Crosslinkable composition based on organosilicon compounds

Abstract

The present invention relates to a compound of formula (A) (R 7 O) 3-a SiR 3 a O(SiR 4 2O) n SiR 3 a (OR 7 ) 3-a The present invention relates to a crosslinkable composition based on (I) and (B) organosilicon compounds containing siloxanes of formula (II), the radicals and indices having the meanings set out in claim 1. The present invention also relates to a method for the preparation and use thereof. TIFF2022543948000005.tif58157

Description

Technical Field

[0001] The present invention relates to a crosslinkable composition based on an organosilicon compound, a method for producing the same, and use thereof.

Background Art

[0002] One-component sealant compositions that can be stored if water is excluded and that cure at room temperature to release alcohol and give an elastomer when exposed to water are already known. These products are used in large quantities, for example, in the construction industry. These mixtures are based on polymers having a silyl group at the end with a reactive substituent such as an OH group or a hydrolyzable group such as an alkoxy group. These sealants can also contain fillers, plasticizers, crosslinking agents, catalysts, and various additives. In order to be usable as a sealant, the cured molded article must have a low modulus of elasticity. For example, DE-A1 102004014216 describes oligomeric siloxanes produced from methyltrimethoxysilane or methyltriethoxysilane. However, it has been found that the efficiency in reducing the modulus of elasticity of the mixtures produced therefrom is low.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

[0004] The present invention relates to a crosslinkable composition based on an organosilicon compound comprising the following.

[0005] (A) An organopolysiloxane of the following formula, - (R 7 O) 3-a SiR 3 a O(SiR 4 2O) nSiR 3 a (OR 7 ) 3-a (I), (wherein, R 4 may be the same or different and is a monovalent optionally substituted hydrocarbon group, R 7 may be the same or different and is a monovalent optionally substituted hydrocarbon group, R 3 may be the same or different and is a monovalent optionally substituted hydrocarbon group, a may be the same or different and is 0 or 1, preferably 1, n is an integer from 30 to 2000), and (B) a siloxane of formula (II)

[0006]

Chemical formula

Modes for Carrying Out the Invention

[0007] Groups R and R 4 Examples of are, independently of each other, an alkyl group such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, and tert-pentyl group; a hexyl group such as n-hexyl group; a heptyl group such as n-heptyl group; an octyl group such as n-octyl group and an isooctyl group such as 2,2,4-trimethylpentyl group; a nonyl group such as n-nonyl group; a decyl group such as n-decyl group; a dodecyl group such as n-dodecyl group; an octadecyl group such as n-octadecyl group; a cycloalkyl group such as cyclopentyl, cyclohexyl and cycloheptyl group and methylcyclohexyl group; an alkenyl group such as vinyl, 1-propenyl and 2-propenyl group; an aryl group such as phenyl, naphthyl, anthryl and phenanthryl group; an alkaryl group such as o-, m-, p-tolyl group; xylyl group and ethylphenyl group; an aralkyl group such as benzyl group or α- and β-phenylethyl group.

[0008] Groups R and R 4 are each independently, preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly preferably a methyl, vinyl or phenyl group, especially a methyl group.

[0009] Group R 1 Examples of are a hydrocarbon group having 2 to 16 carbon atoms specified for R, -CH2-NHCH3, -CH2NHCH2CH3, -CH2NH(CH2)2CH3, -CH2NH(CH2)3CH3, -CH2NH-cyclo C6H 11 , -CH2-N(CH3)2, -CH2N(CH2CH3)2, -CH2N((CH2)2CH3)2, -CH2N((CH2)3CH3)2, -CH2-N[CH2-CH2]2O, -CH2-N[CH2-CH2]2NH and -CH2-N[CH2-CH2]2CH2.

[0010] Group R 1is preferably an aliphatic hydrocarbon group having 2 to 16 carbon atoms, which can be linear, branched or cyclic, particularly preferably a linear, branched or cyclic aliphatic saturated hydrocarbon group having 2 to 8 carbon atoms, especially a 2,2,4-trimethylpentyl group.

[0011] Group R 2 and R 7 Examples are monovalent groups each independently specified for R.

[0012] Group R 2 and R 7 are each independently preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably a methyl, ethyl, n-propyl or isopropyl group, especially a methyl group or an ethyl group.

