Emission-free silicone rubber compound

Abstract

The present invention relates to a composition obtainable by mixing (a) a crosslinking agent or a mixture of crosslinking agents obtainable by reacting (HX (CRc2) oY (CRc2) oX (CRc2) o) 4-pSiKp, and (b) a metal catalyst, and (c) an aminosilane.

Description

[0001] The present invention relates to a composition for preparing a silicone rubber compound, which comprises a crosslinking agent, a metal catalyst and an aminosilane, and to the use of said composition as a sealant, glue, coating agent, bonding material, encapsulating compound, adhesive and in coatings, and to a silicone rubber compound obtainable by curing said composition.

[0002] As an elastic material, silicone rubber compounds have various applications, for example as sealants, bonding materials, coating agents, casting compounds and adhesives for various materials such as glass, porcelain, ceramics, stone, plastics, metals, wood and the like. Cold-curing silicone rubber compounds that cure at room temperature are preferably used. They are also referred to as RTC (room temperature curing) silicone rubber compounds. These can be used, for example, as one-component RTC silicone rubber compounds (RTC-1) or two-component RTC silicone rubber compounds (RTC-2). RTC-1 silicone rubber compounds are generally a plastically deformable mixture of a polyorganosiloxane having crosslinkable functional groups and a suitable crosslinking agent (curing agent), which mixture is stored in the absence of moisture. These mixtures crosslink at room temperature under the influence of water such as atmospheric moisture. This process is referred to as the curing of the crosslinking agent. In the case of RTC-2 silicone rubber compounds, two separately stored mixtures are first mixed, and then the mixture cures at room temperature under the influence of water or moisture.

[0003] In cold-curing silicone rubber compounds, polyorganosiloxanes (silicones) having more than two crosslinkable functional groups are generally used together with multifunctional curing agents. α,ω-dihydroxypolyorganosiloxanes are very important here as bifunctional polyorganosiloxanes. The crosslinking agent or curing agent generally has hydrolysable SiX groups. During crosslinking, the X groups are released as leaving groups. Known leaving groups are, for example, alcohols and oximes.

[0004] EP 3 392 313 A1 and EP 3 613 803 A1 describe curable silicone rubber compounds, in which the composition comprises a curing agent (crosslinking agent) in the form of a silane having a corresponding leaving group (leaving group).

[0005] However, such compositions have the following disadvantages: the leaving groups (for example alcohols, hydroxycarboxylic esters or oximes) diffuse out of the silicone rubber compound after curing and are thus emitted into the environment. The emitted chemicals are sometimes harmful to health, generally harmful to the environment and often have an unpleasant odour. In addition, the emission results in a loss of mass and volume of the silicone rubber material or sealant. Generally, there is a mass loss of about 3 wt% to 4 wt%. This can cause the sealant to crack and no longer perform its sealing function optimally.

[0006] Accordingly, the object of the present invention is to overcome these disadvantages and to provide a composition which cures at room temperature without discharging or discharging as few chemical substances as possible without negatively affecting the desired properties of the room-temperature-curing silicone rubber compounds, in particular their storage stability, curability and good adhesion to all common substrates.

[0007] This object is solved by the composition according to claim 1, the composition according to claim 10, the use according to claim 14 and the silicone rubber compound according to claim 15. Advantageous embodiments can in particular be found in the dependent claims and are explained in more detail below.

[0008] In one embodiment, the present invention relates to a composition obtainable by mixing the following components:

[0009] (a) A crosslinking agent or crosslinking agent mixture obtainable by the reaction of (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p SiK p where

[0010] each X independently represents O, NR b , S or PR b ,

[0011] each R b independently represents H, trialkylsilyl or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0012] each Y independently represents a C-C bond, CR c 2, O, NR e or PR e , where

[0013] each R c independently represents H or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0014] each R e independently represents H or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0015] each K independently represents Cl, OR d or ON=CR g 2,

[0016] each R dindependently represents a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0017] each R g independently represents H or a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0018] each o is independently an integer from 1 to 8, and

[0019] p = 2 or 3,

[0020] (b) a metal catalyst, and

[0021] (c) an aminosilane.

[0022] Surprisingly, after curing, no or almost no chemicals are emitted from the composition. On the one hand, this has the advantage that the composition does not release any unpleasant odors during curing and no toxic substances are emitted. In addition, the emitted substances may negatively affect or damage the surrounding materials of the application, as is the case for acetic acid from acetate groups on concrete, steel or marble, for example. This also reduces volume shrinkage. Volume shrinkage is always accompanied by deformation of the composition, which in particular reduces the risk of leakage in the composition according to the invention after the silicone rubber compound has cured. Therefore, the reduced volume shrinkage is advantageous because it improves the technical properties of the composition. At the same time, the composition also has the same good properties as the most modern and best RTC silicone rubber compounds available today, such as in terms of storage stability, curability, etc.

[0023] Another embodiment of the present invention relates to a composition comprising the following components:

[0024] (a) at least one crosslinking agent of the formula (X(CR c 2) o Z(CR c 2) o Z(CR c 2) o )Si, wherein

[0025] each Z independently represents N, P, N(CR c 2) o X or P(CR c 2) o X

[0026] and X, R c and o are as defined above,

[0027] (b) at least one metal catalyst, and

[0028] (c) at least one aminosilane.

[0029] Another embodiment of the present invention relates to the use of the composition according to the present invention for the preparation of sealants, adhesives, coating agents, joining materials, encapsulating compounds, binders and / or paints.

[0030] Furthermore, an embodiment of the present invention relates to a silicone rubber compound which can be obtained by curing the composition according to the present invention, preferably in the presence of water such as moisture.

[0031] In the context of the present invention, the "crosslinking agent" or "curing agent" is understood to particularly mean a crosslinkable silane compound having cleavable groups (so-called leaving groups or departing groups), wherein the leaving groups can be covalently bonded to each other. In particular, the leaving groups can also be covalently bonded to the residues remaining bonded to the silicon atom of the crosslinking agent, such that the leaving groups continue to be covalently bonded to silicon after leaving. The term "crosslinking agent" also particularly includes a "crosslinking agent system" which can contain more than one crosslinkable silane compound.

[0032] In the context of the present invention, a "covalent bond" (also known as an atomic bond or electron pair bond) is generally understood to be a bond between non-metal atoms, wherein an electron pair is formed between the atoms and thereby holds the atoms together. A covalent bond can be a single bond (e.g., C-C), a double bond (C=C) or even a triple bond (C≡C). If residues or groups are "covalently bonded to each other", this means that the residues or groups are "covalently linked" or "covalently bonded to each other".

[0033] "Sealing reagent", "sealant material", "sealant" or "sealing compound" are used synonymously in the present invention and refer to an elastic substance used in liquid to viscous form or as a flexible profile or sheet for sealing surfaces (especially for sealing against water, gas or other media). The cured composition according to the present invention can preferably be a sealing reagent, a sealant or a sealing compound.

[0034] The term "adhesive" refers to a substance that joins components by surface adhesion (adhesive force) and / or internal strength (cohesion). This term particularly includes adhesive gums, pastes, dispersion adhesives, solvent adhesives, reaction adhesives and contact adhesives.

[0035] "Coating agent" refers to any reagent for coating a surface.

[0036] In the context of the present invention, an "encapsulating compound" or "cable encapsulating compound" is a compound that can be heat- or cold-treated for encapsulating cables and / or cable accessories.

[0037] The term "alkyl" refers to a saturated hydrocarbon residue. In particular, alkyl has the formula -C n H 2n+1The term "having 1 to 16 carbon atoms" specifically refers to a hydrocarbon having 1 to 16 carbon atoms. Examples of alkyl groups are methyl-, ethyl-, propyl-, butyl-, isopropyl-, isobutyl-, sec-butyl-, tert-butyl-, n-pentyl-, and ethylhexyl. In particular, the alkyl group can also be substituted, even if not explicitly stated.

[0038] "Straight-chain alkyl" means an alkyl group without any branches. Examples of straight-chain alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. The terms "group" and "residue" are used synonymously in the context of this application.

