Crosslinkable compositions based on organosilicon compounds

Abstract

The present invention relates to crosslinkable compositions based on organosilicon compounds which cure with the removal of alcohol to form highly stable materials. These compositions comprise (A) an organosilicon compound having at least two OH groups, (B) a compound of the formula A[CR 1 2SiR a (OR 2 ) 3-a ]x (I) heterocyclic compounds of the formula Si(OR4)3O 1 / 2 (III), Si(OR4)2O 2 / 2 (IV), (OR 4 )SiO 3 / 2 (V) and optionally SiO 4 / 2 It can be prepared using at least one compound containing units of formula (VI) (the radicals and subscripts have the meanings given in claim 1), compound (C) containing at least 10 mol % of units of formula (V). The invention also relates to a process for its preparation and to its use.

Description

[Technical field]

[0001] The present invention relates to crosslinkable compositions based on organosilicon compounds which cure by removal of alcohol to give materials with very high stability, to a process for their preparation and to their use. [Background technology]

[0002] Single-component sealing compounds are already known which can be stored under the exclusion of water and which, upon ingress of water at room temperature, cure to elastomers by elimination of alcohol. These products are used in large quantities, for example in the construction industry. These mixtures are based on polymers terminated with silyl groups which carry reactive substituents such as OH groups or hydrolyzable groups, for example alkoxy groups. These sealing compounds may also contain fillers, plasticizers, crosslinkers, catalysts and various additives.

[0003] The catalysts used are often diorganotin compounds, and sometimes titanium compounds are used, but titanium catalysts are not preferred because they cause undesirable yellowing very quickly.

[0004] However, from a chemical law point of view, the preferred organotin compounds are the subject of further important classifications. Therefore, attempts have been made to use less, or even completely avoid, substances such as dioctyltin and dibutyltin compounds in RTV1 sealing compounds.

[0005] EP2176351B1 teaches the production of RTV1 sealing compounds based on 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine. The examples given show that it is also possible to completely dispense with the use of organotin catalysts. However, in that case the processing times for the more rigid variants are too long for use as joint sealants.

[0006] EP2855591B1 describes the addition of hydrolysates formed from unsubstituted alkyltrialkoxysilanes to obtain RTV1 sealing compounds based on 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine. These particular siloxanes improve the resistance of the cured composition to the effects of warm and humid environmental conditions. The composition contains a dialkyltin compound as a catalyst.

[0007] EP3433321B1 describes the preparation of migrating RTV1 coating compositions based on N,N-dialkylaminomethyltrialkoxysilanes. As well as other components, the mixture also contains a partial hydrolysate formed from tetraethoxysilane. The composition here is selected so that the cured mass has good adhesion to various substrates. Due to the high reactivity of the selected alpha-silanes, no additional catalysts or curing accelerators are required. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] European Patent No. 2176351 [Patent Document 2] European Patent No. 2855591 [Patent Document 3] European Patent No. 3433321 Summary of the Invention

[0009] Surprisingly, it has been found that RTV1 sealing compounds based on 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine have very good curing properties even without the addition of an organotin catalyst, when the composition contains a partial hydrolysate of a tetraalkoxysilane.Due to the relatively low reactivity of this partial hydrolysate, for example, a person skilled in the art could not expect that the skin time of an RTV1 sealing compound based on alpha-silane could be shortened in a controlled manner.

[0010] Here, it was particularly surprising that the hardened material had low tensile stress values ​​under strain.

[0011] Furthermore, it was quite particularly surprising that the cured material had low tensile stress values ​​under strain when only small amounts of plasticizer were used.

[0012] The present invention provides compositions that are crosslinkable by a condensation reaction and can be produced by using: (A) an organosilicon compound having at least two OH groups; (B) Heterocyclic compounds of the following formula and / or their partial hydrolysates: A [CR 1 2SiR a (OR 2 ) 3-a ] x (I) [In the formula, A is the heterocycle AH x and containing at least one ring-forming element of main group 3 and / or 5, where x hydrogen atoms are selected from the group consisting of CR 1 is replaced by chemical bonds to two groups, where at least one of these bonds is on a ring-forming element of main group 3 or 5; R represents the same or different monovalent optionally substituted hydrocarbyl groups; R 1 may be the same or different and represent a hydrogen atom or a monovalent optionally substituted hydrocarbyl group; R 2 represent, which may be the same or different, monovalent optionally substituted hydrocarbyl groups; a=0 or 1, preferably 0, and x=1, 2 or 3, preferably 1 or 2, more preferably 1. and (C) at least one compound containing a unit of the formula: Si(OR 4 )3O 1 / 2 (III), Si(OR 4 )2O2 / 2 (IV), (OR 4 )SiO 3 / 2 (V) and Optional SiO 4 / 2 (VI), [In the formula, R 4 may be the same or different and are independently an alkyl group in each case; However, compound (C) contains at least 10 mol % of units of formula (V). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The partial hydrolysates of compounds of formula (I) may be partial homohydrolysates or partial cohydrolysates. When component (B) used according to the invention comprises partial hydrolysates of compounds of formula (I), those having up to 10 silicon atoms are preferred.

[0014] The group R is preferably an optionally substituted monovalent hydrocarbyl group having 1 to 18 carbon atoms, more preferably an alkyl group, a vinyl group, a 3,3,3-trifluoroprop-1-yl group and a phenyl group, especially a methyl group.

[0015] Examples of radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl radicals; hexyl radicals, such as n-hexyl radical; heptyl radicals, such as n-heptyl radical; octyl radicals, such as n-octyl radical and iso-octyl radical, such as 2,2,4-trimethylpentyl radical; nonyl radicals, such as n-nonyl radical; decyl radicals, such as n-decyl radical; dodecyl radicals, such as n-dodecyl radical. cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl; alkenyl groups, such as vinyl, 1-propenyl and 2-propenyl; aryl groups, such as phenyl, naphthyl, anthryl and phenanthryl; alkaryl groups, such as o-, m- and p-tolyl; xylyl and ethylphenyl; and aralkyl groups, such as benzyl and α- and β-phenylethyl.

[0016] Examples of substituted groups R are haloalkyl groups such as 3,3,3-trifluoroprop-1-yl, 1,1,1,3,3,3-hexafluoroprop-2-yl and heptafluoroprop-2-yl, haloaryl groups such as o-, m- and p-chlorophenyl, and 2-methoxyethyl, 2-methoxyprop-1-yl and 2-(2-methoxyethoxy)ethyl.

[0017] base R 1 Examples of are a hydrogen atom and the groups specified for R.

[0018] base R 1 is preferably a hydrogen atom and a hydrocarbyl group having 1 to 20 carbon atoms, in particular a hydrogen atom.

[0019] base R 2 Examples are the groups specified for R.

[0020] base R 2is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl or ethyl group, in particular an ethyl group.

