Silanes and curable compositions containing the same

Abstract

The present invention relates to novel silanes of formula Si (R1) m (R2) 4-m, wherein each R1 independently represents a substituted or unsubstituted alkyl, alkenyl or alkynyl group; a substituted or unsubstituted alicyclic or aryl group; a substituted or unsubstituted heteroalicyclic or heteroaryl group; each R2 independently represents a group of the general formula-O-CHR3-C (= O)-O-R4 wherein R3 independently represents: a substituted or unsubstituted alkenyl group, preferably vinyl or allyl group; r4 represents a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group or a heteroaryl group; and m independently represents 0 or 1, preferably 1. The invention also relates to a curable composition containing said silane and a curable polyorganosiloxane terminated with such a silane. The silane acts as a cross-linking agent in the curable composition and is particularly notably available from renewable resources, providing high overall performance.

Description

[0001] The present invention relates to novel silanes containing at least one specific α-hydroxycarboxylate group and curable compositions containing the silanes and polyorganosiloxanes. The silane acts as an end-capping agent and a cross-linking agent in the curable composition and is particularly noteworthy for being obtainable from renewable resources. In addition, it provides improved properties compared to existing silane cross-linking compounds (such as those based on lactates).

[0002] Silicone polymers (polyorganosiloxanes), particularly polydialkylsiloxanes, such as polydimethylsiloxane (PDMS), are of great significance in the production of adhesives, sealing materials, coatings and insulating materials. Among these, those that are vulcanized at low temperatures and ambient conditions occupy a large market share. Typical formulations contain reactive polyorganosiloxanes, typically silanol-terminated polyorganosiloxanes, wherein the polyorganosiloxane has at least one, preferably two hydroxyl groups bonded to silicon atoms. The polymer is used in combination with a silane-based crosslinking agent, which has a hydrolyzable group bonded to silicon atoms. The term curing agent is sometimes used to replace the crosslinking agent. In the context of the present application, the terms crosslinking agent and curing agent are synonymous. Polyorganosiloxane and crosslinking agent can exist as separate components. However, polyorganosiloxanes are usually selectively reacted with crosslinking agents to form modified polyorganosiloxanes, and then the modified polyorganosiloxanes are added to the remainder of the curable composition. In this context, the term end-capping is also used to describe the process of reacting the polyorganosiloxane with a crosslinker. This can optionally be carried out in the presence of a catalyst, which selectively mediates the end-capping without simultaneously curing the polyorganosiloxane.

[0003] Many crosslinking agents for silicone systems are known. Based on the leaving group released during hydrolysis, these can be divided into acidic, basic and neutral crosslinking agents. Typical acidic crosslinking agents contain acid groups as hydrolyzable groups and release corresponding acids, such as acetic acid, during crosslinking. Typical basic crosslinking agents release amines during crosslinking. In both cases, aggressive compounds are released during crosslinking, which can corrode or decompose metals, stones or mortars, for example, and also have a strong, usually unpleasant odor. Therefore, neutral crosslinking agents are often used in modern curable silicone compositions. Typical representatives of neutral crosslinking agents have hydrolyzable groups that release alcohols or oximes during crosslinking. However, alkoxy systems have the following disadvantages: multiple problems occur in the case of storage stability of the relevant curable compositions, and the cured product only shows poor adhesion to some materials. Oximosilane crosslinking agents, which are accompanied by the release of alkanooximes during hydrolysis, do not usually have these disadvantages and are therefore widely used. The most common representatives of oxime-based silane crosslinkers release butan-2-one oxime during crosslinking. This is suspected to cause cancer, so alternative neutral crosslinkers are urgently needed. In addition to this, the released oxime has a strong malodor and is considered unpleasant to use with curable compositions containing the relevant crosslinkers.

[0004] Silane compounds which release α-hydroxycarboxylates or α-hydroxycarboxylic acid amides (particularly based on lactic acid and lactic acid amide) during crosslinking have been proposed as alternative crosslinking agents. From EP 2 030 976 A1, hardeners for silicone rubber materials are known which have three 2-hydroxypropionate alkyl ester groups, i.e. lactate alkyl ester groups, in particular vinyl tris(ethyl lactyl)silane. EP 2 774 672 A1 describes special catalysts for crosslinking silicone rubber materials with crosslinking agents based on silane compounds with lactate groups. Other crosslinking agent compounds are disclosed in EP 2 030 976 A1, EP 3271421A1, EP 3271367A1 and EP 3613803A1.

[0005] Although many crosslinking silanes have been described, there is a need in the art for alternative crosslinking silanes that are at least partially obtainable from renewable sources without compromising stability and cure properties and, optimally, that exhibit improved technical properties.

[0006] It was therefore an object of the present invention to provide novel silane compounds which can be used as neutral crosslinkers in curable compositions based on polyorganosiloxanes, which are obtainable at least partly from renewable sources and which have superior properties compared to existing crosslinking silanes.

[0007] The present invention achieves this object by providing the silane compounds according to the invention which have at least one specific α-hydroxycarboxylate group derived from a modified glycolic acid ester.

[0008] Thus, in a first aspect, the present invention relates to silanes of formula (1),

[0009] Si(R 1 ) m (R 2 ) 4-m (1)

[0010] in

[0011] R 1 express:

[0012] substituted or unsubstituted alkyl, alkenyl or alkynyl;

[0013] a substituted or unsubstituted alicyclic group or aromatic group;

[0014] a substituted or unsubstituted heteroalicyclic group or heteroaryl group;

[0015] Each R 2 Independently represents a group of the general formula (2):

[0016] -O-CHR 3 -C(=O)-OR 4 (2)

[0017] in

[0018] R 3 express:

[0019] a substituted or unsubstituted alkenyl group, preferably a vinyl group or an allyl group;

[0020] R 4 express:

[0021] substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl or heteroaryl; and

[0022] m is independently 0 or 1, preferably 1,

[0023] The present invention also relates in another aspect to a curable composition containing at least one polyorganosiloxane (A) and at least one silane (B) according to the present invention, wherein the polyorganosiloxane has at least one hydroxyl group bonded to a silicon atom. Optionally, the composition further comprises a blocking catalyst (C) and / or a curing catalyst (D).

