Novel substituted phosphite transition metal compounds

Abstract

The present invention relates to a transition metal compound comprising at least one phosphite compound of formula: P (OR) 3 (I) wherein R represents an organic group, and wherein at least one group R is represented by formula (II): # imgabs0 # wherein the ring represented by A represents an aromatic or heteroaromatic group which may have one or more other substituents other than R1 and R2, the dashed line represents a single bond of the oxygen atom of the phosphite compound of formula (I), R1 and R2 each represent the ortho-substituent of said aromatic or heteroaromatic group with respect to the oxygen atom of the phosphite compound of formula (I), and wherein the substituents R1 and R2 are each independently selected from optionally substituted aliphatic groups, and an optionally substituted aliphatic bridging group forming a fused ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and wherein at least two groups R are different from each other. The invention also relates to the use of transition metal compounds of formula (I) as curing catalysts for curable polyorganosiloxane and / or silane compositions, curable polyorganosiloxane and / or silane compositions comprising one or more transition metal compounds of formula (I), the present invention relates to a curable polyorganosiloxane composition and / or silane composition, the use of the curable polyorganosiloxane composition and / or silane composition for the manufacture of shaped articles, and a process for the manufacture of the curable polyorganosiloxane composition.

Description

Technical Field

[0001] The present invention relates to novel substituted phosphite transition metal compounds, the use of transition metal compounds as curing catalysts for curable polyorganosiloxane compositions and / or silane compositions, curable polyorganosiloxane compositions and / or silane compositions comprising one or more transition metal compounds as mentioned above, the use of one or more phosphites as mentioned above for the manufacture of curable polyorganosiloxane and / or silane compositions, curable polyorganosiloxane and / or silane compositions comprising one or more phosphites as mentioned above, cured polyorganosiloxane and / or silane compositions obtained by curing the curable polyorganosiloxane and / or silane compositions as mentioned above, the use of the curable polyorganosiloxane and / or silane compositions as mentioned above for the manufacture of shaped molded articles, extruded articles, coatings and sealants, and a process for the manufacture of curable polyorganosiloxane compositions as mentioned above.

[0002] Background technology / prior art

[0003] Platinum-(0)-vinylsiloxane complexes such as divinyltetramethyl-disiloxane complexes (Karstedt's catalyst) or tetravinyltetramethyl-cyclotetrasiloxane are able to catalyze hydrosilylation reactions at very high reaction rates. These catalysts are therefore currently used for crosslinking, curing or vulcanizing silicone rubbers with alkenyl and SiH groups via hydrosilylation between 20 and 200° C. However, according to the Arrhenius law, this reaction at room temperature sometimes shortens the pot life or bath-life time (1 to 10 minutes at 25° C.) in an unacceptable manner.

[0004] It is well known from prior art publications that the high reaction rates of platinum catalysts can be slowed down by inhibitors such as esters (e.g. maleates and fumarates), ketones, sulfoxides, phosphines, phosphites, nitrogen or sulfur derivatives, hydroperoxides and acetylene derivatives (e.g. alkinoles). If the effect of such inhibitors is described according to the Arrhenius law, then the 1 / K (K=reaction constant [s)) can usually be plotted on the x-axis with 1 / T (°K) as the x-axis. -1 ]), a shifted line is observed, i.e., if the pot life is extended, a decrease in the reaction rate at higher temperatures can be simultaneously observed.

[0005] Some prior art documents attempt to eliminate the effect on pot life and curing rate at higher temperatures. For example, US3,188,300 discloses specific aliphatic, alicyclic and aromatic phosphites in order to anticipate premature gelation at 20-30°C. EP948565A1 discloses siloxane compositions containing substituted aromatic phosphites, which show different relationships between curing rate at 140°C and pot life at room temperature. US2006 / 0135689 (Fehn) discloses siloxane compositions containing olefin-nitrogen-containing ligand-platinum complexes, which should have an extended pot life at room temperature and a high reaction rate at higher temperatures.

[0006] US2006 / 0128881 A1 and US2004 / 0116561 A1 disclose hydrosilylation-curing polyorganosiloxane compositions containing phosphites, but do not disclose phosphites having aryloxy groups substituted with other alkenyl and / or aryl groups. In addition, these documents do not involve the technical goal of eliminating the effects on pot life and curing rate at higher temperatures in hydrosilylation-curing polyorganosiloxane compositions.

[0007] WO2010009755 (A1) discloses a polyorganosiloxane and / or silane hydrosilylation-curing composition, which contains a specific phosphite and a transition metal compound containing at least one specific compound. The phosphite mentioned therein has three identical aromatic groups, which are substituted by at least one aromatic group or by at least one alkenyl group.

[0008] US 3,188,300 A1 and US 5,380,812 also disclose the use of phosphites as inhibitors in hydrosilylation-curing silicone compositions. Among the possible substituents, monocyclic aliphatic groups, i.e., cyclohexyl and triphenylphosphites, are also mentioned. However, the present inventors have found that the use of tri(cyclohexyl)-phosphites or tri(phenyl)-phosphites shows unacceptably low curing rates at high temperatures, although the pot life or storage stability, respectively, is acceptable.

[0009] JP2007 009041A discloses a curable composition in Examples 1-5, which comprises an organic compound containing at least two carbon-carbon double bonds that react with SiH groups, a compound containing at least two SiH groups in the molecule, and a platinum vinylsiloxane complex and a phosphite compound, thereby forming a hydrosilylation catalyst. In addition, JP2007 009041A discloses the general structure of a phosphite as a component of a curable composition, which comprises an organic compound containing at least two carbon-carbon double bonds that react with SiH groups, a compound containing at least two SiH groups in the molecule, and a hydrosilylation catalyst. The phosphite-based transition metal catalyst of JP2007 009041A is not included in the scope of the present invention, and JP2007 009041A is far from the present invention because it is preferred that the compound containing carbon-carbon double bonds does not contain siloxane units, while the present invention requires that the component with at least two alkenyl groups is a polyorganosiloxane.

[0010] In " Journal of Organometallic Chemistry ", volume 799, pages 201-207, Grice et al. disclose the structure of Pt (II) metal ring, which is obtained by CH activation via cyclometalation from a Pt complex containing a phosphite with three identical aryl substituents. Since one of the aryl alkyl substituents of the phosphite ligand in the disclosed complex is a divalent member of the metal ring, the disclosed structure is different from the transition metal compound of the present invention, in which phosphite carries three monovalent organic residues on the O atom of the phosphite. In " Polymer ", volume 33, issue 1, pages 161-165, Jongsma et al. disclose that phosphite aryl esters coordinate with rhodium central metal atoms to form rhodium hydroformylation catalysts. The catalyst is formed under the background of exploring polymer-bound rhodium hydroformylation catalysts, which is far from the field of the present invention.

[0011] In "Journal of Molecular Catalysis A Chemical", Vol. 259, No. 1-2, pp. 267-274, Gavrilov et al. disclose rhodium, palladium and platinum complexes prepared from phosphite iminoaryl esters containing ferrocenyl or cyclopentadienyl tricarbonyl manganese (cymantrenyl) groups. This publication relates to the use of palladium complexes as catalysts for asymmetric allylic substitution reactions, which is far from the field of the present invention.

[0012] In DE 223770, which is concerned with the development of catalysts for the hydrocyanation of olefins, a tris-(2,5-dimethylphenyl)-phosphite nickel complex is disclosed. Neither transition metal compounds nor any phosphite compounds containing 2,6-substituted aryl groups falling within the scope of the present invention are disclosed in said document.

[0013] The present invention seeks to provide hydrosilylation-curable polyorganosiloxane compositions, particularly "one-component" and "two-component" hydrosilylation-curable polyorganosiloxane compositions, which have a high pot life (i.e., storage stability) and at the same time a high cure rate at elevated temperatures, a property that is not affected by long-term storage. The present inventors have found that, surprisingly, specific phosphites having aromatic groups substituted with specific residues are suitable for solving these problems and can provide better dispersibility due to a lower melting point. Summary of the invention

[0014] Therefore, the present invention relates to a transition metal compound comprising at least one phosphite compound of the following formula:

[0015] P(OR)3 (I),

[0016] in

[0017] R represents an organic group, and at least one group R is represented by formula (II):

[0018]

[0019] in

[0020] The ring represented by A represents an aromatic or heteroaromatic group which may have one or more radicals other than R 1 and R 2 Other substituents besides

[0021] The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I),

[0022] R 1 and R 2 Each represents a substituent in an ortho position of the aromatic or heteroaromatic group relative to the oxygen atom of the phosphite compound of formula (I), and

[0023] wherein the substituent R 1 and R 2each independently selected from optionally substituted aliphatic groups, in particular optionally substituted alkyl groups and optionally substituted alkenyl groups, and optionally substituted aliphatic bridging groups, alkoxy groups, alkoxycarbonyl groups and Si-organic groups which form a condensed ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and wherein at least two radicals R are different from each other,

[0024] The prerequisite is that the transition metal compound is different from:

[0025] -Inclusive Pt complex of phosphite;

[0026] -Rh complex

[0027] The ligand P represents the structure as well as

[0028] - Rh, Pd and Pt complexes comprising phosphites of the general formula:

[0029]

[0030] Where R 7 is a methyl group and X is a ferrocenyl group,

[0031] or R 7 is a methyl group and X is a cyclopentadienyl manganese tricarbonyl group,

[0032] or R 7 is an isopropyl group and X is a ferrocenyl group.

[0033] The present invention also relates to the use of a transition metal compound containing a phosphite 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 comprising one or more such transition metal compounds containing a phosphite of formula (I), the use of one or more phosphites of formula (I) for the manufacture of a curable polyorganosiloxane and / or a silane composition, a curable polyorganosiloxane and / or a silane composition containing 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 a curable polyorganosiloxane and / or a silane composition as mentioned above, the use of a curable polyorganosiloxane and / or a silane composition as mentioned above for the manufacture of shaped molded articles, extruded articles, coatings and sealants, and a method for the manufacture of a curable polyorganosiloxane composition as mentioned above. DETAILED DESCRIPTION

[0034] In a first aspect, the present invention relates to a transition metal compound comprising at least one phosphite compound.

[0035] Specifically, the present invention relates to a transition metal compound comprising at least one phosphite compound of the following formula:

[0036] P(OR)3 (I),

[0037] in

[0038] R represents an organic group, and at least one group R is represented by formula (II):

[0039]

[0040] in

[0041] The ring represented by A represents an aromatic or heteroaromatic group which may have one or more radicals other than R 1 and R 2 Other substituents besides

[0042] The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I),

[0043] R 1 and R 2 Each represents a substituent in an ortho position of the aromatic or heteroaromatic group relative to the oxygen atom of the phosphite compound of formula (I), and

[0044] wherein the substituent R 1 and R 2 Each is independently selected from optionally substituted aliphatic groups, in particular optionally substituted alkyl groups and optionally substituted alkenyl groups, and optionally substituted aliphatic bridging groups, alkoxy groups, alkoxycarbonyl groups and Si-organic groups which form a condensed ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and wherein at least two radicals R are different from each other.

[0045] For transition metal compounds comprising at least one phosphite compound, provided that the compound is different from:

[0046] -Inclusive Pt complex of phosphite;

[0047] -Rh complex

[0048] The ligand P represents the structure as well as

[0049] - Rh, Pd and Pt complexes comprising phosphites of the general formula:

[0050]

[0051] Where R 7 is a methyl group and X is a ferrocenyl group,

[0052] or R 7 is a methyl group and X is a cyclopentadienyl manganese tricarbonyl group,

[0053] or R 7 is an isopropyl group and X is a ferrocenyl group.

[0054] According to the present invention, every compound which contains at least one atom or ion of an element from the d-block (including the f-block lanthanides and actinides) of the Periodic Table of the Elements is regarded as a transition metal compound.

[0055] The transition metal in such transition metal compounds is preferably selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, with platinum being the most preferred transition metal.

[0056] Although the transition metal compound of the present invention containing the specific phosphite ligand of formula (I) can be isolated, in the practice of hydrosilylation curing polyorganosiloxane system, certain common transition metal compounds are usually added to the polyorganosiloxane together with the phosphite without separately forming a transition metal phosphite complex compound, or alternatively, certain transition metal compounds react with the phosphite, so that the reaction product is added to the hydrosilylation curing polyorganosiloxane system in situ.

[0057] Thus, from a technical standpoint, it is generally not necessary to isolate the transition metal phosphite complex compound and only the effect of phosphite addition on pot-life or storage stability and cure rate at elevated temperatures can be determined without precise identification of the catalytically active transition metal species.

[0058] However, the potential transition metal compounds of the phosphites of the present invention can be prepared and separated by well-known ligand exchange reactions. For example, the known Karstedt catalyst can react with the phosphites of formula (I) of the present invention to provide transition metal compounds according to the present invention. The approach followed by this synthesis is that, for example, the binuclear platinum complex (Karstedt catalyst) of the known divinyl-tetramethyldisiloxane ("DVTMDS") bridge can be cleaved by any nucleophilic reagent (for example, phosphites), thereby providing a mononuclear platinum complex:

[0059]

[0060] The transition metal compound according to the present invention comprises at least one phosphite compound of the following formula:

[0061] P(OR)3 (I),

[0062] Wherein R is an organic group.

[0063] Thus, the phosphite compounds of the present invention are organic phosphites which can be considered as esters of the unobserved tautomer of phosphorous acid H3PO3.

[0064] According to the invention, an organic group is any organic substituent group having one free valence on a carbon atom, regardless of the functional type. The term organyl group is used interchangeably.

[0065] According to the present invention, in the phosphites of formula (I), the groups R other than the groups R of formula (II) are preferably selected from optionally substituted aromatic groups, and optionally substituted C1-C12 alkyl groups selected from linear, branched or cyclic alkyl groups, even more preferably optionally substituted C1-C6 alkyl groups.

[0066] Wherein, in the phosphite of formula (I), the aromatic group constituting one or more groups R other than the group R having formula (II) and the C1-C12 alkyl group selected from a linear, branched or cyclic alkyl group may be substituted by 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 by a linear, branched or cyclic C1-C12 alkyl group.

[0067] In the phosphite compound of formula (I), at least one group R is represented by formula (II):

[0068]

[0069] Wherein the ring represented by A represents an aromatic or heteroaromatic group, preferably the two groups R in formula (I) are represented by formula (II).

[0070] The aromatic group according to the present invention is a hydrocarbon group containing at least one cyclic conjugated part, the stability of which is significantly greater than a hypothetical local structure that may carry substituents other than C and H (for example, halides or hydroxyl groups). Preferred aromatic groups according to the present invention are phenyl, benzyl, xylyl, tri-tert-butylated phenyl, di-tert-butylphenyl, di-tert-butylmethylphenyl, tert-butyldimethylphenyl, and naphthyl groups.

[0071] According to the invention, heteroaromatic groups are heterocyclic groups formally derived from aromatic groups by replacing one or more methine and / or vinylidene groups with trivalent or divalent heteroatoms (e.g., S, O or N) in such a way that the continuous π-electron system characteristic of the aromatic system is maintained and significant stabilization is observed, wherein these groups may optionally be substituted by other groups other than H and C (e.g., halides or amino groups). Preferred heterocyclic groups are furanyl, thienyl, pyrrolyl, imidazolyl, pyridyl, triazolyl, isochinolyl and chinoyl groups. Aromatic and heteroaromatic groups represented by formula (II) may carry linear, branched or cyclic C1-C12 alkyl groups, alkoxy groups, alkoxycarbonyl groups, halide groups, nitro groups, cyano groups or Si-organic groups as substituents.

[0072] The dotted line in the structure of formula (II) represents the single bond of the oxygen atom of the phosphite compound of formula (I), which is located in the group R in formula (II). 1 and R 2 The adjacent positions of each.

[0073] As group R, in general, the group of formula (II) is an organic group with one free valence, by which the structure is bonded to one of the oxygen atoms of the phosphite compound. The group R does not have an additional free valence or complexing site by which the group R can be bonded to the transition metal atom of the complex or another ligand of the transition metal compound.

[0074] In the structure of formula (II), R 1 and R 2 Therefore, each represents a substituent in the ortho position of the aromatic or heteroaromatic group relative to the oxygen atom of the phosphite compound of formula (I), and the radical R in formula (II) 1 and R 2 Each is independently selected from optionally substituted aliphatic groups, in particular optionally substituted alkyl groups and optionally substituted alkenyl groups, optionally substituted aliphatic bridging groups forming a condensed ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, alkoxy groups, alkoxycarbonyl groups, and Si-organic groups. 1 or R 2 The aliphatic groups, in particular the alkyl groups, alkenyl groups or aliphatic bridging groups mentioned above, may be substituted by alkoxide groups, alkoxycarbonyl groups, halide groups, nitro groups, cyano groups or Si-organic groups.

[0075] The R according to the present invention 1 or R 2The alkoxy group is understood to be an alkoxide group connected to the ring A via an oxygen atom, and a C1-C12 alkoxy group is preferred. More preferred R 1 and R 2 It may be selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, isopropoxy, isobutoxy, isopentyloxy, cyclopentyloxy and cyclohexyloxy groups.

[0076] An alkoxycarbonyl group according to the invention is understood to be an ester functional group in which R is selected from the group consisting of alkoxycarbonyl 1 and R 2 It consists of a carbonyl group attached to ring A, which also carries an alkoxide group. Preferably, R 1 and R 2 It may be selected from the group consisting of methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl, isopropyloxycarbonyl, isobutoxycarbonyl, isopentyloxycarbonyl, cyclopentyloxycarbonyl and cyclohexyloxycarbonyl groups.

[0077] The term Si-organic group according to the present invention comprises alkyl groups with one or more Si-based functional groups (such as trialkylsilyl, trialkoxysilyl and polyorganosilane groups), carbosilane and carbosiloxane groups, and Si-based functional groups bonded to another part (such as ring A) via a silicon atom, such as silyl groups, especially trialkylsilyl groups, trialkoxysilyl groups, and Si-based functional groups bonded to another part (such as ring A) via an oxygen atom, especially siloxy groups.