[0021] The group A is a cyclic compound having at least two ring-forming atoms of different elements, provided that at least one ring-forming atom is -CR 1 2- Main group 3 and / or 5 elements with bonding sites to carbon atoms of the group.

[0022] The group A is preferably a cyclic organic compound, the ring structure of which contains, as well as carbon atoms, at least one element of main groups 3 and / or 5, more preferably at least one further heteroatom.

[0023] The term "heteroatom" shall hereinafter be understood to mean all ring-forming atoms other than carbon.

[0024] The ring-forming heteroatoms in group A are preferably nitrogen, phosphorus, oxygen, silicon and sulfur, more preferably nitrogen and oxygen.

[0025] The group A may also be a saturated or partially unsaturated heterocyclic ring which may be substituted. When ring A is substituted, the substituents are preferably halogen atoms, hydrocarbyl groups and organyloxy groups, and these substituents may be polyvalent groups which may be bonded to one or more ring-forming atoms.

[0026] The group A may also contain a ring carbon atom having an oxygen or sulfur atom attached through a double bond, provided that such a ring carbon atom is not a CR 1 It is not directly bonded to a ring-forming heteroatom of main group 3 or 5 which is bonded to two groups.

[0027] The group A may also contain a ring carbon atom having a nitrogen or phosphorus atom attached through a double bond, although this is not preferred.

[0028] The group A is preferably a 3-, 4-, 5-, 6-, 7- or 8-membered heterocyclic ring having nitrogen and / or phosphorus and / or oxygen and / or sulfur as heteroatoms in addition to carbon as ring-forming atoms, provided that at least one ring-forming atom is an element of main group 3 and / or 5, and further rings can also be linked by fusion.

[0029] More preferably, the heterocycle on which the A group is based has a further ring heteroatom as well as a CR 1 These are 5- and 6-membered heterocycles containing 3 and / or 5 main group heteroatoms required for bonding to the two groups.

[0030] Examples of heterocycles on which the A group is based are aziridine, azetidine, pyrrole, pyrrolidine, 1,3-oxazolidine, 1,3-thiazolidine, 1H-1,2-diazole, Δ 2 -1,2-Diazoline, Δ 4 -1,2-Diazoline, 1,3-Diazole, Δ 2 -1,3-Diazoline, Δ 4 -1,3-diazoline, 1,3-diazolidine, 1,2,3-triazole, 1,2,4-triazole, tetrazole, Δ 4 1,2-diazolin-3-one, piperidine, tetrahydro-1,4-oxazine, tetrahydro-1,4-thiazine, hexahydro-1,3-diazine, hexahydro-1,4-diazine, 1-methylhexahydro-1,4-diazine, hexahydro-1,3,5-triazine, hexahydro-1,3-diazin-4-one, 4-methylhexahydro-1,4-diazin-3-one, 1H-azepine, hexahydroazepine, octahydroazocine, 1H-benzo[b]pyrrole, 2,3-dihydrobenzo[b]pyrrole, 9H-dibenzopyrrole, benzo[d]-1,2-diazole, benzo[d]-1,3-diazole and benzo[d]-1,2,3-triazole.

[0031] Particularly preferred are pyrrolidine, piperidine, tetrahydro-1,4-oxazine, tetrahydro-1,4-thiazine, tetrahydro-1,4-diazine and 1-methyltetrahydro-1,4-diazine, especially tetrahydro-1,4-oxazine.

[0032] Examples of heterocyclic compounds (B) are 1-(triethoxysilylmethyl)aziridine, 1-(triethoxysilylmethyl)azetidine, 1-(triethoxysilylmethyl)pyrrole, 1-(triethoxysilylmethyl)pyrrolidine, 3-(triethoxysilylmethyl)-1,3-oxazolidine, 3-(triethoxysilylmethyl)-1,3-thiazolidine, 1-(triethoxysilylmethyl)-1H-1,2-diazole, 1-(triethoxysilylmethyl)-Δ 2 -1,2-Diazoline, 1-(triethoxysilylmethyl)-Δ 4 -1,2-Diazoline, 1-(triethoxysilylmethyl)-1,3-diazole, 1-(triethoxysilylmethyl)-Δ 2 -1,3-Diazoline, 1-(triethoxysilylmethyl)-Δ 4 -1,3-diazoline, 1-(triethoxysilylmethyl)-1,3-diazolidine, 1,3-bis(triethoxysilylmethyl)-1,3-diazolidine, 1-(triethoxysilylmethyl)-1H-1,2,3-triazole, 2-(triethoxysilylmethyl)-2H-1,2,3-triazole, 1-(triethoxysilylmethyl)-1H-1,2,4-triazole, 4-(triethoxysilylmethyl)-4H-1,2,4-triazole, 1-(triethoxysilylmethyl)-1H-tetrazole, 2-(triethoxysilylmethyl)-2H-tetrazole, 1-(triethoxysilylmethyl)-Δ 4-1,2-diazolin-3-one, 1-(triethoxysilylmethyl)piperidine, 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine, 4-(1-(triethoxysilyl)ethyl)tetrahydro-1,4-oxazine, 4-(2-(triethoxysilyl)prop-2-yl)tetrahydro-1,4-oxazine, 4-(1-phenyl-1-(triethoxysilyl)-ethyl)tetrahydro-1,4-oxazine, 4-(triethoxysilylmethyl)-tetrahydro-1 ,4-Thiazine, 1-(triethoxysilylmethyl)hexahydro-1,3-diazine, 1-(triethoxysilylmethyl)hexahydro-1,4-diazine, 1-methyl-4-(triethoxysilylmethyl)hexahydro-1,4-diazine, 1,4-bis(triethoxysilylmethyl)hexahydro-1,4-diazine, 1,4-bis(1-(triethoxysilyl)ethyl)hexahydro-1,4-diazine, 1-(triethoxysilylmethyl)hexahydro-1,3,5-triazine , 1,3-bis(triethoxysilylmethyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(triethoxysilylmethyl)-hexahydro-1,3,5-triazine, 1-(triethoxysilylmethyl)-hexahydro-1,3-diazin-4-one, 1-(triethoxysilylmethyl)-4-methylhexahydro-1,4-diazin-3-one, 1-(triethoxysilylmethyl)-1H-azepine, 1-(triethoxysilylmethyl)hexahydroazepine, 1-( 1-(triethoxysilylmethyl)-octahydroazocine, 1-(triethoxysilylmethyl)benzo[b]pyrrole, 1-(triethoxysilylmethyl)-2,3-dihydrobenzo[b]pyrrole, 9-(triethoxysilylmethyl)dibenzopyrrole, 1-(triethoxysilylmethyl)-benzo[d]-1,2-diazole, 1-(triethoxysilylmethyl)benzo[d]-1,3-diazole and 1-(triethoxysilylmethyl)benzo[d]-1,2,3-triazole.

