Mixtures containing phosphorus compounds and their use

Abstract

To provide a mixture containing a phosphorus compound.SOLUTION: A phosphorus compound-containing mixture (M) is provided comprising: (X) Polyethers of the formula R1 - (O-R2) p - O-R1 (I) in which R1 is hydrogen or a hydrocarbyl radical and R2 is a divalent optionally substituted hydrocarbyl radical and p is an integer from 4 to 110. Disclosed is a phosphorus compound represented by the following formula: O = PR5m (OR6) n (OH) 3 - (m+ n) (II) [wherein R5 represents an optionally substituted hydrocarbon group; R6 represents an optionally substituted hydrocarbon group; m is equal to 0 or 1, preferably 1; and n is equal to 0, 1 or 2, wherein m+ n is equal to 1 or 2, preferably 1]. And optionally (Z) water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a phosphorus-containing mixture, a process for its preparation and its use, in particular in crosslinkable compositions based on organosilicon compounds, as well as a process for the preparation of organosilicon compounds containing organyloxy groups. [Background technology]

[0002] One-component sealing compounds are already known that can be stored by excluding moisture and cure to elastomers by the introduction of water at room temperature while releasing alcohol. These products are used in large quantities, for example, in the construction industry. The basis of these mixtures is a polymer terminated with silyl groups bearing reactive substituents such as OH groups or hydrolyzable groups such as alkoxy groups. Furthermore, these sealing compounds may contain fillers, plasticizers, crosslinkers, catalysts, and various additives. Alkoxysilanes are often used as crosslinkers. These sealing compounds require tin- or titanium-based catalysts to accelerate curing.

[0003] Frequently used zinc catalysts include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dioxide, and their reaction products with alkoxysilanes. However, RTV1 sealing compounds prepared using alkoxysilanes have a drawback: after just a few months, they no longer completely cure. Therefore, EP 1397428B1 proposes the use of various organophosphorus compounds to significantly improve storage stability. Unfortunately, phosphorus compounds particularly suitable for stabilizing RTV1 sealing compounds, such as octylphosphonic acid, are solids at room temperature. However, for operational use, liquids are highly preferred because they are much better suited to metering than solids, especially in continuous processes. For example, EP 2030675B1 uses an easily manageable liquid solution of n-octylphosphonic acid in methyltrimethoxysilane.

[0004] However, a particular drawback of methyltrimethoxysilane is its very low flash point. Therefore, handling methyltrimethoxysilane requires complex and undesirable safety measures. Furthermore, it is not guaranteed that undesirable reaction products will not form in the mixture of n-octylphosphonic acid and methyltrimethoxysilane.

[0005] Furthermore, the use of n-octylphosphonic acid and a neutralizing agent in the production of polymers with hydrolyzable end groups is known. EP 3344684 B1 describes the reaction of the terminal silanol groups of linear polydimethylsiloxane with alkoxysilanes. 1,5,7-triazabicyclo[4.4.0]dec-5-ene is used as the catalyst. In the examples, after the reaction, the catalyst is neutralized with n-octylphosphonic acid in a second step. A disadvantageous variant of a solution of n-octylphosphonic acid in methyltrimethoxysilane is also used here. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent No. 1397428 [Patent Document 2] European Patent No. 2030675 [Patent Document 3] European Patent No. 3344684 Summary of the Invention [Problem to be solved by the invention]

[0007] The object of the present invention was to overcome the drawbacks of the prior art. [Means for solving the problem]

[0008] Thus, the present invention provides a mixture (M) comprising: (X) Polyethers of the general formula: R 1 -(OR2 ) p -OR 1 (I), [In the formula, R 1 may be the same or different and represent a hydrogen atom or a hydrocarbon group, R 2 may be the same or different and represent a divalent optionally substituted hydrocarbon group, and p is an integer from 4 to 110. (Y) Phosphorus compounds of the following formula: O=PR 5 m (OR 6 ) n (OH) 3-(m+n) (II), [In the formula, R 5 may be the same or different and represent an optionally substituted hydrocarbon group, R 6 may be the same or different and represent an optionally substituted hydrocarbon group, m is equal to 0 or 1, preferably 1, and n is equal to 0, 1 or 2, wherein m+n is equal to 1 or 2, and preferably 1. and optionally (Z) Water. DETAILED DESCRIPTION OF THE INVENTION

[0009] base R 1Examples of the aryl groups 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 groups such as n-hexyl, heptyl groups such as n-heptyl, octyl groups such as n-octyl and isooctyl groups, 2,2,4-trimethylpentyl, nonyl groups such as n-nonyl, decyl groups such as n-decyl, dodecyl groups such as n- dodecyl, octadecyl, such as n-octadecyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl, and 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-, p-tolyl, xylyl, and ethylphenyl; and aralkyl groups, such as benzyl or α- and β-phenylethyl.

[0010] base R 1 is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and particularly preferably a hydrogen atom.

[0011] Divalent group R 2 Examples of are alkylene groups such as ethane-1,2-diyl, propane-1,2-diyl, 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 groups.

[0012] base R 2 is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and particularly preferably a propane-1,2-diyl group.

[0013] The subscript p is preferably an integer of 4-65.

[0014] The polyethers (X) used according to the invention are preferably of the following formula: R 1 (OCH2CH2) q (OCHCH3CH2) r (OCH2CH2) s OR 1 (III), [In the formula, R 1 has one of the definitions given above, q is 0 or an integer of 1 to 30, preferably 0 or an integer of 1 to 15; s is 0 or an integer of 1 to 30, preferably 0 or an integer of 1 to 15, and and r is an integer of 4 to 50, preferably an integer of 4 to 35.

[0015] Examples of compounds (X) that can be used according to the invention are: H(OCH2CH2)5(OCHCH3CH2)(OCH2CH2) 10 OH, H(OCH2CH2)6(OCHCH3CH2)(OCH2CH2)7OH, H(OCH2CH2)5(OCHCH3CH2)(OCH2CH2) 20 OH, H(OCH2CH2)7(OCHCH3CH2)(OCH2CH2)7OH, H(OCH2CH2)2(OCHCH3CH2)(OCH2CH2) 12 OH, H(OCH2CH2)5(OCHCH3CH2)2(OCH2CH2) 10 OH, H(OCH2CH2)6(OCHCH3CH2)2(OCH2CH2)6OH, CH3(OCH2CH2)5(OCHCH3CH2)(OCH2CH2) 10 OCH3, CH3(OCH2CH2)6(OCHCH3CH2)(OCH2CH2)7OCH3, CH3(OCH2CH2)5(OCHCH3CH2)(OCH2CH2) 20 OCH3, CH3(OCH2CH2)7(OCHCH3CH2)(OCH2CH2)7OH, CH3(OCH2CH2)2(OCHCH3CH2)(OCH2CH2) 12 OH, CH3(OCH2CH2)5(OCHCH3CH2)2(OCH2CH2) 10 OH, and CH3(OCH2CH2)6(OCHCH3CH2)2(OCH2CH2)6OH, H(OCHCH3CH2) p OH, CH3(OCHCH3CH2) p OH or CH3(OCHCH3CH2) p OCH3 is particularly preferred.