[0024] In yet another aspect, the present invention relates to a capped curable polyorganosiloxane obtained by reacting the crosslinking silane disclosed herein with at least one polyorganosiloxane. Such a polyorganosiloxane contains at least one terminal group of formula (3):

[0025] -A-Si(R 1 ) m (R 2 ) 3-m (3)

[0026] in:

[0027] A is a bond, -O- or a linear, branched or cyclic divalent group, the divalent group being selected from a hydrocarbon residue having 1 to 12 carbon atoms, an alkylene group, an arylene group, an oxyalkylene group, an oxyarylene group, a siloxane-alkylene group, a siloxane-arylene group, an ester, an amine, a diol, an imide, an amide, an alcohol, a carbonate, a carbamate, a urea, a sulfide, an ether or a derivative or combination thereof;

[0028] R 1 express:

[0029] substituted or unsubstituted alkyl, alkenyl or alkynyl;

[0030] a substituted or unsubstituted alicyclic group or aromatic group;

[0031] a substituted or unsubstituted heteroalicyclic group or heteroaryl group;

[0032] Each R 2 Independently represents a group of the general formula (2):

[0033] -O-CHR 3 -C(=O)-OR 4 (2)

[0034] in

[0035] R 3 express:

[0036] a substituted or unsubstituted alkenyl group, preferably a vinyl group or an allyl group;

[0037] R 4 express:

[0038] substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl or heteroaryl; and

[0039] m is independently 0 or 1, preferably 1;

[0040] wherein the polyorganosiloxane is obtained by reacting a polyorganosiloxane (Ia) having at least one reactive group / atom A' bonded to a silicon atom, preferably at least one hydroxyl group, with a silane of formula (1), wherein any R 2 reacting with A' to form a linking group A;

[0041] The reaction is optionally carried out in the presence of a (blocked) catalyst for the reaction.

[0042] A "curable composition" is understood to be a substance or a mixture of substances which can be cured by physical or chemical measures. In this respect, these chemical or physical measures can be, for example, the provision of energy in the form of heat, light or other electromagnetic radiation, but also simple contact with ambient moisture, water or reactive components. The composition is thereby brought from its initial state into a state with a higher hardness.

[0043] Whenever the molecular weight of an oligomer or polymer is mentioned in this application, this value refers to the weight average value, i.e. the Mw value, and not the arithmetic mean value, unless otherwise stated. The molecular weight is determined according to DIN 55672-1:2007-08 by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as eluent, preferably at 35° C. The molecular weight of the monomeric compounds is calculated based on the corresponding molecular formula and the known molecular weights of the individual atoms.

[0044] As used herein, "at least one" means one or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the term relates to the type of ingredient and not to the absolute number of molecules. Thus, "at least one polymer" means, for example, at least one type of polymer, i.e. one type of polymer or a mixture of many different polymers can be used. Together with weight data, the term refers to all compounds of a given type contained in the composition / mixture, i.e. the composition does not contain other compounds of this type exceeding the given amount of the relevant compound.

[0045] Unless expressly stated otherwise, all percentage details provided in connection with the compositions described herein refer to % by weight, based in each case on the relevant mixture.

[0046] As used herein, "alkyl" refers to saturated aliphatic hydrocarbons, including straight and branched groups. Alkyl preferably has 1-10 carbon atoms (if a numerical range is given in this article, such as "1-10", this means that the group, in this case alkyl, can have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to 10 carbon atoms and including 10 carbon atoms). In particular, alkyl can be a medium alkyl with 5-6 carbon atoms, or a low alkyl with 1-4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. Alkyl can be substituted or unsubstituted. As used in this regard, "substituted" means that one or more carbon atoms and / or (one or more) hydrogen atoms of alkyl are replaced by heteroatoms or functional groups. Wherein one or more carbon atoms are replaced by heteroatoms (particularly selected from O, S, N and Si) and the heteroalkyl is obtained by replacing one or more carbon atoms with heteroatoms. Examples of such heteroalkyl groups are, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentyloxypropyl, ethylaminoethyl, trimethoxypropylsilyl, etc. The functional groups that can replace hydrogen atoms are particularly selected from =O, =S, -OH, -SH, -NH2, -NO2, -CN, -F, -Cl, -Br, -I, -OCN, -NCO, C 3-8 Cycloalkyl, C 6-14 Aryl, 5-10 membered heteroaryl rings (wherein 1-4 ring atoms are independently nitrogen, oxygen or sulfur) and 5-10 membered heteroalicyclic rings (wherein 1-3 ring atoms are independently nitrogen, oxygen or sulfur).

[0047] As used herein, "alkenyl" refers to an alkyl group as defined herein consisting of at least two carbon atoms and containing at least one carbon-carbon double bond, for example vinyl, propenyl, butenyl or pentenyl and their structural isomers such as 1-propenyl or 2-propenyl; 1-butenyl, 2-butenyl or 3-butenyl, etc. Alkenyl preferably has 2-10 carbon atoms, such as 2-6 or 2, 3, 4 carbon atoms. Alkenyl groups may be substituted or unsubstituted. If they are substituted, the substituents are as defined above for alkyl.

[0048] As used herein, "alkynyl" refers to an alkyl group as defined herein consisting of at least two carbon atoms and containing at least one carbon-carbon triple bond, such as ethynyl (acetylene), propynyl, butynyl or pentynyl and their structural isomers as described above. Alkynyl groups may be substituted or unsubstituted. If they are substituted, the substituents are as defined above for alkyl groups.

[0049] As used herein, "alicyclic group" or "cycloalkyl" refers to a monocyclic or polycyclic group (multiple rings with common carbon atoms), in particular a monocyclic or polycyclic group of 3-8 carbon atoms, wherein the ring does not have a completely conjugated π electron system, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Cycloalkyl can be substituted or unsubstituted. As used in this regard, "substituted" means that one or more hydrogen atoms of the cycloalkyl are replaced by a functional group. The functional group that can replace the hydrogen atom is particularly selected from =O, =S, -OH, -SH, -NH2, -NO2, -CN, -F, -Cl, -Br, -I, -OCN, -NCO, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-8 Cycloalkyl, C 6-14 Aryl, 5-10 membered heteroaryl rings (wherein 1-4 ring atoms are independently nitrogen, oxygen or sulfur) and 5-10 membered heteroalicyclic rings (wherein 1-3 ring atoms are independently nitrogen, oxygen or sulfur).

