CURABLE SILICONE COMPOSITIONS CONTAINING ADDITIVES - Patent application

Abstract

The present invention relates to a curable composition based on a polyorganosiloxane having a specific silicon-containing end group, a curing catalyst, and a polymer having at least one silane functional group. The present invention also relates to an adhesive, sealant, and / or coating material comprising said composition, and to the use of said composition.

Description

[Technical field]

[0001] The present invention relates to curable compositions based on polyorganosiloxanes with special silicon-containing end groups, a curing catalyst, and a polymer with at least one silane functional group. These compositions have improved adhesive properties and excellent storage stability. The present invention also relates to adhesive, sealant, and / or coating materials comprising the compositions, and to the use of the compositions. [Background technology]

[0002] Polymer systems with reactive crosslinkable silyl groups, e.g. alkoxysilyl groups, have been known for a long time. In the presence of atmospheric moisture, these alkoxysilane-terminated polymers can condense with the elimination of alkoxy groups. Depending on the amount of alkoxysilane groups and their structure, mainly long-chain polymers (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers), or highly crosslinked systems (thermosets) are formed.

[0003] Silicone polymers (polyorganosiloxanes), especially polydialkylsiloxanes such as polydimethylsiloxane (PDMS), are of great importance in the manufacture of adhesives, sealants, coatings, and insulating materials. Of these, those that vulcanize at low temperature and ambient conditions constitute a significant share of the market. Typical preparations include reactive polyorganosiloxanes, especially silanol-terminated polyorganosiloxanes having at least one, and preferably two, hydroxyl groups bonded to the silicon atoms. They are usually used in combination with silane-based crosslinkers having hydrolyzable groups bonded to the silicon atoms. Although the polyorganosiloxane and the crosslinker may be present as separate components, they can also be reacted with each other to form modified polyorganosiloxanes, which can also be used in curable compositions. The term endcapping (end group capping) is also used in this regard. This can be done optionally in the presence of a catalyst, which is intended to selectively mediate the endcapping without simultaneously curing the polyorganosiloxane.

[0004] The uses and potential applications of such silane-terminated polymer systems are similarly diverse. For example, they can be used to manufacture elastomers, sealants, adhesives, elastic adhesive systems, rigid and flexible foams, a wide variety of coating systems, and impression materials in the medical field, for example dentistry. These products can be applied in any form, such as painted, sprayed, cast, pressed, filled, etc.

[0005] A large number of crosslinkers are known in the art that act as end-capping or functionalization sites for the respective polymer backbones. Besides the functionality used for coupling to the polymer backbones, they can be differentiated into acidic, basic and neutral crosslinkers based on the type of leaving group released upon hydrolysis. Typical acidic crosslinkers contain an acid group as a hydrolyzable group and release the corresponding acid, e.g., acetic acid, upon crosslinking. Typical basic crosslinkers release an amine upon crosslinking. In both cases, aggressive compounds are released during crosslinking that may, for example, corrode or decompose metals, masonry or mortar, and also have a strong, often unpleasant odor. Therefore, neutral crosslinkers are often used in modern curable silicone compositions. Representatives of neutral crosslinkers have hydrolyzable groups that release alcohols, such as methanol or ethanol, or oximes upon crosslinking.

[0006] Nevertheless, such alkoxy systems have the disadvantage that several problems arise with regard to the storage stability of the associated curable compositions, and the cured products show poor adhesion to some materials. Oxymosilane crosslinkers, which hydrolyze with the release of alkanone oximes, do not usually have such drawbacks and are therefore widely used. Representative oximosilane crosslinkers release butan-2-one oxime during crosslinking. However, this compound is suspected of causing cancer, and therefore alternative neutral crosslinkers are urgently needed. Apart from that, the released oximes also have a strong putrid odor, and working with curable compositions containing such crosslinkers is perceived by users as unpleasant.

[0007] Therefore, silane compounds which release α-hydroxycarboxylic acid esters or α-hydroxycarboxylic acid amides during crosslinking have already been proposed as alternative crosslinking agents.

[0008] DE-A-3210337 discloses related silane compounds as well as their preparation and use in curable compositions based on polydiorganosiloxanes having condensable end groups.

[0009] Hardeners for silicone rubber materials having three 2-hydroxypropionic acid alkyl ester groups, i.e. lactate alkyl ester groups, are known from EP-A-2 030 976. In this case, vinyltris(ethyllactato)silane is particularly preferred.

[0010] EP 2 774 672 describes special catalysts for crosslinking silicone rubber materials with crosslinkers based on silane compounds having lactic acid groups, which may also be compounds known from EP 2 030 976. However, crosslinkers having only one, two or four 2-hydroxypropionic acid alkyl ester groups are also disclosed. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] DE 3210337 A1 [Patent Document 2] European Patent Publication No. 2030976 [Patent Document 3] European Patent Publication No. 2774672 Summary of the Invention

[0012] The use of crosslinking agents based on silane compounds with lactic acid groups or similar α-carbalkoxyalkoxy groups is associated with many advantages, but the resulting preparations may only have moderate adhesion on certain difficult substrates.Another challenge is to prepare curable silicone-based compositions that contain such crosslinking agents and exhibit good storage stability, since storage stability may be particularly poor in the presence of other conventional and often essential components of such compositions, especially curing catalysts and adhesion promoters.

[0013] Although formulations exist that address some of these problems, the object of the present invention is to provide an alternative curable composition based on polyorganosiloxanes that allows the use of crosslinkers that release mainly hydroxycarboxylic acid esters (and hydroxycarboxylic acid amides as possible by-products) during crosslinking, yet with good adhesion to a variety of substrates, including PMMA, and excellent storage stability.

[0014] The present invention achieves the above objectives by providing a curable composition based on specific polyorganosiloxanes, i.e. polyorganosiloxanes endcapped with specific silane groups, whereby the composition comprises at least one curing catalyst and at least one polymer having at least one silane functional group.

[0015] It has been found that the combination of certain endcapped polyorganosiloxanes with the catalysts and special additives disclosed herein provides excellent storage stability while retaining good cure and improved adhesion.

[0016] Thus, in a first aspect, the present invention provides a method for producing a composition comprising: (A) General formula (I): [ka] [In the formula, Each R 1 are independently selected from the group consisting of hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, cycloaliphatic, cycloaliphatic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, and acyloxy groups, or combinations thereof; Each R 2 are independently represented by the general formula (2): [ka] [During the ceremony, Y is a substituted or unsubstituted (hetero)aromatic group having 4 to 14 ring atoms, a substituted or unsubstituted saturated or partially unsaturated 4 to 14-membered (hetero)cyclic group, or -(C(R 5 )2) o - and; R 4 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, or heteroalicyclic group, or combinations thereof; Each R 5 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, and aryl groups; o is an integer from 1 to 10. is the basis of; Each R 3 are independently represented by the general formula (3): [ka] [During the ceremony, Y is as defined above; R 6 is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof, or R 7 selected from the group consisting of; R 7 is represented by the general formula (4): [ka] <In the ceremony, R 8 is an alkylene group optionally interrupted by a heteroatom; Each R 9 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 10is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, and acyl groups; Each p independently represents 0, 1, or 2. is the group is the basis of; m is independently 0, 1 or 2; n is independently 1, 2, or 3, and the sum of n+m is at most 3. at least one polyorganosiloxane containing at least one end group of (B) at least one curing catalyst; and (C) General formula (II): [ka] [In the formula, X is a divalent linking group containing at least one heteroatom; R is selected from divalent hydrocarbon residues having 1 to 12 carbon atoms; Each R a are each independently selected from a hydrocarbon radical containing 1 to 20 carbon atoms, and each R b are each independently selected from a hydroxyl group or a hydrolyzable group, where R a and R b is a substituent directly bonded to the Si atom, or the substituent R a and R b Two of them form a ring with the Si atom to which they are attached; k is 0, 1, or 2; o is 0 or 1] At least one polymer having at least one silane functional group of The present invention relates to a curable composition comprising, or consisting essentially of,

[0017] In another aspect, the invention relates to an adhesive, sealant, or coating material comprising the curable composition.

[0018] The present invention further relates to the use of the curable compositions of the present invention as adhesive, sealant, or coating materials. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] A "curable composition" is understood to be a substance or mixture of substances that can be cured by physical or chemical means. In this respect, these chemical or physical means may be, for example, the supply of energy in the form of heat, light, other electromagnetic radiation, but may also simply be contact with atmospheric moisture, water, or reactive components. This changes the composition from its original state to a state with higher hardness. In the context of the present invention, "curable" primarily relates to the property of the terminal silane groups of formula (I) to condense.

[0020] In this application, when referring to the molecular weight of an oligomer or polymer, unless otherwise specified, the amount is weight average, i.e., M w The molecular weight refers to the molecular weight average value and not to the number average molecular weight. The molecular weight is determined by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 with tetrahydrofuran (THF) as eluent, preferably at 35° C. The molecular weight of the monomeric compounds is calculated based on the respective molecular formula and the known molecular weights of the individual atoms.

[0021] "At least one" as used herein refers to one or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to components, the term relates to the type of component and not to the absolute number of molecules. "At least one polymer" thus means, for example, at least one polymer, i.e. one type of polymer or a mixture of several 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 beyond the given amount of the relevant compound.

[0022] All percentage data provided in relation to the compositions described herein refer in each case to weight % based on the relevant mixture, unless otherwise indicated.

[0023] As used herein, "consisting essentially of" means that the respective composition is predominantly composed of, for example, at least 50% by weight, for example at least 60, 70 or 80% of the referenced component, e.g., in the case of the compositions of the present invention, components (A), (B), (C) and (D) described below and optionally other additives such as fillers and / or plasticizers.

[0024] As used herein, "about" in relation to a numerical value means ±10%, preferably ±5% of the referenced value.

[0025] As used herein, "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain groups. The alkyl group preferably has 1-10 carbon atoms (whenever a numerical range is given herein, e.g., "1-10", this means that the group, in this case the alkyl group, may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to 10 carbon atoms). In particular, the alkyl may be a middle alkyl having 5-6 carbon atoms, or a lower alkyl having 1-4 carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. The alkyl group may be substituted or unsubstituted. "Substituted" as used in this context means that one or more carbon and / or hydrogen atoms of the alkyl group are replaced with a heteroatom or a functional group. Functional groups that may replace hydrogen atoms include, in particular, =O, =S, -OH, -SH, -NH2, -N(C 1-10 alkyl)2, e.g. -N(CH3)2, -NO2, -CN, -F, -CL, -Br, -I, -COOH, -CONH2, -OCN, -NCO, C 3-8 Cycloalkyl, C 6-14The heteroaryl group is selected from aryl, a 5-10 membered heteroaryl ring in which 1-4 ring atoms are independently nitrogen, oxygen, or sulfur, and a 5-10 membered heteroalicyclic ring in which 1-3 ring atoms are independently nitrogen, oxygen, or sulfur. Substituted alkyl includes, for example, alkylaryl groups. Heteroalkyl groups, in which one or more carbon atoms are replaced by heteroatoms selected from O, S, N, and Si, are obtained by replacement of one or more carbon atoms by heteroatoms, preferably the replaced carbon is not the carbon that connects the group to the remainder of the molecule. Examples of such heteroalkyl groups include, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentoxypropyl, ethylaminoethyl, trimethoxypropylsilyl, and the like.

[0026] "Alkoxy" refers to an alkyl group, as defined herein, attached to the remainder of the molecule through -O-. Thus, each term includes groups such as methoxy and ethoxy.

[0027] "Alkenyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon double bond, e.g., ethenyl, propenyl, butenyl, or pentenyl, and structural isomers thereof, such as 1- or 2-propenyl, 1-, 2-, or 3-butenyl. Alkenyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for alkyl. "Alkenyloxy" refers to an alkenyl group, as defined herein, attached to the remainder of the molecule through -O-. Thus, the term includes enoxy groups, such as vinyloxy (HC=CH-O-).

[0028] As used herein, "alkynyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon triple bond, e.g., ethynyl (acetylene), propynyl, butynyl, or petynyl, and structural isomers thereof as described above. Alkynyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for alkyl. "Alkynyloxy" refers to an alkynyl group, as defined herein, attached to the remainder of the molecule via -O-.

