Crosslinkable compositions based on organosilicon compounds

Abstract

This invention relates to crosslinkable compositions, which can be produced using the following components: (A) formula (R) 2 O) 3‑a SiR 1 a O(SiR2O) n SiR 1 a (OR 2 ) 3‑a (I) organopolysiloxane, provided that the viscosity at 25°C is greater than or equal to 6000 mPas, and (B1) formula R 3 4‑b (R 4 O) b Si(II) silanes, provided that the molecular weight of the silane of formula (II) is greater than 195 g / mol, and optionally (B2) is derived from formula R 7 c (R 8 O) d SiO (4‑c‑d) / 2 A silicon compound consisting of units of formula (III), provided that the sum of c+d in formula (III) is less than or equal to 3, and at least two groups (R) are present in the silicon compound. 8 O), and a viscosity of less than 2000 mPas at 25°C, wherein the groups and indicators have the meanings indicated in claim 1, provided that the composition contains, at most less than 0.5 wt% of an organosilicon compound having a molecular weight of less than or equal to 195 g / mol relative to the organopolysiloxane (A). The invention also relates to methods for producing and using the composition.

Description

Technical Field

[0001] This invention relates to compositions based on organosilicon compounds and crosslinkable by condensation reaction, methods for producing them, and their use as sealants, particularly for grouting natural stone. Background Technology

[0002] One-component sealants (RTV1 sealants) are known to be able to be stored in the absence of water and to cure into an elastomer and eliminate alcohol upon the introduction of water at room temperature. These products are widely used, for example, in the construction industry. The basis of these mixtures is organopolysiloxanes with alkoxy groups as hydrolyzable reactive substituents. These reactive polydimethylsiloxanes are typically prepared by so-called end-capping, which is the reaction of the OH-terminated polydimethylsiloxane with an organooxysilane in the presence of a catalyst. Reference can be made, for example, to US-A 5,055,502. To suppress downstream reactions (chain extension and crosslinking) from end-capping, the organooxysilane must always be used in large excess relative to the OH group of the OH-terminated polydimethylsiloxane. As a result, these organooxy polymers always contain an excess of organooxysilane. It has also been found that end-capping can often be carried out with only highly reactive organooxysilanes (such as methyltrimethoxysilane or vinyltrimethoxysilane) without equilibrium.

[0003] Other reactive silanes used are methyltriethoxysilane (MTEO) or vinyltriethoxysilane (VTEO). However, as can be inferred from US-B2 10647822, the reactivity of the latter two silanes is so low that their potential use in the end-capping of long-chain, OH-terminated polydimethylsiloxanes is limited. Nevertheless, these silanes are actually used as additional additives, such as as water scavengers to increase storage stability, or as carrier materials for other active ingredients, such as stabilizers or catalysts.

[0004] Requirements for RTV1 sealants are wide-ranging, but products requiring extremely rapid curing after a certain processing time are particularly desirable. Besides the catalyst used in RTV1 sealants, a decisive factor here is specifically the reactivity of the crosslinking agent used. Specifically, tin and titanium compounds, typically used, have drawbacks that can lead to storage stability problems or undesirable yellowing. Therefore, the issue is limiting the amount of catalyst used in RTV1 sealants. However, in such cases, the pressure to use highly reactive silanes is even greater.

[0005] In addition, these sealants may contain fillers, plasticizers, crosslinking agents and various additives.

[0006] In addition, functionalized alkylsilanes are commonly used as so-called adhesion promoters. A typical example is the use of aminopropyltrimethoxysilane.

[0007] Of course, all these alkoxysilanes and methyltrimethoxysilanes present in RTV1 sealant can also affect curing properties, such as skinning time, early strength, and complete curing. However, this effect is very small and can usually be ignored. However, there are disadvantages to production, storage, and use when using these silanes in the described RTV1 sealant.

[0008] A key drawback of existing RTV1 sealants is that, in grouting applications, the substrate adjacent to the RTV1 sealant, especially natural stone, can become soiled. This is primarily caused by plasticizers not incorporated into the polymer matrix. These plasticizers can migrate from the sealant and form dark edges with an oily appearance in the area in contact with the substrate.

[0009] The known solution to this problem is to use very short-chain plasticizers, as disclosed in DE-B 102 27 590. However, another type of contaminant has been found, which only appears when the substrate becomes wet. The areas adjacent to the sealant are so strongly hydrophobic that they are not wetted by water and, in this case, exhibit a lighter color than the rest of the substrate. This phenomenon occurs regardless of the specific plasticizer used. It also occurs if no plasticizer is added at all.

[0010] In contrast to the highly reactive organooxysilanes mentioned above, high molecular weight organooxysilanes are characterized by low reactivity because they contain long-chain organooxy groups as well as long-chain organic groups directly bonded to silicon. Summary of the Invention

[0011] One subject of the present invention is a composition that can be crosslinked by a condensation reaction and can be produced using the following components:

[0012] (A) Organopolysiloxanes of the following formula:

[0013] (R 2 O) 3-a SiR 1 a O(SiR2O) n SiR 1 a (OR 2 ) 3-a (I),

[0014] in

[0015] R can be the same or different, and represents a monovalent, optionally substituted hydrocarbon group.

[0016] R 1 They can be the same or different, and represent the monovalent, optionally substituted hydrocarbon groups.

[0017] R 2 They can be the same or different, and represent the monovalent, optionally substituted hydrocarbon groups.

[0018] a can be the same or different, and can be 0 or 1, preferably 1, and

[0019] n is an integer from 380 to 2000.

[0020] The condition is that the viscosity at 25°C is greater than or equal to 6000 mPas.

[0021] (B1) Silanes of the following formula:

[0022] R 3 4-b (R 4 O) b Si (II),

[0023] in,

[0024] R 3 They can be the same or different, and represent monovalent, SiC-linked, optionally substituted hydrocarbon groups.

[0025] R 4 They can be the same or different, and represent monovalent, optionally substituted hydrocarbon groups, and

[0026] b can be 2, 3, or 4, with 2 or 3 being preferred.

[0027] The condition is that the molecular weight of the silane in formula (II) is greater than 195 g / mol.

