WO2015156703A2 - Functional metallosiloxanes, products of their partial hydrolysis and their use - Google Patents

Functional metallosiloxanes, products of their partial hydrolysis and their use Download PDF

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WO2015156703A2
WO2015156703A2 PCT/RU2015/000242 RU2015000242W WO2015156703A2 WO 2015156703 A2 WO2015156703 A2 WO 2015156703A2 RU 2015000242 W RU2015000242 W RU 2015000242W WO 2015156703 A2 WO2015156703 A2 WO 2015156703A2
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functional
metallosiloxane
product
partial hydrolysis
metal
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WO2015156703A3 (en
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Aziz Mansurovich Muzafarov
Nadezhda Andreevna Tebeneva
Ivan Borisovich Meshkov
Alexander Nikolaevich TARASENKOV
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Enikolopov Institute Of Synthetic Polymeric Materials, A Foundation Of The Russian Academy Of Sciences (Ispm Ras)
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Publication of WO2015156703A3 publication Critical patent/WO2015156703A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the invention relates to the field of chemical technology of organic silicon compounds and may find industrial application in compositions based on rubber, especially silicone rubber, as a crosslinker. More specifically, the invention relates to functional metallosiloxanes, their partial hydrolysis products, as well as to the method of manufacturing and use as crosslinking agents in compositions based on silicone rubber.
  • Metallosiloxanes which are the nearest in structure to the Claimed functional metallosiloxanes and to the method of their manufacture, are compounds that are described in Russian Patent Publication RU 2296767 of 2007. This document describes functional metallosiloxanes of the following general formula:
  • M [OSiR'R n "(OAlk) 2 -n ] wherein M represents a di- or trivalent metal, and m corresponds to the valence of the metal.
  • the process for their preparation consists of reacting sodium oxy(alkoxy) organosilane with salt of a di- or trivalent metal.
  • the resulting compounds have improved compatibility with polymer compositions and are used for functional polymetallosiloxanes of statistic cyclolinear structure obtained by the method of hydrolytic condensation. Use of said functional metallosiloxanes as crosslinking agents has not been described.
  • Oligomeric and polymeric organic silicon compounds containing metal atoms in the structure are known from US Patent No. 6,336,026, US Patent No. 6,297,302, US Patent No. 6,297,302, and US Patent No.6,037,092.
  • Such compounds are prepared by reacting organic acid salts of metals of the following series: Zr 2+ , Zn 2+ , Fe 2+ , Fe 3+ , Ce 3+ , Cr 2+ , and Cr 3+ with linear or cyclic organosiloxane oligomers containing unsaturated groups on the silicon atoms.
  • the reaction results are siloxane oligomers or polymers containing in their composition some quantity of metal atoms.
  • the reaction mechanism is not established, the reaction is insufficiently studied, and the synthesized compounds have an undefined structure.
  • the obtained metallosiloxanes possess a number of advantages. They are compatible with different types of polymers, including various polyorganosiloxanes, both liquid and solid, and their molecular weight, which is controlled by a type of siloxane oligomer used in metallosiloxane synthesis, is sufficiently high.
  • M represents a metal series of Cr, Mo, W, Fe, Ni, Co, Mn, Re, Rh, Os, and Ir.
  • Compounds are prepared by reacting methylsesquioxalic resin with metal carbonyls. The yield of target compounds is approximately 50%. The reaction is performed in organic solvents at high temperatures. The resulting compounds are not regarded as crosslinking agents but only as catalysts for the conversion of organic silicon compounds.
  • An object of the present invention is to provide a new technical result that consists of creating functional metallosiloxanes and products of their partial hydrolysis that possess the properties required for their effective use as crosslinking agents.
  • these functional metallosiloxanes and the products of their partial hydrolysis should contain in their structure a certain number of atoms of a corresponding metal, show good solubility in organic solvents, possess good compatibility with the polymer matrix, and contain functional groups capable of reacting with components of the polymer composition into which they are to be introduced.
  • they should have improved compatibility with high-molecular polymers such as organosiloxane resins and rubbers.
  • M is a two-, three-, or four-valent metal; p + m correspond to the valence of the metal, provided that p and m ⁇ 0; n is 0 or 1 ;
  • R represents C1-C4 alk l
  • Alk is a C1-C4 alkyl substituent.
  • M may be a divalent metal selected from Zn, Fe (II), Cu, and n may have the value of 0 or 1.
  • M may be a trivalent metal selected from Fe (III), Ce, Cr, Sm, Eu, or a four-valent metal selected from Zr and Ti, and n may have the value 0 or 1.
  • Alk may comprise CH 3 -, and R' may have a value of CH 3 - or - C 6 H 5 - or NH 2 (CH 2 ) 3 -.
  • Functional metallosiloxanes are prepared by reacting sodium oxy(alkoxy) organosilane of the general formula (IV):
  • Chlorides or bromides are used as the metal salts in the production of functional metallosiloxanes.
  • the interaction of sodium oxy(alkoxy) organosilane with the metal salt may be performed simultaneously with the formation of sodium oxy(alkoxy) organosilane from sodium hydroxide and alkoxysilane of the general formula (V):
  • the process is carried out without isolation of the sodium (alkoxy) organosilane, and the metallosiloxane is obtained in one step according to the following general scheme:
  • the interaction of the components can be carried out in an organic solvent selected from the group consisting of tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, 2-propanol, and 1-butanol.
  • the process of interaction with the sodium alkoxide is carried out simultaneously with the process of its formation from alcohol and sodium.
  • the metal salt may be selected from a number of metal salts in general formula MX b , wherein M is a divalent metal selected from Zn, Fe (II), Cu, or where M is a trivalent metal selected from Fe (III), Ce Cr, Sm, Eu, or a four- valent metal selected from Zr and Ti.
  • the sodium oxy(alkoxy) organosilane may be represented by sodium oxymethyl diethoxysilane, and the metal salt may be represented by iron chloride (III).
  • the alkoxyorganosilane may be represented by methylvinyldiethoxy silane
  • the metal salt may be represented by iron chloride (III) or zirconium chloride, respectively.
  • the functional metallosiloxanes obtained according to the present invention are partially hydrolyzed to obtain a product of partial hydrolysis.