[0050] As used herein, "aryl" refers to a monocyclic or polycyclic group (i.e., rings having common adjacent carbon atoms), in particular a monocyclic or polycyclic group of 6-14 carbon ring atoms having a completely conjugated π-electron system. Examples of aryl groups are phenyl, naphthyl and anthracenyl. Aryl groups may be substituted or unsubstituted. If they are substituted, the substituents are as defined above for cycloalkyl.

[0051] As used herein, "heteroaryl" refers to a monocyclic or polycyclic (i.e., rings that share adjacent pairs of ring atoms) aromatic ring having, in particular, 5-10 ring atoms, of which one, two, three or four are nitrogen, oxygen or sulfur and the remaining ring atoms are carbon. Examples of heteroaryl are pyridyl, pyrrolyl, furanyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-triazinyl, 1,2,3-triazinyl, benzofuranyl, isobenzofuranyl, benzo Thienyl, benzotriazolyl, isobenzothienyl, indolyl, isoindolyl, 3H-indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolizinyl, quinazolinyl, phthalazinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, quinolyl, isoquinolyl, tetrazolyl, 5,6,7,8-tetrahydroquinolyl, 5,6,7,8-tetrahydroisoquinolyl, purinyl, pteridinyl, pyridinyl, pyrimidinyl, carbazolyl, xanthenyl or benzoquinolyl. Heteroaryl may be substituted or unsubstituted. If they are substituted, the substituents are as defined above for cycloalkyl.

[0052] As used herein, "heteroalicyclic" or "heterocycloalkyl" refers to a monocyclic or fused ring having 5-10 ring atoms, containing one, two or three heteroatoms selected from N, O and S, wherein the remaining ring atoms are carbon. "Heterocycloalkenyl" groups additionally contain one or more double bonds. However, the ring does not have a completely conjugated π electron system. Examples of heteroalicyclic groups are pyrrolidone, piperidine, piperazine, morpholine, imidazoline, tetrahydropyridazine, tetrahydrofuran, thiomorpholine, tetrahydropyridine, etc. Heterocycloalkyl groups may be substituted or unsubstituted. If they are substituted, the substituents are as defined above for cycloalkyl.

[0053] The silane of the present invention is a silane of formula (1):

[0054] Si(R 1 ) m (R 2 ) 4-m (1).

[0055] In this case, each R 1 and independently represent a substituted or unsubstituted alkyl, alkenyl or alkynyl group; a substituted or unsubstituted alicyclic or aryl group; or a substituted or unsubstituted heteroalicyclic or heteroaryl group.

[0056] In various embodiments, each R 1 Independently of one another, represent an alkyl group having 1 to 10 carbon atoms, preferably having 1 to 4 carbon atoms, in particular methyl, ethyl, propyl or isopropyl, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, in particular vinyl or allyl, or an aryl group having 6 to 10 carbon atoms, in particular phenyl.

[0057] In various preferred embodiments, R1 independently of one another represents methyl, vinyl or phenyl, very particularly preferably represents methyl or vinyl, most preferably represents vinyl.

[0058] In formula (1), each R 2 independently represent groups of the general formula (2):

[0059] -O-CHR 3 -C(=O)-OR 4 (2)

[0060] in

[0061] R 3 represents a substituted or unsubstituted alkenyl group, preferably a vinyl group or an allyl group;

[0062] R 4 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, heterocyclic group or heteroaryl group.

[0063] In various embodiments, each R 2 independently represent a group of formula (2) in which R 3 represents a vinyl group or an allyl group, preferably a vinyl group, and R 4 It represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0064] In a preferred embodiment, each R 2 independently represent a group of formula (2) in which R 3 stands for vinyl, and R 4 It is methyl or ethyl, preferably methyl.

[0065] In various embodiments, all R 2 The groups are the same.

[0066] In formula (1), m may be 0 or 1, but is preferably 1.

[0067] Particularly suitable silanes of the formula (1) are those derived from methyl vinyl glycolate (methyl vinyl glycolate).

[0068] Another aspect of the present invention relates to a curable composition comprising at least one polyorganosiloxane (A) and at least one silane (B) of formula (1). The composition may further comprise a (blocked) catalyst (C) catalyzing the reaction between the polyorganosiloxane and the silane of formula (1) and a curing catalyst (D). When the amounts of the individual components (A) to (D) are given below, these amounts refer to the total amount of (A) to (D), unless otherwise expressly stated.

[0069] Based on the total weight of the curable composition or the total weight of polymer (A), cross-linked silane (B) and optionally present catalyst (C) and (D), such curable composition may contain 1-15% by weight, particularly preferably 3-10% by weight of the silane (B) of the present invention. If a mixture of silanes of formula (1) is used, the amount refers to the total amount of silanes of formula (1) in the composition. The amount given for components (A), (B), (C) and (D) relates to the total weight of the curable composition or the combined weight of components (A)-(D). In some cases where the curable composition includes a significant amount of additives (such as fillers), the amount given herein may also refer to the total weight of components (A)-(D), i.e., without additives. However, if not otherwise specified, the amount may also refer to the total weight of the composition including all additives, etc.

[0070] At least one polyorganosiloxane (A) may be a polyorganosiloxane having at least one hydroxyl group bonded to a silicon atom. Preferably, the polyorganosiloxane has at least two hydroxyl groups bonded to a silicon atom. Furthermore, it may be preferred that one or more hydroxyl groups are bonded to a terminal silicon atom. If the polyorganosiloxane is branched, it preferably has a hydroxyl group at each end.

[0071] In such embodiments, at least one hydrogen atom or hydroxyl group is allowed to react / end-cap with the silane of formula (1). In the case of hydroxyl groups, the silane of formula (1) can react with the polyorganosiloxane in a condensation reaction.

[0072] The at least one polyorganosiloxane (A) is preferably a polydiorganosiloxane, more preferably a polydimethylsiloxane.

[0073] In various embodiments, α,ω-dihydroxy-terminated polydiorganosiloxane, preferably α,ω-dihydroxy-terminated polydimethylsiloxane is used as the polyorganosiloxane. Particularly preferred is α,ω-dihydroxy-terminated polydimethylsiloxane having a kinematic viscosity of 5000 to 120,000 cSt, particularly 10,000 to 100,000 cSt, particularly preferably 15,000 to 90,000 cSt at 25°C.