[0078] Examples of siloxy groups are linear or branched oligo- and polysiloxy groups having 1 to 5000 siloxy units selected from dimethylsiloxy units, benzylsiloxy units, diphenylsiloxy units, methylsiloxy units, phenylsiloxy units or SiO2 with hydroxyl, trimethylsilyl, dimethylsilyl or vinyl end groups. 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 with up to 12 siloxy units (wherein the organic residue is preferably a methyl group), most preferably a siloxy group comprising a D2, D3, D4, D5 or D6 siloxane moiety.

[0079] Preferably, the group R in formula (II) 1 and R 2The alkyl radicals are independently selected from C1-C20 linear, branched or cyclic alkyl groups, 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 groups, more preferably the groups are independently selected from methyl, ethyl, isopropyl and tert-butyl, most preferably methyl and tert-butyl groups.

[0080] Also preferably, the group R in formula (II) 1 and R 2 independently selected from alkyl groups carrying one or more trialkylsilyl or trialkoxysilyl groups, or Si-based functional groups bonded to ring A via a silicon atom, in particular trialkylsilyl groups and trialkoxysilyl groups, or Si-based functional groups bonded to ring A via an oxygen atom, in particular siloxy groups.

[0081] Within the scope of the present invention, the substituent R 1 and R 2 One of the substituents is selected from an optionally substituted aliphatic group and the other substituent is selected from a Si-organic group, an alkoxy group or an alkoxycarbonyl group.

[0082] In formula (II), the ring A is 1 and R 2 The optional one or more further substituents other than R 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.

[0083] The alkyl group and alkenyl group constituting the optional additional substituent of ring A may be substituted by an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group or a Si-organic group. 1 and R 2 The additional substituents other than EMI15.1 are selected from C1-C12 alkyl substituents, more preferably methyl, ethyl, isopropyl and tert-butyl groups, and most preferably methyl and tert-butyl groups.

[0084] According to the definition of the phosphite of formula (I) and the radical R of formula (II), the phosphite may contain up to six different ortho-substituents R per phosphite compound. 1 and R 2Preferably, one group R of the phosphite of formula (I) is a C1-C12 alkyl group, in particular a methyl group, an ethyl group or an isopropyl group, and the two groups R in formula (I) are represented by formula (II), wherein ring A is a phenyl group, and the group R of each phenyl group is 1 and R 2 One or both of them are selected from tert-butyl substituents.

[0085] According to the present invention, at least two groups R of the phosphite compound of formula (I) comprised by the transition metal compound are different from each other. Preferably, one of the groups R is a C1-C12 alkyl group, and the other two R groups are aryl groups, more preferably the other two R groups are represented by formula (II), wherein the ring represented by A is each carrying a group R 1 and R 2 and a phenyl group with no or one further substituent, most preferably one of the groups R is a C1-C12 alkyl group and the other two groups R are represented by formula (II), wherein the ring represented by A is an R group independently selected from methyl and tert-butyl groups 1 and R 2 phenyl groups, and most preferably groups R other than methyl and tert-butyl groups independently selected 1 and R 2 In addition, the phenyl radical may have a further substituent selected from the group consisting of a methyl radical and a tert-butyl radical or may have no further substituent.

[0086] It is particularly preferred that one radical R of the phosphite of formula (I) is a methyl, ethyl or isopropyl radical and the other two R radicals in formula (I) are radicals R represented by formula (II) which are identical phenyl radicals which carry substituents selected from methyl, ethyl and tert-butyl radicals as radicals R 1 , R 2 and additional substituents, if any.

[0087] The transition metal compounds of the present invention are different from:

[0088] -Inclusive Pt complex of phosphite;

[0089] - Rh complex of the formula:

[0090]

[0091] as well as

[0092]

[0093] Wherein the ligand P represents the structure:

[0094]

[0095] - Rh, Pd and Pt complexes comprising phosphites of the formula:

[0096]

[0097] Where R 7 is a methyl group and X is a ferrocenyl group,

[0098] or R 7 is a methyl group and X is a cyclopentadienyl manganese tricarbonyl group,

[0099] or R 7 is isopropyl and X is a ferrocenyl group; and

[0100] -Ni complex of the following formula:

[0101]

[0102] And preferably the transition metal compound is different from:

[0103] - A Pt complex comprising a phosphite of the formula:

[0104]

[0105] Where R 8 is a monovalent organic group having 1 to 5 carbon atoms;

[0106] And / or the transition metal compound is preferably different from:

[0107] -Contains structural formula Transition metal complexes with ligands;

[0108] And / or the transition metal compound is preferably different from:

[0109] - A transition metal complex comprising a ligand of the following formula:

[0110]

[0111] Where R 7 is a methyl group and X is a ferrocenyl group,

[0112] or R 7 is a methyl group and X is a cyclopentadienyl manganese tricarbonyl group,

[0113] or R 7 is an isopropyl group and X is a ferrocenyl group;

[0114] And / or the transition metal compound is preferably different from:

[0115] - A transition metal complex comprising a ligand of the following formula:

[0116]

[0117] In an embodiment according to the invention, the transition metal compound according to the invention comprises at least one phosphite of formula (III):

[0118]

[0119] wherein at least two groups of formula (II) are different groups:

[0120]

[0121] According to this embodiment, it is preferred that two radicals R of formula (II) are identical and that the third radical R of formula (II) is different from the two identical radicals R of formula (II).

[0122] It is further preferred that all the radicals R having the structure of formula (II) are based on a phenyl radical, i.e., the ring A in formula (II) represents a ring each having two or three substituents (including the mandatory substituent R 1 and R 2 ) benzene ring.

[0123] According to this embodiment it is even further preferred that the substituent R having the structure of formula (II) 1 , R 2 and (if present) the third substituent is each independently selected from methyl, ethyl, isopropyl and tert-butyl groups, most preferably methyl and tert-butyl groups.

[0124] Even further preferably, one or more groups R having a structure of formula (II) in the phosphite of formula (III) are di- or tri-tert-butylated phenyl groups, and more preferably two or more groups R having a structure of formula (II) in the phosphite of formula (III) are di- or tri-tert-butylated phenyl groups.

[0125] If one or more radicals R of the structure of the formula (II) in the phosphite of the formula (III) are di- or tri-tert-butylated, it is also preferred that the substituents R on the ring A of one or two further radicals R of the structure of the formula (II) are 1 , R 2 and (if present) a further substituent is a methyl group.

[0126] In another embodiment according to the present invention, the transition metal compound according to the present invention comprises the phosphite compound of at least one formula (I), wherein in formula (I), at least one group R is an organic group different from the group of formula (II). One or more groups R in the phosphite of formula (I) different from the organic group represented by formula (II) are selected from unsubstituted aromatic or heteroaromatic groups, aromatic or heteroaromatic groups or aliphatic groups, particularly C1-C28 alkyl groups, not having or only having a substituent on the ortho position of the bond of the R group with the oxygen atom. Preferably, the phosphite compound of formula (I) contains a group R different from the structure of formula (II), and two groups R represented by formula (II), which can be identical or different.

[0127] According to this embodiment, it is preferred that the phosphite compound contains a group different from the structure of formula (II), and more preferably the group R different from the structure of formula (II) is selected from C1-C28 alkyl group, more preferably C1-C12 alkyl group, even further preferably C1-C6 alkyl group, even more preferably methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, hexyl or cyclohexyl group, most preferably methyl and ethyl groups. In addition, according to this embodiment, the two groups R represented by formula (II) of the phosphite compound of formula (I) can be the same or different.

[0128] According to this embodiment, it is preferred that in the phosphite compound of formula (I), all the groups R represented by formula (II) are based on phenyl groups, that is, ring A is a benzene ring, and each ring A carries two or three substituents, including the mandatory substituent R 1 and R 2 According to this embodiment, it is further preferred that the substituent R 1 , R 2 and (if present) the third substituent is each independently selected from methyl, ethyl, isopropyl and tert-butyl groups, most preferably methyl and tert-butyl groups.

[0129] Even further preferably, in the phosphite compound of formula (I), the radical R with the structure of formula (II) is a di- or tri-tert-butylated phenyl group, more preferably, two radicals R in the phosphite compound of formula (I) have the structure of formula (II) and are di- or tri-tert-butylated phenyl groups. If one or more radicals R with the structure of formula (II) are di- or tri-tert-butylated, it is also preferred that one of the other radicals or the other radical R in the phosphite compound of formula (I) is a C1-C6 normal alkyl group, most preferably a methyl or ethyl group.

[0130] In a further embodiment according to the invention, the transition metal compound according to the invention comprises at least one phosphite selected from the group consisting of formula (IV) or (V):

[0131]

[0132] Wherein in formula (IV), the group of formula (II):

[0133]

[0134] are identical or different groups, and are preferably identical groups, and are both in formula (IV) or (V) as defined above, and wherein in formula (V), the group R 6 are identical or different groups, and preferably the group R 6 are the same group, and the group R 6 In both formula (IV) and (V) is selected from organic groups different from those of formula (II), and is preferably selected from optionally substituted aliphatic groups, such as optionally substituted alkyl or optionally substituted cycloalkyl groups. 6 Such an aliphatic group, for example, an alkyl group or a cycloalkyl group may be substituted with an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group or a Si-organic group.

[0135] Preferably, one or more groups R in formula (IV) or (V) are 6 is selected from a C1-C28 alkyl group, more preferably a C1-C12 alkyl group, even further preferably a C1-C6 alkyl group, even more preferably a methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, hexyl or cyclohexyl group, most preferably a methyl, ethyl, n-propyl or isopropyl group.

[0136] The one or more radicals R of formula (II) in formula (IV) or (V) are preferably selected from substituted phenyl radicals, ie, ring A represents a phenyl radical, wherein R 1 , R 2 and (if present) the further substituents are each independently selected from methyl, ethyl, isopropyl and tert-butyl groups, most preferably methyl and tert-butyl groups, and even further preferably, in formula (IV) or (V) one or more groups R having a structure of formula (II) are di- or tri-tert-butylated phenyl groups, more preferably two or more groups R having a structure of formula (II) are di- or tri-tert-butylated phenyl groups.

[0137] In another 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 the ring represented by "A" in at least one group represented by formula (II) is an aromatic group, which may optionally have one or more radicals other than R. 1 and R 2 Other substituents other than .

[0138] 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.

[0139] It is also preferred that at least one ring A in the group represented by formula (II) is selected from the preferred aromatic groups listed above, and R 1 , R 2 and (if present) the further substituents are identical or different from each other, and preferably R 1 and R 2 Selected from C1-C6 alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentane, isopentyl, neopentyl, or cyclohexyl groups.

[0140] Most preferably, R 1 , R 2 and (if present) one further substituent bonded to the benzene ring constituting Ring A of the structure of formula (II) is selected from a methyl group and a tert-butyl group.

[0141] In another preferred embodiment according to the present invention, at least one ring represented by "A" in the group represented by formula (II) in the transition metal compound of the present invention is a phenyl group, which may optionally have one or more radicals other than R. 1 and R 2 Other substituents other than .

[0142] As mentioned above, R 1 and R 2 are identical or different from each other and are preferably independently selected from C1-C6 alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentane, isopentyl, neopentyl, or cyclohexyl groups. Even more preferably, the substituent R 1 and R 2 are identical and are selected from the group consisting of a tert-butyl group, or R 1 is a tert-butyl group and R 2 Selected from methyl or ethyl, most preferably R 1 is tert-butyl and R 2 Also tert-butyl or methyl.

[0143] Further preferably, in addition to the above-mentioned R 1 and R 2In addition, at least one of the benzene rings A in the group represented by formula (II) carries one, two or three additional substituents selected from Si-organic groups, C1-C6 alkyl groups, more preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopentane, isopentyl, neopentyl, or cyclohexyl groups.

[0144] According to this embodiment, it is also preferred that the benzene ring A is 1 and R 2 The meta position of R carries an additional 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, the additional 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, a triisopropylsilyl group, and even more preferably, R 1 , R 2 And in R 1 and R 2 The additional substituents at the meta position of are independently selected from methyl, isobutyl or tert-butyl groups, trimethylsilyl, triethylsilyl, triisopropylsilyl, and most preferably, R 1 , R 2 And in R 1 and R 2 The further substituents at the meta position of are substituents of the same type selected from methyl, isobutyl, tert-butyl or trimethylsilyl groups.

[0145] In another 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 the group R in the group R represented by formula (II) 1 and R 2 Each is an optionally substituted linear, branched or cyclic alkyl group preferably having up to 10 carbon atoms, more preferably up to 6 carbon atoms.

[0146] According to this embodiment, the group R in the group represented by formula (II) 1 and R 2 The alkyl radicals may be identical or different and are preferably selected from the following: an optionally substituted straight-chain alkyl radical selected from a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl radical; an optionally substituted branched cyclic alkyl radical selected from an isobutyl, tert-butyl, isopentyl, neopentyl, isohexyl or neohexyl radical; or an optionally substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radical.

[0147] The group R in the group represented by formula (II) is1 and R 2 The linear, branched or cyclic alkyl group may be substituted with an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group or a Si-organic group.

[0148] In another embodiment according to the invention, the phosphite of formula (I) comprised by the transition metal compound according to the invention is selected from compounds of formula (VI):

[0149]

[0150] or a compound selected from formula (VII):

[0151]

[0152] Wherein in formula (VI) and (VII), R 1 , R 2 and R 6 Each is as defined above, and R 3 , R 4 and R 5 Each is independently selected from hydrogen, halogen, cyano, nitro, Si-organic groups and organic groups, preferably optionally substituted aliphatic groups, and wherein in formula (VI), at least two of the following substituent groups are different from each other:

[0153]

[0154] wherein the dotted line represents a single bond of the oxygen atom of the phosphite compound of formula (I), and wherein in formula (VII), the two following substituent groups are preferably the same:

[0155]

[0156] The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I).

[0157] Although R 1 and R 2 As defined above, but preferably R 3 -R 5 Independently selected from hydrogen, C1-C12 alkyl groups and organosilyl groups, more preferably hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclopentenyl, cyclohexyl and trimethylsilyl groups.

[0158] It is further preferred that one or more groups R of formula (II) contained in formula (VI) and (VII) are mono-, di- or tri-tert-butylated benzene rings, and the total number of substituents on the benzene rings other than hydrogen is four or less, even more preferably three or two. 3 , R4 and R 5 The aliphatic group may be substituted with an alkoxy group, an alkoxycarbonyl group, a halide group, a nitro group, a cyano group or a Si-organic group.

[0159] In another embodiment according to the present invention, the phosphite of formula (I) comprised by transition metal compound is monodentate ligand.Therefore, the phosphite of formula (I) only has the single site with the metal center atom coordination of transition metal compound.Equally, one or more transition metal atoms of the transition metal compound of the phosphite comprising formula (I) are not a part for metallacycle (metallacycle).

[0160] In yet another embodiment according to the invention, the group R of the phosphite of formula (I) comprised of a transition metal compound does not contain any metal atom. According to this embodiment, any group R of the phosphite of formula (I) containing a metal atom is explicitly excluded, whether as a constituent element of a metal ring, as a cation of a counterion of an organic anion group, or as part of an organometallic residue, such as a ferrocenyl group.

[0161] In another embodiment according to the invention, the radical R of the phosphite of the formula (I) comprised by the transition metal compound does not contain any nitrogen atoms.

[0162] According to this embodiment, the group R of the phosphite of formula (I) does not contain any nitrogen atoms and therefore 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.

[0163] In another embodiment according to the present invention, the group R of the phosphite of formula (I) comprised by the transition metal compound does not contain any group containing N or P atoms, preferably does not contain any group containing N, P, S or Se atoms, and most preferably does not contain any group containing N, P, S, Se or O atoms.

[0164] According to this embodiment, the absence of the above-mentioned heteroatoms is preferred, since they may exhibit coordination with the central metal atom of the transition metal compound and thus the presence of heteroatoms or functional groups comprising heteroatoms may interfere in an undesirable manner with the coordination of the phosphorus atom of the phosphite of formula (I) with the central metal atom.

[0165] In a preferred embodiment according to the present invention, the group R of the phosphite of formula (I) may only contain C, H, O atoms and halogen atoms, wherein O atoms may only be present in ether bonds or ester groups, and preferably the group R may only contain C, H and halogen atoms, and most preferably the group R in the phosphite of formula (I) consists of C and H atoms.

[0166] In a specific embodiment according to the invention, the transition metal compound according to the invention comprises at least one phosphite of formula (I) selected from the group consisting of:

[0167]

[0168]

[0169] It has been found that when used as a curing catalyst for curable polyorganosiloxane and / or silane compositions, the compounds according to this embodiment provide particularly excellent results with respect to pot life (i.e., storage stability) and at the same time have a high curing rate at high temperatures. The provision of a high curing rate does not affect the long-term storage of the transition metal compound according to this embodiment.

[0170] In another preferred embodiment according to the embodiment, the phosphite compound of formula (I) of the transition metal compound is selected from

[0171]

[0172] in

[0173]

[0174] is preferred.

[0175] Among them, even further preferred is that the phosphite of formula (I) is

[0176]

[0177] And the transition metal is platinum.

[0178] In another embodiment according to the present invention, the transition metal of the transition metal compound according to the present invention is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.

[0179] The choice of a transition metal from the above list (i.e. the choice of a suitable precursor compound containing this transition metal for the preparation of the transition metal compound according to the invention) is made in each individual case on the basis of the desired temperature and the required time for carrying out the hydrosilylation reaction envisaged in particular in the curing of the organosilicon composition in the presence of all other ingredients of the reactive composition.

