Mixtures containing phosphorus compounds and their use

Abstract

The present invention relates to a phosphorus-compound-containing mixture (M) comprising: (X) Polyethers of the following general formula: R 1 -(OR 2 ) p -OR 1 (I), (Y) A phosphorus compound of the formula: O=PR 5 m (OR 6 ) n (OH) 3-(m+n) (II), and optionally (Z) Water. [wherein the radicals and subscripts have the definitions specified in claim 1], its preparation method and its use, in particular its use in crosslinkable compositions based on organosilicon compounds, and a process for the preparation of organosilicon compounds containing organyloxy groups.

Description

[Technical Field]

[0001] The present invention relates to phosphorus compound-containing mixtures, a process for preparing the same, and in particular to their use in crosslinkable compositions based on organosilicon compounds, as well as a process for preparing organosilicon compounds containing organyloxy groups. [Background technology]

[0002] One-component encapsulating compounds are known to be storable when moisture is removed and to harden upon introduction of water at room temperature, releasing alcohol, to yield elastomers. These products are used extensively, for example, in the construction industry. The basis of these mixtures is a polymer terminated by a silyl group having a reactive substituent such as an OH group or a hydrolyzable group such as an alkoxy group. Furthermore, these encapsulating compounds may contain fillers, plasticizers, crosslinking agents, catalysts, and various additives. Alkoxysilanes are often used as crosslinking agents. These encapsulating compounds require a tin or titanium-based catalyst to accelerate hardening.

[0003] Commonly used zinc catalysts include, for example, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dioxide, and their reaction products with alkoxysilanes. However, RTV1 encapsulated compounds produced using alkoxysilanes have drawbacks. After only a few months, they no longer fully harden. Therefore, EP1397428B1 proposes various organophosphorus compounds to significantly improve storage stability. Unfortunately, however, phosphorus compounds particularly suitable for stabilizing RTV1 encapsulated compounds, such as octylphosphonic acid, are solid at room temperature. However, in operational use, liquids are much preferred over solids, especially in continuous processes, because they are much more suitable for metering and addition. For example, in EP2030675B1, an easily manageable liquid solution of n-octylphosphonic acid in methyltrimethoxysilane is used.

[0004] However, a particular drawback of methyltrimethoxysilane is its very low flash point. Therefore, complex and undesirable safety measures are required when handling methyltrimethoxysilane. Furthermore, there is no guarantee that undesirable reaction products will not form in a mixture of n-octylphosphonic acid and methyltrimethoxysilane.

[0005] Furthermore, the use of n-octylphosphonic acid and neutralizing agents in the production of polymers having hydrolyzable terminal groups is known. EP3344684B1 describes the reaction of terminal silanol groups of linear polydimethylsiloxanes with alkoxysilanes. 1,5,7-triazabicyclo[4.4.0]deca-5-ene is used as a catalyst. In the example, after the reaction, the catalyst is neutralized with n-octylphosphonic acid in the second step. An unfavorable modification of the 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 [Overview of the project] [Problems that the invention aims to solve]

[0007] The objective of this invention was to overcome the shortcomings of the prior art. [Means for solving the problem]

[0008] Therefore, the present invention provides a mixture (M) comprising the following: (X) Polyethers of the following general formulas R 1 -(OR2 ) p -O-R 1 (I), [Wherein, R 1 may be the same or different and represents a hydrogen atom or a hydrocarbon group, R 2 may be the same or different and represents a divalent optionally substituted hydrocarbon group, 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), [Wherein, R 5 may be the same or different and represents an optionally substituted hydrocarbon group, R 6 may be the same or different and represents an optionally substituted hydrocarbon group, m is equal to 0 or 1, preferably 1, and n is equal to 0, 1 or 2, provided that m + n is equal to 1 or 2, preferably 1.] And optionally (Z) Water.

Mode for Carrying Out the Invention

[0009] Group R 1Examples include alkyl groups, e.g., methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl group, hexyl group, e.g., n-hexyl group, heptyl group, e.g., n-heptyl group, octyl group, e.g., n-octyl group and isooctyl group, e.g., 2,2,4-trimethylpentyl group, nonyl group, e.g., n-nonyl group, decyl group, e.g., n-decyl group, dodecyl group, e.g., n- These include dodecyl groups, octadecyl groups, such as n-octadecyl groups, cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl groups, alkenyl groups, such as vinyl, 1-propenyl, and 2-propenyl groups, aryl groups, such as phenyl, naphthyl, anthryl, and phenanthryl groups, alkaryl groups, such as o-, m-, and p-tolyl groups, xylyl, and ethylphenyl groups, and aralkyl groups, such as benzyl or α- and β-phenylethyl groups.