[0033] Further examples are all of the above compounds in which the triethoxysilyl groups are replaced by trimethoxysilyl, diethoxymethylsilyl or dimethoxymethylsilyl groups.

[0034] The heterocyclic compounds (B) used according to the invention are standard commercially available compounds or can be prepared by standard chemical methods.

[0035] The composition of the present invention contains component (B) in an amount of preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and especially 1 to 10 parts by weight, per 100 parts by weight of component (A).

[0036] The organosilicon compound (A) used according to the invention can be any organosilicon compound having at least two OH groups which has been used to date in compositions crosslinkable by condensation reactions.

[0037] The organosilicon compounds (A) used according to the invention are preferably those which contain units of the following formula: R 3 b (OH) c SiO (4-b-c) / 2 (II) [In the formula, R3 may be the same or different and represent optionally substituted hydrocarbyl groups optionally interrupted by oxygen atoms; b is 0, 1, 2 or 3, preferably 2; c is 0, 1, 2 or 3, preferably 0 or 1; However, the sum of b+c is ≦3, and at least two condensable OH groups are present per molecule.

[0038] base R 3 is preferably a monovalent hydrocarbyl group having 1 to 18 carbon atoms and optionally substituted by a halogen atom, an amino group, an ether group, an ester group, an epoxy group, a mercapto group, a cyano group or a (poly)glycol group, the latter being formed from oxyethylene units and / or oxypropylene units and more preferably an alkyl group having 1 to 12 carbon atoms, in particular a methyl group.

[0039] base R 3 Examples of are those given for the group R.

[0040] More preferably, the organosilicon compounds (A) used according to the invention are essentially linear OH-terminated organopolysiloxanes, in particular α,ω-dihydroxydialkylpolysiloxanes.

[0041] An example of an organosilicon compound (A) is (HO)Me2SiO[SiMe2O] 30-2000 SiMe2(OH) where Me = methyl group.

[0042] The organosilicon compounds (A) used according to the invention are in each case preferably at 10° C. 3 ~10 6 mPas, more preferably 10 4 It has a viscosity of ~350,000 mPas.

[0043] The organosilicon compounds (A) are commercially available or can be prepared by standard methods in silicon chemistry.

[0044] base R 4 Examples of are, independently, the examples given above for the group R.

[0045] base R 4 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

[0046] The compound (C) used according to the invention preferably comprises units of the formulae (III), (IV) and (V) in a total amount of at least 70 mol %, more preferably at least 85 mol %, in particular at least 90 mol %.

[0047] The compound (C) used according to the present invention contains at least 10 mol %, preferably 10 to 50 mol %, more preferably 12 to 30 mol %, of units of the formula (III).

[0048] The compound (C) used according to the invention preferably contains from 15 to 60 mol % of units of formula (III).

[0049] The compound (C) used according to the invention preferably contains from 20 to 60 mol % of units of formula (IV).

[0050] Compound (C) used according to the invention preferably comprises 10-50 mol % of units of formula (V), 15-60 mol % of units of formula (III) and 20-60 mol % of units of formula (IV).

[0051] Compound (C) used according to the invention may also contain, apart from units of formulae (III), (IV) and (V), units of formula (VI), although this is not preferred.

[0052] When the compound (C) used according to the invention contains units of formula (VI), preferably less than 2 mol % of these units are present.

[0053] Preferably, the compound (C) used according to the invention consists of units of formulae (III), (IV) and (V) and optionally (VI).

[0054] Although not represented by formulae (III)-(VI), the compounds (C) used according to the invention may contain up to 1% by weight of residual Si-OH as an impurity as a result of their preparation.

[0055] Examples of siloxanes (C) which can be used according to the invention are: (Si(OEt)O 2 / 2 ) 0.42 (Si(OEt)O 3 / 2 ) 0.19 (Si(OEt)O 1 / 2 ) 0.39 , and (Si(OEt)O 2 / 2 ) 0.47 (Si(OEt)O3 / 2 ) 0.35 (Si(OEt)O 1 / 2 ) 0.16 (SiO 4 / 2 ) 0.02 It is.

[0056] The siloxane (C) preferably has a weight average Mw of 500 to 10,000 g / mol, more preferably 500 to 8,000 g / mol.

[0057] The siloxane (C) preferably has a number average Mn of 200 to 5000 g / mol, more preferably 200 to 3000 g / mol.

[0058] The siloxane (C) preferably has a polydispersity Mw / Mn of 1-5, more preferably 1-4.

[0059] In the present invention, the weight average Mw and number average Mn are rounded to the nearest hundred according to DIN 1333:1992-02 part 4 and are determined by gel permeation chromatography (GPC or size exclusion chromatography (SEC)) according to DIN 55672-1 using polystyrene standards and a refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent for phenyl-containing components and toluene is used as the eluent for non-phenyl-containing components, and the analysis is performed at a column temperature of 45°C. Polydispersity is the quotient Mw / Mn.

[0060] The organosiloxane (C) is preferably liquid at 25° C. and 1000 hPa.

[0061] The siloxanes (C) used according to the invention are commercially available, for example under the name WACKER® TES 40 from Wacker Chemie (Munich, Germany) or can be prepared by standard methods in silicon chemistry. For example, the compounds (C) used according to the invention can be prepared by hydrolysis and subsequent condensation of tetraalkoxysilanes.

[0062] In any case, the composition of the present invention contains component (C) in an amount of preferably 1 to 20 parts by weight, more preferably 4 to 10 parts by weight, per 100 parts by weight of component (A).

[0063] In addition to components (A), (B) and (C), the compositions of the invention may then contain all the substances which have been used to date in compositions crosslinkable by condensation reactions, such as catalysts (D), compounds containing basic nitrogen (E), fillers (F), adhesion promoters (G), plasticizers (H), further crosslinkers (J), additives (K) and solvents (L), components (J), (E) and (G) being different from components (B) and (C) and component (L) being different from the plasticizer (H).

[0064] Examples of catalysts (D) are the known titanium compounds, such as tetraisopropoxytitanate, zirconium compounds and hafnium compounds, and metal carboxylates, such as zinc(2-ethylhexoate) and octylphosphonic acid or its derivatives.

[0065] The optional catalysts (D) used are preferably alkoxides of metals of the 4th transition group of the periodic table of the elements, carboxylates and phosphonates of metals of the 12th transition group of the periodic table of the elements, more preferably alkoxides of titanium, carboxylates of zinc and derivatives of octylphosphonic acid, in particular derivatives of octylphosphonic acid, tetrabutyl titanate, zinc ethylhexanoate or octylphosphonic acid ester.

[0066] When the composition of the present invention contains a catalyst (D), the amount thereof is preferably 0.0001 to 2 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the composition of the present invention. The composition of the present invention preferably contains a catalyst (D).