[0028] and optional

[0029] (B2) Silicon compounds composed of units of the following formula:

[0030] R 7 c (R 8 O) d SiO (4-c-d) / 2 (III),

[0031] in,

[0032] R 7 They can be the same or different, and represent monovalent, SiC-linked, optionally substituted hydrocarbon groups.

[0033] R 8 They can be the same or different, and represent the monovalent, optionally substituted hydrocarbon groups.

[0034] c is 0, 1, or 2, and

[0035] d is 0, 1, 2, or 3.

[0036] The condition is that the sum of c+d in formula (III) is ≤3, and at least two groups (R) are present in these silicon compounds. 8 O), and its viscosity at 25°C is less than 2000 mPa·s.

[0037] The condition is that, in each case, based on the organopolysiloxane (A), the compositions of the present invention contain a maximum amount of less than 0.5 wt%, preferably less than 0.1 wt%, of an organosilicon compound with a molecular weight of less than or equal to 195 g / mol.

[0038] Examples of group R are alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl; hexyl, such as n-hexyl; heptyl, such as n-heptyl; octyl, such as n-octyl and isooctyl, such as 2,2,4-trimethylpentyl; nonyl, such as n-nonyl; decyl, such as n-decyl; dodecyl, such as n-dodecyl; octadecyl, such as n-octadecyl; cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl; alkenyl, such as vinyl, 1-propenyl and 2-propenyl; aryl, such as phenyl, naphthyl, anthracene and phenanthrene; alkylaryl, such as o-, m-, p-tolyl; xylyl and ethylphenyl; and aralkyl, such as benzyl, α- and β-phenylethyl.

[0039] The group R is preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms, more preferably methyl, vinyl or phenyl, and especially methyl.

[0040] Group R 1 Examples are the monovalent hydrocarbon groups indicated by R, as well as hydrocarbon groups substituted with amino groups.

[0041] Group R 1 Preferably, it comprises a monovalent hydrocarbon group having 1 to 12 carbon atoms and optionally substituted with an amino group, and more preferably comprises methyl, ethyl, vinyl, phenyl, or CH2-NR groups. 6' R 5' or group CH2NR 11' , where R 5' R represents a hydrocarbon group having 1 to 12 carbon atoms. 11' R represents a hydrogen atom or group 5' And R 11' This indicates a divalent hydrocarbon group that can be interrupted by a heteroatom.

[0042] More specifically, group R 1 Includes the group -CH2-NR 6' R5' or group CH2NR 11' , where R 5' R 6' and R 11' Having the same meaning as described above, and very preferably containing -CH2-N[(CH2)2]2O, -CH2-N(Bu)2 or -CH2-NH(cHex), where Bu represents a n-butyl group and cHex represents a cyclohexyl group.

[0043] Group R 5 and R 5' The instances are independent of each other and refer to the hydrocarbon group indicated by R.

[0044] Preferably, the group R 5 and R 5' Each of the following can be independently composed of methyl, ethyl, isopropyl, n-propyl, n-butyl, cyclohexyl or phenyl, more preferably n-butyl.

[0045] hydrocarbon group R 6 and R 6' Examples are hydrocarbon groups indicated by R, which are independent of each other.

[0046] Preferably, the group R 6 and R 6' Each of the following components independently contains a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a n-propyl group, a n-butyl group, or a cyclohexyl group, more preferably a n-butyl group.

[0047] Divalent group R 11 and R 11' Examples of these, independently of each other, are alkylene groups, such as propane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, 2,2-dimethylpropane-1,3-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, and 2-methylheptane-1,7-diyl and 2,2,4-trimethylpentane-1,5-diyl; alkenyl groups, such as propene-1,3-diyl; and also groups -CH2-CH2-O-CH2-CH2- and -CH2-CH2-NH-CH2-CH2-.

[0048] Group R 11 and R 11' Each of the components preferably contains a divalent hydrocarbon group having 4 to 6 carbon atoms that can be interrupted by a heteroatom (preferably oxygen-O- or nitrogen-NH-), and more preferably contains CH2-CH2-O-CH2-CH2-.

[0049] Group R 2 An example is the monovalent group indicated by R.

[0050] Group R 2 Preferably, it includes alkyl groups having 1 to 12 carbon atoms, more preferably methyl, ethyl, n-propyl or isopropyl, and even more particularly methyl or ethyl.

[0051] The organopolysiloxane (A) used in this invention preferably comprises:

[0052] (MeO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OMe)2,

[0053] (MeO)2Si(DBA)O(SiMe2O) 30-2000 Si(DBA)(OMe)2,

[0054] (MeO)2Si(cHx)O(SiMe2O) 30-2000 Si(cHx)(OMe)2,

[0055] (MeO)2Si(R 3 O(SiMe2O) 700 Si(R 3 (OMe)2,

[0056] (EtO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OEt)2,

[0057] (EtO)2Si(DBA)O(SiMe2O) 30-2000 Si(DBA)(OEt)2,

[0058] (EtO)2Si(cHx)O(SiMe2O) 30-2000 Si(cHx)(OEt)2 or

[0059] (EtO)2Si(R 1 O(SiMe2O) 700 Si(R 1 (OEt)2, more preferably

[0060] (EtO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OEt)2,

[0061] (EtO)2Si(DBA)O(SiMe2O) 30-2000 Si(DBA)(OEt)2 or

[0062] ((EtO)2Si(cHx)O(SiMe2O) 30-2000Si(cHx)(OEt)2, more specifically

[0063] (EtO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OEt)2, where Me is methyl, Et is ethyl, Ox is CH2-N[(CH2)2]2O, DBA is -CH2-N(nBu)2, cHx is CH2-NH(cHex), Bu is n-butyl and cHex is cyclohexyl, and R 1 It represents Me, Et, vinyl, phenyl, DBA, Ox, or cHx and has the same meaning in individual compounds.

[0064] In each case, at 25°C, the organopolysiloxane (A) used in this invention has a viscosity preferably from 6,000 to 350,000 mPas, more preferably from 20,000 to 120,000 mPas.

[0065] Organopolysiloxane (A) is a commercially available product and / or can be prepared using methods commonly used in silicon chemistry.