[0016] In particular, the polyethers (X) used according to the invention are of the following formula: H(OCHCH3CH2) r OH(IV) wherein r has the above definition.

[0017] The mixture (M) according to the invention preferably comprises the polyether (X) in an amount of 40 to 90 parts by weight, particularly preferably 50 to 70 parts by weight, based in each case on 100 parts by weight of the mixture (M).

[0018] The polyethers (X) are commercially available or can be prepared by conventional methods in organic chemistry.

[0019] base R 5 An example of this is R 1 is a group specified for

[0020] base R 5 is preferably a linear or branched alkyl group having 4 to 16 carbon atoms, an aryl group or a vinyl group, particularly preferably a linear or branched alkyl group having 4 to 16 carbon atoms, in particular an n-octyl group.

[0021] R 6 An example of this is R 1 The groups specified for and groups interrupted by oxygen, e.g., R 1 -(O-CH2CH2)3-, R 1 -(O-CH2CH2)4-, R 1 -(O-CH2CH2)5- and R 1 -(O-CH2CH2)6-, nC 12 H 25 -(O-CH2CH2) z -, nC 14 H 29 -(O-CH2CH2) z -, nC 16 H 33 -(O-CH2CH2) z - and nC 18 H 37 -(O-CH2CH2) z - and z is 4 to 25.

[0022] base R 6 is preferably a straight-chain or branched alkyl group having 1 to 18 carbon atoms, or an alkyl group having 10 to 68 carbon atoms interrupted by oxygen.

[0023] Examples of phosphorus compounds (Y) to be used according to the invention are alkylphosphonic acids, such as butylphosphonic acid, sec-butylphosphonic acid, isobutylphosphonic acid, tert-butylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n-decylphosphonic acid, n-undecylphosphonic acid, n-dodecylphosphonic acid, n-tridecylphosphonic acid, n-tetradecylphosphonic acid, n-pentadecylphosphonic acid, n-hexadecylphosphonic acid, benzylphosphonic acid, 2-phenylethylphosphonic acid, arylphosphonic acids, such as phenylphosphonic acid, 1-naphthylphosphonic acid, phosphoric acid monoesters, such as methyl phosphate, ethyl phosphate, n-propyl phosphate, isopropyl phosphate, n-butyl phosphate, n-pentyl phosphate. , n-hexyl phosphate, n-heptyl phosphate, n-octyl phosphate, 2-ethylhexyl phosphate, n-decyl phosphate, n-dodecyl phosphate, n-tetradecyl phosphate, n-hexadecyl phosphate, phosphoric acid diesters such as dimethyl phosphate, diethyl phosphate, di-n-butyl phosphate, di-n-hexyl phosphate, di-n-octyl phosphate, di-2-ethylhexyl phosphate, di-n-decyl phosphate, di-n-dodecyl phosphate, di-n-tetradecyl phosphate, di-n-hexadecyl phosphate, and polyoxyethylene alkyl phosphates each having 4 to 25 oxyethylene units such as polyoxyethylene lauryl phosphate, polyoxyethylene cetyl phosphate, and polyoxyethylene stearyl phosphate.

[0024] The phosphorus compound (Y) used according to the invention is preferably an alkylphosphonic acid having 4 to 18 carbon atoms, particularly preferably n-octylphosphonic acid.

[0025] The phosphorus compound (Y) is commercially available. For example, n-octylphosphonic acid can be obtained as a pure substance or as a solution in ethanol and water, for example, from Clariant under the names "Hostaphat OPS 100" (pure product) or "Hostaphat OPS 75" (solution in ethanol and water).

[0026] The mixture (M) according to the invention preferably comprises the phosphorus compound (Y) in an amount of 10 to 50 parts by weight, particularly preferably 25 to 35 parts by weight, based in each case on 100 parts by weight of the mixture (M).

[0027] The mixture (M) according to the invention preferably comprises water (Z).

[0028] The mixture (M) according to the invention preferably comprises water (Z) in an amount of 0.5 to 3.0 mol, particularly preferably 1.0 to 2.0 mol, in particular 1.0 to 1.5 mol, based in each case on 1 mol of phosphorus compound (Y), preferably n-octylphosphonic acid.

[0029] In addition to components (X), (Y) and (Z), the mixture (M) according to the invention may comprise further components such as alcohols, in particular ethanol.

[0030] The mixture (M) according to the invention preferably consists of components (X), (Y) and (Z) to the extent of at least 98% by weight, particularly preferably to the extent of at least 99.8% by weight and in particular to the extent of 100% by weight.

[0031] The mixture (M) according to the invention is a colorless to pale yellow liquid or low-melting solid, preferably having a melting point below 35°C, particularly preferably below 0°C, in particular below -30°C.

[0032] To prepare the mixture (M) according to the invention, all components can be mixed with one another in any order, and this can be done at room temperature or at elevated temperatures between 30°C and 150°C, at ambient pressure, i.e., about 900-1100 hPa, or at reduced pressure between 1 and 900 hPa.

[0033] The present invention further provides a process for preparing the mixture (M) according to the invention by mixing the individual components.

[0034] In the process according to the invention, the polyether (X) is preferably first charged into a suitable vessel, and then the phosphorus compound (Y) is metered in while stirring. This is preferably carried out at ambient temperature. The mixture is then heated, with stirring, to a temperature of preferably 80 to 150°C under a reduced pressure of up to 20 mbar, and any impurities present, such as water and alcohol, are removed by distillation. The temperature and reduced pressure are preferably maintained until no more distillate is removed. The mixture is then cooled to room temperature, and, if desired, a specified amount of water (Z) is added.

[0035] The process according to the invention can be carried out continuously, discontinuously or semi-continuously by known methods and using known equipment.

[0036] It was unexpected that phosphorus compound (Y) could be dissolved in polyether (X) without visible residue up to a concentration of 50% by weight. For practical use, it was necessary that n-octylphosphonic acid did not crystallize from the mixture even at low temperatures. Particularly surprising was that the addition of a specified amount of water (Z) significantly improved the stability of mixture (M), even down to a temperature of -30°C.

[0037] The mixtures (M) according to the invention have the advantage that they allow handling as liquids with low hazard potential, without the formation of undesirable by-products.

[0038] Furthermore, the mixtures (M) according to the invention have the advantage that they can be easily prepared without forming undesired by-products.