[0067] The composition of the present invention may contain an organotin compound, preferably in an amount of not more than 0.01 part by weight, more preferably not more than 0.001 part by weight, per 100 parts by weight of the composition of the present invention, but the composition of the present invention is specifically free of an organotin compound.

[0068] The optional compound (E) containing a basic nitrogen used according to the invention is preferably a compound of the formula NR 6 3(IX) [In the formula, R 6 are the same or different and are hydrocarbyl groups optionally substituted with hydrogen atoms, hydroxy groups, halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or polyglycol residues, the latter being formed from oxyethylene and / or oxypropylene units, However, in formula (IX), there are two or less R 6 has the meaning of a hydrogen atom, and two or more R 6 When present, they can also be linked together to form a cyclic structure. An organosilicon compound having at least one organic group containing a basic nitrogen atom different from component (B), which is composed of units of the following formula: R 7 k Y l Si(OR 8 ) m O (4-k-1-m) / 2 (X), [In the formula, R 7 are the same or different monovalent SiC-bonded organic groups that do not contain basic nitrogen, R 8 may be the same or different, and the group R 2 With the definition given for Y, which may be the same or different, are monovalent SiC-bonded organic groups containing basic nitrogen; k is 0, 1, 2, or 3; l is 0, 1, 2, 3 or 4; m is 0, 1, 2 or 3; provided that the sum of k+l+m is 4 or less and at least one group Y is present per molecule. is selected from the group consisting of:

[0069] R 6 Groups and R 7 Examples of groups are in each case independently the examples of optionally substituted hydrocarbyl groups given for R.

[0070] an optionally substituted hydrocarbyl group R 6 Preferably, it has 1 to 18 carbon atoms.

[0071] base R 7 is preferably a hydrocarbyl group having 1 to 18 carbon atoms, with methyl, ethyl and n-propyl groups being particularly preferred, in particular methyl.

[0072] base R 8 Examples of the group R 2 Here is an example given for

[0073] base R 8 are preferably methyl and ethyl groups.

[0074] Examples of the group Y are those of the formula H2NCH2-, H2N(CH2)2-, H2N(CH2)3-, H2N(CH2)2NH(CH2)2-, H2N(CH2)2NH(CH2)3-, H2N(CH2)2NH(CH2)2NH(CH2)3-, H3CNH(CH2)3-, C2H5NH(CH2)3-, H3CNH(CH2)2-, C2H5NH(CH2)2-, H2N(CH2)4-, H2N(CH2)5-, H(NHCH2CH2)3-, C4H9NH(CH2)2NH(CH2)2-, cyclo-CH 11 NH(CH2)3-, cyclo-CH 11 The groups are NH(CH2)2-, (CH3)2N(CH2)3-, (CH3)2N(CH2)2-, (C2H5)2N(CH2)3- and (C2H5)2N(CH2)2-.

[0075] Preferably, Y is H2N(CH2)3-, H2N(CH2)2NH(CH2)3-, H3CNH(CH2)3-, C2H5NH(CH2)3- and cyclo-CH6 11The NH(CH2)3- group is particularly preferred, with H2N(CH2)2NH(CH2)3- and cyclo-CH 11 It is the NH(CH2)3- group.

[0076] When the organosilicon compound comprised of units of formula (X) is a silane, k is preferably 0, 1 or 2, more preferably 0 or 1; l is preferably 1 or 2, more preferably 1; and m is preferably 1, 2 or 3, more preferably 2 or 3, with the proviso that the sum of k+1+m is 4.

[0077] Examples of silanes of formula (X) that may be optionally used according to the present invention are H2N(CH2)3-Si(OCH3)3, H2N(CH2)3-Si(OC2H5)3, H2N(CH2)3-Si(OCH3)2CH3, H2N(CH2)3-Si(OC2H5)2CH3, H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OCH3 )2CH3, H2N(CH2)2NH(CH2)3-Si(OC2H5)2CH3, H2N(CH2)2NH(CH2)2NH(CH2)3-Si(OC2H5)3, cyclo-C6H 11 NH(CH2)3-Si(OCH3)3, cyclo-CH 11 NH(CH2)3-Si(OC2H5)3, cyclo-CH 11 NH(CH2)3-Si(OCH3)2CH3, cyclo-CH 11 NH(CH2)3-Si(OC2H5)2CH3, HN((CH2)3-Si(OCH3)3)2 and HN((CH2)3-Si(OC2H5)3)2 and partial hydrolysates thereof, and preferred are H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3, H2N(CH2)2NH(CH2)3-Si(OC2H5)2CH3, cyclo-CH 11 NH(CH2)3-Si(OC2H5)3, cyclo-CH 11NH(CH2)3-Si(OCH3)2CH3 and cyclo-CH 11 NH(CH2)3-Si(OC2H5)2CH3, and particularly preferred are H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)2CH3, cyclo-CH 11 NH(CH2)3-Si(OC2H5)3 and cyclo-CH 11 NH(CH2)3-Si(OC2H5)2CH3 and their respective partial hydrolysates.

[0078] When the organosilicon compound composed of units of formula (X) is an organopolysiloxane, the average value of k is preferably between 0.5 and 2.5, more preferably between 1.4 and 2.0, the average value of l is preferably between 0.01 and 1.0, more preferably between 0.01 and 0.6, and the average value of m is preferably between 0 and 2.0, more preferably between 0 and 0.2, with the proviso that the sum of k, l, and m is 3 or less.

[0079] The organopolysiloxanes composed of units of formula (X) that can be used according to the present invention preferably have a molecular weight of 5 to 10 5 mPas, more preferably 10 to 10 4 It has a viscosity of 1000 mPas at 25°C.