[0074] In various embodiments, the curable composition contains at least one polyorganosiloxane in an amount of 30-95 wt. %, for example 40-95 wt. %, 40-90 wt. %, 40-80 wt. %, 40-70 wt. %, 50-95 wt. %, 60-95 wt. %, 70-95 wt. % or 70-90 wt. %, based on the total weight of the composition or the sum of components (A) to (D) as detailed above. If a mixture of polyorganosiloxanes is used, the amounts given relate to the total amount of polyorganosiloxane in the composition.

[0075] The curable composition may contain polyorganosiloxane and silane of formula (1) as separate components. However, it is also possible that these components exist in the form of prepolymers. Prepolymers are the reaction products of two components. Suitable reactions are known and are also referred to as end-capping. This can optionally be carried out in the presence of a catalyst (C), wherein the catalyst selectively mediates the end-capping without curing the polyorganosiloxane at the same time. Suitable catalysts are, for example, acids, organolithium compounds (as they are described in, for example, EP0 564 253 A1), amines, inorganic oxides, potassium acetate, organic titanium derivatives, titanium / amine combinations, and carboxylic acid / amine combinations. In various embodiments, the end-capping catalyst (C) may be lithium hydroxide or aminosilane (for example, γ-aminopropyltrimethoxysilane) in an alcohol (for example, methanol).

[0076] The curable composition may therefore contain blocked catalyst (C) in an amount of generally 0.01 to 2% by weight, preferably 0.05 to 2% by weight, particularly preferably 0.1 to 0.5% by weight, based in each case on the total weight of the composition or on the total weight of components (A) to (D). If a mixture of catalysts is used, the amount given refers to the total amount of blocked catalyst in the composition.

[0077] If the polyorganosiloxane and the silane of the formula (1) are present as prepolymers, the above amounts of polyorganosiloxane and silane given individually are added to give the amount of end-capped polyorganosiloxane. The curable composition thus contains the prepolymer in an amount preferably of 31 to 99% by weight, particularly preferably of 43 to 80% by weight, based in each case on the total weight of (A) to (D) or on the total weight of the composition. If mixtures of prepolymers are used, the amount refers to the total amount of prepolymers in the composition.

[0078] Prepolymers or end-capped polymers also form an aspect of the present invention. These end-capped curable polyorganosiloxanes are obtainable by reacting a crosslinking silane of formula (1) disclosed herein with at least one polyorganosiloxane comprising at least one end group of formula (3):

[0079] -A-Si(R 1 ) m (R 2 ) 3-m (3)

[0080] in:

[0081] A is a bond, -O- or a linear, branched or cyclic divalent group, the divalent group being selected from a hydrocarbon residue having 1 to 12 carbon atoms, an alkylene group, an arylene group, an oxyalkylene group, an oxyarylene group, a siloxane-alkylene group, a siloxane-arylene group, an ester, an amine, a diol, an imide, an amide, an alcohol, a carbonate, a carbamate, a urea, a sulfide, an ether or a derivative or combination thereof;

[0082] R 1 express:

[0083] substituted or unsubstituted alkyl, alkenyl or alkynyl;

[0084] a substituted or unsubstituted alicyclic group or aromatic group;

[0085] a substituted or unsubstituted heteroalicyclic group or heteroaryl group;

[0086] Each R 2 Independently represents a group of the general formula (2):

[0087] -O-CHR 3 -C(=O)-OR 4 (2)

[0088] in

[0089] R 3 express:

[0090] a substituted or unsubstituted alkenyl group, preferably a vinyl group or an allyl group;

[0091] R 4 express:

[0092] substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl or heteroaryl; and

[0093] m is independently 0 or 1, preferably 1.

[0094] The polyorganosiloxane is obtained by reacting a polyorganosiloxane (Ia) having at least one reactive group / atom A' bonded to a silicon atom, preferably at least one hydroxyl group, such as the above-mentioned polyorganosiloxane (A), with a silane of formula (1) in which m is 1. In the reaction, any one of the radicals R 2 The reaction is optionally carried out in the presence of a (capping) catalyst for the reaction, in particular those described herein as component (C). In a specific example, A is -O-, m is 1, and R 1 and R 2 As defined above for the silanes of formula (1). To the extent applicable, all embodiments disclosed herein for the silanes of formula (1) apply analogously to these end-capped polyorganosiloxanes.

[0095] The present invention also relates to curable compositions comprising such blocked polyorganosiloxanes, optionally in combination with a blocking catalyst and / or a curing catalyst and any one or more of the other components disclosed below.

[0096] The composition of the invention crosslinks in the presence of moisture and cures with the formation of Si-O-Si bonds. The curing can be accelerated by adding a suitable curing catalyst.

[0097] Preferably, the curable composition therefore further comprises at least one curing catalyst (D), for example a tin compound.

[0098] Preferably, the tin compound is an organotin compound or an inorganic tin salt. The tin in these tin compounds is preferably divalent or tetravalent. Suitable inorganic tin salts are, for example, tin(II) chloride and tin(IV) chloride. However, organotin compounds (tin organyles) are preferably used as tin compounds. Suitable organotin compounds are, for example, 1,3-dicarbonyl compounds of divalent or tetravalent tin, for example acetylacetonates such as di(acetylacetonato)di(n-butyl)tin(IV), di(acetylacetonato)di(n-octyl)tin(IV), di(acetylacetonato)(n-octyl)(n-butyl)tin(IV); dialkyltin(IV) dicarboxylates, for example di-n-butyltin dilaurate, di-n-butyltin maleate, di-n-butyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin diacetate, or the corresponding dialkoxides, for example di-n-butyltin dimethoxide; tetravalent tin oxides, for example dialkyltin oxides, for example di-n-butyltin oxide and di-n-octyltin oxide; and tin(II) carboxylates such as tin(II) octoate or tin(II) phenoxide.

[0099] Also suitable are tin compounds of the following substances: ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate; for example di(methyl maleate)di(n-butyl)tin(IV), di(butyl maleate)di(n-butyl)tin(IV), di(methyl maleate)di(n-octyl)tin(IV), di(butyl maleate)di(n-octyl)tin(IV), Di(isooctyl maleate)di(n-octyl)tin(IV); and di(n-butyl)tin(IV) sulfide, (n-butyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2CH2COO), (n-octyl)2Sn(SCH2CH2COO), (n-octyl)2Sn(SCH2CH2COOCH2CH2OCOCH2S), (n-butyl)2-Sn(SCH2COO-i-C8H 17 )2、(n-octyl)2Sn(SCH2COO-i-C8H 17 )2 and (n-octyl)2Sn(SCH2COO-n-C8H 17 )2.