[0039] "Branched-chain alkyl" means an alkyl group that is not straight-chain, i.e., in which the hydrocarbon chain has branches in particular. Examples of branched-chain alkyl groups are isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.

[0040] The term "alkenyl" means a hydrocarbon residue containing at least one double bond. For example, an alkenyl group having a double bond particularly has the formula -C n H 2n-1 However, the alkenyl group can also have more than one double bond. The number of hydrogen atoms changes according to the number of double bonds in the alkenyl group. Examples of alkenyl groups are vinyl, allyl, 2-butenyl, and 2-hexenyl.

[0041] "Straight-chain alkenyl" means an alkenyl group without any branches. Examples of straight-chain alkenyl groups are vinyl, allyl, n-2-butenyl, and n-2-hexenyl.

[0042] "Branched-chain alkenyl" means an alkenyl group that is not straight-chain, i.e., in which the hydrocarbon chain has branches in particular. Examples of branched-chain alkenyl groups are 2-methyl-2-propenyl-, 2-methyl-2-butenyl-, and 2-ethyl-2-pentenyl-.

[0043] The term "alkynyl" means a hydrocarbon residue containing at least one triple bond. For example, an alkynyl group having a triple bond has the formula -C n H 2n-3 The alkynyl group can also contain more than one triple bond. Double bonds and triple bonds can also be present. Examples are ethynyl, propynyl, butynyl, or pentynyl. The alkynyl group can be substituted or unsubstituted, and they can be unbranched or branched.

[0044] An alkylene, alkenylene, or alkynylene residue is the corresponding residue having two bonding sites respectively. Correspondingly, an alkane triyl, alkene triyl, or alkyne triyl residue is a residue having three bonding sites.

[0045] The terms "aryl group", "aryl residue" or "aromatic group" are understood to denote monocyclic or polycyclic aromatic residues. "Aromatic" denotes a cyclic planar hydrocarbon having a conjugated aromatic π - electron system. An aryl is, for example, a monocyclic (e.g., phenyl), bicyclic (e.g., indenyl, naphthyl, tetrahydronaphthyl or tetrahydroindenyl) and tricyclic (e.g., fluorenyl, tetrahydrofluorenyl, anthryl or tetrahydroanthryl) ring system, wherein at least one ring in the monocyclic ring system or in the bicyclic or tricyclic ring system is aromatic. In particular, C4 - C14 aryl denotes an aryl having 4 to 14 carbon atoms. In particular, an aryl may also be substituted, even if not explicitly stated.

[0046] An aromatic group can be monocyclic, bicyclic, tricyclic or polycyclic. An aromatic group may also contain 1 to 5 heteroatoms selected from the group consisting of N, O and S. These groups are also referred to as heteroaryl (see below). Examples of aromatic groups are benzene, naphthalene, anthracene, phenanthrene, furan, pyrrole, thiophene, isoxazole, pyridine and quinoline, wherein in each of the above examples, the necessary number of hydrogen atoms are removed to enable incorporation into the corresponding structural formula.

[0047] An "aliphatic residue" is a non - aromatic hydrocarbon residue. A "cycloalkyl" or "alicyclic residue" denotes a non - aromatic monocyclic or polycyclic hydrocarbon residue. In particular, a cycloalkyl having 4 to 14 carbon atoms denotes a non - aromatic hydrocarbon ring having 4 to 14 carbon atoms. A cycloalkyl can be saturated or partially unsaturated. A saturated cycloalkyl is non - aromatic and also has no double or triple bonds. Compared with a saturated cycloalkyl, a partially unsaturated cycloalkyl has at least one double or triple bond, but the cycloalkyl is not aromatic. In particular, a cycloalkyl may also be substituted, even if not explicitly stated.

[0048] "Aralkyl" or "aliphatic - aromatic group / residue" denotes an alkyl substituted by an aryl or an aliphatic residue substituted by an aryl. "C5 - C15 aralkyl" particularly denotes an aralkyl having 5 to 15 carbon atoms, wherein the carbon atoms of the alkyl and the aryl are both included therein. Examples are benzyl and phenethyl. An aralkyl may also be particularly substituted, even if not explicitly stated.

[0049] A "cyclic ring system" denotes a non - aromatic hydrocarbon ring. In particular, a cyclic ring system having 4 to 14 carbon atoms denotes a non - aromatic hydrocarbon ring system having 4 to 14 carbon atoms. A cyclic ring system can consist of a single hydrocarbon ring (monocyclic), two hydrocarbon rings (bicyclic) or three hydrocarbon rings (tricyclic). In particular, a cyclic ring system may also contain 1 to 5 heteroatoms, preferably selected from the group consisting of N, Si, O and S. An alicyclic is an aliphatic and cyclic residue.

[0050] A "saturated cyclic ring system" is non-aromatic and also has no double or triple bonds. Examples of saturated cyclic ring systems are cyclopentane, cyclohexane, decalin, norbornane, and 4H-pyran, where in each of the foregoing examples, the necessary number of hydrogen atoms are removed in each case to enable incorporation into the corresponding structural formula. For example, in the structural formula HO-R*-CH3, where R* is a cyclic ring system having 6 carbon atoms, particularly cyclohexane, two hydrogen atoms will be removed from the cyclic ring system, particularly from cyclohexane, to enable incorporation into the structural formula.

[0051] As used herein, a "heteroaryl" group denotes a monocyclic or polycyclic aromatic ring, particularly having 5 to 10 ring atoms, where one, two, three, or four of the ring atoms are nitrogen, oxygen, or sulfur, and the remainder are carbon. The heteroaryl can be substituted or unsubstituted. If they are substituted, the substituents are as defined above for cycloalkyl.

[0052] As used herein, "heteroalicyclic residue" or "heterocycloalkyl" denotes a monocyclic or fused ring having 5 to 10 ring atoms, which contains one, two, or three heteroatoms selected from N, O, and S, where the remaining ring atoms are carbon. The "heterocycloalkenyl" group also contains one or two double bonds. However, the ring does not have a fully conjugated π-electron system. When substituted, the substituents are as defined above for cycloalkyl.

[0053] Unless otherwise specified, N particularly denotes nitrogen. Further, unless otherwise specified, O particularly denotes oxygen.

[0054] "Optionally substituted" means that the carbon atoms in the corresponding group or in the corresponding residue can be substituted by substituents. In particular, the substituents can be selected from the group consisting of C1 to C4 alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogen, fluorine, chlorine, bromine, iodine, hydroxy, amino, alkylamino, dialkylamino, C1 to C4 alkoxy, phenoxy, benzyloxy, cyano, nitro, and sulfanyl. If a group is designated as optionally substituted, 0 to 50, particularly 0 to 20 hydrogen atoms in the group can be substituted by substituents. If the group is substituted, at least one hydrogen atom is substituted by a substituent.

[0055] "Alkoxy" denotes an alkyl group linked to the main carbon chain through an oxygen atom.

[0056] The term "polysiloxane" or "polyorganosiloxane" denotes an organosilicon compound.

[0057] "Silicone rubber compounds" in the sense of the present invention are synthetic silicone-containing rubber compounds, which in the present context are also synonymously referred to as (curable) compositions or silicone compositions, which include rubber polymers, polycondensates and polyaddition polymers which can be converted into a highly elastic cured state by crosslinking using suitable crosslinking agents. In addition, these are plastically formable mixtures, such as plastically formable mixtures of α,ω-dihydroxypolyorganosiloxanes with suitable curing agents or crosslinking agents, which can be stored with the exclusion of moisture, wherein these silicone rubber compounds polymerize at room temperature under the influence of water or air humidity.

[0058] The term "catalyst" refers to a substance that reduces the activation energy of a particular reaction and thereby increases the reaction rate. In the sense of the present invention, a metal catalyst is understood to be a compound containing atoms or ions of a metal or semimetal. It can be, for example, a salt or an organometallic compound.

[0059] "Elongation at break" is the ratio of the change in length after the test piece breaks to the initial length. It indicates the ability of a material to undergo a change in shape without breaking. The elongation at break is determined in a tensile test in accordance with DIN EN ISO 8339 and DIN 53504.