[0013] Group R 3 Examples are a monovalent hydrocarbon group specified for R and a hydrocarbon group substituted with an amino group.

[0014] Group R 3 is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, which may be substituted with an amino group, particularly preferably a methyl group, an ethyl group, a vinyl group, a phenyl group, -CH2-NR 6’ R 5’ group or -CH2NR 11’ group, where R 5’ is a hydrocarbon group having 1 to 12 carbon atoms, R 6’ is a hydrogen atom or group R 5’ and R 11’ is a divalent hydrocarbon group which may be interrupted by a heteroatom.

[0015] Group R 3 is particularly preferably a -CH2-NR 6’ R 5’ group or -CH2NR 11’ group, where R 5’ R 6’ and R 11’has the definitions specified above and is in particular -CH2-N[(CH2)2]2O, -CH2-N(Bu)2 or CH2-NH(cHex), where Bu is an n-butyl group and cHex is a cyclohexyl group.

[0016] Group R 5 and R 5’ Examples are hydrocarbon groups each independently specified as R.

[0017] Group R 5 and R 5’ are each independently preferably a methyl, ethyl, isopropyl, n-propyl, n-butyl, cyclohexyl or phenyl group, particularly preferably an n-butyl group.

[0018] Hydrocarbon group R 6 and R 6’ Examples are hydrocarbon groups each independently specified as R.

[0019] Group R 6 and R 6’ are each independently preferably a hydrogen atom, methyl, ethyl, isopropyl group, n-propyl group, n-butyl or cyclohexyl group, particularly preferably an n-butyl group.

[0020] Divalent group R 11 and R 11’ Examples are alkylene groups such as propane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, 2,2-dimethylpropane-1,3-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl and 2-methylheptane-1,7-diyl and 2,2,4-trimethylpentane-1,5-diyl groups, alkenylene groups such as propene-1,3-diyl group, and the groups -CH2-CH2-O-CH2-CH2- and CH2-CH2-NH-CH2-CH2-.

[0021] Group R 11 and R 11’ are each independently, preferably a divalent hydrocarbon group having 4 to 6 carbon atoms, which may be interrupted by a hetero atom, preferably oxygen - O - or nitrogen - NH -, and particularly preferably -CH2-CH2-O-CH2-CH2-.

[0022] 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, Particularly 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 is Si(Ox)(OEt)2, where 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, and cHex is a cyclohexyl group, and R 3 is Me, Et, a vinyl group, a phenyl group, DBA, Ox or cHx, and the group R 3 has the same definition within each individual compound.

[0023] The organopolysiloxane (A) used according to the present invention in each case has a viscosity of preferably 6000 to 350000 mPas, particularly preferably 20000 to 120000 mPas at 25°C.

[0024] The organopolysiloxane (A) is a commercially available product or can be produced by methods common in silicon chemistry.

[0025] The siloxane (B) used according to the present invention preferably has, in the formula, R is Me, and R 2 is Me or Et, the sum of x is 1 to 9, z is 1 or 2, and R 1 may be the same or different and is a monovalent hydrocarbon group having 2 to 16 carbon atoms of formula (II), Particularly preferably, in the formula, R is Me, and R 2 is Me, the sum of x is 1 to 9, z is 1 or 2, and R 1 is a monovalent hydrocarbon group having 2 to 16 carbon atoms of formula (II), In particular, in the formula, R is Me, and R 2 is Me, the sum of x is 1 to 9, z is 1 or 2, and R 1 is a 2,2,4-trimethylpentyl group of formula (II), where Me is a methyl group and Et is an ethyl group.

[0026] Examples of the compounds of formula (II) are EtO(SiMe2O)3SiR 1 (OEt)2, (EtO(SiMe2O)3)2SiR 1 (OEt), MeO(SiMe2O)3SiR 1 (OMe)2, (MeO(SiMe2O)3)2SiR 1 OMe), EtO(SiMe2O)3SiR 1 (OEt)O(SiMe2O)3SiR 1 (OEt)2, MeO(SiMe2O)3SiR 1 (OMe)O(SiMe2O)3SiR 1 (OMe)2, EtO(SiMe2O) x Si(iOct)(OEt)2, (EtO(SiMe2O) x )2Si(iOct)(OEt), MeO(SiMe2O) x Si(iOct)(OMe)2, (MeO(SiMe2O) x )2Si(iOct)(OMe), EtO(SiMe2O) x Si(iOct)(OEt)O(SiMe2O)3Si(IOct)(OEt)2 or MeO(SiMe2O) x Si(iOct)(OMe)O(SiMe2O)3Si(IOct)(OMe)2, where Me is a methyl group, Et is an ethyl group, iOct is a 2,2,4-trimethylpentyl group, x = 1 to 9, and R 1 is a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 8 carbon atoms, where the group R 1 has the same definition within each individual compound.