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

[0011] divalent group R 2 Examples include 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, 2-methylheptane-1,7-diyl, and 2,2,4-trimethylpentane-1,5-diyl groups.

[0012] base R 2 This 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 between 4 and 65.

[0014] The polyether (X) used in accordance with the present invention is preferably of the following formula. R 1 (OCH2CH2) q (OCHCH3CH2) r (OCH2CH2) s Ure 1 (III) [In the formula, R 1 It has one of the aforementioned definitions, q is an integer between 0 and 30, preferably between 0 and 15. s is an integer from 0 to 30, preferably 0 to 15, and r is an integer between 4 and 50, preferably between 4 and 35.

[0015] Examples of compounds (X) used in accordance with the present 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 It is 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 polyether (X) used in accordance with the present invention is given by the following formula. H(OCHCH3CH2) r OH (IV) [In the formula, r has the definition described above.]

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

[0018] Polyether(X) is commercially available or can be prepared by conventional methods in organic chemistry.

[0019] base R 5 An example is R 1 This is a identified basis.

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

[0021] R 6 An example is R 1 The identified groups and the groups interrupted by oxygen, for example, 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 between 4 and 25.

[0022] base R 6 Preferably, this is a linear or branched alkyl group having 1 to 18 carbon atoms, or an alkyl group having 10 to 68 carbon atoms interposed by oxygen.

[0023] Examples of phosphorus compounds (Y) used in accordance with the present invention include alkylphosphonic acids, e.g., 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, e.g., phenylphosphonic acid, 1-naphthylphosphonic acid, and phosphate monoesters, e.g., methyl phosphate, ethyl phosphate, n-propyl phosphate, isopropyl phosphate, n-butyl phosphate, n-pentyl phosphate. These include n-hexyl phosphate, n-heptyl phosphate, n-octyl phosphate, 2-ethylhexyl phosphate, n-decyl phosphate, n-dodecyl phosphate, n-tetradecyl phosphate, n-hexadecyl phosphate, phosphate 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, and di-n-hexadecyl phosphate, 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 in accordance with the present invention is preferably an alkylphosphonic acid having 4 to 18 carbon atoms, and particularly preferably an 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 "Hos-taphat OPS 75" (solution in ethanol and water).

[0026] In any case, the mixture (M) according to the present invention contains, based on 100 parts by weight of mixture (M), preferably 10 to 50 parts by weight, and particularly preferably 25 to 35 parts by weight, of phosphorus compound (Y).

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

[0028] The mixture (M) according to the present invention in any case comprises 1 mole of a phosphorus compound (Y), preferably n-octylphosphonic acid, and water (Z) in an amount preferably 0.5 to 3.0 moles, particularly preferably 1.0 to 2.0 moles, and especially 1.0 to 1.5 moles.

[0029] In addition to components (X), (Y), and (Z), the mixture (M) according to the present invention may also contain further components such as alcohol, particularly ethanol.

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

[0031] The mixture (M) according to the present invention is a colorless to pale yellow liquid or a low-melting-point solid, preferably having a melting point of less than 35°C, particularly preferably less than 0°C, and especially less than -30°C.

[0032] To prepare mixture (M) according to the present invention, all components can be mixed with each other in any order. This mixing can be carried out at room temperature or at a high temperature of 30°C to 150°C, at ambient atmospheric pressure, i.e., about 900 to 1100 hPa, or under reduced pressure of 1 to 900 hPa.

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

[0034] In the process according to the present invention, the polyether (X) is preferably first charged into a suitable container, and then the phosphorus compound (Y) is metered in while stirring. This is preferably done at ambient temperature. The mixture is then heated to a temperature of preferably 80-150°C while stirring under reduced pressure 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 distillates are to be removed. The mixture is then cooled to room temperature, and optionally, a specified amount of water (Z) is added.

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

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

[0037] The mixtures (M) according to the present invention have the advantage of allowing them to be handled as liquids with a low potential for hazard without the formation of undesirable by-products.

[0038] Furthermore, the mixture (M) according to the present invention has the advantage of being easily prepared without forming undesirable by-products.

[0039] The mixture (M) according to the present invention has the advantage of being liquid even at low temperatures and having a low flash point.

[0040] The mixture (M) according to the present invention has the advantage of exhibiting good storage stability and high resistance to low temperatures.