[0080] Examples of organopolysiloxanes composed of units of formula (X) that can be used according to the invention are H2N(CH2)3-Si(OCH3)2-O-Si(CH3)(OCH3)2, H2N(CH2)3-Si(OC2H5)2-O-Si(CH3)(OCH3)2, H2N(CH2)3-Si(OC2H5)2-O-Si(CH3)(OC2H5)2, H2N(CH2)3-Si(OCH3)(CH3)-O-Si(CH3)(OCH3)2, H2N(CH2)3-Si(OCH3)(CH3)-O-Si(OCH3)3, H2N(CH2)3-Si(OC2H5)(CH3)-O-Si(OCH3)3, H2N(CH2)2NH(CH2)3 - Si(OCH3)2 - O - Si(CH3)(OCH3)2, H2N(CH2)2NH(CH2)3 - Si(OC2H5)2 - O - Si(CH3)(OCH3)2, H2N(CH2)2NH(CH2)3 - Si(OC2H5)2 - O - Si(CH3)(OC2H5)2, H2N(CH2)2NH(CH2)3 - Si(OCH3)(CH3) - O - Si(CH3)(OCH3)2, H2N(CH2)2NH(CH2)3 - Si(OCH3)(CH3) - O - Si(OCH3)3, H2N(CH2)2NH(CH2)3 - Si(OC2H5)(CH3) - O - Si(OCH3)3, cyclo - C6H 11 NH(CH2)3 - Si(OCH3)2 - O - Si(CH3)(OCH3)2, cyclo - C6H 11 NH(CH2)3 - Si(OC2H5)2 - O - Si(CH3)(OCH3)2, cyclo - C6H 11 NH(CH2)3 - Si(OC2H5)2 - O - Si(CH3)(OC2H5)2, cyclo - C6H 11 NH(CH2)3 - Si(OCH3)(CH3) - O - Si(CH3)(OCH3)2, cyclo - C6H 11 NH(CH2)3 - Si(OCH3)(CH3) - O - Si(OCH3)3 and cyclo - C6H 11 NH(CH2)3 - Si(OC2H5)(CH3) - O - Si(OCH3)3, H2N(CH2)3 - Si(OCH3)2 - (O - Si(CH3)2) 1-100 - O - Si(OCH3)2 - (CH2)3NH2, H2N(CH2)2NH(CH2)3 - Si(OCH3)2 - (O - Si(CH3)2) 1-100 - O - Si(OCH3)2 - (CH2)3NH(CH2)2NH2 and cyclo - C6H 11NH(CH2)3-Si(OCH3)2-(O-Si(CH3)2) 1-100 -O-Si(OCH3)2-(CH2)3NHcyclo-CH 11 and partial hydrolysates thereof, particularly preferred is the hydrolysate of H2N(CH2)3-Si(OC2H5)2-O-Si(CH3)(OC2H5)2.

[0081] Organosilicon compounds composed of units of formula (X) are either commercially available products or can be prepared by standard methods in silicon chemistry.

[0082] Examples of amines of formula (IX) are cyclohexylamine, triethylamine, trioctylamine, butylamine, dodecylamine, diethyl-n-propylamine, cyclohexylmethylamine, 2-aminoethanol, 2-amino-n-propanol, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol, N,N-diethylethanolamine, ethylenediamine, cocoamine, cocomethylamine, N,N-dimethylethanolamine and aniline.

[0083] When component (E) is used, preferably component (E) comprises an organosilicon compound comprised of units of formula (X).

[0084] When the composition of the present invention contains component (E), the amount thereof is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably contains component (E).

[0085] The optional organosilicon compound (E) used according to the invention may also assume the function of a curing catalyst or cocatalyst in the composition of the invention.

[0086] Additionally, any organosilicon compound (E) used in accordance with the present invention may act as an adhesion promoter and / or a water scavenger.

[0087] Examples of fillers (F) are non-reinforcing fillers, i.e., 50m 2 fillers having a BET specific surface area of ​​up to 50 m, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders, such as aluminum oxide, titanium oxide, iron oxide or zinc oxide or mixed oxides thereof, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass powders and polymer powders, such as polyacrylonitrile powder; reinforcing fillers, i.e. 2 Fillers having a BET specific surface area of ​​more than 1000 nm, such as fumed silica, precipitated silica, precipitated calcium carbonate, carbon black, such as furnace black and acetylene black, and mixed silicon-aluminum oxides with high BET specific surface area; fibrous fillers, such as asbestos, and polymer fibers. The mentioned fillers may be hydrophobized, for example, by treatment with organosilanes or siloxanes or by etherification of hydroxyl groups to alkoxy groups. When fillers (F) are used, they are preferably hydrophilic fumed silica, precipitated calcium carbonate and ground marble.

[0088] When the composition of the present invention contains component (F), the amount thereof is preferably 1 to 80 parts by weight, more preferably 5 to 65 parts by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably contains component (F).

[0089] The optional adhesion promoter (G) used in the composition of the present invention may be silanes and organopolysiloxanes having functional groups, such as those having glycidoxypropyl, ureidopropyl or methacryloyloxypropyl groups. Examples of adhesion promoters (G) are epoxysilanes, such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmethyldiethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 2-(3-triethoxysilylpropyl)maleic anhydride, N-(3-trimethoxysilylpropyl)urea, N-(3-trimethoxysilylmethyl)urea, N-(methyldimethoxysilylmethyl)urea, N-(3-triethoxysilylmethyl)urea, N-(3-methyldiethoxysilylmethyl)urea, O-methylcarbamatomethylmethyldimethoxysilane ... trimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethylmethyldimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, acryloyloxymethyltrimethoxysilane, acryloyloxymethylmethyldimethoxysilane, acryloyloxymethyltriethoxysilane, acryloyloxymethylmethyldiethoxysilane, and partial condensates thereof.

[0090] When the composition of the present invention contains component (G), the amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably does not contain any component (G), except when calcium carbonate is used as a filler. When the composition of the present invention contains calcium carbonate as a filler (F), it is preferable to use component (G).

[0091] Examples of plasticizers (H) are dimethylpolysiloxanes which are liquid at room temperature and have a viscosity at 25° C. ranging, in particular, between 5 and 10,000 mPas, endblocked with trimethylsiloxy groups, and high-boiling hydrocarbons, such as paraffin oil or mineral oils consisting of naphthenic and paraffinic units.

[0092] When the composition of the present invention contains component (H), the amount thereof is preferably 1 to 50 parts by weight, more preferably 10 to 35 parts by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably contains component (H).

[0093] The optional further crosslinker (J) used in the composition of the present invention can be any crosslinker known to date having at least three condensable groups, for example a silane having at least three organyloxy groups different from component (B).

[0094] The optional further crosslinking agent (J) used in the composition of the present invention is preferably a silane crosslinking agent, such as methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1,2-bis(trimethoxysilyl)ethane or 1,2-bis(trimethylsilyl)ethane and partial hydrolysates thereof.

[0095] The further crosslinkers (J) used are more preferably the partial hydrolysates of alkyltrialkoxysilanes, very particularly preferably the partial hydrolysates of methyltrimethoxysilane.

[0096] The optional further crosslinkers (J) used in the compositions of the present invention are commercially available products or can be prepared by known methods in silicon chemistry. The partial hydrolysates of methyltrimethoxysilane are commercially available, for example, from Wacker Chemie (Munich, Germany) under the TRASIL brand name.

[0097] When the composition of the present invention contains a further crosslinking agent (J), the amount thereof is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and even more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably contains a crosslinking agent (J).

[0098] Examples of additives (K) are pigments, dyes, odorants, antioxidants, agents for influencing electrical properties, such as conductive carbon black, flame retardants, light stabilizers and skin time extenders, such as silanes with SiC-bonded mercaptoalkyl groups, cell generators, such as azodicarbonamide, heat stabilizers and thixotropic agents, such as polyethers, biocides, such as fungicides, bactericides, acaricides and modulus regulators, such as polydimethylsiloxanes with only one OH end group, and storage stability improvers, such as alkylphosphonic acids.