[0029] As used herein, a "cycloaliphatic group" or "cycloalkyl group" refers to a monocyclic or polycyclic group (multiple rings having a carbon atom in common), particularly those having 3 to 8 carbon atoms and in which the rings do not have a completely conjugated pi-electron system, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. The cycloalkyl group may be substituted or unsubstituted. "Substituted" in this context means that one or more hydrogen atoms of the cycloalkyl group are replaced with a functional group. Functional groups which may replace hydrogen atoms include, inter alia, =O, =S, -OH, -SH, -NH2, -NO2, -CN, -F, -CL, -Br, -I, -COOH, -CONH2, -OCN, -NCO, -C, -CH, -CH2, -CH3, -CH4, -CH5, -CH6, -CH7, -CH8, -CH9, -CH10, -CH11, -CH2, -CH3, -CH4, -CH5, -CH6, -CH7, -CH8, -CH10, -CH11, -CH12, -CH13, -CH2, -CH3, -CH4, -CH5, -CH6, -CH7, -CH8, -CH14, -CH15, -CH16, -CH17, -CH2O, -CH3, -CH4, -CH5, -CH6, -CH18, -CH2O, -CH3, -CH4, -CH5, -CH6, -CH10, -CH1 ...2O, -CH3, -CH4 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-8 Cycloalkyl, C 6-14 and a 5-10 membered heteroaryl ring in which one to four ring atoms are independently nitrogen, oxygen, or sulfur, and a 5-10 membered heteroalicyclic ring in which one to three ring atoms are independently nitrogen, oxygen, or sulfur. "Cycloalkyloxy" refers to a cycloalkyl group, as defined herein, attached to the remainder of the molecule through -O-.

[0030] As used herein, "aryl" refers to a monocyclic or polycyclic group (i.e., rings having adjacent carbon atoms in common), particularly a ring atom having 6 to 14 carbon atoms and a completely conjugated pi-electron system. Examples of aryl groups are phenyl, naphthalenyl, and anthracenyl. Aryl groups are substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. "Aryloxy" refers to an aryl group, as defined herein, attached to the remainder of the molecule through -O-.

[0031] As used herein, a "heteroaryl" group refers specifically to a monocyclic or polycyclic (i.e., rings which share adjacent pairs of ring atoms) aromatic ring having from 5 to 10 ring atoms, in which 1, 2, 3, or 4 ring atoms are nitrogen, oxygen, or sulfur, and the remainder are carbon. Examples of heteroaryl groups include pyridyl, pyrrolyl, furyl, 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, benzofuryl, isobenzofuryl, benzothienyl, 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 groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. As used herein, "(hetero)aryl" refers to both aryl and heteroaryl groups as defined herein. "Heteroaryloxy" refers to a heteroaryl group linked to the remainder of the molecule as defined herein via -O-.

[0032] As used herein, a "heteroalicyclic group" or "heterocycloalkyl group" refers to a monocyclic or fused ring having 5-10 ring atoms, which contains one, two, or three heteroatoms selected from N, O, S, and the remaining ring atoms are carbon accordingly. A "heterocycloalkenyl" group further contains one or more double bonds. However, the ring does not have a completely conjugated pi-electron system. Examples of heteroalicyclic groups include pyrrolidinone, piperidine, piperazine, morpholine, imidazolidine, tetrahydropyridazine, tetrahydrofuran, thiomorpholine, tetrahydropyridine, and the like. Heterocycloalkyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. "Heteroalicyclic" refers to a heteroalicyclic group, as defined herein, attached to the remainder of the molecule via -O-.

[0033] Combinations of the foregoing groups include, for example, alkylaryl or arylalkyl groups, in which each group may be substituted or unsubstituted as defined above.

[0034] The curable composition of the present invention comprises, as component (A) as defined herein, at least one polyorganosiloxane comprising at least one terminal silane group of general formula (I). Preferably, such a polymer is obtained by providing at least one polyorganosiloxane having at least one hydroxy group bonded to a silicon atom. More preferably, the polyorganosiloxane has at least two hydroxy groups bonded to the silicon atom. Furthermore, it is preferred that a hydroxy group or groups are bonded to the terminal silicon atom. If the polyorganosiloxane is branched, it preferably has a hydroxy group at each end. Thus, the present invention is directed to polymers having a silane group of formula (I) at only one end, but it is preferred that all polymer chain ends are end-capped with said group, i.e. a linear polymer will thus have two terminal silane groups. If the polymer is branched, it is preferred that each end is end-capped with a group of formula (I).

[0035] The polyorganosiloxane having at least one hydroxy group bonded to a silicon atom is preferably a polydiorganosiloxane, preferably polydimethylsiloxane (PDMS).

[0036] Thus, as polyorganosiloxanes, α,ω-dihydroxy-terminated polydiorganosiloxanes, in particular α,ω-dihydroxy-terminated polydimethylsiloxanes, which have at least one hydroxy group bonded to a silicon atom, are preferably used. Particular preference is given to α,ω-dihydroxy-terminated polydimethylsiloxanes which have a dynamic viscosity, measured to DIN 53019, at 23° C. of 5000 to 120,000 mPas, in particular 10,000 to 100,000 mPas, particularly preferably 50,000 to 90,000 mPas.

[0037] The polyorganosiloxane may be linked to the end groups of formula (I) through a variety of different linking groups -A-. In preferred embodiments, -A- is a bond, -O-, or a linear, branched or cyclic divalent group selected from a hydrocarbon residue having 1 to 12 carbon atoms, an alkylene, an arylene, an oxyalkylene, an oxyarylene, a siloxane-alkylene, a siloxane-arylene, an ester, an amine, a glycol, an imide, an amide, an alcohol, a carbonate, a urethane, a urea, a sulfide, an ether, or a derivative or combination thereof. In various embodiments, -A- is a direct covalent bond, -O-, an oxyalkylene such as -O-CH2- or -O-(CH2)3-, or a group preferably of the formula -(CH2) 1-10 -(Si(Alk)2-O-Si(Alk)2) 1-10 -(CH2) 1-10 [Wherein, Alk is C 1-10 -A- is a linear or branched divalent radical selected from the group consisting of siloxane-alkylenes of the formula -(CH2) 1-10 -(Si(Alk)2-O-Si(Alk)2) 1-10 -(CH2) 1-10 When it is a siloxane-alkylene, it is preferably selected from -(CH2)2-Si(CH3)2-O-Si(CH3)2-(CH2)2-.

[0038] Alternatively, in various embodiments, the polyorganosiloxane may be bonded to the end groups of formula (I) through a moiety selected from -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, NR'-C(=O)-NH-, -NH-C(=O)-NR'-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, and -NR'-, where R' is a hydrocarbon moiety having 1 to 6 carbon atoms, preferably C1-C2 alkyl or hydrogen, optionally substituted with hydrogen or halogen. In such an embodiment, -A- may be composed of the aforementioned groups, optionally further linked to a divalent alkylene group having 1 to 10 carbon atoms, which may be substituted, preferably -CH2- or -(CH2)3-, optionally interrupted by a heteroatom. When such an alkylene group is present, the orientation is such that the alkylene group is linked to the silicon atom of the terminal group of formula (I), while the above functional group is linked to the terminal silicon atom of the polymer chain, i.e. the full linker -A- is -OC(=O)-NH-C 1-10 Alkylene- or OC 1-10 It can be alkylene-.

[0039] In a preferred embodiment, the polyorganosiloxane (A) can be obtained by reacting a polyorganosiloxane having at least one terminal reactive group A' (Ia) that can be reacted with a suitable silane crosslinker to yield the desired polymer (A). Preferably, the silane crosslinker has the formula (Ib): [ka] [In the formula, C is a reactive group that reacts with the terminal reactive group A'; R 1 , R 2 , R 3 , m and n are the same as defined for general formula (I). has.

[0040] In a preferred embodiment, the polyorganosiloxane having at least one terminal reactive group A'(Ia) has a dynamic viscosity, measured to DIN 53019, at 23°C of 5000 to 120,000 mPas, in particular 10,000 to 100,000 mPas, particularly preferably 50,000 to 90,000 mPas.

[0041] In a preferred embodiment, the terminal reactive group A' is selected from a hydroxy, amino, or isocyanate group, more preferably A' is a hydroxy group.

[0042] In a preferred embodiment, the reactive group C is a leaving group, more preferably R 2 or R 3 In a preferred embodiment, C is a leaving group that reacts with the terminal reactive group A' of the polyorganosiloxane (Ia) to give the linker group -A-.

[0043] Suitable reactions are known, also called endcapping. These can be carried out optionally in the presence of a catalyst, which selectively mediates endcapping without simultaneously curing the polyorganosiloxane. Suitable catalysts are, for example, acids, organolithium compounds, such as those described in EP-A-0564253, amines, inorganic oxides, potassium acetate, organotitanium derivatives, titanium / amine combinations, carboxylic acid / amine combinations.

[0044] The catalyst may, in various embodiments, be a specific catalyst of formula (Ic), whereby the catalyst selectively mediates endcapping without simultaneously curing the polyorganosiloxane.

[0045] The catalyst has the formula (Ic): [ka] [In the formula, R11 is an alkylene group, optionally interrupted by a heteroatom, preferably C-C 10 alkylene, more preferably C1 or C3 alkylene; Each R 12 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 13 is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; q independently represents 0, 1, or 2; D is of formula (Id), (Ie), (If), or (Ig): [ka] [ka] [ka] [ka] [During the ceremony, Each R 14 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 14a , R 14b , R 14c , R 15 and R 16 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; R 17 is hydrogen or -Si(R 19 ) 3 are selected from R 18 is -Si(R 193, selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; or R 17 and R 18 are bonded together with the nitrogen atom to which they are attached to form the formula: -Si(R 19 )2-C 2-3 Alkylene-Si(R 19 )2- (In the formula, Each R 19 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, or aryl groups, or combinations thereof. Forming a base of; r is 1, 2, 3 or 4. is a nitrogen-containing group selected from the group The compound may be:

[0046] In various embodiments, the catalyst (Ic) is a compound in which q is 0 or 1, preferably 0.

[0047] In formula (Ic), R 13 is an unsubstituted alkyl group, preferably C 1-3 It may be an alkyl group, more preferably methyl or ethyl.

[0048] In various embodiments of the catalyst of formula (Ic), R 11 is C1-C6 alkylene, which may be branched or linear, preferably C1 or C3 alkylene, more preferably propylene.

[0049] In various embodiments, in formula (Ic), D is a group of formula (Id), and one R 14 is hydrogen, the others are unsubstituted alkyl, preferably C 1-4 Alkyl, for example methyl, ethyl, propyl or butyl, including isopropyl and isobutyl.

[0050] In various other embodiments, in formula (Ic), D is a group of formula (Ie), and R 14b and R 14c are each hydrogen or unsubstituted alkyl, preferably C 1-4 alkyl, such as methyl, ethyl, propyl or butyl, including isopropyl and isobutyl. In such embodiments, R 14a R may be hydrogen. 14a , R 14b and R 14c If none of are hydrogen, it may be preferred that at least one of these residues contains a CH moiety alpha to the carbon / nitrogen atom to which it is attached.

[0051] In various embodiments, in the group of formula (Id), both R 14 If is not hydrogen, then at least one R 14 contains a CH moiety alpha to the carbon atom to which it is attached.

[0052] In various embodiments, r in the group of formula (If) is 1, 2, 3 or 4, preferably 1 or 2.

[0053] In various embodiments, R in the group of formula (Ig) 17 and R 18 is -Si(R 19 )3 or hydrogen. 17 and R 18 may both be hydrogen.

[0054] The catalyst (Ic) can be used in any amount suitable to ensure sufficient formation of the desired polyorganosiloxane of formula (I).Typical amounts range from 0.05 to 1.5% by weight, preferably 0.1 to 1.0% by weight or 0.2 to 0.8% by weight, based on the total amount of polyorganosiloxane (Ia) and the compounds of formulae (Ib) and (Ic).