[0066] Group R 3 An example is the group indicated by R.

[0067] Group R 3 Preferably, it is a straight-chain, branched, or cyclic hydrocarbon group having 1 to 16 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms and having an amino group substituted on the carbon atom bonded to the silicon atom, and more preferably a straight-chain, branched, or cyclic alkyl, vinyl, phenyl, or -CH2-NR group having 1 to 8 carbon atoms. 6' R 5' or group CH2NR 11' , where R 5' R represents a hydrocarbon group having 1 to 12 carbon atoms. 6' R represents a hydrogen atom or group 5' And R 11' This indicates a divalent hydrocarbon group that can be interrupted by a heteroatom.

[0068] Group R 4 An example is the group indicated by R.

[0069] Preferred group R 4 It can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or isobutyl, more preferably ethyl, n-propyl, or isopropyl.

[0070] Examples of components (B1) optionally used in this invention are n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-nonyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxysilane, n-heptyltriethoxysilane, n-octyltriethoxysilane, n-nonyltriethoxysilane, n- Decyltriethoxysilane, n-hexadecyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, methyltri-n-propoxysilane, ethyltri-n-propoxysilane, n-propyltri-n-propoxysilane, n-butyltri-n-propoxysilane, n-pentyltri-n-propoxysilane, n-hexyltri-n-propoxysilane, n-heptyltri-n-propoxysilane, n-octyltri-n-propoxysilane, n-nonyltri-n-propoxysilane, n-decyltri-n-propoxysilane, n-hexadecyltri-n-propoxysilane, cyclohexyltri-n-propoxysilane, Phenyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, n-propyltriisopropoxysilane, n-butyltriisopropoxysilane, n-pentyltriisopropoxysilane, n-hexyltriisopropoxysilane, n-heptyltriisopropoxysilane, n-octyltriisopropoxysilane, n-nonyltriisopropoxysilane, n-decyltriisopropoxysilane, n-hexadecyltriisopropoxysilane, cyclohexyltriisopropoxysilane, phenyltriisopropoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, tetraethyl Oxysilanes, tetra-n-propoxysilane, tetraisopropoxysilane, 2,2,4-trimethylpentyltriethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, N,N-di-n-butylaminomethyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltrimethoxysilane, N,N-di-n-butylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyltrimethoxysilane.

[0071] Preferably, the silane (B1) used in this invention is tetraethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, phenyltrimethoxysilane, or n-hexadecyltrimethoxysilane.

[0072] Component (B1) includes commercially available products or can be prepared using methods common in silicon chemistry.

[0073] In each case, based on 100 parts by weight of component (A), the composition of the present invention preferably contains component (B1) in an amount of 0.5 to 7 parts by weight, more preferably 1 to 3.5 parts by weight.

[0074] Group R 7An example is the group indicated by R.

[0075] Group R 7 Preferably, it is methyl or 2,2,4-trimethylpentyl.

[0076] Group R 8 An example is the group indicated by R.

[0077] Group R 8 Preferably, it is methyl or ethyl, more preferably methyl.

[0078] Preferred examples of silicon compounds (B2) optionally used in this invention are:

[0079] EtO(SiMe2O)3SiR 7 (OEt)2,

[0080] (EtO(SiMe2O)3)2SiR 7 (OEt),

[0081] MeO(SiMe2O)3SiR 7 (OMe)2,

[0082] (MeO(SiMe2O)3)2SiR 7 OMe),

[0083] EtO(SiMe2O)3SiR 7 (OEt)O(SiMe2O)3SiR 7 (OEt)2,

[0084] MeO(SiMe2O)3SiR 7 (OMe)O(SiMe2O)3SiR 7 (OMe)2

[0085] EtO(SiMe2O) x Si(iOct)(OEt)2,

[0086] (EtO(SiMe2O) x )2Si(iOct)(OEt),

[0087] MeO(SiMe2O) x Si(iOct)(OMe)2,

[0088] (MeO(SiMe2O) x )2Si(iOct)(OMe),

[0089] EtO(SiMe2O) xSi(iOct)(OEt)O(SiMe2O)3Si(iOct)(OEt)2,

[0090] MeO(SiMe2O) x Si(iOct)(OMe)O(SiMe2O)3Si(iOct)(OMe)2,

[0091] [(EtO)3SiO 1 / 2 [(EtO)2SiO] 2 / 2 [(EtO)SiO] 3 / 2 ][SiO 4 / 2 ]or

[0092] [(EtO)2SiMeO 1 / 2 [(EtO)SiMeO] 2 / 2 [MeSiO] 3 / 2 ],

[0093] Where Me is methyl, Et is ethyl, iOct is 2,2,4-trimethylpentyl, x = 1-9, and R 7 This refers to a straight-chain, branched, or cyclic aliphatic hydrocarbon group having 2 to 8 carbon atoms, wherein the group R 7 The same definition applies to all compounds.

[0094] The silicon compound (B2) optionally used in this invention is more preferred.

[0095] MeO(SiMe2O) x Si(iOct)(OMe)2,(MeO(SiMe2O) x )2Si(iOct)(OMe),

[0096] MeO(SiMe2O) x Si(iOct)(OMe)O(SiMe2O)3Si(iOct)(OMe)2,

[0097] [(EtO)3SiO 1 / 2 ] 0.37 [(EtO)2SiO 2 / 2 ] 0.41 [(EtO)SiO 3 / 2 ] 0.20 [SiO 4 / 2 ] 0.02 or

[0098] [(EtO)2SiMeO 1 / 2 ] 0.18 [(EtO)SiMeO 2 / 2 ] 0.48 [MeSiO3 / 2 ] 0.34 Where Me is methyl, Et is ethyl, iOct is 2,2,4-trimethylpentyl, and x = 1-9.

[0099] Optionally, the silicon compound (B2) used in this invention has a viscosity preferably of 5 to 15 mPas at 25°C.

[0100] The silicon compound (B2) optionally used in this invention preferably has a molecular weight greater than 195 g / mol.

