally be a non-reinforcing filler, i.e., preferably a filler with a BET specific surface area of up to 50 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolite, metal oxide powders, such as aluminum oxide, titanium oxide, iron oxide, or zinc oxide and their respective mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass powder, or polymer powders, such as polyacrylonitrile powder, or a reinforcing filler, i.e., a filler with a BET specific surface area of m 2 / g or more, such as precipitated chalk, carbon black, such as furnace carbon black and acetylene carbon black, and silicon-aluminum mixed oxides with a large BET specific surface area; aluminum hydroxide, fillers formed into spheres, such as ceramic microparticles, spheres of elastic polymers or glass spheres; fibrous fillers, such as asbestos and polymer fibers. These fillers may be hydrophobized, for example, by treatment with respective organosilanes or organosiloxanes, or by treatment with stearic acid, or by etherifying hydroxyl groups to alkoxy groups.

[0219] Preferred are mineral fillers, such as silicates, carbonates, nitrides, oxides, carbon black, or silica such as fumed silica or precipitated silica with a BET specific surface area of 0.3 to 400 m 2 / g, which are preferably surface hydrophobized. Preferred silicas are, for example, Aerosil 登録商標 200, 300, HDK 登録商標 N20 or T30, Cab-O-Sil 登録商標 MS7 or HS5, precipitated silica with a BET specific surface area exceeding 200 m 2 / g, or wet silica is Vulkasil 登録商標VN3, or Degussa's FK160, or Nipsil of Nippon Silica Industries Co., Ltd. 登録商標 LP and others. Examples of commercially available silica pre-hydrophobized with various silanes include: Aerosil 登録商標 R972, R974, R976, or R812, or for example, HDK 登録商標 2000 or HDK 登録商標 H30. Names of materials known as hydrophobized precipitated silica or wet silica include Sipernat 登録商標 D10 or D15.

[0220] Surface-treated fillers with low BET specific surface area values are preferred because they reduce the property of accumulating the shearing effect. Preferred surface treatments can be carried out with polyorganosiloxane diols, polyorganosiloxanes, alkoxysilanes or chlorosilanes, thereby making it possible to obtain a filler with a given concentration having the lowest degree of thickening and shearing properties.

[0221] Another class of fillers that act as opaque and non-reinforcing fillers are quartz powder, diatomaceous earth, cristobalite powder, mica, aluminum oxide, aluminum hydroxide, oxides and salts of Fe, Mn, Ti, Zn, Zr, chalk, or carbon black with a BET specific surface area of 0.3 - 50 m 2 / g.

[0222] These fillers are available under various trade names, examples of which include Sicron 登録商標 、Min-U-Sil 登録商標 、Dicalite 登録商標 、Crystallite 登録商標 and act as matting additives. When such fillers are present, they are used at a concentration of about 1 - 300 parts by weight, preferably 5 - 100 parts by weight, based on 100 parts by weight of (A).

[0223] Several very special fillers can be used as matting additives, as additives for increasing mechanical modulus, or as antiblocking agents. Such fillers are selected from the group of spherical or fibrous thermoplastic powders or fibers such as PTFE powder, PTFE emulsion or polyamide, polyurethane or silsesquioxane powder, thermoplastic fiber cured silicone elastomer or resin, and when present, are used in an amount of up to 10 parts by weight per 100 parts by weight of (A). The trade names are Teflon 登録商標 emulsion, Nylon 登録商標 powder, Tospearl 登録商標 、Acemat 登録商標 、Twaron 登録商標 、Kevlar 登録商標 、Dralon 登録商標 、Diolen 登録商標 and others.

[0224] This type of filler can preferably be used as an antiblocking agent for the release layer, especially when the particles are spherical, and can impart a particularly soft feel and low friction characteristics to the rubber surface.

[0225] Another class of additives are stabilizers such as metal compounds, organic or inorganic salts, and stabilizers selected from the group consisting of complexes of Ce, Fe, La, Mn, Ti and Zr.

[0226] Leveling agents and release agents are selected from the group consisting of polyether siloxanes, polyols, polyethers, polyhalides, aliphatic alcohols or fluoroalkyl derivatives.

[0227] Another important class of auxiliary additives are adhesion promoters, which can be incorporated into compositions (A) to (C) or (A) to (D), or can be applied in a suitable form as a primer pre-coated on a substrate expected to adhere to the cured rubber composition.

[0228] The promoter is preferably an alkoxysilane, its condensation product, an alkoxysiloxane having an additional organic functional group selected from the group of alkenyls bonded via Si-C bonds, especially epoxyalkyl, acryloxyalkyl, methacryloxyalkyl, NCO alkyl, aminoalkyl, urethane alkyl, and further capable of having an SiH group. Along with this, the alkoxysilane as an adhesion promoter may further contain additional functional groups capable of interacting with groups on a substrate, such as a plastic substrate. Thus, the alkoxysilane may further contain groups such as, but not limited to, epoxides, esters, or anhydrides.

[0229] Preferably, the ester is an ester of fumaric acid, succinic acid, or maleic acid. Also preferably, the anhydride is succinic anhydride, and at least one alkoxysilane may contain an ester or anhydride group. The alkoxysilane may be selected from the group including glycidoxypropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)fumarate, and (3-triethoxysilyl)propyl succinic anhydride. The applied adhesion promoter may contain at least two alkoxysilanes, preferably at least two alkoxysilanes further containing additional functional groups. The alkoxysilane applied as an adhesion promoter may be selected from bis(3-trimethoxysilylpropyl)fumarate and / or (3-triethoxysilyl)propyl succinic anhydride.

[0230] Such silanes / siloxanes can be combined with a condensation catalyst selected from the group of organometallic compounds of Ca, Zr, Zn, Sn, Al or Ti and / or polycyclic aromatic compounds having reactive groups such as alkenyl-substituted aromatic biphenyl ethers and esters. The adhesion effect is further improved by adding the selected compounds of component (B), for example, US4,082,726; US5,438,094; US5,405,896; US5,536,803; US5,877,256; US6,602,551; EP581504A; and EP875536 are incorporated herein by reference.

[0231] According to the present invention, particularly preferred auxiliaries are - conventional inhibitors known for use in hydrosilylation-curing compositions, such as tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168) or 1-ethynyl-1-cyclohexanol; these inhibitors are preferably present in a weight w / w of 0 to 1000 ppm, more preferably 0 to 800 ppm, even more preferably 10 to 500 ppm, based on the weight of component (A); - adhesion promoters, especially alkoxysilanes, such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-(trimethoxysilyl)propyl α,2,4,6,6,8-hexamethylcyclotetrasiloxanepropionate (CAS 113684-56-3); these adhesion promoters are preferably present in an amount of 0 to 5 parts by weight (pw), more preferably 0 to 3 parts by weight, even more preferably 0 to 2 parts by weight, and even more preferably 0 to 1 part by weight, based on the weight of 100 parts by weight of component (A); - fillers, preferably silica fillers, more preferably surface-modified silica fillers, such as Evonik Aerosil R8200 silica with a BET specific surface area of 155 m 2 / g and hydrophobized with HMDZ; These fillers are preferably present in an amount of 0 to 200 parts by weight, more preferably 1 to 150 parts by weight, even more preferably 5 to 100 parts by weight, even more preferably 10 to 75 parts by weight, and still more preferably 20 to 50 parts by weight, based on the weight of component (A) which constitutes 100 parts by weight.