[0055] In the following, various embodiments of end-capped curable polyorganosiloxanes are described, which are optionally obtained by reacting polyorganosiloxane (Ia) with a compound of formula (Ib) in the presence of a catalyst of formula (Ic).

[0056] In the group of formula (I), each R 1 represent, independently of each other, a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; a substituted or unsubstituted cycloaliphatic or aryl group; or a substituted or unsubstituted heteroalicyclic or heteroaryl group. Alternatively, or in addition, one or more R 1 represents hydrogen, halogen, amino, oxyimino, alkenyloxy, alkylnyloxy, cycloaliphatic -O-, aryloxy, heteroaryloxy, heteroalicyclicoxy, acyl, acyloxy, or a combination thereof.

[0057] In various embodiments, each R 1 are each independently an alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl, or isopropyl, an alkenyl group having 2 to 10 carbon atoms, in particular vinyl or allyl, an aryl group having 6 to 10 carbon atoms, in particular phenyl, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, preferably acetoxy, oxyimino, an alkenyloxy group having 2 to 10 carbon atoms, or amino.

[0058] In specific embodiments, each R 1 each independently represents methyl, vinyl, or phenyl, and is particularly preferably methyl or vinyl.

[0059] In formula (I), each R 2 are independently represented by the general formula (2): [ka] [In the formula, Y is a substituted or unsubstituted (hetero)aromatic group having 4 to 14 ring atoms, a substituted or unsubstituted saturated or partially unsaturated 4 to 14-membered (hetero)cyclic group or a C(R 5 )2) o - and; R 4 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, or heteroalicyclic group, or combinations thereof; Each R 5 is independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, or aryl group; and o is an integer of 1 to 10, preferably 1 to 5, more preferably 1 or 2. represents a group.

[0060] In various embodiments, each R 2 are each independently represented by the general formula (2) [wherein R 4 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl. In some embodiments, Y represents a substituted or unsubstituted aromatic group having 6 carbon ring atoms, preferably 1,2-phenylene, or -(C(R 5 )2) o - [wherein o is 1 and R 5 One of the groups is hydrogen and the second R 5 The group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or its (alkyl) esters, such as ethylcarboxymethyl.

[0061] In various embodiments, each R 2 represent independently of one another a lactate ester, preferably the ethyl ester, or a malic acid mono- or diester, preferably the mono- or diethyl ester.

[0062] In other embodiments, each R 2is derived from salicylic acid, i.e. Y is 1,2-phenylene. The salicylic acid residue is an ester, for example a methyl or ethyl ester, preferably the ethyl ester.

[0063] In various embodiments, each R 3 are each independently represented by the general formula (3): [ka] represents a group.

[0064] In various embodiments, Y is as defined above; R 6 is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof, or R 7 R 7 is represented by the general formula (4): [ka] [In the formula, R 8 is an alkylene group optionally interrupted by a heteroatom such as O, N, S or Si, preferably C 1-10 or C 1-8 Alkylene group, more preferably C 1-3 an alkylene group, most preferably a methylene (CH2) or propylene ((CH2)3) group; Each R 9 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 10 are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, and acyl groups, preferably unsubstituted lower alkyl groups, more preferably methyl or ethyl groups; and Each p independently represents 0, 1 or 2, preferably 0 or 1, more preferably 0.

[0065] In various embodiments, in the radical of formula (3), Y is as defined for the radical of formula (2) above, i.e., Y is a substituted or unsubstituted aromatic group having six carbon ring atoms, preferably 1,2-phenylene, or -(C(R 5 )2) o - [wherein o is 1 and R 5 One of the groups is hydrogen and the second R 5 The group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or its (alkyl) esters, such as ethylcarboxymethyl.

[0066] In various embodiments, R 6 represents preferably hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, or hydrogen.

[0067] In various embodiments, R 8 is preferably of the formula -(CH2) 1-8 -, more preferably -(CH2) 1-5 -, even more preferably -(CH2) 1-3 and most preferably an alkylene group of the form -CH2- or -(CH2)3-.

[0068] In various embodiments, each R 9 are each independently a substituted or unsubstituted alkyl group having preferably 1 to 10 carbon atoms, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl.

[0069] In various embodiments, each R 10are each independently a substituted or unsubstituted alkyl group having preferably 1 to 10 carbon atoms, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl, most preferably methyl.

[0070] Preferably, each R 3 are each independently represented by the general formula (3): 5 )2) o - [wherein o is 1 and R 5 One of the groups is hydrogen and the second R 5 R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or an (alkyl) ester thereof; 6 represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, R 7 is represented by the general formula (4) [wherein R 8 is C 1-10 an alkylene group, preferably a C1 or C3 alkylene group, and each R 9 are each independently a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and each R 10 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and p is 0 or 1, preferably 0.

[0071] In a first embodiment, n and m in the general formula (I) are selected such that the sum of n+m is 3. In this case, the silane of formula (I) is R 3groups, i.e., do not contain hydroxycarboxylic acid amide groups. Preferred silane groups of formula (I) in this case are selected from methylbis(ethyllactato)silane, ethylbis(ethyllactato)silane, phenylbis(ethyllactato)silane, vinylbis(ethyllactato)silane, tri(ethyllactato)silane, methylbis(ethylsalicylate)silane, ethylbis(ethylsalicylate)silane, phenylbis(ethylsalicylate)silane, vinylbis(ethylsalicylate)silane, tri(ethylsalicylate)silane, methylbis(diethylmalato)silane, ethylbis(diethylmalato)silane, phenylbis(diethylmalato)silane, vinylbis(diethylmalato)silane, tri(diethylmalato)silane, and mixtures thereof.

[0072] In a second embodiment, n and m in general formula (I) are selected such that the sum of n+m is at most 2. In this case, the silane of general formula (I) contains at least one R 3 group, i.e. at least one hydroxycarboxylic acid amide group. Preferably, each R 3 are each independently represented by the general formula (3): 5 )2) o - [wherein o is 1 and R 5 One of the groups is hydrogen and the second R 5 R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or an (alkyl) ester thereof; 6 represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, R 7 is represented by the formula (4) [wherein R 8 is C 1-10 an alkylene group, preferably a C1 or C3 alkylene group, and each R 9 are each independently a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and each R 10are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and p is 0 or 1, preferably 0. Preferred silanes of general formula (I) in this case are methylbis(ethyllactato)silane, ethylbis(ethyllactato)silane, phenylbis(ethyllactato)silane, vinylbis(ethyllactato)silane, tri(ethyllactato)silane, methylbis(ethylsalicylato)silane, ethylbis(ethylsalicylato)silane, phenylbis(ethylsalicylato)silane, vinylbis(ethylsalicylato)silane, tri(ethylsalicylato)silane, methylbis(diethylmalato)silane, ethylbis(diethylmalato)silane, phenylbis(diethylmalato)silane, vinylbis(diethylmalato)silane, tri(diethylmalato)silane and mixtures thereof with silanes of general formula (5): [ka] [In the formula, p, R 6 , R 8 , R 9 and R 10have, in each case independently of one another, the general, preferred and particularly preferred meanings given above], are selected from the compounds obtained by selective amidation with amines of the formula: methyl bis(ethyl lactato)silane, ethyl bis(ethyl lactato)silane, phenyl bis(ethyl lactato)silane, vinyl bis(ethyl lactato)silane, tri(ethyl lactato)silane, methyl bis(ethyl salicylato)silane, ethyl bis(ethyl salicylato)silane, phenyl bis(ethyl salicylato)silane, vinyl bis(ethyl salicylato)silane, tri(ethyl salicylato)silane, methyl bis(diethyl malate)silane The present invention relates to the amidation products of 3-aminopropyltrimethoxysilane and / or 3-aminopropyltriethoxysilane, and mixtures thereof, with 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and mixtures thereof, with 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and mixtures thereof, with ... and / or 3-aminopropyltriethoxysilane, and mixtures thereof, with 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and / or 3-aminopropyltriethoxysilane.

[0073] In various embodiments, the curable composition contains polyorganosiloxane (A) in an amount of 20 to 97% by weight, particularly preferably 25 to 70% by weight, in each case based on the total weight of the composition. When mixtures of polyorganosiloxanes are used, the amount relates to the total amount of polyorganosiloxanes in the composition. When such mixtures are used, only one of the polyorganosiloxanes may be a polyorganosiloxane as described herein. However, it is preferred that essentially all of the polyorganosiloxanes used in the composition, i.e. at least 50% by weight, preferably at least 70 or 80% by weight, are those described herein.

[0074] The curable composition comprises as component (B) at least one curing catalyst, preferably selected from a tin, titanium, aluminum, or zirconium catalyst, more preferably a tin or titanium catalyst, or a mixture thereof.

[0075] In various embodiments, the curing catalyst may be a tin compound, preferably an organic tin compound or an inorganic tin salt. The tin in these tin compounds is preferably divalent or tetravalent. Component (B) is added to the composition, in particular as a crosslinking catalyst. Suitable inorganic tin salts are, for example, tin(II) chloride and tin(IV) chloride. However, as the tin compound, organic tin compounds (tin organyls) are preferably used. Suitable organic tin compounds are, for example, 1,3-dicarbonyl compounds of divalent or tetravalent tin, such as acetylacetonates, such as di(n-butyl)tin(IV) di(acetylacetonate), di(n-octyl)tin(IV) di(acetylacetonate), (n-octyl)(n-butyl)tin(IV) di(acetylacetonate); dialkyltin(IV) dicarboxylates, such as di-n-butyltin dilaurate, di-n-butyltin malate, di-n-butyltin mercaptoacetate ... di-n-butyltin dilaurate, di-n-octyltin diacetate, or the corresponding dialkoxylates, for example di-n-butyltin dimethoxide; oxides of tetravalent tin, for example dialkyltin oxides, for example di-n-butyltin oxide, di-n-octyltin oxide; and tin(II) carboxylates, for example tin(II) octoate or tin(II) phenolate.

[0076] Further suitable are tin compounds such as, for example, ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, e.g. di(n-butyl)tin(IV) di(methyl maleate), di(n-butyl)tin(IV) di(butyl maleate), di(n-octyl)tin(IV) di(methyl maleate), di(n-octyl)tin(IV) di(butyl maleate), di(n-octyl)tin(IV) di(isooctyl maleate); and di(n-butyl)tin(IV) sulfide, (n-butyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2CH2COO), (n-octyl)2Sn(SCH2CH2COOCH2CH2OCOCH2S), (n-butyl)2-Sn(SCH2COO-i-CH 17 )2, (n-octyl)2Sn(SCH2COO-i-C8H 17 )2, and (n-octyl)2Sn(SCH2COO-n-CH 17 )2.

[0077] Preferably, the tin compound is selected from 1,3-dicarbonyl compounds of divalent or tetravalent tin, dialkyltin(IV) dicarboxylates, dialkyltin(IV) dialkoxylates, dialkyltin(IV) oxides, tin(II) carboxylates, and mixtures thereof.

[0078] Particularly preferably, the tin compound is a dialkyltin(IV) dicarboxylate, especially di-n-butyltin dilaurate or di-n-octyltin dilaurate.

[0079] Additionally or alternatively, other metal-based condensation catalysts can be used, including, but not limited to, compounds of titanium such as organic titanates or chelate complexes, cerium compounds, zirconium compounds, molybdenum compounds, manganese compounds, copper compounds, aluminum compounds, or zinc compounds or their salts, alkoxylates, chelate complexes, or catalytically active compounds of main group elements or salts of bismuth, lithium, strontium, or boron.

[0080] Further suitable (tin-free) curing catalysts are, for example, organometallic compounds of iron, in particular 1,3-dicarbonyl compounds of iron, such as, for example, iron(III) acetylacetonate.

[0081] Boron halides, such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, or mixtures of boron halides, can also be used as curing catalysts. Particularly preferred are boron trifluoride complexes, such as boron trifluoride diethyl etherate, which are liquids and therefore easier to handle than gaseous boron halides.