[0027] In particular, the siloxane (B) used according to the present invention is MeO(SiMe2O) xSi(iOct)(OMe)2, (MeO(SiMe2O) x )2Si(iOct)(OMe) or MeO(SiMe2O) x Si(iOct)(OMe)O(SiMe2O)3Si(iOct)(OMe)2, where Me is a methyl group, iOct is a 2,2,4 - trimethylpentyl group, and x = 1 - 9.

[0028] The siloxane (B) used according to the present invention preferably has a viscosity of 5 - 15 mPas at 25°C.

[0029] The siloxane (B) preferably has the following average composition.

[0030] [R 1 (OMe)2O 1 / 2 a [R 1 Si(OMe)O 2 / 2 b [R 1 SiO 3 / 2 c [Me2SiO 2 / 2 d [Me2Si(OMe)O 1 / 2 e (where a = 0.05 - 0.15, b = 0.10 - 0.20, c = 0.00 - 0.10, d = 0.40 - 0.65, and e = 0.10 - 0.30, where a + b + c < d + e and a + b + c + d + e = 1, where Me is a methyl group and R 1 has the definition specified above.)

[0031] The siloxane (B) can be produced by a general method in silicon chemistry, for example, by equilibration of polydimethylsiloxane with trialkoxysilane under a basic catalyst.

[0032] ​​​​​The composition according to the invention contains, in each case, based on 100 parts by weight of component (A), preferably in an amount of 1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, in particular 2 to 6 parts by weight of component (B).

[0033] The present invention further provides that R may be the same or different and can be a monovalent optionally substituted hydrocarbon group, R 1 is -CH2-NR 6 R 5 group or -CH2NR 11 group, where R 5 is a hydrocarbon group having 1 to 12 carbon atoms, and R 6 is a hydrogen atom or group R 5 and R 11 is a divalent hydrocarbon group which may be interrupted by heteroatoms, R 2 may be the same or different and can be a monovalent optionally substituted hydrocarbon group, x may be the same or different and is 0 or an integer from 1 to 9, z is 1 or 2, provided that for the siloxane of formula (II), the sum of all x is greater than 0.

[0034] In addition to the siloxanes (A) and (B), the composition according to the invention may contain a component (C) consisting of a silane of the following formula and / or its partial hydrolyzate.

[0035] (R 8 O) 4-b SiR 9 b (III) In the formula, b is 0, 1 or 2, preferably 0 or 1, R 8 may be the same or different and is a monovalent, optionally substituted hydrocarbon group, R 9 is a monovalent, optionally substituted hydrocarbon group.

[0036] Group R 8 Preferably has 1 to 12 carbon atoms, particularly preferably a methyl, ethyl, n-propyl or isopropyl group, especially a methyl or ethyl group.

[0037] Group R 9 Is preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be optionally substituted by a glycidoxy, ureido, methacryloxy or amino group, particularly preferably an alkyl group, vinyl or phenyl group, especially a methyl group or 2,2,4-trimethylpentyl group.

[0038] In a preferred embodiment, component (C) used is, in whole or in part, a silane having a functional group and / or its partial hydrolyzate, especially when adhesion promoting properties are desired, for example, those having a glycidoxypropyl, aminopropyl, aminoethylaminopropyl, ureidopropyl or methacryloxypropyl group.

[0039] The optionally used partial hydrolyzate (C) can be a partial homohydrolyzate, i.e., a partial hydrolyzate of one kind of silane of formula (III), and a partial cohydrolyzate, i.e., a partial hydrolyzate of at least two different kinds of silanes of formula (III).

[0040] In the context of the present invention, the term "partial hydrolyzate" is understood to mean a product formed by hydrolysis and / or condensation.