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

[0042] The mixture (M) according to the present invention is preferably used to prepare a crosslinkable composition based on an organosilicon compound.

[0043] The present invention further provides a crosslinkable composition based on an organosilicon compound, which can be obtained by mixing the following: (A) Organopolysiloxane of the following formula (R 7 O) 3-a SiR 3 a O(SiR 4 20) n SiR 3 x (OR 7 ) 3-a (V) [In the formula, R 4 This represents a hydrocarbon group that may be the same or different, and may be monovalent or substituted. R 7 This represents a hydrocarbon group that may be the same or different, and may be monovalent or substituted. R 3 This represents a hydrocarbon group that may be the same or different, and may be monovalent or substituted. 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) Polyether of general formula (I), (Y) Phosphorus compound of formula (II), and optionally (Z) Water.

[0044] Group R 4 and R 7 Examples of each are, independently, the groups specified above for Group R 1 with respect to Group R

[0045] Group R 4 is 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, especially a methyl group

[0046] Group R 7 is 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, especially a methyl group or an ethyl group

[0047] Group R 3 Examples of are hydrocarbon groups substituted by the monovalent hydrocarbon groups and amino groups specified for R 1 with respect to R

[0048] Group R 3 is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms and optionally substituted by an amino group, particularly preferably a methyl group, an ethyl group, a vinyl group, a phenyl group, -CH2-NR 6’ R 5’ group or the group -CH2NR 11’ where R 5’ means a hydrocarbon group having 1 to 12 carbon atoms, R 6’ means a hydrogen atom or a group R 5’ where R 11’ means a divalent hydrocarbon group optionally interrupted by a heteroatom

[0049] Group R 3 is particularly preferably the group -CH2-NR 6’ R 5’ group or the group -CH2NR 11’ wherein, in the formula, R 5’ R 6’ and R 11’is as defined above, especially -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] Group R 5’ Examples of 1 are the hydrocarbon groups specified for R.

[0051] Group 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’ Examples of 1 are the hydrocarbon groups specified for R.

[0053] Group 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’ Examples of 2 are the examples specified for R, and also the groups -CH2-CH2-O-CH2-CH2- and -CH2-CH2-NH-CH2-CH2-.

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

[0056] The organopolysiloxane (A) used according to the present 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(SiMe2O) 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(SiMe2O) 700 Si(R 3 )(OEt)2, comfortably (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 is the same as 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 -CH2-N[(CH2)2]2O, DBA is -CH2-N(nBu)2, cHx is -CH2-NH(cHex), Bu is an n-butyl group, cHex is a cyclohexyl group, and R 3 R means Me, Et, vinyl group, phenyl group, DBA, Ox or cHx, and the group R 3 This has the same definition within each individual compound.

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

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

[0059] The component (B) used in accordance with the present invention is preferably a mixture (M) containing water (Z).

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

[0061] The composition according to the present invention comprises siloxanes (A) and (B), in addition to component (C) consisting of a silane of the following formula. (R 8 O) 4-b SiR 9 b (VI) and / or may include a partial hydrolysate thereof, in the formula, b is 0, 1, or 2, preferably 0 or 1. R 8 These may be the same or different, and represent a monovalent, substituted hydrocarbon group, and R 9 This refers to monovalent, optionally substituted hydrocarbons.

[0062] base R 8 The group 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, especially a methyl group or an ethyl group.

[0063] base R 9The group is 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, and especially a methyl group or a 2,2,4-trimethylpentyl group.

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

[0065] The optionally used partial hydrolysate (C) may be a partial homohydrolysate, i.e., a partial hydrolysate of one type of silane of formula (III), or a partial cohydrolysate, i.e., at least two different types of partial hydrolysates of silanes of formula (III).

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

[0067] In the composition according to the present invention, if component (C) used optionally is a partial hydrolysate of silane of formula (VI), it is preferable that it has up to 20 silicon atoms.

[0068] Examples of components (C) that can be optionally used according to the present invention include 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, and N,N-di-n-butylaminomethyltriethoxysilane. The preferred methyltrimethoxysilanes are N-cyclohexylaminomethyltriethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltrimethoxysilane, N,N-di-n-butylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyltrimethoxysilane, with methyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, and (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane being preferred.

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

[0070] If 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 especially particularly 0.05 to 2 parts by weight, based on 100 parts by weight of component (A). The composition according to the present invention preferably contains component (C), which preferably contains at least partially a functional silane and / or a partial hydrolysate thereof.