[0101] More specifically, the silicon compound (B2) used optionally has an average composition

[0102] [R 7 (OMe)2O 1 / 2 ] e [R 7 Si(OMe)O 2 / 2 ] f [R 7 SiO 3 / 2 ] g [Me2SiO 2 / 2 ] h [Me2Si(OMe)O 1 / 2 ] i ,

[0103] Where e = 0.05 - 0.15, f = 0.10 - 0.20, g = 0.00 - 0.10, h = 0.40 - 0.65, and i = 0.10 - 0.30, where e + f + g < h + i and e + f + g + h + i = 1, where Me is a methyl group and R 7 It has the above definition.

[0104] Optionally, the silicon compound (B2) used can be prepared by methods commonly used in silicon chemistry, such as by balancing polydimethylsiloxane with trialkoxysilane under basic catalysis.

[0105] If the composition of the present invention contains component (B2), in each case based on 100 parts by weight of component (A), the amount discussed is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and more specifically 2 to 6 parts by weight.

[0106] In addition to components (A), (B1) and optionally (B2), the compositions of the present invention may contain all substances that have been used to date in compositions that are crosslinkable by condensation reaction, such as adhesion promoters (C), curing promoters (D), plasticizers (E), fillers (F) and additives (G).

[0107] The adhesion promoter (C) used can be any adhesion promoter that has been used to date in compositions that can be crosslinked by condensation reaction.

[0108] Preferably, the adhesion promoter (C) comprises an organooxysilane having a glycidoxy group, an amino group, a urea group, an acryloxy group or a methacryloyloxy group, and a partial condensate thereof.

[0109] Examples of adhesion promoters (C) are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-(2-aminoethyl)aminopropyldimethoxymethylsilane, and 3-(2-aminoethyl)aminopropyldiethoxymethylsilane.

[0110] If the composition of the present invention includes an adhesion promoter (C), the amount involved is preferably 0.5 to 5.0 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of component (A) in each case.

[0111] The curing accelerator (D) used can be any curing accelerator that has been used to date in crosslinkable compositions via condensation reactions.

[0112] Examples of curing accelerators (D) are titanium compounds, such as tetrabutyl titanate or tetraisopropyl titanate, or titanium chelates, such as di(ethylacetoacetate)diisobutoxytitanium, or organotin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n-butyltin oxide, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin dinedecate, dimethyltin oxide, di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide, and reaction products of these compounds with alkoxysilanes, such as reaction products of di-n-butyltin diacetate and tetraethoxysilane, wherein di-n-octyltin diacetate, di-n-octyltin dilaurate, di-octyltin oxide, reaction products of di-n-octyltin oxide and tetraethoxysilane, tetrabutyl titanate, tetraisopropyl titanate, or di(ethylacetoacetate)diisobutoxytitanium are preferred.

[0113] If the composition of the present invention contains a curing accelerator (D), the amount involved in each case based on 100 parts by weight of component (A) is preferably 0.001 to 20 parts by weight, more preferably 0.001 to 1 part by weight.

[0114] Optionally, examples of plasticizers (E) used are dimethylpolysiloxane, which is liquid at room temperature and is end-capped with trimethylsiloxy groups, having a viscosity in the range of 5 to 1000 mPas at 25°C, as well as high-boiling hydrocarbons, such as liquid paraffin or mineral oil composed of cycloalkanes and paraffinic hydrocarbon units.

[0115] If the composition of the present invention includes component (E), in each case, based on 100 parts by weight of siloxane (A), the amount involved is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight. The composition of the present invention preferably does not contain any plasticizer (E).

[0116] The filler (F) optionally used in the compounds of the present invention can be any desired filler known to date.

[0117] An example of optional packing material (F) is unreinforced packing material (F), which has a maximum of 20m². 2 Fillers with a BET surface area of ​​ / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolite, metal oxide powders such as alumina, titanium oxide, iron oxide or zinc oxide and / or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass powder, and plastic powders such as polyacrylonitrile powder; reinforcing fillers, these having a BET surface area greater than 20m². 2 Fillers with a BET surface area of ​​ / g, such as precipitated chalk and carbon black, such as furnace black and acetylene black; silica, such as pyrolytic silica and precipitated silica; and fiber fillers, such as plastic fibers.

[0118] The filler (F) used optionally is preferably calcium carbonate or silica, more preferably silica or a mixture of silica and calcium carbonate.

[0119] The preferred calcium carbonate product (F) is ground or precipitated and optionally surface-treated with a fatty acid such as stearic acid or its salt. The preferred silica is pyrolytic silica.

[0120] If the composition of the present invention includes filler (F), in each case, based on 100 parts by weight of organopolysiloxane (A), the amount involved is preferably 10 to 150 parts by weight, more preferably 10 to 130 parts by weight, and more specifically 10 to 100 parts by weight. The composition of the present invention preferably contains filler (F).

[0121] Examples of additives (G) are pigments, dyes, flavoring agents, oxidation inhibitors, agents that affect electrical properties (such as conductive carbon black), flame retardants, light stabilizers, biocides (such as fungicides, bactericides, and acaricides), cell-generating agents (such as azodicarbonamide), heat stabilizers, scavengers (such as Si-N-containing silazanes or silylamides, such as N,N'-bis(trimethylsilylurea) or hexamethyldisilazane), cocatalysts (such as Lewis acids and Brønsted acids, such as sulfonic acids, phosphoric acids, phosphate esters, phosphonic acids, and phosphonate esters), thixotropic agents (such as hydrogenated castor oil or polyethylene glycol with OH ends on one or both sides), agents for further modulus adjustment (such as polydimethylsiloxanes with OH end groups, and any desired siloxanes different from components (A), (B), and (C)).

[0122] If the composition of the present invention contains additive (G), in each case, based on 100 parts by weight of organopolysiloxane (A), the amount contained is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and more specifically 0.1 to 10 parts by weight. The composition of the present invention preferably contains component (G).

[0123] Each component of the composition of the present invention may, in each case, be one such component or a mixture of at least two different kinds of such components.

[0124] The compositions of the present invention are preferably produced without using any components other than components (A) to (G).

[0125] The compositions of the present invention are preferably compositions produced using the following components:

[0126] (A) Organic polysiloxanes of formula (I),

[0127] Silanes of formula (II) (B1),

[0128] (B2) Silicon compounds composed of units of formula (III),

[0129] Optional (C) adhesion promoter,

[0130] Optional (D) curing accelerator,

[0131] Optional (E) plasticizer,

[0132] Optional (F) packing, and

[0133] Optional (G) additives.