[0100] Preferably, the tin compound is selected from the group consisting of divalent or tetravalent tin 1,3-dicarbonyl compounds, dialkyltin(IV) dicarboxylates, dialkyltin(IV) dialkoxylates, dialkyltin(IV) oxides, tin(II) carboxylates and mixtures thereof.

[0101] Particularly preferably, the tin compound is a dialkyltin(IV) dicarboxylate, in particular di-n-butyltin dilaurate or di-n-octyltin dilaurate.

[0102] As an alternative to tin compounds, tin-free curing catalysts may be used.

[0103] Suitable tin-free curing catalysts are, for example, organometallic compounds of iron, for example 1,3-dicarbonyl compounds of iron, for example iron(III) acetylacetonate.

[0104] Boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide or mixtures of boron halides may also be used as curing catalysts. Preferred are boron trifluoride complexes, such as boron trifluoride diethyl etherate, which are liquids that are easier to handle than gaseous boron halides.

[0105] Furthermore, amines, nitrogen-containing heterocycles and guanidine derivatives are also generally suitable as curing catalysts. A known suitable catalyst from this group of compounds is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0106] In addition, titanium, aluminum and zirconium compounds or mixtures thereof can also be used as catalysts. On the one hand, the use of tin compounds can be avoided, and on the other hand, better adhesion to organic surfaces (such as acrylates) that usually adhere poorly can be achieved. Among titanium, aluminum and zirconium catalysts, titanium catalysts are preferred.

[0107] Suitable titanium catalysts are compounds having hydroxyl groups and / or substituted or unsubstituted alkoxy groups.

[0108] Thus, the group comprises titanium alkoxides of the following general formula:

[0109] Ti(OR z )4,

[0110] Where R z is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and the 4 alkoxy groups -OR z Same or different. In addition, -OR z One or more of the groups may be acyloxy-OCOR z Likewise suitable as titanium catalysts are titanium alkoxides in which one or more alkoxy groups are replaced by hydroxyl groups or halogen atoms.

[0111] In various other embodiments, titanium chelate complexes may be used.

[0112] Another alternative is an aluminum catalyst, such as an aluminum alkoxide of the formula:

[0113] Al(OR z )3,

[0114] Where R zAs defined above, i.e., it is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and the three R z In such aluminum alkoxides, one or more of the alkoxy groups may also be replaced by an acyloxy group -OC(O)R z Replacement.

[0115] Also suitable are aluminum alkoxides in which one or more alkoxy groups are replaced by hydroxyl groups or halogen atoms.

[0116] Among the aluminum catalysts, pure aluminum alkoxides are preferred in view of their stability to moisture and the curability of a mixture to which they are added. In addition, aluminum chelate complexes are preferred.

[0117] Suitable zirconium catalysts include, but are not limited to, tetramethoxyzirconium or tetraethoxyzirconium.

[0118] Other examples include zirconium bis(ethyl acetoacetate) diisopropoxide, zirconium (ethyl acetoacetate) triisopropoxide, and zirconium tris(ethyl acetoacetate) isopropoxide.

[0119] Also suitable are zirconium acylates, zirconium halide catalysts and zirconium chelate complexes.

[0120] In various other embodiments, metal carboxylates or mixtures of a number of such salts may be used as curing catalysts, wherein these are selected from carboxylates of metals selected from calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt and / or zirconium.

[0121] Among the carboxylates, carboxylates of calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese and zirconium are preferred because they show particularly high activity. Carboxylates of calcium, vanadium, iron, zinc, titanium and zirconium are particularly preferred. Carboxylates of iron and titanium are very particularly preferred.

[0122] The curable composition may contain a curing catalyst (D) in an amount of 0.01 to 2% by weight, preferably in an amount of 0.05 to 2% by weight, particularly preferably in an amount of 0.1 to 0.5% by weight, in each case based on the total weight of the curable composition or the total weight of components (A) to (D) of the composition. If a mixture of curing catalysts is used, the amount given refers to the total amount of curing catalyst in the composition.

[0123] In addition to the above-mentioned components, the curable composition may contain one or more components useful for affecting specific properties of the curable composition and / or the cured product.

[0124] These other components can be selected from, for example, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, desiccants, adhesion promoters, UV stabilizers, rheological additives and / or solvents. In this case, adhesion promoters, plasticizers, fillers and stabilizers, including antioxidants and UV stabilizers, are particularly important.

[0125] Preferably, the curable composition therefore contains at least one further component.

[0126] The curable composition of the invention may further comprise one or more adhesion promoters.An adhesion promoter is understood to be a substance which improves the adhesion properties of the adhesive layer on a surface.

[0127] Suitable are silane adhesion promoters having (additional) functional groups, in particular alkoxysilanes, such as amino, mercapto, epoxy, carboxyl, vinyl, isocyanate, isocyanurate or halogen. Examples are γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-acryloxypropylmethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, tris(trimethoxysilyl)isocyanurate and γ-chloropropyltrimethoxysilane.

[0128] In various embodiments, the adhesion promoter is selected from aminosilanes (amino-functional alkoxysilanes or aminoalkylalkoxysilanes), such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)-3-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, Silanes, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane, and oligomeric aminosilanes, for example aminoalkyl-modified alkylpolysiloxanes (Dynasylan 1146).

[0129] In various embodiments, the curable composition comprises one or more adhesion promoters in an amount of up to 20% by weight, predominantly in an amount of 0.05 to 4% by weight, preferably in an amount of 0.1 to 2% by weight, particularly preferably in an amount of 0.2 to 2% by weight, in each case based on the total weight of the composition (including all auxiliaries).

[0130] The viscosity of the curable composition can be reduced by using a reactive diluent.

[0131] Preferably, the reactive diluent has at least one functional group which reacts after application, for example with moisture or atmospheric oxygen. Examples of groups of this type are silyl groups, isocyanate groups, ethylenically unsaturated groups and polyunsaturated systems.

[0132] All compounds which can be mixed with the other components to cause a reduction in viscosity and which have at least one group which reacts with the polymer can be used as reactive diluents.

[0133] The viscosity of the reactive diluent is preferably less than 20,000 mPas, particularly preferably about 0.1 to 6000 mPas, very particularly preferably 1 to 1000 mPas (Brookfield RVT, 23° C., rotor 7, 10 rpm).