  • M- is a two-, three-, or four-valent metal; a is 1, 2 or 3; and n is 0 or 1 ;
  • Alk is a Q-C4 alkyl substituent, or by the following general formula (III):
  • M is a three- or four-valent metal
  • R represents d -C 4 alkyl
  • q has a value from 2 to 50
  • a is 1 or 2
  • M may be a divalent metal selected from Zn, Fe (II), and Cu, and n may have the value of 0 or 1.
  • M may be a trivalent metal selected from Fe (III), Ce, Cr, Sm, and Eu, or a four-valent metal selected from Zr and Ti, and n may have the value 0 or 1.
  • Alk may represent CH 3 or C 2 H 5 -, and R 1 and R" may have a value of CH 3 .
  • a product of partial hydrolysis of the functional metallosiloxane is obtained by mixing the functional metallosiloxane in ambient conditions with the solvent having a given content of water required for obtaining a product of partial hydrolysis.
  • a mole ratio of metallosiloxane to water is in the range of 1 : 0.5. Furthermore, metallosiloxanes as starting reagents for products of partial hydrolysis are optional isolated from the reaction mixture.
  • a solvent used in the process for preparing the partial hydrolysed products is selected from the group consisting of tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, 2-propanol, and 1-butanol.
  • Functional metallosiloxanes of the present invention are polyfunctional compounds containing in their composition silicon-bonded functional groups as well as a catalytic center. In this regard, they exhibit a broad spectrum of possible applications; in particular, they can be used as crosslinking agents and as curing catalysts in polymer compositions. Their activity in the crosslinking of polymer chains is associated with the presence of reactive functional groups that can interact both with the functional groups of the polymer (i.e., with the basis of the composition) and with each other during hydrolytic condensation. The combination of these processes results in the formation of crosslinked structures. In curing, the catalytic activity of metallosiloxane is demonstrated most clearly when concentration of the metallosiloxane in the composition is low. In this case, the functional groups of the polymer (the basics of the composition) quite effectively condense with each other due to interaction. At that the reaction proceeds with the participation of a metal atom by coordination of the functional groups on such a catalytic center.
  • the functional metallosiloxanes and products of their partial hydrolysis may be used as crosslinking agents independently or in combinations, as well as components of curing compositions used for curing rubber-based compositions, in particular, on the basis of siloxane rubber.
  • a curing composition according to the present invention comprises a functional metallosiloxane and/or a product of its partial hydrolysis and a silicate.
  • a silicate used in the curing composition is a polyethoxysiloxane having linear and branched structures.
  • Data on the production and characteristics of the branched polyethoxysiloxane are given in the article by V.V azakova, E.A. Rebrov, V.D. Myakushev, T.V. Strelkova, A.N. Ozerin, L.A. Ozerina, T.B. Chenskaya, S.S. Sheiko, E. Yu. Sharipov, A.M. Muzafarov, "Silicones and Silicone-Modified Materials", ACS Symposium Book Series 729 (ISSN No. 0097- 6156; 729; Editors S. J.
  • Linear polyethoxysiloxane is a commercial sample of ETS-40, the product of Penta® Silicones (Moscow).
  • a content of silicate in the curing composition ranges from 1 to 10 parts by mass per 100 parts by mass of the functional metallosiloxane and/or a product of its partial hydrolysis.
  • Curable compositions in which a functional metallosiloxane and/or a product of its partial hydrolysis is used as a crosslinking agent or in which a curing composition of the present invention is used, are based on rubber, preferably based on siloxane rubber. The most accessible are low-molecular-weight polydimethylsiloxane rubbers of different molecular weights (CKTH type)
  • a curable composition based on rubber preferably, silicone rubber, comprises a rubber, a crosslinking agent, or a curing composition, or the curing catalyst and optionally a filler.
  • the content ranges from 10 to 100 parts by mass per 100 parts by mass of rubber.
  • a curing catalyst which is a functional metallosiloxane
  • its content ranges from 0.1 to 1 part by mass per 100 parts by mass of rubber, in particular siloxane rubber.
  • the filler used in these compositions is selected from known fillers such as zinc oxide, silica, talc, etc.
  • Curing is carried out by maintaining the composition for 24 hours at ambient conditions, optionally followed by heat treatment at a temperature of 100°C to 200°C for 1 to 2 hours to obtain a cured composition.
  • Curable compositions obtained according to the present invention may be used for forming coatings, films, and composite materials.
  • Functional metallosiloxanes and products of their partial hydrolysis obtained according to the present invention are effective as crosslinking agents since they contain in their structure a certain amount of the corresponding metal atoms, and exhibit good solubility in organic solvents and good compatibility with the polymer matrix. Furthermore, they contain in their structure functional groups that are capable of interacting with components of a polymer composition into which they are to be introduced.
  • use of the functional metallosiloxanes of the present invention as crosslinking agents or catalysts and use of the products of their partial hydrolysis as crosslinking agents in the rubber- based compositions contribute toresult in improving physical, mechanical, and thermal stability characteristics.
  • the desired product obtained after evaporation [of the solution] was a dark brown pasty mass readily soluble in organic solvents.
  • the yield was 10.04 g (98 %).
  • the elemental analysis showed the following results (%): Si 6.98; C 31.04; H 6.36; and Fe 27.80. Calculated values (%) were the following: Si 12.70; C 27.14; H 5,93; and Fe 25.27.
  • the ethanol that was formed in this process and the excess of methyltriethoxysilane were removed in a rotary evaporator with an oil pump under a vacuum of 1 torr and at a temperature in the range of 60°C to 75°C.
  • the product was obtained in the amount of 3.59 g (101%) in the form of a white pasty mass.
  • the mixed solution prepared from 2.79 g (0.041 mol) of sodium ethylate in 26 ml of ethanol and 3.59 g (0.021 mol) of sodium-oxymethyl-diethoxy silane in 55 mL of toluene was added dropwise to a suspension of 2.74 g (0.021 mol) of aluminum chloride in 20 ml of toluene, while the mixture was maintained at a temperature of approximately 30°C.
  • the reaction mixture was stirred for 4 hours at 40°C until the medium was neutralized.
  • the reaction mixture was separated from the sodium chloride precipitate by centrifugation, and the precipitate was washed with toluene and again centrifuged.
  • the desired product obtained after evaporation [of the solution] comprised a colorless transparent mass readily soluble in organic solvents.