[0134] The compositions of the present invention are more preferably compositions that can be produced using the following components:

[0135] (A) Organic polysiloxanes of formula (I),

[0136] Silanes of formula (II) (B1),

[0137] (B2) Silicon compounds composed of units of formula (III),

[0138] (C) Adhesion accelerator,

[0139] Optional (D) curing accelerator,

[0140] Optional (E) plasticizer,

[0141] Optional (F) packing, and

[0142] Optional (G) additives.

[0143] The compositions of the present invention are more particularly compositions that can be produced using the following components:

[0144] (A) Organic polysiloxanes of formula (I),

[0145] Silanes of formula (II) (B1),

[0146] (B2) Silicon compounds composed of units of formula (III),

[0147] (C) Adhesion accelerator,

[0148] (D) Curing accelerator,

[0149] Optional (E) plasticizer,

[0150] (F) packing, and

[0151] Optional (G) additives.

[0152] In another preferred embodiment, the composition of the present invention is a composition that can be produced using the following components:

[0153] (A) Organic polysiloxanes of formula (I),

[0154] Silanes of formula (II) (B1),

[0155] (B2) Silicon compounds composed of units of formula (III),

[0156] (C) Adhesion accelerator,

[0157] (D) Curing accelerator,

[0158] (F) packing, and

[0159] Optional (G) additives,

[0160] The condition is that they do not contain (E) plasticizers.

[0161] In a further preferred embodiment, the composition of the present invention is a composition that can be produced using the following components:

[0162] (A) Organic polysiloxanes of formula (I),

[0163] Silanes of formula (II) (B1),

[0164] (B2) Siloxanes composed of units of formula (III),

[0165] (C) Adhesion accelerator,

[0166] (D) Curing accelerator,

[0167] (F) packing, and

[0168] (G) Additives,

[0169] The condition is that they do not contain (E) plasticizers.

[0170] To prepare the compositions of the present invention, all components can be mixed with each other in any order. This mixing can occur at room temperature and ambient atmospheric pressure (in other words, about 900 to 1100 hPa). However, if desired, such mixing can also occur at higher temperatures, for example, in the range of 35°C to 135°C. Furthermore, for example, mixing can be carried out temporarily or continuously under reduced pressure, such as at an absolute pressure of 30 to 500 hPa, to remove volatile compounds or air.

[0171] The mixing of the present invention is preferably carried out largely in the absence of water, i.e., using raw materials having a water content preferably less than 10,000 mg / kg, more preferably less than 5,000 mg / kg, and more particularly less than 1,000 mg / kg. This mixing operation is preferably carried out under a cover of dry air or an inert gas (such as nitrogen), wherein the gas in question has a moisture content preferably less than 10,000 μg / kg, more preferably less than 1,000 μg / kg, and more specifically less than 500 μg / kg. After their production, these compositions are preferably dispensed into commercially conventional moisture-proof containers, such as shells, tubular bags, buckets, and canisters.

[0172] In a preferred procedure, components (A), (B), optional (C) and (E) are first mixed together, followed by the addition of any filler (F), and finally any additional components (D) and (G), wherein the temperature during the mixing process preferably does not exceed 60°C.

[0173] Another subject of the present invention is a method for producing the composition of the present invention by mixing the various components.

[0174] The method of the present invention can be carried out continuously, in batches, or semi-batch using known methods and known apparatus.

[0175] The compositions of the present invention and / or compositions produced according to the present invention are storable in the absence of moisture and are crosslinkable when moisture enters.

[0176] Typical water content in air is sufficient to crosslink the compositions of the present invention. The compositions of the present invention are preferably crosslinked at room temperature. If desired, they can also be crosslinked at temperatures above or below room temperature, for example, at -5°C to 15°C or at 30°C to 50°C, and / or by a water concentration exceeding the normal water content of air.

[0177] Crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, more specifically at ambient atmospheric pressure, in other words, about 900 to 1100 hPa.

[0178] Another subject of the present invention is the production of molded articles by crosslinking the compositions of the present invention.

[0179] The molded article of the present invention has a stress preferably less than 0.4 MPa at 100% elongation, as measured on an ISO 37 Type 2 test sample.

[0180] The compositions of the present invention can be used for all purposes of compositions that are storable in the absence of water and crosslink with elastomers when exposed to water at room temperature.

[0181] Surprisingly, it has been found that sealants with good reactivity and high storage stability can be produced using only silanes with a molecular weight greater than 195 μg / mol.

[0182] It is also possible, perhaps surprisingly, that crosslinkable compositions exclusively based on high molecular weight silanes do not lead to edge contamination affecting natural stone grouting, even when they do not contain any inert plasticizers. No one had expected that such an undesirable effect could be completely avoided by a relatively small increase in molecular weight. Instead, those skilled in the art would expect that high molecular weight alkoxysilanes, due to their lower reactivity, would require more time to diffuse out of the RTV1 sealant during the sealant's curing process. Therefore, the effect of edge contamination due to the hydrophobicity of the natural stone surface would tend to be amplified, at least because the longer alkyl groups further enhance the hydrophobicity.

[0183] Therefore, the compositions of the present invention are excellently suitable, for example, in buildings, land vehicles, ships and aircraft as sealing compounds for seams (including vertical seams) and similar cavities having a clear width of, for example, 10 mm to 40 mm, or as adhesives or bonding compounds in window construction or in the production of display cases, and also, for example, in protective coatings (including those for surfaces exposed to continuous action of fresh or salt water) or anti-slip coatings or in the production of elastomeric molded articles.

[0184] One advantage of the compositions of the present invention is that they are easy to manufacture and, notably, have very high storage stability.

[0185] Another advantage of the compositions of the present invention is that they exhibit very good processing quality in use and have excellent processing characteristics in a variety of applications.

[0186] One advantage of the crosslinkable compositions of the present invention is that the modulus can be customized.

[0187] One advantage of the crosslinkable compositions of the present invention is that they adhere very well to multiple substrates.