[0232] The curable polyorganosiloxane and / or silane composition can be used for all purposes for which curable polyorganosiloxane and / or silane compositions have been used in the art, and can be used for coating and impregnating any type of substrate, for example, the production of molded parts by injection molding, vacuum extrusion, extrusion, casting molding, compression molding, etc., for printing, and as a sealant, potting compound or casting compound.

[0233] The curable composition according to the present invention is preferably used for coating a solid substrate such as paper, fabric or plastic, a metal substrate such as a metal foil, a metal sheet, a metal surface of an article, optionally together with an adhesive release layer, or for extruding, calendering or molding a molded article or a laminate, or for a "field-formed" seal.

[0234] In an embodiment according to the present invention, the curable polyorganosiloxane composition and / or silane composition according to the present invention described above further contains one or more phosphites of formula (I) as defined above.

[0235] In addition to the phosphite of formula (I) that forms a complex with the transition metal of the transition metal compound of the present invention, typically, the phosphite of formula (I) is present in a slight excess in the composition, because the phosphite of formula (I) is used in an excess amount in the synthesis of the catalyst to effect complete conversion of the transition metal-containing precursor compound. According to the present invention, one or more additional phosphites of formula (I) or an excess amount of the phosphite of formula (I) composed of the transition metal compound of the present invention may further be present in the curable polyorganosiloxane composition and / or silane composition described above to improve and modify the pot life and cure time of the transition metal catalyst due to the stabilizing and inhibiting properties of the additional phosphite of formula (I).

[0236] In a preferred embodiment of the present invention, the transition metal of the transition metal compound composed of the curable polyorganosiloxane composition and / or silane composition of the present invention is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, and preferably platinum.

[0237] In another embodiment of the present invention, the curable polyorganosiloxane composition and / or silane composition according to the present invention comprises: (A) one or more polyorganosiloxanes and / or silanes having on average at least two alkenyl groups, (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups, (C) one or more transition metal compounds, wherein the metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, (D) optionally one or more phosphites of formula (I) as defined above, and (E) optionally one or more auxiliary agents and contains.

[0238] Herein, components (A) to (E) are as defined in the embodiments described above.

[0239] Preferably, one or more polyorganosiloxanes and / or silanes (A) having on average at least two alkenyl groups are - General average composition MVi 2 D m Dimethylvinylsilyl-terminated polydimethylsiloxane of, where m is in the range of 50 to 1500, preferably 300 to 1300, more preferably 400 to 1100, and even more preferably 450 to 1000; - Average general composition MVi 2 D n DVi o Dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane) of, where n is in the range of 1000 to 1000, preferably 200 to 900, more preferably 300 to 800, and even more preferably 400 to 700, and o is independently selected from the range of 10 to 120, preferably 15 to 90, more preferably 20 to 70, and even more preferably 25 to 50; One or more polyorganosiloxanes and / or silanes (B) having on average at least two SiH groups are independently - Average general composition MH 2 D a Hydride-terminated poly(dimethylsiloxane) of, where a is in the range of 5 to 100, preferably 8 to 80, more preferably 10 to 50, and even more preferably 12 to 40, and most preferably 13 to 25; - Average general composition M 2 D b DH c Trimethylsilyl-terminated poly(dimethylsiloxane-co-methylmethylhydrogensiloxane) of, where b is in the range of 10 to 50, preferably 12 to 40, more preferably 14 to 40, and even more preferably 15 to 30, and c is independently in the range of 2 to 50, preferably 4 to 40, more preferably 6 to 40, and even more preferably 8 to 30; - Average general composition MH dx Qx of the resin type, where d is in the range of 1.1 to 2.5, preferably in the range of 1.2 to 2.2, more preferably in the range of 1.3 to 2.1, and even more preferably in the range of 1.5 to 2.0; - average general composition M 2 DH e trimethylsilyl-terminated polymethylhydrogensiloxane of, where e is in the range of 5 to 100, preferably in the range of 10 to 80, more preferably in the range of 15 to 60, and even more preferably in the range of 20 to 40; or - average general composition M 2 D(Ph 2 ) f DH g D h trimethylsilyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane-co-methylhydrogensiloxane) of, where f is in the range of 1 to 50, preferably in the range of 1 to 40, more preferably in the range of 1 to 25, and even more preferably in the range of 1 to 15, g is independently in the range of 2 to 50, preferably in the range of 6 to 40, more preferably in the range of 12 to 30, and h is in the range of 1 to 50, preferably in the range of 2 to 40, more preferably in the range of 3 to 25, and even more preferably in the range of 5 to 15; The transition metal compound (C) containing one or more phosphites of formula (I) is preferably {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{bis(2-tert-butyl-6-methylphenyl)ethyl phosphite}platinum, {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{bis(2-tert-butyl-6-methylphenyl)methyl phosphite}platinum, {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite}platinum, and {η 4 -(H 2 C=CHSiMe 2 ) 2selected from O}ethylbis(2,4,6-tri-tert-butylphenyl)phosphite}platinum; Any one or more phosphites (D) of formula (I), if present, are preferably selected from bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite, bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methyl-phenyl)ethyl phosphite, and ethylbis(2,4,6-tri-tert-butylphenyl)phosphite; The optional coagent (E) is preferably - conventional inhibitors known for use in hydrosilylation curable compositions such as organophosphites and acetylenic alcohols, - adhesion promoters, especially alkoxysilanes, - fillers, preferably silica fillers, more preferably surface-treated silica fillers, such as Evonik's BET surface area 155 m 2 / g of Aerosil R8200 silica hydrophobized with HMDZ.

[0240] Here, the curable composition may further contain components (D) or (E) different from those described above.

[0241] More preferably, the composition contains one or more phosphites (D) of formula (I) or one or more coagents (E), and more preferably the composition contains both one or more phosphites (D) of formula (I) and one or more coagents (E).

[0242] In a more specific embodiment according to the present invention, the curable polyorganosiloxane composition and / or silane composition according to any of the above embodiments is: 100 parts by weight of component (A), 0.1 to 200 pw, preferably 0.5 to 150 pw, more preferably 1 to 100 pw, even more preferably 1.5 to 75 pw, still more preferably 1.5 to 50 pw of component (B), 0.1 to 1000 ppm, preferably 0.2 to 750 ppm, more preferably 0.5 to 500 ppm, even more preferably 2 to 250 ppm, and still more preferably 4 to 100 ppm of the transition metal contained in component (C) with respect to components (A) and (B). 0.0 to 12000 ppm, preferably 0.2 to 12000 ppm of component (D) with respect to components (A) and (B). Contains component (E) in an amount of 0 to 200 pw, preferably 1 to 150 pw, more preferably 5 to 100 pw, even more preferably 10 to 75 pw, still more preferably 20 to 50 pw, and yet even more preferably 20 to 45 pw.

[0243] The unit "ppm" refers to the total weight of components (A) and (B) in the curable composition as indicated.

[0244] The unit "pw" indicates "parts by weight" and is used such that the weight of component (A) present in the composition represents 100 parts by weight.

[0245] The amounts of components (B) and (E) are thus expressed relative to the amount of component (A).