[0180] The choice of the central atom or atoms of the catalytic complex is generally based on the nature of the transition metal compound and the ease with which such complexes can be prepared either in advance or in situ from transition metal-containing precursor compounds and the corresponding phosphites.

[0181] According to this embodiment, the most preferred transition metal compound is platinum.

[0182] In another preferred embodiment according to the present invention, the transition metal of the transition metal compound according to the present invention is platinum.

[0183] As already mentioned, platinum is the most preferred transition metal for forming transition metal complexes. The Pt-based transition metal compound according to the invention (i.e., a compound comprising at least one phosphite compound of formula (I), the phosphite compound containing at least one group R represented by formula (II)) can be formed starting from a platinum compound such as hexachloroplatinic acid, a Speier catalyst, an Ashby catalyst or a Custer catalyst.

[0184] In another embodiment according to the present invention, the transition metal compound is a transition metal complex compound, wherein the transition metal has the zero (0) oxidation state, preferably the transition metal complex compound is a Pt(0)-compound.

[0185] Oxidation state (0) complexes, particularly Pt (0) complexes, can catalyze hydrosilylation reactions at very high reaction rates. Compounds according to this embodiment that also contain at least one phosphite compound as described in the previous embodiment show a desired high reaction rate at elevated temperatures, which enables the provision of a curable composition having a rare long pot life and a high curing rate at elevated temperatures.

[0186] In a further embodiment according to the invention, the transition metal compounds according to the invention comprise one or more alkenyl ligands.

[0187] The one or more alkenyl ligands may be any compound having at least one CC double bond, wherein the CC double bond may be an internal CC bond or a CC bond in a terminal position of the carbon skeleton of the ligand compound.

[0188] Preferably, at least one of the one or more CC double bonds of the alkenyl ligand is in terminal position.

[0189] Typically, the alkenyl ligand according to embodiments is selected from monoenes, dienes, trienes, polyenes or keto-olefins, preferably monoenes, dienes and trienes.

[0190] Examples of monoolefins, ie compounds containing one CC double bond which serve as alkenyl ligands according to this embodiment, are ethylene, isobutylene, cyclohexene, cyclooctene, tetrafluoroethylene, maleic anhydride and esters of fumaric acid, for example dimethyl fumarate, diethyl fumarate, or diisopropyl fumarate.

[0191] Examples of dienes, ie compounds containing two CC double bonds which serve as alkenyl ligands according to this embodiment, are butadiene, isoprene, cyclohexadiene, cyclooctadiene, norbornadiene, and C5-C10 dienes terminated by a CC double bond, such as 1,7-octadiene.

[0192] Examples of trienes and tetraenes, ie compounds containing three or four CC double bonds, respectively, which serve as alkenyl ligands according to this embodiment, are cycloheptatriene and cyclooctatetraene.

[0193] The alkenyl ligands may also be selected from polyenes, or ketoenes, containing even more than four CC double bonds.

[0194] Further preferred alkenyl ligands from the group mentioned above are alkenylsiloxane ligands, which according to the invention are characterized in that at least one organosiloxane group and at least one alkenyl group are present.

[0195] In a further preferred embodiment according to the invention, the transition metal compounds according to the invention comprise one or more alkenylsiloxane ligands.

[0196] According to the present invention, any ligand containing one or more CC double bonds and one or more organosiloxane units is considered to be an alkenyl siloxane ligand. Preferably, the alkenyl siloxane ligand contains two or more CC double bonds, wherein it is further preferred that the siloxane ligand contains two terminal CC double bonds, in particular two terminal CC double bonds provided by terminal vinylsiloxane moieties. In addition, it is also preferred that the alkenyl siloxane ligand contains two or more siloxane groups, preferably two to 100 adjacent siloxane groups, wherein it is particularly preferred that the adjacent siloxane groups form an unbranched linear structure or an unbranched cyclic structure.

[0197] Examples of preferred alkenylsiloxane ligands are 1,3-divinyltetramethyldisiloxane (vinyl-M2, used, for example, as ligand in Caster catalysts), and tetravinyltetramethyl-tetracyclosiloxane (vinyl-D4).

[0198] In a still further preferred embodiment according to the present invention, the transition metal compound according to the present invention is represented by the following formula:

[0199]

[0200] wherein P(OR)3 is a phosphite of formula (I) and is as defined above and described in the above embodiments.

[0201] The transition metal compound according to this embodiment can be obtained by adding the phosphite of formula (I) as described above to a solution of a Pt-based Castel catalyst, or to a curable composition or a portion of a curable composition comprising a Pt-based Castel catalyst. It should be noted that, in general, the features of the embodiments of the transition metal compound comprising the phosphite of formula (I) described above can be combined independently, unless this is not possible simply for logistic reasons.

[0202] Another aspect of the present invention relates to the use of a transition metal compound of formula (I) as defined in any one of the preceding embodiments as a curing catalyst for a curable polyorganosiloxane composition and / or a silane composition.

[0203] The transition metal compounds according to the present invention as described above can be advantageously used as curing catalysts for curable polyorganosiloxane and / or silane compositions, since they catalyze the hydrosilylation reaction required for curing such compositions at elevated temperatures at a high reaction rate, while also allowing the provision of compositions having an extended pot life when compared to prior art curing catalysts.

[0204] Among them, the transition metal compound according to the present invention used for curing the curable polyorganosiloxane composition and / or the silane composition can be prepared before being used to cure the above-mentioned composition and can be optionally isolated as needed, or the transition metal compound can be formed in the composition to be cured by adding a suitable precursor compound (for example, a transition metal salt or complex and a phosphite of formula (I) as described above).

[0205] Although the use of the transition metal compound comprising the phosphite of formula (I) according to the present invention as a curing catalyst for all types of curable polyorganosiloxane compositions and / or silane compositions as detailed above falls within the scope of the present invention, the present invention mainly relates to hydrosilylation-curing polyorganosiloxane compositions and / or silane compositions, i.e., compositions wherein curing of the composition is achieved by a hydrosilylation reaction of at least one compound containing one or more Si-H groups with at least one compound containing one or more unsaturated C-C bonds via an addition reaction of said groups.

[0206] In particular, the transition metal compound comprising the phosphite of formula (I) as defined above is used to cure the curable polyorganosiloxane composition and / or the silane composition as described in the next aspect of the invention below:

[0207] Another aspect of the present invention relates to a curable polyorganosiloxane composition and / or a silane composition comprising one or more transition metal compounds comprising a phosphite of formula (I) as defined above.

[0208] While this aspect of the invention relates to all types of compound-curable polyorganosiloxane compositions and / or silane compositions comprising the phosphite of formula (I), it primarily relates to hydrosilylation-curable polyorganosiloxane compositions and / or silane compositions, i.e., compositions wherein curing of the composition is achieved by a hydrosilylation reaction of a compound containing one or more Si-H groups with a compound containing one or more unsaturated C-C bonds via an addition reaction of said groups.

[0209] Such a curable polyorganosiloxane composition and / or silane composition according to the present invention comprises one or more compounds containing one or more unsaturated CC bonds, and one or more compounds containing one or more Si-H moieties.

[0210] Transition metal compounds comprising phosphites of formula (I) as described above can be advantageously used as curing catalysts for curable polyorganosiloxane and / or silane compositions because they catalyze the hydrosilylation reaction required to cure such compositions at elevated temperatures at a high reaction rate, while also allowing for the provision of compositions having an extended pot life when compared to prior art curing catalysts.

[0211] The transition metal compounds comprising the phosphites of formula (I) comprised by the curable polyorganosiloxane composition and / or silane composition according to the present invention may be added as separate compounds, or they may be carried out in situ by mixing a transition metal-containing precursor compound and one or more phosphites of formula (I), preferably in a solvent, and added without isolating the transition metal compound of the present invention or without any further post-treatment (e.g., as a solution in a solvent), or they may be formed in situ in the curable composition by adding a suitable transition metal-containing precursor compound (e.g., a transition metal salt or complex, such as a Custer catalyst or an Ashby catalyst) and one or more phosphites of formula (I) as described above to the curable polyorganosiloxane and / or silane composition.

[0212] The curable polyorganosiloxane composition and / or silane composition according to the present invention thus typically comprises one or more compounds containing two or more unsaturated CC bonds, one or more compounds containing two or more Si-H moieties, and one or more transition metal compounds comprising a phosphite of formula (I).

[0213] It should be noted that an excess of the phosphite of formula (I) is usually present in the curable composition according to the present invention, because in order to achieve complete conversion of the transition metal-containing precursor compound, the phosphite of formula (I) is used in excess relative to the transition metal-containing precursor compound when forming the transition metal compound comprising the phosphite of formula (I).

[0214] Thus, the curable composition preferably contains one or more phosphites of formula (I) in addition to the phosphites of formula (I) comprised by the one or more transition metal compounds comprising phosphites of formula (I) comprised by the curable composition.

[0215] According to the present invention, preferably, the curable polyorganosiloxane composition and / or the silane composition comprises

[0216] (A) one or more polyorganosiloxanes and / or silanes having an average of at least two alkenyl groups, and

[0217] (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups,

[0218] (C) one or more transition metal compounds, wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum,

[0219] (D) optionally one or more phosphites of formula (I) as defined in any of the preceding embodiments, and

[0220] (E) optionally one or more adjuvants.

[0221] The curable polyorganosiloxane composition and / or silane composition comprising the phosphite of formula (I) can be dissolved, dispersed, suspended or emulsified in a liquid as required. Unless otherwise specified, all viscosities indicated herein are according to DIN 53019 and at 25°C and D=10s -1 The measurement was carried out at a shear rate of .

[0222] The above-mentioned components (A) to (E) are defined as follows:

[0223] Component (A)

[0224] The composition of the present invention comprises one or more polyorganosiloxanes and / or silanes (A) having an average of at least two alkenyl groups, such as those disclosed in US 3,096,303, US 5,500,148 A (Examples). Suitable compounds (A) can be represented by the general formula (III'),

[0225] [M a D b T c Q d ] m (III')

[0226] Wherein formula (III') represents the ratio of siloxane units M, D, T and Q, which may be distributed in blocks or randomly in the polymer chain. In the polysiloxane chain, each siloxane unit may be the same or different, and preferably

[0227] a=1-10, preferably 2-8, more preferably 2-7, even more preferably 2-6,

[0228] b=0-12000, preferably 1-10000, more preferably 2-8000, even more preferably 5-6000, further preferably 20-4000,

[0229] c=0-50, preferably 0-25, more preferably 0-8, and further preferably 1-48, more preferably 2-45, even more preferably 3-40, further preferably 5-30,

[0230] d=0-1

[0231] m=1-5000, preferably 1-4800, more preferably 1-4200, even more preferably 1-3500, further preferably 1-2500.

[0232] These indices should be expressed based on the number average molecular mass M n The average degree of polymerization P n .

[0233] The polymer (A) is selected from alkenyl-containing polyorganosiloxanes, which can undergo a hydrosilylation reaction with hydrogensiloxane to form silicon-carbon bonds.

[0234] The polymer (A) or a mixture thereof comprises a group selected from the group consisting of:

[0235] M=R'3SiO 1 / 2 , or M*

[0236] D=R'2SiO 2 / 2 , or D*

[0237] T=R'SiO 3 / 2 , or T*

[0238] Q=SiO 4 / 2 ,

[0239] Two-price R 2 '-group,

[0240] Where M* = R 1 ' p R' 3-p SiO 1 / 2 、D*=R 1 ' q R' 2-q SiO2 / 2 , T*=R 1 'SiO 3 / 2 ,

[0241] in

[0242] p = 1-3,

[0243] q=1-2.

[0244] R' is preferably selected from normal, iso, or tertiary C1-C 30 -alkyl, alkoxyalkyl, C5-C 30 -Cyclic alkyl, or C6-C 30 - aryl, alkylaryl, which groups may be substituted by one or more O-, N-, S- or F-atoms, for example ethers or amides or poly(C2-C4)alkylene ethers having up to 1000 alkylene oxide units.

[0245] Examples of the monovalent residue R' in component (A) include hydrocarbon groups and halogenated hydrocarbon groups.

[0246] Examples of suitable monovalent hydrocarbon groups include alkyl groups, preferably CH3-, CH3CH2-, (CH3)2CH-, C8H 17 - and C 10 H 21 -, alicyclic groups such as cyclohexylethyl, aryl groups such as phenyl, tolyl, xylyl, aralkyl groups such as benzyl and 2-phenylethyl. Preferred monovalent halogenated hydrocarbon groups have the formula C n F 2n+1 CH2CH2-, wherein n has a value of 1 to 10, such as CF3CH2CH2-, C4F9CH2CH2-, C6F 13 CH2CH2-, C2F5-O(CF2-CF2-O) 1-10 CF2-, F[CF(CF3)-CF2-O] 1-5 -(CF2) 0-2 -, C3F7-OCF(CF3)- and C3F7-OCF(CF3)-CF2-OCF(CF3)-.

[0247] Preferred groups for R' are methyl, phenyl, 3,3,3-trifluoropropyl.

[0248] R 1 ' is selected from unsaturated groups containing groups containing C=C groups (alkenyl groups), for example: n-, iso-, tert- or cyclic-C2-C 30 -Alkenyl, C6-C 30 -cycloalkenyl, C8-C 30-alkenylaryl, cycloalkenylalkyl, vinyl, allyl, methallyl, 3-butenyl, 5-hexenyl, 7-octenyl, ethylidene-norbornyl, styryl, vinylphenethyl, norbornyl-ethyl, limonenyl, substituted by one or more O- or F-atoms, such as ethers, amides or C2-C4-polyethers with up to 1000 polyether units. The alkenyl group is preferably attached to the terminal silicon atom, the olefin function being at the end of the alkenyl group of the higher alkenyl group, since the α,ω-dienes used for the preparation of the alkenylsiloxanes are more readily available.

[0249] R 1 Preferred groups of ' are vinyl and 5-hexenyl.

[0250] R 2 ' includes, for example, divalent aliphatic or aromatic n-, iso-, tert- or cyclo-C1-C 14 - alkylene, arylene or alkylene aryl groups. Their content does not exceed 30 mol % of all siloxy units. Suitable divalent hydrocarbon groups R 2 Preferred examples include any alkylene residue, preferably -CH2-, -CH2CH2-, -CH2(CH3)CH-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)6-, -(CH2)8- and -(CH2) 18 -; Cycloalkylene groups, such as cyclohexylene; Arylene groups, such as phenylene, xylene and a combination of hydrocarbon groups, such as benzylidene, i.e., -CH2CH2-C6H4-CH2CH2-, -C6H4CH2-. Preferred groups are α,ω-ethylene, α,ω-hexylene or 1,4-phenylene.

[0251] Suitable divalent halogenated hydrocarbon groups R 2’ Examples include any divalent hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen such as fluorine, chlorine or bromine. Preferred divalent halogenated hydrocarbon residues have the formula -CH2CH2(CF2) 1-10 CH2CH2-, such as -CH2CH2CF2CF2CH2CH2- or other examples of suitable divalent hydrocarbon ether groups and halogenated hydrocarbon ether groups include -CH2CH2OCH2CH2-, -C6H4-0-C6H4-, -CH2CH2CF2OCF2CH2CH2- and -CH2CH2OCH2CH2CH2-.

[0252] This contains R', R 1 and / or R 2The polymer of the ' group is a polyorganosiloxane, for example, an alkenyl-dimethylsiloxy or trimethylsiloxy terminated polydimethylsiloxane, which may contain other siloxane units besides alkenylmethylsiloxy groups and dimethylsiloxy groups, such as poly-(dimethyl-co-diphenyl)siloxane.

[0253] Generally speaking, component (A) of the composition of the present invention may contain two or more oxygen and / or divalent groups R 2 ' any polysilicon compound having silicon atoms bonded thereto, wherein for each silicon atom, silicon is bonded to from 0 to 3 monovalent groups, provided that the organosilicon compound contains at least two silicon-bonded unsaturated hydrocarbon residues. The component may be solid or liquid, free-flowing or colloidal, i.e., it has a D = 1s -1 The invention has a shear rate of 1000 kPa.s and a measurable viscosity of less than 100 kPa.s at 25°C.

[0254] The polyorganosilicon compound (A) containing at least two silicon-bonded unsaturated hydrocarbon residues is preferably -1 The viscosity of the present invention is preferably in the range of 10 to 100,000,000 mPa.s at a shear rate of 1.5 to 2.0, preferably in the range of about 100 to 10,000,000 mPa.s, more preferably 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).

[0255] For each silicon atom, there is a group R' and / or R 1 The siloxane units of ' may be the same or different. In a preferred form, the structure is represented by the general formula (III'a) to (III'b) shown below.

[0256] Preferred polyorganosiloxane components (A) for the composition of the present invention are substantially linear polyorganosiloxanes (A) having formula (III'a) or (III'e) to (III'i). The expression "substantially linear" includes polyorganosiloxanes containing no more than 0.2 mol % (trace amount) of T or Q type siloxy units. This means that the polymer (A) is preferably a linear flowable fluid or colloid (A1) having a Newtonian viscosity but not being solid at 25°C.

[0257] R 1 ' p R' 3-p SiO(R'2SiO) b SiR' 3-p R' p 1 (III'a)(A1)

[0258] R 1 ' p R' 3-p (R'2SiO) b1 (R 1 ' q R' 2-q SiO) b1x SiR' 3-p R p 1 ' (III'b)

[0259] b=>0-12000, more preferably 10 to 9000, even more preferably 50 to 5000, and even further preferably 50 to 1000,

[0260] b1=>0-12000, more preferably 10 to 9000, even more preferably 50 to 5000, and even further preferably 50 to 1000,

[0261] b1x=0-1000, more preferably 1 to 500, even more preferably 10 to 200, and even further preferably 10 to 100,

[0262] b1+b1x=>0-12000, more preferably 10 to 9000, even more preferably 50 to 5000, and even further preferably 60 to 1000,

[0263] p = 0 to 3

[0264] q = 1 to 2,

[0265] A prerequisite is that at least two alkenyl groups are present per molecule.