  • the yield was 5.26 g (96 %).
  • the elemental analysis showed the following results (%): C, 35.63; H, 7.64; Si, 12.16; and Al, 12.29. C9H23O5S1AI. Calculated values (%) were the following: C, 40.59; H, 8.70; Si, 10.54; and Al, 10.13.
  • a mixture solution of 1.52 g (0.022 mol) of sodium ethylate in 12 ml of ethanol and 3.83 g (0.022 mol) in 40 ml of sodium oxymethyl diethoxysilane in monoglyme was added dropwise to a solution of 2.61 g (0.011 mol) of zirconium chloride in 50 ml monoglyme, while the temperature of the mixture was maintained at approximately 30°C.
  • the reaction mixture was further stirred for 4 hours at 40°C until the reaction medium neutralized.
  • the reaction mixture was then separated from the sodium chloride precipitate by centrifugation, and the precipitate was washed with monoglyme and centrifuged again.
  • the desired product obtained after evaporation [of the monoglyme] comprised a yellowish transparent mass readily soluble in organic solvents.
  • the yield of the product was 3.64 g (68%).
  • the elemental analysis showed the following results (%): C, C, 28.26; H, 6.37; Si, 13.04; and Zr, 22.99.
  • Liquid silicone rubber was mixed at a predetermined ratio (calculation was performed with reference to the mass of the dissolved metallosiloxane) with a solution of a functional metallosiloxane.
  • the obtained homogeneous solution was poured onto a Teflon® substrate so that the layer thickness was ranged from 0.1 to 2 mm. After retaining for 10 hours at room temperature, the mold was placed in a thermostat and was retained for 1 hour at a temperature of 80°C and then for 2 hours at a temperature of 200°C. The substrate was cooled, and the obtained solid colored or colorless transparent film was removed and tested.
  • the ratios of components and test results are shown in Table 2.

Abstract

The invention relates to the field of chemical technology of organic silicon compounds, in particular, to functional metallosiloxanes, products of their partial hydrolysis, the method of their preparation, and to their use as crosslinking agents in compositions based on rubber. Disclosed are functional metallosiloxanes of the general formula (I): wherein M is a two-, three-or four-valent metal; p+m correspond to the valence of the metal, provided that p and m ≠ 0; n is 0 or 1; R represents C1-C4 alkyl; R' and R" are independently the same or different and represent C1 -C4 alkyl, C6H5-, CH2=CH- and NH2(CH2)x, where x has a value from 2 to 5; and Alk is a C1-C4 alkyl substituent. Also disclosed is the method for preparing functional metallosiloxanes, products of their partial hydrolysis and the method of their preparation, and their use as crosslinkers in curable compositions based on rubber, preferably silicone rubber.

Description

FUNCTIONAL METALLOSILOXANES, PRODUCTS OF THEIR
PARTIAL HYDROLYSIS AND THEIR USE
The invention relates to the field of chemical technology of organic silicon compounds and may find industrial application in compositions based on rubber, especially silicone rubber, as a crosslinker. More specifically, the invention relates to functional metallosiloxanes, their partial hydrolysis products, as well as to the method of manufacturing and use as crosslinking agents in compositions based on silicone rubber.
The addition of organic salts of certain metals to polymer compositions as additives is known from such documents as US Patent No. 4193885 issued in 1980 and US Patent No. 4528313 issued in 1985. These documents disclose the use [in these compositions] of a fairly wide range of metals. However, poor compatibility of such compounds with polymeric matrices and problems associated with their dispersion in polymer significantly reduce their efficiency and complicate the introduction of additives.
Known in the art are partially functional metallasiloxane functional compounds obtained by reacting 1,4-trimethylsiloxybenzole with sodium hydroxide followed by the exchange of sodium for aluminum, calcium, and zinc (J Chem. Soc, Dalton Trans, 1999, 4535-4540). However, these compounds have low solubility, contain traces of water, and their structure is not deterministic.
It was described that interaction of copper dichloride with phenylsilane in the presence of sodium hydroxide and sodium metal results in obtaining phenyl- copper-sodium siloxane. Similarly obtained was nickel-containing metallosiloxane {Metal loorgan. Chemistry, 1991, 4, 74; Far-East Academy of Sciences of USSR, Vol. 325, JYO 6, 1992; and Eur. J Inorg. Chem., 2004, 1253-1261). The use of other radicals of silicon atoms and other metals was not considered. Furthermore, the use of the resulting compounds as crosslinking agents for polymer blends has not been investigated. A disadvantage of the aforementioned processes is the use of metallic sodium and its presence in the composition of water and alcohol, which complicates treatment in subsequent steps.
Known in the art is a diethoxyalumoethyl silicate obtained by interacting dialkoxyaluminum bromide with potassium oxy triethoxy silane (Journal of General Chemistry [)KOX], 1995, Vol. 65, issue 4, pp. 612-615). In the obtained compound, along with metal, a silicon atom is bound to a functional group, which allows for further transformations. A disadvantage of such a compound is the lack of organic radicals on silicon atoms, which makes this compound substantially inorganic and imposes restrictions on the compatibility thereof with polymeric matrices. In addition, the proposed method is not universal and is carried out only with participation of aluminum-containing compounds. Introduction of other metals has not been studied. There is no reference to use of the synthesized compound as a crosslinking agent for polymer compositions.
Metallosiloxanes, which are the nearest in structure to the Claimed functional metallosiloxanes and to the method of their manufacture, are compounds that are described in Russian Patent Publication RU 2296767 of 2007. This document describes functional metallosiloxanes of the following general formula:
M [OSiR'Rn"(OAlk)2 -n] wherein M represents a di- or trivalent metal, and m corresponds to the valence of the metal. The process for their preparation consists of reacting sodium oxy(alkoxy) organosilane with salt of a di- or trivalent metal. The resulting compounds have improved compatibility with polymer compositions and are used for functional polymetallosiloxanes of statistic cyclolinear structure obtained by the method of hydrolytic condensation. Use of said functional metallosiloxanes as crosslinking agents has not been described.