[0188] One advantage of the crosslinkable compositions of the present invention is that they do not cause any edge area contamination of adjacent substrates. In particular, they have excellent adaptability to allow grouting of both natural and artificial stones without contaminating the edge areas.

[0189] One advantage of the crosslinkable compositions of the present invention is that they are very economical in terms of the materials used. Detailed Implementation

[0190] In the examples described below, all viscosity data are relative to a temperature of 25°C. Unless otherwise stated, the following examples were conducted at ambient atmospheric pressure (i.e., about 1000 hPa) and room temperature (i.e., about 23°C), or at the temperature generated when reactants are combined at room temperature without additional heating or cooling, and at a relative atmospheric humidity of about 50%. Furthermore, unless otherwise specified, all parts and percentage data are by weight.

[0191] Tensile strength, elongation at break, and stress at 100% elongation were determined on type 2 test specimens according to ISO 37.

[0192] In the context of this invention, the dynamic viscosity of organosilicon compounds is measured according to DIN 53019. The procedure used here is as follows: Unless otherwise specified, the viscosity is measured at 25°C using a Physica MCR 300 rotational rheometer from Anton Paar. For viscosities from 1 to 200 mPas, a coaxial cylindrical measuring system (CC 27) with an annular measuring gap of 1.13 mm is used, while for viscosities greater than 200 mPas, a cone / plate measuring system (Searle system with a CP 50-1 measuring cone) is used. The shear rate is adjusted to the polymer viscosity (in 100 s). -1 The time ranges from 1 to 99 mPa·s; in 200 s -1 The time ranges from 100 to 999 mPas; at 120 s -1 The time ranges from 1000 to 2999 mPas; in 80s -1 The pressure ranged from 3000 to 4999 mPas; at 62 s -1 The pressure ranges from 5000 to 9999 mPas; in 50 seconds -1 The time ranged from 10000 to 12499 mPas; at 38.5 s -1 The time ranges from 12500 to 15999 mPas; at 33 s -1 The time ranged from 16000 to 1999 mPas; at 25 s -1 The time ranges from 20,000 to 24,999 mPas; in 20 seconds -1 The time was 25000 to 29999 mPas; at 17s -1 The time ranges from 30,000 to 39,999 mPas; in 10 s -1 The pressure ranges from 40,000 to 5,999 mPas; in 5 seconds -1 The time ranged from 60,000 to 149,999; in 3.3 seconds -1 The time ranged from 150,000 to 199,999 mPas; at 2.5 s -1 The time ranges from 200,000 to 299,999 mPas; at 1.5 s -1 The time ranges from 300,000 to 1,000,000 mPas.

[0193] In the context of this invention, the number-average molecular weight Mn and the weight-average molecular weight Mw were determined as follows:

[0194] Method: Size exclusion chromatography (SEC) according to DIN 55672-1

[0195] Flow rate: 1.00 mL / min

[0196] Injection system: Agilent 1200 autosampler (Agilent Technologies)

[0197] Injection volume: 100μL

[0198] Eluent: For products containing phenyl groups, use >99.5% tetrahydrofuran, stabilized with 250 ppm 2,6-di-tert-butyl-4-methylphenol (BHT); for phenyl-free materials, use >99.9% toluene, analytical grade. All chemicals are commercially available from, for example, Merck KGaA, D-Darmstadt (DE).

[0199] Column: Stationary phase: Polystyrene-divinylbenzene from Agilent Technologies.

[0200] Four columns are connected in series, consisting of a 50 mm long pre-column and three 300 mm long separation columns. All columns have an inner diameter of 7.8 mm. The gel used has a particle size of 5 μm. The pore size of the pre-column is... The orifice diameters of the three separation columns are as follows: and

[0201] Column temperature: Oven temperature 45℃. Concentration was determined using an RI detector (measurement principle: deflection, type: Agilent 1200; cell volume: 8 μL; temperature: 45℃).

[0202] The system was calibrated using a commercially available polystyrene standard from Agilent. Concentration: 0.4 μg / L (EasiCal, readily available polystyrene calibrator; injection volume: 100 μL). Tetrahydrofuran was used as a labeling material as an internal standard with toluene as the eluent, and toluene was used as a labeling material as an internal standard with tetrahydrofuran as the eluent. Calibration curve fitting: Third-order polynomial fitting to PSS.

[0203] Sample preparation: Dissolve approximately 15–50 mg of the sample to be tested in the corresponding eluent (c = approximately 3–10 mg / mL). Prepare the sample amount to allow for different RI signals. All samples should be completely dissolved in the eluent.

[0204] Evaluation: In each case, the measured molar weight is rounded to the nearest hundred.

[0205] Edge contamination of the porous substrate was measured according to ASTM (American Society for Testing and Materials) C 1248. Test samples composed of sealant and sandstone were cured for 21 days at 23°C and 50% relative humidity and then compressed by 25%, after which they were stored for a total of 28 days.

[0206] 1) At 23℃ and 50% relative humidity,

[0207] 2) At 70℃ in a hot cabinet, and

[0208] 3) In a UV test chamber as described in ASTM C 1248.

[0209] Next, visually assess the contamination of the edge areas. If no visible edge area contamination is found, the result is 0 mm. If edge area contamination is determined, report the maximum width of the area showing the most contamination, in mm, rounded to the nearest integer.

[0210] In the following embodiments, all mixtures are produced in a Labmax planetary mixer.

[0211] Example 1

[0212] Preparation of siloxane A1

[0213] A mixture of 660 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80000 mPas and 220 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20000 mPas was stirred with 30.44 g of a solution at 200 rpm for 5 minutes. The solution was a solution of 0.04 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in 30.4 g of (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane. After a reaction time of 5 minutes, a mixture of 98.0 wt% α,ω-bis((2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilyl)polydimethylsiloxane, 1.9 wt% (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, and 0.1 wt% ethanol was obtained with a viscosity of 52,000 mPas.