[0039] The mixtures (M) according to the invention have the advantage that they are liquid even at low temperatures and have a low flash point.

[0040] The mixtures (M) according to the invention have the advantage that they exhibit good storage stability and are highly resistant to low temperatures.

[0041] The mixture (M) according to the invention can be used in all applications in which phosphorus compounds can also be used to date, for example as a stabilizer for compositions based on organosilicon compounds that can be crosslinked by elimination of alcohol.

[0042] The mixtures (M) according to the invention are preferably used to prepare crosslinkable compositions based on organosilicon compounds.

[0043] The present invention further provides a crosslinkable composition based on organosilicon compounds that can be obtained by mixing: (A) an organopolysiloxane of the formula: (R 7 O) 3-a SiR 3 a O(SiR 4 2O) n SiR 3 x (OR 7 ) 3-a (V), [In the formula, R 4 may be the same or different and represent a monovalent optionally substituted hydrocarbon group, R 7 may be the same or different and represent a monovalent optionally substituted hydrocarbon group, R 3 may be the same or different and represent a monovalent optionally substituted hydrocarbon group, a may be the same or different and is 0 or 1, preferably 1; and x is an integer between 30 and 2000. and (B) A mixture containing (M (X) polyethers of general formula (I), (Y) a phosphorus compound of formula (II), and optionally (Z) Water.

[0044] base R 4 and R 7 Examples of R are each independently a group R 1 are the groups identified above for

[0045] base R 4 are preferably each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly preferably a methyl group, a vinyl group or a phenyl group, in particular a methyl group.

[0046] base R 7 are preferably each independently an alkyl group having 1 to 12 carbon atoms, particularly preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, in particular a methyl group or an ethyl group.

[0047] base R 3 An example of this is R 1 The monovalent hydrocarbon groups specified above and hydrocarbon groups substituted with amino groups are also included.

[0048] base R 3 is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms and optionally substituted with an amino group, particularly preferably a methyl group, an ethyl group, a vinyl group, a phenyl group, or —CH—NR 6’ R 5’ group or group -CH2NR 11’ and R 5’ means a hydrocarbon group having 1 to 12 carbon atoms, and R 6’ is a hydrogen atom or a group R 5’ means R 11’ means a divalent hydrocarbon group optionally interrupted by heteroatoms.

[0049] base R 3 is particularly preferably the group —CH—NR 6’ R 5’ group or group -CH2NR 11’ where R 5’ , R 6’ and R 11’is as defined above, in particular -CH2-N[(CH2)2]2O, -CH2-N(Bu)2 or -CH2-NH(cHex), where Bu means an n-butyl group and cHex means a cyclohexyl group.

[0050] base R 5’ An example of this is R 1 is a hydrocarbon group specified for

[0051] base R 5’ is preferably a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, a cyclohexyl group or a phenyl group, particularly preferably an n-butyl group.

[0052] Hydrocarbon group R 6’ An example of this is R 1 is a hydrocarbon group specified for

[0053] base R 6’ is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group or a cyclohexyl group, particularly preferably an n-butyl group.

[0054] Divalent group R 11’ An example of this is R 2 and the groups -CH2-CH2-O-CH2-CH2- and -CH2-CH2-NH-CH2-CH2-.

[0055] base R 11’ is preferably a divalent hydrocarbon radical having 4 to 6 carbon atoms, which may be interrupted by heteroatoms, preferably oxygen -O- or nitrogen -NH-, particularly preferably -CH2-CH2-O-CH2-CH2-.

[0056] The organopolysiloxane (A) used according to the invention is preferably (MeO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OMe)2, (MeO)2Si(DBA)O(SiMe2O)30-2000 Si(DBA)(OMe)2, (MeO)2Si(cHx)O(SiMe2O) 30-2000 Si(cHx)(OMe)2, (MeO)2Si(R 3 )O(SiMeO) 700 Si(R 3 )(OMe)2, (EtO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OEt)2, (EtO)2Si(DBA)O(SiMe2O) 30-2000 Si(DBA)(OEt)2, (EtO)2Si(cHx)O(SiMe2O) 30-2000 Si(cHx)(OEt)2 or (EtO)2Si(R 3 )O(SiMeO) 700 Si(R 3 )(OEt)2, More preferably (EtO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OEt)2, (EtO)2Si(DBA)O(SiMe2O) 30-2000 Si(DBA)(OEt)2 or (EtO)2Si(cHx)O(SiMe2O) 30-2000 Si(cHx)(OEt)2, In particular, (EtO)2Si(Ox)O(SiMe2O) 30-2000 Si(Ox)(OEt)2 In the formula, Me is a methyl group, Et is an ethyl group, Ox is —CH—N[(CH)]O, DBA is —CH—N(nBu)O, cHx is —CH—NH(cHex), Bu is an n-butyl group, cHex is a cyclohexyl group, and R 3 means Me, Et, vinyl, phenyl, DBA, Ox or cHx, and the group R 3 has the same definition within each compound.

[0057] The organopolysiloxane (A) used according to the invention preferably has a viscosity at 25°C of 6,000 to 350,000 mPas, particularly preferably 20,000 to 120,000 mPas.

[0058] Organopolysiloxane (A) is commercially available or may be prepared by the method described below.

[0059] Component (B) used according to the invention is preferably a mixture (M) containing water (Z).

[0060] The composition according to the invention preferably contains component (B) in an amount of 0.001 to 5 parts by weight, particularly preferably 0.01 to 5 parts by weight, in particular 0.1 to 1 part by weight, based in each case on 100 parts by weight of component (A).

[0061] The composition according to the invention comprises, in addition to the siloxanes (A) and (B), a component (C) consisting of a silane of the formula (R 8 O) 4-b SiR 9 b (VI) and / or partial hydrolysates thereof, wherein: b is 0, 1 or 2, preferably 0 or 1; R 8 may be the same or different and represent a monovalent hydrocarbon group which may be substituted, and R 9 means a monovalent optionally substituted hydrocarbon.

[0062] base R 8 is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, in particular a methyl group or an ethyl group.

[0063] base R 9is preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with a glycidoxy group, a ureido group, a methacryloxy group or an amino group, and is particularly preferably an alkyl group, a vinyl group or a phenyl group, in particular a methyl group or a 2,2,4-trimethylpentyl group.

[0064] In a preferred embodiment, silanes and / or their partial hydrolysates having functional groups, such as those having glycidoxypropyl, aminopropyl, aminoethylaminepropyl, ureidopropyl or methacryloxypropyl groups, are used in whole or in part as component (C), especially when adhesion-promoting properties are desired.