Oligomeric and polymeric organic silicon compounds containing metal atoms in the structure are known from US Patent No. 6,336,026, US Patent No. 6,297,302, US Patent No. 6,297,302, and US Patent No.6,037,092. Such compounds are prepared by reacting organic acid salts of metals of the following series: Zr2+, Zn2+, Fe2+, Fe3+, Ce3+, Cr2+, and Cr3+ with linear or cyclic organosiloxane oligomers containing unsaturated groups on the silicon atoms. The reaction results are siloxane oligomers or polymers containing in their composition some quantity of metal atoms. It is stated in these patents that the reaction mechanism is not established, the reaction is insufficiently studied, and the synthesized compounds have an undefined structure. However, the obtained metallosiloxanes possess a number of advantages. They are compatible with different types of polymers, including various polyorganosiloxanes, both liquid and solid, and their molecular weight, which is controlled by a type of siloxane oligomer used in metallosiloxane synthesis, is sufficiently high.
Known in the art are compounds based on a methylsesquioxalic resin with inclusion of metal atoms:
[(CH3)3Si0,5][SiO2](M) wherein, as described in Russian Patent SU 1743173, M represents a metal series of Cr, Mo, W, Fe, Ni, Co, Mn, Re, Rh, Os, and Ir. Compounds are prepared by reacting methylsesquioxalic resin with metal carbonyls. The yield of target compounds is approximately 50%. The reaction is performed in organic solvents at high temperatures. The resulting compounds are not regarded as crosslinking agents but only as catalysts for the conversion of organic silicon compounds.
The closest to the Claimed products of partial hydrolysis of functional metallosiloxanes are polymeric functional polymetallosiloxanes, which are described in Russian Patent Publication No. RU2293746 dated 2007. This publication describes polyfunctional metallosiloxanes that have a random cyclolinear structure and are obtained by hydrolytic polycondensation of a functional metallosiloxane of the following general formula:
M [OSiRRn"(OAlk)2.n]m wherein M is a di-or trivalent metal, and m corresponds to the valence of the metal. The obtained polymetallosiloxanes have improved compatibility with polymer compositions. However, this patent does not address the use of the described functional metallosiloxanes as crosslinking agents for polymeric compositions.
An object of the present invention is to provide a new technical result that consists of creating functional metallosiloxanes and products of their partial hydrolysis that possess the properties required for their effective use as crosslinking agents. In other words, these functional metallosiloxanes and the products of their partial hydrolysis should contain in their structure a certain number of atoms of a corresponding metal, show good solubility in organic solvents, possess good compatibility with the polymer matrix, and contain functional groups capable of reacting with components of the polymer composition into which they are to be introduced. In particular, they should have improved compatibility with high-molecular polymers such as organosiloxane resins and rubbers.
The problem is solved by obtaining functional metallosiloxanes of the following general formula (I):
(RO)p-M-[OSiR*R"n(OAlk)2-n]m
(I) wherein
M is a two-, three-, or four-valent metal; p + m correspond to the valence of the metal, provided that p and m≠ 0; n is 0 or 1 ;
R represents C1-C4 alk l;
R' and R" are independently the same or different and represent C1-C4 alkyl; C6H5 -, CH2 = CH- and NH2 (CH2)x, wherein x has a value from 2 to 5; and
Alk is a C1-C4 alkyl substituent.
In particular, M may be a divalent metal selected from Zn, Fe (II), Cu, and n may have the value of 0 or 1. In particular, M may be a trivalent metal selected from Fe (III), Ce, Cr, Sm, Eu, or a four-valent metal selected from Zr and Ti, and n may have the value 0 or 1.
As in the case of a divalent metal, in the case of a trivalent metal and a four- valent metal, Alk may comprise CH3-, and R' may have a value of CH3- or - C6H5- or NH2(CH2)3-. In particular, when n is 0, R" represents a substituent CH2 = CH-.
Functional metallosiloxanes are prepared by reacting sodium oxy(alkoxy) organosilane of the general formula (IV):
NaOSiR'R"n(OAlk)2.n (IV) wherein n, R', R", Alk, and M are as defined above, with a metal salt of the general formula: MXb wherein M is a two-, three-, or four-valent metal, b corresponds to the valence of the metal, and X represents halogen, followed by reaction with sodium alkoxide of the general formula: AlkONa wherein Alk represents CrC4 alkyl, and wherein the reaction is carried out in an organic solvent.
Chlorides or bromides are used as the metal salts in the production of functional metallosiloxanes.
A general scheme for the preparation of functional metallosiloxanes can be represented as follows:
MXb+ mNaOSiR,R,, n(OAlk)2-n+ pAlkONa = (RO)p-M-[OSiR*R"n(OAlk)2-n]m
-bNaX
In particular, the interaction of sodium oxy(alkoxy) organosilane with the metal salt may be performed simultaneously with the formation of sodium oxy(alkoxy) organosilane from sodium hydroxide and alkoxysilane of the general formula (V):
SiR'R"n(OAlk)3-n (V) wherein n, R, R", Alk are as defined above.
In this case, the process is carried out without isolation of the sodium (alkoxy) organosilane, and the metallosiloxane is obtained in one step according to the following general scheme:
MXb+ SiR'R"n(OAlk)3-n + mNaOH + pAlkONa = (RO)p-M-[OSiR,RM n(OAlk)2-n]m
-bNaX
-mAlkOH
In both cases, the interaction of the components can be carried out in an organic solvent selected from the group consisting of tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, 2-propanol, and 1-butanol. The interaction of the starting components is preferably carried out at a temperature ranging from -5°C to 50°C, with a molar ratio of AlkONa to NaOSiR*R"n (OAlk)2.„ in the range of 0.1 to 3.9 and within the time required for complete conversion of the metal salt.
In particular, the process of interaction with the sodium alkoxide is carried out simultaneously with the process of its formation from alcohol and sodium.
In particular, the metal salt may be selected from a number of metal salts in general formula MXb, wherein M is a divalent metal selected from Zn, Fe (II), Cu, or where M is a trivalent metal selected from Fe (III), Ce Cr, Sm, Eu, or a four- valent metal selected from Zr and Ti.
The sodium oxy(alkoxy) organosilane may be represented by sodium oxymethyl diethoxysilane, and the metal salt may be represented by iron chloride (III).
In particular, the alkoxyorganosilane may be represented by methylvinyldiethoxy silane, and the metal salt may be represented by iron chloride (III) or zirconium chloride, respectively.