[0214] Production of mixture M1

[0215] 455 g of the reaction mixture obtained in the preparation of siloxane A1 was mixed with the following: 10.6 g of tetraethoxysilane hydrolysis product oligomer (with a total SiO2 content of 40% from hydrolysis and condensation, purchased from Wacker Chemie AG, Munich, (DE), named "SILIKATTES40"), 12.6 g of equilibrium product consisting of 6.3 g of methyltriethoxysilane hydrolysis product oligomer having an average of 10 Si atoms per molecule and 6.3 g of 3-aminopropyltriethoxysilane equilibrium product, and the mixture was stirred at 200 rpm for 5 minutes. Then 44 g of a 150 m 2 Hydrophilic pyrolytic silica with a surface area of ​​ / g can be obtained from Wacker Chemie AG under the name V15A was obtained, and the mixture was initially stirred at 200 rpm for 5 minutes until all the pyrolytic silica was wetted. Then, stirring was continued at 600 rpm for 10 minutes under reduced pressure (200 mbar). Finally, 1.58 g of a solution consisting of 0.27 g of dioctyltin oxide in 1.31 g of an equilibrium product composed of 0.655 g of methyltriethoxysilane hydrolysate oligomer (with an average of 10 Si atoms per molecule) and 0.655 g of 3-aminopropyltriethoxysilane, and 3 g of a 33 wt% solution of octylphosphonic acid in phenyltrimethoxysilane were added, and the mixture was stirred again under reduced pressure (200 mbar) for 5 minutes.

[0216] The mixture was then dispensed into standard commercial containers and stored in a moisture-free environment. 24 hours after the mixture was produced, 2 mm thick sheets were stretched from these sheets, and Type 2 dumbbell-shaped samples were produced from these sheets after curing for 7 days at 23°C and 50% relative humidity, in accordance with ISO 37, 2017-11, 6th edition.

[0217] The results are given in Table 1.

[0218] Example 2

[0219] Preparation of oligomer mixture B2-2

[0220] 240 g (3.25 mol) of α,ω-bis(trimethylsiloxy)polydimethylsiloxane with a viscosity of 1000 mPas and 234 g (1.0 mol) of trimethoxy(2,4,4-trimethylpentyl)silane (=iOctSi(OMe)3) (as trade name) BS 1316 (purchased from Wacker Chemie AG) and a solution of 0.80 g sodium ethoxide (21%) in ethanol were mixed and heated at 110 °C for 4 hours. After cooling, the mixture was neutralized by adding a solution of 1.60 g dimethyl dichlorosilane (10%) in n-heptane. The mixture was then devolatiled on a rotary evaporator at 120 °C under reduced pressure of 50 mbar. The composition of the mixture was determined by 29-Si NMR spectroscopy. The mixture contained 1.4 wt% iOctSi(OMe)3, 0.4 wt% Me2Si(OMe)2, and 98.2 wt% [iOctSi(OMe)2O] 1 / 2 ] 0.08 [iOctSi(OMe)O 2 / 2 ] 0.15 [iOctSiO 3 / 2 ] 0.05 [Me2SiO 2 / 2 ] 0.43[Me2Si(OMe)O 1 / 2 ] 0.29 The average composition is an oligomer mixture. The molecular weights, determined by gel permeation chromatography, are 929 g / mol (Mw) and 635 (Mn). The polydispersity (Mw / Mn) is 1.46.

[0221] Production of mixture M2

[0222] Repeat the production of mixture M1 as described in Example 1. Additionally, mix 36g of the above-described oligomer mixture B2-2.

[0223] The mixture M2 was then dispensed into standard commercial containers and stored in a moisture-free environment. 24 hours after the mixture was produced, 2 mm thick sheets were stretched from these sheets, and from these sheets, after curing for 7 days at 23°C and 50% relative humidity, Type 2 dumbbell-shaped samples were produced according to ISO 37, 2017-11, 6th edition.

[0224] The results are given in Table 1.

[0225] Example 3

[0226] Preparation of siloxane A3

[0227] A mixture of 660 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas and 220 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20,000 mPas was stirred with 30.44 g of a solution consisting of 0.04 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in 30.4 g of phenyltrimethoxysilane for 30 minutes at 200 rpm. After a reaction time of 30 minutes, a mixture of 98.0 wt% α,ω-bis((phenyldimethoxysilyl)polydimethylsiloxane), 1.9 wt% phenyltrimethoxysilane, and 0.1 wt% methanol with a viscosity of 51,000 mPas was obtained.

[0228] Production of mixture M3

[0229] Repeat the procedure for producing mixture M1 as described in Example 1, except that the siloxane used is siloxane A3 instead of A1.

[0230] The mixture M3 was then dispensed into standard commercial cylinders and stored in a moisture-free environment. 24 hours after the mixture was produced, 2 mm thick sheets were stretched from these sheets, and from these sheets, after curing for 7 days at 23°C and 50% relative humidity, Type 2 dumbbell-shaped samples were produced according to ISO 37, 2017-11, 6th edition.

[0231] The results are given in Table 1.

[0232] Example 4

[0233] Production of Mixture M4

[0234] Repeat the procedure for producing mixture M1 as described in Example 1, except that the siloxane used is siloxane A3 instead of A1. Additionally, mix 36g of the above-described oligomer mixture B2-2.

[0235] The mixture M4 was then dispensed into standard commercial containers and stored in a moisture-free environment. 24 hours after the mixture was produced, 2 mm thick sheets were stretched from these sheets, and Type 2 dumbbell-shaped samples were produced from these sheets after curing for 7 days at 23°C and 50% relative humidity, in accordance with ISO 37, 2017-11, 6th edition.

[0236] The results are given in Table 1.

[0237] Example 5

[0238] Preparation of siloxane A5

[0239] A mixture of 660 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas and 220 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20,000 mPas was stirred with 53.2 g of a solution consisting of 0.1 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in 53.1 g of n-hexadecyltrimethoxysilane for 60 minutes at 200 rpm. After a reaction time of 60 minutes, a mixture of 95.3 wt% α,ω-bis(n-hexadecyldimethoxysilyl)polydimethylsiloxane, 4.6 wt% phenyltrimethoxysilane, and 0.1 wt% methanol with a viscosity of 50,200 mPas was obtained.

[0240] Production of Mixture M5

[0241] Repeat the procedure for producing mixture M1 as described in Example 1, except that the siloxane used is siloxane A5 instead of A1. Additionally, mix 36g of the above-described oligomer mixture B2-2.