[0099] When the composition of the present invention contains component (K), the amount thereof is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably contains component (K).

[0100] Examples of solvents (L) are toluene, xylene, ethanol and methanol, which may be present as impurities in one or more of the components (A)-(K), for example as a result of production, or may be added intentionally, for example when component (C) is used as a solvent mixture.

[0101] When the composition of the present invention contains a solvent (L), the amount thereof is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the composition of the present invention in any case. The composition of the present invention preferably does not contain any solvent (L).

[0102] The compositions of the present invention are preferably prepared using: (A) an organosilicon compound comprising a unit of formula (II), (B) a compound of formula (I), (C) a compound comprising units of formulae (III), (IV) and (V) in a total amount of at least 80 mol %, with the proviso that it comprises at least 10 mol % of units of formula (V); optionally (D) a catalyst; optionally (E) a compound containing a basic nitrogen; optionally (F) a filler; optionally (G) an adhesion promoter; optionally (H) a plasticizer; Optionally (J) a further cross-linking agent; Optionally, (K) additives, and Optionally, (L) a solvent.

[0103] In addition, the compositions of the present invention are preferably prepared using: (A) an essentially linear OH-terminated organopolysiloxane; (B) Compounds of formula (I) in which the heterocycle on which group A is based is pyrrolidine, piperidine, tetrahydro-1,4-oxazine, tetrahydro-1,4-thiazine, tetrahydro-1,4-diazine and 1-methyltetrahydro-1,4-diazine, in particular tetrahydro-1,4-oxazine, (C) a compound containing units of the formulae (III), (IV) and (V) in a total amount of at least 90 mol % (including 12 to 30 mol % of units of the formula (V)); optionally (D) a catalyst; (E) Compounds containing basic nitrogen; optionally (F) a filler; optionally (G) an adhesion promoter; optionally (H) a plasticizer; Optionally (J) a further cross-linking agent; Optionally, (K) additives, and Optionally, (L) a solvent.

[0104] More preferably, the composition of the present invention is produced without using any other constituent components than the components (A) to (L).

[0105] Each individual component of the composition of the present invention may be one such component or may be a mixture of at least two different types of such components.

[0106] For the preparation of the composition of the invention, all the components can be mixed with each other in any order. This mixing can be carried out at room temperature and the pressure of the ambient atmosphere, i.e. about 900-1100 hPa, or under reduced pressure of about 20 hPa-800 hPa. However, if desired, this mixing can alternatively be carried out at a higher temperature, for example in the range of 35-135° C. Heating or cooling is possible if desired.

[0107] The present invention further provides a process for making the compositions of the present invention by mixing the individual components in any order.

[0108] The inventive mixing of the individual components is preferably carried out with very substantial exclusion of water from the surrounding atmosphere, which can be achieved, for example, by blanketing with dry air.

[0109] The component (C) used according to the invention can be mixed at any time, for example before the addition of compound (B) to the organosilicon compound (A), before or after the addition of the filler (F), or as the final component, in each case before or after degassing. It is preferred to add component (C) before the filler (F).

[0110] The order in which the polymer, crosslinker and plasticizer are mixed is not important. For reasons of convenient processing, the initial charge is preferably first formed by the polymer (A) and optionally the plasticizer (H), then component (B) and optionally the crosslinker (J) are added, after which component (C) is preferably added.

[0111] When filler (F) is added, it is preferred to intimately mix components (A), (B), (C), optionally (J) and optionally (E) with one another before adding filler (F), preferably hydrophilic silica.

[0112] Preferably, when component (E) is used, the ratio of (E) to (F) is selected such that at least 0.2 μmol of basic nitrogen-containing compound (E) is used per square meter of BET specific surface area of ​​filler (F).

[0113] When the filler (F) and plasticizer (H) are added, the mixture of polymer (A), plasticizer (H), components (C) and (B) and optionally crosslinker (J) is intimately mixed by stirring.

[0114] When hydrophilic fumed silica is added as filler (F), it is preferred to intimately mix component (A), plasticizer (H), component (C), component (B), and optionally component (J) with component (E) added at any time prior to the addition of the fumed silica until at least 90% of the OH groups of the organosilicon compound (A) have reacted with components (B) and (J) prior to the addition of the filler (F). The ratio of (E) to (F) is preferably selected such that a compound (E) containing 0.2 μmol of basic nitrogen per square meter of the BET specific surface area of ​​the filler is used.

[0115] Moreover, the time of adding the catalyst (D) is generally not critical. However, it is only reasonable to add the catalyst at the end, since the mixture is then activated. Those skilled in the art will generally want to avoid excessively long mixing of the already very reactive blocking compound, since the complete exclusion of moisture in the preparation of the mixture is difficult or at least uneconomical. In some cases, it is even necessary that the catalyst does not come into contact with the polymer-crosslinker mixture, which still contains a relatively large amount of unconverted OH groups, since premature crosslinking of the mixture may occur. For this reason, those skilled in the art will also avoid adding the catalyst too early. As an exception, those skilled in the art will add the crosslinking catalyst at the beginning of the preparation of the mixture only if there is a catalyst for the reaction of the OH polymer with the crosslinker at the same time.

[0116] The mixing of the components can be interrupted at any time and for any amount of time, with an interruption of at least about 1 minute being preferred, particularly after mixing of the organosilicon compound (A) with compound (B) and optional component (E) / optional crosslinker (J), with component (C) being added, preferably only after the interruption.

[0117] After all desired components are mixed, the mixture is preferably degassed and placed in a moisture-proof container.

[0118] The inventive preparation of the crosslinkable compositions of the invention can be carried out either batchwise or continuously.

[0119] In the continuous procedure, it is preferred to first mix the organosilicon compound (A) with the compound (B) and the optional plasticizer (H) continuously, preferably using a dynamic mixer, in which case the reaction time between the organosilicon compound (A) and the compound (B) is 1-60 minutes, and then mix any further mixture components. For example, the reaction time can be adjusted by controlled design of the length of the conduit and the cross section of the conduit in the continuous system. The reaction time in the continuous process of the invention is preferably such that at least 90% of the OH groups of the organosilicon compound (A) react with the compound (B). The organosilicon compound (C) of the invention can then be mixed continuously with the optional crosslinker (J), the compound containing basic nitrogen (E), the adhesion promoter (G) and the plasticizer (H), for example using a static mixer.

[0120] If desired, this can be followed by continuously mixing in a filler (F), such as finely divided silica, preferably without intermediate storage, using a mixer, for example having a rotor / stator system.

[0121] Prior to the possible addition of catalyst (D) and additives (K), the composition according to the invention can be continuously degassed, for example using a twin-screw extruder.

[0122] The compositions of the present invention are preferably single-component compositions that are storable under the exclusion of water and that harden upon the ingress of water, which are commonly referred to in the art as RTV-1 compositions.