[0134] Suitable reactive diluents are, but are not limited to, polyalkylene glycols that react with isocyanatosilanes (e.g., Synalox 100-50B, DOW), carbamoylpropyltrimethoxysilane, alkyltrimethoxysilanes, alkyltriethoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane (XL10, Wacker), vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (IO Trimethoxy), isooctyltriethoxysilane (IO Trimethoxy). Triethoxy, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (XL63, Wacker), N-dimethoxy(methyl)silylmethyl-O-methylcarbamate (XL65, Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane and partial hydrolysis products of the compounds.

[0135] In addition, the following polymers from Kaneka Corp. can also be used as reactive diluents: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.

[0136] Also suitable are silane-modified polyethers obtainable, for example, from the reaction of isocyanatosilanes with Synalox-type products.

[0137] Also suitable are polymers which can be prepared from organic backbones by grafting with vinylsilanes or by reacting polyols, polyisocyanates and alkoxysilanes.

[0138] Preferably, the compounds used as reactive diluents in the context of the present invention have at least one alkoxysilyl group, with dialkoxysilyl and trialkoxysilyl groups being preferred.

[0139] Suitable polyisocyanates for preparing the reactive diluent are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate, bis(2-isocyanatoethyl)fumarate, and mixtures of two or more thereof, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2 ,4-hexahydrotolylene diisocyanate and 2,6-hexahydrotolylene diisocyanate, hexahydro-1,3-phenylene diisocyanate or hexahydro-1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4 - tolylene diisocyanate or 2,6-tolylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate (MDI) or their partially or fully hydrogenated cycloalkyl derivatives (for example fully hydrogenated MDI (H12-MDI)), alkyl-substituted diphenylmethane diisocyanates (for example mono-, di-, tri- or tetraalkyl diphenylmethane diisocyanates and their partially or fully hydrogenated cycloalkyl derivatives), 4,4'-diisocyanatophenylperfluoroethane , bis-isocyanatoethyl phthalate, 1-chloromethylphenyl-2,4-diisocyanate or 1-chloromethylphenyl-2,6-diisocyanate, 1-bromomethylphenyl-2,4-diisocyanate or 1-bromomethylphenyl-2,6-diisocyanate, 3,3-dichloromethyl ether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates (such as those obtainable by reacting 2 moles of diisocyanate with 1 mole of thiodiglycol or dihydroxydihexyl sulfide), diisocyanates and triisocyanates of dimerized and trimerized fatty acids, or mixtures of two or more of the above diisocyanates.

[0140] Trivalent or higher-valent isocyanates, such as are obtainable, for example, by oligomerization of diisocyanates, in particular by oligomerization of the above-mentioned isocyanates, can also be used as polyisocyanates. Examples of such trivalent and higher-valent polyisocyanates are triisocyanurates of HDI or IPDI or mixtures thereof or mixed triisocyanurates thereof, and polyphenylmethylene polyisocyanates obtainable by phosgenation of aniline-formaldehyde condensation products.

[0141] To reduce the viscosity of the curable composition, solvents and / or plasticizers may be used in addition to or instead of the reactive diluents.

[0142] Suitable solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters and ether esters.

[0143] In various embodiments, compositions disclosed herein may include hydrophilic plasticizers. These are used to improve moisture absorption, thereby improving reactivity at low temperatures. Suitable as plasticizers are, for example, esters of rosin acid, adipic acid esters, azelaic acid esters, benzoates, butyrates, acetates, esters of higher fatty acids with about 8 to about 44 carbon atoms, epoxidized fatty acids, fatty acid esters and fats, glycolates, phosphates, phthalates, straight or branched alcohols comprising 1-12 carbon atoms, propionates, sebacates, sulfonates, thiobutyrates, trimellitates, citrates and esters and polyvinyl acetates based on nitrocellulose, and mixtures of two or more thereof.

[0144] For example, from the group of phthalates, dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate or butylbenzyl phthalate are particularly suitable, and from the group of adipates, preference is given to dioctyl adipate, diisodecyl adipate, diisodecyl succinate, dibutyl caprate or butyl oleate.

[0145] Similarly, suitable plasticizers are monofunctional, linear or branched C 4-16 Pure or mixed ethers of alcohols, or mixtures of two or more different ethers of such alcohols, for example dioctyl ether.

[0146] Other suitable plasticizers include end-capped polyethylene glycols, such as polyethylene glycol or polypropylene glycol di-C 1-4 - Alkyl ethers, in particular the dimethyl ether or diethyl ether of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.

[0147] Preferred plasticizers include, but are not limited to, end-capped polyethylene glycols, such as polyethylene glycol or polypropylene glycol dialkyl ethers, wherein the alkyl group has up to four C atoms, in particular dimethyl ether and diethyl ether of diethylene glycol and dipropylene glycol. Also under less favorable application conditions (low humidity, low temperature), good curing is achieved, in particular with dimethyl diethylene glycol. For further details on plasticizers, reference is made to the relevant technical chemical literature.

[0148] Similarly suitable as plasticizers within the scope of the present invention are diurethanes, which can be prepared, for example, by reacting diols having OH end groups with monofunctional isocyanates, by selecting the stoichiometry so that essentially all free OH groups react. Optionally, excess isocyanate can then be removed from the reaction mixture, for example by distillation. Another method for preparing diurethanes consists of reacting monofunctional alcohols with diisocyanates, wherein, if possible, all NCO groups react.

[0149] Preferably, the curable composition comprises at least one plasticizer, in particular polydimethylsiloxane.

[0150] The curable composition may contain reactive diluents, solvents and / or plasticizers in an amount preferably of 1 to 50% by weight, preferably of 10 to 40% by weight, particularly preferably of 20 to 40% by weight, in each case based on the total weight of the composition. If mixtures of a plurality of reactive diluents, solvents and / or plasticizers are used, the amounts given refer to the total amount of reactive diluents, solvents and / or plasticizers in the composition.

[0151] The curable composition may contain a stabilizer selected from antioxidants, UV stabilizers and desiccants.

[0152] All customary antioxidants can be used as antioxidants. They are preferably present in the composition in an amount of up to about 7% by weight, in particular up to about 5% by weight.

[0153] The composition may also contain UV stabilizers, which are preferably used in an amount of up to about 2% by weight, preferably about 1% by weight. So-called hindered amine light stabilizers (HALS) are particularly suitable as UV stabilizers. In the context of the present invention, preference is given to using UV stabilizers which carry silyl groups and are incorporated into the end product during crosslinking or curing. In addition, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus and / or sulfur may also be added.