[0065] The optionally used partial hydrolysates (C) may be partial homohydrolysates, i.e. partial hydrolysates of one type of silane of formula (III), and partial cohydrolysates, i.e. partial hydrolysates of at least two different types of silanes of formula (III).

[0066] In the context of the present invention, the term partial hydrolysate is understood to mean a product formed by hydrolysis and / or condensation.

[0067] When the component (C) optionally used in the composition according to the invention is a partial hydrolysate of a silane of formula (VI), those having up to 20 silicon atoms are preferred.

[0068] Examples of component (C) optionally used in accordance with the present invention are methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltriethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, N,N-di-n-butylaminomethyltriethoxysilane, Examples of the silanes include methyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltrimethoxysilane, N,N-di-n-butylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyltrimethoxysilane, and among these, methyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, and (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane are preferred.

[0069] Component (C) is commercially available or can be prepared by methods common in silicon chemistry.

[0070] When the composition according to the present invention contains component (C), the amount contained is preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 2 parts by weight, and in particular 0.05 to 2 parts by weight, based in each case on 100 parts by weight of component (A). The composition according to the present invention preferably contains component (C), which preferably comprises at least in part a silane having a functional group and / or a partial hydrolysate thereof.

[0071] In addition to components (A), (B) and optionally (C), the compositions according to the invention may now contain all substances which have also been used up to now in compositions crosslinkable by condensation reactions, such as accelerators (D), plasticizers (E), fillers (F) and additives (G).

[0072] All curing accelerators that have been used in compositions crosslinkable by condensation reaction can be used as the curing accelerator (D). Examples of the curing accelerator (D) are titanium compounds, such as tetrabutyl titanate or tetraisopropyl titanate, or titanium chelates, such as bis(ethylacetoacetate)diisobutoxytitanium, or organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n-butyltin oxide, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin dineodecanoate, dimethyltin oxide, di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide, and reaction products of these compounds with alkoxysilanes, such as the reaction product of di-n-butyltin diacetate and tetraethoxysilane; Reaction products of di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide, di-n-butyltin dilaurate, di-n-butyltin diacetate, or di-n-octyltin oxide with tetraethoxysilane, tetrabutyl titanate, tetraisopropyl titanate, or bis(ethylacetoacetate)diisobutoxytitanium are preferred, and reaction products of di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide, or di-n-butyltin dilaurate, di-n-butyltin diacetate, or di-n-octyltin oxide with tetraethoxysilane are particularly preferred.

[0073] If the composition according to the invention comprises a curing accelerator (D), this is preferably contained in an amount of 0.001 to 20 parts by weight, particularly preferably 0.001 to 1 part by weight, in each case based on 100 parts by weight of component (A).

[0074] Examples of optionally used plasticizers (E) are dimethylpolysiloxanes end-capped with trimethylsiloxy groups that are liquid at room temperature, especially with a viscosity at 25° C. in the range of 5 to 1000 mPas, and high-boiling hydrocarbons, such as paraffin oils or mineral oils composed of naphthenic and paraffinic units.

[0075] If the composition according to the invention comprises component (E), it is preferably present in an amount of 5 to 30 parts by weight, preferably 5 to 25 parts by weight, in each case based on 100 parts by weight of siloxane (A). The composition according to the invention preferably does not comprise a plasticizer (E).

[0076] The filler (F) optionally used in the composition according to the invention can be any previously known filler.

[0077] Examples of optionally used fillers (F) are non-reinforcing fillers (F), i.e., up to 20 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders, such as oxides or mixed oxides of aluminum, titanium, iron or zinc, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders, such as polyacrylonitrile powder, reinforcing fillers, i.e., 20m 2 / g, such as precipitated chalk and carbon black, e.g. furnace black and acetylene black, silica, e.g. fumed silica and precipitated silica, fibrous fillers, e.g. plastic fibers.

[0078] The optionally used filler (F) is preferably calcium carbonate or silica, particularly preferably silica or a mixture of silica and calcium carbonate.

[0079] The preferred calcium carbonate grade (F) is ground or precipitated and optionally surface treated with a fatty acid such as stearic acid or its salt. The preferred silica is preferably fumed silica.

[0080] When the composition according to the present invention contains a filler (F), the amount contained is preferably 10 to 150 parts by weight, particularly preferably 10 to 130 parts by weight, and especially 10 to 100 parts by weight, based on 100 parts by weight of the organopolysiloxane (A). The composition according to the present invention preferably contains a filler (F).

[0081] Examples of additives (G) include pigments, dyes, fragrances, antioxidants, agents for influencing electrical properties such as conductive carbon black, flame retardants, light stabilizers, biocides such as fungicides, bactericides and miticides, cell formers such as azodicarbonamide, heat stabilizers, scavengers such as Si-N-containing silazanes or silylamides, for example, N,N'-bis(trimethylsilyl)urea or hexamethyldisilazane, cocatalysts, thixotropic agents such as polyethylene glycol terminated at one or both ends with OH or hydrogenated castor oil, agents for further adjusting the modulus of elasticity such as polydimethylsiloxanes with OH end groups, and any siloxane other than components (A), (B) and (C).

[0082] Depending on the type and amount of mixture (M) used as component (B) according to the invention, the addition of thixotropic agent (G) may be omitted.

[0083] The individual components of the composition according to the invention may in each case be one type of such component or a mixture of at least two different types of such component.

[0084] The composition according to the invention preferably comprises: (A) an organopolysiloxane of formula (V), (B) mixture (M), optionally (C) a silane of formula (VI) and / or a partial hydrolysate thereof; optionally (D) a cure accelerator; optionally (E) a plasticizer; optionally (F) a filler; and Optionally, (G) additives.

[0085] The composition according to the invention is particularly preferably one which comprises: (A) an organopolysiloxane of formula (V), (B) mixture (M), (C) silanes of formula (VI) and / or partial hydrolysates thereof, optionally (D) a cure accelerator; optionally (E) a plasticizer; optionally (F) a filler; and Optionally, (G) additives.

[0086] The composition according to the invention is in particular one which comprises: (A) an organopolysiloxane of formula (V), (B) mixture (M), (C) silanes of formula (VI) and / or partial hydrolysates thereof, (D) a cure accelerator; (F) filler; optionally (E) a plasticizer and Optionally, (G) additives.

[0087] The composition according to the present invention preferably does not contain any further constituents other than components (A) to (G).

[0088] The composition according to the invention is preferably a viscous to pasty mass.

[0089] To prepare the composition according to the present invention, all components can be mixed together in any order. This mixing can be carried out at room temperature and atmospheric pressure, i.e., about 900 to 1100 hPa. However, if desired, this mixing can also be carried out at higher temperatures, for example, at temperatures in the range of 35 to 135°C. Furthermore, in order to remove undesired volatile compounds or air, it is possible to mix intermittently or continuously under reduced pressure, such as 30 to 500 hPa absolute.