[0246] According to this embodiment, it is preferred that the composition contains 0.2 to 12000 ppm of phosphite (D) of formula (I). This component (D) may contain the remaining amount of phosphite of formula (I) because usually an excess amount of phosphite of formula (I) is used over the transition metal-containing precursor compound for the synthesis of the catalyst, based on the addition of a preformed and optionally purified transition metal compound (C), or usually still 1.1 to 12 times excess of phosphite of formula (I) is used to reach complete conversion of the transition metal-containing precursor compound, and is present based on the in-situ formation of component (C) in the curable composition.

[0247] Also, one or more phosphites of formula (I) may be further added to the composition to show an inhibitory effect.

[0248] In a further embodiment according to the present invention, in the curable polyorganosiloxane composition and / or silane composition according to any of the above-described or below-described embodiments, the molar ratio of platinum to one or more phosphites of formula (I) is from 1:1 to 1:10 in order to avoid free platinum moieties.

[0249] In the ratio of the phosphite of formula (I) to the platinum moiety, both the phosphite of formula (I) constituting the transition metal compound (C) and additional phosphites of formula (I) not in the complexed state (D) are taken into account.

[0250] Preferably, the molar ratio of platinum to one or more phosphites of formula (I) is from 1:1 to 1:8, more preferably from 1:1 to 1:5, even more preferably from 1:1 to 1:3, and most preferably from 1:1 to 1:2.

[0251] In a further embodiment of the present invention, in the curable polyorganosiloxane composition and / or silane composition described above, the phosphite of formula (I) constituted by the transition metal compound is

Chemical formula

Chemical formula

Chemical formula

[0252] In a further embodiment according to the invention, in the curable polyorganosiloxane composition and / or silane composition, the transition metal compound containing the phosphite of formula (I) is [Chemical formula] bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite, and the complex is a platinum complex.

[0253] Another embodiment of the invention relates to the use of one or more phosphites of formula (I) as defined in any of the above-described embodiments for the production of curable polyorganosiloxane and / or silane compositions.

[0254] One or more phosphites of formula (I) may be added directly to the polyorganosiloxane and / or silane composition before or after the addition of the transition metal catalyst precursor, or may be used to form the transition metal compound, which is then used for the production of the curable polyorganosiloxane and / or silane composition.

[0255] Preferably, the transition metal compound containing the phosphite of formula (I) is formed beforehand and then added to the mixture of components to form the curable composition.

[0256] Yet another aspect of the invention relates to the use of one or more phosphites of formula (I) as defined in any of the above-described embodiments as an inhibitor of the hydrosilylation reaction in the curing of polyorganosiloxane compositions and / or silane compositions.

[0257] By adding one or more phosphites of formula (I) to a curable composition containing a transition metal compound that acts as a curing catalyst, at least a part of the curing catalyst is converted into a transition metal compound containing the phosphite of formula (I) as a ligand, which in most cases results in a decrease in the reaction rate, especially at relatively low reaction temperatures, because this transition metal compound has the property of showing very low catalytic activity towards the hydrosilylation reaction at low temperatures. Thus, a composition containing such a catalyst provides a long pot life, shows a high reaction rate at high temperatures, and as a result, rapid curing occurs by thermal activation. The result that the catalytic activity decreases at low temperatures and the pot life of the curable composition becomes long is considered to be the inhibitory effect of the phosphite of formula (I) according to the present invention.

[0258] A further embodiment of the present invention relates to a one-component curable polyorganosiloxane and / or silane composition containing one or more phosphites of formula (I) as defined in any of the above-described embodiments.

[0259] The expression "one-component" hydrosilylation curable polyorganosiloxane and / or silane composition means, according to the present invention, that the curable composition described in the embodiments according to the present invention, in particular the composition containing components (A) to (C) and optionally components (D) and / or (E), contains all the components for curing at appropriate conditions, especially at a temperature increase level higher than 25°C, preferably higher than 40°C, more preferably higher than 70°C, even more preferably higher than 80°C, and most preferably higher than 90°C.

[0260] For the preparation of one-component curable polyorganosiloxane and / or silane compositions, the components of such compositions, preferably components (A) to (E) as defined above, are first mixed to form a non-reactive composition, i.e., a polyorganosiloxane and / or silane having one or more alkenyl groups, preferably two or more alkenyl groups, a polyorganosiloxane and / or silane having one or more SiH groups, preferably two or more SiH groups, and a composition that does not simultaneously contain a transition metal compound capable of catalyzing the hydrosilylation reaction.

[0261] The curable composition according to the invention has very high stability, i.e., a very long storage period.

[0262] In yet another aspect according to the invention, the invention relates to a two-component curable polyorganosiloxane and / or silane composition comprising one or more phosphites of formula (I) described in embodiments according to the invention.

[0263] Such two-component curable compositions are prepared and supplied based on two components, where each of the components does not contain all of components (A) to (C) as defined above. These partial components can practically be stored for more than 100 days. Manufacturers usually prepare the reactive composition by mixing these partial compositions. This reactive curable composition still has a storage stability of more than 30 days at this time.

[0264] Accordingly, the invention also relates to a partial composition comprising components (A) + (C) + optionally (D) + optionally (E).

[0265] Such partial compositions require the addition of one or more polyorganosiloxanes and / or silanes (B) having on average at least two SiH groups in order to become the curable polyorganosiloxane composition and / or silane composition as defined above.

[0266] The present invention also relates to a partial composition comprising component (A)+(B)+optionally (D)+optionally (E), which requires the addition of component (C) to become the curable composition defined above. The present invention also relates to a partial composition comprising component (B)+(C)+optionally (D)+optionally (E), which requires the addition of component (A) to become the curable composition defined above.

[0267] In particular, the present invention includes a set of two partial compositions as described above, which, when mixed, form a curable polyorganosiloxane and / or silane composition comprising components (A), (B), (C), optionally (D) and optionally (E), preferably components (A), (B), (C), (D) and (E) as defined above.

[0268] This two-component curable composition is curable in a temperature range of 20°C to 250°C, preferably 80°C to 130°C, more preferably 80°C to 120°C, and has a pot life of at least 48 hours.

[0269] It is also within the scope of the present invention that the curable composition is prepared and supplied based on three compositions.

[0270] In selecting components (A), (B), (C) and optionally (D) and / or (E), the same compounds as described for the embodiments of the curable composition presented above are preferred. Similarly, when the components are combined into partial compositions, the same weights and weight ratios as described above are preferably used.

[0271] Another aspect of the present invention relates to a cured polyorganosiloxane and / or silane composition obtained by curing a curable polyorganosiloxane and / or silane composition defined in any of the embodiments according to the present invention described above.

[0272] Preferably, the crosslinking of the composition according to the invention to obtain a cured composition is carried out at a pressure of 30 to 25000 hPa, in particular at atmospheric pressure of 900 to 1100 hPa, or at a pressure of 100000 to 250000 hPa which is the normal pressure in an injection molding machine.

[0273] Preferably, the curing temperature of the curable composition of the present invention is higher than 25 ° C, more preferably higher than 50 ° C, even more preferably higher than 70 ° C, still more preferably higher than 80 ° C, and most preferably higher than 90 ° C.

[0274] The cured polyorganosiloxane and / or silane composition can be used for any purpose for which a cured polyorganosiloxane and / or silane composition has been used in the art so far, for example, coating and impregnation of any kind of substrate, for example, manufacturing of molded parts such as injection molding, vacuum extrusion, extrusion, molding casting, compression molding, printing, and can be used as a sealant, potting compound, or casting compound.