[0266] Preferred groups for R' are methyl, phenyl, 3,3,3-trifluoropropyl.

[0267] R 1 Preferred groups of ' are vinyl, hex-5-enyl and cyclohexenyl-2-ethyl.

[0268] The average degree of polymerization Pn or "b" is based on M n As the number average molar mass in the range up to 12,000, a preferred range is 400 to 5,000.

[0269] The polyorganosilicon compound (A) containing at least two silicon-bonded unsaturated hydrocarbon residues is preferably -1The viscosity of the present invention is preferably in the range of 10 to 100,000,000 mPa.s at a shear rate of 1.5 to 2.0, preferably in the range of about 100 to 10,000,000 mPa.s, more preferably 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.

[0270] This viscosity of component (A) at 25°C is suitable for use in making a variety of products such as molded or extruded rubber parts, curable "form-in-place" sealants, and substrate coating applications using liquid silicone rubbers and high viscosity rubbers.

[0271] In the group of alkenyl-containing siloxanes (A), the addition of further so-called vinyl-rich polymers (A2) is preferred in order to modify the mechanical properties.

[0272] Polymer (A2) is selected from polymers of formula (III'b) to (III'd) or (III'h) to (III'i), i.e. linear polyorganosiloxanes with additional alkenyl side groups or branched polyorganosiloxanes with a higher concentration of T- and Q-groups than the previous types:

[0273] Me3SiO(Me2SiO) b1 (MeViSiO) b1x SiMe3 (III'c), and

[0274] ViMe2SiO(Me2SiO) b1 (MeViSiO) b1x SiMe2Vi (III'd), thus

[0275] Vi = vinyl.

[0276] Preferred values ​​for b1x are 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.

[0277] Other preferred structures according to formulae (III'e) to (III'i) achieve suitable viscosities as defined later and describe polymers suitable for adjusting the viscosity without any solvent. The range of sub-indices defines the possible average degree of polymerization P n range.

[0278] Vi p Me 3-p SiO(Me2SiO) 10-12000 SiMe 3-p Vi p(III'e)

[0279] PhMeViSiO(Me2SiO) 10-12000 SiPhMeVi (III'f),

[0280] Vi p Me 3-p SiO(Me2SiO) 10-12000 (MeViSiO) 1-2500 SiMe 3-p Vi p (III'g),

[0281] Me3SiO(Me2SiO) 10-12000 (MeViSiO) 1-2500 SiMe3 (III'h),

[0282] PhMeViSiO(Me2SiO) 10-12000 (MePhSiO) 1-1000 SiPhMeVi (III'i), and

[0283] Where Ph = phenyl,

[0284] p=0 to 3, preferably p=1.

[0285] In a preferred embodiment, polymer component (A) is a mixture of polymers of formula (III'a) and formula (III'b) or (III'h), whereby (III'b) has an alkenyl content of 1 to 50 mol %, in a ratio such that the alkenyl content of the mixture of (A1) and (A2) is less than 2 mol %.

[0286] Another preferred class of polymers is those having a high concentration of SiMe (3-p) (Alkenyl) p Branched polyorganosiloxanes (A2) containing alkenyl groups and having different curing rates. Such structures are particularly useful for mold release coating applications. The branched polymers are described, for example, in US 5,616,672 and are preferably selected from those of formula (III'), wherein the polyorganosiloxane (A2) containing alkenyl groups has a T=R'SiO of more than 0.2 mol %. 3 / 2 Or Q=SiO 4 / 2 -unit.

[0287] Preferably, the branched vinyl-rich polymer has a D:T>10:1, preferably>33:1 range and / or respectively (M 烯基 :Q)=0.6-4:1.

[0288] All of these polymers can be prepared by any conventional method for preparing triorganosiloxane-terminated polydiorganosiloxanes. For example, suitable hydrolyzable silanes (e.g., vinyldimethylchlorosilane and dimethyldichlorosilane) in suitable ratios can be co-hydrolyzed and condensed, or alternatively, suitable 1,3-divinyltetraorganodisiloxanes (e.g., symmetric divinyldimethyldiphenylsiloxane or divinyltetramethylsiloxane) providing the end groups of the polydiorganosiloxane can be equilibrated with suitable dipolyorganosiloxanes (e.g., octamethylcyclotetrasiloxane) in the presence of an acidic or basic catalyst. Regardless of the method of preparation of the polydiorganosiloxane (A), varying amounts of volatile cyclic polydiorganosiloxanes are generally co-produced.

[0289] For the purposes of the present invention, the viscosity of the polydiorganosiloxane (A) defined above preferably refers to the fraction of polydiorganosiloxane that is substantially free of cyclic polydiorganosiloxanes (less than 1 wt.%, preferably 0.5 wt.%, measured at 150° C., 20 mbar for 1 hour). This substantially acyclic fraction can be prepared by stripping the polydiorganosiloxane at 150° C. for at least 1 hour to obtain a polymer residue of this type. This residue is substantially free of cyclic materials, except for traces of macrocyclic polydiorganosiloxanes (molecular weight>518 g / mol), which are non-volatile as defined above.

[0290] Based on the number average molar weight M n The average degree of polymerization P of the polymer (A) measured by GPC relative to a polystyrene standard is n Preferably in the range of >10 to 12000, more preferably in the range of 40 to 6000, the range of 60 to 3000 is even more preferred, and the range of 70 to 1500 is even further preferred. At 25°C and D=10s -1 The viscosity of such polymers is in the range of 10 to 50,000,000 mPa.s at a shear rate of 1.5 to 2.0. n Or the value of 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 ranges from about 40 mPa.s to 35,000,000 mPa.s, and more preferably from 100 mPa.s to 25,000,000 mPa.s, further preferably from 500 to 1,000,000 mPa.s, even more preferably in the range of 800 to 500,000 mPa.s, and even further preferably in the range of 2,000 to 200,000 mPa.s, and most preferably in the range of 2000 to 100,000 mPa.s. The viscosity corresponds approximately to the average P indicated by "b" or "b1+b1x". n The value of .

[0291] The concentration of unsaturated functional groups is in the range of 50 mol% to 0.033 mol% (mol% of functionalized Si atoms to total Si atoms), i.e., in the case of polydimethylsiloxane, preferably about 0.002 to 12 mmol / g, more preferably 0.004-3 mmol / g. The siloxane units may be combined in any molecular arrangement such as linear, branched, cyclic and combinations thereof to provide polyorganosiloxanes (A1) and (A2) useful as component (A). In a preferred embodiment, the hydrosilylation-curable composition is solvent-free (less than 1 wt% volatiles).

[0292] The alkenyl content of component (A) can be determined by 1 H NMR determination - see AL Smith (ed.): The Analytical Chemistry of Silicones, J. Wiley & Sons 1991, Vol. 112, p. 356 et seq., Chemical Analysis, JD Winefordner ed.

[0293] Component (A) can also be selected from silanes of the following general formula:

[0294] R' e R 1 ' f Si(OR 9 ') (4-e-f)

[0295] R' e R 1 ' f Si(NR 9 '2) (4-e-f)

[0296] Among them, R', R 1 'As defined above, R 9 'As defined below, and

[0297] e=0-3

[0298] f = 1-4, and

[0299] e+f=4;

[0300] (R 9 'O) (3-g-h) (R 1 ' g )(R' h )Si-R 2 '-Si(R' h )(R 1 ' g )(OR9 ') (3-h-g) ,

[0301] (R 9 '2N) (3-g-h) (R 1 ' g )(R' h )Si-R 2 '-Si(R' h )(R 1 ' g )(NR 9 '2) (3-h-g) ,

[0302] Among them, R', R 1 ' and R 2 'As defined above, R 9 'As defined below, and

[0303] g = 1-3,

[0304] h = 0-2, and

[0305] g+h=3.

[0306] Particularly preferred polyorganosiloxanes having on average at least two alkenyl groups according to the invention are

[0307] -General average composition is MVi2D m A dimethylvinylsilyl-terminated polydimethylsiloxane wherein m is in the range of 50 to 1500, preferably 60 to 1400, more preferably 70 to 1400, even more preferably 70 to 1000.

[0308] -General average composition is MVi2D n DVi o dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane) 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 15 to 90, more preferably 20 to 70, even more preferably 25 to 50, for example, with an average composition of MVi2D 560 DVi 36 Dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane).

[0309] Component (B)——(cross-linking agent)

[0310] The curable composition of the present invention comprises a crosslinker and / or chain extender component (B) for (A) a polymer defined below. Component (B) is selected from silanes and polyorganosiloxanes having an average of at least 2 SiH groups capable of reacting with the alkenyl groups of polymer (A) and crosslinking the two polymers into an elastomeric network. In order to obtain a more elastic behavior than a gel, it is preferred that at least 30 mol % of components (A) or (B) should have a functionality of 3 or more reactive groups (the number of Si alkenyl groups per total Si atoms for (A) and the number of SiH groups per total Si atoms for (B)).

[0311] Component (B) is preferably selected from SiH-containing polyorganosiloxanes and SiH-containing organosilanes, which are respectively hydrosilyl-modified hydrocarbons. Suitably, component (B) is selected from the group M=R'3SiO 1 / 2 、M H =R'YSiO 1 / 2 、D=R'2SiO 2 / 2 , D H =R'YSiO 2 / 2 、T=R'SiO 3 / 2 , T H =YSiO 3 / 2 、SiO 4 / 2 siloxane units, wherein R' is as defined above and Y = R 1 ' and / or H, provided that there are on average at least two SiH-groups per molecule.

[0312] For example, they include:

[0313] R' e H f Si(OR 9 ') (4-e-f)

[0314] R' e H f Si(NR 9 '2) (4-e-f)

[0315] Where R' is as defined above, R 9 'As defined below, and

[0316] e=0-3

[0317] f = 1-4, and

[0318] e+f=4.

[0319] in addition,

[0320] (R 9 'O)(3-g-h) (H g )(R' h )Si-R 2 '-Si(R' h )(H g )(OR 9 ') (3-h-g) ,

[0321] (R 9 '2N) (3-g-h) (H g )(R' h )Si-R 2 '-Si(R' h )(H g )(NR 9 '2) (3-h-g) ,

[0322] Among them, g, h, R', R 2 '、R 9 'As defined above or below.

[0323] This means that the polymer (B) can be formally described by the ratio of the general formula (IV'),

[0324] [M a2 D b2 T c2 Q d2 ] m2 (IV')

[0325] The siloxy units M, D, T and Q are as defined above, including possible SiH-containing M, D, T groups. It is also possible that a portion of the siloxy groups are alkenyl siloxy groups, as long as there are at least two SiH-groups per molecule on average. The siloxy units may be distributed in blocks or randomly in the polymer chain. Within the polysiloxane chain, each siloxane unit may be identical or different, and preferably

[0326] a2=1-100, preferably 1 to 40, more preferably 1-10, even more preferably 2-5

[0327] b2=0-1000, preferably 2-500, more preferably 5 to 250

[0328] c2=0-50, preferably 0-45, more preferably 0 to 40, even more preferably 0 to 30, even further preferably 0-20, still further preferably 1 to 20

[0329] d2=0-1

[0330] m2=1-2000, preferably 1-1500, more preferably 1 to 120, even more preferably 1 to 100, even further preferably 1-80.

[0331] The above index should be expressed based on the number average molecular weight M n The average degree of polymerization P n .

[0332] The range of M-, D-, T- and Q-units present in the molecule covers almost all values ​​representing fluids, flowable polymers, liquids and solid resins. Preference is given to using liquid silanes or liquid linear, cyclic or branched siloxanes containing optionally remaining C1-C3-alkoxy or Si-hydroxy groups remaining from the synthesis. These compounds may be of low molecular weight or may be partially hydrolyzable condensation products, as well as siloxanes which polymerize via equilibrium or condensation with the aid of acidic catalysts.

[0333] For each silicon atom, the siloxane units having a group R' or Y can be identical or different.

[0334] Preferred structures of the reactive polyorganosiloxane of component (B) in the composition of the present invention are silanes or condensed silane / siloxanes of formula (IV'a) to (IV'd).

[0335] The preferred structure consisting of these units is selected from

[0336] Y r R' 3-r SiO(R'2SiO) z (R'YSiO) v SiR' 3-r Y r (IV'a)

[0337] Y r Me 3-r SiO(Me2SiO) z (MeYSiO) v SiMe 3-r Y r (IV'b)

[0338] Me3SiO(MeYSiO) v SiMe3 (IV'c)

[0339] [YR'SiO] w (IV'd)

[0340] z=0 to 1000, preferably 1-250, more preferably 5 to 150, even more preferably 10 to 50,

[0341] v=0 to 100, preferably 2 to 80, more preferably 4 to 60, even more preferably 6 to 40,

[0342] z+v=1 to 1000, preferably 2 to 300, more preferably 5 to 250, even more preferably 10 to 80,

[0343] w=3 to 9

[0344] r = 0 or 1,

[0345] And the following structure:

[0346] {[YSiO 3 / 2 ][R 9 'O 1 / 2 ] n2} m2 (IV'e)

[0347] {[SiO 4 / 2} ][R 9 'O 1 / 2 ] n2 [R'2YSiO 1 / 2 ] 0,01-10 [YSiO 3 / 2 ] 0-50 [R'YSiO 2 / 2 ] 0-1000} m2 (IV'f)

[0348] in

[0349] R 9 'O 1 / 2 is the alkoxy residue on the silicon atom

[0350] R' is as defined above,

[0351] n2 = 0.001 to 3

[0352] a2=0.01-10

[0353] b2=0-1000

[0354] c2=0-50

[0355] m2=1 to 2000

[0356] Y = hydrogen or R 1 '

[0357] R 9 ' is hydrogen, n-, iso-, tert- or cyclo-C1-C 25 -alkyl, such as methyl, ethyl, propyl, alkanoyl such as acyl, aryl, -N=CHR- such as butanone oxime, alkenyl such as propenyl, the group R 9' may be substituted by one or more halogen atoms, pseudohalogen groups such as cyano.

[0358] A preferred group for Y is hydrogen.

[0359] A preferred embodiment of compounds of classes (IV'e) and (IV'f) is, for example, a compound which can be prepared by the formula [(Me2HSiO 0.5 ) k SiO 4 / 2 ] m2 The monomeric to polymeric compounds described are provided wherein the index k may have an integer or decimal value from 0.01 to (2*m2+2). Such liquid or resin molecules may contain a significant concentration of SiOH- and / or (C1-C6)-alkoxy-Si groups of up to 10 mol % relative to silicon atoms.

[0360] The indices z and v of other types of preferred compounds of formula (IV'a) to (IV'c) are in the range of 0-1000 and are defined as the number average molar mass M measured by GPC relative to polystyrene standards. n The average P n .

[0361] Other examples of preferred suitable compounds for component (B) in the composition of the present invention include HMe2SiO(Me2SiO) z SiMe2H, HMe2SiO(HMeSiO) w (Me2SiO) z SiMe2H, Me3SiO-(MeHSiO) v -SiMe3, Me3SiO(HMeSiO) w (Me2SiO) z SiMe3, (MeHSiO) 3-6 、Si(OSiMe2H)4、Si x (OSiMe2H) 1,7x , MeSi(OSiMe2H)3, HMe2SiO(Me2SiO) z1 (MePhSiO) z2 (MeHSiO) v SiMe2H, Me3SiO(Me2SiO) z1 (MePhSiO) z2 (MeHSiO) v SiMe3, HMe2SiO(Me2SiO) z1 (Ph2SiO) z2 (MeHSiO) v SiMe2H, Me3SiO(Me2SiO)z1 (Ph2SiO) z2 (MeHSiO) v SiMe3, where z1+z2=z.

[0362] Component (B) can be used as a single component of the polyorganosiloxane polymer or as a mixture thereof. In another embodiment, it is preferred to use a mixture of formula (IV'b) and (IV'c). If it is necessary to increase the curing rate, it is preferred to use some HMe2SiO 0,5 -unit organopolysiloxane (B) adjusts the curing rate to a shorter time.

[0363] Component (B) has a smaller molecular weight; compared to component (A), the functionality per molecule in (B) is higher.

[0364] If it is necessary to further increase the curing rate, this can be achieved, for example, by increasing the molar ratio of SiH to Si-alkenyl, or increasing the amount of catalyst (C), or increasing the amount of HMe2SiO 0.5 Therefore, in order to provide a faster curing rate, the preferred component (B) includes HMe2SiO 0.5 (MH group).

[0365] In a further preferred embodiment of component (B), the component is selected from the group according to formula (IV'a), which constitutes component (B1), such as YR'2SiO (R'2SiO) z (R'YSiO) v SiR'2Y, or formula (IV'c) with a Y functionality of 3 or more, and component (B2) with an average Y functionality of 2, such as YR'2SiO (R'2SiO) z SiR'2Y, wherein Y, R' and z are as defined above.

[0366] If (B1) and (B2) are used together, the preferred ratio of functional SiH (B1) to (B2) is greater than 0 to 70 mol %, and more preferably 30 to 100 mol % of (B2), based on (B1) and (B2).

[0367] The molecular weight of component (B) is not critical; however, it is preferably such that the polyorganosiloxane component (B) (in the case of R' = methyl) is 100 Å at 25°C and D = 10 s -1The viscosity at shear rate is up to 3 to 10,000 mPa.s, preferably 5 to 3,000 mPa.s, more preferably 8 to 2500 mPa.s, even more preferably 10 to 1500 mPa.s. In general, the aforementioned viscosities are also preferred for the polyorganosiloxane component (B). The viscosity depends on the types of R' and Y substituents, and the ratio and molar weight of the units M, D, T and Q. For polyorganosiloxanes containing only methyl groups as R' groups, the ratio of M to Q is 1.5 to 2.0. n The molecular weight indicated ranges from 136 to 100,000 g / mol, preferably from 250 to 50,000, more preferably from 400 to 25,000, and even more preferably from 1000 to 10000.