[0060] The “elongation stress value” defines the stress exerted on the bonding surface or adjacent build material when the sealant is 100% elongated.

[0061] The "secant coefficient" is the ratio of stress to strain at any point on the curve of a stress-strain diagram. It is the slope of the curve from the starting point to any point on the stress-strain curve.

[0062] "Resilience" describes the tendency of a flexible beam to return completely or partially to its original dimensions after the force causing the extension or deformation has been removed. The average resilience is determined in accordance with DIN EN ISO 7389.

[0063] In one embodiment, the present invention relates to a composition obtainable by mixing the following components:

[0064] (a) a crosslinking agent or a mixture of crosslinking agents, wherein the crosslinking agent or the mixture of crosslinking agents can be c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p S K p The reaction is obtained, where

[0065] Each X independently represents O, NR b , S or PR b,

[0066] Each R b independently represents H, a trialkylsilyl group, or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0067] Each Y independently represents a C-C bond, CR c 2, O, NR e or PR e , where

[0068] each R c independently represents H or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0069] each R e independently represents H or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0070] each K independently represents Cl, OR d or ON=CR g 2,

[0071] each R d independently represents a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0072] each R g independently represents H or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0073] each o independently is an integer from 1 to 8, and

[0074] p = 2 or 3,

[0075] (b) a metal catalyst, and

[0076] (c) an aminosilane.

[0077] In a preferred embodiment, K represents Cl, OR d or ON=CR g 2, especially OR d . Particularly preferably, the present invention relates to a composition that can be obtained by mixing the following components:

[0078] (a) a crosslinking agent or a crosslinking agent mixture that can be obtained by (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p Si(ORd ) p is obtained by the reaction, wherein

[0079] X, Y, R c , R d and o are as defined above, and

[0080] p = 2 or 3,

[0081] (b) a metal catalyst, and

[0082] (c) an aminosilane.

[0083] In the reaction of (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p SiK p (preferably (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p Si(OR d ) p ) the residue K (preferably OR d ) is nucleophilically substituted by X or Y, thereby producing an intramolecular chelate-like compound, or a compound in which the Si atoms are intermolecularly bonded to each other via the residues HX(CR c 2) o Y(CR c 2) o X(CR c 2) o As a result, after forming a sealant by polymerization and / or crosslinking using, for example, a polyorganosiloxane (HO-(SiR q R r O) s -H), most of these compounds unexpectedly remain in the sealant matrix. According to the present invention, without being bound by them, it is considered that the compounds are still partially bound to the Si atoms and thus incorporated into the polymer, and / or are less volatile due to hydrogen bonding because they are retained by the polar components of the sealant matrix. Both result in the advantage of low emission of undesired compounds.

[0084] (HX(CR c 2) o Y(CR c 2) o X(CR c 2)o ) 4-p SiZ p (preferably (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p Si(OR d ) p ) is shown by way of example below, showing both the preferred reaction path to monomeric compounds and the reaction path to oligomeric compounds. Both lead to the desired result of a low-emission sealant.

[0085] In the reaction and oligomerization scheme DTC (Part 1) shown below, the reaction of trimethoxysilylalkyltriamine is shown as an example, where the nucleophilic substitution of the methoxy groups on silicon preferably occurs intramolecularly. The conversion to DTC is shown in the middle:

[0086]

[0087] DTC

[0088] The left and right reaction paths in the reaction and oligomerization scheme DTC (Part 1) show further intramolecular and intermolecular reaction possibilities. Part 2 of the reaction and oligomerization scheme DTC shows further possible reactions of the dimer product A from said part of the scheme. Here, all these reaction products and their further reaction products can also serve as the crosslinking agent or crosslinking agent mixture (a) according to claim 1, and result in the advantage of low emission of the leaving groups of the crosslinking agent or crosslinking agent mixture.

[0089]

[0090] Reaction and oligomerization scheme DTC (Part 1)

[0091]

[0092] Reaction and oligomerization scheme DTC (Part 2)

[0093] In the formula of the present invention, each residue R d independently represents a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly 1 to 4 carbon atoms.

[0094] Preferably, each residue R d independently represents

[0095] Optionally substituted alkyl, alkenyl or alkynyl residues,

[0096] Optionally substituted alicyclic residues, aromatic residues or aliphatic-aromatic residues, or

[0097] Optionally substituted heterocycloaliphatic residues or heteroaromatic residues,

[0098] each having from 1 to 16 carbon atoms, more preferably from 1 to 12 carbon atoms, even more preferably from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

[0099] In a particularly preferred embodiment, each residue R d independently represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, octyl, isooctyl, allyl, vinyl or phenyl. More preferably methyl, ethyl, n-propyl, isopropyl, isobutyl, octyl, isooctyl, vinyl or phenyl. Most preferably, each residue R d independently represents methyl or ethyl.

[0100] Each residue R c 、R e and R g independently represents H or a saturated or unsaturated optionally substituted hydrocarbon residue having from 1 to 16 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 8 carbon atoms, even more preferably from 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

[0101] Preferably, each residue R c 、R e and R g independently represents

[0102] H or an optionally substituted alkyl, alkenyl or alkynyl residue,

[0103] optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue, or

[0104] optionally substituted heterocycloaliphatic residue or heteroaromatic residue,

[0105] each having from 1 to 16 carbon atoms, more preferably from 1 to 12 carbon atoms, even more preferably from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

[0106] In a particularly preferred embodiment, each residue R c 、R e and R gIndependently represent H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, octyl, isooctyl, allyl, vinyl or phenyl. More preferably, they are H, methyl, ethyl, n-propyl, isopropyl, isobutyl, octyl, isooctyl, vinyl or phenyl. Most preferably, each R c , R e and R g independently represent H or methyl.

[0107] Each residue R b independently represents H, trialkylsilyl or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

[0108] Preferably, each residue R b independently represents

[0109] H, trialkylsilyl or an optionally substituted alkyl, alkenyl or alkynyl residue,

[0110] an optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue, or

[0111] an optionally substituted heterocycloaliphatic residue or heteroaromatic residue,

[0112] each having 1 to 16 carbon atoms, more preferably having 1 to 12 carbon atoms, even more preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

[0113] In a particularly preferred embodiment, each residue R b independently represents H, trialkylsilyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, octyl, isooctyl, allyl, vinyl or phenyl. More preferably, they are H, trialkylsilyl, methyl, ethyl, n-propyl, isopropyl, isobutyl, octyl, isooctyl, vinyl or phenyl.

[0114] The alkyl groups in the trialkylsilyl group are preferably independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, octyl, isooctyl, allyl, vinyl or phenyl. The trialkylsilyl is more preferably trimethylsilyl, triethylsilyl, tripropylsilyl or tributylsilyl, most preferably trimethylsilyl and triethylsilyl. Most preferably, each residue R b independently represents H, trimethylsilyl or methyl.

[0115] In the formula of the present invention, o is preferably 1, 2 or 3, more preferably 2 or 3, and particularly preferably 2. More preferably, R b is H, trialkylsilyl or CH3, and / or R c =H and / or p = 2 or 3, particularly p = 3.

[0116] In a preferred embodiment of the present invention, Y = N(CR c 2) o X or P(CR c 2) o X, preferably N(CR( c 2) o XH, where R c , o and X are as defined above, and more preferably where R c =H, o = 2 or 3, and / or X = O or NH.

[0117] In a preferred embodiment of the present invention, (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p SiK p or (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p Si(OR d ) p are respectively

[0118] (CH3O)3Si(CH2)3NH(CH2)2NH(CH2)2NH2, where R, X, Y, R c , R d , m, o and p are as defined in this specification.

[0119] Without departing from the scope of the present invention, the above-mentioned features and preferred embodiments and those described below can be combined in any combination. For example, in a preferred embodiment, the present invention relates to a composition that can be obtained by mixing the following components:

[0120] (a) A crosslinking agent or a mixture of crosslinking agents, which can be obtained by the reaction of the following components:

[0121] (HX(CR c 2) o Y(CRc 2) o X(CR c 2) o ) 4-p SiK p , preferably (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p Si(OR d ) p , wherein X, Y, K, R c 、R d and o are as defined in this patent application, and

[0122] p = 2 or 3,

[0123] (b) a metal catalyst, and

[0124] (c) an aminosilane.