[0154] It is often useful to stabilize the composition with respect to penetrating moisture with the aid of a desiccant in order to further increase the storage properties (shelf life). All compounds which react with water and form groups which are inert towards the reactive groups present in the formulation are suitable in principle as desiccants and thus undergo the smallest possible change in their molecular weight. Furthermore, the reactivity of the desiccant towards the moisture penetrating into the formulation must be higher than the reactivity of the groups of the silyl-carrying polymers according to the invention present in the formulation.

[0155] Therefore, suitable as a desiccant is, for example, isocyanate. However, in various preferred embodiments, silanes are used as desiccant, for example, vinyl silanes such as 3-vinylpropyltriethoxysilane, oxime silanes such as methyl-O,O',O"-butyl-2-ketone trioxime silane or O,O',O",O"'-butyl-2-ketone tetraoxime silane (CAS No. 022984-54-9 and 034206-40-1), or benzamido silanes such as bis(N-methylbenzamido)methylethoxysilane (CAS No. 16230-35-6), or carbamate silanes such as carbamate methyltrimethoxysilane. It is also possible to use methyltrimethoxysilane, ethyltrimethoxysilane or vinyltrimethoxysilane, tetramethylethoxysilane or tetraethylethoxysilane. In terms of cost and efficiency, vinyltrimethoxysilane and tetraethoxysilane are particularly preferred.

[0156] Likewise suitable as drying agents are the reactive diluents mentioned above, provided that they have a molecular weight (M) of less than about 5000 g / mol. n ) and have end groups whose reactivity towards penetrating moisture is at least as high as the reactivity of the reactive groups of the polymers used according to the invention, preferably higher than the reactivity of the reactive groups of the polymers used according to the invention.

[0157] Finally, alkyl orthoformates or orthoacetates can also be used as drying agents, for example methyl or ethyl orthoformate or methyl or ethyl orthoacetate.

[0158] The compositions generally contain from about 0 to about 6 weight percent of a desiccant.

[0159] The compositions described herein may contain fillers. Suitable fillers include, but are not limited to, chalk, lime powder, precipitated and / or pyrolytic silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, aluminum oxide, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals as well as carbon black and graphite. Organic fillers may also be used, including but not limited to wood fiber, wood powder, sawdust, cellulose, cotton, paper pulp, cotton, wood chips, chopped straw and husks. In addition, short fibers such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers or polyethylene fibers may also be added. Aluminum powder is also suitable as a filler.

[0160] The pyrogenic and / or precipitated silica advantageously has a particle size of 10-90 m 2 When used, they do not cause any additional increase in the viscosity of the composition of the present invention, but contribute to strengthening the cured composition.

[0161] It is likewise conceivable to use materials having a higher BET surface area, advantageously 100-250 m 2 / g, especially 110-170m 2 / g of pyrogenic and / or precipitated silica as filler. Due to the higher BET surface area, the same effect, such as strengthening of cured formulations, can be achieved with a smaller weight proportion of silica. Therefore, other substances can be used to improve the compositions described herein with respect to other requirements.

[0162] Further suitable as fillers are hollow spheres with a mineral shell or a plastic shell. These can be, for example, hollow glass spheres, which are available under the trade name Glass Commercially available. For example, EP 0 520 426 B1 describes hollow spheres based on plastics, such as or They are composed of an inorganic or organic substance and each has a diameter of 1 mm or less, preferably 500 μm or less.

[0163] Fillers which impart thixotropy to the formulation are preferred for many applications. Such fillers are also described as rheological aids, for example hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC. In order to be easily extruded from a suitable dispensing device (e.g. a tube), such formulations have a viscosity of 3000-15,000 mPas, preferably 40,000-80,000 mPas, or even 50,000-60,000 mPas at 20°C.

[0164] The filler is preferably used in an amount of 1-80% by weight, particularly preferably 2-50% by weight or 2-30% by weight or 2-25% by weight or 5-20% by weight, in each case based on the total weight of the composition. Of course, mixtures of several fillers can also be used. In this case, the amounts given refer to the total amount of filler in the composition.

[0165] The preparation of the curable composition can be carried out by simply mixing the polyorganosiloxane having at least one hydroxyl group bonded to a silicon atom, the silane of formula (1) and the optionally present further ingredients. This can be carried out in a suitable dispersing unit, for example a high-speed mixer. In this case, preferably, care is taken that the mixture is not brought into contact with moisture as far as possible, which could lead to undesirable premature curing. Suitable measures are sufficiently known and include, for example, working in an inert atmosphere, possibly under a protective gas, and drying / heating the individual components before adding them.

[0166] A preferred production process comprises mixing in a first step a polyorganosiloxane having at least one hydroxyl group bonded to a silicon atom and a silane of formula (1), wherein this can be carried out in the presence of at least an aminosilane or lithium hydroxide in an alcohol (e.g. methanol) and at least one plasticizer, in a second step optionally adding further ingredients except the curing catalyst and mixing all ingredients, and in a third step finally adding the curing catalyst and mixing it with the other components.

[0167] The present invention further relates to the use of the composition of the present invention as an adhesive or sealing material or coating material.

[0168] The compositions or preparations according to the invention can therefore be used as adhesives, sealants, coatings and for the production of moulded parts.

[0169] The compositions and formulations disclosed herein are generally suitable for bonding a variety of materials, such as plastics, metals, glass, ceramics, wood, wood-based materials, paper, paper-based materials, rubber and textiles, for gluing floors, and generally for sealing building elements, windows, wall and floor coverings, and joints.

[0170] The following examples are provided to illustrate the present invention, but the present invention is not limited thereto. Example

[0171] Embodiment 1:

[0172] The following compositions were prepared, wherein Ref1 and Ref2 are reference compositions, and Ex1 is a composition according to the present invention.