[0275] Furthermore, the present invention relates to the use of the curable polyorganosiloxane composition and / or silane composition defined in any of the above-described embodiments for the production of molded articles, extruded articles, coatings, and sealants.

[0276] Depending on the viscosity of the components of the curable polyorganosiloxane composition and / or silane composition according to the present invention and the filler component, the curable composition can be injectable with low viscosity, have a paste-like consistency, be a powder, or be a smooth and very viscous mass. Similarly, the elastomeric elastic properties of the cured composition according to the present invention include the entire range starting from a very soft silicone gel, include rubbery substances, and extend to highly crosslinked silicones having glassy properties. Therefore, the curable composition according to the present invention may be advantageously applied in many applications.

[0277] Especially in the manufacture of molded articles formed by extrusion, there is an increasing demand to cure rubber articles by hydrosilylation reaction to replace peroxides. The curing rate required for such technologies is high, that is, the curing time is short. Generally, in order to obtain a cured elastomeric article without bubbles, it is less than 3 minutes at 110 °C. Such conditions can be achieved with the hydrosilylation curable polyorganosiloxane and / or silane compositions according to the present invention. At the same time, the hydrosilylation curable polyorganosiloxane and / or silane compositions according to the present invention have a storage stability preferably exceeding 2 days at 25 °C.

[0278] The term storage stability as used in accordance with the present invention means the t at 25 °C after the preparation of the reactive composition 10 time, that is, the time until reaching 10% of the elastic modulus of the fully cured material at 25 °C. On the other hand, the curing time of the hydrosilylation curable polyorganosiloxane and / or silane composition is the t 90 time at 110 °C, which is the time until reaching 90% of the elastic modulus of the fully cured material at 110 °C after the preparation of the reactive composition. The elastic modulus is measured with a rheometer MDR2000 from Alpha Technologies.

[0279] Another important use of the hydrosilylation curable polyorganosiloxane and / or silane compositions according to the present invention is siloxane coatings, for example, when the coating thickness is usually between 0.05 and 1 mm at a coating device belt speed usually between 50 and 1000 m / min, it is necessary to cure within a reasonably short curing time at less than 110 °C. It is a release coating for plastics.

[0280] A further aspect of the present invention relates to a method for manufacturing a curable polyorganosiloxane composition defined in any of the above-described embodiments, which is (A) one or more polyorganosiloxanes and / or silanes having on average at least two alkenyl groups, (B) One or more polyorganosiloxanes and / or silanes having on average at least two SiH groups, (C) One or more transition metal compounds, where the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, (D) Optionally one or more phosphites of formula (I), and (E) Optionally one or more auxiliaries which comprises mixing in a mixing device.

[0281] According to the invention, the production of the curable composition is achieved by mixing the aforementioned components in any order using any method or any mixing process known in the art.

[0282] Preferably, the mixing is carried out at 10 °C to 130 °C under a pressure of 30 to 1100 hPa, more preferably under a reduced pressure of 30 to 500 hPa, or under atmospheric pressure of 900 to 1100 hPa.

[0283] The process according to the invention may be carried out continuously or discontinuously, i.e., batchwise.

[0284] According to the invention, in the production of the curable composition, the transition metal compound (C) is homogeneously mixed with the mixture of components (A) and (B), and optionally with the mixture of (D) and (E).

[0285] The transition metal compound (C) may be added as a substance or as a solution in a suitable solvent, or it may be added as a so-called batch, i.e., as a homogeneous mixture with a small amount of (A) or (A) and (E).

[0286] The curable composition according to the invention may be either a one-component composition or a two-component composition. In the latter case, both partial compositions may contain all the components in any ratio, but preferably the partial composition containing the transition metal compound (C) does not contain the SiH-containing component, such as component (B).

[0287] In the preparation of the one-component composition, components (A) to (E) are first mixed to form a non-reactive composition, that is, a composition that does not contain components (A), (B), and (C) simultaneously.

[0288] In practice, it is preferable to prepare and supply two-component or three-component partial compositions, in which case each partial composition does not contain components (A) to (E) simultaneously. These partial compositions can be stored for more than 100 days in practice. The manufacturer usually prepares the reactive composition by mixing these partial compositions. In that case, the reactive composition still has a storage stability of more than two days.

[0289] Such preferred partial compositions are most preferably two-component compositions and contain the following components: -(A)+(B)+ optionally (D)+ optionally (E), such as a filler; -(A)+(C)+ optionally (E), such as a filler.

[0290] The reason why such combinations of partial compositions are preferred is that a 1:1 mixture by volume, which can be easily mixed by a static mixer, can be achieved. Another advantage of such combinations of partial compositions is to avoid the simultaneous presence of component (B) and component (C), which may be disadvantageous because it may cause fading. On the other hand, the combination of component (A) and component (C) has a stabilizing effect on the transition metal catalyst component (C).

[0291] The partial compositions defined above are preferably prepared in a mixing device selected from, for example, a kneader, a dissolver, an extruder, a LIST mixing device, a kneader of BUSS, a Banbury mixer or a "press mixer" of Voith, or a two-roll mixer.

[0292] The reactive "one-component type" composition is preferably prepared by mixing the partial compositions with a mixing device selected from, for example, a static mixer, a kneader such as a two-blade kneader, a dissolver, an extruder, a LIST mixing device, a kneader of BUSS, a Banbury mixer or a "press mixer" of Voith, a two-roll mixer, or a multi-roller coating mixer.

[0293] Thus, the present invention also relates to a partial composition containing component (A) + component (B) + optionally component (D) + optionally component (E).

[0294] Preferred composition: The composition of the present invention, preferably applied as a "two-component type" composition, can preferably be used as a so-called release paper coating, a gel as a liquid rubber, or a highly viscous rubber composition optionally incorporating a reinforcing filler, and has, for example, the following composition: (A) 100 parts by weight on average of one or more polyorganosiloxanes and / or silanes having at least two alkenyl groups and a viscosity of 50 mPa·s to 100 kPa·s at 25°C, (B) 0.1 to 100 parts by weight on average of one or more polyorganosiloxanes and / or silanes having at least two SiH groups in an amount to achieve a molar ratio of SiH:Si-alkenyl group of 0.8 to 6:1, (C) A transition metal compound containing one or more phosphites of formula (I) in an amount of 1 to 500 ppm calculated as a metal with respect to components (A) and (B), wherein the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, (D) Optionally one or more phosphites according to formula (I), preferably in an amount to achieve a molar ratio of 1:1 to 10:1 with respect to the metal atoms of component (C) of the phosphite composed of a phosphite of formula (I) not in a complexed state with respect to the transition metal and the transition metal compound, and (E) 0 to 200 parts by weight of 50 m 2One or more reinforcing silicas having a BET specific surface area exceeding / g, and optionally further auxiliary additives.

[0295] Summary of Preferred Embodiments The following outlines preferred embodiments of the present invention:

[0296] 1. A transition metal compound comprising at least one phosphite compound of the following formula: P(OR) 3 (I) In the formula, R represents an organic group, and here at least one R group is represented by formula (II)

Chemical formula

[0297] 2. A transition metal compound according to any of the above embodiments, wherein the transition metal compound is Platinum complex containing a primary phosphite;

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0298] 3. A transition metal compound according to Embodiment 1 or 2, comprising at least one phosphite having the formula (III):

Chem.

Chem.

