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WO2023186269A1 - Compositions réticulables à base de composés organosiliciés - Google Patents

Compositions réticulables à base de composés organosiliciés Download PDF

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Publication number
WO2023186269A1
WO2023186269A1 PCT/EP2022/058266 EP2022058266W WO2023186269A1 WO 2023186269 A1 WO2023186269 A1 WO 2023186269A1 EP 2022058266 W EP2022058266 W EP 2022058266W WO 2023186269 A1 WO2023186269 A1 WO 2023186269A1
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Prior art keywords
optionally
formula
compositions according
radicals
siloxanes
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PCT/EP2022/058266
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German (de)
English (en)
Inventor
Marko Prasse
Stephan Rensing
Peter Schoeley
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Wacker Chemie Ag
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Priority to PCT/EP2022/058266 priority Critical patent/WO2023186269A1/fr
Publication of WO2023186269A1 publication Critical patent/WO2023186269A1/fr

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Classifications

    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

Definitions

  • Wa12208-S/Bu Crosslinkable compositions based on organosilicon compounds The invention relates to crosslinkable compositions based on organosilicon compounds, processes for their production and their use.
  • One-component sealing compounds that can be stored in the absence of water and harden to form elastomers when water is added at room temperature with the release of acetic acid are already known. These products are used in large quantities, for example in the construction industry. The basis of these mixtures are polymers that are terminated by silyl groups that carry reactive substituents such as OH groups or hydrolyzable groups such as acetoxy groups.
  • these sealing compounds can contain fillers, plasticizers, crosslinkers, catalysts and various additives.
  • DE-A 102004046179 describes crosslinkable masses based on organosilicon compounds with a controllable modulus using monohydroxy-functional organosilicon compounds. However, these connections can only be created in a targeted manner with great effort.
  • DE-A1102004014216 describes oligomeric siloxanes which were produced from methyltrimethoxysilane or methyltriethoxysilane. However, these compounds cannot be used in crosslinkable masses that release acetic acid through a condensation reaction, since the masses are no longer stable in storage. The production of oligomeric siloxanes containing acetoxy groups is not described.
  • Wa12208-S/Bu 2 The production of oligomeric siloxanes containing acetoxy groups is already known and described many times.
  • EP-A10003285 methyltrichlorosilane, octamethyltetracyclosiloxane and excess acetic acid are reacted in the presence of perfluorobutanesulfonic acid. This creates gaseous HCl.
  • EP-A1 3611215 claims a process for producing siloxanes bearing acetoxy groups from alkoxy-containing siloxanes, acetic anhydride, acetic acid and trifluoromethanesulfonic acid with the elimination of an alcohol.
  • One subject of the invention are crosslinkable compositions that can be produced using (A) organosilicon compounds with at least two OH groups and (B) siloxanes of the formula (II) Wa12208-S/Bu 3 where R can be the same or different and means monovalent, optionally substituted hydrocarbon radicals, R 1 can be the same or different and means monovalent hydrocarbon radicals with 1 to 16 carbon atoms, R 2 can be the same or different and Acyl radicals means that x can be the same or different and is 0 or an integer from 1 to 9 and z is 1 or 2, with the proviso that the sum of all x in formula (II) is greater than 0.
  • R can be the same or different and means monovalent, optionally substituted hydrocarbon radicals
  • R 1 can be the same or different and means monovalent hydrocarbon radicals with 1 to 16 carbon atoms
  • R 2 can be the same or different and Acyl radicals means that x can be the same or different and is 0 or an integer from 1 to 9 and z is
  • radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radical; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as
  • radicals R and R 3 are preferably monovalent hydrocarbon radicals with 1 to 18 carbon atoms, particularly preferably the methyl radical, the vinyl or the phenyl radical, in particular the methyl radical.
  • radicals R 1 are the hydrocarbon radicals given for R with 1 to 16 carbon atoms.
  • the radicals R 1 are preferably monovalent hydrocarbon radicals with 1 to 16 carbon atoms, particularly preferably straight-chain, branched or cyclic hydrocarbon radicals with 1 to 8 hydrocarbon atoms, in particular the methyl radical, the vinyl, the ethyl radical. , the propyl or the phenyl radical.
  • the organosilicon compounds (A) used according to the invention can be all organosilicon compounds with at least two OH groups, which have also previously been used in masses that can be crosslinked by a condensation reaction.
  • the organosilicon compounds (A) used according to the invention are preferably essentially linear, OH-terminated organopolysiloxanes, particularly preferably organopolysiloxanes of the formula HO(SiR 3 2O)nH (I), where Wa12208-S/Bu 5 R 3 can be the same or different and means monovalent, optionally substituted hydrocarbon radicals, and n is an integer from 30 to 2000.
  • radicals R 3 are the examples given for radical R.
  • the radical R 3 independently of one another, is preferably a monovalent hydrocarbon radical with 1 to 18 carbon atoms, particularly preferably the methyl radical, the vinyl or the phenyl radical, in particular the methyl radical.
  • organosilicon compounds (A) are (HO)Me 2 SiO[SiMe 2 O] 30-2000 SiMe 2 (OH) with Me equal to methyl radical.