The functional metallosiloxanes obtained according to the present invention are partially hydrolyzed to obtain a product of partial hydrolysis.
According to the present invention, a product of partial hydrolysis is represented by the following general formula (II):
[(Alk)2-nR"nR,SiO]a-M-O-M-[OSiR,R"n(OAlk)2-n]a (H) wherein
M- is a two-, three-, or four-valent metal; a is 1, 2 or 3; and n is 0 or 1 ;
R', R" are independently the same or different and represent C] -C4 alkyl, C6H5 -, CH2= CH-, and NH2(CH2)X, where x has a value from 2 to 5, and
Alk is a Q-C4 alkyl substituent, or by the following general formula (III):
I
RO-(M-0-)qR
[OSiR'R"n(OAlk)2.n]a (III) wherein
M is a three- or four-valent metal, R represents d -C4 alkyl, q has a value from 2 to 50, a is 1 or 2,
"-" represents -(M-O )q-R, when M is a four-valent metal and a = 1, q' has a value from 2 to 50, and n, R, R", and Alk have the same meanings as defined above.
M may be a divalent metal selected from Zn, Fe (II), and Cu, and n may have the value of 0 or 1.
Also, M may be a trivalent metal selected from Fe (III), Ce, Cr, Sm, and Eu, or a four-valent metal selected from Zr and Ti, and n may have the value 0 or 1.
Similar to a divalent metal, in the case of a trivalent metal, and a four-valent metal, Alk may represent CH3 or C2H5 -, and R1 and R" may have a value of CH3.
A product of partial hydrolysis of the functional metallosiloxane is obtained by mixing the functional metallosiloxane in ambient conditions with the solvent having a given content of water required for obtaining a product of partial hydrolysis.
In the process of partial hydrolysis, a mole ratio of metallosiloxane to water is in the range of 1 : 0.5. Furthermore, metallosiloxanes as starting reagents for products of partial hydrolysis are optional isolated from the reaction mixture.
A solvent used in the process for preparing the partial hydrolysed products is selected from the group consisting of tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, 2-propanol, and 1-butanol.
Functional metallosiloxanes of the present invention are polyfunctional compounds containing in their composition silicon-bonded functional groups as well as a catalytic center. In this regard, they exhibit a broad spectrum of possible applications; in particular, they can be used as crosslinking agents and as curing catalysts in polymer compositions. Their activity in the crosslinking of polymer chains is associated with the presence of reactive functional groups that can interact both with the functional groups of the polymer (i.e., with the basis of the composition) and with each other during hydrolytic condensation. The combination of these processes results in the formation of crosslinked structures. In curing, the catalytic activity of metallosiloxane is demonstrated most clearly when concentration of the metallosiloxane in the composition is low. In this case, the functional groups of the polymer (the basics of the composition) quite effectively condense with each other due to interaction. At that the reaction proceeds with the participation of a metal atom by coordination of the functional groups on such a catalytic center.
The products of partial hydrolysis of functional metallosiloxanes also exhibit a broad spectrum of other possible applications, and, in particular, can be used as crosslinking agents.
The functional metallosiloxanes and products of their partial hydrolysis may be used as crosslinking agents independently or in combinations, as well as components of curing compositions used for curing rubber-based compositions, in particular, on the basis of siloxane rubber.
A curing composition according to the present invention comprises a functional metallosiloxane and/or a product of its partial hydrolysis and a silicate.
A silicate used in the curing composition is a polyethoxysiloxane having linear and branched structures. Data on the production and characteristics of the branched polyethoxysiloxane are given in the article by V.V azakova, E.A. Rebrov, V.D. Myakushev, T.V. Strelkova, A.N. Ozerin, L.A. Ozerina, T.B. Chenskaya, S.S. Sheiko, E. Yu. Sharipov, A.M. Muzafarov, "Silicones and Silicone-Modified Materials", ACS Symposium Book Series 729 (ISSN No. 0097- 6156; 729; Editors S. J. Clarson, et al), February 2000, Chapter 34, pp. 503-515]. Linear polyethoxysiloxane is a commercial sample of ETS-40, the product of Penta® Silicones (Moscow). A content of silicate in the curing composition ranges from 1 to 10 parts by mass per 100 parts by mass of the functional metallosiloxane and/or a product of its partial hydrolysis.
Curable compositions, in which a functional metallosiloxane and/or a product of its partial hydrolysis is used as a crosslinking agent or in which a curing composition of the present invention is used, are based on rubber, preferably based on siloxane rubber. The most accessible are low-molecular-weight polydimethylsiloxane rubbers of different molecular weights (CKTH type)
Type of CKTH Rubber Conventional Viscosity
CKTH-A 90 - 150 sec
CKTH-B 151 - 240 sec
CKTH-B 241 - 600 sec
CKTH-r 601 - 1080 sec
CKTH-A 18000 - 25000 mPa* s CKTH-E 80000 - 120000 mPa* s
CKTH-E1 500 - 1000 mPa* s
According to the present invention, a curable composition based on rubber, preferably, silicone rubber, comprises a rubber, a crosslinking agent, or a curing composition, or the curing catalyst and optionally a filler.
When using the crosslinking agent or a curing composition, the content ranges from 10 to 100 parts by mass per 100 parts by mass of rubber.
When using a curing catalyst, which is a functional metallosiloxane, its content ranges from 0.1 to 1 part by mass per 100 parts by mass of rubber, in particular siloxane rubber.
The filler used in these compositions is selected from known fillers such as zinc oxide, silica, talc, etc.
Curing is carried out by maintaining the composition for 24 hours at ambient conditions, optionally followed by heat treatment at a temperature of 100°C to 200°C for 1 to 2 hours to obtain a cured composition.
Curable compositions obtained according to the present invention may be used for forming coatings, films, and composite materials.
Functional metallosiloxanes and products of their partial hydrolysis obtained according to the present invention are effective as crosslinking agents since they contain in their structure a certain amount of the corresponding metal atoms, and exhibit good solubility in organic solvents and good compatibility with the polymer matrix. Furthermore, they contain in their structure functional groups that are capable of interacting with components of a polymer composition into which they are to be introduced. In addition to the above, use of the functional metallosiloxanes of the present invention as crosslinking agents or catalysts and use of the products of their partial hydrolysis as crosslinking agents in the rubber- based compositions contribute toresult in improving physical, mechanical, and thermal stability characteristics.