[0299] 4. A transition metal compound according to any of the above-described embodiments, wherein at least one group R in formula (I) is an organic group different from the group of formula (II).

[0300] 5. A transition metal compound according to Embodiment 1 or 3, comprising at least one phosphite selected from the group consisting of formula (IV) or formula (V):

Chem.

Chem.

Chemical formula

[0301] 6. A transition metal compound according to any of the above-described embodiments, wherein in at least one group represented by formula (II), the ring represented by "A" is an aromatic group, which may optionally have one or more additional substituents apart from R 1 and R 2 .

[0302] 7. A transition metal compound according to any of the above-described embodiments, wherein in at least one group represented by formula (II), the ring represented by "A" is a phenyl group, which may optionally have one or more additional substituents apart from R 1 and R 2 .

[0303] 8. A transition metal compound according to any of the above-described embodiments, wherein the groups R 1 and R 2 are each preferably an optionally substituted straight-chain, branched-chain, or cyclic alkyl group having up to 10 carbon atoms, more preferably up to 6 carbon atoms.

[0304] 9. A transition metal compound according to any of the above-described embodiments, wherein the phosphite of formula (I) is selected from compounds of formula (VI):

Chem.

Chem.

Chem.

Chem.

[0305] 10. A transition metal compound according to any of the above-described embodiments, which is a phosphite monodentate ligand of formula (I).

[0306] 11. A transition metal compound according to any of the above-described embodiments, wherein in the phosphite of formula (I), the group R does not contain a metal atom.

[0307] 12. A transition metal compound according to any of the above-described embodiments, wherein the group R does not contain a nitrogen atom.

[0308] 13. A transition metal compound according to any of the above-described embodiments, wherein the group R does not contain any group containing an N atom or a P atom, preferably does not contain any group containing an N atom, a P atom, an S atom or a Se atom, and most preferably does not contain any group containing an N atom, a P atom, an S atom, a Se atom or an O atom.

[0309] 14. A transition metal compound according to any of the above-described embodiments, wherein the group R of the phosphite of formula (I) can contain only C atoms, H atoms, O atoms and halogen atoms, where the O atom can be present only either in a bond or in an ester group, preferably the group R can contain only C atoms, H atoms and halogen atoms, and most preferably the group R of the phosphite of formula (I) consists of C atoms and H atoms.

[0310] 15. A transition metal compound according to any of the above-described embodiments, wherein the phosphite of formula (I) is

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0311] 16. A transition metal compound according to any of the above-described embodiments, wherein the phosphite compound of formula (I) of the transition metal compound is [Chemical formula] bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite, and [Chemical formula] is selected from bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite, where [Chemical formula] bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite is preferred.

[0312] 17. A transition metal compound according to any of the above-described embodiments, wherein the transition metal of the transition metal compound is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.

[0313] 18. A transition metal compound according to any of the above-described embodiments, wherein the transition metal is platinum, and preferably the phosphite compound of formula (I) of the transition metal compound is [Chemical formula] bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite.

[0314] 19. A transition metal compound according to any of the above-described embodiments, wherein the transition metal compound is a transition metal complex compound, wherein the transition metal has an oxidation state of zero (0), and preferably the transition metal complex compound is a Pt(0) compound.

[0315] 20. A transition metal compound according to any of the above-described embodiments, comprising one or more alkenyl ligands.

[0316] 21. A transition metal compound according to any of the above-described embodiments, comprising one or more alkenylsiloxane ligands.

[0317] 22. A transition metal compound according to any of the above-described embodiments, having the following formula:

Chemical formula

[0318] 23. Use of a transition metal compound containing a phosphite of formula (I) as defined in any of the above-described embodiments as a curing catalyst for a curable polyorganosiloxane composition and / or a silane composition.

[0319] 24. A curable polyorganosiloxane composition and / or a silane composition, comprising one or more transition metal compounds containing a phosphite of formula (I) as defined above.

[0320] 25. A curable polyorganosiloxane composition and / or a silane composition according to embodiment 24, further comprising one or more phosphites of formula (I) as defined above.

[0321] 26. A curable polyorganosiloxane composition and / or silane composition according to Embodiments 24 and 25, wherein the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, preferably platinum.

[0322] 27. A curable polyorganosiloxane composition and / or silane composition according to Embodiments 24 to 26 described above, comprising: (A) One or more polyorganosiloxanes and / or silanes having on average at least two alkenyl groups, (B) One or more polyorganosiloxanes and / or silanes having on average at least two SiH groups, (C) A transition metal compound containing one or more phosphites of formula (I), wherein the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, (D) Optionally one or more phosphites of formula (I) as defined above, and (E) Optionally containing one or more auxiliary agents.

[0323] 28. A curable polyorganosiloxane composition and / or silane composition according to any one of Embodiments 24 to 27 described above, comprising: 100 parts by weight of component (A), 0.1 - 200 parts by weight of component (B), 0.1 to 1000 ppm of the transition metal contained in component (C) in relation to components (A) and (B), 0.0 to 12000 ppm of component (D) in relation to components (A) and (B), 0 to 200 parts by weight of component (E).

[0324] 29. A curable polyorganosiloxane composition and / or silane composition according to any one of Embodiments 24 to 28 described above, wherein the molar ratio of platinum to one or more phosphites of formula (I) is 1:1 to 1:10.

[0325] 30. A curable polyorganosiloxane composition and / or a silane composition according to Embodiments 24 to 29 described above, wherein the transition metal compound containing a phosphite of formula (I) is

Chemical formula

Chemical formula

Chemical formula

[0326] 31. A curable polyorganosiloxane composition and / or a silane composition according to Embodiments 24 to 30 described above, wherein the transition metal compound containing a phosphite of formula (I) is

Chemical formula

[0327] 32. Use of one or more phosphites of formula (I) as defined in any of the above embodiments for the production of a curable polyorganosiloxane and / or a silane composition.

[0328] 33. Use of one or more phosphites of formula (I) as defined in any of the above embodiments as an inhibitor of the hydrosilylation reaction in the curing of a polyorganosiloxane composition and / or a silane composition.

[0329] One-component curable polyorganosiloxane and / or silane composition containing one or more phosphites of formula (I) as defined in any of the above-described embodiments.

[0330] 35. Two-component curable polyorganosiloxane and / or silane composition containing one or more phosphites of formula (I) as defined in any of the above-described embodiments.

[0331] 36. Cured polyorganosiloxane and / or silane composition obtained by curing the curable polyorganosiloxane and / or silane composition as defined in any of the above-described embodiments.

[0332] 37. Use of the curable polyorganosiloxane composition and / or silane composition as defined in any of the above-described embodiments for the production of molded articles, extruded articles, coatings, and sealants.

[0333] 38. A method for producing a curable polyorganosiloxane composition as defined in any of the above-described embodiments, (A) One or more polyorganosiloxanes and / or silanes having on average at least two alkenyl groups, (B) One or more polyorganosiloxanes and / or silanes having on average at least two SiH groups, (C) One or more transition metal compounds, where the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, (D) Optionally one or more phosphites of formula (I), and (E) Optionally one or more auxiliary agents comprising mixing in a mixing device.