[0071] In addition to components (A), (B), and optionally (C), the compositions according to the present invention may now include all substances that have been used in compositions that can be crosslinked by condensation reactions, such as curing accelerators (D), plasticizers (E), fillers (F), and additives (G).

[0072] All curing accelerators that have been used in compositions that can be crosslinked by condensation reactions can be used as curing accelerator (D). Examples of curing accelerator (D) include titanium compounds, such as tetrabutyl titanate or tetraisopropyl titanate, or titanium chelates, such as bis(ethylacetate)diisobutoxytitanium, or organotin 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. The reaction product 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(ethylacetacetate)diisobutoxytitanium is preferred, and the reaction product 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 is particularly preferred.

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

[0074] Examples of optional plasticizers (E) include, in particular, dimethylpolysiloxanes that are liquid at room temperature, end-capped with trimethylsiloxy groups, and high-boiling hydrocarbons, such as paraffinic oil or mineral oil, which consist of naphthenic and paraffinic units.

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

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

[0077] An example of a filler (F) used optionally is a non-reinforced filler (F), i.e., up to 20 m 2 Fillers having a BET specific surface area of ​​20m / g, for example, quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolite, metal oxide powders, for example, 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, for example, polyacrylonitrile powder, reinforcing fillers, i.e., 20m 2 Fillers having a BET specific surface area greater than / g, such as precipitated chalk and carbon black, such as furnace black and acetylene black; silica, such as fumed silica and precipitated silica; and fiber fillers, such as plastic fibers.

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

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

[0080] If 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 particularly 10 to 100 parts by weight, based on 100 parts by weight of 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 affecting electrical properties, e.g., conductive carbon black, flame retardants, light stabilizers, biocides, e.g., fungicides, bactericides and acaricides, cell-forming agents, e.g., azodicarbonamides, heat stabilizers, scavengers, e.g., Si-N-containing silazanes or silylamides, e.g., N,N'-bis(trimethylsilyl)urea or hexamethyldisilazanes, cocatalysts, thixotropic agents, e.g., polyethylene glycol or hydrogenated castor oil terminated with OH groups at one or both ends, agents for further modulating the elastic modulus, e.g., polydimethylsiloxane having OH-terminated groups, and any siloxane other than components (A), (B), and (C).

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

[0083] In any case, each component of the composition according to the present invention may be one of such components, or a mixture of at least two different types of such components.

[0084] The composition according to the present invention preferably comprises the following: (A) Organopolysiloxane of formula (V), (B) mixture (M), (C) Optionally, silane of formula (VI) and / or partial hydrolysates thereof, (D) Curing accelerator, (E) Plasticizer, (F) Filler and (G) Additive (optional).

[0085] The composition according to the present invention is particularly preferably comprised of the following: (A) Organopolysiloxane of formula (V), (B) mixture (M), (C) Silane of formula (VI) and / or partial hydrolysates thereof, (D) Curing accelerator, (E) Plasticizer, (F) Filler and (G) Additive (optional).

[0086] The composition according to the present invention particularly includes the following: (A) Organopolysiloxane of formula (V), (B) mixture (M), (C) Silane of formula (VI) and / or partial hydrolysates thereof, (D) Curing accelerator, (F) Filler, (E) Plasticizer and (G) Additive (optional).

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

[0088] The composition according to the present invention is preferably a paste-like mass due to its viscosity.

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

[0090] The mixing according to the present invention is preferably carried out with maximum removal of moisture from the atmosphere. All raw materials except (M) preferably have a water content of less than 10,000 mg / kg, preferably less than 5,000 mg / kg, and especially less than 1,000 mg / kg. During the mixing process, a protective gas such as dry air or nitrogen is preferably used, and each gas preferably has a water content of less than 10,000 μg / kg, preferably less than 1,000 μg / kg, and especially 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 the filler (F) is added, and finally (B) and optionally further components (D) and (G) are added, preferably at a temperature not exceeding 60°C during mixing.

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

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

[0094] The composition according to the present invention or the composition prepared according to the present invention can be stored free of moisture and can be crosslinked upon contact with moisture.

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

[0096] Crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, particularly at the ambient pressure, i.e., about 900 to 1100 hPa.

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

[0098] The compositions according to the present invention can be used for all purposes in which it is possible to use compositions that can be stored without water and that crosslink upon water ingress at room temperature to provide an elastomer.