[0041] When component (C) used in the composition of the present invention is a partial hydrolyzate of a silane of formula (III), those having up to 20 silicon atoms are preferred.

[0042] Examples of component (C) optionally used according to 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, N-cyclohexylaminomethyltriethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltrimethoxysilane, N,N-di-n-butylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltrimethoxysilane, and methyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane are preferred.

[0043] Component (C) is a commercially available product or can be produced by methods common in silicon chemistry.

[0044] When the composition according to the present invention contains component (C), the amount involved is in each case preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 2 parts by weight, especially 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), and these preferably contain at least partially silanes having functional groups and / or their partial hydrolyzates.

[0045] In addition to components (A), (B) and optionally (C), the composition according to the present invention can contain all substances that have hitherto been used in compositions that can be crosslinked by a condensation reaction, such as a curing accelerator (D), a plasticizer (E), a filler (F) and an additive (G).

[0046] The curing accelerator (D) to be used can be any of the curing accelerators that have been used in compositions that can be crosslinked by a condensation reaction heretofore. Examples of the curing accelerator (D) include titanium compounds such as titanium chelates such as tetrabutyl titanate or tetraisopropyl titanate, or bis(ethylacetoacetato)diisobutoxytitanium, or di-n-butyltin dilaurate, 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, for example, the reaction product of di-n-octyltin diacetate and tetraethoxysilane, and di-n-octyltin diacetate, di-n-octyltin dilaurate, dioctyltin oxide, the reaction product of di-n-octyltin oxide and tetraethoxysilane, tetrabutyl titanate, tetraisopropyl titanate or bis(ethylacetoacetato)diisobutoxytitanium are preferred.

[0047] When the composition of the present invention contains the curing accelerator (D), the amount involved is in any case preferably 0.001 to 20 parts by weight, particularly preferably 0.001 to 1 part by weight, based on 100 parts by weight of the component (A).

[0048] Examples of the plasticizer (E) optionally used are dimethylpolysiloxanes which are liquid at room temperature and end-blocked with trimethylsiloxy groups and in particular have a viscosity in the range of 5 to 1000 mPa·s at 25°C, and high-boiling hydrocarbons such as paraffin oils or mineral oils consisting of naphthene units and paraffin units.

[0049] When the composition according to the present invention contains the component (E), the amount involved is in any case 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the siloxane (A). The composition according to the present invention preferably does not contain any plasticizer (E) at all.

[0050] The filler (F) optionally used in the composition according to the invention can be any conventionally known filler.

[0051] Examples of the optionally used filler (F) are non-reinforcing fillers (F), i.e., metal oxide powders such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolite, aluminum, titanium, iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder, etc. with a BET specific surface area of up to 20 m 2 / g; reinforcing fillers, i.e., fillers with a BET surface area exceeding 20 m 2 / g, such as precipitated calcium carbonate and carbon blacks such as furnace black and acetylene black; silicas such as fumed silica and precipitated silica; fibrous fillers such as plastic fibers.

[0052] The filler (F) optionally used is preferably calcium carbonate or silica, particularly preferably silica or a mixture of silica and calcium carbonate.

[0053] Preferred types of calcium carbonate (F) are 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.

[0054] When the composition according to the invention contains a filler (F), the amount involved is in each case preferably 10 to 150 parts by weight, particularly preferably 10 to 130 parts by weight, especially 10 to 100 parts by weight, based on 100 parts by weight of the organopolysiloxane (A). The composition according to the invention preferably contains a filler (F).

[0055] Examples of the additive (G) include pigments, dyes, fragrances, antioxidants, agents that affect electrical properties such as conductive carbon black, agents that render them flame-retardant, light stabilizers, fungicides, biocides such as bactericides and acaricides, cell generators such as azodicarbonamide, heat stabilizers such as Si-N-containing silazanes or silylamides, scavengers such as N,N'-bis(trimethylsilyl)urea or hexamethyldisilazane, co-catalysts such as Lewis acids and Bronsted acids such as sulfonic acids, phosphoric acids, phosphate esters, phosphonic acids and phosphonate esters, thixotropic agents such as polyethylene glycols having OH terminals on one or both sides or hydrogenated castor oil, agents for further adjusting the elastic modulus such as polydimethylsiloxane having an OH terminal group, and any siloxane different from components (A), (B) and (C).