[0334] Examples A) Production of phosphite 1. General procedure The phosphite of formula (I) was synthesized according to the following general reaction system 2R'O - M + +ROPCl 2 →ROP(OR') 2 +2MCI wherein R' = R as defined in the embodiment, the group R' and the group R are different from each other, and M is Li or Na, wherein ROPCl 2 is obtained from the reaction of PCl 3 with the corresponding metal oxide RO - M + and the metal alkoxides R'O - M + and RO - M + are obtained from the reaction of the corresponding phenol with sodium hydride or n-butyllithium and the reaction is carried out in dry tetrahydrofuran (see also A. Earnshaw, N. Greenwood (1997): Chemistry of the Elements, 2nd Edition).

[0335] A solution of alcohol R'OH in dry THF (tetrahydrofuran) was added dropwise at 6 °C with vigorous stirring under a dry argon atmosphere to a suspension of NaH dissolved in THF or n-butyllithium dissolved in hexane. After the specified stirring time at room temperature, the phosphonic acid dichloride ROPCl 2 was added dropwise to THF. After the addition, the mixture was further stirred at 40 °C for 2 hours. Then hexane was added and the resulting solid was removed by filtration. The solvent was removed from the filtrate and hexane was added to the remaining product. The resulting solution was flash filtered through an aluminum oxide column to obtain the purified phosphite ROP(OR') 2 was obtained.

[0336] 2. Specific phosphites prepared 2.1. Bis(2-tert-butyl-6-methylphenyl)ethyl phosphite (present invention)

Chemical formula

[0337] A solution of 10.37 g (63 mmol) of 2-tert-butyl-6-methylphenol in 50 ml of dry THF was added dropwise at 0 °C to a suspension of 2.35 g of NaH (59 mmol) in 25 ml of THF, and the mixture was stirred under nitrogen for 60 minutes. Then, 4.23 g (29 mmol) of ethyldichlorophosphite (or dichloro(ethoxy)phosphane) in THF:

Chemical formula

[0338] The reaction mixture was then allowed to cool to room temperature, 15 ml of hexane was added, and the residue was removed by filtration. The solvent was evaporated from the filtrate, and the residue was dissolved in 10 ml of n-hexane. This solution was then filtered through a flash column of aluminum oxide to purify the phosphite. Evaporation of the solvent gave 20.26 g (80%) of a slightly yellow oil.

[0339] NMR data: ( 1 1H-NMR (400 MHz, CDCl 3 , 300 K); 31 31P-NMR (121.47 MHz, CDCl 3 , 300 K))

Table A

[0340] 2.2. Bis(2-tert-butyl-6-methylphenyl)methyl phosphite

Chemical formula

[0341] Bis(2-tert-butyl-6-methylphenyl)methyl phosphite was prepared in the same manner as in Example 2.1, using methyldichlorophosphite (or dichloro(methoxy)phosphane) instead of ethyldichlorophosphite (or dichloro(ethoxy)phosphane).

[0342] NMR data: ( 1 1H-NMR (400 MHz, CDCl 3 , 300 K); 31 31P-NMR (121.47 MHz, CDCl 3 , 300 K))

Table B

[0343] 2.3. Bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite (comparison)

Chemical formula

[0344] NMR data: ( 1 1H-NMR (400 MHz, CDCl 3 , 300 K); 31 31P-NMR (121.47 MHz, CDCl 3 , 300 K))

Table C

[0345] 2.4. Ethylbis(2,4,6-tri-tert-butylphenyl)phosphite (present invention)

Chemical formula

[0346] Ethylbis(2,4,6-tri-tert-butylphenyl)phosphite was prepared starting from ethyldichlorophosphite (or dichloro(ethoxy)phosphane) and 2,4,6-tri-tert-butylphenol as described above in 2.1.

[0347] NMR data: ( 1 1H-NMR (400 MHz, CDCl 3 , 300 K); 31 31P-NMR (121.47 MHz, CDCl 3 , 300 K))

Table D

[0348] 2.5. Tris(2,4-di-tert-butylphenyl)phosphite (comparison) Tris(2,4-di-tert-butylphenyl)phosphite:

Chemical formula

[0349] 2.6. Bis(2,4-di-tert-butyl-5-methylphenyl)ethyl phosphite (comparison) Bis(2,4-di-tert-butyl-5-methylphenyl)ethylphosphite:

Chemical formula

[0350] 2.7. Bis(2-allylphenyl)ethyl phosphite (comparison) Bis(2-allylphenyl)ethyl phosphite:

Chemical formula

[0351] 2.8. 3,9-Bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (comparison) 3,9-Bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane

Chemical formula

[0352] B) Production of transition metal compound 1. General procedure The platinum phosphite catalyst complex was synthesized by standard procedures. The Pt catalyst, phosphite, and a divinyl polymer with a viscosity of 10,000 mPa·s were dissolved in toluene and reacted in a flask under an N 2 atmosphere at 80 °C for 30 minutes. Then, the toluene was completely removed by distillation to obtain the catalyst complex in a stoichiometric yield with respect to the amount of Pt.

[0353] 3. Examples of catalysts 3.1. Catalyst example 1 (catalyst of the present invention) {η 4 -(H 2 C=CHSiMe 2 ) 2O}{Bis(2-tert-butyl-6-methylphenyl)ethyl phosphite}platinum [Chemical] {η 4 -(H 2 C=CHSiMe 2 ) 2 O}bis(2-tert-butyl-6-methylphenyl)ethylphosphite platinum was prepared in the same manner as in Catalyst Example 3 starting from Karstedt's catalyst (Pt 2 (1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3 -20%-available commercially from JM) and bis(2-tert-butyl-6-methylphenyl)ethylphosphite (Example 2.1 of phosphite) (see Catalyst Example 3.3 below).

[0354] NMR data: ( 1 H-NMR (400 MHz, CDCl 3 , 300 K); 31 P-NMR (121.47 MHz, CDCl 3 , 300 K)) The NMR spectrum showed signals for the free phosphite and the complex: [Table E]

[0355] 3.2. Catalyst example 2 (catalyst of the present invention) {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{Bis(2-tert-butyl-6-methylphenyl)methyl phosphite}platinum

[0356] [Chemical] {η 4 -(H 2 C=CHSiMe 2 )2 O} bis(2-tert-butyl-6-methylphenyl)methylphosphite} platinum is prepared starting from Karstedt's catalyst (Pt 2 (1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3 -20%-JM, commercially available) and bis(2-tert-butyl-6-methylphenyl)methylphosphite (Example 2.2 of phosphite) according to the same method as in Catalyst Example 3 (see Catalyst Example 3.3 below).

[0357] NMR data: ( 1 H-NMR (400 MHz, CDCl 3 , 300 K); 31 P-NMR (121.47 MHz, CDCl 3 , 300 K)) The NMR spectrum showed signals for the free phosphite and the complex:

Table F

[0358] 3.3. Catalyst example 3 (comparative catalyst) {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{Bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite}platinum

Chemical formula

[0359] NMR data: ( 1 H - NMR (400 MHz, CDCl 3 , 300 K); 31 P - NMR (121.47 MHz, CDCl 3 , 300 K)) The NMR spectrum showed signals for the free phosphite and the complex:

Table G

Chemical formula

[0360] NMR data: ( 1 H-NMR (400 MHz, CDCl 3 , 300 K); 31 P-NMR (121.47 MHz, CDCl 3 , 300 K)) The NMR spectrum showed signals of the free phosphite and the complex:

Table H

[0361] 3.5. Catalyst example 5 (comparative catalyst)

[0362] Ashby catalyst, 15 wt% Pt This is a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane and isopropanol of the following general formula:

Chemical formula

[0363] 3.6. Catalyst example 6 (comparative catalyst) {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{Tris(2,4-di-tert-butylphenyl)phosphite}platinum

[0364]

Chemical formula

[0365] 3.7. Catalyst example 7 (comparative catalyst) {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{Tris(2,4-di-tert-butyl-5-methylphenyl)phosphite}platinum

[0366]

Chem.