[0099] Accordingly, the compositions according to the present invention have excellent suitability for joints including vertical joints, and for sealants for similar cavities, for example, 10 to 40 mm in internal width, in buildings, land vehicles, ships and aircraft, or for adhesives or cement compositions, for example, in window configurations or for example, in the manufacture of glass cabinets, for surfaces exposed to the constant action of fresh or seawater, for protective coatings, anti-slip coatings, or for the manufacture of elastomer molded articles.

[0100] The composition according to the present invention has the advantages of being easy to manufacture and having very high storage stability.

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

[0102] Furthermore, the present invention provides a process for preparing organosilicon compounds containing organyloxy groups, the process being characterized by the following: In the 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 strongly basic catalyst (c); and in the second step, after the reaction between the hydroxyl group of component (a) and the compound (b) containing organyloxy groups has occurred, a mixture (M) according to the present invention is added.

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

[0104] In a preferred embodiment of the process according to the present 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]deca-5-ene (c), and in a second step, a mixture (M) according to the present invention is added.

[0105] Component (a) used in accordance with the present invention may be any organosilicon compound known to date having 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 compound (a) used in accordance with the present invention is preferably 10 at 25°C in all cases. 2 ~10 8 It has a viscosity of mPas, particularly preferably 1,000 to 350,000 mPas.

[0109] An example of an organosilicon compound (a) used in accordance with the present invention is: 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, Here, 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 either commercially available or can be prepared by standard chemical methods.

[0111] Component (b) used in accordance with the present invention may be any previously known compound having at least two organyloxy groups, preferably a siloxane or silane.

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

[0113] Examples of compounds (b) used in accordance with the present invention include 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 present invention, component (b) is used in any case preferably in an excess of 1 to 100 times, and particularly preferably in an excess of 2 to 50 times, based on the molar amount of Si-OH groups in compound (a).

[0116] In the process according to the present invention, catalyst (c) is used in any case in an amount preferably 5 to 10,000 ppm by weight, and particularly preferably 100 to 3,000 ppm by weight, 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 with each other in any order and in any currently known manner. A premix may also be prepared from a mixture of several components, for example, components (b) and (c), which are then mixed with other components. Individual components may also be present or supplied at the start or during the mixing process. For example, some of component (b) or preparation (c) may 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 present invention may be one such component or a mixture of at least two such components.

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

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

[0121] The process according to the present invention is preferably carried out in a dry environment, such as dry air or nitrogen, to remove moisture.

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

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

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

[0125] Multiple organosilicon compounds containing organyloxy groups can be advantageously prepared by the process according to the present invention.

[0126] The process according to the present invention has the advantage of being able to prepare organosilicon compounds containing organyloxy groups in a simple manner. [Examples]

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

[0128] In relation to the present invention, the dynamic viscosity of organosilicon compounds is measured according to DIN 53019. The preferred procedure was as follows: Unless otherwise specified, viscosity is measured at 25°C using an Anton Paar "Physica MCR 300" rotational rheometer. In this case, for viscosities of 1 to 200 mPa·s, a coaxial cylinder measuring system (CC27) with an annular measuring gap of 1.13 mm is used, and for viscosities greater than 200 mPa·s, a cone-plate measuring system (Searle system with CP50-1 measuring cone) is used. The shear rate is adjusted to match the polymer viscosity (100 s). 1 1-99 mPa·s, 200s 1 100-999 mPa·s, 120s 1 At 1000-2999 mPa·s, at 80s1, 3000-4999 mPa / s, at 62s 1 5000-9999 mPa·s, 50s 1 1000-12499 mPa·s, 38.5s 1 At 12500-15999 mPa·s, 33s 1 16000~19999 mPa·s, 25s 1 20000~24999 mPa·s, 20s 1 25000~29999 mPa·s, 17s 1 30000~39999 mPa·s, 10s 140000~59999 mPa·s, 5s 1 60,000 to 1,499,999 mPa·s, 3.3s 1 150,000 to 199,999 mPa·s, 2.5s 1 200,000 to 299,999 mPa·s, 1.5s 1 (300,000 to 1,000,000 mPa·s).

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

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

[0131] [Example 1] 100g of OPS75 was mixed with 75g of PPG425 and heated to 105°C under reduced pressure of 20mbar, maintaining this temperature for 1 hour. Ethanol and water were then removed by distillation.

[0132] A clear solution was obtained that began to crystallize at 28°C and remained solid at room temperature.

[0133] The results are shown in Table 1.

[0134] [Example 2] 100g of OPS75 was mixed with 75g of PPG1000 and heated to 105°C under reduced pressure of 20mbar, maintaining this temperature for 1 hour. Ethanol and water were then removed by distillation.