[0242] The mixture M5 was then dispensed into standard commercial containers and stored in a moisture-free environment. 24 hours after the mixture was produced, 2 mm thick sheets were stretched from these sheets, and Type 2 dumbbell-shaped samples were produced from these sheets after curing for 7 days at 23°C and 50% relative humidity, in accordance with ISO 37, 2017-11, 6th edition.

[0243] The results are given in Table 1.

[0244] Example 6

[0245] Preparation of siloxane A6

[0246] A mixture of 660 g of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas and 280 g of α,ω-trimethylsiloxypolydimethylsiloxane with a viscosity of 10 mPas was stirred with 38.24 g of a solution consisting of 0.04 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in 38.2 g of phenyltrimethoxysilane for 30 minutes at 200 rpm. After a reaction time of 30 minutes, a mixture of 98.0 wt% α,ω-bis(phenyldimethoxysilyl)polydimethylsiloxane, 1.9 wt% phenyltrimethoxysilane, and 0.1 wt% methanol with a viscosity of 50,800 mPas was obtained.

[0247] Preparation of mixture M6

[0248] 455 g of the reaction mixture obtained in the preparation of siloxane A6 was mixed with 11.1 g of the equilibrium product, which consisted of 5.55 g of methyltriethoxysilane hydrolysis product oligomers having an average of 10 Si atoms per molecule and 5.55 g of 3-aminopropyltriethoxysilane equilibrium product, and the mixture was stirred at 200 rpm for 5 minutes. Then, 42.2 μg of a 150 m... 2 Hydrophilic pyrolytic silica with a surface area of ​​ / g can be obtained from Wacker Chemie AG under the name V15A was obtained, and the mixture was initially stirred at 200 rpm for 5 minutes until all the pyrolytic silica was wetted. Then, stirring was continued for 10 minutes at 600 rpm under reduced pressure (200 mbar). Finally, 1.78 g of a solution consisting of 0.30 g of dioctyltin oxide in 1.48 g of an equilibrium product composed of 0.74 g of methyltriethoxysilane hydrolysis product oligomer (with an average of 10 Si atoms per molecule) and 0.74 g of 3-aminopropyltriethoxysilane, and 2.2 g of a 33 wt% solution of octylphosphonic acid in phenyltrimethoxysilane were added, and the mixture was stirred again under reduced pressure (200 mbar) for 5 minutes.

[0249] The mixture M6 was then dispensed into standard commercial containers and stored in a moisture-free environment. 24 hours after the mixture was produced, 2 mm thick sheets were stretched from these sheets, and Type 2 dumbbell-shaped samples were produced from these sheets after curing for 7 days at 23°C and 50% relative humidity, in accordance with ISO 37, 2017-11, 6th edition.

[0250] The results are given in Table 1.

[0251] Table 1:

[0252]

[0253] No contamination was found in the edge areas in any embodiment.

[0254] No hydrophobic regions were found in the sandstone after the test sample was wetted with water.

Claims

1. A composition which is crosslinked by condensation reaction and which is produced using the following components: (A) an organopolysiloxane of the formula: ###0001### wherein R can be the same or different and represents a monovalent, optionally substituted hydrocarbon group having from 1 to 18 carbon atoms, (R 2 O) 3-a SiR 1 a O(SiR2O) n SiR 1 a (OR 2 ) 3-a (I), a is 1, and n is an integer from 380 to 2000, (B1) a silane of the formula: ###0002### wherein b is 2, 3 or 4, R 1 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R R 2 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R with the proviso that the molecular weight of the silane of formula (II) is greater than 195 g / mol, and (B2) a silicon compound consisting of units of the formula: ###0003### wherein c is 0, 1 or 2, and d is 0, 1, 2 or 3, with the condition that the viscosity at 25°C is greater than or equal to 6000 mPas and R 1 is phenyl, the group -CH2-NR 6' R 5' or the group CH2NR 11' wherein R 5' denotes a hydrocarbon group having 1 to 12 carbon atoms, R 6' denotes a hydrogen atom or a group R 5' and R 11' denotes a divalent hydrocarbon group which can be interrupted by a heteroatom, wherein the composition comprises component (B1) in an amount of 0.5 to 7 parts by weight, based on 100 parts by weight of component (A), R 3 4-b (R 4 O) b Si (II), wherein the composition comprises a maximum amount of less than 0.1 wt% of an organosilicon compound having a molecular weight of less than or equal to 195 g / mol, based on the organopolysiloxane (A). R 3 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R R 4 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, Component (B1) includes tetraethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, (2,3,5,6-tetrahydro-l,4-oxazin-4-yl)methyltriethoxysilane, phenyltrimethoxysilane or n-hexadecyltrimethoxysilane. It is a composition which is produced using the following components: (A) an organopolysiloxane of the formula (I), (B1) a silane of the formula (II), R 7 c (R 8 O) d SiO (4-c-d) / 2 (III), (B2) a silicon compound consisting of units of the formula (III), R 7 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R R 8 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R optionally (C) an adhesion promoter, optionally (D) a cure promoter, with the proviso that the sum of c + d in formula (III) is < 3, at least 2 groups (R 8 O) are present in the silicon compound and the viscosity at 25°C is less than 2000 mPas, optionally (E) a plasticizer, optionally (F) a filler, and 2. The composition of claim 1, wherein, the group R 3 is a linear, branched or cyclic hydrocarbon group having 1 to 16 carbon atoms, or is a monovalent hydrocarbon group having 1 to 12 carbon atoms and substituted with an amino group on the carbon atom bonded to the silicon atom.

3. The composition according to claim 1 or 2, characterized in that, optionally (G) an additive.

4. The composition according to claim 1 or 2, characterized in that, It does not contain a plasticizer (E).

6. A process for producing the composition according to any one of claims 1 to 5, which is carried out by mixing the individual components.

7. A shaped article which is prepared by crosslinking the composition according to any one of claims 1 to 5 or which is prepared according to the process of claim 6. ​ ​ ​ ​ ​ ​ 5. The composition according to claim 1 or 2, characterized in that, ​ ​ ​

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