[0125] In a particularly preferred embodiment of the present invention, the composition can be obtained by mixing the above components (a) to (c) and an additional following component:

[0126] (d) a polyorganosiloxane of the formula HO-(SiR q R r O) s -H, wherein

[0127] each R q and R r independently represents a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, and s is an integer from 5 to 5000.

[0128] Preferably, each R q and R r independently represents

[0129] an optionally substituted alkyl, alkenyl or alkynyl residue;

[0130] an optionally substituted alicyclic residue, aryl residue or aralkyl residue; or

[0131] an optionally substituted heterocyclic aliphatic residue or heteroaryl residue each having 1 to 16 carbon atoms.

[0132] The polyorganosiloxane is polymerized and / or crosslinked to form an organosilicon composition.

[0133] In one embodiment, the present invention relates to a composition obtainable by mixing components (a) to (c). Component (a) is obtainable by reaction (chemical reaction) of the starting components described under (a). Components (a) to (c) will generally have already reacted with each other partially after mixing. In a preferred embodiment of the present invention, the composition according to the present invention comprises components (a) to (c).

[0134] Mix components (a), (b) and (c), where (a) is the reaction mixture according to (a). The reaction product (a) can be worked up or purified, for example by separating by-products or isolating the product therefrom. Generally, the reaction product (a) will be a mixture of various compounds.

[0135] (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p SiK p The desired product of the preferred reaction pathway of the reaction of is a monomeric compound.

[0136] In a preferred embodiment of the present invention, the composition according to the present invention thus comprises the following components:

[0137] (a) at least one crosslinking agent of the formula (X(CR c 2) o Z(CR c 2) o Z(CR c 2) o )Si, where X, Z, R c and o are as defined herein,

[0138] (b) at least one metal catalyst, and

[0139] (c) at least one aminosilane.

[0140] In the above formulae, the preferred and particularly preferred embodiments described are also preferred and particularly preferred.

[0141] For example, each R d preferably independently represents a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms.

[0142] More preferably, each residue R d independently represents

[0143] Optionally substituted alkyl, alkenyl or alkynyl residues

[0144] Optionally substituted alicyclic residues, aromatic residues or aliphatic-aromatic residues, or

[0145] Optionally substituted heterocycloaliphatic residues or heteroaromatic residues,

[0146] each having from 1 to 16 carbon atoms, more preferably from 1 to 12 carbon atoms, even more preferably from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

[0147] In a particularly preferred embodiment, each residue R d independently represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, octyl, isooctyl, allyl, vinyl or phenyl. More preferably, methyl, ethyl, n-propyl, isopropyl, isobutyl, octyl, isooctyl, vinyl or phenyl. Most preferably, each R d independently represents methyl or ethyl.

[0148] Each residue R b and R c independently represents the groups described.

[0149] In the formula of the present invention, o is preferably 1, 2 or 3, more preferably 2 or 3.

[0150] Preferably, the crosslinking agent in the composition according to the present invention is

[0151] .

[0152] In a particularly preferred embodiment of the present invention, in addition to components (a) to (c), the composition further comprises the following component:

[0153] (d) a polyorganosiloxane of the formula HO-(SiR q R r O) s -H, wherein

[0154] each R q and R r independently represents a saturated or unsaturated optionally substituted hydrocarbon group having 1 to 16 carbon atoms, and s is an integer from 5 to 5000.

[0155] Preferably, each R q and R r independently represents

[0156] an optionally substituted alkyl, alkenyl or alkynyl group;

[0157] Optionally substituted alicyclic group, aryl group or aralkyl group; or

[0158] Optionally substituted heterocycloaliphatic or heteroaryl group each having 1 to 16 carbon atoms.

[0159] As described above, each X in the formula independently represents O, NR b , S or PR b . Preferably, each X independently represents O or NR b , more preferably O or NH, especially O.

[0160] In another embodiment, the composition according to the invention comprises:

[0161] A crosslinking agent of the formula Si(R) m (XR a ) 4-m , wherein

[0162] Each R and R a independently represents a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms,

[0163] m is an integer from 0 to 2;

[0164] Each X independently represents NR b or O, wherein each R b independently represents

[0165] H, trialkylsilyl or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, wherein

[0166] At least two XR a residues are covalently bonded to each other and additionally to the residue R.

[0167] For the purposes of the present invention, "at least two" is understood to particularly mean two, three or four, i.e., two, three or four residues XR a can be bonded to each other.

[0168] In the case of residues R and / or XR a covalently bonded to each other, two H atoms in the residues are replaced by a covalent bond. For example, two methyl groups become an ethylidene group, or two -N(R)CH3 groups can become -N(R)-CH2-CH2-N(R) groups. In this case, instead of an alkyl residue, an alkylene diyl residue is present due to the covalent bond with another residue, and an alkylene triyl residue is present in the case of a covalent bond with two other residues.

[0169] In a preferred embodiment of the present invention, in the formula Si(R) m (XR a )4-m in which each residue R or R not covalently bonded to another residue R or R a and each residue R and R covalently bonded to one another a independently represents

[0170] an optionally substituted alkyl, alkenyl or alkynyl group;

[0171] an optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue; or

[0172] an optionally substituted heterocycloaliphatic residue or heteroaromatic residue each having from 1 to 16 carbon atoms.

[0173] and each residue R or R covalently bonded to another residue R or R a and each residue R covalently bonded to one another a and R preferably independently represent

[0174] an optionally substituted alkylene, alkenylene or alkynylene residue;

[0175] an optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue; or

[0176] an optionally substituted heterocycloaliphatic residue or heteroaromatic residue each having from 1 to 16 carbon atoms.

[0177] and each residue R and / or R covalently bonded to two other residues R and / or R a and each residue R covalently bonded to one another a and R preferably independently represent

[0178] an optionally substituted alkanetriyl, alkenetriyl or alkynetriyl residue;

[0179] an optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue; or

[0180] an optionally substituted heterocycloaliphatic residue or heteroaromatic residue each having from 1 to 16 carbon atoms.

[0181] In a preferred embodiment, residues R and R covalently bonded to one another a are obtained from the following residues by replacing two H atoms with a covalent bond:

[0182] an optionally substituted alkyl, alkenyl or alkynyl residue;

[0183] an optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue; or

[0184] an optionally substituted heterocycloaliphatic residue or heteroaromatic residue each having from 1 to 16 carbon atoms.

[0185] The residue has 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly 1 to 4 carbon atoms. The residue has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly 1 to 4 carbon atoms.

[0186] In a particularly preferred embodiment, for the crosslinking agent of formula Si(R) m (XR a ) 4-m each residue R and / or R a that is not covalently bonded to another residue independently represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl or phenyl. Each residue R and R a of the crosslinking agent that is covalently bonded to another residue is obtained by replacing a hydrogen atom with a covalent bond from the residues methyl, ethyl, n-butyl, sec-butyl, isobutyl or tert-butyl or phenyl.

[0187] As described above, each X independently represents NR b , PR b or O. Each residue R b in the above formula independently represents H, trialkylsilyl or a saturated or unsaturated optionally substituted hydrocarbon residue having 1 to 16 carbon atoms. R b preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly 1 to 6 carbon atoms.

[0188] Preferably, each residue R b in the above formula independently represents

[0189] H, trialkylsilyl or an optionally substituted alkyl, alkenyl or alkynyl residue;

[0190] an optionally substituted alicyclic residue, aromatic residue or aliphatic-aromatic residue; or

[0191] an optionally substituted heterocycloaliphatic residue or heteroaromatic residue, each having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.

[0192] In a preferred embodiment, R b represents H, trialkylsilyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, octyl, isooctyl, allyl, vinyl or phenyl. H, trialkylsilyl, methyl, ethyl, n-propyl, isopropyl, isobutyl, octyl, isooctyl, vinyl and phenyl are more preferred. Most preferably, R b =H or trimethylsilyl.