[0123] The usual water content of air is sufficient for crosslinking of the compositions of the invention. The compositions of the invention are preferably crosslinked at room temperature. This can also be carried out, if desired, at temperatures higher or lower than room temperature, for example from -5°C to 15°C or from 30°C to 50°C, and / or with water concentrations exceeding the usual water content of air.

[0124] The crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the ambient atmosphere.

[0125] The present invention further provides a molded article prepared by crosslinking the composition of the present invention.

[0126] The compositions of the present invention can be used in any end use where it is possible to use a composition that is storable under the exclusion of water and that can crosslink to an elastomer upon ingress of water at room temperature.

[0127] The compositions of the invention are therefore of excellent suitability, for example, as sealing compounds for joints, including vertical joints and similar cavities, with a defined width of, for example, 10 to 40 mm, in buildings, land vehicles, ships and aircraft, or as adhesives or putties, for example in window construction or in the manufacture of aquariums or glass cabinets, as well as protective coatings, including surfaces exposed to the constant action of, for example, fresh or salt water, or as anti-slip coatings, or for the manufacture of elastomeric molded articles and for the insulation of electrical or electronic devices.

[0128] The compositions of the present invention have the advantages of being easy to prepare and having high storage stability over long periods of time.

[0129] The compositions of the present invention have the advantage that they form only a small proportion, if any, of cleavage products that are of toxicological concern.

[0130] The compositions of the present invention have the advantage that only small proportions, if any, of catalysts are present which are of toxicological concern.

[0131] The compositions of the present invention have the advantage that they are highly resistant to deformation during processing.

[0132] The composition of the present invention has the advantage that when a water-based leveling agent is used, no easily visible spots are formed on the surface of the sealant.

[0133] In addition, the compositions according to the invention have the advantage that the skin time can be adjusted within wide limits.

[0134] In addition, the compositions of the invention have the advantage that they can be produced completely continuously.

[0135] In addition, the compositions of the present invention have the advantage that variation in the type and proportion of compound (C) allows for controlled tuning of the modulus of the cured composition within very wide limits, while at the same time the rheological properties of the uncured composition remain substantially unchanged, which is generally desirable. EXAMPLES

[0136] In the examples described below, all viscosity values ​​refer to a temperature of 25° C. Unless otherwise specified, the following examples are carried out at ambient pressure, i.e., approximately 1000 hPa, at room temperature, i.e., about 23° C., or at a temperature established by combining the reactants at room temperature without additional heating or cooling, and at a relative humidity of about 50%. Additionally, all parts and percentage values ​​are by weight, unless otherwise specified.

[0137] The abbreviations used in the examples have the following meanings: Me: Methyl group Et: Ethyl group

[0138] Hydrolyzate (S1): 39 mol% of formula Si(OEt)O 1 / 2 units of the formula Si(OEt)O 2 / 2 and 19 mol % of the formula (OEt)SiO 3 / 2 An oligomeric tetraethoxysilane hydrolyzate consisting of units.

[0139] Hydrolyzate (S2): 16 mol% of formula Si(OEt)O 1 / 2 units of the formula Si(OEt)O 2 / 2 35 mol% of the formula (OEt)SiO 3 / 2 and 2 mol % of units of the formula Si(OEt)4.

[0140] Product (P): 16.0 mol% of formula MeSi(OEt)O 1 / 2 units of the formula MeSi(OEt)O 2 / 2 units of formula MeSiO 3 / 2 units, 0.2 mol% of formula Me2Si(OEt)O 1 / 2 and 0.9 mol% of the formula Me2SiO 2 / 2 An oligomeric silane hydrolyzate consisting of units.

[0141] <Skin Time> For the purposes of the present invention, the expression "skin time" defines the time until a thin elastic film is formed on the surface of the composition, distinct from the material underneath. If this surface is touched, for example, with the tip of a pencil, no material will adhere to it. A skin time of more than 30 minutes clearly indicates that the desired rapid complete cure of the sealing compound is not achieved.

[0142] <Yield point> The yield point measurements were performed using an air-bearing rotational rheometer (MCR 301 rheometer from Anton Paar, Ostfildern-Scharnhausen, Germany). Before starting the measurements, the complete cartridge was subjected to a pre-heat treatment at 25 °C for 3 h in a climate-controlled cabinet. The measurement settings were as follows: Temperature: 25℃ Measuring element: PP25 Gap distance: 0.2mm Measurement mode: Oscillation Measurements: 5 times per decade, every 10 seconds Shear stress: log10Pa~10000Pa Frequency: 1Hz constant The yield point corresponds to the interpolated shear stress (Pa) at a loss factor of 1.

[0143] [Comparative Example 1 (V1)] An initial charge of 300 g of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s (commercially available under the name "Polymer FD 80" from Wacker Chemie, Munich, Germany), 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.s (commercially available under the name "Weichmacher 1000" from Wacker Chemie, Munich, Germany), 9 g of 4-(triethoxysilylmethyl)-tetrahydro-1,4-oxazine, 5 g of product (P), 11 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 7 g of vinyltriethylsilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 1 g of 1,2-dihydroxypropyl ... 56) and 3.3 g of tetraethyl silicate (available under the name "Silikat TES 28" from Wacker Chemie, Munich, Germany) were mixed in a planetary mixer for 30 min. 2 45 g of fumed silica (commercially available under the name HDK®V15 from Wacker Chemie, Munich, Germany) with a BET specific surface area of ​​100 μg / g were mixed and thoroughly homogenized at a pressure of 50 hPa.

[0144] The RTV1 composition thus obtained was dispensed into moisture-proof conventional polyurethane cartridges.

[0145] [Example 1] An initial charge of 300 g of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s (commercially available under the name "Polymer FD 80" from Wacker Chemie, Munich, Germany), 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.s (commercially available under the name "Weichmacher 1000" from Wacker Chemie, Munich, Germany), 9 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine, 5 g of product (P), 11 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 7 g of vinyltriethylsilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 1 g of 1,2-dihydroxypropyl ... 56) and 3.3 g of hydrolysate (S1) were mixed in a planetary mixer for 30 minutes. 2 45 g of fumed silica (commercially available under the name HDK®V15 from Wacker Chemie, Munich, Germany) with a BET specific surface area of ​​100 μg / g were mixed and thoroughly homogenized at a pressure of 50 hPa.

[0146] The RTV1 composition thus obtained was dispensed into moisture-proof conventional polyurethane cartridges.

[0147] [Example 2] An initial charge of 300 g of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s (commercially available under the name "Polymer FD 80" from Wacker Chemie, Munich, Germany), 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.s (commercially available under the name "Weichmacher 1000" from Wacker Chemie, Munich, Germany), 9 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine, 5 g of product (P), 11 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 7 g of vinyltriethylsilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 1 g of 1,2-dihydroxypropyl ... 56) and 3.3 g of hydrolysate (S1) were mixed in a planetary mixer for 30 minutes. 2 45 g of fumed silica (available under the name HDK®V15 from Wacker Chemie, Munich, Germany) with a BET specific surface area of ​​1000 μg / g were mixed and thoroughly homogenized at a pressure of 50 hPa. Finally, 2.5 g of zinc(II) octoate were added and the mixture was homogenized again for 5 min at a pressure of approximately 50 hPa (absolute).