[0368] For each silicon atom, the siloxane units carrying the radical R' or Y may be identical or different. Each molecule may independently carry one or more radicals.

[0369] The crosslinking agent (B) should have at least 2 or more reactive groups Y per molecule, whereas the chain extender (B2) has an average functionality Y of 2 to 3 per molecule.

[0370] The concentration of reactive groups Y is in the range of 0.2 to 100 mol % Y groups relative to Si atoms, ie for polydimethyl-methylhydrogensiloxane, preferably about 0.1-17 mmol SiY / g, with a preferred range of 0.15 to 16 mmol / g.

[0371] In a preferred embodiment, a mixture of compounds of formula (IV'c) or (IV'd) is used together with (IV'a) and / or (IV'b) (wherein z=0, R'=methyl), and the SiH concentration is preferably >7-17 mmol SiH / g, and in the second compound of (B), the index z>0, wherein the SiH concentration preferably has a value of 0.2 to 7 mmol SiH / g.

[0372] If adhesion to other substrates, such as thermoplastic substrates, has to be achieved, preference is given to using compounds of the formula (IV'a) and / or (IV'b) in which R'=aryl, in particular phenyl.

[0373] The SiH content of the present invention is determined by 1 H-NMR was used for determination, see AL Smith (editor): The Analytical Chemistry of Silicones, J. Wiley & Sons 1991, Vol. 112, p. 356 and subsequent, Chemical Analysis, JD Winefordner ed.

[0374] The ratio of crosslinker (B) to polymer (A) required to obtain an elastomeric network (i.e., a non-sticky surface) can be calculated by the ratio of reactive groups in (B) and (A). It is preferred to have an excess of reactive groups (B):(A) of 0.7 to 20:1, preferably 1.2 to 6:1, more preferably 1.5 to 4:1, in order to ensure a certain level of multifunctional structure in the cured elastomeric network.

[0375] Particularly preferred polyorganosiloxanes having on average at least two SiH groups according to the invention are

[0376] -General average composition is MH2D a A hydride-terminated poly(dimethylsiloxane) wherein 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, with an average composition of MH2D 17 Hydride terminated poly(dimethylsiloxane);

[0377] -General average composition is M2D b DH c trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane) wherein 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, the average composition is M2D 20 DH 20 Or the average composition is M2D 20 DH 10 trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane);

[0378] -General average composition is MH dx Q x A resin type wherein 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, for example, with an average composition of MH 1.7x Q x ;

[0379] -General average composition is M2DH e trimethylsilyl-terminated polymethylhydrogensiloxane, wherein 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 is M2DH 30 trimethylsilyl-terminated polymethylhydrogensiloxane; or

[0380] -General average composition is M2D (Ph2) f DH g D h trimethylsilyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane-co-methylhydrogensiloxane) wherein 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, with an average composition of M2D(Ph2)2DH 24 D2 trimethylsilyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane-co-methylhydrogensiloxane).

[0381] Component (C)——(Transition metal compound)

[0382] The curable composition according to the present invention comprises at least one transition metal compound comprising a phosphite of formula (I) as described above acting as a hydrosilylation catalyst, wherein the transition metal is selected from Ni, Ir, Rh, Ru, Os, Pd and Pt compounds, as taught in US 3,159,601; US ​​3,159,662; US 3,419,593; US 3,715,334; US 3,775,452 and US 3,814,730.

[0383] Component (C) for the hydrosilylation reaction of the composition according to the present invention is a catalyst compound that promotes the reaction of the silicon-bonded hydrogen atoms of component (B) with the silicon-bonded olefin substituents of component (A). The transition metal compound can be any catalytically active component containing a transition metal and comprising the phosphite of formula (I). Catalyst (C) includes a complex of a carbon ligand with σ- and π-bonding and a ligand containing S-, N- or P atoms, a colloidal metal or a salt of the aforementioned metal. The catalyst may be present on a carrier such as silica gel or charcoal powder of a metal-bearing or metal compound or complex. Preferably, the metal of component (C) is any platinum complex compound.

[0384] Typical platinum-containing catalyst components in the polyorganosiloxane composition of the present invention are any form of platinum (0), (II) or (IV) compounds (which include the phosphites of formula (I) of the present invention). Preferred complexes are Pt (0) -alkenyl complexes such as alkenyl, cycloalkenyl, alkenyl siloxanes such as vinyl siloxanes due to their easy dispersibility in polyorganosiloxane systems.

[0385] Particularly useful forms of platinum complexes are Pt(0)-complexes with aliphatically unsaturated organosilicon compounds, such as 1,3-divinyltetramethyldisiloxane (derived from vinyl-M2 or Custer's catalyst) (as disclosed by US 3,419,593, which is incorporated herein by reference), cyclohexene-Pt, cyclooctadiene-Pt and tetravinyltetramethyl-tetracyclosiloxane (vinyl-D4) are particularly preferred.

[0386] Pt 0 The -olefin complex is prepared, for example, in the following manner: Vi 2), for example, by reducing hexachloroplatinic acid or other platinum chlorides in the presence of an alcohol in the presence of a basic compound such as an alkali metal carbonate or hydroxide. The transition metal compound comprising the phosphite of formula (I) is prepared by reacting the phosphite of formula (I) with a corresponding precursor compound (e.g., Pt 0 -olefin complex) in the curable composition or separately react to form.

[0387] The amount of the platinum-containing catalyst component used in the composition of the present invention is not strictly limited, as long as there is a sufficient amount to accelerate the hydrosilylation between (A) and (B) at the desired temperature within the time required for (B) in the presence of all other ingredients of the composition of the present invention. The exact necessary amount of the catalyst component will depend on the specific catalyst, the amount of other inhibiting compounds, and the ratio of SiH to olefin, and is not easy to predict. This applies to all transition metal-containing catalysts in the same way. However, for platinum catalysts, the amount can be as low as possible for cost reasons. Preferably, for every million parts by weight of the organosilicon components (A) and (B), more than one part by weight of platinum should be added to ensure curing in the presence of other uncertain inhibitory traces. For the composition of the present invention, the amount of the platinum-containing catalyst component to be applied is preferably sufficient to provide 1 to 200 ppm, preferably 2 to 100 ppm, and particularly preferably 4 to 60 ppm of platinum per weight of the polyorganosiloxane component (A) plus (B).

[0388] Preferably, the amount is at least 4 ppm by weight, based on the sum of (A) and (B).

[0389] Other Pt catalysts which can be used as precursor compounds are mentioned, for example, in US 3,715,334 or US 3,419,593, EP 1 672 031 A1 and Lewis, Colborn, Grade, Bryant, Sumpter and Scott, Organometallics, 1995, 14, 2202-2213, all of which are incorporated herein by reference.

[0390] As already explained above, the specific phosphites of formula (I) used according to the invention interact with conventional transition metal compounds via a ligand exchange reaction, thereby forming transition metal compounds comprising the phosphites of formula (I) and influencing the hydrosilylation activity of the catalyst, thereby surprisingly providing an excellent balance between storage stability on the one hand and reactivity at elevated temperatures during curing.

[0391] Based on the above description of the formation of the transition metal compound comprising the phosphite of formula (I), the presence of the phosphite of formula (I) and a transition metal-containing precursor compound (e.g., a conventional transition metal-based hydrosilylation catalyst) in the curable composition is equivalent to the presence of the transition metal compound (C) comprising the phosphite of formula (I).

[0392] According to the present invention, particularly preferred transition metal compounds (C) are {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite}platinum, {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)methylphosphite}platinum, {η 4 -(H2C=CHSiMe2)2O}{bis(2,4-di-tert-butyl-6-methyl-phenyl)ethylphosphite}platinum, and {η 4 -(H2C=CHSiMe2)2O}{bis(2,4,6-tri-tert-butylphenyl)ethyl phosphite}platinum.

[0393] Component (D) :

[0394] Optionally, one or more additional phosphites (D) of formula (I) are included in the curable polyorganosiloxane and / or silane composition according to the invention. The one or more phosphites of formula (I) in excess of the amount of phosphites present in complexed form in compound (C) are present for the following reasons: when preparing compound (C), in order to ensure complete conversion of the transition metal-based precursor compound, an excess of phosphites of formula (I) relative to the transition metal-containing precursor compound is used; or in order to further retard the hydrosilylation reaction at room temperature, it is added in sufficient amount to allow mixing of components (A) to (C) and the dispensing and coating steps without prior curing.

[0395] As regards component (D), it may refer to the phosphite ester as defined above having the following formula:

[0396] P(OR)3 (I).

[0397] One or more phosphites (D) of formula (I) may preferably be incorporated therein in small amounts, such as less than 2% by weight (20,000 ppm), based on the total weight of (A) to (B).

[0398] A particularly preferred range is 0.2 to 12000 ppm of component (D) relative to (A) and (B).

[0399] Furthermore, preferably, the molar ratio of the transition metal derived from platinum in component (C) to the phosphite (D) (including the complexed phosphite in component (C)) is 1:1 to 1:6, preferably 1:1.1 to 1:5, more preferably 1:1.2 to 1:4.

[0400] Due to their interaction with the transition metal hydrosilylation catalyst compound, components (D) act as inhibitors of the hydrosilylation reaction, thereby increasing storage stability (ie, extending pot life), and at the same time do not exert their inhibitory activity during the curing reaction.

[0401] 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 bis(2,4,6-tri-tert-butylphenyl)ethyl phosphite.

[0402] Component (E):

[0403] The polyorganosiloxane and / or silane composition according to the invention may contain further ingredients (E) as auxiliary additives. The siloxane composition according to the invention may also contain further ingredients (E), such as conventional inhibitors, stabilizers, solvents, fillers, pigments or processing aids, which are added to achieve better processing properties of the polymer composition (A) to (C) or (A) to (D) according to the invention.

[0404] In general, auxiliary additives can be used to adjust the processing time, the starting behavior and the curing rate of the curable composition.

[0405] In order to further adjust the hydrosilylation activity, it may be desirable, as the case may be, to additionally add other conventional inhibitors, that is, to combine the phosphite component (D) of the present invention with other conventional inhibitors.

[0406] Thus, the compositions of the invention may contain suitable amounts of one or more additional conventional inhibitors. Preferably, however, the compositions of the invention do not contain other phosphorus inhibitor compounds than those of formula (I).

[0407] Conventional inhibitors for platinum group metal catalysts are well known in the silicone art. Examples of various classes of such metal catalyst inhibitors include unsaturated organic compounds such as ethylenically or aromatically unsaturated amides, U.S. Pat. No. 4,337,332; acetylenic compounds, U.S. Pat. No. 3,445,420 and U.S. Pat. No. 4,347,346; ethylenically unsaturated isocyanates, U.S. Pat. No. 3,882,083; olefinic siloxanes, U.S. Pat. No. 3,989,667; unsaturated hydrocarbon diesters, U.S. Pat. No. 4,256,870, U.S. Pat. No. 4,476,166 and U.S. Pat. No. 4,562,096; and conjugated enynes, U.S. Pat. No. 4,465,818 and U.S. Pat. No. 4,472,563; other organic compounds such as hydroperoxides, U.S. Pat. No. 4,061,609; ketones, U.S. Pat. No. 3,418,731; sulfoxides, amines, nitriles, U.S. Pat. No. 3,344,111; diaziridines, U.S. Pat. No. 3,989,667; 4,043,977; and various salts, such as US 3,461,185, phosphorus compounds are preferably excluded. Examples include alkynols such as ethynylcyclohexanol and methylbutynol, 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1-dodecin-3-ol of US 3,445,420, unsaturated carboxylic acid esters such as diallyl maleate and dimethyl maleate of US 4,256,870; and maleic acid esters and fumarates such as diethyl fumarate, diallyl fumarate and bis(methoxyisopropyl) maleate of US 4,562,096 and US 4,774.111. 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 trialkylcyanurates, organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and pinane hydroperoxide, organic peroxides, organic sulfoxides, phosphanes, triazoles and oximes. The above mentioned patents relating to conventional inhibitors for platinum group metal containing catalysts are incorporated herein by reference.

[0408] If the composition of the present invention optionally contains solvents, these are common organic solvents in the range of less than 20 wt %, preferably less than 10 wt % and most preferably less than 5 wt % relative to (A) to (C) or (A) to (D). Suitable reactive solvents may be selected from olefins such as α-olefins, e.g. C8-C 25 -α-olefins, preferably C 14 -C 20 - α-olefins or evaporable siloxanes having a molecular weight below 518 g / mol and containing no alkenyl groups or SiH groups. Mixtures of α-olefins can also be used.

[0409] Other additives falling within the definition of component (E) are selected from heat stabilizers, coloring compounds or pigments, antioxidants, biocides, fungicides such as Fillers, especially spherical silsesquioxanes for obtaining additional anti-blocking properties of the release layer, anti-fog additives as disclosed in US 6,586,535 or US 2003 / 0134043, anchoring additives, slip agents as disclosed in EP 819735 A1, and further auxiliary components typically used in silicone release compositions. These other ingredients can be contained in the reactive silicon-based composition in a total amount of up to 20% by weight.

[0410] If fillers are used in the composition of the invention, the amount of filler is 1 to 300 parts by weight, preferably 15 to 80 parts by weight, relative to 100 parts by weight of component (A). The filler is preferably selected from hydrophilic or hydrophobic, preferably surface-modified fillers. The filler may act as reinforcing filler, thickening additive, anti-blocking or anti-friction or matting additive.

[0411] The fillers include, for example, all fine-grained fillers, i.e. fillers with particles smaller than 100 μm (screening residues), i.e. preferably consist of particles smaller than this value. In general, the fillers may be non-reinforcing fillers, i.e. the BET surface area is preferably up to 50 m 2 / g fillers such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolite, metal oxide powders (such as aluminum, titanium, iron, or zinc oxides and their mixed oxides) - barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass or polymer powders such as polyacrylonitrile powder, or reinforcing fillers, i.e., with a BET surface area greater than m 2 / g fillers, such as precipitated chalk, carbon black (such as furnace black and acetylene black) and silicon-aluminum mixed oxides with a large BET surface area; aluminum trihydroxide, spherical shaped fillers, such as ceramic microspheres, elastic polymer spheres or glass spheres; fibrous fillers, such as asbestos and polymer fibers. The fillers can be hydrophobized, for example, by treatment with organosilanes or organosiloxanes, or by treatment with stearic acid, or by etherification of hydroxyl groups into alkoxy groups.

[0412] Preferred are mineral fillers such as silicates, carbonates, nitrides, oxides, carbon black, or silicon dioxide (i.e. fumed or precipitated silicon dioxide) having a BET surface area of ​​0.3 to 400 m 2 / g, these are preferably especially surface-hydrophobized. Preferred silicon dioxides are, for example, silicon dioxides with a BET surface area of ​​more than 200 m 2 / g 200, 300, N20 or T30, MS 7 or HS 5, or precipitated silica or wet silica is VN3, or FK160 (obtained from Degussa), or LP (obtained from Nippon Silica KK) etc. Examples of commercially available silica pre-hydrophobized with various silanes are: R 972, R 974, R 976, or R 812, or for example 2000 or H30, the material name for hydrophobized precipitated silica or wet silica is D10 or D15 (available from Degussa).

[0413] Surface treated fillers with low BET values ​​are preferred because the ability to establish a shear thinning effect is reduced. Preferred surface treatments can be achieved with polyorganosiloxane diols, polyorganosiloxanes, alkoxy- or chlorosilanes, which allow a specific concentration of filler with minimal thickening properties and shear thinning.

[0414] Another class of fillers that serve as opaque, non-reinforcing fillers are powdered quartz, diatomaceous earth, powdered cristobalite, mica, aluminum oxide, aluminum hydroxide, oxides and salts of Fe, Mn, Ti, Zn, Zr, chalk, or carbon black, which have a BET surface area of ​​0.3 to 50 m 2 / g.

[0415] These fillers are available under various trade names, examples being And acts as a matting agent. Such fillers are used if present in a concentration of about 1 to 300 parts by weight, preferably 5 to 100 parts by weight, relative to 100 parts by weight of (A).

[0416] Some very specific fillers can be used as matting agents, agents to increase the mechanical modulus, or anti-blocking agents, these fillers are selected from spherical or fibrous thermoplastic powders or fibers, such as PTFE powders, PTFE emulsions or polyamide, polyurethane or silsesquioxane powders, thermoplastic fiber cured silicone elastomers or resins, and are used if present in an amount of up to 10 parts by weight relative to 100 parts by weight of (A). Lotion, powder, wait.

[0417] Especially if the particles have a spherical shape, fillers of this type can preferably be used as antiblocking agents in release layers and can impart particularly soft touch and low-friction properties to rubber surfaces.

[0418] Another class of additives is stabilizers, such as heat stabilizers, which may be selected from metal compounds, organic or inorganic salts, complexes of Ce, Fe, La, Mn, Ti and Zr.

[0419] The leveling agent and the mold release agent are selected from polyether-siloxane, polyol, polyether, polyhalide, fatty alcohol or fluoroalkyl derivative.

[0420] Another important class of auxiliary additives are tackifiers, which may be incorporated into compositions (A) to (C) or (A) to (D), respectively, or applied in a suitable form as a primer previously applied to the substrate, which primer is intended to adhere to the rubber composition when cured.

[0421] The adhesion promoter is preferably selected from alkoxysilanes, the condensation products of which are alkoxysiloxanes carrying additional organic functional groups connected via Si-C bonds, in particular epoxyalkyl, acryloxyalkyl, methacryloxyalkyl, NCO-alkyl, aminoalkyl, carbamatealkyl, alkenyl, which may also carry SiH groups. In line with this, the alkoxysilanes acting as adhesion promoters may also contain additional functional groups capable of interacting with groups on the substrate (e.g., plastic substrates). Thus, the alkoxysilanes may also contain groups such as, but not limited to, epoxides, esters, or anhydrides.