[0082] Furthermore, amines, nitrogen heterocycles, and guanidine derivatives are generally suitable for catalysis. A particularly suitable catalyst from this group is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0083] Titanium, aluminum, zirconium compounds, or mixtures of one or more catalysts from the aforementioned group may also be used as catalysts.

[0084] Suitable titanium catalysts are compounds having hydroxy groups and / or substituted or unsubstituted alkoxy groups, thus having the general formula: [ka] [In the formula, R z is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms, containing 4 alkoxy groups -OR zare the same or different. In addition, OR z One or more of the groups is replaced with an acyloxy group -OCOR z can be replaced by .] It is a titanium alkoxide.

[0085] Also suitable as titanium catalysts are titanium alkoxides in which one or more of the alkoxy groups are replaced with a hydroxy group or a halogen atom.

[0086] Additionally, titanium chelate complexes may also be used.

[0087] Aluminum catalysts, such as aluminum alkoxides: [ka] [In the formula, R z has the above meaning; i.e. an organic radical, preferably a substituted or unsubstituted hydrocarbon radical having 1 to 20 C atoms, with three R z The groups may be the same or different. Similarly, in the case of aluminum alkoxides, one or more alkoxy groups may be replaced by an acyloxy group -OC(O)R z can be replaced by can also be used as a curing catalyst.

[0088] Additionally, aluminum alkoxides in which one or more alkoxy groups are substituted with hydroxy groups or halogen atoms can be used.

[0089] Of the aluminum catalysts mentioned, the pure aluminum alcoholates are preferred in terms of their stability towards moisture and the curability of the mixtures to which they are added. Furthermore, aluminum chelate complexes are preferred.

[0090] Suitable zirconium catalysts are, for example, tetramethoxyzirconium or tetraethoxyzirconium.

[0091] Diisopropoxyzirconium bis(ethylacetoacetate), triisopropoxyzirconium(ethylacetoacetate) and isopropoxyzirconium tris(ethylacetoacetate) are very particularly preferably used.

[0092] Additionally, zirconium acylates, zirconium halide catalysts, or zirconium chelate complexes may also be used.

[0093] Additionally, metal carboxylates, or mixtures of several such salts, can also be used as curing catalysts, selected from the following metal carboxylates: calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt, and / or zirconium.

[0094] Among the carboxylates, calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, and zirconium carboxylates are preferred because they exhibit high activity. Calcium, vanadium, iron, zinc, titanium, and zirconium carboxylates are particularly preferred. Iron and titanium carboxylates are particularly preferred.

[0095] The curable composition preferably contains a curing catalyst in an amount of about 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, in each case based on the total weight of the composition. If a mixture of different catalysts is used, the amount refers to the total amount in the composition.

[0096] The composition of the present invention crosslinks in the presence of moisture, forming Si-O-Si bonds and curing.

[0097] The curable composition contains, as an essential component (C), a compound represented by the general formula (II): [ka] [In the formula, X is a divalent linking group containing at least one heteroatom; R is selected from divalent hydrocarbon residues having 1 to 12 carbon atoms; Each R a are each independently selected from a hydrocarbon radical containing 1 to 20 carbon atoms, and each R b are each independently selected from a hydroxyl group or a hydrolyzable group, where R a and R b is a substituent directly bonded to the Si atom, or the substituent R a and R b Two of them form a ring with the Si atom to which they are attached; k is 0, 1, or 2; and o is 0 or 1] The composition further comprises at least one polymer having at least one silane functional group of

[0098] In this context, a divalent bonding (linking) group X containing at least one heteroatom is understood to be a divalent chemical group which links the polymer backbone of the polymer (C) with the residue R of general formula (II).

[0099] In various embodiments, the divalent linking group X in general formula (II) is selected from -O-, -S-, -N(R'')-, -R'''-O-, substituted or unsubstituted amide, carbamate, urethane, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate groups, where R'' is hydrogen or a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms; and R''' is a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms. The term "substituted" with respect to these groups means that the hydrogen atom present in these groups is replaced by an alkyl or aryl group, preferably a C 1-12 Alkyl or C 6-14 It means that it may be substituted with a non-hydrogen moiety such as an aryl group.

[0100] In a preferred embodiment, the linking group X is a urethane or urea group, more preferably a urethane group. Urethane groups can be formed, for example, when the polymer backbone contains terminal hydroxy groups and isocyanatosilane is used as an additional component, or conversely, when a polymer with terminal isocyanate groups reacts with an alkoxysilane containing terminal hydroxy groups. Similarly, terminal primary or secondary amino groups on a silane or polymer can be used to obtain urea groups, which react with terminal isocyanate groups present in the respective reactants. This means that an aminosilane reacts with a polymer with terminal isocyanate groups or a polymer terminated with amino groups reacts with an isocyanatosilane. Urethane or urea groups advantageously increase the strength of the polymer chain or the entire crosslinked polymer.

[0101] In preferred embodiments, the linking group X is selected from the group consisting of -OC(=O)-N(R'')-, -N(R'')-C(=O)O-, -N(R'')-C(=O)-N(R'')-, -N(R'')-C(=O)-, -C(=O)-N(R'')-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-N(R'')-, -N(R'')-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, -NR''-, and -R'''-O-, where R'' and R''' are as defined above. In more preferred embodiments, the linking group X is selected from -OC(=O)-N(R'')-, -N(R'')-C(=O)O-, -N(R'')-C(=O)-N(R'')-, -S-, -O-, -N(R'')-, or -R'''-O-, where R'' and R''' are as defined above. In particularly preferred embodiments, the linking group X is selected from -OC(=O)-N(R'')-, -N(R'')-C(=O)-N(R'')-, -O-, or -R'''-O-, where R'' and R''' are as defined above, more preferably -OC(=O)-NH- or -NH-C(=O)-NH-, and most preferably -OC(=O)-NH-.

[0102] The index "o" corresponds to 0 (zero) or 1, i.e., the linking group X connects the polymer backbone to the residue R (o=1), or the polymer backbone is directly bonded or connected to the residue R (o=0). In a preferred embodiment, o is 1.

[0103] The residue R is a divalent hydrocarbon residue having 1 to 12 carbon atoms. The hydrocarbon residue may be a linear, branched or cyclic alkylene residue and may be substituted or unsubstituted. The hydrocarbon residue may be saturated or unsaturated. In a preferred embodiment, R is a divalent hydrocarbon residue having 1 to 6 carbon atoms. The curing speed of the composition may be influenced by the length of the hydrocarbon residue forming one of the bonding links or the length of the bonding link between the polymer backbone and the silyl residue. Particularly preferably, R is methylene, ethylene or n-propylene, in particular methylene or n-propylene.

[0104] Alkoxysilane-functional compounds that have a methylene group as the attachment link to the polymer backbone, the so-called "alpha-silanes", have particularly high reactivity of the silyl group.

[0105] Generally, the longer the connecting hydrocarbon chain, the lower the reactivity of the polymer. In particular, "gamma-silanes" (containing unbranched propylene residues as connecting links) have a balanced ratio of required reactivity (acceptable cure time) and delayed cure (open assembly time, possibility of post-bonding modification).

[0106] R a and R b is a substituent directly bonded to the Si atom, or R a and R b can form a ring together with the Si atom to which they are attached. In a preferred embodiment, R a and R b is a substituent bonded directly to the Si atom.

[0107] Each R in the general formula (II) a are each independently selected from a hydrocarbon radical containing 1 to 20 carbon atoms, preferably a C1-C8 alkyl group, more preferably methyl or ethyl.

[0108] Each R in the general formula (II) bare each independently a hydroxyl group or a hydrolyzable group, preferably a C1-C8 alkoxy group, a C1-C8 acyloxy group, or -OY-COOR 4 where Y and R 4 is as defined for general formula (2) above. b G-OY-COOR 4 then the preferred embodiments disclosed herein in terms of general formula (2) apply.

[0109] In a preferred embodiment, each R b are, independently of one another, a C1-C8 alkoxy group, in particular a methoxy, ethoxy, i-propyloxy or i-butyloxy group, or -OY-COOR 4 where Y and R 4 is as defined above for general formula (2), in particular an ethyl lactate, ethyl salicylate or diethyl malate group. When k is 0 or 1, combinations of several groups are also possible. For example, R b one of R may be selected from a C1-C8 alkoxy group; b The other one is -OY-COOR 4 However, the acetoxy group -O-Co-CH 3 Acyloxy groups such as the following can also be used as hydrolyzable groups.

[0110] In a preferred embodiment, k is 0 or 1.

[0111] In a particularly preferred embodiment, the silyl group, i.e., -Si(R a ) k (R b ) 3-kis selected from alkyldialkoxysilyl or trialkoxysilyl, preferably methyldimethoxysilyl, ethyldiethoxysilyl, trimethoxysilyl, or triethoxysilyl, most preferably methyldimethoxysilyl or trimethoxysilyl. Alkoxy groups are advantageous because no substances irritating to mucous membranes are released during the hardening of compositions containing alkoxy groups. The alcohols produced by hydrolysis of the residues are harmless in the amounts released and evaporate.

[0112] In general, polymers containing di- or trialkoxysilyl groups have highly reactive linkages, allowing for rapid curing, high crosslinking, and therefore good final strength.The special advantage of dialkoxysilyl groups is the fact that after curing, the corresponding compositions are more elastic, softer, and more flexible than systems containing trialkoxysilyl groups.Therefore, they are particularly suitable for use as sealants.In addition, they release even less alcohol during curing, which is of particular interest when the amount of alcohol released should be reduced.

[0113] On the other hand, with trialkoxysilyl groups a higher degree of crosslinking can be achieved, which is particularly advantageous when a hard and strong material is desired after curing. Furthermore, the trialkoxysilyl groups are more reactive, which allows for faster crosslinking, reduces the amount of catalyst required and favors the "cold flow" (dimensional stability of the corresponding adhesive under the influence of force and, in some cases, temperature).

[0114] The relatively small hydrolyzable groups methoxy and ethoxy have low steric bulk and therefore are highly reactive, allowing rapid curing even with low amounts of catalyst, making them particularly attractive in systems where rapid cure is desired, such as adhesives that require high initial adhesion.

[0115] Combining the two groups also opens up interesting configuration possibilities. For example, R b Select methoxy for one of the R bWhen ethoxy is selected for the silyl group, the desired reactivity of the silyl group can be particularly finely adjusted if a silyl group containing only methoxy groups is deemed too reactive and a silyl group containing ethoxy groups is deemed not reactive enough for the intended use.

[0116] In addition to methoxy and ethoxy groups, larger residues can of course also be used as hydrolyzable groups, which are inherently less reactive. This is of particular interest when delayed curing is also to be achieved by the placement of alkoxy groups.

[0117] The silane functional group of general formula (II) can be a side group in the polymer chain of polymer (C) or a terminal group of polymer (C). In a preferred embodiment, the silane functional group of general formula (II) is a terminal group of the polymer.

[0118] In a preferred embodiment, the polymer (C) has at least two silane functional groups of general formula (II). In this case, the polymer (C) may have at least one lateral silane functional group of general formula (II) and at least one terminal silane functional group of general formula (II); or at least two lateral silane functional groups of general formula (II); or at least two terminal silane functional groups of general formula (II).

[0119] In a particularly preferred embodiment, the polymer (C) has at least two terminal silane functional groups of general formula (II). Each polymer chain then has at least two linking points at which the condensation of the polymer is completed and the hydrolyzed residues can be separated in the presence of atmospheric moisture. In this way, regular and rapid crosslinking is achieved, resulting in bonds of good strength. In addition, the amount and structure of the hydrolyzable groups allows the control of the configuration of the network that can be achieved as long-chain systems (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers) or highly crosslinked systems (thermosets), for example by using di- or trialkoxysilyl groups, methoxy groups or longer residues, thus influencing in particular the elasticity, flexibility and heat resistance of the finished crosslinked composition.

[0120] In a preferred embodiment, the polymer backbone of polymer (C) is selected from polyethers, poly(meth)acrylates, polyesters, polyurethanes, poly-α-olefins, more preferably polyethers or polyurethanes, or copolymers of at least two of the aforementioned polymers, such as polyether and poly(meth)acrylate copolymers.