[0090] The mixing according to the present invention is preferably carried out with maximum exclusion of moisture from the atmosphere. All raw materials except (M) preferably have a moisture content of less than 10,000 mg / kg, preferably less than 5,000 mg / kg, and particularly less than 1,000 mg / kg. During the mixing process, a protective gas such as dry air or nitrogen is preferably used, each gas preferably having a moisture content of less than 10,000 μg / kg, preferably less than 1,000 μg / kg, and particularly less than 500 μg / kg. After preparation, the paste is filled into commercially available moisture-proof containers such as cartridges, tubular bags, buckets, and drums.

[0091] In a preferred procedure, components (A), optionally (C) and (E) are first mixed together, then optionally filler (F) is added, and finally (B) and optionally further components (D) and (G) are added, preferably with a temperature during mixing not exceeding 60°C.

[0092] The present invention further provides a process for preparing the composition according to the invention by mixing the individual components.

[0093] The process according to the invention can be carried out continuously, discontinuously or semi-continuously by known methods and using known equipment.

[0094] The compositions according to the invention or compositions prepared according to the invention can be stored with the exclusion of moisture and can crosslink upon the ingress of moisture.

[0095] The normal water content of air is sufficient for crosslinking the compositions according to the invention. The compositions according to the invention are preferably crosslinked at room temperature. They may also be crosslinked, if desired, at temperatures higher or lower than room temperature, for example, between -5°C and 15°C or between 30°C and 50°C, and / or using water concentrations that exceed the normal water concentration of air.

[0096] The crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the ambient atmosphere, ie about 900 to 1100 hPa.

[0097] The present invention further provides a molded article produced by crosslinking a composite composition according to the present invention.

[0098] The compositions according to the invention can be stored with the exclusion of water and can be used for any purpose for which a composition can be used which crosslinks to give an elastomer on ingress of water at room temperature.

[0099] The compositions according to the invention therefore have excellent suitability for use as sealants for joints, including vertical joints, and similar cavities, e.g. of 10 to 40 mm internal width, for example in buildings, land vehicles, ships and aircraft, or as protective coatings, including those for surfaces exposed to the constant action of fresh or sea water, e.g. in window construction or as adhesive or cement compositions, e.g. in the manufacture of glass cabinets, or as anti-slip coatings, or for the production of elastomeric mouldings.

[0100] The compositions according to the invention have the advantage that they are easy to prepare and are characterised by very high storage stability.

[0101] More preferably, the mixture (M) according to the invention can be used as a neutralizing agent in the preparation process of polymers having hydrolyzable end groups.

[0102] The present invention further provides a process for preparing organosilicon compounds containing organyloxy groups, characterized in that in a first step, an organosilicon compound (a) containing at least one silanol group is reacted with a compound (b) containing at least two organyloxy groups in the presence of a strong basic catalyst (c), and in a second step, after the reaction of the hydroxyl groups of component (a) with the compound (b) containing organyloxy groups has taken place, a mixture (M) according to the present invention is added.

[0103] In the process according to the invention, the strongly basic catalyst (c) can be a lithium compound such as lithium alkoxylate or lithium hydroxide, and an amidine or guanidine, with cyclic guanidines being preferred as component (c), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being particularly preferred.

[0104] In a preferred embodiment of the process according to the invention, in a first step, an organosilicon compound (a) containing at least one silanol group is reacted with a compound (b) containing at least two organyloxy groups in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (c), and in a second step, a mixture (M) according to the invention is added.

[0105] Component (a) used according to the present invention can be any organosilicon compound known to date which contains at least one silanol group.

[0106] The organosilicon compound (a) is preferably an organosilicon compound having at least two silanol groups.

[0107] The organosilicon compound (a) is preferably a substantially linear organopolysiloxane.

[0108] The organosilicon compounds (a) used according to the invention are in each case at 25° C., preferably at 10 2 ~10 8 The viscosity of the resin is preferably 1,000 to 350,000 mPas.

[0109] Examples of organosilicon compounds (a) that can be used according to the invention are: HO(Si(CH3)2O) 29-1000 Si(CH3)2(CH2)3NH2, HO(Si(CH3)2O) 29-1000 Si(CH3)2(OH), HO(Si(CH3)2O) 29-1000 Si(CH3)3, HO(Si(CH3)2O) 0-100 Si(CH3)2(CH2)3O(CH2CH(CH3)O) 10-1000 (CH2)3(Si(CH3)2O) 0-100 Si(CH3)2(OH), HO(Si(CH3)2O) 3-500 Si(O)3[(Si(CH3)2O) 3-500 H]3 and HO(Si(CH3)2O) 3-500 Si(CH3)(O)2[(Si(CH3)2O) 3-500 H]2, where HO(Si(CH3)2O) 30-1000 Si(CH3)2(CH2)3NH2, HO(Si(CH3)2O) 30-1000 Si(CH3)2(OH), HO(Si(CH3)2O) 30-1000 Si(CH3)3 and HO(Si(CH3)2O) 3-500 Si(CH3)(O)2[(Si(CH3)2O) 3-500 H]2 is preferred, HO(Si(CH3)2O) 30-1000 Si(CH3)2(OH) is particularly preferred.

[0110] Component (a) is commercially available or can be prepared by standard chemical methods.

[0111] Component (b) used according to the invention can be any previously known compound having at least two organyloxy groups, preferably a siloxane or a silane.

[0112] Component (b) is particularly preferably a silane of formula (VI) and / or a partial hydrolysate thereof.

[0113] Examples of compounds (b) to be used according to the invention are methyltrimethoxysilane, dimethyldimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane and tert-butyltrimethoxysilane, as well as their partial hydrolysates, preferred are methyltrimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane and n-butyltrimethoxysilane, particularly preferred are methyltrimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, tetraethoxysilane and n-butyltrimethoxysilane.

[0114] Component (b) is commercially available or can be prepared by standard chemical methods.

[0115] In the process according to the invention, component (b) is preferably used in a 1- to 100-fold excess, particularly preferably a 2- to 50-fold molar excess, based in each case on the molar amount of Si—OH groups in compound (a).

[0116] In the process according to the invention, the catalyst (c) is preferably used in an amount of 5 to 10 000 ppm by weight, particularly preferably 100 to 3000 ppm by weight, in each case based on the total amount of components (a) and (b).

[0117] In the process according to the present invention, the individual components can be mixed together in any order and in any currently known manner. A premix can also be prepared from a mixture of several components, for example, components (b) and (c), which are then mixed with the other components. The individual components can also be present or added at the beginning or during the mixing process. For example, some of the components (b) or preparation (c) can be added only 1 to 60 minutes after the mixing of the other respective components.