[0367] 3.8. Catalyst example 8 (comparative catalyst) {η 4 -(H 2 C=CHSiMe 2 ) 2 O}{Bis(2-allylphenyl)ethyl phosphite}platinum

Chem.

[0368] 3.9. Catalyst example 9 (comparative catalyst) {η 4 -(H 2 C=CHSiMe 2 ) 2 O}3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane platinum was prepared in the same manner as in Catalyst Example 3 starting from Karstedt's catalyst (commercially available from Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20%-JM) and 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (Phosphite Comparative Example 2.8.).

[0369] C) Production of curable polyorganosiloxane composition Examples 1 to 15 and Comparative Examples 1 to 5

[0370] Production of silicone-based compound In Examples 1 to 11 and Comparative Examples 1 to 5, 38 parts of dimethylvinylsilyl-terminated polydimethylsiloxane having an average composition MVi with a viscosity of 10 Pa·s and a SiVi content of 0.05 mmol / g, and an average composition MVi with a viscosity of 65 Pa·s and a SiVi content of 0.03 mmol / g 2 D 539 of 2 D 89932 parts of dimethylvinylsilyl-terminated polydimethylsiloxane, and fumed silica having a BET specific surface area of 300 m 2 / g and surface-treated with hexamethyldisilazane and divinyltetramethyldisilazane and having a vinyl content of 1.3% by weight (Aerosil 登録商標 300) 30 parts were used. This base compound was further mixed with the other components listed in Tables 1 to 4 to prepare various silicone rubber formulations. The catalyst was added last when all the other components were mixed.

[0371] The indication of the catalyst amount using the unit "ppm" indicates the weight of the platinum present in the applied catalyst with respect to the weight of the entire composition.

[0372] The indication of the inhibitor amount using the unit "ppm" indicates the amount of the applied inhibitor compound, i.e., the weight of ECH or the compound of phosphite Example 2.5, with respect to the weight of the entire composition.

[0373] The pot life of the liquid curable elastomer composition of the present invention is defined as the time until the viscosity of the mixed composition measured at 25 °C at a shear rate of 10 / s by a parallel plate rheometer increases to 200% of the initial value. This parameter represents the minimum processing time.

[0374] The curing time of the liquid curable elastomer composition was measured by a rheometer MDR2000 of Alpha Technologies using DIN53529-3. The times t90, t60, and t10 are defined as the times until reaching 90%, 60%, or 10% of the maximum torque at 100 °C.

[0375] As shown in Table 1, the composition of the present invention using the phosphite catalyst of the present invention had a pot life of at least 48 hours and at the same time retained a curing reactivity corresponding to t90 of 2 minutes or less.

[0376] Further detailed description of the components used: Vinyl siloxane 1: RT (room temperature 25°C) and shear rate 10 s -1 Dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane) having a viscosity of 5 Pa·s (according to DIN 53019), average composition MVi 2 D 560 DVi 36 Vinyl siloxane 2: Viscosity at RT is 10 Pa·s and average composition MVi 2 D 539 Dimethylvinylsilyl-terminated polydimethylsiloxane Vinyl siloxane 3: Viscosity at RT is 65 Pa·s and average composition MVi 2 D 899 Dimethylvinylsilyl-terminated polydimethylsiloxane Chain extender 1: Viscosity at RT is 20 mPa·s and average composition MH 2 D 17 Hydride-terminated poly(dimethylsiloxane) Crosslinker 1: Viscosity at RT is 40 mPa·s and average composition M 2 D 20 DH 20 Trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane) Irgafos 168 (see phosphite example 2.5) Crosslinker 2: Viscosity at RT is 30 mPa·s and average composition MH 1.7x Q x Resin type Crosslinker 3: Viscosity at RT is 35 mPa·s and average composition M 2 D 20 DH 10 Trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane) Crosslinker 4: Viscosity at RT is 15 mPa·s and average composition M 2 DH 30 Trimethylsilyl-terminated polymethylhydrogensiloxane Crosslinker 5: Viscosity at RT is 35 mPa·s and average composition M 2 D(Ph 2 )​2 DH 24 D 2 Trimethylsilyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane-co-methylhydrogensiloxane) Adhesion promoter 1: Gamma-methacryloxypropyltrimethoxysilane Adhesion promoter 2: Gamma-glycidoxypropyltrimethoxysilane Adhesion promoter 3: 3-(Trimethoxysilyl)propyl ester of α,2,4,6,6,8-hexamethylcyclotetrasiloxanepropanoic acid (CAS 113684-56-3) Filler 1: Evonik's Aerosil R8200 silica with a BET specific surface area of 155 m 2 / g hydrophobized with HMDZ

[0377]

Table 1

[0378]

Table 2

[0379] As shown in Table 2 (Examples 5 to 8), even when different SiH-crosslinking agents were used, the target pot life of at least 48 hours and the target reactivity t90 of 2 minutes or less were achieved.

[0380]

Table 3

[0381] As shown in Table 3 (Examples 9 to 11), even when different adhesion promoters were added, the target pot life of at least 48 hours and the target reactivity t90 of 2 minutes or less were achieved.

[0382]

Table 4

[0383] As shown in Table 4 (Examples 12 to 15), even when the filler content was different, the target pot life of at least 48 hours and the target reactive t90 of 2 minutes or less were achieved.

Claims

1. A transition metal compound comprising at least one phosphite compound of the following formula, P(OR) ３ (I) During the ceremony, R represents an organic group, and here at least one R group is represented by formula (II), 【Chemical 095】 Here The ring indicated by A represents an aromatic group or a heteroaromatic group, and this is R １ and R ２ It may have one or more additional substituents in addition to the above. The dotted line represents a single bond to the oxygen atom of the phosphite compound in formula (I). R １ and R ２ Each of the above aromatic group or heteroaromatic group represents a substituent located in the ortho position relative to the oxygen atom of the phosphite compound of formula (I), and In the formula, the substituent R １ and R ２ Each of these is independently selected from the group consisting of optionally substituted aliphatic groups, particularly optionally substituted alkyl groups and optionally substituted alkenyl groups, as well as optionally substituted aliphatic bridge groups, alkoxy groups, alkoxycarbonyl groups, and Si-organic groups that form a fused ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and therein at least two R groups are different from each other. The transition metal in the transition metal compound is selected from the group consisting of nickel, ruthenium, palladium, osmium, iridium, and platinum, and preferably the transition metal is platinum. However, this is subject to the condition that transition metal compounds are different from the following. - Platinum complex containing the phosphite of the following formula 【Chemistry 096】 - Pd complexes and Pt complexes containing phosphites of the following general formulas 【Chemical 099】 In the formula R ７ X is a methyl group and X is a ferrocenyl group. or R ７ R is a methyl group and X is a simantrenyl group, or R ７ X is an isopropyl group and X is a ferrocenyl group. Transition metal compounds.

2. The phosphate comprises at least one phosphite having formula (III): 【Chemistry 100】 Here the basis of equation (II): 【Chemistry 101】 The transition metal compound according to claim 1, wherein at least two of the groups are different groups.