[0135] A clear solution was obtained that began to crystallize at 25°C and remained solid at room temperature. Therefore, viscosity could not be measured at 25°C.

[0136] The results are shown in Table 1.

[0137] [Examples 4-7] The procedure described in Example 1 was repeated using the amounts of raw materials listed in Table 1.

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

[0139] [Table 1]

[0140] [Example 8] The procedure described in Example 7 was repeated with the modification of using PPG400 instead of PPG425. In this case, no difference was observed. In particular, the melting point was similarly below -30°C.

[0141] [Example 9] 309 g of α,ω-bis[(tetrahydro-1,4-oxazine-4-yl)methyldiethoxysilyl]polydimethylsiloxane with a viscosity of 80,000 mPa·s, 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane (commercially sold by Wacker Chemie AG (Munich, Germany) under the name "Weichmacher 1000") with a viscosity of 1,000 mPa·s, and 16.0 mol% of the compound with the formula MeSi(OEt)2O 1 / 2The unit is 46.4 mol%, and the formula is MeSi(OEt)O 2 / 2 The unit is 36.5 mol%, formula MeSiO 3 / 2 The unit is 0.2 mol%, and the formula is Me2Si(OEt)O 1 / 2 The units and the formula Me2SiO2 for 0.9 mol% 2 / 2 First, 1 g of the product consisting of units, 8 g of 3-aminopropyltriethoxysilane (commercially available from Wacker Chemie AG (Munich, Germany) under the name GENIOSIL(R) GF93), 2 g of vinyltriethoxysilane (commercially available from Wacker Chemie AG (Munich, Germany) under the name GENIOSIL(R) GF56), and 5 g of tetraethyl silicate (commercially available from Wacker Chemie AG (Munich, Germany) under the name "Silikat TES28") were placed in a planetary mixer and mixed for 30 minutes. Then, 150 ml 2 45 g of fumed silica having a BET specific surface area of ​​1 / g (commercially available from Wacker Chemie AG (Munich, Germany) under the name HDK(R) V15) was mixed, and the mixture was completely homogenized under 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 (commercially available from Wacker Chemie AG (Munich, Germany) under the name "Katalysator 41") were added, and the mixture was further homogenized under a pressure of approximately 50 hPa (absolute) for 5 minutes.

[0142] The RTV1 composition obtained in this manner was filled into a commercially available moisture-proof polyethylene cartridge and stored at room temperature for 24 hours. Further samples were stored at 70°C for 7 days. Then, 2 mm thick slabs were spread from each of the samples stored in this manner and stored at 23°C and 50% relative humidity for 7 days. Test specimens of form S2 according to DIN 53504 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 modification of adding 1.57g of the mixture from Example 7 instead of 1g of the mixture from Example 1.

[0144] The results are shown in Table 2.

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

[0146] α,ω-bis(vinyldimethoxysilyl)polydimethylsiloxane with a viscosity of 100 Pas was obtained as a colorless and transparent product without further post-treatment.

[0147] [Example 12] First, 300 g of the product prepared according to Example 11 is placed in a planetary mixer with 130 g of α,ω-bis(trimethylsiloxy)polydimethylsiloxane (commercially available from Wacker Chemie AG (Munich, Germany) under the name "Weichmacher 1000") having a viscosity of 1000 mPa·s, 5 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG (Munich, Germany) under the name GENIOSIL(R) GF91), and 2 g of vinyltrimethoxysilane (commercially available from Wacker Chemie AG (Munich, Germany) under the name GENIOSIL(R) XL10), and mixed for 30 minutes. Then, 150 m 245 g of fumed silica with a BET specific surface area of ​​1 / g (commercially available from Wacker Chemie AG (Munich, Germany) under the name HDK(R) V15) was mixed, and the mixture was completely homogenized at a pressure of 50 hPa. Finally, 1 g of the solution from Example 1 and 2 g of the reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available from Wacker Chemie AG (Munich, Germany) under the name "Katalysator 41") were added, and the mixture was further homogenized at a pressure of approximately 50 hPa (absolute) for approximately 5 minutes.