[0056] When the composition according to the invention contains the additive (G), the amounts involved are in each case, based on 100 parts by weight of the organopolysiloxane (A), preferably from 0.1 to 20 parts by weight, particularly preferably from 0.1 to 15 parts by weight, especially from 0.1 to 10 parts by weight. The composition according to the invention preferably contains the component (G).

[0057] Each of the individual constituents of the composition according to the invention may be one such constituent or a mixture of at least two different types of such constituents.

[0058] The composition according to the invention preferably comprises the following.

[0059] (A) an organopolysiloxane of formula (I), (B) a siloxane of formula (II), optionally (C) a silane of formula (III) and / or its partial hydrolyzate, optionally (D) a curing accelerator, optionally (E) a plasticizer, optionally (F) a filler and optionally (G) an additive.

[0060] The composition according to the present invention preferably contains the following.

[0061] (A) An organopolysiloxane of formula (I), (B) A siloxane of formula (II), (C) A silane of formula (III) and / or its partial hydrolyzate, Optionally (D) a curing accelerator, Optionally (E) a plasticizer, Optionally (F) a filler and Optionally (G) an additive.

[0062] In particular, the composition according to the present invention contains the following.

[0063] (A) An organopolysiloxane of formula (I), (B) A siloxane of formula (II), (C) A silane of formula (III) and / or its partial hydrolyzate, (D) A curing accelerator, Optionally (E) a plasticizer, (F) A filler and Optionally (G) an additive.

[0064] In a more preferred embodiment, the composition according to the present invention is as follows, namely, (A) An organopolysiloxane of formula (I), (B) A siloxane of formula (II), (C) A silane of formula (III) and / or its partial hydrolyzate, (D) A curing accelerator, (F) A filler and Optionally (G) an additive and does not contain (E) a plasticizer.

[0065] Apart from components (A) to (G), the composition according to the present invention preferably does not contain other constituents.

[0066] The composition according to the present invention is preferably a viscous to paste-like composition.

[0067] To produce the composition according to the invention, all the constituents can be mixed with one another in any order. This mixing can be carried out at room temperature and the pressure of the ambient atmosphere, i.e., about 900 - 1100 hPa. However, if desired, this mixing can be carried out at a higher temperature, for example, in the range of 35 - 135 °C. Also, to remove volatile compounds or air, mixing can be carried out intermittently or continuously under reduced pressure, for example, at an absolute pressure of 30 - 500 hPa.

[0068] The mixing according to the invention is preferably carried out using raw materials having the maximum possible exclusion of water, i.e., preferably having a water content of less than 10000 mg / kg, preferably less than 5000 mg / kg, particularly less than 1000 mg / kg. During the mixing process, the mixture is preferably covered with a protective gas such as dry air or nitrogen, and the associated gas preferably has a water content of less than 10000 μg / kg, preferably less than 1000 μg / kg, particularly less than 500 μg / kg. After production, the paste is filled into commercially available moisture-proof containers such as cartridges, tubular bags, bottles, and drums.

[0069] In a preferred procedure, components (A), (B), optionally (C) and (E) are first mixed with one another, then optionally the filler (F) is added, and finally optionally the further constituents (D) and (G) are added, with the mixing temperature not exceeding 60 °C.

[0070] The present invention also provides a method for producing the composition according to the invention by mixing the individual components.

[0071] The method according to the invention can be carried out continuously, batchwise, or semi - continuously using known devices according to known methods.

[0072] The composition according to the invention or the composition produced by the present invention can be stored in the absence of moisture and can cross - link upon entry of moisture.

[0073] The normal water content of air is sufficient to crosslink the composition according to the invention. The composition according to the invention preferably crosslinks at room temperature. If desired, crosslinking can also be carried out at a temperature higher or lower than room temperature, for example -5 to 15 °C or 30 to 50 °C, and / or at a water concentration exceeding the normal water content of air.

[0074] Crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the ambient atmosphere, i.e. about 900 to 1100 hPa.

[0075] The invention further relates to a molded article produced by crosslinking the composition according to the invention.

[0076] The molded article according to the invention preferably has a stress of less than 0.4 MPa measured on type 2 test specimens in accordance with ISO 37 at 100% elongation.

[0077] The composition according to the invention can be stored if water is excluded and can be used for all purposes for which it is possible to use a composition which crosslinks upon entry of water at room temperature to form an elastomer.