[0118] The components used in the process according to the invention may be one such component or a mixture of at least two respective components.

[0119] The process according to the invention is preferably carried out at ambient temperature or at the temperature resulting from mixing the individual components without additional heating, which is preferably between 10 and 60°C, particularly preferably between 15 and 40°C.

[0120] The process according to the invention is preferably carried out at the pressure of the ambient atmosphere, i.e., 900 to 1100 hPa. However, it is also possible to operate at positive pressure, for example at absolute pressures between 1100 and 3000 hPa, especially in the case of continuous operation, when these pressures arise in the closed system, for example due to pumping pressures and the vapor pressure of the materials used at high temperatures.

[0121] The process according to the invention is preferably carried out with the exclusion of moisture, for example in dry air or nitrogen.

[0122] The process according to the invention can, if desired, be carried out under a protective gas such as nitrogen.

[0123] In the process according to the invention, the reaction mixture can be liquefied after completion of the reaction, the liquefaction being carried out in the same apparatus or in a downstream apparatus, with or without an inert gas supply, at room temperature or at elevated temperature, by means of reduced pressure. The highly volatile component is preferably an alcohol, such as methanol or ethanol.

[0124] The process according to the invention can be carried out continuously or discontinuously.

[0125] A number of organosilicon compounds containing organyloxy groups can be advantageously prepared by the process according to the invention.

[0126] The process according to the invention has the advantage that organosilicon compounds containing organyloxy groups can be prepared in a simple manner. [Example]

[0127] In the examples described below, all viscosity data is based on a temperature of 25° C. Unless otherwise specified, the following examples are carried out at ambient atmospheric pressure, i.e., about 1000 hPa, at room temperature, i.e., about 23° C., or at the temperature that occurs when the reactants are combined at room temperature and about 50% relative humidity without additional heating or cooling. Furthermore, unless otherwise specified, all reported parts and percentages are by weight.

[0128] In the context of the present invention, the dynamic viscosity of organosilicon compounds is measured in accordance with DIN 53019. The preferred procedure was as follows: Unless otherwise stated, viscosity is measured at 25°C using an Anton Paar "Physica MCR 300" rotational rheometer. In this case, for viscosities between 1 and 200 mPa·s, a coaxial cylinder measuring system (CC27) with an annular measuring gap of 1.13 mm is used, and for viscosities above 200 mPa·s, a cone-plate measuring system (Searle system with a CP50-1 measuring cone) is used. The shear rate is adapted to the polymer viscosity (100 s 1 1 to 99 mPa·s, 200 s 1 100 to 999 mPa·s, 120s 1 1000-2999 mPa·s for 80 s, 3000-4999 mPa / s for 62 s 1 5000~9999mPa·s, 50s 1 1000~12499mPa·s, 38.5s 1 12500~15999mPa·s, 33s 1 16000~19999mPa·s, 25s 1 20,000 to 24,999 mPa·s for 20 seconds 1 25,000 to 29,999 mPa·s, 17 s 1 30,000 to 39,999 mPa·s for 10 seconds 140,000 to 59,999 mPa·s at 5 s 1 60,000 to 1,499,999 mPa·s, 3.3 s 1 150,000 to 199,999 mPa·s at 2.5 s 1 200,000 to 299,999 mPa·s at 1.5 s 1 300,000 to 1,000,000 mPa·s).

[0129] number average molar mass M n is determined in the context of the present invention by size exclusion chromatography (SEC) on a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA in THF at 60°C against polystyrene standards with an injection volume of 100 μl and a flow rate of 1.2 ml / min and detection by RI (refractive index detector).

[0130] PPG425: Average molecular weight M of 425g / mol n Polypropylene glycol having PPG1000: Average molecular weight M of 1000g / mol n Polypropylene glycol having PPG400: Average molecular weight M of 400g / mol n Polypropylene glycol having OPS75: n-octylphosphonic acid, 75% by weight in water and ethanol (commercially available, for example, from Clariant under the name "Hostaphat OPS 75").

[0131] [Example 1] 100 g of OPS75 was mixed with 75 g of PPG425 and heated to 105° C. under a vacuum of 20 mbar and maintained at this temperature for 1 hour, whereupon ethanol and water were distilled off.

[0132] Crystallization began at 28° C., giving a clear solution that was solid at room temperature.

[0133] The results are shown in Table 1.

[0134] [Example 2] 100 g of OPS75 was mixed with 75 g of PPG1000 and heated to 105° C. under a vacuum of 20 mbar and maintained at this temperature for 1 hour, whereupon ethanol and water were distilled off.

[0135] At 25°C, crystallization began to occur, giving a clear solution that was solid at room temperature, and therefore the viscosity could not be measured at 25°C.

[0136] The results are shown in Table 1.

[0137] [Examples 4 to 7] The procedure described in Example 1 was repeated with the amounts of feedstock listed in Table 1.

[0138] In Examples 4 and 7, after completion of the distillation step, the mixture was cooled to 80°C and the amount of deionized water specified in Table 1 was added. Stirring was continued in these cases for an additional hour to obtain a homogeneous solution. A clear solution was obtained, and the viscosity and temperature of the onset of crystallization are listed in Table 1.

[0139] [Table 1]

[0140] [Example 8] The procedure described in Example 7 was repeated, with the change that PPG400 was used instead of PPG425. In this case, no differences were observed. In particular, the melting point was also below -30°C.

[0141] [Example 9] 309 g of α,ω-bis[(tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilyl]polydimethylsiloxane having a viscosity of 80,000 mPa·s, 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1,000 mPa·s (commercially available under the name "Weichmacher 1000" from Wacker Chemie AG, Munich, Germany), 16.0 mol % of MeSi(OEt)O 1 / 2units of the formula MeSi(OEt)O, 46.4 mol % 2 / 2 units of formula MeSiO 3 / 2 units, 0.2 mol% of the formula MeSi(OEt)O 1 / 2 and 0.9 mol % of the formula MeSiO 2 / 2 1 g of the product consisting of units, 8 g of 3-aminopropyltriethoxysilane (available commercially under the name GENIOSIL® GF93 from Wacker Chemie AG, Munich, Germany), 2 g of vinyltriethoxysilane (available commercially under the name GENIOSIL® GF56 from Wacker Chemie AG, Munich, Germany), and 5 g of tetraethyl silicate (available commercially under the name "Silikat TES28" from Wacker Chemie AG, Munich, Germany) were initially charged into a planetary mixer and mixed for 30 minutes. Then, 150 ml 2 45 g of fumed silica (available commercially under the name HDK® V15 from Wacker Chemie AG, Munich, Germany) having a BET specific surface area of ​​1 / g was mixed in, and the mixture was thoroughly homogenized at a pressure of 50 hPa. Finally, 1 g of the mixture prepared in Example 1 and 2 g of the reaction product of dibutyltin diacetate and tetraethoxysilane (available commercially under the name "Katalysator 41" from Wacker Chemie AG, Munich, Germany) were added, and the mixture was homogenized for a further 5 minutes under a pressure of approximately 50 hPa (absolute).