[0121] As used interchangeably herein, "polyether", "polyoxyalkylene" or "polyalkylene glycol" is understood to be a polymer whose organic repeating unit contains an ether functional group COC in the main chain. Examples of such polymers are polypropylene glycol, polyethylene glycol and their copolymers. Polyethers do not include polymers with lateral ether groups, such as cellulose ethers, starch ethers, vinyl ether polymers, and polyacetals, such as polyoxymethylene (POM).

[0122] By "poly(meth)acrylates" is meant polymers based on (meth)acrylates, which are therefore understood to have the structural motif -CH2-CR'(COOR'')- as repeating unit, where R' denotes a hydrogen atom (acrylates) or a methyl group (methacrylates) and R'' denotes a linear, branched or cyclic alkyl residue and / or an alkyl residue containing functional substituents, such as methyl, ethyl, isopropyl, cyclohexyl, 2-ethylhexyl or 2-hydroxyethyl residues.

[0123] By "polyurethane" is understood a polymer which has at least two urethane groups --NH--CO--O-- in the main chain.

[0124] In a particularly preferred embodiment, the silane-modified polymer (C) has a polyether backbone. Polyethers have a flexible elastic structure, which allows the production of compositions with excellent elastic properties. Polyethers are not only flexible in backbone, but are also tough at the same time. Thus, for example, polyethers are not attacked or decomposed by water or bacteria, in contrast to, for example, polyesters.

[0125] The number average molecular weight M of the polyether that is the base of the polymer n is preferably 500 to 100,000 g / mol (Daltons), more preferably 500 to 50,000, particularly preferably 1,000 to 30,000, particularly preferably 2,000 to 20,000 g / mol, and most preferably 8,000 to 20,000 g / mol. A number average molecular weight of at least 500 g / mol is advantageous for the polyethers of the present invention, since the corresponding compositions have a balanced ratio of viscosity (ease of processing), strength and elasticity.

[0126] Particularly advantageous viscoelastic properties are obtained by using polyethers with narrow molecular weight distributions and therefore low polydispersities. These can be prepared, for example, by so-called double metal cyanide catalysis (DMC catalysis). The polyethers prepared in this way are characterized by particularly narrow molecular weight distributions, high average molecular weights and a very low number of double bonds at the ends of the polymer chains.

[0127] In a particular embodiment of the present invention, the maximum polydispersity M of the polyether on which the polymer is based is w / M n is 2, particularly preferably 1.5 and most particularly preferably 1.3.

[0128] Ratio M w / M n(Polydispersity) indicates the width of the molecular weight distribution and thus the different degrees of polymerization of the individual chains in a polydisperse polymer. For many polymers and polycondensates, a polydispersity of about 2 applies. Strict monodispersity exists at the value 1. A low polydispersity, for example less than 1.5, indicates a relatively narrow molecular weight distribution, which results in a specific expression of molecular weight-related properties, such as viscosity. Thus, particularly in the context of the present invention, the polyether on which polymer C is based has a polydispersity (M) of less than 1.3. w / M n ).

[0129] In a particularly preferred embodiment, the polymer (C) having at least one silane functional group of general formula (II) can be obtained by reacting at least one polyol with at least one isocyanatosilane, which can, if necessary, first be chain-extended by reacting it with at least one polyisocyanate.

[0130] In a particular embodiment, the polymer (C) having at least one silane functional group of general formula (II) can be obtained by reacting at least one polyol with a stoichiometric excess of at least one polyisocyanate and reacting the resulting NCO-terminated polyurethane prepolymer with at least one aminosilane, such as 3-aminopropyltrimethoxysilane.

[0131] A "polyol" is understood to be a compound containing at least two OH groups, whether or not it contains other functional groups. However, the polyols used according to the invention preferably contain only OH groups as functional groups, or, if other functional groups are present, none of these other functional groups are reactive, at least towards isocyanates, under the conditions prevailing during the reaction of the polyol with the isocyanatosilane or polyisocyanate.

[0132] The polyol suitable for preparing the silane-terminated polymer (C) is preferably a polyether polyol. The above explanations regarding the molecular weight and polydispersity of the polyether apply to the polyether polyol. The polyether polyol is preferably a polyalkylene oxide, particularly preferably a polyethylene oxide and / or a polypropylene oxide. In a preferred embodiment, one polyether or a mixture of two polyethers is used.

[0133] The polyols used according to the invention preferably have an OH number of about 1 to about 250.

[0134] In addition to the polyether, the polyol mixture can include other polyols, such as polyester polyols having a molecular weight of about 200 to about 30,000.

[0135] The isocyanatosilane used in the above reaction is OCN-R-Si(R a ) k (R b ) 3-k wherein R, R a , R b and k is as defined for general formula (II).

[0136] By "polyisocyanate" is understood a compound having at least two isocyanate groups -NCO. This compound does not necessarily have to be a polymer, but is often a low molecular weight compound.

[0137] Polyisocyanates suitable for preparing the polyurethanes of the present invention include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, bis(2-isocyanatoethyl) fumarate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-furan, 1,2-dimethylphenyl diisocyanate ... 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- and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate (MDI), and isomeric mixtures thereof. Also included are partially or fully hydrogenated cycloalkyl derivatives of MDI, such as fully hydrogenated MDI (H 12Also suitable are diisocyanates such as mono-, di-, tri- or tetraalkyldiphenylmethane diisocyanates and their partially or fully hydrogenated cycloalkyl derivatives, 4,4'-diisocyanatophenylperfluoroethane, phthalic acid bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4- or -2,6-diisocyanate, 1-bromomethylphenyl-2,4- or -2,6-diisocyanate, 3,3'-bischloromethylether-4,4'-diphenyldiisocyanate, sulfur-containing diisocyanates such as those obtained by reacting two moles of a diisocyanate with one mole of thiodiglycol or dihydroxydihexylsulfide, diisocyanates of dimeric fatty acids or mixtures of two or more of the aforementioned diisocyanates. The polyisocyanate is preferably IPDI, TDI or MDI.

[0138] Other polyisocyanates suitable for use in the present invention are isocyanates with a functionality of 3 or more, obtained for example by oligomerization of diisocyanates, more particularly by oligomerization of the isocyanates mentioned above. Examples of such triisocyanates and higher are the triisocyanurates of HDI or IPDI or mixtures thereof, or mixed triisocyanurates thereof, and the polyphenylmethylene polyisocyanates obtained by phosgenation of aniline / formaldehyde condensates.

[0139] The total proportion of polymer (C) having at least one silane functional group of general formula (II) in the composition of the present invention is preferably about 0.1 to about 10.0% by weight, more preferably about 0.1 to about 5.0% by weight, most preferably about 0.5 to about 2.0% by weight, based on the total weight of the curable composition. If the content of polymer (C) is less than 0.1% by weight, sufficient adhesion to various substrates, especially acrylic substrates such as PMMA, is not obtained. If the content of polymer (C) is more than 10.0% by weight, phase separation may occur during the preparation of the composition, which has a negative effect on the mechanical properties.

[0140] The curable composition may further comprise at least one adhesion promoter (D).

[0141] The compositions described herein may contain up to about 20% by weight of conventional adhesion promoters (tackifiers). Suitable as adhesion promoters are, for example, resins, terpene oligomers, coumarone / indene resins, aliphatic petrochemical resins, and modified phenolic resins. Suitable within the context of the present invention are, for example, hydrocarbon resins obtainable by polymerization of terpenes, such as mainly α- or β-pinene, dipentene, or limonene. These monomers are generally initiated with Friedel-Crafts catalysts and are cationic polymerized. Terpene resins also include, for example, copolymers of terpenes with other monomers, such as styrene, α-methylstyrene, isoprene, and the like. The aforementioned resins are used, for example, as adhesion promoters in contact adhesives and coatings. Also suitable are terpene-phenolic resins, which are prepared by acid-catalyzed addition of phenols to terpenes or rosins. Terpene-phenolic resins are soluble in most organic solvents and oils and are miscible with other resins, waxes, and natural rubber. Rosin resins and their derivatives, such as their esters, are also suitable as additives in the aforementioned sense within the context of the present invention.

[0142] Also suitable are silane adhesion promoters, especially alkoxysilanes, which have (further) functional groups, such as, for example, amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurate groups or halogens. Also suitable are, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl-dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis-(2-methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, tris(trimethoxysilyl)isocyanurate, and γ-chloropropyltrimethoxysilane.

[0143] In a preferred embodiment, the adhesion promoter comprises at least one compound selected from the following: (i) aminosilanes, optionally oligomerized with alkyl-, alkenyl-, or aryl-alkoxysilanes; (ii) oligomers resulting from the condensation of aminosilanes, optionally oligomerized with alkyl-, alkenyl- or aryl-alkoxysilanes; or (iii) Mixtures thereof.

[0144] More preferably, the adhesion promoter is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2-aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylaminomethyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, tri[(3-triethoxysilyl)propyl]amine, tri[(3-trimethoxysilyl)propyl]amine, and oligomers thereof, 3-(N,N-dimethylamino)propyltrimethoxysilane, 3-(N,N-dimethylamino)propyltriethoxy Silane, (N,N-dimethylamino)methyltrimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, bis(3-trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine, 4-amino-3,3-dimethylbutyl Trimethoxysilane, and 4-amino-3,3-dimethylbutyltriethoxysilane, and mixtures thereof, particularly preferably 3-aminopropyltri(m)ethoxysilane, aminomethyltri(m)ethoxysilane, 3-(N,N-dimethylamino)propyltri(m)ethoxysilane, (N,N-dimethylamino)methyltri(m)ethoxysilane, 3-(N,N-diethylamino)propyltri(m)ethoxysilane, (N,N-diethylamino)methyltri(m)ethoxysilane, 4-amino-3,3-dimethylbutyltri(m)ethoxysilane, bis(3-tri(m)ethoxysilyl)propylamine, N-(n-butyl)-3-aminopropyltrimethoxysilane, oligomers resulting from the condensation of at least one of the above aminosilanes, or mixtures thereof. The above monomeric aminosilanes or oligomers can be oligomerized with alkyl-, alkenyl- or aryl-alkoxysilanes, preferably methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, and / or octyltrimethoxysilane.

[0145] As used herein, "(m)ethoxy" refers to both methoxy and ethoxy. Thus, "aminopropyltri(m)ethoxysilane" refers to both aminopropyltrimethoxysilane and aminopropyltriethoxysilane.

[0146] In a preferred embodiment, the composition of the present invention can comprise at least one aminosilane as described above, more preferably at least two aminosilanes, in particular at least one primary aminosilane and at least one tertiary aminosilane. As used herein, "tertiary aminosilane" refers to an aminosilane in which the nitrogen atom of the amino group is covalently bonded to three non-hydrogen residues. In various embodiments, the aminosilane is selected from the group consisting of tri[(3-tri(m)ethoxysilyl)propyl]amine and its oligomers, 3-(N,N-dimethylamino)propyltri(m)ethoxysilane, (N,N-dimethylamino)methyltri(m)ethoxysilane, 3-(N,N-diethylamino)-propyltri(m)ethoxysilane, (N,N-diethylamino)methyltri(m)ethoxysilane, bis(3-tri(m)ethoxysilyl)propylamine, and mixtures thereof, particularly preferably 3-(N,N-dimethylamino)propyltri(m)ethoxysilane, (N,N-dimethylamino)methyltri(m)ethoxysilane, 3-(N,N-diethylamino)propyltri(m)ethoxysilane, and (N,N-diethylamino)methyltri(m)ethoxysilane.

[0147] In various embodiments, the adhesion promoter used has the formula (III): [ka] [In the formula, R 11 is an alkylene group optionally interrupted by a heteroatom such as O, N, S or Si, preferably C 1-10 alkylene, more preferably C1 or C3 alkylene; Each R 12 is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic, or combinations thereof; Each R 13is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups, preferably an ethyl group; q independently represents 0, 1, or 2; B is represented by formula (6), (7), (8) or (9): [ka] [During the ceremony, Each R 14 , R 14a , R 14b , R 14c , R 15 and R 16 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; r is 1, 2, 3 or 4; R 17 is -Si(R 19 )3, and R 18 -Si(R 19 )3, selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof, or R 17 and R 18 are bonded together with the nitrogen atom to which they are attached to form a group of the formula -Si(R 19 )2-C 2-3 Alkylene-Si(R 19 )2-(where each R 19 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl groups, or combinations thereof. is a nitrogen-containing group selected from the group The adhesion promoter may be a capped adhesion promoter.