[0422] 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 comprise an ester or anhydride group. The alkoxysilane may be selected from glycidyloxypropyl trimethoxysilane, bis (3-trimethoxysilylpropyl) fumarate and (3-triethoxysilyl) propyl succinic anhydride. The applied tackifier may also include at least two alkoxysilanes, and preferably they include at least two alkoxysilanes that also include additional functional groups. The alkoxysilane used as the tackifier may also be selected from bis (3-trimethoxysilylpropyl) fumarate and / or (3-triethoxysilyl) propyl succinic anhydride.

[0423] Such silanes / siloxanes can be combined with organic metal compounds selected from Ca, Zr, Zn, Sn, Al or Ti and / or condensation catalysts of polycyclic aromatic compounds with reactive groups (e.g., aromatic diphenyl ethers, esters substituted with alkenyl groups). The adhesion effect can be further improved by adding selected compounds of component (B) (e.g., as incorporated by reference in US 4,082,726, US 5,438,094; US 5,405,896; US 5,536,803; US 5,877,256; US 6,602,551; EP 581504A; and EP 875536).

[0424] According to the present invention, particularly preferred adjuvants are

[0425] - conventional inhibitors known for use in hydrosilylation curable compositions, for example, tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168) or 1-ethynyl-1-cyclohexanol; the inhibitor is preferably present in an amount of 0-1000 ppm w / w, more preferably 0 to 800 ppm w / w, even more preferably 10 to 500 ppm w / w, relative to the weight of component (A);

[0426] - adhesion promoters, in particular alkoxysilanes, for example γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-(trimethoxysilyl)propyl α,2,4,6,6,8-hexamethylcyclotetrasiloxanepropionate (CAS 113684-56-3); the adhesion promoter is 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 further preferably 0 to 1 part by weight, relative to the weight constituting 100 parts by weight of component (A);

[0427] - filler, preferably silica filler, more preferably surface-modified silica filler, for example, HMDZ hydrophobized silica with a BET surface area of ​​155 m 2 / g of Evonik Aerosil R8200 silica;

[0428] The filler is 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, relative to the weight constituting 100 parts by weight of component (A).

[0429] The curable polyorganosiloxane and / or silane compositions can be used for all purposes for which curable polyorganosiloxane and / or silane compositions have been used to date in the art, such as coating and impregnation of substrates of any kind, production of molded parts (e.g. by injection molding, vacuum extrusion, extrusion, molding, compression molding, for molding), and as sealants, potting compounds or casting compounds.

[0430] The curable compositions according to the invention are preferably used for coating solid substrates such as paper, fabric or plastic, optionally with an adhesive release layer, metal substrates such as metal foils, metal sheets and metal surfaces of articles, or for extrusion, calendaring or molding into shaped articles, laminates or for "formed in place" sealing blocks.

[0431] In one embodiment according to the present invention, the above-mentioned curable polyorganosiloxane composition and / or silane composition according to the present invention further comprises one or more phosphites of formula (I) as defined above.

[0432] In addition to the phosphite of formula (I) complexed by the transition metal of the transition metal compound of the present invention, a slight excess of the phosphite of formula (I) is typically present in the composition because an excess of the phosphite of formula (I) is used in the synthesis of the catalyst in order to obtain 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 of the phosphite of formula (I) contained by the transition metal compound of the present invention may further be present in the curable polyorganosiloxane composition and / or silane composition as described above, so as to improve and modify the pot life and curing time of the transition metal catalyst due to the stabilizing and inhibiting properties of the additional phosphite of formula (I).

[0433] In a preferred embodiment according to the present invention, the transition metal of the transition metal compound comprised by the curable polyorganosiloxane composition and / or silane composition according to the present invention is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably platinum.

[0434] In another embodiment according to the present invention, the curable polyorganosiloxane composition and / or the silane composition according to the present invention comprises:

[0435] (A) one or more polyorganosiloxanes and / or silanes having an average of at least two alkenyl groups,

[0436] (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups,

[0437] (C) one or more transition metal compounds, wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum,

[0438] (D) optionally one or more phosphites of formula (I) as defined above, and

[0439] (E) optionally one or more adjuvants.

[0440] Wherein, components (A) to (E) are as defined in the aforementioned embodiment.

[0441] Preferably, the one or more polyorganosiloxanes and / or silanes (A) having on average at least two alkenyl groups are selected from

[0442] -General average composition is MVi2D m dimethylvinylsilyl-terminated polydimethylsiloxane, wherein m is in the range of 50 to 1500, preferably 300 to 1300, more preferably 400 to 1100, even more preferably 450 to 1000;

[0443] -General average composition is MVi2Dn DVi o dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane) wherein 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 in the range of 10 to 120, preferably 15 to 90, more preferably 20 to 70, even more preferably 25 to 50;

[0444] One or more polyorganosiloxanes and / or silanes (B) having an average of at least two SiH groups are independently selected from: a A hydride-terminated poly(dimethylsiloxane) wherein a is in the range of 5 to 100, preferably 8 to 80, more preferably in the range of 10 to 50, even more preferably in the range of 12 to 40, most preferably in the range of 13 to 25;

[0445] -General average composition is M2D b DH c trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane) wherein 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;

[0446] -General average composition is MH dx Q x A resin type wherein 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;

[0447] -General average composition is M2DH e trimethylsilyl-terminated polymethylhydrogensiloxane, wherein e is in the range of 5 to 100, preferably 10 to 80, more preferably 15 to 60, even more preferably 20 to 40; or

[0448] -General average composition is M2D (Ph2) f DH g D htrimethylsilyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane-co-methylhydrogensiloxane) wherein f is in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 25, even more preferably 1 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;

[0449] The one or more transition metal compounds (C) comprising the phosphite of formula (I) are preferably selected from {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite}platinum, {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)methylphosphite}platinum, {η 4 -(H2C=CHSiMe2)2O}{bis(2,4-di-tert-butyl-6-methyl-phenyl)ethylphosphite}platinum, and {η 4 -(H2C=CHSiMe2)2O}{bis(2,4,6-tri-tert-butylphenyl)ethylphosphite}platinum;

[0450] The optional 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 bis(2,4,6-tri-tert-butylphenyl)ethyl phosphite;

[0451] The optional auxiliary agent (E) is preferably selected from

[0452] - conventional inhibitors known for use in hydrosilylation curable compositions, such as organic phosphites and acetylenic alcohols,

[0453] - Adhesion promoters, especially alkoxysilanes

[0454] - filler, preferably silica filler, more preferably surface-modified silica filler, for example, HMDZ hydrophobized silica with a BET surface area of ​​155 m 2 / g of Evonik Aerosil R8200 silica.

[0455] Therein, the curable composition may contain additional components (D) or (E) in addition to those mentioned above.

[0456] Further preferably, the composition comprises one or more phosphites (D) of formula (I) or one or more adjuvants (E), more preferably, the composition comprises both one or more phosphites (D) of formula (I) and one or more adjuvants (E).

[0457] In a more specific embodiment according to the present invention, the curable polyorganosiloxane composition and / or the silane composition according to any one of the preceding embodiments comprises:

[0458] 100pw of component (A),

[0459] 0.1-200 pw, preferably 0.5 to 150 pw, more preferably 1 to 100 pw, even more preferably 1.5 to 75 pw, even further preferably 1.5 to 50 pw of component (B)

[0460] 0.1-1000 ppm, preferably 0.2 to 750 ppm, more preferably 0.5 to 500 ppm, even more preferably 2 to 250 ppm, even further preferably 4 to 100 ppm of the transition metal contained in component (C), relative to (A) and (B),

[0461] 0.0 to 12000 ppm, preferably 0.2 to 12000 ppm, of component (D) relative to (A) and (B),

[0462] 0 to 200 pw, preferably 1 to 150 pw, more preferably 5 to 100 pw, even more preferably 10 to 75 pw, even further preferably 20 to 50 pw, and still further preferably 20 to 45 pw of component (E).

[0463] As indicated, the unit "ppm" refers to the total weight of components (A) and (B) in the curable composition.

[0464] The unit "pw" indicates "parts by weight", and is used in such a way that the weight of component (A) present in the composition represents 100 parts by weight.

[0465] The amounts of components (B) and (E) are therefore indicated relative to the amount of component (A).

[0466] According to this embodiment, it is preferred that the composition comprises 0.2 to 12000 ppm of a phosphite (D) of formula (I). The presence of this component (D) is due to the addition of a preformed and optionally purified transition metal compound (C), since the phosphite of formula (I) is usually in excess relative to a transition metal-containing precursor compound for the synthesis of the catalyst, which may contain a residual amount of the phosphite of formula (I); or due to the in-situ formation of compound (C) in the curable composition, wherein in order to achieve complete conversion of the transition metal-containing precursor compound, a phosphite of formula (I) is usually also used in an excess of 1.1 to 12 times.

[0467] Furthermore, in order to exhibit an inhibitory effect, one or more phosphites of the formula (I) may be additionally added to the composition.

[0468] In another embodiment according to the present invention, in the curable polyorganosiloxane composition and / or silane composition according to any of the previous and following embodiments, the molar ratio of platinum to one or more phosphites of formula (I) is from 1:1 to 1:10 to avoid free platinum moieties.

[0469] In the ratio of phosphite of formula (I) to platinum moieties, both the phosphite of formula (I) comprised by the transition metal compound (C) and also further additional phosphite of formula (I) which is not in a complexed state are taken into account.

[0470] Preferably, the molar ratio of platinum to the 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.

[0471] In another embodiment of the present invention, in the curable polyorganosiloxane composition and / or silane composition as described above, the phosphite of formula (I) contained in the transition metal compound is selected from

[0472]

[0473] as well as

[0474]

[0475] in

[0476] is preferred.

[0477] In another embodiment according to the present invention, in the curable polyorganosiloxane composition and / or the silane composition,

[0478] The transition metal compound comprising the phosphite of formula (I) comprises

[0479]

[0480] And the complex is a platinum complex.

[0481] Another aspect of the present invention relates to the use of one or more phosphites of formula (I) as defined in any of the preceding embodiments for the manufacture of a curable polyorganosiloxane and / or silane composition.

[0482] One or more phosphites of formula (I) can be added directly to the polyorganosiloxane and / or silane composition before or after the addition of the transition metal precatalyst, or it can be used to form a transition metal compound which is then used to make a curable polyorganosiloxane and / or silane composition.

[0483] Preferably, the transition metal compound comprising the phosphite of formula (I) is preformed and then added to the mixture of components to form the curable composition.

[0484] Yet another aspect of the present invention relates to the use of one or more phosphites of formula (I) as defined in any of the preceding embodiments as inhibitors of the hydrosilylation reaction in the curing of polyorganosiloxane compositions and / or silane compositions.

[0485] By adding one or more phosphites of formula (I) to the curable composition comprising the transition metal compound serving as a curing catalyst, at least a portion of the curing catalyst is converted into the transition metal compound of the phosphite comprising the formula (I) as a part, which in most cases results in a reduction in reaction rate at least at low reaction temperatures, because the feature of the transition metal compound is that very low catalytic activity is shown in the hydrosilylation reaction at low temperatures. Therefore, for the composition comprising such a catalyst, an extended pot life is provided, high reaction rate is shown at an elevated temperature, thereby resulting in rapid curing when thermally activated. The reduction of catalytic activity at low temperatures causing the curable composition to extend the pot life is considered to be the inhibitory effect of the phosphite according to the formula (I) of the present invention.

[0486] Another aspect of the present invention relates to a one-component curable polyorganosiloxane and / or silane composition comprising one or more phosphites of formula (I) as defined in any of the preceding embodiments.

[0487] Under the expression "one-component" hydrosilylation-curing polyorganosiloxane and / or silane composition, according to the present invention, this means that the curable composition as described in the embodiments according to the present invention (in particular, the composition comprising components (A) to (C) and optionally (D) and / or (E)) comprises all ingredients to be cured under appropriate conditions, in particular at elevated temperature levels above 25°C, preferably above 40°C, more preferably above 70°C, even more preferably above 80°C, and most preferably above 90°C.

[0488] To prepare a one-component curable polyorganosiloxane and / or silane composition, the components of such a composition, preferably components (A) to (E) as defined above, are first mixed into a non-reactive composition, that is, a composition that does not simultaneously contain 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 transition metal compound capable of catalyzing a hydrosilylation reaction.

[0489] The curable compositions according to the invention have a very high stability, ie a very long storage time.

[0490] In yet another aspect of the present invention, it relates to a two-component curable polyorganosiloxane and / or silane composition, which comprises one or more phosphites of formula (I) as described in the embodiments of the present invention.

[0491] This two-component curable composition is prepared and supplied based on two compositions, wherein each part composition does not contain all components (A) to (C) as defined above. These part compositions can actually be stored for more than 100 days. Manufacturers usually prepare reactive compositions by mixing the part compositions. Reactive curable compositions still have a storage stability of more than 30 days.

[0492] The present invention therefore also relates to partial compositions comprising components (A) + (C) + optionally (D) + optionally (E).

[0493] In order to obtain a curable polyorganosiloxane composition and / or silane composition as defined above, such a partial composition requires the addition of one or more polyorganosiloxanes and / or silanes (B) having on average at least two SiH groups.

[0494] The present invention also relates to a partial composition comprising components (A) + (B) + optionally (D) + optionally (E), which requires the addition of component (C) to obtain a curable composition as defined above, and to a partial composition comprising components (B) + (C) + optionally (D) + optionally (E), which requires the addition of component (A) to obtain a curable composition as defined above.

[0495] In particular, the present invention comprises a set of two-part compositions as described above, which upon mixing of the part compositions 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 described above.

[0496] The two-component curable compositions can be cured in a temperature range of 20°C to 250°C, preferably 80°C to 130°C, more preferably 80°C to 120°C, and they have a pot life of at least 48 hours.

[0497] It is also within the scope of the present invention to prepare and supply a curable composition based on three compositions.

[0498] In the selection of components (A), (B), (C), and optionally (D) and / or (E), the same compounds as described for the embodiments of the curable compositions presented above are preferred; likewise, when the components are first combined in a partial composition, the same amounts (by weight) and weight ratios as discussed above are preferably used.

[0499] 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 as defined above according to any one of the embodiments of the present invention.

[0500] Preferably, the crosslinking of the composition according to the invention is carried out at a pressure of 30 to 25,000 hPa, in particular at an ambient pressure of 900 to 1,100 hPa, or at pressures customary in injection molding machines of 100,000 to 250,000 hPa, in order to obtain a cured composition.

[0501] Preferably, the curing temperature of the curable composition used in the present invention is above 25°C, more preferably above 50°C, even more preferably above 70°C, still further preferably above 80°C, and most preferably above 90°C.

[0502] The cured polyorganosiloxane and / or silane compositions can be used for all purposes for which cured polyorganosiloxane and / or silane compositions have been used to date in the art, such as coating and impregnation of substrates of any kind, production of molded parts (e.g. by injection molding, vacuum extrusion, extrusion, molding, compression molding, for stamping), and as sealants, potting compounds or casting compounds.

[0503] Additionally, the present invention relates to the use of a curable polyorganosiloxane composition and / or a silane composition as defined in any of the preceding embodiments for the manufacture of shaped molded articles, extruded articles, coatings and sealants.

[0504] Depending on the viscosity of the components of the curable polyorganosiloxane composition and / or silane composition according to the invention and the filler content, the curable composition can be low viscosity and pourable, have a pasty consistency, be a powder, or a smooth high viscosity substance. Likewise, the elastic properties of the curable composition according to the invention encompass the full range starting with extremely soft silicone gels, covering colloid materials, and spanning up to highly cross-linked silicones with glass-like properties. Therefore, the curable composition according to the invention can be advantageously used in a variety of applications.

[0505] In particular, in the production of extruded shaped articles, there is an increasing demand for curing such rubber articles via a hydrosilylation reaction, in place of peroxides. In order to obtain bubble-free cured elastomeric articles, the curing rates required for this technology are quite high, i.e., the curing times are short and, in general, below 3 minutes at 110° C. These requirements can be met with the hydrosilylation-curing polyorganosiloxane and / or silane composition according to the invention. At the same time, the hydrosilylation-curing polyorganosiloxane and / or silane composition according to the invention has a storage stability of preferably more than 2 days at 25° C.

[0506] The term storage stability as used in accordance with the present invention means the stability of the reactive composition after preparation at t 10 The curing time of the hydrosilylation-curing polyorganosiloxane and / or silane composition is the time t at 110° C. after the reactive composition is prepared. 90 , i.e. the time to reach 90% of the elastic modulus of a fully cured material at 110° C. The elastic modulus is measured using a Rheometer MDR 2000 from Alpha Technologies.

[0507] Another important application of the hydrosilylation-curing polyorganosiloxane and / or silane compositions according to the invention are siloxane coatings, for example, mold release coatings for plastics, which have to cure below 110° C. within reasonably short curing times given by the belt speed of the coater (usually between 50 and 1000 m / min), whereby the coating thickness is usually between 0.05 and 1 mm.

[0508] Another aspect of the present invention relates to a method for making a curable polyorganosiloxane composition as defined in any one of the preceding embodiments, the method comprising mixing in a mixing device:

[0509] (A) one or more polyorganosiloxanes and / or silanes having an average of at least two alkenyl groups,

[0510] (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups,

[0511] (C) one or more transition metal compounds, wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum,

[0512] (D) optionally one or more phosphites of formula (I), and

[0513] (E) optionally one or more adjuvants.

[0514] According to the present invention, the manufacture of the curable composition is achieved by mixing the components in any order using any method or mixing process known in the art.

[0515] Preferably, mixing is performed 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 at an atmospheric pressure of 900 to 1100 hPa.

[0516] The method according to the invention can be performed continuously or discontinuously, ie batchwise.