[0078] Thus, the composition according to the invention can be used, for example, as a sealing composition for joints such as longitudinal joints and for similar cavities of a width of, for example, 10 to 40 mm in buildings, land vehicles, ships and aircraft, or as an adhesive or cement-forming composition in the manufacture of window structures or display cases, and also, for example, as a protective coating, an anti-slip coating or for the production of elastomeric molded articles, starting from surfaces exposed to the action of fresh or sea water.

[0079] The composition according to the invention has the advantage of being easy to manufacture and being distinguished by very high storage stability.

[0080] Furthermore, the composition according to the invention has the advantage of being very easy to handle during use and having excellent processing properties in a wide range of applications.

[0081] The crosslinkable composition according to the present invention has the advantage that the elastic modulus can be particularly adjusted.

[0082] The crosslinkable composition according to the present invention has the advantage of adhering very well to a wide range of substrates.

[0083] The crosslinkable composition according to the present invention has the advantage of not causing any contamination of the edge regions of adjacent substrates. In particular, these are ideally suitable for coating and hardening natural and artificial stones without contaminating the edge regions.

[0084] The crosslinkable composition according to the present invention has the advantage of being very economical with respect to the substances used.

Examples

[0085] In the examples described below, all viscosity data relate to a temperature of 25 °C. Unless otherwise stated, the following examples are carried out at ambient atmosphere, i.e. about 1000 hPa, and room temperature, i.e. about 23 °C, or the temperature that occurs when the reactants are combined at room temperature without additional heating or cooling, and a relative humidity of about 50%. Further, specifications for parts and percentages are by weight, unless otherwise specified.

[0086] Tensile strength, elongation at break and stress at 100% elongation are determined according to ISO 37 for type 2 test specimens.

[0087] In the context of the present invention, the dynamic viscosity is measured at 25 °C in accordance with DIN 53019 using a "Physica MCR 300" rotational rheometer from Anton Paar, unless otherwise specified. For values exceeding 200 mPa·s, a cone-plate measurement system (Searle system including measurement cone CP 50-1) is used. The shear rate is adjusted according to the polymer viscosity and is 62 l / s for 5000 - 9999 mPa·s, 50 l / s for 10000 - 12499 mPa·s, 38.5 l / s for 12500 - 15999 mPa·s, 33 l / s for 16000 - 19999 mPa·s, 25 L / s for 20000 - 24999 mPa·s, 20 l / s for 25000 - 29999 mPa·s, 17 l / s for 30000 - 39999 mPa·s, 10 l / s for 40000 - 59999 mPa·s, 5 l / s for 60000 - 149999 mPa·s.

[0088] After setting the temperature of the measurement system to the measurement temperature, a three-step measurement program consisting of a conditioning stage, a pre-shear, and a viscosity measurement is applied. The conditioning stage is performed by gradually increasing the shear rate over 1 minute to the aforementioned shear rate according to the expected viscosity at which the measurement is intended to be carried out. Once this is reached, the pre-shear is carried out at a constant shear rate for 30 seconds, and then 25 individual measurements are each carried out for 4.8 seconds to measure the viscosity and determine the average value therefrom. The average value corresponds to the dynamic viscosity reported in mPa·s.

[0089] In the following Examples B1 to B3, the molecular composition was determined by nuclear magnetic resonance spectroscopy (terms refer to ASTM E 386: High-resolution nuclear magnetic resonance (NMR) spectroscopy: Terms and Symbols), where the 29Si nucleus was measured.

[0090] The abbreviations used below are as follows.

[0091] For the methyl group, Me, For the ethyl group, Et, The n-butyl group includes Bu, and The 2,2,4-trimethylpentyl group includes iOct.

[0092] <Production of Oligomer Mixture B1> Mix 240 g (3.25 mol) of α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPas, 234 g (1.0 mol) of trimethoxy(2,4,4-trimethylpentyl)silane (=iOctSi(OMe)3) available from Wacker Chemie AG under the name SILRES(R) BS 1316, and 0.80 g of an ethanol solution of sodium ethoxide (21%), and heat at 110 °C for 4 hours. After cooling the solution, neutralize the mixture by adding 1.60 g of an n-heptane solution of dimethyldichlorosilane (10%). Evaporate this mixture on a rotary evaporator at 120 °C under a reduced pressure of 50 mbar.