[0148] As used herein, the terms "blocked" and "capped" in relation to compounds of formula (III) are used interchangeably. Further, compounds of formula (III) are referred to herein as blocked / capped adhesion promoters. As used herein, "blocked" in relation to compounds of formula (III) refers to compounds that have been derivatized such that the active compound is released only upon contact with water and / or oxygen.

[0149] In various embodiments, in formula (6), one R 14 is hydrogen or methyl, preferably hydrogen, and the other R 14 is an unsubstituted alkyl group having 1 to 10 carbon atoms, preferably having 1 to 4 carbon atoms, such as, for example, isobutyl or methyl, or an unsubstituted aryl group, preferably phenyl.

[0150] In various embodiments, in formula (7), R 14a and R 14b And one R14 c is hydrogen or methyl, preferably hydrogen, and the other R 14c is an unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an unsubstituted aryl group having 1 to 4 carbon atoms, preferably phenyl.

[0151] In various embodiments, R in formula (8) 15 and R 16 In other embodiments, one is hydrogen and the other is alkyl, preferably C-C such as 3-heptyl or 2-propyl. 10 In another embodiment, R in formula (8) is an alkyl, aryl, or alkylaryl of up to 15 carbon atoms, such as 2-(1-(4-tert-butyl-phenyl)propyl. 15 and R 16 are not hydrogen and may preferably be selected from the groups mentioned above.

[0152] In formula (8), r is preferably 1 or 2, and more preferably 1.

[0153] In formula (9), R 17 -Si(R 19 )3, and each R 19 are preferably independently hydrogen, unsubstituted alkyl, more preferably C such as ethyl or methyl. 1-4 R is an alkyl, or an alkylene such as vinyl. 18 is preferably hydrogen, -Si(R 19 )3 substituted propylene or methylene, or -Si(R 19 )3, preferably -Si(R 19 )3, and each R 19 are independently unsubstituted alkyl, preferably methyl or ethyl, more preferably methyl, or alternatively alkylene, such as vinyl. 19 If is hydrogen, other R 19 The group is preferably not hydrogen. 17 Preferred groups include, but are not limited to, SiH(CH), Si(CH)(CH=CH), -Si(CH)(CH), and -Si(CH). In such embodiments, q can be 0 or 1, and R 11 may be propylene, R 12 When present, R may be methyl; 13 may be methyl or ethyl, preferably ethyl.

[0154] In another preferred embodiment, R 17 and R 18 are bonded together with the nitrogen atom to which they are attached to form a group of the formula -Si(R 19 )2-C 2-3 Alkylene-Si(R 19 )2-, especially -Si(R 19 )2-(CH2)2-Si(R 19 )2- group, where R 19 is unsubstituted alkyl, preferably methyl or ethyl, more preferably methyl, or alternatively vinyl.

[0155] In various embodiments, the capped adhesion promoter is a ketimine of formula (III), q is 0, and R 11 is methylene or propylene, preferably propylene, and each R 13 is ethyl and B is a group of formula (6), (i) One R 14 is methyl, other R 14 is isobutyl or methyl; or (ii) One R 14 is hydrogen, and the other R 14 is phenyl.

[0156] In various other embodiments, the capped adhesion promoter is a silazane of formula (III), q is 0, and R 11 is methylene or propylene, preferably propylene, and each R 13 is ethyl or methyl, preferably ethyl, and B is a group of formula (9), where R 17 -Si(R 19 )3, and R 18 is hydrogen, -Si(R 19 )3 substituted alkyl, or -Si(R 19 )3, preferably -Si(R 19 )3, and each R 19 is independently alkyl, preferably methyl or ethyl, more preferably methyl. In various alternative embodiments, at least one R 19 may be alkylene, preferably vinyl.

[0157] In a preferred embodiment, the curable composition contains an adhesion promoter in an amount of up to about 5% by weight, more preferably from about 0.01 to about 5% by weight, and particularly preferably from about 0.1 to about 2% by weight, in each case based on the total weight of the composition. If a mixture of (capped) adhesion promoters is used, the amount refers to the total amount of such (capped) adhesion promoters in the composition.

[0158] In various embodiments, the amount of uncapped adhesion promoter can be minimized. In contrast to conventional aminosilanes, such capped adhesion promoters are less susceptible to side reactions. Thus, the present invention encompasses embodiments in which no additional adhesion promoter is added beyond the capped adhesion promoter of formula (III).

[0159] In various embodiments, the molar ratio of the (capped) adhesion promoter (D) to the curing catalyst (B), preferably a tin compound, can be adjusted to be at least 1:1, for example in the range of 1:1 to 50:1, which can help to ensure that the curable composition, on the one hand, has very high storage stability and, on the other hand, cures reliably and at a sufficient rate after application, even at room temperature (23°C) and in the presence of atmospheric moisture.

[0160] The curable composition has the formula (IV): [ka] [In the formula, R 20 is selected from substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, cycloaliphatic, cycloaliphatic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups or combinations thereof; R 21 is selected from hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, cycloaliphatic, cycloaliphatic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups, or combinations thereof; or R 20 and R 21 together with the carbon atoms to which they are attached form a 5- to 18-membered substituted or unsubstituted alicyclic or heteroalicyclic group; R 20 and R 21contain a total of up to 24, preferably up to 18 carbon atoms. The composition may further comprise at least one additive (E) having a ketone functionality of

[0161] In various embodiments, additive (E) has a molecular weight of at most 500 g / mol, preferably at most 300 g / mol.Additive (E) is preferably a monomeric component.

[0162] In various embodiments, the additive (E) is selected from ketones and aldehydes of formula (IV), (i)R 20 is a substituted or unsubstituted alkyl, aryl, heteroaryl, or combinations thereof, preferably C 1-10 Alkyl, C 6-14 Aryl and C 5-13 R is selected from heteroaryl, more preferably substituted or unsubstituted phenyl, most preferably phenyl or methoxy-phenyl; 21 is hydrogen; or (ii)R 20 and R 21 are each independently selected from substituted or unsubstituted alkyl, aryl, heteroaryl, or combinations thereof, preferably C 1-10 Alkyl, C 6-14 Aryl and C 5-13 It is heteroaryl.

[0163] In various embodiments, the additive (E) is selected from, but is not limited to, 4-(4-hydroxyphenyl)-butan-2-one, cyclohexanone, benzophenone, acetophenone, 1,1,1-trichloroacetone, 2-butanone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone, iso-propyl methyl ketone, 2-hexanone, 4-methyl-2-pentanone, iso-butyl methyl ketone, 3,3-dimethyl-2-butanone, tert-butyl methyl ketone, 4-heptanone, cyclopentanone, 2,6-dimethyl-4-heptanone, di-iso-butyl ketone, 5-nonanone, di-n-butyl ketone, 2,4-dimethyl-3-pentanone, di-iso-propyl ketone, 2,4-pentanedione, acetylacetone, civetone, carvone, and camphor.

[0164] In various embodiments, the additive (E) is selected from aldehydes including, but not limited to, p-tolualdehyde, vanillin (4-hydroxy-3-methoxybenzaldehyde), valeraldehyde, salicylaldehyde, cinnamaldehyde, butyraldehyde, isovaleraldehyde, n-pentanal, n-hexanal, n-heptanal, 2-ethylhexanal, n-octanal, n-nonanal, n-decanal, n-undecanal, dodecanal, trans-hexen-2-al, benzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, and 4-methoxybenzaldehyde.

[0165] In various embodiments, the additive (E) may be an aldehyde that is also used as part of a fragrance or fragrance composition. Such aldehydes have the added advantage of improving the odor of the composition and masking or preventing malodors caused by other ingredients. Suitable aldehydes include adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), simal (3-(4-isopropyl-phenyl)-2-methylpropanal), ethyl vanillin, furohydral (3-(3-isopropylphenyl)butanal), helional (3-(3,4-methylenedioxyphenyl)-2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral. (3- and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, lilial (3-(4-tert-butylphenyl)-2-methylpropanal), phenylacetaldehyde, undecylenal, dehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptanal), 2,4-Di-methyl-3-cyclohexene-1-carboxaldehyde (triplal), 4-Methoxybenzaldehyde, benzaldehyde, 3-(4-tert-butylphenyl)-propanal, 2-Methyl-3-(para-methoxyphenyl)propanal, 2-Methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal, 3-phenyl-2-propenal, cis / trans-3,7-dimethyl-2,6-octadiene-1-al , 3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2-methyl-3-(isopropylphenyl)propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4-(tricyclo[5.2.1.0(2,6)]-Decylidene-8)-butanal, Octahydro-4,7-methane-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha,alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde, 3,4-(methylenedioxy)-benzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethylo Ctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl 5,9-Undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, dihydrocinnamaldehyde, 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5- or 6-Methoxyhexahydro-4,7-methaneindan-1- or -2-carboxaldehyde, 3,7-Dimethyloctan-1-al, 1-Undecanal, 10-Undecen-1-al, 4-Hydroxy-3-methoxybenzaldehyde, 1-Methyl-3-(4-methylpentyl)-3-cyclohexene-1-carboxaldehyde carboxyaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, 6,These include, but are not limited to, 10-dimethyl-3-oxa-5,9-undecadien-1-al, hexahydro-4,7-methaneindan-1-carboxyacetaldehyde, 2-methyloctanal, alpha-methyl-4-(1-methylethyl)benzeneacetaldehyde, 6,6-dimethyl-2-norpinen-2-propionaldehyde, para-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphtharaldehyde, 3-propyl-bicyclo-[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal, and trans-2-hexenal.

[0166] In various embodiments, the additive (E) may be a ketone, which is also used as part of a fragrance or fragrance composition. Such ketones have the added advantage of improving the odor of the composition and masking or preventing the malodor caused by other ingredients. Suitable ketones include, methyl-beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), tonalide (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, isodamascone, damaskenone, methyl dihydrojasmonate, menthone, carvone, camphor, 3,4,5,6,6-pentamethylhept-3- En-2-one, fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, floramon (2-heptylcyclopentanone), dihydrojasmone, cis-jasmone, iso-E-super (1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one (and isomers), methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl-beta-naphthalene ... Phthyl ketone, benzyl acetone, benzophenone, parahydroxyphenyl butanone, 3-methyl-5-propyl-2-cyclohexenone, 6-isopropyl decahydro-2-naphthone, dimethyl octenone, frescomene (2-butan-2-yl-cyclohexan-1-one), 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2-(2-(4-methyl-3-cyclohexen-1-yl)propyl)cyclopentanone, 1-(p- Menthen-6(2)yl)-1-propanone, 4-(4-hydroxy-3-methoxyphenyl)-2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 4-damascol (5-methyl-5-phenylhexan-3-one), dalcinyl (4-(1,3-benzodioxol-5-yl)butan-2-one), hexalone (1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadiene-3-one), isocyclimone E (1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanone), methyl nonyl ketone, methyl cyclocitron, methyl lavender ketone, orivon (4-tert-amyl-cyclohexanone), 4-tert-butylcyclohexanone, delphon (2-pentylcyclopentanone), muscone (CAS 541-91-3), neobutenone (1-(5,5-dimethyl-1-cyclohexenyl)pent-4-en-1-one), plicatone (CAS 41724-19-0), velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one, and tetramelane (6,10-dimethylundecen-2-one).

[0167] These other ingredients may be selected, for example, from the group comprising plasticizers, extenders, stabilizers, antioxidants, fillers, reactive diluents, drying agents, UV stabilizers, rheological aids, and / or solvents. Of particular interest are the plasticizers, fillers, and stabilizers, which usually include antioxidants and UV stabilizers.

[0168] Preferably, the curable composition comprises at least one further component.