[0517] 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 (D) and (E).

[0518] The transition metal compound (C) can be added in bulk or as a solution in a suitable solvent, or as a so-called batch, which means in a homogeneous mixture with small amounts of (A) or (A) and (E).

[0519] The curable composition according to the invention may be a one-component composition or a two-component composition. In the latter case, the two parts may contain all components in any ratio, preferably the part containing the transition metal compound (C) does not contain any Si-H containing component, such as component (B).

[0520] In the preparation of a one-component composition, components (A) to (E) are first mixed to form a non-reactive composition, that is to say a composition which does not simultaneously contain (A), (B) and (C).

[0521] In practice, it is preferred to prepare and supply a two or three part composition, wherein each part composition does not contain all components (A) to (E). These part compositions can actually be stored for more than 100 days. Manufacturers usually prepare the reactive composition by mixing the part compositions. The reactive composition still has a storage stability of more than 2 days.

[0522] Those preferred one-part compositions are most preferably two-part compositions comprising:

[0523] - (A) + (B) + optionally (D) + optionally (E), for example a filler;

[0524] - (A) + (C) + optionally (E), for example a filler.

[0525] This combination of partial compositions is preferred because a 1:1 mixture per volume is achievable, which is easy to mix by a static mixer. Another advantage of this combination of partial compositions is that the simultaneous presence of (B) and (C) is avoided, which is detrimental due to possible discoloration. On the other hand, the combination of (A) and (C) has a stabilizing effect on the transition metal catalyst component (C).

[0526] The partial composition as defined above is preferably prepared, for example, in a mixing apparatus selected from a kneader, a dissolver, an extruder, a LIST mixing apparatus, a BUSS co-kneader, a Banbury mixer or a Voith "press mixer", or a two-roll mixer.

[0527] Reactive "one-component" compositions are preferably prepared by mixing the partial compositions in the following manner: they are mixed, for example, in a mixing device selected from static mixers, kneaders (such as twin-blade kneaders), dissolvers, extruders, LIST mixing equipment, BUSS co-kneaders, Banbury mixers or Voith "press mixers", two-roll mixers, or multiroll coating mixtures.

[0528] The present invention therefore also relates to partial compositions comprising components (A) + (B) + optionally (D) + optionally (E).

[0529] Preferred compositions:

[0530] The compositions of the invention, which are preferably applied as "two-component" compositions, can preferably be used as so-called paper release coatings, as gels of liquid rubber or as high-consistency rubber compositions with optionally incorporated reinforcing fillers, for example having the following composition:

[0531] (A) 100 pw. of one or more polyorganosiloxanes and / or silanes having an average of at least two alkenyl groups and a viscosity of 50 mPa.s to 100 kPa.s at 25° C.,

[0532] (B) 0.1 to 100 of one or more polyorganosiloxanes and / or silanes having an average of at least two SiH groups, in an amount to achieve a molar ratio of SiH:Si-alkenyl groups of 0.8 to 6:1,

[0533] (C) 1 to 500 ppm, calculated as metal, relative to (A) and (B) of one or more transition metal compounds comprising a phosphite of formula (I), wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum,

[0534] (D) optionally one or more phosphites according to formula (I), preferably in an amount to achieve a molar ratio of phosphites of formula (I) not in a complex state with the transition metal and the transition metal compound to metal atoms of component (C) of 1:1 to 10:1, and

[0535] (E) 0-200 pwt. of one or more BET surface areas greater than 50 m 2 / g of reinforcing silica, and optionally further auxiliary additives.

[0536] Overview of the Preferred Embodiments

[0537] In the following, preferred embodiments of the present invention are summarized:

[0538] 1. A transition metal compound comprising at least one phosphite compound of the following formula:

[0539] P(OR)3 (I),

[0540] in

[0541] R represents an organic group, and at least one group R is represented by formula (II):

[0542]

[0543] in

[0544] The ring represented by A represents an aromatic or heteroaromatic group which may have one or more radicals other than R 1 and R 2 Other substituents besides

[0545] The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I),

[0546] R 1 and R 2 Each represents a substituent in the aromatic or heteroaromatic group at an ortho position relative to the oxygen atom of the phosphite compound of the formula (I), and

[0547] wherein the substituent R 1 and R 2 each independently selected from optionally substituted aliphatic groups, in particular optionally substituted alkyl groups and optionally substituted alkenyl groups, and optionally substituted aliphatic bridging groups, alkoxy groups, alkoxycarbonyl groups and Si-organic groups which form a condensed ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A,

[0548] And at least two radicals R are different from each other.

[0549] 2. The transition metal compound according to any one of the preceding embodiments, wherein the transition metal compound is different from:

[0550] -Inclusive Pt complex of phosphine;

[0551] - Rh complex of the formula:

[0552]

[0553] as well as

[0554]

[0555] The ligand P represents the structure

[0556]

[0557] - Rh, Pd and Pt complexes comprising phosphites of the formula:

[0558]

[0559] Where R 7 is a methyl group and X is a ferrocenyl group,

[0560] or R 7 is a methyl group and X is a cyclopentadienyl manganese tricarbonyl group,

[0561] or R 7 is an isopropyl group and X is a ferrocenyl group;

[0562] -Ni complex of the following formula:

[0563]

[0564] And preferably the transition metal compound is different from:

[0565] A Pt complex comprising a phosphite of the formula:

[0566]

[0567] Where R 8 is a monovalent organic group having 1 to 5 carbon atoms;

[0568] And / or the transition metal compound is preferably different from:

[0569] -Contains structural formula Transition metal complexes with ligands;

[0570] And / or the transition metal compound is preferably different from:

[0571] - A transition metal complex comprising a ligand of the following formula:

[0572]

[0573] Where R 7 is a methyl group and X is a ferrocenyl group,

[0574] or R 7 is methyl and X is cyclopentadienyl manganese tricarbonyl group (cymantrenyl),

[0575] or R 7 is an isopropyl group and X is a ferrocenyl group;

[0576] And / or the transition metal compound is preferably different from:

[0577] - A transition metal complex comprising a ligand of the following formula:

[0578]

[0579] 3. The transition metal compound according to embodiment 1 or 2, comprising at least one phosphite having formula (III):

[0580]

[0581] wherein at least two groups of formula (II) are different groups:

[0582]

[0583] 4. The transition metal compound according to any one of the preceding embodiments, wherein in formula (I), at least one group R is an organic group different from the group of formula (II).

[0584] 5. The transition metal compound according to embodiment 1 or 3, comprising at least one phosphite selected from formula (IV) or (V):

[0585]

[0586] Wherein in formula (IV), the group of formula (II):

[0587]

[0588] are identical or different groups, and are preferably identical groups, and are in both formula (IV) or (V) as defined above, and

[0589] Wherein in formula (V), the group R 6 are identical or different groups, and preferably the group R 6 are the same group, and the group R 6 In both formula (IV) or (V) is selected from organic groups different from those of formula (II), and preferably selected from optionally substituted aliphatic groups, such as optionally substituted alkyl or optionally substituted cycloalkyl groups.

[0590] 6. The transition metal compound according to any one of the preceding embodiments, wherein the ring represented by "A" in at least one group represented by formula (II) is an aromatic group, which optionally may have one or more radicals other than R 1 and R 2 Other substituents other than .

[0591] 7. The transition metal compound according to any one of the preceding embodiments, wherein the ring represented by "A" in at least one group represented by formula (II) is a phenyl group, which optionally may have one or more radicals other than R 1 and R 2 Other substituents other than .

[0592] 8. A transition metal compound according to any one of the preceding embodiments, wherein the group R 1 and R 2Each is an optionally substituted linear, branched or cyclic alkyl group preferably having up to 10 carbon atoms, more preferably up to 6 carbon atoms.

[0593] 9. The transition metal compound according to any one of the preceding embodiments, wherein the phosphite of formula (I) is selected from compounds of formula (VI):

[0594]

[0595] or a compound selected from formula (VII),

[0596]

[0597] Wherein in formula (VI) and (VII), R 1 , R 2 and R 6 Each is as defined above, and R 3 , R 4 and R 5 Each is independently selected from hydrogen, halogen, cyano, nitro, Si-organic groups and organic groups, preferably optionally substituted aliphatic groups, and wherein in formula (VI), at least two of the following substituent groups are different from each other:

[0598]

[0599] wherein the dotted line represents a single bond of the oxygen atom of the phosphite compound of formula (I), and wherein in formula (VII), the two following substituent groups are preferably the same:

[0600]

[0601] The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I).

[0602] 10. The transition metal compound according to any one of the preceding claims, wherein the phosphite of formula (I) is a monodentate ligand.

[0603] 11. The transition metal compound according to any one of the preceding embodiments, wherein in the phosphite of formula (I), the group R does not contain any metal atoms.

[0604] 12. The transition metal compound according to any one of the preceding embodiments, wherein the group R does not contain any nitrogen atoms.

[0605] 13. A transition metal compound according to any one of the preceding embodiments, wherein the group R does not contain any N or P atom-containing group,

[0606] preferably does not contain any groups containing N, P, S or Se atoms,

[0607] And most preferably does not contain any groups containing N, P, S, Se or O atoms.

[0608] 14. A transition metal compound according to any one of the preceding embodiments, wherein the group R of the phosphite of formula (I) may contain only C, H, O atoms and halogen atoms, wherein the O atoms may only be present in ether bonds or ester groups,

[0609] Preferably, the radical R may contain only C, H and halogen atoms,

[0610] And most preferably, the group R in the phosphite of formula (I) consists of C and H atoms.

[0611] 15. A transition metal compound according to any one of the preceding embodiments, wherein the phosphite of formula (I) is selected from

[0612]

[0613]

[0614] 16. The transition metal compound according to any one of the preceding embodiments, wherein the phosphite compound of formula (I) of the transition metal compound is selected from

[0615]

[0616] as well as

[0617]

[0618] in

[0619]

[0620] is preferred.

[0621] 17. The transition metal compound according to any one of the preceding embodiments, wherein the transition metal of the transition metal compound is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.

[0622] 18. A transition metal compound according to any one of the preceding embodiments, wherein the transition metal is platinum, and preferably the phosphite compound of formula (I) of the transition metal compound is

[0623]

[0624] 19. The transition metal compound according to any one of the preceding embodiments, wherein the transition metal compound is a transition metal complex compound, wherein the transition metal has a zero (0) oxidation state, preferably the transition metal complex compound is a Pt(0)-compound.

[0625] 20. The transition metal compound according to any one of the preceding embodiments, comprising one or more alkenyl ligands.

[0626] 21. The transition metal compound according to any one of the preceding embodiments, comprising one or more alkenyl siloxane ligands.

[0627] 22. A transition metal compound according to any one of the preceding embodiments of the formula:

[0628]

[0629] wherein P(OR)3 is a phosphite of formula (I) as defined above.

[0630] 23. Use of a transition metal compound comprising a phosphite of formula (I) as defined in any one of the preceding embodiments as a curing catalyst for a curable polyorganosiloxane composition and / or a silane composition.

[0631] 24. A curable polyorganosiloxane composition and / or silane composition comprising one or more transition metal compounds comprising a phosphite of formula (I) as defined above.

[0632] 25. The curable polyorganosiloxane composition and / or silane composition according to embodiment 24, further comprising one or more phosphites of formula (I) as defined above.

[0633] 26. The curable polyorganosiloxane composition and / or silane composition according to the preceding embodiments 24 and 25, wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably platinum.

[0634] 27. The curable polyorganosiloxane composition and / or silane composition according to embodiments 24 to 26, comprising:

[0635] (A) one or more polyorganosiloxanes and / or silanes having an average of at least two alkenyl groups,

[0636] (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups,

[0637] (C) one or more transition metal compounds comprising the phosphite of formula (I), wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum,

[0638] (D) optionally one or more phosphites of formula (I) as defined above, and

[0639] (E) optionally one or more adjuvants.

[0640] 28. The curable polyorganosiloxane composition and / or silane composition according to any one of the preceding embodiments 24 to 27, comprising:

[0641] 100pw of component (A),

[0642] 0.1-200pw component (B)

[0643] 0.1 to 1000 ppm of the transition metal contained in component (C) relative to (A) and (B),

[0644] 0.0 to 12000 ppm of component (D) relative to (A) and (B),

[0645] 0 to 200 pw of component (E).

[0646] 29. The curable polyorganosiloxane composition and / or silane composition according to any one of the preceding embodiments 24 to 28, wherein the molar ratio of platinum to the one or more phosphites of formula (I) is from 1:1 to 1:10.

[0647] 30. The curable polyorganosiloxane composition and / or silane composition according to embodiments 24 to 29 above,

[0648] The transition metal compound comprising the phosphite of formula (I) comprises

[0649]

[0650] in

[0651] is preferred.

[0652] 31. The curable polyorganosiloxane composition and / or silane composition according to embodiments 24 to 30 above,

[0653] The transition metal compound comprising the phosphite of formula (I) comprises

[0654]

[0655] And the complex is a platinum complex.

[0656] 32. Use of one or more phosphites of formula (I) as defined in any one of the preceding embodiments for the manufacture of a curable polyorganosiloxane and / or silane composition.

[0657] 33. Use of one or more phosphites of formula (I) as defined in any one of the preceding embodiments as inhibitors of the hydrosilylation reaction in the curing of polyorganosiloxane compositions and / or silane compositions.

[0658] 34. A one-component curable polyorganosiloxane and / or silane composition comprising one or more phosphites of formula (I) as defined in any one of the preceding embodiments.

[0659] 35. A two-component curable polyorganosiloxane and / or silane composition comprising one or more phosphites of formula (I) as defined in any one of the preceding embodiments.

[0660] 36. A cured polyorganosiloxane and / or silane composition obtained by curing a curable polyorganosiloxane and / or silane composition as defined in any one of the preceding embodiments.

[0661] 37. Use of a curable polyorganosiloxane composition and / or a silane composition as defined in any one of the preceding embodiments for the manufacture of shaped molded articles, extruded articles, coatings and sealants.

[0662] 38. A method for making a curable polyorganosiloxane composition as defined in any one of the preceding embodiments, comprising mixing in a mixing device:

[0663] (A) one or more polyorganosiloxanes and / or silanes having an average of at least two alkenyl groups,

[0664] (B) one or more polyorganosiloxanes and / or silanes having on average at least two SiH groups,

[0665] (C) one or more transition metal compounds, wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum,

[0666] (D) optionally one or more phosphites of formula (I), and

[0667] (E) optionally one or more adjuvants.

[0668] Example

[0669] A) Manufacturing of phosphites

[0670] 1. General Procedure

[0671] The phosphites of formula (I) are synthesized according to the following general reaction scheme:

[0672] 2R'O - M + +ROPCl2→ROP(OR')2+2MCI

[0673] in

[0674] R'=R (as defined in the embodiments), and the groups R' and R are different from each other, and

[0675] M is Li or Na,

[0676] ROPCl2 is composed of PCl3 and the corresponding metal oxide RO - M + The reaction obtains metal alkoxide R'O - M + and RO - M + Obtained by reacting the corresponding phenol with sodium hydride or n-butyl lithium, and reacted in anhydrous tetrahydrofuran (see also A. Earnshaw, N. Greenwood (1997): The Chemistry of the Elements - 2nd edition).

[0677] At 6 ℃, under dry argon atmosphere and vigorous stirring, an anhydrous THF (tetrahydrofuran) solution of alcohol R'OH is added dropwise to a suspension of NaH dissolved in THF or n-butyl lithium dissolved in hexane. After stirring at room temperature for a specified time, phosphorus dichloride ROPCl2 in THF is added dropwise. After addition, the mixture is stirred for another two hours at 40 ℃. Hexane is then added and the precipitated solid is removed by filtration. The filtrate is removed from the solvent, and hexane is added to the remaining crude product. The resulting solution is quickly filtered through an alumina column to obtain purified phosphite ROP (OR') 2.

[0678] 2. The prepared specific phosphite

[0679] 2.1. Bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite (the present invention)

[0680]

[0681] At 0°C, a solution of 10.37 g (63 mmol) of 2-tert-butyl-6-methylphenol and 50 ml of anhydrous THF was added dropwise to a suspension of 2.35 g of NaH (59 mmol) in 25 ml of THF and stirred under nitrogen for 60 minutes. Then, at 0°C and under a nitrogen atmosphere, a mixture containing 4.23 g (29 mmol) of ethyl dichlorophosphite (or dichloro(ethoxy)phosphine) was added over 10 minutes. of THF, after the addition was complete, the temperature was raised to 40 °C and it was stirred for an additional 2 h.

[0682] The reaction mixture was then allowed to cool to room temperature, 15 ml of hexane was added, and the residue was filtered off. The solvent was evaporated from the filtrate, and the residue was dissolved in 10 ml of n-hexane. The solution was then filtered through an alumina rapid column to purify the phosphite. The solvent was evaporated to give 20.26 g (80%) of a light yellow oil.

[0683] NMR data:

[0684] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)

[0685]

[0686]

[0687] 2.2. Bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite

[0688]

[0689] Bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite was prepared as in Example 2.1 using methyl dichlorophosphite (or dichloro(methoxy)phosphine) instead of ethyl dichlorophosphite (or dichloro(ethoxy)phosphine).

[0690] NMR data:

[0691] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)

[0692] <![CDATA[ 31 P]]> <![CDATA[ 1 H]]> ppm model ppm model 142.6 s 1.57 s 2.48 d 3.65 d 7.03 t 7.12 dd 7.33 dd

[0693] 2.3. Bis(2,4-di-tert-butyl-6-methyl-phenyl)ethyl phosphite (Comparison)

[0694]

[0695] Commercially available as Irgafos 38 from BASF.