[0193] In a preferred embodiment of the present invention, at least two residues R covalently bonded to each other a can be bonded to each other via a C-C bond or via a heteroatom. These heteroatoms can be of the formula Si(R) m (XR a ) 4-m the heteroatom X of the residue XR a in or the heteroatom of the substituent of said residue. Preferably, at least two residues R a are covalently bonded to each other via a C-C bond, a C-N bond or a C-O bond, particularly preferably via a C-C bond or a C-N bond.

[0194] In a preferred embodiment of the present invention, in the formula Si(R) m (XR a ) 4-m of the crosslinking agent, m = 1 or 2, and at least two residues R covalently bonded to each other a are additionally covalently bonded to the residue R. This has the advantage that the groups are not volatile but remain bound to the polymer and thus do not emit compounds generated by the leaving groups from the obtained silicone rubber compound.

[0195] In yet another preferred embodiment, in the formula Si(R) m (XR a ) 4-m m = 1, and three residues R a are covalently bonded to each other. This results in a higher molecular weight leaving group with multiple HXR a groups that are hardly emitted. More preferably, the three residues R covalently bonded to each other a are also covalently bonded to the residue R. This has the advantage described above: the leaving group remains bound to the polymer and is thus not volatile.

[0196] In yet another preferred embodiment, in the formula Si(R) m (XR a ) 4-m m is 1, three residues R a are covalently bonded to each other and to the residue R. It is also preferred that in the formula Si(R) m (XR a ) 4-m m is 2, and two R a residues are covalently bonded to each other and to one residue R.

[0197] In another particularly preferred embodiment, a mixture of the described crosslinking agents is used for the composition according to the present invention.

[0198] In a particularly preferred embodiment of the present invention, R represents: an optionally substituted straight-chain or branched C1 to C12 alkyl group, especially an optionally substituted straight-chain or branched C1 to C8 alkyl group; an optionally substituted straight-chain or branched C2 to C12 alkenyl group, especially an optionally substituted straight-chain or branched C2 to C8 alkenyl group; an optionally substituted C4 to C10 aryl group or an optionally substituted C5 to C15 aralkyl group. In a particularly preferred embodiment, R represents a residue selected from the group consisting of: methyl, ethyl, n-propyl and isopropyl, and n-butyl, sec-butyl, isobutyl and tert-butyl, vinyl and phenyl or an allyl residue. Most preferably, R is methyl or ethyl.

[0199] R c Particularly preferably: H or an optionally substituted straight-chain or branched C1 to C12 alkyl group, especially an optionally substituted straight-chain or branched C1 to C8 alkyl group; an optionally substituted straight-chain or branched C2 to C12 alkenyl group, especially an optionally substituted straight-chain or branched C2 to C8 alkenyl group; an optionally substituted C4 to C10 aryl group or an optionally substituted C5 to C15 aralkyl group. In a particularly preferred embodiment, R c represents a residue selected from the group consisting of: H, methyl, ethyl, n-propyl and isopropyl, and n-butyl, sec-butyl, isobutyl and tert-butyl, vinyl, allyl and phenyl. Most preferably, R c = H, methyl or ethyl.

[0200] In a preferred embodiment of the present invention, the crosslinking agent is a compound of the formula compound.

[0201] The mass loss of the composition according to the present invention after curing is preferably less than 1% by weight (based on the total weight of the composition), particularly less than 0.75% by weight, and even more preferably less than 0.5% by weight (based on the total weight of the composition) (the mass loss is measured according to DIN EN ISO 10563).

[0202] The composition according to the present invention further comprises a metal catalyst. The metal catalyst catalyzes the curing of the composition by catalyzing the crosslinking of a polyorganosiloxane (silicone) with an OH group and a crosslinking agent in the presence of water or moisture. After curing, a silicone rubber compound according to the present invention is obtained. The metal catalyst is preferably a compound containing a metal or a metalloid and organic residues. More preferably, the metal catalyst is an organometallic compound.

[0203] The metal in the metal catalyst is preferably selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals, and metalloids, particularly preferably selected from the group consisting of metals of the first, second, third, fourth, fifth, eighth, tenth, and eleventh subgroups, and metals of the first, second, third, fourth, and fifth main groups. More preferably, the metal in the metal catalyst is selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Ca, Sn, and Bi, preferably selected from the group consisting of Ti, Zr, Zn, Ca, Sn, and Bi.

[0204] In another preferred embodiment, the metal catalyst contains tin. Particularly preferred catalysts are dialkyltin(II) salts, such as dialkyltin(II) carboxylates, for example, dibutyltin dilaurate.

[0205] In another preferred embodiment, the metal catalyst does not contain tin. Such tin-free catalysts have the advantage of avoiding toxic tin, especially toxic tin from organotin compounds. Therefore, the metal in the metal catalyst is preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Ca, and Bi, preferably selected from the group consisting of Ti, Zr, Zn, Ca, and Bi.

[0206] In a preferred embodiment of the present invention, the composition contains a metal siloxane-silanol(salt) compound (= metal siloxane-silanol / silanolate compound), which is also referred to as an "M3S" compound. These M3S compounds are described in EP 3 392 313 A1 and can be advantageously used as catalysts in the compositions of the present invention.

[0207] In a preferred embodiment of the present invention, the composition contains a metal siloxane, particularly a metal siloxane of the formula R* A Si B O C M D as the metal catalyst, where

[0208] each R* is independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 to C20 alkenyl, optionally substituted C6 to C10 aryl, -OH, and -O-(C1 to C20 alkyl), where

[0209] M is a metal,

[0210] A is an integer from 4 to 19,

[0211] B is an integer from 4 to 10,

[0212] C is an integer from 8 to 30, and

[0213] D is an integer from 1 to 8.

[0214] The metal siloxane is preferably a metal sesquisiloxane, in particular a polyhedral metal sesquisiloxane. A polyhedral metal sesquisiloxane is understood to be a metal sesquisiloxane in which the silicon atoms and the metal atoms at least partially occupy the corners of a polyhedron (such as a cube).

[0215] The metal sesquisiloxane is particularly preferably a polyhedral titanium and / or zirconium sesquisiloxane. An example is given below:

[0216]

[0217] Furthermore, the composition according to the invention contains an aminosilane as component (c), and the aminosilane can particularly act as an adhesion promoter in the composition.

[0218] An aminosilane is an organic compound containing a silicon atom and an amino group. The amino group can optionally be substituted. In particular, the amino group can be a primary amino group, a secondary amino group or a tertiary amino group.

[0219] In a preferred embodiment of the composition according to the invention, the aminosilane is:

[0220] (a) a compound of formula (X)3Si-R E -N(R F )R G ,

[0221] where each X is independently selected from the group consisting of: -OMe, -OEt, -O i Pr, -O n Pr, -O n Bu, -O sec Bu, -O iso Bu, -O t Bu and -OPh,

[0222] R E is -(CH2) s -, where s is an integer from 1 to 10,

[0223] R F is H, an optionally substituted C1 to C16 alkyl group or R (I) ,

[0224] R G is an optionally substituted C1 to C16 alkyl group, RI or -C(O)-R (H) ,

[0225] wherein if R G is -C(O)-R H , then R F represents only H, and

[0226] wherein R H is an optionally substituted straight-chain or branched C1-C16 alkoxy group, -O-R I , an optionally substituted straight-chain or branched C1-C16 alkyl group, R I or -CHMe-O-C(O)-Me,

[0227] or wherein R F and R G together with the atoms to which they are bonded form an optionally substituted heterocyclic ring system having 3 to 14 carbon atoms and 1 to 5 heteroatoms selected from the group consisting of N and O, and

[0228] each R I independently represents an optionally substituted cyclic ring system having 4 to 14 carbon atoms or an optionally substituted aromatic group having 4 to 14 carbon atoms,

[0229] or an oligomer or polymer thereof,

[0230] or

[0231] (b) a heterocyclic aminosilane in which the silicon atom and the nitrogen atom are directly connected to each other.