[0142] The RTV1 compositions thus obtained were filled into commercially available moisture-proof polyethylene cartridges and stored at room temperature for 24 hours, and additional samples were stored at 70°C for 7 days. 2 mm thick slabs were then rolled out from each of the samples thus stored and stored at 23°C and 50% relative humidity for 7 days. Test specimens according to DIN 53504, form S2, were punched out from the cured material and their mechanical properties were measured. The results are shown in Table 2.

[0143] [Example 10] Example 9 was repeated with the change that instead of 1 g of the mixture from Example 1, 1.57 g of the mixture from Example 7 was added.

[0144] The results are shown in Table 2.

[0145] [Example 11] 880 kg of α,ω-dihydroxypolydimethylsiloxane (commercially available under the name POLYMER FD80 from Wacker Chemie AG, Munich, Germany) having a viscosity of 80,000 mPa·s was mixed with a solution of 91 g of triazabicyclo[4.4.0]dec-5-ene in 27 kg of vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL10 from Wacker Chemie AG, Munich, Germany). After a reaction time of 45 minutes at room temperature, 255 g of the mixture from Example 1 was added and mixed until homogeneous.

[0146] The α,ω-bis(vinyldimethoxysilyl)polydimethylsiloxane with a viscosity of 100 Pas was obtained as a clear, colorless product without further workup.

[0147] [Example 12] 300 g of the product prepared according to Example 11 are first charged into a planetary mixer with 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 AG, Munich, Germany), 5 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available under the name GENIOSIL® GF91 from Wacker Chemie AG, Munich, Germany), and 2 g of vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL10 from Wacker Chemie AG, Munich, Germany), and mixed for 30 minutes. 245 g of fumed silica (available commercially under the name HDK® V15 from Wacker Chemie AG, Munich, Germany) having a BET specific surface area of ​​1 / g was mixed in, and the mixture was thoroughly homogenized at a pressure of 50 hPa. Finally, 1 g of the solution according to Example 1 and 2 g of the reaction product of dibutyltin diacetate and tetraethoxysilane (available commercially under the name "Katalysator 41" from Wacker Chemie AG, Munich, Germany) were added, and the mixture was homogenized for a further 5 minutes at a pressure of about 50 hPa (absolute).

[0148] The RTV1 compositions thus obtained were filled into commercially available moisture-proof polyethylene cartridges and stored at room temperature for 24 hours, and further samples were stored for 7 days at 70° C. From each of the samples thus stored, 2 mm thick slabs were then rolled out and stored for 7 days at 23° C. and 50% relative humidity. Test specimens according to DIN 53504 in form S2 were punched out of the cured material and their mechanical properties were measured.

[0149] The results are shown in Table 2.

[0150] [Example 13] <Preparation of Oligomer Mixture 13a> 240 g (3.25 mol) of α,ω-bis(trimethylsiloxy)polydimethylsiloxane with a viscosity of 1000 mPas, 234 g (1.0 mol) of trimethoxy(2,4,4-trimethylpentyl)silane (= iOctSi(OMe)3) (obtained from Wacker Chemie AG under the name SILRES® BS1316), and 0.80 g of an ethanolic solution of sodium ethoxide (21%) are mixed and heated to 110°C for 4 hours. After the solution has cooled, the mixture is neutralized by adding 1.60 g of an n-heptane solution of dimethyldichlorosilane (10%). The mixture is liquefied in a rotary evaporator at 120°C under a reduced pressure of 50 mbar. The composition of the mixture is: 29The mixture consisted of 1.4 wt% iOctSi(OMe)3, 0.4 wt% Me2Si(OMe)2, and 98.2 wt% average composition [iOctSi(OMe)2O 1 / 2 ] 0.08 [iOctSi(OMe)O 2 / 2 ] 0.15 [iOctSiO 3 / 2 ] 0.05 [MeSiO 2 / 2 ] 0.43 [MeSi(OMe)O 1 / 2 ] 0.29 The molecular weight determined by gel permeation chromatography was 929 g / mol (Mw - weight average) and 635 (Mn - number average). The polydispersity (Mw / Mn) was 1.46.

[0151] A mixture of 660 g of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPas and 220 g of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 20,000 mPas was stirred at 200 rpm for 5 minutes with 30.44 g of 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, this gives a mixture of 98.0% by weight of α,ω-bis((2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilyl)polydimethylsiloxane, 1.9% by weight of (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane and 0.1% by weight of ethanol, with a viscosity of 52000 mPas.

[0152] <RTV1 Cap Compound Using Oligomer Mixture 13a> 455 g of the reaction mixture thus obtained was added to 10.6 g of a tetraethoxysilane hydrolyzate oligomer having an SiO content of 40% upon total hydrolysis and condensation, commercially available from Wacker Chemie AG (Munich, Germany) under the name "SILIKAT TES40," and 12.6 g of the equilibrium product of 6.3 g of a methyltriethoxysilane hydrolyzate oligomer having an average of 10 Si atoms per molecule with 6.3 g of 3-aminopropyltriethoxysilane, and the mixture was stirred for another 5 minutes at 200 rpm. Then, 150 ml of the mixture was added to the equilibrium product of 6.3 g of a methyltriethoxysilane hydrolyzate oligomer having an average of 10 Si atoms per molecule with 6.3 g of 3-aminopropyltriethoxysilane, and the mixture was stirred for another 5 minutes at 200 rpm. 2 44 g of hydrophilic fumed silica (HDK® V15A, available from Wacker Chemie AG) having a surface area of ​​1 / g was added, and the mixture was initially stirred at 200 rpm for another 5 minutes until all of the fumed silica was wetted. The mixture was then stirred at 600 rpm for 10 minutes under a vacuum of 200 mbar. Finally, 1.58 g of a solution of 0.27 g of dioctyltin oxide in 1.31 g of the equilibration product of 0.655 g of methyltriethoxysilane hydrolyzate oligomer having an average of 10 Si atoms per molecule and 0.655 g of 3-aminopropyltriethoxysilane, 2.6 g of the additive of the present invention from Example 7, and 25.6 g of oligomer mixture 13a were added, and the mixture was stirred under reduced pressure (200 mbar) for another 5 minutes.