[0696] NMR data:

[0697] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)

[0698] <![CDATA[ 31 P]]> <![CDATA[ 1 H]]> ppm model ppm model 143.8 s 0.93 t 1.29 s 1.47 s 2.38 d 3.88 dq 7.02 d 7.24 d

[0699] 2.4. Ethyl bis(2,4,6-tri-tert-butylphenyl)phosphite (the present invention)

[0700]

[0701] Ethyl bis(2,4,6-tri-tert-butylphenyl)phosphite was prepared as described above under 2.1 starting from ethyl dichlorophosphite (or dichloro(ethoxy)phosphine) and 2,4,6-tri-tert-butylphenol.

[0702] NMR data:

[0703] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)

[0704]

[0705] 2.5 Tris(2,4-di-tert-butylphenyl)phosphite (Comparison)

[0706] Tris(2,4-di-tert-butylphenyl)phosphite:

[0707]

[0708] Commercially available as Irgafos 168

[0709] 2.6 Bis(2,4-di-tert-butyl-5-methyl-phenyl)ethyl phosphite (Compare)

[0710] Bis(2,4-di-tert-butyl-5-methyl-phenyl)ethyl phosphite:

[0711]

[0712] Prepared in a similar manner to that described above for Phosphite Example 2.1. from ethyl dichlorophosphite (or dichloro(ethoxy)phosphine) and 2,4-di-tert-butyl-5-methyl-phenol.

[0713] 2.7 Bis(2-allylphenyl)ethyl phosphite(Comparison)

[0714] Bis(2-allylphenyl)ethyl phosphite:

[0715]

[0716] Prepared from ethyl dichlorophosphite (or dichloro(ethoxy)phosphane) and 2-allylphenol in a manner analogous to that described above for Phosphite Example 2.1.

[0717] 2.8 3,9-Bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecyl Alkane (Comparison)

[0718] 3,9-Bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane

[0719]

[0720] Commercially available as Irgafos 126.

[0721] B) Production of transition metal compounds

[0722] 1. General Procedure

[0723] The platinum phosphite catalyst complex was synthesized according to a standardized procedure. The Pt catalyst and phosphite, as well as a divinyl polymer having 10.000 mPas, were dissolved in toluene and reacted in a flask at 80° C. for 30 minutes under a N2 atmosphere. The toluene was then completely removed by distillation to obtain a catalyst complex in quantitative yield in terms of the amount of Pt.

[0724] 3. Catalyst Examples

[0725] 3.1. Catalyst Example 1 (Catalyst of the present invention)

[0726] {η 4 -(H2C=CHSiMe2)2O}{Bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite}platinum

[0727]

[0728] {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite}platinum was prepared according to the same method as Catalyst Example 3 (see 3.3., Catalyst Example 3.3 below) starting from Castel catalyst (Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and bis(2-tert-butyl-6-methyl-phenyl)ethyl phosphite (Phosphite Example 2.1.).

[0729] NMR data:

[0730] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)) NMR spectrum shows signals of free phosphite and complex:

[0731]

[0732] 3.2. Catalyst Example 2 (Catalyst of the present invention)

[0733] {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite}platinum

[0734]

[0735] {η 4 -(H2C=CHSiMe2)2O}{bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite}platinum was prepared according to the same method as Catalyst Example 3 (see 3.3., Catalyst Example 3.3 below) starting from Castel catalyst (Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and bis(2-tert-butyl-6-methyl-phenyl)methyl phosphite (Phosphite Example 2.2.).

[0736] NMR data:

[0737] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)) NMR spectrum shows signals of free phosphite and complex:

[0738]

[0739] 3.3. Catalyst Example 3 (Comparative Catalyst)

[0740] {η 4 -(H2C=CHSiMe2)2O}{Bis(2,4-di-tert-butyl-6-methyl-phenyl)ethylphosphite}platinum

[0741]

[0742] Under nitrogen, 10 g (0.76 mmol platinum) of Custer's catalyst (Pt2 (1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) was dissolved in 20 ml toluene. To this solution was added 0.40 g of the phosphite of phosphite Example 2.3. (bis (2,4-di-tert-butyl-6-methyl-phenyl) ethyl phosphite (Irgafos 38)) (96% purity, 0.95 mmol in 10 ml toluene) and stirred at 60° C. for 4 hours. The Custer's catalyst reacted quantitatively with the phosphite to form the corresponding Pt-phosphite complex.

[0743] NMR data:

[0744] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)) NMR spectrum shows signals of free phosphite and complex:

[0745]

[0746]

[0747] 3.4. Catalyst Example 4 (Catalyst of the present invention)

[0748] {η 4 -(H2C=CHSiMe2)2O}{bis(2,4,6-tri-tert-butylphenyl)ethyl phosphite}platinum

[0749]

[0750] {η 4 -(H2C=CHSiMe2)2O}{bis(2,4,6-tri-tert-butylphenyl)ethyl phosphite}platinum was prepared according to the same method as Catalyst Example 3 starting from Custer's catalyst (Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and bis(2,4,6-tri-tert-butylphenyl)ethyl phosphite (Phosphite Example 2.4.).

[0751] NMR data:

[0752] ( 1 H-NMR (400MHz, CDCl3, 300K); 31 P NMR (121.47 MHz, CDCl3, 300 K)) NMR spectrum shows signals of free phosphite and complex:

[0753]

[0754] (S means singlet, d means doublet, m means multiplet, and dq means double quartet; sat means satellite peak)

[0755] 3.5. Catalyst Example 5 (Comparative Catalyst)

[0756] Ashby catalyst, 15 wt% Pt

[0757] It is a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane and isopropanol with the general formula:

[0758]

[0759] 3.6. Catalyst Example 6 (Comparative Catalyst)

[0760] {η 4 -(H2C=CHSiMe2)2O}{tris(2,4-di-tert-butylphenyl)phosphite}platinum

[0761]

[0762] The preparation was carried out according to the same method as Catalyst Example 3 starting from Custer's catalyst (Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and tris(2,4-di-tert-butylphenyl)phosphite (Phosphite Example 2.5., Irgafos 168).

[0763] 3.7. Catalyst Example 7 (Comparative Catalyst)

[0764] {η 4 -(H2C=CHSiMe2)2O}{tris(2,4-di-tert-butyl-5-methyl-phenyl)phosphite}platinum

[0765]

[0766] The preparation was carried out according to the same method as Catalyst Example 3 starting from Custer's catalyst (Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and bis(2,4-di-tert-butyl-5-methyl-phenyl)ethyl phosphite (Phosphite Example 2.6.).

[0767] 3.8. Catalyst Example 8 (Comparative Catalyst)

[0768] {η 4 -(H2C=CHSiMe2)2O}{bis(2-allylphenyl)ethylphosphite}platinum

[0769]

[0770] Preparation was carried out according to the same method as Catalyst Example 3 starting from Custer's catalyst (Pt2(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and bis(2-allylphenyl)ethylphosphite (Phosphite Example 2.7.).

[0771] 3.9. Catalyst Example 9 (Comparative Catalyst)

[0772] {η 4 -(H2C=CHSiMe2)2O}{3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane}platinum

[0773] The preparation was carried out according to the same method as Catalyst Example 3 starting from Castel catalyst (Pt2 (1,1,3,3-tetramethyl-1,3-divinyldisiloxane) 3-20% - commercially available from JM) and 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (Phosphite Example 2.8.).

[0774] C) Preparation of curable polyorganosiloxane compositions

[0775] Examples 1-15 and Comparative Examples 1-5

[0776] Manufacturing of silicone-based compounds

[0777] For Examples 1-11 and Comparative Examples 1-5, a silicone base compound consisting of the following substances was used: 38 parts of an average composition of MVi2D 539 dimethylvinylsilyl-terminated polydimethylsiloxane having a viscosity of 10 Pa.s and a SiVi content of 0.05 mmol / g; the average composition of 32 parts is MVi2D 899 of dimethylvinylsilyl-terminated polydimethylsiloxane having a viscosity of 65 Pa.s and a SiVi content of 0.03 mmol / g, and 30 parts of fumed silica ( 300, obtained from Evonik), which has 300m 2 / g Brunauer-Emmett-Teller (BET) specific surface area and surface treated with hexamethyldisilazane and divinyltetramethyldisilazane with a Vi content of 1.3 wt%. The base compound was further mixed with other components as listed in Tables 1-4 to prepare various silicone rubber formulations. When all other ingredients have been mixed, the catalyst is added last.

[0778] The amount of catalyst indicated using the unit "ppm" refers to the weight of the amount of platinum present in the catalyst used relative to the weight of the overall composition.

[0779] The amount of inhibitor indicated using the unit "ppm" refers to the weight of the inhibitor compound (ie, ECH or the compound of phosphite Example 2.5) applied relative to the weight of the total composition.

[0780] The pot life of the liquid curable silicone elastomer composition of the present invention is defined as the time for the mixed viscosity of the composition to increase to 200% of its initial value as measured by a plate-plate rheometer at a shear rate of 10 / s and 25° C. This parameter represents the minimum processing time.

[0781] The cure time of the liquid curable silicone elastomer composition was measured using DIN 53529-3 with an Alpha Technologies Rheometer MDR 2000. The t90, t60 and t10 times were defined as the time to reach 90%, 60% or 10% of the maximum torque at 100°C.

[0782] As shown in Table 1, the composition of the present invention using the phosphite catalyst of the present invention has a pot life of at least 48 hours while maintaining a cure reactivity corresponding to t90 ≤ 2 minutes.

[0783] Further detailed explanation of the components used:

[0784] Vinylsiloxane 1: dimethylvinylsiloxy-terminated poly(dimethylsiloxane-co-methylvinylsiloxane), average composition MVi2D 560 DVi 36 , viscosity at RT (room temperature 25°C) and 10s -1 The shear rate is 5 Pas (according to DIN 53019).

[0785] Vinylsiloxane 2: dimethylvinylsilyl-terminated polydimethylsiloxane, average composition MVi2D 539 , and the viscosity is 10 Pas at RT.

[0786] Vinylsiloxane 3: dimethylvinylsilyl-terminated polydimethylsiloxane, average composition MVi2D 899 , and the viscosity is 65 Pas at RT.

[0787] Chain extender 1: hydride terminated poly(dimethylsiloxane), average composition MH2D 17 , the viscosity is 20 mPas at RT.

[0788] Crosslinker 1: trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane), average composition M2D 20 DH 20, the viscosity is 40 mPas at RT.

[0789] Irgafos 168 (see Phosphite Example 2.5).

[0790] Crosslinker 2: Resin type, average composition MH 1.7x Q x And the viscosity is 30 mPas at RT.

[0791] Crosslinker 3: trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane), average composition M2D 20 DH 10 , and the viscosity is 35 mPas at RT.

[0792] Crosslinker 4: trimethylsilyl-terminated polymethylhydrogensiloxane, average composition M2DH 30 And the viscosity is 15 mPas at RT.

[0793] Crosslinker 5: trimethylsilyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane-co-methylhydrogensiloxane), average composition M2D(Ph2)2DH 24 D2 and a viscosity of 35 mPas at RT.

[0794] Adhesion promoter 1: γ-methacryloxypropyltrimethoxysilane.

[0795] Adhesion Promoter 2: γ-Glycidoxypropyltrimethoxysilane.

[0796] Tackifier 3: 3-(trimethoxysilyl)propyl α,2,4,6,6,8-hexamethylcyclotetrasiloxane propionate (CAS 113684-56-3).

[0797] Filler 1: HMDZ hydrophobized with a BET surface area of ​​155 m 2 / g of Evonik Aerosil R8200 silica.

[0798]

[0799] Table 2 (Changes in SiH-crosslinking agent)

[0800]

[0801] As shown in Table 2 (Examples 5 to 8), even with different SiH-crosslinkers, the target pot life of at least 48 hours and the target reactivity t90 of ≤ 2 minutes were achieved.

[0802] Table 3 (Effect of Thickener)

[0803]

[0804] As shown in Table 3 (Examples 9 to 11), even with the addition of different tackifiers, the target pot life of at least 48 hours and the target reactivity t90 of ≤ 2 minutes were achieved.

[0805] Table 4 (Changes in filler content)

[0806] For Examples 12-15, various silicone rubber formulations were prepared by mixing all of the components listed in Table 4. The catalyst was added last when all other ingredients had been mixed.

[0807]

[0808] As shown in Table 4 (Examples 12 to 15), even with different filler contents, the target pot life of at least 48 hours and the target reactivity t90 of ≤ 2 minutes were achieved.

Claims

1. A transition metal compound comprising at least one phosphite compound of the following formula: P(OR)3(I), in R represents an organic group, and at least one group R is represented by formula (II): in The ring represented by A represents an aromatic or heteroaromatic group which may have one or more radicals other than R 1 and R 2 Other substituents besides The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I), R 1 and R 2 Each represents a substituent in an ortho position of the aromatic or heteroaromatic group relative to the oxygen atom of the phosphite compound of formula (I), and wherein the substituent R 1 and R 2 each independently selected from optionally substituted aliphatic groups, in particular optionally substituted alkyl groups and optionally substituted alkenyl groups, and optionally substituted aliphatic bridging groups, alkoxy groups, alkoxycarbonyl groups and Si-organic groups which form a condensed ring system with another atom of the aromatic or heteroaromatic group corresponding to the ring represented by A, and wherein at least two radicals R are different from each other, Provided that the transition metal compound is different from: -Inclusive Pt complex of phosphite; -Rh complex Wherein the ligand P represents the structure as well as - Rh, Pd and Pt complexes comprising phosphites of the general formula: Where R 7 is a methyl group and X is a ferrocenyl group, or R 7 is a methyl group and X is a cyclopentadienyl manganese tricarbonyl group, or R 7 is an isopropyl group and X is a ferrocenyl group.

2. The transition metal compound according to claim 1, comprising at least one phosphite of formula (III): wherein at least two groups of formula (II) are different groups:

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

4. The transition metal compound according to claim 1 or claim 3, comprising at least one phosphite selected from formula (IV) or (V): Wherein in formula (IV), the group of formula (II): are identical or different groups, and are preferably identical groups, and are in both formula (IV) or (V) as defined above, and Wherein in formula (V), the group R 6 are identical or different groups, and preferably the group R 6 are the same group, and the group R 6 In both formula (IV) or (V) is selected from organic groups different from those of formula (II), and preferably selected from optionally substituted aliphatic groups, such as optionally substituted alkyl or optionally substituted cycloalkyl groups.

5. A transition metal compound according to any one of the preceding claims, wherein the ring represented by "A" in at least one group represented by formula (II) is an aromatic group, which may optionally have one or more radicals other than R 1 and R 2 Other substituents besides Preferably, the ring represented by "A" in at least one group represented by formula (II) is a phenyl group, which optionally may have one or more radicals other than R 1 and R 2 Other substituents other than .

6. A transition metal compound according to any one of the preceding claims, wherein the group R 1 and R 2 Each is an optionally substituted linear, branched or cyclic alkyl group preferably having up to 10 carbon atoms, more preferably up to 6 carbon atoms.

7. The transition metal compound according to any one of the preceding claims, wherein the phosphite of formula (I) is selected from compounds of formula (VI): or a compound selected from formula (VII), Wherein in formula (VI) and (VII), R 1 , R 2 and R 6 Each is as defined above, and R 3 , R 4 and R 5 Each is independently selected from hydrogen, halogen, cyano, nitro, Si-organic groups and organic groups, preferably optionally substituted aliphatic groups, and wherein in formula (VI), at least two of the following substituent groups are different from each other: wherein the dotted line represents a single bond of the oxygen atom of the phosphite compound of formula (I), and wherein in formula (VII), the two following substituent groups are preferably the same: The dotted line represents the single bond of the oxygen atom of the phosphite compound of formula (I).

8. A transition metal compound according to any one of claims 1 and 3 to 7, wherein the phosphite of formula (I) is selected from as well as 9. The transition metal compound according to any one of the preceding claims, wherein the transition metal of the transition metal compound is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, Preferably the transition metal is platinum, or Wherein the transition metal compound is a transition metal complex compound, wherein the transition metal has a zero (0) oxidation state, preferably the transition metal complex compound is a Pt(0)-compound.

10. A transition metal compound according to any one of the preceding claims, comprising one or more alkenyl ligands, preferably one or more alkenyl siloxane ligands, more preferably a transition metal compound of the formula: wherein P(OR)3 is a phosphite of formula (I) as defined above.

11. A curable polyorganosiloxane composition and / or a silane composition comprising: (A) one or more polyorganosiloxanes and / or silanes having an average of 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 comprising the phosphite of formula (I), wherein the transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably platinum, (D) optionally one or more phosphites of formula (I) as defined above, and (E) optionally one or more adjuvants.

12. The curable polyorganosiloxane composition and / or silane composition according to claim 11, comprising: (A) one or more polyorganosiloxanes and / or silanes having an average of 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 comprising the phosphite of formula (I), wherein the transition metal is selected from 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 adjuvants, Wherein the composition comprises: 100pw of component (A), 0.1-200pw component (B) 0.1 to 1000 ppm of the transition metal contained in component (C) relative to (A) and (B), 0.0 to 12000 ppm of component (D) relative to (A) and (B), 0 to 200 pw of component (E), And preferably The molar ratio of platinum to the one or more phosphites of formula (I) is from 1:1 to 1:

10.

13. A two-component curable polyorganosiloxane and / or silane composition comprising one or more phosphites of formula (I) as defined in any one of the preceding claims.

14. Use of a curable polyorganosiloxane composition and / or a silane composition as defined in any one of the preceding claims for the manufacture of shaped molded articles, extruded articles, coatings and sealants.

15. A process for making a curable polyorganosiloxane composition as defined in any one of the preceding claims, comprising mixing in a mixing apparatus: (A) one or more polyorganosiloxanes and / or silanes having an average of 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 transition metal is selected from nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, (D) optionally one or more phosphites of formula (I), and (E) optionally one or more adjuvants.

16. A cured polyorganosiloxane and / or silane composition obtained by curing a curable polyorganosiloxane and / or silane composition as defined in any one of claims 11 to 13.

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