[0232] In a particularly preferred embodiment, the aminosilane is selected from the group consisting of: 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, butylaminopropyltriethoxysilane, butylaminopropyltrimethoxysilane, propylaminopropyltriethoxysilane, propylaminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltriethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, trimethoxypropylsilylacetoxypropionamide, N,N'-bis(trimethoxysilylpropyl)urea, N,N'-bis(triethoxysilylpropyl)urea, tris(triethoxysilylpropyl)diethylenetriurea, dimethylaminopropyltrimethoxysilane, 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, N-methyl(3-trimethoxysilyl)propyl)carbamate, N-ethyl(3-triethoxysilyl)propyl)carbamate, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and mixtures thereof.

[0233] In another preferred embodiment of the present invention, the composition comprises a heterocyclic aminosilane as the aminosilane, wherein the silicon atom and the nitrogen atom are directly connected to each other.

[0234] The heterocyclic aminosilane may preferably be a heterocyclic organosilane as described in EP 3 613 803 A1, wherein the heteroatom is preferably a nitrogen atom.

[0235] In a particularly preferred embodiment, the heterocyclic aminosilane is a compound of the following formula:

[0236]

[0237] wherein

[0238] a is 0, 1 or 2;

[0239] n = 0 to 6;

[0240] R K 、R L 、R M 、R O 、R P and R QEach of the residues R is independently H or an optionally substituted linear or branched C1 to C20 alkyl, an optionally substituted linear or branched C2 to C20 alkenyl, an optionally substituted C3 to C20 cycloalkyl, an optionally substituted C4 to C20 cycloalkenyl, an optionally substituted linear, branched or cyclic C4 to C20 alkynyl, or an optionally substituted linear or branched C2 to C20 heteroalkyl, an optionally substituted linear, branched or cyclic C3 to C20 heteroalkyl, an optionally substituted linear, branched or cyclic C3 to C20 heteroalkyl, or an optionally substituted C4 to C14 aryl or heteroaryl, or two residues R K , R L , R M , R O , R P and R Q Together they form a 5- to 8-membered ring.

[0241] (R P ) a OR Q ) 2-a The parameter a in represents an alkoxy residue OR as defined herein. Q With residue R P Here, a can have a value from 0 to 2. If a=0, the corresponding heterocyclic organosilane does not contain a residue R P , and contains two residues OR Q The parameter a can also be 1. In this case, a residue R P and a residue OR Q Directly bonded to the silicon atom of the heterocyclic organosilane. If a=2, then only the residue R P Without the residue OR Q Connected to silicon atoms.

[0242] The residue (R) in formula (III) M ) n Each is directly related to the ring size determined by the parameter n. The possible number of residues on the ring atoms is also adjusted here by the value n. For example, if there is a 6-membered ring, n=2, and the residue R c or R C The number of is adjusted accordingly to 2. In this way, each ring atom can carry one residue.

[0243] Heterocyclic aminosilanes may carry different residues on each ring atom. K , R L , R M , R O , R P and R QR is independently H or an optionally substituted linear or branched C1 to C20 alkyl, an optionally substituted linear or branched C2 to C20 alkenyl, an optionally substituted C3 to C20 cycloalkyl, an optionally substituted C4 to C20 cycloalkenyl, an optionally substituted linear, branched or cyclic C4 to C20 alkynyl, or an optionally substituted linear or branched C2 to C20 heteroalkyl, an optionally substituted linear, branched or cyclic C3 to C20 heteroalkenyl, or an optionally substituted C4 to C14 aryl or heteroaryl. Preferably, each R K , R L , R M , R O , R P and R Q R is independently H, or an optionally substituted linear or branched C1 to C10 alkyl, an optionally substituted linear or branched C2 to C10 alkenyl, an optionally substituted linear or branched C2 to C10 heteroalkyl, an optionally substituted C3 to C10 cycloalkyl, or an optionally substituted C4 to C8 aryl or heteroaryl. Most preferably, each R K , R L , R M , R O , R P and R Q is independently H, optionally substituted linear or branched C1 to C8 alkyl, optionally substituted linear or branched C2 to C8 alkenyl, optionally substituted linear or branched C4 to C8 heteroalkyl, optionally substituted C4 to C6 cycloalkyl, or optionally substituted C5 to C6 aryl or heteroaryl.

[0244] Particularly preferred heterocyclic aminosilanes are substituted or unsubstituted, in particular unsubstituted N-n-butyl-1-aza-2,2-dimethoxy-2-silacyclopentane ((BDC), CAS No.: 618914-44-6), 2,2-diethoxy-1-(3-triethoxysilylpropyl)aza-2-silacyclopentane ((TESPDC), CAS No.: 1184179-50-7) and / or 2,2-diethoxy-1-(trimethylsilyl)aza-2-silacyclopentane ((TMS)DEC), CAS No.: 21297-72-3), BnDC (CAS No.: 2411737-55-6) of the following structure:

[0245]

[0246] In a preferred embodiment, the composition according to the invention contains the aminosilane in an amount of 0.1% to 3% by weight, preferably 0.2% to 2% by weight, particularly preferably 0.3% to 1.5% by weight, based on the total weight of the composition.

[0247] The composition according to the invention preferably further comprises a polyorganosiloxane of the formula HO-(SiR q R r O) s -H, wherein

[0248] each R q and R r independently represents

[0249] an optionally substituted alkyl, alkenyl or alkynyl group;

[0250] an optionally substituted alicyclic group, aryl group or aralkyl group; or

[0251] an optionally substituted heterocycloaliphatic residue or heteroaryl residue;

[0252] and s is an integer from 5 to 5000.

[0253] If the composition according to the invention contains a polyorganosiloxane of the formula HO-(SiR q R r O) s -H, there is present an RTC-1 silicone rubber compound which can be cured in the presence of water. If the composition according to the invention does not contain polyorganosiloxane, there is present an RTC-2 composition into which polyorganosiloxane must be added before curing.

[0254] One polyorganosiloxane contained in the composition is an α,ω-dihydroxy-terminated polyorganosiloxane. In addition to homopolymeric α,ω-dihydroxy-terminated polydiorganosiloxanes, heteropolymeric α,ω-dihydroxy-terminated polydiorganosiloxanes with different organic substituents can also be used, including both copolymers of monomers having similar organic substituents on the silicon atoms and copolymers of monomers having different organic substituents on the silicon atoms, for example, those having mixed alkyl, alkenyl and / or aryl substituents. Preferred organic substituents include straight-chain and branched-chain alkyl groups having 1 to 8 carbon atoms, especially methyl, ethyl, n-propyl and isopropyl, as well as n-butyl, sec-butyl and tert-butyl, vinyl and phenyl. In the individual organic substituents, single or all of the carbon-bonded hydrogen atoms can be substituted by conventional substituents such as halogen atoms or functional groups such as hydroxyl and / or amino groups. For example, α,ω-dihydroxy-terminated polydiorganosiloxanes with partially fluorinated or fully fluorinated organic substitution can be used, or α,ω-dihydroxy-terminated polydiorganosiloxanes with organic substituents substituted by hydroxyl and / or amino groups on the silicon atoms can be used.

[0255] Preferred examples of the organosilicon compounds are α,ω-dihydroxy-terminated polydialkylsiloxanes, such as α,ω-dihydroxy-terminated polydimethylsiloxane, α,ω-dihydroxy-terminated polydiethylsiloxane or α,ω-dihydroxy-terminated polydivinylsiloxane, and α,ω-dihydroxy-terminated polydiarylsiloxanes, such as α,ω-dihydroxy-terminated polydiphenylsiloxane.

[0256] In a preferred embodiment, each R q and R r independently represents an optionally substituted straight-chain or branched C1-C16 alkyl group, an optionally substituted straight-chain or branched C2-C16 alkenyl group or an optionally substituted C4-C14 aryl group.

[0257] In another preferred embodiment, in the polyorganosiloxane HO-(SiR q R r O) s -H, s is an integer from 5 to 3500, more preferably from 10 to 3500, still more preferably from 100 to 3000, particularly from 800 to 2000, and most preferably from 1000 to 1800.