[0148] The RTV1 composition obtained in this manner was filled into a commercially available moisture-proof polyethylene cartridge and stored at room temperature for 24 hours. Further samples were stored at 70°C for 7 days. Then, 2 mm thick slabs were spread from each of the samples stored in this manner and stored at 23°C and 50% relative humidity for 7 days. Test specimens of form S2 according to DIN 53504 were punched out from 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> A mixture of 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(R) BS1316), and 0.80 g of sodium ethoxide (21%) in ethanol was heated at 110°C for 4 hours. After cooling the solution, the mixture was neutralized by adding 1.60 g of dimethyldichlorosilane (10%) in n-heptane solution. This mixture was liquefied in a rotary evaporator at 120°C under reduced pressure of 50 mbar. The composition of the mixture was 29The composition was determined by Si-NMR spectroscopy. The 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 [Me2SiO 2 / 2 ] 0.43 [Me2Si(OMe)O 1 / 2 ] 0.29 It contained an oligomer mixture. The molecular weights determined by gel permeation chromatography were 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 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 at 200 rpm for 5 minutes with 30.4 g of a solution of 0.04 g of 1,5,7-triazabicyclo[4.4.0]deca-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 yields a mixture with a viscosity of 52,000 mPas containing 98.0 wt% α,ω-bis((2,3,5,6-tetrahydro-1,4-oxazine-4-yl)methyldiethoxysilyl)polydimethylsiloxane, 1.9 wt% (2,3,5,6-tetrahydro-1,4-oxazine-4-yl)methyltriethoxysilane, and 0.1 wt% ethanol.

[0152] <RTV1 encapsulation compound using oligomer mixture 13a> 455 g of the reaction mixture thus obtained was added to the equilibrium product of 6.3 g of methyltriethoxysilane hydrolysate oligomer and 6.3 g of 3-aminopropyltriethoxysilane, which have an average of 10 Si atoms per molecule and are commercially available from Wacker Chemie AG (Munich, Germany) under the name "SILIKAT TES40," having a 40% SiO2 content during total hydrolysis and condensation. The mixture was then stirred for a further 5 minutes at 200 rpm. Next, 150 m 2 44 g of hydrophilic fumed silica, having a surface area of ​​ / g and available from Wacker Chemie AG under the name HDK(R) V15A, was added, and the mixture was first stirred at 200 rpm for a further 5 minutes until all the fumed silica was wet. The mixture was then stirred at 600 rpm for 10 minutes under reduced pressure of 200 mbar. Finally, 1.58 g of a solution of 0.27 g of dioctyl tin oxide in 1.31 g of equilibrium product of 0.655 g of methyltriethoxysilane hydrolysate 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 according to Example 7, and 25.6 g of oligomer mixture 13a were added, and the mixture was stirred under reduced pressure (200 mbar) for a further 5 minutes.

[0153] Next, the mixture was filled into commercially available cartridges, and the moisture was removed for storage. 24 hours after the preparation of the mixture, 2 mm thick slabs were drawn from these mixtures and cured at 23°C and 50% relative humidity for 7 days. After that, Type 2 dumbbell-shaped test specimens were prepared according to ISO 37 6th edition 2017-11.

[0154] The results are shown in Table 2.

[0155] Without the additive of the present invention according to Example 7, a mixture similar to that in Example 13 did not harden into a non-tacky material after pre-storage at 70°C for 7 days.

[0156] [Table 2]

[0157] The skin formation times were within the normal range of 15 to 25 minutes.

[0158] Without the additives according to the present invention, the mixtures according to Examples 9, 10, 12, and 13 did not harden into a non-tacky material after pre-storage at 70°C for 7 days.

[0159] [Example 14] In a laboratory dissolving machine, 400 g of α,ω-dihydroxypolydimethylsiloxane was vigorously mixed for 5 minutes at an initial temperature of 25°C with a solution of 8.5 g of phenyltrimethoxysilane and 0.25 g of isooctyltriethoxysilane containing 20% ​​by mass of 1,5,7-triazabicyclo[4.4.0]deca-5-ene. The mixing shaft, which had a dissolving machine gearing with a diameter of approximately 5 cm, was set to 1000 revolutions per minute.

[0160] The absence of silanol groups in the mixture after 30 minutes was confirmed by the titanate rapid test described on page 7 of EP2170995B1. Therefore, the end-capping reaction was already complete at this point.

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

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

[0163] [Example 15 (Non-inventive)] Experiment 13 was repeated with the modification that the additive according to the present invention was not mixed afterward.

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

[0165] Without the stabilizer according to the present invention, a rapid loss of viscosity occurs.

[0166] [Example 16] In a laboratory dissolving machine, 400 g of α,ω-dihydroxypolydimethylsiloxane was vigorously mixed for 5 minutes at an initial temperature of 25°C with a solution of 7 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine and 0.25 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene in isooctyltriethoxysilane. The mixing shaft, which had a dissolving machine gearing with a diameter of approximately 5 cm, was set to 1000 revolutions per minute.