[0169] The viscosity of the curable composition may be too high for some applications, in which case the use of reactive diluents generally provides a simple and convenient way to reduce the viscosity without any signs of separation (e.g., plasticizer migration) in the cured mass.

[0170] Solvents and / or plasticizers can be used in addition to, or in place of, the reactive diluents to reduce the viscosity of the curable composition.

[0171] Suitable as solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters and ether esters.

[0172] The compositions described herein may further include hydrophilic plasticizers. These are used to improve moisture absorption and thereby improve reactivity at low temperatures. Suitable plasticizers are, for example, abietic acid esters, adipates, azelates, benzoates, butyrates, acetates, esters of higher fatty acids having from about 8 to about 44 carbon atoms, epoxidized fatty acids, fatty acid esters and fats, glycolates, phosphates, phthalates, linear or branched alcohols having 1 to 12 carbon atoms, propionates, sebacates, sulfonates, thiobutyrates, trimellitates, citrates, esters based on nitrocellulose and polyvinyl acetate, and mixtures of two or more thereof.

[0173] For example, among the phthalic acid esters, dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate or butyl benzyl phthalate are suitable, and among the adipic acid esters, dioctyl adipate, diisodecyl adipate, diisodecyl succinate, dibutyl sebacate or butyl oleate are suitable.

[0174] Also suitable as plasticizers are monofunctional, linear or branched C 4-16 These are pure or mixed ethers of alcohols or mixtures of two or more different ethers of such alcohols, for example dioctyl ether (available as Cetiol OE, Cognis Deutschland GmbH, Düsseldorf).

[0175] For example, di-C of polyethylene or polypropylene glycol 1-4-Alkyl ethers, particularly the dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof, are also suitable as end-capped polyethylene glycol plasticizers.

[0176] Suitable plasticizers are end-capped polyethylene glycols such as polyethylene or polypropylene glycol dialkyl ethers in which the alkyl group has up to 4 C atoms, in particular the dimethyl and diethyl ethers of diethylene glycol and dipropylene glycol. With dimethyldiethylene glycol in particular, acceptable hardening is achieved even under less favorable application conditions (low humidity, low temperature). For more information on plasticizers, reference is made to the relevant chemical and technical literature.

[0177] Diurethanes are also suitable as plasticizers, and can be prepared, for example, by reacting diols with OH end groups with monofunctional isocyanates, selecting a stoichiometry such that substantially all free OH groups react.Optionally, excess isocyanate can be removed from the reaction mixture, for example by distillation.Another method for preparing diurethanes consists of reacting monofunctional alcohols with diisocyanates, and as far as possible all NCO groups react.

[0178] In various embodiments, the plasticizer may be a polydimethylsiloxane different from (A), particularly a PDMS that does not have the end groups of formula (I).

[0179] In various embodiments, the hardenable composition includes at least one plasticizer, such as polydimethylsiloxane.

[0180] The curable composition may contain plasticizers preferably in an amount of 1 to 50% by weight, preferably in an amount of 10 to 40% by weight, particularly preferably in an amount of 20 to 30% by weight, in each case based on the total weight of the composition. If a mixture of plasticizers is used, the amount refers to the total amount of plasticizers in the composition.

[0181] The curable composition may further comprise at least one stabilizer selected from an antioxidant, a UV stabilizer, and a drying agent.

[0182] As antioxidants all conventional antioxidants can be used, which are preferably present in an amount of up to about 7% by weight, in particular up to about 5% by weight.

[0183] The compositions herein may contain UV stabilizers, which are preferably used in amounts up to about 2% by weight, more preferably about 1% by weight. So-called hindered amine light stabilizers (HALS) are particularly suitable as UV stabilizers. Within the context of the present invention, UV stabilizers are preferably used that have silyl groups and are incorporated into the final product during crosslinking or curing. The products Lowilite 75 and Lowilite 77 (Great Lakes, USA) are particularly suitable for this purpose. In addition, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and / or sulfur may also be added.

[0184] To further enhance shelf life, it is often useful to stabilize the composition against penetrating moisture with a desiccant.

[0185] Such improved preservability can be achieved, for example, by using a desiccant.All compounds that react with water to form a group that is inactive to the reactive group present in the formulation are suitable as desiccant, thereby causing the change in molecular weight to be as small as possible.Furthermore, the reactivity of the desiccant to the moisture that penetrates into the formulation must be higher than the reactivity of the group of the polymer having silyl groups of the present invention present in the formulation.

[0186] For example, isocyanates are suitable as drying agents.

[0187] However, advantageously, silanes are used as drying agents, for example vinyl silanes such as 3-vinylpropyltriethoxysilane, oximesilanes such as methyl-O,O',O''-butan-2-one-trioximosilanes or O,O',O'',O''''-butan-2-one-tetraoximosilanes (CAS Nos. 022984-54-9 and 034206 40-1), or benzamidosilanes such as bis(N-methylbenzamido)methylethoxysilane (CAS No. 16230-35-6), or carbamatosilanes such as carbamatomethyltrimethoxysilane. It is also possible to use methyl-, ethyl- or vinyltrimethoxysilane, tetramethyl- or tetraethylethoxysilane. Vinyltrimethoxysilane and tetraethoxysilane are particularly suitable in terms of cost and efficiency.

[0188] Molecular weight (M n The aforementioned reactive diluents are also suitable as drying agents, provided that they have a molecular weight (Mg / mol) of less than about 5000 g / mol and have end groups whose reactivity towards penetrating moisture is at least as high as, and preferably higher than, the reactivity of the reactive groups of the polymers used according to the invention.

[0189] Finally, alkyl orthoformates or alkyl orthoacetates, such as methyl or ethyl orthoformate or methyl or ethyl orthoacetate, can also be used as drying agents.

[0190] The compositions generally contain from about 0 to about 6% by weight of a desiccant.

[0191] The compositions described herein may further comprise a filler. Suitable here are, for example, chalk, lime powder, precipitated and / or pyrogenic (fumed) silica, zeolites, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, tallow, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground mineral substances. Organic fillers may also be used, such as, for example, carbon black, graphite, wood fibers, wood flour, sawdust, cellulose, cotton, pulp, wood chips, shredded straw, rice husk, etc. Short fibers may also be added, such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers, polyethylene fibers, etc. Aluminum powder is also suitable as a filler.

[0192] The pyrogenic (fumed) silica and / or precipitated silica is preferably 10 to 250 m 2 When used, they do not further increase the viscosity of the compositions of the present invention, but rather contribute to strengthening the cured composition.

[0193] As a filler, advantageously 100-250 m 2 / g, especially 110-170m 2 It is also conceivable to use pyrogenic and / or precipitated silicas with a BET specific surface area of ​​1000 / g. Due to the high BET specific surface area, the same effect, for example the strengthening of the hardening formulation, can be achieved with a smaller weight percentage of silicic acid. Thus, the compositions described herein can be improved in terms of other requirements using further substances.

[0194] Further suitable as fillers are hollow spheres with a mineral or plastic shell. These may be, for example, hollow glass spheres available under the trade name Glass Bubbles®. Plastic-based hollow spheres, such as Expancel® and Dualite®, are described, for example, in EP 0 520 426. They are composed of inorganic or organic materials and have a diameter of less than or equal to 1 mm, preferably less than or equal to 500 μm, respectively.

[0195] Fillers that impart thixotropic properties 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. To be easily squeezed out of a suitable dispensing device (for example a tube), such formulations have a viscosity of 3000-15000, preferably 40000-80000 mPas, or even 50000-60000 mPas.

[0196] The filler is preferably used in an amount of 1 to 80% by weight, particularly preferably 2 to 60% by weight. Of course, a mixture of multiple fillers can also be used. In this case, the quantitative data naturally refers to the total amount of fillers in the composition.

[0197] In a preferred embodiment, the curable composition of the present invention comprises the following components in the weight percentages listed: at least one polyorganosiloxane (A), from about 20 to 97% by weight, preferably from 25 to 70% by weight; at least one curing catalyst (B), about 0.05-2 wt.%, preferably 0.1-1.5 wt.%; At least one polymer (C), about 0.1 to 10% by weight, preferably 0.1 to 5% by weight; and Optionally, at least one or more auxiliary substances (wherein the weight percentages total 100% by weight, the weight percentages being based on the total weight of the curable composition).

[0198] In another preferred embodiment, the curable composition of the present invention contains the following components in the weight proportions listed: at least one polyorganosiloxane (A), from about 20 to 97% by weight, preferably from 25 to 70% by weight; at least one curing catalyst (B), about 0.05-2 wt.%, preferably 0.1-1.5 wt.%; at least one polymer (C), about 0.1-10% by weight, preferably 0.1-5% by weight; At least one adhesion promoter (D), from about 0.01 to 5% by weight, preferably from 0.1 to 2% by weight; and Optionally, at least one or more auxiliary substances (wherein the weight percentages total 100% by weight, the weight percentages being based on the total weight of the curable composition).

[0199] With regard to preferred representatives of the individual components and their preferred amounts used, the statements made above in the description of the respective components apply.

[0200] The preparation of the curable compositions of the present invention can be carried out by simply mixing the polyorganosiloxane (A), the curing catalyst (B), the silane-functional polymer (C), and optionally the other components described herein. This can be done in a suitable dispersing device, for example a high-speed mixer. In this case, it is preferable to take care to avoid as much as possible the contact of the mixture with moisture, which may cause undesired premature curing. Suitable measures are well known and include, for example, working in an inert atmosphere, possibly under a protective gas, and drying / heating each component before addition.

[0201] The present invention also relates to an adhesive, sealant, or coating material comprising the curable composition of the present invention.

[0202] The present invention further relates to the use of the curable composition of the present invention as an adhesive, sealant or coating material. A further field of application of the composition is its use as a plugging compound, hole filler, crack filler. The use as an adhesive and / or sealant is preferred. The composition is particularly suitable for bonding plastics such as PVC (polyvinyl chloride), ABS (acrylonitrile-butadiene-styrene copolymer), polycarbonate, acrylic materials, in particular PMMA (poly(methyl methacrylate)), metals, glass, ceramics, tiles, wood, wood-based materials, paper, paper-based materials, rubber and textiles, bonding floors, sealing building elements, windows, wall coverings, floor coverings, joints in general. In this case, the materials can be bonded to themselves or to each other as desired.

[0203] The following examples serve to illustrate the invention without, however, limiting it thereto. EXAMPLES

[0204] Formulations were prepared as described in the table below and subjected to cure performance testing as follows:

[0205] Skin Over Time (SOT) Measurement : Skin over time (SOT) is defined as the time required for a material to form a tack-free surface skin. Skin over time measurements are carried out according to DIN 50014 under standard climatic conditions (23 ± 2 °C, 50 ± 5% relative humidity). The temperature of the sealant must be 23 ± 2 °C and the sealant must be stored in the laboratory for at least 24 hours beforehand. The sealant is applied to a piece of paper and spread with a putty knife to form a skin (approximately 2 mm thick and 7 cm wide). A stopwatch is started immediately. At intervals, lightly touch the surface with the tip of your finger and pull the finger away; apply enough pressure to the surface to leave a mark on it until the skin formation time is reached. The skin over time is reached when the sealing compound no longer adheres to the fingertip. Skin over time (SOT) is expressed in minutes.

[0206] Shore A hardness measurement : Shore A hardness was measured according to ISO868.

[0207] Depth of case (DOC) measurement : A strip of material 10 mm (± 1 mm) high and 20 mm (± 2 mm) wide was applied onto a plastic foil (PP) using a Teflon spatula. After storing the samples for 24 hours under normal conditions (23 ± 2 °C, 50 ± 5% relative humidity), a part of the strip was cut out and the thickness of the cured layer was measured with a vernier caliper. The depth of cure after 24 hours is expressed in millimeters.