[0173] Table 1 (All amounts are in % by weight relative to the total weight)

[0174]

[0175] *Silane of formula (1) wherein m=1, R1=vinyl, R3=vinyl and R4=methyl

[0176] All three compositions were tested for SOT and TFT as follows:

[0177] SOT: The above compositions were homogenized and applied to a frame (50×130×2 mm). Each mixture was evenly distributed so that the frame could be completely filled. A thin polymer film was thus obtained. The time for forming a skin (skinning time / SOT) of these compositions was determined using a tool (150×5 mm) with a round scraper at the tip. The tip of the scraper was gently brought into contact with the surface of the polymer film and carefully removed every 1 to 5 minutes. Once no residue of the formulation remained on the scraper when the scraper was removed from the surface of the polymer film, the SOT was measured. The resulting line must then be removed from the scraper without residue. The polymer film returns to its original shape. When checking the SOT, a different part of the polymer film surface must be used each time. The test was carried out at room temperature (20°C).

[0178] TFT: To determine the surface tack of the adhesive sealing material, the above composition was homogenized and applied to a frame (50×130×2 mm) in the same manner as the SOT determination. After 60 minutes, the tack of the surface was evaluated by carefully contacting the surface of the polymer film using a tool (150×5 mm) with a round scraper at the tip, and a TFT of "<60 minutes" indicated "non-sticky", and a TFT of ">60 minutes" indicated "sticky (including slightly sticky)".

[0179] The Shore A hardness was determined as described in DIN EN ISO 868:2003.

[0180] The results are shown in Table 2.

[0181] Table 2: Properties of the compositions

[0182] Ref1 Ref2 Ex1 Skin formation time (min) 38 50 15 Surface drying time (min) 270 180 60 Xiao A 1 day 20 19 20 Xiao A 7 days 22 19 20

[0183] The results show that the SOT and TFT of the compositions of the present invention are significantly shorter relative to the prior art compositions Ref1 and Ref2 using known silane crosslinkers. The Shore A hardness is comparable between all tested compositions.

Claims

1. A silane of formula (1), Si(R 1 ) m (R 2 ) 4-m (1) in Each R 1 Independently represents: substituted or unsubstituted alkyl, alkenyl or alkynyl; a substituted or unsubstituted alicyclic group or aromatic group; a substituted or unsubstituted heteroalicyclic group or heteroaryl group; Each R 2 Independently represents a group of the general formula (2): -O-CHR 3 -C(=O)-O-R 4 (2) in R 3 Independently represents: a substituted or unsubstituted alkenyl group, preferably a vinyl group or an allyl group; R 4 represent: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl or heteroaryl; and m independently represents 0 or 1, preferably 1.

2. The silane according to claim 1, characterized in that Each R 1 Independently of one another represent alkyl having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl or isopropyl, or represent alkenyl having 2 to 10 carbon atoms, in particular vinyl or allyl.

3. The silane according to any one of claims 1 to 2, characterized in that Each R 2 independently represent a group of formula (2) in which R 3 represents an unsubstituted alkenyl group having 2 to 4 carbon atoms, in particular vinyl.

4. The silane according to any one of claims 1 to 3, wherein R 4 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group.

5. The silane according to any one of claims 1 to 4, wherein all R 2 are the same.

6. The silane according to any one of claims 1 to 5, wherein m is 1, R 1 It's vinyl, R 3 is vinyl or allyl, preferably vinyl, and R 4 It is methyl or ethyl, preferably methyl.

7. A polyorganosiloxane containing at least one terminal group of formula (3): -A-Si(R 1 ) m (R 2 ) 3-m (3) in: A is a bond, -O- or a linear, branched or cyclic divalent group, the divalent group being selected from a hydrocarbon residue having 1 to 12 carbon atoms, an alkylene group, an arylene group, an oxyalkylene group, an oxyarylene group, a siloxane-alkylene group, a siloxane-arylene group, an ester, an amine, a diol, an imide, an amide, an alcohol, a carbonate, a carbamate, a urea, a sulfide, an ether or a derivative or combination thereof; R 1 express: substituted or unsubstituted alkyl, alkenyl or alkynyl; a substituted or unsubstituted alicyclic group or aromatic group; a substituted or unsubstituted heteroalicyclic group or heteroaryl group; Each R 2 Independently represents a group of the general formula (2): -O-CHR 3 -C(=O)-O-R 4 (2) in R 3 express: a substituted or unsubstituted alkenyl group, preferably a vinyl group or an allyl group; R 4 express: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl or heteroaryl; and m is independently 0 or 1, preferably 1; wherein the polyorganosiloxane is obtained by reacting a polyorganosiloxane (Ia) having at least one reactive group / atom A' bonded to a silicon atom, preferably at least one hydroxyl group, with a silane of formula (1) according to any one of claims 1 to 6, wherein any R of the silane of formula (1) is 2 reacts with A' to form a linking group -A-; The reaction is optionally carried out in the presence of a (blocked) catalyst for the reaction.

8. A curable composition comprising: (A) at least one polyorganosiloxane having at least one hydroxyl group bonded to a silicon atom, (B) at least one cross-linking silane, wherein the cross-linking silane is the silane according to any one of claims 1-6.

9. The curable composition according to claim 8, further comprising (C) at least one blocked catalyst.

10. The curable composition according to claim 8 or 9, further comprising (D) at least one curing catalyst, preferably a tin compound.

11. The curable composition according to any one of claims 8 to 10, wherein the composition comprises, relative to the total weight of the curable composition or the total amount of components (A) to (D): (1) at least one polyorganosiloxane (A) having at least one hydroxyl group bonded to a silicon atom in an amount of 30 to 95% by weight; (2) at least one silane (B) of formula (1) in an amount of 1 to 15% by weight, preferably 3 to 10% by weight; (3) optionally at least one blocked catalyst (C) in an amount of 0.01-2 wt %, preferably 0.05-2 wt %, particularly preferably 0.1-0.5 wt %; and / or (4) Optionally, at least one curing catalyst (D) in an amount of 0.01 to 2% by weight, preferably in an amount of 0.05 to 2% by weight, particularly preferably in an amount of 0.1 to 0.5% by weight.

12. A curable composition comprising at least one polyorganosiloxane according to claim 7, optionally further comprising (C) at least one blocking catalyst and / or (D) at least one curing catalyst, preferably a tin compound.

13. The curable composition according to any one of claims 8 to 12, wherein the composition comprises any one or more other components selected from plasticizers, stabilizers, antioxidants, fillers, reactive diluents, desiccants, adhesion promoters, UV stabilizers, rheology aids and solvents.

14. The curable composition of any one of claims 8 to 13, wherein the composition is an adhesive, sealant or coating composition.

15. Use of the curable composition according to any one of claims 8 to 13 as an adhesive, sealant or coating.

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