[0093] The composition of the mixture was determined by 29-Si-NMR spectroscopy. The mixture contained 1.4 wt% of iOctSi(OMe)3, 0.4 wt% of Me2Si(OMe)2 and 98.2 wt% of an oligomer mixture with an average composition of [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 .

[0094] The molecular weights measured by gel permeation chromatography were 929 g / mol (Mw - weight average) and 635 (Mn - number average). The polydispersity (Mw / Mn) was 1.46.

[0095] <Production of Oligomer Mixture B2> ​​​​​The preparation procedure of oligomer mixture B1 was repeated with the modification that 178 g of n-butyltrimethoxysilane was used instead of trimethoxy(2,4,4-trimethylpentyl)silane. The mixture contained 0.7 wt% of n-BuSi(OMe)3, 0.2 wt% of Me2Si(OMe)2, and 99.1 wt% of an oligomer mixture with an average composition of [n-BuSi(OMe)2O 1 / 2 0.08 [n-BuSi(OMe)O 2 / 2 0.15 [n-BuSiO 3 / 2 0.07 [Me2SiO 2 / 2 0.46 [Me2Si(OMe)O 1 / 2 0.24 .

[0096] <Production of Oligomer Mixture B3> The preparation procedure of oligomer mixture B1 was repeated with the modification that 346 g of n-hexadecyltrimethoxysilane was used instead of trimethoxy(2,4,4-trimethylpentyl)silane. The mixture contained 3.6 wt% of n-C 16 H 33 Si(OMe)3, 0.5 wt% of Me2Si(OMe)2, and 95.9 wt% of an oligomer mixture with an average composition of [n-C 16 H 33 Si(OMe)2O 1 / 2 0.14 [n-C 16 H 33 Si(OMe)O 2 / 2 0.13 [n-C 16 H 33 SiO 3 / 2 0.02 [Me2SiO 2 / 2 0.61 [Me2Si(OMe)O 1 / 2 0.10 .

[0097] <Production of Siloxane A1> ​​​​​​​​​​A mixture of 330 kg of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPas and 110 kg of α,ω-dihydroxypolydimethylsiloxane having a viscosity of 20,000 mPas was added to 15.22 kg of a solution of 0.02 kg of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in 15.2 kg of (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane and stirred for 200 minutes -1 and stirred for 5 minutes. After a reaction time of 5 minutes, a mixture of 98.0 wt% α,ω-bis(2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilylpolydimethylsiloxane having a viscosity of 52,000 mPas, 1.9 wt% (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, and 0.1% ethanol was obtained.

[0098] <Production of RTV1 base mixture BM1> 455 kg of siloxane A1 was added to 10.6 kg of a tetraethoxysilane hydrolyzate oligomer having a SiO2 content of 40% upon complete hydrolysis and condensation, available from Wacker Chemie AG under the name SILIKAT TES 40, 6.3 kg of a methyltriethoxysilane hydrolyzate oligomer having an average of 10 silicon atoms per molecule, and 12.6 kg of a mixture of 6.3 kg of 3-aminopropyltriethoxysilane, and the mixture was stirred for an additional 5 minutes at 200 revolutions per minute. Thereafter, 44 kg of hydrophilic fumed silica having a specific surface area of 150 m 2 / g, available from Wacker Chemie AG under the name HDK(R) V15A, was added and the mixture was stirred for an additional 5 minutes, initially at 200 revolutions per minute until all of the fumed silica was wet. Next, the mixture was held at a reduced pressure of 200 mbar for 600 minutes -1It was stirred for 10 minutes. Finally, 1.58 kg of a solution of 0.27 kg of dioctyltin oxide in a mixture of 1.31 kg of a mixture of 0.655 kg of a methyltriethoxysilane hydrolyzate oligomer having an average of 10 silicon atoms per molecule and 0.655 kg of 3-aminopropyltriethoxysilane, and 2 kg of a 50 wt% solution of octylphosphonic acid in methyltrimethoxysilane were added, and the mixture was further stirred under reduced pressure (200 mbar) for 5 minutes. This base mixture BM1 serves as the basis for the production of the following inventive examples.