The following are examples illustrating the present invention.
Example 1 :
Preparation of diethylate (methyl-diethoxysiloxy) iron
Na + C2H5OH *- C2H5ONa + 1/2 H2
ONa
NaOH
CH3Si(OC2H5)3 * CH3Si(OC2H5)2
- C2H5OH
OC2H5
CH3 : OC2H5
ONa O
FeCl3 + 2 C2H5ONa + CH3Si(OC2H5)2 >· Fe
-3 NaCl c2H50 OC2H5
All operations were performed in an inert atmosphere. Under vigorous stirring, 2.16 g (0.0939 mol) of sodium metal was introduced to 44 g of ethanol (0.956 mol). While maintaining the temperature of the mixture no higher than 25°C, the metallic sodium was completely dissolved within 1 hour, whereby 6.39 g of a solution of sodium ethylate (0.094 mol) in ethanol was produced.
Sodium hydroxide in the amount of 1.84 g (0.046 mol) was introduced under vigorous stirring to 24.60 g (0.138 mol) of methyltriethoxysilane, which was precooled to 10°C. While maintaining the temperature of the mixture no higher than 25°C, the alkali completely dissolved within 1 hour. The resulting ethyl alcohol and excess methyltriethoxysilane were removed in a rotary evaporator with an oil pump under a vacuum of 1 torr and at a temperature of 45 to 60°C. As a result, 7.66 g (97%) of a pasty white mass was obtained.
A mixture solution of 6.39 g (0.094 mol) of sodium ethylate in 56 ml of ethanol and 7.66 g (0.045 mol) of sodium oxymethyl diehtoxysilane in 30 ml of toluene was added dropwise to a suspension of 7.52 g (0.046 mol) of iron chloride (III) in 60 ml of toluene, while the mixture was maintained at approximately 27°C. The reaction mixture was stirred for 3 hours at 40°C until the reaction medium was neutralized. The reaction mixture was separated from the sodium chloride precipitate by centrifugation, and the precipitate was washed with toluene and again centrifuged. The desired product obtained after evaporation [of the solution] was a dark brown pasty mass readily soluble in organic solvents. The yield was 10.04 g (98 %). The elemental analysis showed the following results (%): Si 6.98; C 31.04; H 6.36; and Fe 27.80. Calculated values (%) were the following: Si 12.70; C 27.14; H 5,93; and Fe 25.27.
Example 2:
Partial hydrolysis of diethylate (methyl-diethoxysiloxy) iron A solution of 0.274 g (0.0152 mol) of water in 15 ml of ethanol was added dropwise to a solution of 9 g (0.0305 mol) of (methyl-diethoxysiloxy) iron diethylate in a mixture of toluene and ethanol. The mixture was stirred for 1 hour at room temperature. The desired product obtained after evaporation [of the solution] comprised a dark brown hard brittle mass readily soluble in organic solvents. The yield was 8.36 g (93 %). The elemental analysis showed the following results (%): Si 9,14; C 26,41 ; H 5,59; and Fe 29,39. Calculated values (%) were the following: Si 12,70; C 27,14; H 5,93; and Fe 25,27.
Example 3 :
Preparation of diethylate (methyl-diethoxysiloxy) aluminum
Na + C2H5OH *► C2H5ONa + 1/2 H2
ONa
NaOH
CH3Si(OC2H5)3 ^ CH3Si(OC2H5)2
- C2H5OH
OC2H5
CH3 gj^OC2H5
ONa O
A1C13 + 2 C2H5ONa + CH3Si(OC2H5)2 Al
-3 NaCl C2H50 OC2H5
All operations were performed in an inert atmosphere. Under conditions of vigorous stirring, 0.94 g (0.041 mol) of metallic sodium was introduced to 15.78 g of ethanol (0.343 mol). While maintaining the temperature of the mixture no higher than 30°C, the metallic sodium completely dissolved within 1 hour, whereby 2.79 g of a solution of sodium ethoxide (0.041 mol) in ethanol was produced. Under vigorous stirring conditions, with 0.82 g (0.021 mol) of sodium hydroxide was introduced to 10.97 g (0.062 mol) of methyltriethoxysilane precooled to 10°C. While maintaining the temperature of the mixture no higher than 25°C, the alkali completely dissolved within 30 minutes. The ethanol that was formed in this process and the excess of methyltriethoxysilane were removed in a rotary evaporator with an oil pump under a vacuum of 1 torr and at a temperature in the range of 60°C to 75°C. The product was obtained in the amount of 3.59 g (101%) in the form of a white pasty mass.
The mixed solution prepared from 2.79 g (0.041 mol) of sodium ethylate in 26 ml of ethanol and 3.59 g (0.021 mol) of sodium-oxymethyl-diethoxy silane in 55 mL of toluene was added dropwise to a suspension of 2.74 g (0.021 mol) of aluminum chloride in 20 ml of toluene, while the mixture was maintained at a temperature of approximately 30°C. The reaction mixture was stirred for 4 hours at 40°C until the medium was neutralized. The reaction mixture was separated from the sodium chloride precipitate by centrifugation, and the precipitate was washed with toluene and again centrifuged. The desired product obtained after evaporation [of the solution] comprised a colorless transparent mass readily soluble in organic solvents. The yield was 5.26 g (96 %). The elemental analysis showed the following results (%): C, 35.63; H, 7.64; Si, 12.16; and Al, 12.29. C9H23O5S1AI. Calculated values (%) were the following: C, 40.59; H, 8.70; Si, 10.54; and Al, 10.13.
Example 4:
Partial hydrolysis of diethylate (methyldiethoxysiloxy) aluminum 0.018 g (0.001 mol) of water was introduced to a solution of 0.53 g (0.002mol) of diethylate (methyldiethoxysiloxy) aluminum in toluene and ethanol. The mixture was stirred for 1 hour at room temperature. The desired product obtained after evaporation of the solution comprised a solid, colorless, glassy mass well soluble in organic solvents. The product had a mass of 0.44 g. The structure of the synthesized compounds was determined by elemental analysis and NMR spectroscopy (see Fig. 1). The elemental analysis showed the following results (%): C, 31.47; H, 7.02; Si, 14.16; and Al, 13.67. C5H1304SiAl. Calculated values (%) were the following: C, 31.24; H, 6.82; Si, 14.61 ; and Al, 14.04.