3. The transition metal compound according to claim 1, wherein at least one group R in formula (I) is an organic group different from the group in formula (II).

4. The compound comprises at least one phosphite selected from the group consisting of formula (IV) or formula (V): 【Chemical Engineering 102】 【Chemistry 103】 Here, in equation (IV), the basis of equation (II): 【Chemical 104】 R is the same or different group, preferably the same group, and is as defined above in both formula (IV) and formula (V), and here the group R in formula (V) ６ These are the same or different groups, and preferably group R ６ These are the same group, and also group R ６ The transition metal compound according to claim 1, wherein is selected from an organic group different from the organic group of formula (II) in both formula (IV) and formula (V), and preferably selected from an optionally substituted aliphatic group, such as an optionally substituted alkyl group or an optionally substituted cycloalkyl group.

5. In at least one group represented by formula (II), the ring indicated by "A" is an aromatic group, and it is optionally R １ and R ２ In addition, it may have one or more further substituents, preferably at least one group represented by formula (II) in which the ring indicated by "A" is a phenyl group, which is optionally R １ and R ２ The transition metal compound of claim 1, which may have one or more additional substituents in addition to the above.

6. group R １ and R ２ The transition metal compound of claim 1, wherein each of the atoms is preferably an optionally substituted linear, branched, or cyclic alkyl group having up to 10 carbon atoms, more preferably up to 6 carbon atoms.

7. The phosphite of formula (I) was selected from the compounds of formula (VI): 【Chemistry 105】 Or selected from the compounds of formula (VII), 【Chemistry 106】 Here, R in equations (VI) and (VII) １ , R ２ and R ６ These are defined above, and also R ３ , R ４ , and R ５ Each is independently selected from hydrogen, a halogen group, a cyano group, a nitro group, a Si-organic group, and an organic group which is preferably an optionally substituted aliphatic group, and in formula (VI), at least two substituents: 【Chemistry 107】 Here, the dotted lines represent single bonds to the oxygen atom of the phosphite compound in formula (I), which are distinct from each other, and the two substituents in formula (VII) 【Chemistry 108】 Here, the dotted line represents a single bond to the oxygen atom of the phosphite compound of formula (I), preferably the same as the transition metal compound of claim 1.

8. The phosphite in formula (I) is 【Chemistry 109】 Bis(2-tert-butyl-6-methylphenyl)ethyl phosphite, 【Chemical 110】 Bis(2-tert-butyl-6-methylphenyl)methylphosphite, 【Chemistry 111】 Ethylbis(2,4,6-tritert-butylphenyl) phosphite, 【Chemistry 112】 Methylbis(2,4,6-tritert-butylphenyl) phosphite, and 【Chemistry 113】 Bis(2,4-ditert-butyl-6-methylphenyl)methyl phosphite. A transition metal compound according to claim 1, selected from the following.

9. The transition metal compound according to claim 1, wherein the transition metal compound is a transition metal complex compound, in which the transition metal has an oxidation state of zero (0), and preferably the transition metal complex compound is a Pt(0) compound.

10. It comprises one or more alkenyl ligands, preferably one or more alkenylsiloxane ligands, and more preferably a transition metal compound of the following formula: 【Chemical 114】 In the formula, P(OR) ３ The transition metal compound of claim 1, wherein is a phosphite of formula (I) as defined above.

11. Use of a transition metal compound comprising a phosphite compound of formula (I) as a curing catalyst for curable polyorganosiloxane compositions and / or silane compositions, P(OR) 3(I) During the ceremony, R represents an organic group, and here at least one R group is represented by formula (II), 【Chemical 095】 Here The ring represented by A represents an aromatic group or a heteroaromatic group, which may have one or more additional substituents in addition to R1 and R2. The dotted line represents a single bond to the oxygen atom of the phosphite compound in formula (I). R1 and R2 each represent substituents located in the ortho position relative to the oxygen atom of the phosphite compound of formula (I) in the aromatic group or heteroaromatic group, and In the formula, the substituents R1 and R2 are each independently selected from the group consisting of optionally substituted aliphatic groups, particularly optionally substituted alkyl groups and optionally substituted alkenyl groups, as well as optionally substituted aliphatic bridge groups, alkoxy groups, alkoxycarbonyl groups, and Si-organic groups that form a fused ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and therein at least two R groups are different from each other.

12. A curable polyorganosiloxane composition and / or silane composition: (A) One or more polyorganosiloxanes and / or silanes having at least two alkenyl groups on average, (B) One or more polyorganosiloxanes and / or silanes having at least two SiH groups on average, (C) One or more transition metal compounds containing the phosphite of formula (I), P(OR) 3(I) During the ceremony, R represents an organic group, and here at least one R group is represented by formula (II), 【Chemical 095】 Here The ring represented by A represents an aromatic group or a heteroaromatic group, which may have one or more additional substituents in addition to R1 and R2. The dotted line represents a single bond to the oxygen atom of the phosphite compound in formula (I). R1 and R2 each represent substituents located in the ortho position relative to the oxygen atom of the phosphite compound of formula (I) in the aromatic group or heteroaromatic group, and In the formula, the substituents R1 and R2 are each independently selected from the group consisting of optionally substituted aliphatic groups, particularly optionally substituted alkyl groups and optionally substituted alkenyl groups, as well as optionally substituted aliphatic crosslinking groups, alkoxy groups, alkoxycarbonyl groups, and Si-organic groups that form a fused ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and therein at least two R groups are different from each other. Here, the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, and is preferably platinum. (D) one or more phosphites of formula (I) as defined above, and (E) A curable polyorganosiloxane composition and / or silane composition comprising one or more auxiliary agents optionally.

13. Composition: 100 parts by weight of component (A), 0.1 to 200 parts by weight of component (B), Transition metals contained in component (C) in relation to components (A) and (B) in concentrations of 0.1 to 1000 ppm, Components (A) and components (D) related to component (B) in concentrations of 0.0 to 12000 ppm. Component (E) 0 to 200 parts by weight, And here, preferably A curable polyorganosiloxane composition and / or silane composition according to claim 12, wherein the molar ratio of platinum to one or more phosphites of formula (I) is 1:1 to 1:

10.

14. The curable polyorganosiloxane composition and / or silane composition according to claim 12, wherein the composition is a two-component curable polyorganosiloxane and / or silane composition.

15. The curable polyorganosiloxane composition and / or silane composition of claim 12, wherein the transition metal compound comprising the phosphite compound of formula (I) is (i) an isolated compound, or (ii) pre-formed by mixing a transition metal-containing precursor compound with one or more phosphites of formula (I).

16. Use of a curable polyorganosiloxane composition / or silane composition according to claim 12 for the manufacture of molded articles, extruded articles, coatings, and sealants.

17. A method for producing a curable polyorganosiloxane composition according to claim 12, (A) One or more polyorganosiloxanes and / or silanes having at least two alkenyl groups on average, (B) One or more polyorganosiloxanes and / or silanes having at least two SiH groups on average, (C) One or more transition metal compounds, where the transition metal is selected from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. (D) one or more phosphites of formula (I) at will, and (E) One or more adjuvants at will. A manufacturing method comprising mixing in a mixing apparatus.

18. A cured polyorganosiloxane and / or silane composition obtained by curing a curable polyorganosiloxane and / or silane composition according to claim 12.

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