[0208] Mechanical property evaluation (tensile test) : In the tensile test, the breaking strength, breaking elongation and yield stress values ​​(e-module) are determined according to DIN 53504. The test was carried out with S3 specimens under normal conditions (23 ± 2 °C, relative humidity 50 ± 5%). The measurements were carried out after 7 days of curing. Procedure: The prepolymer mixture (preparation) was spread on a uniform surface to form a film with a thickness of 2 mm. After the film was cured for 7 days under normal conditions (see above), dumbbell specimens were punched out. Three specimens were used for each measurement. The test was carried out under normal conditions. The specimens must be at the same temperature at which the measurements are carried out. Prior to the measurements, the thickness of the specimen is measured with a vernier caliper in at least three different positions (center and both ends). The average value is entered into the measurement software. The specimen is clamped in the tensile tester so that its longitudinal axis coincides with the mechanical axis of the tensile tester and includes the widest possible surface of the rod head without clamping the middle bar. The dumbbell is then pulled to <0.1 MPa at a rate of 50 mm / min. The force-elongation curve is then recorded at a linear speed of 50 mm / min. Evaluation: The following values ​​are measured: Breaking strength [N / mm 2 ], elongation at break [%] and modulus of elasticity at 100% elongation [N / mm 2 ].

[0209] Peel test: If possible and necessary, the substrate (test panel) is cleaned before application using a suitable solvent. Strips of material 10 mm (± 1 mm) high and 20 mm (± 2 mm) wide were applied onto the substrate using a Teflon spatula / cartridge and cartridge gun. The samples were stored for 7 days under normal conditions (23 ± 2°C, 50 ± 5% relative humidity). The cured material was cut to at least 15 mm with a shape blade and the bead was pulled by hand. The failure mode was recorded as follows: TIFF2025508506000022.tif2366

[0210] Example 1 Inventive compositions 1-A and 1-B, as well as comparative compositions 1-C through 1-F, were prepared using the ingredients listed in Table 1. In particular, α,ω-dihydroxy-terminated polydimethylsiloxane was first reacted with vinyltris(ethyllactato)silane in the presence of a plasticizer, extender, and (endcapping) catalyst to produce lactatesilane-terminated polydimethylsiloxane. In subsequent steps, other ingredients were added. Mixing was performed using a dual asymmetric centrifugal mixer (SpeedMixer™ DAC 400.2 VAC-P) under vacuum (80-200 mbar) at 0-2500 RPM for 100-120 seconds per step.

[0211] [Table 1]

[0212] [Table 2]

[0213] Example 2 Compositions 2-A to 2-F of the present invention were prepared according to the same method as described in Example 1 using the raw materials listed in Table 3.

[0214] [Table 3]

[0215] [Table 4]

[0216] Example 3 Compositions 3-A and 3-B of the present invention, as well as Comparative Composition 3-C, were prepared using the ingredients listed in Table 5. In particular, α,ω-dihydroxy-terminated polydimethylsiloxane was first reacted with vinyltris(ethyllactato)silane in the presence of a plasticizer, extender, and (endcapping) catalyst to produce a lactatesilane-terminated polydimethylsiloxane. In subsequent steps, other ingredients were added. Mixing was performed using a PC Lab Mixer (manufactured by PC Laborsystem GmbH) equipped with a blade stirrer and dissolver blade at 0-200 RPM under N2 atmosphere or vacuum (80-200 mbar) for 3-10 minutes per step.

[0217] [Table 5]

[0218] [Table 6]

[0219] [Table 7]

[0220] [Table 8]

Claims

1. (A) Formula (I): 【Chemistry 1】 [In the formula, Each R １ are independently selected from the group consisting of hydrogen, halogen, amino, oximino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, cycloaliphatic, cycloaliphatic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, and acyloxy groups, or combinations thereof; Each R ２ are independently represented by the general formula (2): 【Chemistry 2】 [During the ceremony, Y is a substituted or unsubstituted (hetero)aromatic group having 4 to 14 ring atoms, a substituted or unsubstituted saturated or partially unsaturated 4 to 14-membered (hetero)cyclic group, or -(C(R ５ ) ２ ) ｏ - and; R ４ is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, or heteroalicyclic group, or combinations thereof; Each R ５ are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, and aryl groups; and o is an integer of 1 to 10. is a group of Each R ３ are independently represented by the general formula (3): 【Transformation 3】 [During the ceremony, Y is as defined above; R ６ is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof, or R ７ selected from the group consisting of: R ７ is represented by the general formula (4): 【Chemistry 4】 <During the ceremony, R ８ is an alkylene group optionally interrupted by a heteroatom; Each R ９ are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R １０ are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, and acyl groups; each p independently represents 0, 1 or 2; is the base of is a group of m is independently 0, 1 or 2; n is independently 1, 2, or 3, and the sum of n and m is at most 3. at least one polyorganosiloxane containing at least one end group of (B) at least one curing catalyst; and (C) General formula (II): 【Transformation 5】 [In the formula, X is a divalent linking group containing at least one heteroatom; R is selected from divalent hydrocarbon residues having 1 to 12 carbon atoms; Each R ａ are each independently selected from a hydrocarbon group containing 1 to 20 carbon atoms, and each R ｂ are independently selected from a hydroxyl group or a hydrolyzable group, where R ａ and R ｂ is a substituent directly bonded to the Si atom, or a substituent R ａ and R ｂ two of which form a ring together with the Si atom to which they are attached; k is 0, 1, or 2; o is 0 or 1. At least one polymer having at least one silane functional group of A curable composition comprising:

2. The polyorganosiloxane is linked to the end groups of formula (I) through a linking group -A-, where -A- is a bond, -O-, or a linear, branched, or cyclic divalent radical selected from a hydrocarbon residue having 1 to 12 carbon atoms, alkylene, arylene, oxyalkylene, oxyarylene, siloxane-alkylene, siloxane-arylene, ester, amine, glycol, imide, amide, alcohol, carbonate, urethane, urea, sulfide, ether, or derivatives or combinations thereof, preferably -A- is a bond, -O-, or siloxane-alkylene, preferably a group of formula -(CH ２ ) １－１０ -(Si(Alk) ２ -O-Si(Alk) ２ ) １－１０ - (CH ２ ) １－１０ wherein Alk is C １ - １０ 2. The curable composition of claim 1, wherein the siloxane-alkylene group is a linear or branched divalent group selected from the group consisting of siloxane-alkylenes or derivatives thereof, each of which is alkyl, preferably methyl.

3. 2. The curable composition of claim 1, wherein the polyorganosiloxane is a polydiorganosiloxane, preferably polydimethylsiloxane (PDMS).

4. Each R １ represent, independently of one another, an alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl or isopropyl, an alkenyl group having 2 to 10 carbon atoms, in particular vinyl or allyl, an aryl group having 6 to 10 carbon atoms, in particular phenyl, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, preferably acetoxy, oximino, an alkenyloxy group having 2 to 10 carbon atoms, or amino; and / or Each R ２ are each independently represented by the general formula (2) [wherein R ４ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and Y represents a substituted or unsubstituted aromatic group having 6 carbon ring atoms, preferably 1,2-phenylene, or -(C(R ５ ) ２ ) ｏ - [wherein o is 1 and R ５ One of the groups is hydrogen and the second R ５ the group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or their (alkyl) esters; and / or the sum of n+m is 2 or 3, preferably 3; The curable composition of claim 1.

5. The polyorganosiloxane (A) has the formula (Ib): 【Transformation 6】 [In the formula, C is a reactive group that reacts with the terminal reactive group A′, preferably R ２ or R ３ and A' is preferably a hydroxy, amino, or isocyanate group, more preferably a hydroxy group; R １ , R ２ , R ３ , m and n are the same as defined for general formula (I).

2. The curable composition of claim 1, obtained by reacting a polyorganosiloxane having at least one terminal reactive group A′(Ia) capable of reacting with a silane crosslinker having the formula:

6. The group -Si(R １ ) ｍ (R ２ ) ｎ (R ３ ) ３－（ｍ＋ｎ） 2. The curable composition of claim 1, wherein is selected from methylbis(ethyllactato)silane, ethylbis(ethyllactato)silane, phenylbis(ethyllactato)silane, vinylbis(ethyllactato)silane, tri(ethyllactato)silane, methylbis(ethylsalicylato)silane, ethylbis(ethylsalicylato)silane, phenylbis(ethylsalicylato)silane, vinylbis(ethylsalicylato)silane, tri(ethylsalicylato)silane, methylbis(diethylmalato)silane, ethylbis(diethylmalato)silane, phenylbis(diethylmalato)silane, vinylbis(diethylmalato)silane, tri(diethylmalato)silane, and mixtures thereof.

7. 10. The curable composition of claim 1, wherein the curing catalyst (B) is selected from a tin catalyst, a titanium catalyst, an aluminum catalyst, or a zirconium catalyst, or mixtures thereof.

8. 2. The curable composition of claim 1, wherein the polymer (C) has at least two silane functional groups of general formula (II), preferably at least two terminal silane functional groups of general formula (II).

9. 2. The curable composition of claim 1, wherein the polymer backbone of polymer (C) is selected from polyethers, poly(meth)acrylates, polyesters, polyurethanes, or poly-α-olefins, preferably polyethers or polyurethanes, or copolymers of at least two of said polymers.

10. The divalent linking group X in the general formula (II) is selected from —O—, —S—, —N(R″)—, —R′″-O—, substituted or unsubstituted amide, carbamate, urethane, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate, or sulfinate groups, preferably —O—C(═O)—N(R″)—, —N(R″)—C(═O)O—, —N(R″)—C(═O)—N(R″)—C(═O)—, —C(═O)—N(R″)—O—, —C(═O)—N(R″)—O—, —O -C(=O)-, -O-C(=O)-O-, -S-C(=O)-N(R")-, -N(R")-C(=O)-S-, -C(=O)-S-, -S-C(=O)-, -S-C(=O)-S-, -C(=O)-, -S-, -O-, -N(R")- and -R"'-O-, wherein R" is hydrogen or a straight-chain or branched, substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms and R'" is a straight-chain or branched, substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms; and / or R in general formula (II) is selected from methylene, ethylene or n-propylene, preferably methylene or n-propylene; and / or Each R in general formula (II) ａ are, independently of each other, C １ -C ８ alkyl groups, preferably selected from methyl or ethyl; and / or Each R in general formula (II) ｂ are each independently a hydroxyl, C １ -C ８ Alkoxy group, C １ -C ８ Acyloxy group, or —O—Y—COOR ４ (Wherein, Y and R ４ is as defined for general formula (2) above), preferably C １ -C ８ an alkoxy group, in particular methoxy or ethoxy, or -O-Y-COOR ４ , in particular an ethyl lactate, ethyl salicylate, or diethyl malate group; and / or and k is 0 or 1.

11. 2. The curable composition of claim 1, wherein the composition comprises about 0.1 to 10 wt. %, preferably about 0.1 to 5 wt. %, more preferably about 0.5 to 2 wt. % of polymer (C), based on the total weight of the composition.

12. The curable composition further comprises (D) at least one adhesion promoter, preferably the adhesion promoter is one of the following: (i) aminosilanes, optionally oligomerized with alkyl-, alkenyl-, or aryl-alkoxysilanes; (ii) oligomers resulting from the condensation of aminosilanes, optionally oligomerized with alkyl-, alkenyl-, or aryl-alkoxysilanes; or (iii) Mixtures thereof The curable composition of claim 1 , comprising at least one compound selected from:

13. (i) the amount of polyorganosiloxane (A) is from about 20 to about 97 wt. %, preferably from 25 to 70 wt. %, based on the total weight of the composition; and / or (ii) the amount of curing catalyst (B) is from about 0.05 to about 2 wt. %, preferably from 0.1 to 1.5 wt. %, based on the total weight of the composition; and / or (iii) the amount of polymer (C) is from about 0.1 to about 10% by weight, preferably from 0.1 to 5% by weight, more preferably from about 0.5 to 2% by weight, based on the total weight of the composition; and / or (iv) the amount of adhesion promoter (D) is 0 to about 5 wt. %, preferably 0.01 to 5 wt. %, based on the total weight of the composition; The curable composition of claim 1.

14. An adhesive, sealant, or coating material comprising the curable composition of any one of claims 1 to 13.

15. Use of the curable composition according to any one of claims 1 to 13 as an adhesive, sealant or coating material.

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