Example 5 :
Preparation of diethylate-bis(methyldiethoxysiloxy) zirconium
All operations were performed in an inert atmosphere. Under conditions of vigorous stirring, 0.52 g (0.022 mol) of metallic sodium was introduced to 10.26 g of ethanol (0.223 mol). While maintaining the temperature of the mixture no higher than 30°C, the metallic sodium completely dissolved within 1 hour, whereby 1.52 g (0.022 mol) of a solution of sodium ethylate in ethanol was obtained.
Under conditions of vigorous stirring, 0.90 g (0.022 mol) of sodium hydroxide was introduced to 1 1.98 g (0.067 mol) of methyltriethoxysilane precooled to 10°C. While maintaining the temperature of the mixture no higher than 25°C, the alkali completely dissolved within 30 minutes. The ethanol formed in this process and the excess of methyltriethoxysilane were removed in a rotary evaporator with an oil pump in a vacuum of 1 torr and at a temperature in the range of 60°C to 75°C. The white pasty product was obtained in an amount of 3.83 g (99 %). A mixture solution of 1.52 g (0.022 mol) of sodium ethylate in 12 ml of ethanol and 3.83 g (0.022 mol) in 40 ml of sodium oxymethyl diethoxysilane in monoglyme was added dropwise to a solution of 2.61 g (0.011 mol) of zirconium chloride in 50 ml monoglyme, while the temperature of the mixture was maintained at approximately 30°C. The reaction mixture was further stirred for 4 hours at 40°C until the reaction medium neutralized. The reaction mixture was then separated from the sodium chloride precipitate by centrifugation, and the precipitate was washed with monoglyme and centrifuged again. The desired product obtained after evaporation [of the monoglyme] comprised a yellowish transparent mass readily soluble in organic solvents. The yield of the product was 3.64 g (68%). The elemental analysis showed the following results (%): C, C, 28.26; H, 6.37; Si, 13.04; and Zr, 22.99. C14H3608Si2Zr. Calculated values (%) were the following: C, 35.04; H, 7.56; Si, 11.71 ; and Zr, 19.01.
Example 6:
Partial hydrolysis of diethylate-bis(methyldiethoxysiloxy) zirconium
A solution of 0.34 g (0.0007 mol) of diethylate-bis(methyldiethoxysiloxy) zirconium in a mixture of monoglyme and ethanol was combined with 0.007 g (0.0004 mol) of water. The mixture was stirred for 1 hour at room temperature. The desired product obtained after evaporation of the solution comprised a solid, yellowish glassy mass well soluble in organic solvents. The product yield was 0.31 g (108%). The structure of the synthesized compounds was determined by elemental analysis and NMR spectroscopy (see Fig. 2). The elemental analysis showed the following results (%): C, 24.43; H, 5.99; Si, 13.77; and Zr, 26.19. C10H26O7Si2Zr. Calculated values (%) were the following: C, 29.60; H, 6.46; Si, 13.85; and Zr, 22.48.
Example 7:
Preparation of films from a composition based on silicone rubber comprising functional metallosiloxane as crosslinking agent
Liquid silicone rubber was mixed at a predetermined ratio (calculation was performed with reference to the mass of the dissolved metallosiloxane) with a solution of a functional metallosiloxane. The obtained homogeneous solution was poured onto a Teflon® substrate so that the layer thickness was ranged from 0.1 to 2 mm. After retaining for 10 hours at room temperature, the mold was placed in a thermostat and was retained for 1 hour at a temperature of 80°C and then for 2 hours at a temperature of 200°C. The substrate was cooled, and the obtained solid colored or colorless transparent film was removed and tested. The ratios of components and test results are shown in Table 2.
Table 2: Ratios of Components and Test Results
Metal, M Metallosilox Liquid σ, MPa/ε, ane siloxane rubber, %*
H Me Ί parts by mass
! OS OEt)2 ί χ
-ΓΜ-(ί—
— — n
x = 1.2, parts by
mass Al 1 CKTH-A(6) 3.6/89
3
2 CKTH-A(6) 4.5/4
3
Fe 1 CKTH-A(6) 3.7/85
3
2 CKTH-A 6.1/51
3
1 CKTH-D 3.2/252
3
1 CKTH-E 2.4/150
3
Zr 1 CKTH-A 2.4/132
3
CKTH-A 3.6/113
2 3
1 CKTH-D 2.0/537
3
1 CKTH-E 2.5/581
3
* σ = rupture strength of the film; ε = elongation
Use of the obtained functional metallosiloxane not only as a crosslinking agent but also as a catalyst for processes of condensation can be illustrated by adding a small amount of the functional metallosiloxane to a composition that— in addition to the silicone rubber— contain a branched or linear ethylsilicate (preparation of the composition is similar to one described in Example 7). In particular, introduction of 5 part by mass of metallosiloxane into a composition that contains 3 parts by mass of the rubber and 1 part by mass of the silicate leads to complete curing of the composition.

Claims

1. A functional metallosiloxane of the following general formula (I): (RO)p-M-[OSiR'R"n(OAlk)2.n]m (I) wherein
M is a two-, three-or four-valent metal; p + m corresponds to the valence of the metal, provided that p and m≠ 0; n is 0 or 1 ;
R represents Cj -C4 alkyl;
R' and R" are independently the same or different and represent Q -C4 alkyl, C6H5-, CH2=CH-, and NH2(CH2)X, where x has a value from 2 to 5; and
Alk is a C 1-C4 alkyl substituent.
2. The functional metallosiloxane according to Claim 1, wherein M represents a divalent metal selected from Zn, Fe (II), and Cu.
3. The functional metallosiloxane according to Claim 1 , wherein M represents a trivalent metal selected from Fe (III), Ce, Cr, Sm, and Eu, or a four- valent metal selected from Zr and Ti.
4. The functional metallosiloxane according to any of Claims 1 to 3, wherein n is 0.
5. The functional metallosiloxane according to any of Claims 1 to 3, wherein n is 1.
6. The functional metallosiloxane according to any of Claims 1 to 3, wherein Alk represents CH3- or C2H5-.
7. The functional metallosiloxane according to any of Claims 1 to 3, wherein R, R' and R" represent CH3-.
8. The functional metallosiloxane according to any of Claims 1 to 3, wherein metallosiloxane is used as the crosslinking agent, a component, a curing composition, or a curing catalyst.