[0167] The absence of silanol groups in the mixture after 30 minutes was confirmed by the titanate rapid test described on page 7 of EP2170995B1. Therefore, the end-capping reaction was already complete at this point.

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

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

[0170] [Example 17 (Non-inventive)] Experiment 15 was repeated with the modification that the additive according to the present invention was not mixed afterward.

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

[0172] This further demonstrates that without the additives according to the present invention, there is an extreme decrease in viscosity.

Claims

1. A mixture (M) comprising: (X) Polyethers of the following general formulas R １ -(O-R ２ ) ｐ -O-R １ (I)、 [In the formula, R １ They may be the same or different, and represent a hydrogen atom or a hydrocarbon group. R ２ This represents a hydrocarbon group that may be the same or different, and may be optionally substituted with a divalent hydrocarbon group. p is an integer between 4 and 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 This represents a hydrocarbon group that may be the same or different, and may be substituted. R ６ This represents a hydrocarbon group that may be the same or different, and may be substituted. m is equal to 0 or 1, and n is equal to 0, 1, or 2. However, m + n is equal to 1 or 2. and (Z) 0.5 to 3.0 moles of water based on 1 mole of phosphorus compound (Y).

2. The mixture (M) according to claim 1, characterized in that the polyether (X) has 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 It has one of the aforementioned definitions, q is an integer from 0 to 30. s is an integer from 0 to 30, and r is an integer between 4 and 50.

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 by containing the phosphorus compound (Y) in an amount of 10 to 50 parts by weight.

5. A process for preparing a mixture (M) according to any one of claims 1 to 4 by mixing individual components.

6. A crosslinkable composition based on organosilicon compounds that can be obtained by mixing the following: (A) Organopolysiloxane of the following formula (R ７ O) ３－ａ SiR ３ ａ O(SiR ４ ２ O) ｘ SiR ３ ａ (OR ７ ) ３－ａ (V)、 [In the formula, R ４ This represents a hydrocarbon group that may be the same or different, and may be optionally substituted with a monovalent hydrocarbon group. R ７ This represents a hydrocarbon group that may be the same or different, and may be optionally substituted with a monovalent hydrocarbon group. R ３ This represents a hydrocarbon group that may be the same or different, and may be optionally substituted with a monovalent hydrocarbon group. a may be the same or different, and is 0 or 1, and x is an integer between 30 and 2000. and (B) A mixture containing (M) (X) Polyether of the following general formula (I), R １ -(O-R ２ ) ｐ -O-R １ (I)、 [In the formula, R １ They may be the same or different, and represent a hydrogen atom or a hydrocarbon group. R ２ This represents a hydrocarbon group that may be the same or different, and may be optionally substituted with a divalent hydrocarbon group. p is an integer between 4 and 110. (Y) A phosphorus compound of the following formula (II), O=PR ５ ｍ (OR ６ ) ｎ (OH) ３－（ｍ＋ｎ） (II)、 [In the formula, R ５ This represents a hydrocarbon group that may be the same or different, and may be substituted. R ６ This represents a hydrocarbon group that may be the same or different, and may be substituted. m is equal to 0 or 1, and n is equal to 0, 1, or 2. However, m + n is equal to 1 or 2. and (Z) 0.5 to 3.0 moles of water based on 1 mole of phosphorus compound (Y).

7. The composition according to claim 6, characterized in that it includes the following: (A) Organopolysiloxane of formula (V), (B) mixture (M), (C) Silane of formula (VI) and / or partial hydrolysates thereof, (R 8 O) 4-b SiR 9 b (VI) [In the formula, b is 0, 1, or 2. R 8 may be the same or different, and represents a monovalent, substituted hydrocarbon group, and R9 represents a monovalent, possibly substituted hydrocarbon. (D) Curing accelerator, (E) Plasticizer, (F) Filler and (G) Additives as an option.

8. A process for preparing the composition according to claim 6 or 7 by mixing the individual components.

9. A molded article produced by crosslinking the composition described in claim 6 or 7, or by mixing the individual components.

10. A process for preparing an organosilicon compound containing an organyloxy group, 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 alkoxylate, lithium hydroxide, amidine, or guanidine; and in a second step, after the reaction between the hydroxyl group of component (a) and the compound (b) containing the organyloxy group has occurred, a mixture (M) according to any one of claims 1 to 4 is added.

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