[0148] The RTV1 composition thus obtained was dispensed into moisture-proof conventional polyurethane cartridges.

[0149] [Example 3] An initial charge of 300 g of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s (commercially available under the name "Polymer FD 80" from Wacker Chemie, Munich, Germany), 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.s (commercially available under the name "Weichmacher 1000" from Wacker Chemie, Munich, Germany), 9 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine, 5 g of product (P), 11 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 7 g of vinyltriethylsilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 1 g of 1,2-dihydroxypropyl ... 56) and 3.3 g of hydrolysate (S2) were mixed in a planetary mixer for 30 minutes. 2 45 g of fumed silica (commercially available under the name HDK®V15 from Wacker Chemie, Munich, Germany) with a BET specific surface area of ​​100 μg / g were mixed and thoroughly homogenized at a pressure of 50 hPa.

[0150] The RTV1 composition thus obtained was dispensed into moisture-proof conventional polyurethane cartridges.

[0151] [Example 4] An initial charge of 300 g of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s (commercially available under the name "Polymer FD 80" from Wacker Chemie, Munich, Germany), 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.s (commercially available under the name "Weichmacher 1000" from Wacker Chemie, Munich, Germany), 9 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine, 5 g of product (P), 11 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 7 g of vinyltriethylsilane (commercially available under the name GENIOSIL®GF 93 from Wacker Chemie, Munich, Germany), 1 g of 1,2-dihydroxypropyl ... 56) and 3.3 g of hydrolysate (S2) were mixed in a planetary mixer for 30 minutes. 2 45 g of fumed silica (available under the name HDK®V15 from Wacker Chemie, Munich, Germany) with a BET specific surface area of ​​1000 μg / g were mixed and thoroughly homogenized at a pressure of 50 hPa. Finally, 2.5 g of zinc(II) octoate were added and the mixture was homogenized again for 5 min at a pressure of approximately 50 hPa (absolute).

[0152] The RTV1 composition thus obtained was dispensed into moisture-proof conventional polyurethane cartridges.

[0153] [Example 5] The mixtures prepared in the examples and comparative examples were each spread on a polyethylene film to prepare a sheet of 2 mm thickness, which was cured for one day, peeled off from the film, and suspended so that it could be exposed to air from all sides for another 6 days, so that the samples were cured for a total of 7 days. The relative humidity was adjusted to 50% and the temperature was maintained at a controlled level of 23°C. Then, test specimens in the S2 form according to ISO 37:2017 were punched out from these sheets, and their respective elastic moduli (stress value at 100% elongation of the test specimen for ISO 37 S2) were confirmed.

[0154] The identified guidelines are listed in Table 1.

[0155] All samples cured to give tack-free elastomeric materials.

[0156] [Table 1]

[0157] Surprisingly, inventive examples 1-4 have the desired small reduction in hardness values, meaning that the elastomeric properties were maintained under the specified storage conditions.

Claims

1. A composition that is crosslinkable by a condensation reaction and can be produced by using: (A) an organosilicon compound having at least two OH groups; (B) A heterocyclic compound represented by the following formula and / or a partial hydrolyzate thereof: A[CR １ ２ SiR ａ (OR ２ ) ３‐ａ ] ｘ (I) [In the formula, A is the heterocycle AH ｘ and containing at least one ring-forming element of main group 3 and / or 5, where x hydrogen atoms are selected from the group consisting of CR １ ２ groups, where at least one of these bonds is on a ring-forming element of main group 3 or 5; R represents the same or different monovalent optionally substituted hydrocarbyl groups; R １ may be the same or different and represent a hydrogen atom or a monovalent optionally substituted hydrocarbyl group; R ２ represent, which may be the same or different, monovalent optionally substituted hydrocarbyl groups; a=0 or 1; x=1, 2 or 3. and (C) at least one compound containing a unit of the following formula: Si (OR ４ ) ３ O １／２ (III), Si (OR ４ ) ２ O ２／２ (IV), (OR ４ ) SiO ３／２ (V) and Optional SiO ４／２ (VI)、 [In the formula, R ４ may be the same or different and are independently an alkyl group in each case; However, compound (C) contains at least 10 mol % of units of formula (V).

2. 2. The composition of claim 1, wherein the organosilicon compound (A) comprises a unit of the formula: ( ３ ｂ () ｃ 3) （４－ｂ－ｃ）／２ (=) [In the formula, R ３ represent optionally substituted hydrocarbyl groups which may be the same or different and which may be interrupted by oxygen atoms, b is 0, 1, 2 or 3; c is 0, 1, 2 or 3; However, the sum of b+c is ≦3, and at least two condensable OH groups are present per molecule.

3. 3. The composition according to claim 1 or 2, characterized in that compound (C) comprises units of formulae (III), (IV) and (V) in a total amount of at least 70 mol %.

4. 4. Composition according to one or more of claims 1 to 3, characterized in that compound (C) comprises from 10 to 50 mol% of units of formula (V), from 15 to 60 mol% of units of formula (III) and from 20 to 60 mol% of units of formula (IV).

5. 5. Composition according to one or more of claims 1 to 4, characterized in that the compound (C) consists of units of formulae (III), (IV) and (V) and optionally (VI).

6. 6. The composition according to claim 1, further comprising component (C) in an amount of from 1 to 20 parts by weight relative to 100 parts by weight of component (A).

7. A composition according to one or more of claims 1 to 6, characterized in that it can be produced using: (A) an organosilicon compound comprising a unit of formula (II): (B) a compound of formula (I), (C) a compound comprising units of formulae (III), (IV) and (V) in a total amount of at least 80 mol %, provided that it comprises at least 10 mol % of units of formula (V); Optionally, (D) a catalyst; optionally (E) a compound containing a basic nitrogen; Optionally, (F) a filler; Optionally, (G) an adhesion promoter; Optionally, (H) a plasticizer; Optionally (J) a further cross-linking agent; Optionally, (K) additives, and Optionally, (L) a solvent.

8. 8. The composition according to claim 1, characterized in that the catalyst (D) comprises an alkoxide of a metal of the fourth transition group of the periodic table of the elements, a carboxylate of a metal of the twelfth transition group of the periodic table of the elements, and a phosphonate.

9. A process for the preparation of a composition according to one or more of claims 1 to 8 by mixing the individual components in any order.

10. A moulded body produced by crosslinking a composition according to one or more of claims 1 to 8 or a composition produced by the process according to claim 9.

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