[0153] The mixtures were then filled into commercially available cartridges and stored with the moisture removed. 24 hours after the mixtures were prepared, 2 mm thick slabs were extracted from the mixtures and cured at 23 °C and 50% relative humidity for 7 days. Type 2 dumbbell-shaped test specimens were then prepared according to ISO 37 6th Edition 2017-11.

[0154] The results are shown in Table 2.

[0155] Without the additive of the invention according to Example 7, a mixture similar to Example 13 did not harden into a material that was no longer tacky after pre-storage at 70° C. for 7 days.

[0156] [Table 2]

[0157] The skin formation time was typically in the range of 15 to 25 minutes.

[0158] Without the additive according to the invention, the mixtures according to Examples 9, 10, 12 and 13 no longer hardened into tack-free materials after pre-storage at 70° C. for 7 days.

[0159] [Example 14] In a laboratory dissolver, 400 g of α,ω-dihydroxypolydimethylsiloxane was vigorously mixed with 8.5 g of phenyltrimethoxysilane and 0.25 g of a 20 wt % solution of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in isooctyltriethoxysilane for 5 minutes at an initial temperature of 25° C. The mixing shaft, with dissolver gearing approximately 5 cm in diameter, was set at 1000 rpm.

[0160] The mixture was found to be free of silanol groups after 30 minutes using the titanate rapid test described in EP 2170995 B1, page 7. The end-capping reaction was therefore already complete at this point.

[0161] Subsequently, 0.5 g of the additive according to the invention from Example 7 was mixed in for 10 minutes.

[0162] Viscosity after 2 hours: 90.0 Pa.s Viscosity after 22 hours: 85.5 Pa.s

[0163] [Example 15 (Non-invention)] Experiment 13 was repeated with the modification that no additive according to the invention was subsequently mixed in.

[0164] Viscosity after 2 hours: 89.0 Pa.s Viscosity after 22 hours: 48.5 Pa.s

[0165] It can be seen that without the stabilizer according to the invention there is a rapid loss of viscosity.

[0166] [Example 16] In a laboratory dissolver, 400 g of α,ω-dihydroxypolydimethylsiloxane was vigorously mixed with 7 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine and 0.25 g of a 20 wt % solution of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in isooctyltriethoxysilane for 5 minutes at an initial temperature of 25° C. The mixing shaft, with dissolver gearing approximately 5 cm in diameter, was set at 1000 rpm.

[0167] The mixture was found to be free of silanol groups after 30 minutes using the titanate rapid test described in EP 2170995 B1, page 7. The end-capping reaction was therefore already complete at this point.

[0168] Subsequently, 0.5 g of the additive according to the invention from Example 7 was mixed in for 10 minutes.

[0169] Viscosity after 2 hours: 190.0 Pa.s Viscosity after 22 hours: 162.5 Pa.s

[0170] [Example 17 (Non-invention)] Experiment 15 was repeated with the modification that no additive according to the invention was subsequently mixed in.

[0171] Viscosity after 2 hours: 184.5 Pa.s Viscosity after 22 hours: 113.0 Pa.s

[0172] It can again be seen that without the additive according to the invention there is a drastic drop in viscosity.

Claims

1. A mixture (M) comprising: (X) a polyether of the following general formula: R １ -(O-R ２ ) ｐ -O-R １ (I)、 [In the formula, R １ may be the same or different and represent a hydrogen atom or a hydrocarbon group, R ２ may be the same or different and represent a divalent optionally substituted hydrocarbon group; and p is an integer from 4 to 110. (Y) a phosphorus compound of the following formula: O=PR ５ ｍ (OR ６ ) ｎ (OH) ３－（ｍ＋ｎ） (II)、 [In the formula, R ５ may be the same or different and represent an optionally substituted hydrocarbon group, R ６ may be the same or different and represent an optionally substituted hydrocarbon group, m is equal to 0 or 1, preferably 1, and n is equal to 0, 1 or 2; However, m+n is equal to 1 or 2, and is preferably 1. and optionally (Z) Water.

2. 2. The mixture (M) according to claim 1, characterized in that the polyether (X) is of the following formula: R １ (OCH) ２ CH ２ ) ｑ (OCHCH ３ CH ２ ) ｒ (OCH) ２ CH ２ ) ｓ OR １ (III) [In the formula, R １ has one of the definitions given above, q is 0 or an integer of 1 to 30, preferably 0 or an integer of 1 to 15; s is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15; and r is an integer of 4 to 50, preferably an integer of 4 to 35.

3. 3. The mixture (M) according to claim 1 or 2, characterized in that the phosphorus compound (Y) is an alkylphosphonic acid having 4 to 18 carbon atoms.

4. The mixture (M) according to any one of claims 1 to 3, characterized in that it contains the phosphorus compound (Y) in an amount of 10 to 50 parts by weight.

5. 5. The mixture (M) according to claim 1, characterized in that it contains water (Z) in an amount of 0.5 to 3.0 moles based on 1 mole of phosphorus compound (Y).

6. A process for preparing the mixture (M) according to any one of claims 1 to 5 by mixing the individual components.

7. Crosslinkable compositions based on organosilicon compounds that can be obtained by mixing: (A) an organopolysiloxane of the formula: (R ７ O) ３－ａ SiR ３ ａ O(SiR ４ ２ O) ｎ SiR ３ ｘ (OR ７ ) ３－ａ (V)、 [In the formula, R ４ may be the same or different and represent a monovalent optionally substituted hydrocarbon group; R ７ may be the same or different and represent a monovalent optionally substituted hydrocarbon group; R ３ may be the same or different and represent a monovalent optionally substituted hydrocarbon group; a may be the same or different and is 0 or 1, preferably 1; and and x is an integer from 30 to 2000. and (B) A mixture containing (M) (X) a polyether of general formula (I), (Y) a phosphorus compound of formula (II), and optionally (Z) Water.

8. 8. The composition of claim 7, comprising: (A) an organopolysiloxane of formula (V), (B) mixture (M), optionally (C) a silane of formula (VI) and / or a partial hydrolyzate thereof; optionally (D) a cure accelerator; optionally (E) a plasticizer; optionally (F) a filler; and Optionally, (G) additives.

9. A process for preparing a composition according to claim 7 or 8 by mixing the individual components.

10. 10. A molded article produced by crosslinking a composition according to claim 7 or 8, or produced according to claim 9.

11. 1. A process for preparing organosilicon compounds containing organyloxy groups, characterized in that in a first step, an organosilicon compound (a) containing at least one silanol group is reacted with a compound (b) containing at least two organyloxy groups in the presence of a catalyst (c) selected from lithium alkoxylates, lithium hydroxide, amidines or guanidines, and in a second step, after the reaction of the hydroxyl groups of component (a) with the compound (b) containing organyloxy groups has taken place, a mixture (M) according to the invention is added.

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