[0258] In another embodiment, the polyorganosiloxane HO-(SiR q R r O) s -H has a weight-average molecular weight M w of 400 to 5,000,000, particularly 3,000 to 2,500,000, 15,000 to 1,000,000, 30,000 to 750,000, 50,000 to 500,000 or 110,000 to 150,000.

[0259] In a preferred embodiment, a polyorganosiloxane HO-(SiR q R r O) s -H has a kinematic viscosity at 25 °C of 20 to 350,000 cSt, or 20,000 to 100,000 cSt, or 20,000 to 90,000 cSt, or 20,000 to 80,000 cSt.

[0260] In a particularly preferred embodiment, the composition according to the invention comprises a polyorganosiloxane HO-(SiR q R r O) s -H, wherein R l and R m are independently selected from the group consisting of methyl-, ethyl-, propyl-, butyl-, trifluoromethyl-, vinyl-, allyl-, butenyl-, phenyl- and naphthyl-.

[0261] In a particularly preferred embodiment, the composition according to the invention comprises a polyorganosiloxane HO-(SiR q R r O) s -H, wherein the polyorganosiloxane is an α,ω-dihydroxy-dimethyl-polysiloxane.

[0262] The weight ratio of the polyorganosiloxane, in particular an α,ω-dihydroxy-terminated polydialkylsiloxane, to the crosslinking agent is preferably from 100:1 to 2:1, particularly preferably from 50:1 to 5:1, especially from 15:1 to 6:1.

[0263] The composition according to the invention may contain a compound of the formula HO-(SiR q R r O) s -H in the form of a prepolymer and a crosslinking agent, each independently of one another. The prepolymer is the reaction product of these two components. These reactions are known and are also referred to as capping, as described, for example, in WO 2016 / 146648 A1.

[0264] In addition to the abovementioned components, the composition according to the invention may also optionally contain further ingredients / components, in particular conventional additives such as fillers, plasticizers, reactive diluents, colorants, thixotropic agents, rheological additives, wetting agents, UV stabilizers, antioxidants, desiccants, etc. Preferably, the composition according to the invention contains at least one further ingredient.

[0265] The composition according to the invention may also preferably contain a plasticizer. Preferred plasticizers are capped polyethylene glycols, such as polyethylene glycol or polypropylene glycol dialkyl ethers, wherein the alkyl residue has from one to four carbon atoms, in particular the dimethyl and diethyl ethers of diethylene glycol and dipropylene glycol. Diurethanes are also preferred plasticizers, which can be prepared, for example, by reacting a diol having OH end groups with a monofunctional isocyanate. In a preferred embodiment of the invention, a polyalkylsiloxane, particularly preferably polydimethylsiloxane, is used as the plasticizer.

[0266] In each case, the composition preferably contains the plasticizer in an amount of from 2% to 50% by weight, preferably from 10% to 40% by weight, particularly preferably from 20% to 35% by weight, based on the total weight of the composition. If a mixture of several plasticizers is used, the amounts given refer to the total amount of plasticizer in the composition.

[0267] If it is desired to further reduce the viscosity of the composition, a reactive diluent may also be added. Suitable reactive diluents are compounds that are miscible with the composition and have at least one group that reacts with the polymer. Preferably, the reactive diluent has at least one functional group that reacts with moisture or atmospheric oxygen. Examples are isocyanate groups, silyl groups or unsaturated groups such as vinyl groups. To prepare a preferred reactive diluent, for example, the corresponding polyol component can be reacted with at least one difunctional isocyanate.

[0268] The composition according to the invention may also contain fillers. Suitable fillers include chalk, lime powder, precipitated and / or pyrogenic silica, zeolites, bentonites, magnesium carbonate, alumina, animal fats, titanium oxide, iron oxide, zinc oxide, quartz, mica and other powdery or ground minerals. In addition, organic fillers can also be used, especially wood fibers, wood flour, sawdust, cellulose, cotton and rice husks.

[0269] In a particularly preferred embodiment of the invention, silica is added to the composition in untreated and / or treated form, preferably in hydrophobized form, particularly preferably pyrogenic silica, which is also known as fumed silica. In a particularly preferred embodiment of the invention, a mixture of untreated and hydrophobized silica is added as a filler to the composition.

[0270] In each case, the filler is preferably used in an amount of 1% to 60% by weight, particularly preferably 2% to 20% by weight and very particularly preferably 5% to 15% by weight, based on the total weight of the composition. Mixtures of several fillers can also be used. In this case, the amounts given refer to the total amount of fillers in the composition.

[0271] For some applications, additives or fillers that impart thixotropy to the composition are preferred. Such fillers are also described as rheology modifiers, such as hydrogenated castor oil, fatty acid amides or swellable plastics.

[0272] In addition to the aminosilanes, the composition according to the invention may also contain additional tackifiers. Suitable tackifiers here are, for example, resins such as aliphatic or petrochemical resins and modified phenolic resins, and terpene oligomers. Such resins are used, for example, as tackifiers for pressure-sensitive adhesives and coatings. Terpene-phenolic resins are also suitable.

[0273] Preferably, the composition contains at least one stabilizer. All stabilizers that have previously been used in the preparation of similar compositions can be used as stabilizers. Examples of stabilizers are phosphorus compounds in all oxidation states. The stabilizer is particularly preferably a phosphorus compound such as a monoester of phosphoric acid, a diester of phosphoric acid or a phosphonic acid; octylphosphonic acid is particularly preferred.

[0274] The composition according to the invention can also be stabilized against the penetration of moisture by means of a desiccant in order to further increase the shelf life. All compounds which react with water to form groups which are inert towards the reactive groups present in the composition are suitable as desiccants. Suitable desiccants include isocyanates and silanes, such as vinylsilanes, for example 3 - vinylpropyltriethoxysilane, oximesilanes or urethane - based silanes. However, the use of methyl, ethyl or vinyltrimethoxysilane, tetramethyl or tetraethylethoxysilane is also possible. Vinyltrimethoxysilane and tetraethoxysilane are particularly preferred.

[0275] In a preferred embodiment of the invention, the components of the invention are mixed together, in particular in the form of a single - phase mixture.

[0276] The invention also relates to a process for preparing the composition according to the invention, in which components (a), (b) and (c) and optionally further components, in particular (d), are mixed together.

[0277] The invention also relates to the use of the composition according to the invention for preparing sealants, adhesives, coating agents, joining materials, encapsulating compounds, binders and / or paints.

[0278] The invention also relates to a silicone rubber compound which can be obtained by curing the composition according to the invention, preferably in the presence of water (for example water in the form of moisture). The silicone rubber compound which can be obtained can be a sealant, an adhesive, a coating agent, a joining material, an encapsulating compound or a binder, and it can be used in paints or for preparing paints.

[0279] The invention also relates to a process for preparing a silicone rubber compound by curing the composition according to the invention in the presence of water (for example water in the form of moisture).

[0280] It is to be understood that, without departing from the scope of the invention, the above - mentioned features and the features explained below can be used not only in the specified combinations, but also in other combinations or individually. The aforementioned advantages of the combination of features or multiple features are merely exemplary and can act alternatively or cumulatively. The combination of features of different embodiments of the invention or the combination of features of different claims can deviate from the selected reference of the claims.

[0281] The following examples are used to further explain the invention, but the invention is not limited thereto. Examples

[0282] The mass change is determined according to DIN EN ISO 10563. The comparative examples are reference compositions based on commercially available sealants.

[0283] Example 1: DTC

[0284] Two-component sealant (RTC2):

[0285] Prepare the silicone rubber compound according to the following formula:

[0286] Component A:

[0287] 496 g of α,ω-hydroxy-terminated polydimethylsiloxane with a viscosity of 80,000 cSt (centistokes)

[0288] 372 g of chalk Socal U

[0289] 124 g of chalk BLH 3

[0290] Component B:

[0291] 61.3 g of polydimethylsiloxane with a viscosity of 100 cSt

[0292] 13.0 g of DTC

[0293] 5.3 g of hydrophilic highly dispersed silica

[0294] 14.2 g of adhesion promoter BDC (1-butyl-2,2-dimethoxy-1,2-azasilolane)

[0295] 0.6 g of catalyst dibutyltin dilaurate

[0296] Mix components A and B in a ratio of 10:1 and process immediately.