9. A product of partial hydrolysis of the functional metallosiloxane according to Claim 1, the product being represented by the following general formula (II):
[(Alk)2.nR"nR:SiO]a-M-0-M-[OSiR'R"n(OAlk)2-n]a, (II) where M is a two-, three-or four-valent metal; a is 1, 2 or 3; n is 0 or 1;
R' and R" are independently the same or different and represent Ci -C4 alkyl, C6H5-, CH2=CH- and NH2(CH2)X, where x has a value from 2 to 5; and
Alk is a Cj-C4 alkyl substituent; or is represented by the following general formula (III): RO-(M-0-)qR
[OSiR'R"n(OAlk)2-n]a (III)
wherein
M is a three-or four-valent metal;
R represents a C\ -C4 alkyl; q has a value from 2 to 50; a is 1 or 2;
"-" represents -(M-0)q'-R, when M is a four-valent metal and a = 1; q' has a value from 2 to 50; and n, R, R", and Alk have the same meanings as defined above.
10. The product of partial hydrolysis according to Claim 9, wherein M represents a divalent metal selected from Zn, Fe (II), and Cu.
1 1. The product of partial hydrolysis according to Claim 9, wherein M is a trivalent metal selected from Fe (III), Ce, Cr, Sm, and Eu, or a four-valent metal selected from Zr and Ti.
12. The product of partial hydrolysis according to any of Claims 9 to 1 1, wherein n is 0.
13. The product of partial hydrolysis according to any of Claims 9 to 1 1 , wherein n is i.
14. The product of partial hydrolysis according to any of Claims 9 to 11, wherein Alk represents CH3- or C2H5-.
15. The product of partial hydrolysis according to any of Claims 9 to 11, wherein R' and R" represent CH3-.
16. The product of partial hydrolysis according to any of Claims 9 to 11, wherein the product is used as a crosslinking agent or a component of a curing composition.
17. A method of preparing a functional metallosiloxane according to any one of Claims 1 to 8, comprising [the step of] reacting sodium oxy(alkoxy) organosilane of the following general formula (IV):
NaOSiR'R"n(OAlk)2-n
(IV) where n, R', R", Alk, and M are as defined above; with a metal salt of the following general formula: MXb, where M is a two-, three-or four-valent metal, b corresponds to the valence of the metal, and X represents halogen; followed by reaction with sodium alkoxide of the general formula:
AlkONa where Alk represents a Cx - C4 alkyl, and where the process is carried out in an organic solvent.
18. The method according to Claim 17, wherein the process of interaction of sodium oxy(alkoxy) organosilane with the metal salt is carried out simultaneously with the formation of sodium oxy(alkoxy) organosilane from sodium hydroxide and the alkoxysilane of the following general formula (V):
SiR'R"n(OAlk)3.„
(V) where n, R', R", and Alk are the same as defined above.
19. The method of Claim 17, wherein the process of interaction with the sodium alkoxide is carried out simultaneously with the process of its formation from alcohol and sodium.
20. The method of Claim 17, wherein the metal salts are chlorides or bromides.
21. The method of Claim 17, wherein the organic solvent is selected from the group consisting of tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, 2- propanol, and 1-butanol.
22. The method of Claim 17, wherein interaction of the reaction components is carried out at a temperature from -5°C to 50°C, at a mole ratio of AlkONa to NaOSiR'R"n(OAlk)2 -n in the range of 0.1 to 3.9.
23. The method according to any of Claims 17 to 22, wherein the metal salt is selected from salts of a divalent metal selected from Zn, Fe (II), and Cu.
24. The method according to any of Claims 17 to 21, wherein the metal salt is selected from salts of a trivalent metal selected from Fe (III), Cr, Sm, Eu, or a four-valent metal selected from Zr and Ti.
25. The method of Claim 17, wherein the sodium oxy(alkoxy) organosilane comprises sodium oxymethyl diethoxy silane and wherein the metal salt comprises FeCl3.
26. A method for preparing a product of partial hydrolysis as Claimed in Claims 9 to 16, comprising mixing of a functional metallosiloxane in ambient conditions with a solvent having a specified content of water needed for obtaining the product of partial hydrolysis.
27. The method of Claim 26, wherein the solvent is selected from the group consisting of tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, 2-propanol, and 1-butanol.
28. A curing composition comprising:
- a functional metallosiloxane according to any of Claims 1 to 8 and/or a product of partial hydrolysis according to any of Claims 9 to 16, and
- silicate, where the silicate content ranges from 1 to 10 parts by mass per 100 parts by mass of the functional metallosiloxane and/or a product of its partial hydrolysis.
29. A cross-linking agent comprising a functional metallosiloxane according to any of Claims 1 to 8 and/or a product of partial hydrolysis according to any of Claims 9 to 16.
30. A curing catalyst which is a functional metallosiloxane according to any of Claims 1 to 8.
31. Use of a functional metalllosiloxane according to any of claims 1 to 8 as a crosslinking agent.
32. Use of a product of partial hydrolysis product according to any of claims 8 to 16 as a crosslinking agent.
33. Use of a functional metalllosiloxane according to any of claims 1 to 8 as a curing catalyst.
34. A curable composition based on silicone rubber, comprising:
- a silicone rubber;
- a crosslinking agent according to Claim 29 or a curing composition according to Claim 28, or a curing catalyst according to Claim 30; and
- optionally, a filler; where, when the crosslinking agent or a curing composition is used, its content ranges from 10 to 100 parts by mass per 100 parts by mass of the silicone rubber, and when a curing catalyst is used, its content ranges from 0.1 to 1 part by mass per 100 parts by mass of the silicone rubber.
35. A cured composition obtained from a curable composition according to Claim 34 when the latter is retained for 24 hours in ambient conditions, and optionally followed by heat treatment at a temperature of 100°C to 200°C for 1 to 2 hours.
36. A product obtained from the curable composition according to Claim 34, selected from the group consisting of a coating, a film, and a composite material.
37. A coating obtained from the curable composition according to Claim 34.
38. A film obtained from the curable composition according to Claim 34.
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