[0099] [Examples 1 - 9] The amount of oligomer mixture B1 specified in Table 1 was added to 250 g of the RTV1 base mixture BM1 in each case and mixed in a planetary mixer of the Labmax type. Next, the mixtures thus obtained were filled into moisture-proof containers in each case. 24 hours after the production of the mixtures, plates with a thickness of 2 mm were taken out from these mixtures, cured at 23 °C and a relative humidity of 50% for 7 days, and then type 2 dumbbell-shaped test specimens according to ISO 37, 6th edition, 2017 - 11 were made from them. The mechanical properties measured for these test specimens are shown in Table 1.

[0100] [Comparative Example 1 (C1)] 250 g of the RTV1 base mixture BM1 was filled into a moisture-proof container without further additives. 24 hours after the production of the base mixture, a plate with a thickness of 2 mm was taken out, cured at 23 °C and a relative humidity of 50% for 7 days, and then type 2 dumbbell-shaped test specimens according to ISO 37, 6th edition, 2017 - 11 were made from it. The mechanical properties measured for these test specimens are shown in Table 1.

[0101] [Example 10] The experiment according to Example 1 was repeated with the modification that 5 g of oligomer mixture B2 was added instead of oligomer mixture B1. The mechanical properties measured for these test specimens are shown in Table 1.

[0102] [Example 11] The experiment according to Example 1 was repeated with the modification that 5 g of oligomer mixture B3 was added instead of oligomer mixture B1. The mechanical properties measured for these test pieces are shown in Table 1.

[0103]

Table 1

Claims

1. A crosslinkable composition based on an organosilicon compound comprising: (A) An organopolysiloxane of the following formula - (R ７ O) ３－ａ SiR ３ ａ O(SiR ４ ２ O) ｎ SiR ３ ａ (OR ７ ) ３－ａ (I), (In the formula, R ４ is a methyl group, R ７ which may be the same or different and is a monovalent hydrocarbon group which may be substituted, R ３ may be the same or different and is a -CH₂-NR₆'R₅' group or a -CH₂NR₁₁' group (where R₅' is a hydrocarbon group having 1 to 12 carbon atoms, R₆' is a hydrogen atom or group R₅', and R₁₁' is a divalent hydrocarbon group which may be interrupted by a heteroatom), a may be the same or different and is 0 or 1, n is an integer from 30 to 2000), and (B) A siloxane of formula (II) 【Chemical 1】 (In the formula, R is a methyl group, R １ which may be the same or different and is a monovalent hydrocarbon group having 2 to 16 carbon atoms, R ２ is a methyl group, x may be the same or different and is 0 or an integer from 1 to 9, z is 1 or 2, provided that the sum of all x in formula (II) is 1 to 9.) The crosslinkable composition is characterized in that the composition contains a component (C) consisting of a silane of the following formula (R8O)4-bSiR9b (III) and / or its partial hydrolyzate (In the formula, b is 0 or 1, R8 may be the same or different and is a methyl or ethyl group, R9 is a monovalent hydrocarbon group having 1 to 18 carbon atoms.)

2. Group R １ The composition according to claim 1, wherein R is an aliphatic hydrocarbon group having 2 to 16 carbon atoms.

3. The composition according to claim 1 or 2, characterized in that the composition contains component (B) in an amount of 1 to 20 parts by weight based on 100 parts by weight of component (A).

4. The composition according to any one of claims 1 to 3, characterized in that it is a composition containing the following (A) An organopolysiloxane of formula (I), (B) A siloxane of formula (II), (C) A silane of formula (III) and / or its partial hydrolyzate, Optionally (D) A curing accelerator, Optionally (E) A plasticizer, Optionally (F) A filler, and Optionally (G) An additive.

5. The composition according to any one of claims 1 to 4, characterized in that it contains the following and does not contain (E) a plasticizer (A) An organopolysiloxane of formula (I), (B) A siloxane of formula (II), (C) A silane of formula (III) and / or its partial hydrolyzate, (D) A curing accelerator, (F) A filler and Optionally (G) An additive.

6. A method for producing the composition according to any one of claims 1 to 5 by mixing the individual components.

7. A molded article produced by crosslinking the composition according to any one of claims 1 to 5 or the composition produced as described in claim 6.

8. The molded article according to claim 7, characterized in that it has a stress preferably less than 0.4 MPa at 100% elongation.

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