[0297] After exposure to air after application, the sealant has the following properties:

[0298] - Skinning time: 20 minutes

[0299] - Bonding time: 40 minutes

[0300] - Early exposure after 50 minutes

[0301] - Good notch resistance after 24 hours

[0302] - Shore hardness A of 22 after 4 days

[0303] - Complete cure after 4 days (9 mm layer thickness)

[0304] - Good adhesion to wood, painted wood, varnished wood, aluminum, powder-coated aluminum, glass, PVC, polyamide, steel, concrete, polyethylene, and Plexiglas

[0305] - The mass loss is 0.40% (according to DIN 10563)

[0306] Comparative Example 1 : Methyl-tris(2-pentanone oxime)silane / vinyl-tris(2-pentanone oxime)silane

[0307] One-component sealant (RTC1):

[0308] Prepare the silicone rubber compound according to the following formulation:

[0309] 530 g of α,ω-hydroxy terminated polydimethylsiloxane with a viscosity of 80,000 cSt

[0310] 312.8 g of polydimethylsiloxane with a viscosity of 100 cSt

[0311] 13.0 g of vinyl-tris(2-pentanone oxime)silane

[0312] 30.0 g of methyl-tris(2-pentanone oxime)silane

[0313] 105 g of hydrophilic highly dispersed silica

[0314] 8.0 g of adhesion promoter 5201 (a mixture of aminoethylaminopropyltrimethoxysilane and α,ω-hydroxy terminated polydimethylsiloxane)

[0315] 1.2 g of catalyst 271 (a mixture of dioctyltin oxide and tetrapropoxysilane)

[0316] After exposure to air after application, the sealant has the following properties:

[0317] - The skinning time is 9 minutes

[0318] - The tack time is 23 minutes

[0319] - Early exposure after 170 minutes

[0320] - Good notch resistance after 24 hours

[0321] - The Shore hardness A is 26 after 4 days

[0322] - Complete curing after 5 days (9 mm layer thickness)

[0323] - Good adhesion to glass, wood, painted wood, varnished wood, aluminum, PVC, polyamide, steel, concrete

[0324] - The mass loss is 3.8% (according to DIN 10563)

[0325] Comparative Example 2 : Methyl-tris(2-pentanone oxime) silane / Vinyl-tris(2-pentanone oxime) silane

[0326] Two-component sealant (RTC2):

[0327] Prepare the silicone rubber compound according to the following formulation:

[0328] Component A:

[0329] 361 g of α,ω-hydroxy terminated polydimethylsiloxane with a viscosity of 80,000 cSt

[0330] 225 g of polydimethylsiloxane with a viscosity of 100 cSt

[0331] 150 g of chalk Socal U

[0332] 150 g of chalk BLH 3

[0333] 63 g of hydrophilic highly dispersed silica

[0334] Component B:

[0335] 39.2 g of polydimethylsiloxane with a viscosity of 100 cSt

[0336] 31.0 g of methyl-tris(2-pentanone oxime) silane

[0337] 8.0 g of vinyl-tris(2-pentanone oxime) silane

[0338] 10.0 g of hydrophilic highly dispersed silica

[0339] 8.0 g of adhesion promoter 5201

[0340] 0.8 g of catalyst 271 (a mixture of dioctyltin oxide and tetrapropoxysilane)

[0341] Mix Component A and B in a ratio of 10:1 (by weight) and process immediately.

[0342] After exposure to air after application, the sealant has the following properties:

[0343] - Skinning time: 7 minutes

[0344] - Bonding time: 70 minutes

[0345] - Early exposure after 100 minutes

[0346] - Good notch resistance after 24 hours

[0347] - Shore hardness A: 20 after 4 days

[0348] - Completely cured after 2 days (9 mm layer thickness)

[0349] - Good adhesion to glass, wood, painted wood, varnished wood, aluminum, PVC, polyamide, steel, concrete and in some cases Plexiglas

[0350] - Mass loss of 4.05% (according to DIN 10563)

[0351] The above examples show that compared with known silicone rubber compounds, the mass loss is significantly reduced (0.40 wt% in Example 1 compared to 3.8 wt% to 4 wt% for conventional silicone rubber compounds). In addition, the adhesion to polyethylene and Plexiglas is improved.

Claims

1. A composition, which can be obtained by mixing the following components: (a) A crosslinking agent or a mixture of crosslinking agents, which can be obtained by the reaction of (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p SiK p , wherein Each X independently represents O, NR b , S or PR b , Each R b independently represents H, a trialkylsilyl group, or a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, Each Y independently represents a C-C bond, CR c 2, O, NR e or PR e , where Each R c independently represents H or a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, Each R e independently represents H or a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, Each K independently represents Cl, OR d or ON=CR g 2, Each R d independently represents a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, Each R g independently represents H or a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, Each o is independently an integer from 1 to 8, and p = 2 or 3, (b) a metal catalyst, and (c) an aminosilane.

2. The composition according to claim 1, wherein Each o is independently an integer from 1 to 3, and / or R b =H, a trialkylsilyl group, or CH3, and / or R c =H and / or p = 3.

3. The composition according to claim 1 or 2, characterized in that, Each R d independently represents methyl, ethyl, n-propyl, isopropyl, isobutyl, octyl, isooctyl, vinyl or phenyl.

4. The composition according to any one of claims 1 to 3, characterized in that, Each X independently represents O or NR b .

5. The composition according to any one of claims 1 to 4, characterized in that, Y = N(CR c 2) o XH, where R c 、o and X are as defined above, preferably characterized in that, R c = H, o = 2 or 3, and / or X = O or NR b .

6. The composition according to any one of claims 1 to 5, characterized in that (HX(CR c 2) o Y(CR c 2) o X(CR c 2) o ) 4-p SiK p is (CH3O)3Si(CH2)3NH(CH2)2NH(CH2)2NH2.

7. The composition according to any one of claims 1 to 6, characterized in that, The metal in the metal catalyst is selected from the group consisting of: Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Ca, Sn, and Bi, preferably selected from the group consisting of Ti, Zr, Zn, Ca, Sn, and Bi.

8. The composition according to any one of claims 1 to 7, characterized in that, The composition can be obtained by further mixing with the following components: (d) Polyorganosiloxane of the formula HO-(SiR q R r O) s -H, wherein Each R q and R r independently represent a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, and s is an integer from 5 to 5000.

9. The composition according to claim 8, wherein Each R q and R r independently represent Optionally substituted alkyl, alkenyl, or alkynyl residues; Optionally substituted cycloaliphatic residues, aryl residues, or aralkyl residues; or Optionally substituted heterocycloaliphatic residues or heteroaryl residues each having 1 to 16 carbon atoms.

10. A composition, which comprises: (a) At least one crosslinking agent of the formula (X(CR c 2) o Z(CR c 2) o Z(CR c 2) o )Si, wherein Each Z independently represents N, P, N(CR c 2) o X or P(CR c 2) o X And X, R c and o are as defined above, (b) at least one metal catalyst, and (c) at least one aminosilane.

11. The composition according to claim 10, wherein The crosslinking agent includes .

12. The composition according to claim 10 or 11, characterized in that, The composition further comprises: (d) Polyorganosiloxane of the formula HO-(SiR q R r O) s -H, wherein Each R q and R r independently represent a saturated or unsaturated, optionally substituted hydrocarbon residue having 1 to 16 carbon atoms, and s is an integer from 5 to 5000.

13. The composition according to claim 12, wherein Each R q and R r independently represent Optionally substituted alkyl, alkenyl, or alkynyl residues; Optionally substituted cycloaliphatic residues, aryl residues, or aralkyl residues; or Optionally substituted heterocycloaliphatic residues or heteroaryl residues each having 1 to 16 carbon atoms.

14. Use of the composition according to any one of claims 1 to 13 for preparing a sealant, glue, coating agent, joining material, encapsulating compound, adhesive, or paint.

15. A cured silicone rubber compound, which can be obtained by curing the composition according to any one of claims 8 - 9 or 12 - 13, preferably in the presence of moisture.

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