  • the organosilicon compounds (A) used according to the invention have a viscosity of preferably 50 to 10 6 mPas, particularly preferably 1,000 to 350,000 mPas, in each case at 25 ° C.
  • the organopolysiloxanes (A) are commercially available products or can be produced using methods common in silicon chemistry.
  • the siloxanes (B) used according to the invention are preferably AcO(SiMe2O)1-5SiR 1 (OAc)2, (AcO(SiMe2O)1-5)2SiR 1 (OAc) or AcO(SiMe 2 O) 1-5 SiR 1 (OAc)O(SiMe 2 O) 1-5 SiR 1 (OAc) 2 Wa12208-S/Bu 6 with Me equal to methyl radical, Ac equal to acetyl radical and R 1 equal to straight-chain, branched or cyclic hydrocarbon radicals with 1 to 8 hydrocarbon atoms, the radicals R 1 within the individual compounds having an identical meaning, particularly preferred around AcO(SiMe2O)1-5SiMe(OAc)2, (AcO(SiMe2O)1-5)2SiMe(OAc), AcO(SiMe2O)1-5SiMe(OAc)O(SiMe2O)1-5SiMe(OA
  • the siloxanes (B) used according to the invention have a viscosity of preferably 1 to 100 mPas, particularly preferably 3 to 50 mPas, in each case at 25 ° C.
  • the compositions according to the invention contain component (B) in amounts of preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 8 parts by weight, in particular Wa12208-S/Bu 7 0.3 to 5 parts by weight, each based on 100 parts by weight of component (A).
  • the siloxanes (B) can be prepared using methods common in silicon chemistry, such as equilibration or ring opening of D3.
  • the siloxanes (B) used according to the invention are preferably prepared by equilibration of polydiorganylsiloxanes with triacyloxysilanes under acidic catalysis with halogenated sulfonic acids or from triacyloxysilanes with hexaorganylcyclotrisiloxanes and catalysts such as basic ammonium compounds.
  • a further subject of the invention is a process (process 1) for producing the siloxanes (B) used according to the invention by equilibrating (i) cyclic and/or linear polydiorganylsiloxanes with (ii) triacyloxysilanes under acidic catalysis with (iii ) halogenated sulfonic acids.
  • the siloxanes (i) used according to the invention are preferably cyclic diorganylsiloxanes with 3 to 8 silicon atoms per molecule and/or linear polydiorganylsiloxanes which are terminated with hydroxyl groups, preferably ⁇ , ⁇ -OH, polydiorganylsiloxanes, methyl groups, preferably ⁇ , ⁇ -triorganylsiloxy-terminated polydiorganylsiloxanes, vinyl groups, preferably ⁇ , ⁇ -diorganylvinylsiloxy-terminated polydiorganylsiloxanes, hydrogen atoms, preferably ⁇ , ⁇ -hydrogendiorganylsiloxy-terminated polydiorganylsiloxanes, or acyloxy groups, preferably ⁇ , ⁇ -organyldiacetoxysiloxy group-terminated polydiorganylsiloxanes, terminated are, particularly preferably cyclic dimethylsiloxanes with 3 to 8
  • silanes (ii) used according to the invention are preferably organotriacetoxysilanes.
  • the sulfonic acids (iii) used according to the invention are preferably chlorinated or fluorinated sulfonic acids, such as trichloromethanesulfonic acid, trifluoromethanesulfonic acid or perfluorobutanesulfonic acid, particularly preferably trifluoromethanesulfonic acid.
  • sulfonic acids (iii) are preferably added in amounts of 50 ppm by weight to 2000 ppm by weight, based on the total weight of the reaction mixture.
  • further components such as solvents, can be used in process (1) according to the invention, but this is not preferred.
  • the components used can be mixed with one another in any order.
  • the siloxane (i) is preferably first mixed with the silane (ii) and then sulfonic acid (iii) is added.
  • Wa12208-S/Bu 9 The mixing according to the invention is preferably carried out at the pressure of the surrounding atmosphere, i.e. approximately 900 to 1100 hPa.
  • the process (1) according to the invention is preferably carried out at temperatures in the range from 20 to 120 ° C.
  • the reaction time is preferably 5 minutes to 5 hours.
  • the amount of catalyst, reaction time and reaction temperature are preferably adjusted so that a conversion of 20% to 80% of the equilibration equilibrium is achieved.
  • the equilibration equilibrium is reached when all acyloxy groups are randomly distributed, i.e. preferably continuing the reaction no longer leads to a change in the distribution of the acyloxy groups in the 29 Si NMR.
  • the acidic catalyst (iii) can be neutralized or removed using customary methods. Basic compounds of sodium or potassium are preferably used for neutralization.
  • Process (1) Weakly or strongly basic ion exchangers are preferably used for separation, such as those available under the trade names Purolite A103, Amberlyst A21 or Amberlyst A26.
  • the products obtained by process (1) according to the invention can, if desired, be filtered and/or devolatilized.
  • Another subject of the invention is a process (process 2) for producing the ones used according to the invention Wa12208-S/Bu 10 Siloxanes (B) by ring opening of (iv) hexaorganylcyclotrisiloxanes with (ii) triacyloxysilanes in the presence of (v) basic catalysts.
  • the hexaorganylcyclotrisiloxanes (iv) used according to the invention are preferably hexamethylcyclotrisiloxane.
  • the basic catalysts (v) used according to the invention are preferably ammonium bases, such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium hydroxide or benzyltrimethylammonium hydroxide, strongly basic ion exchange resins with ammonium hydroxide groups, such as those commercially available under the trade name Amberlyst® A26 from Merck, D-Darmstadt, or phosphonium bases, such as tetrabutylphosphonium hydroxide.
  • basic catalysts (v) are preferably added in amounts of 500 ppm by weight to 10,000 ppm by weight, based on the total weight of the reaction mixture.
  • further components such as solvents, can be used in process (2) according to the invention, but this is not preferred.
  • solvents are preferably aprotic solvents, such as paraffins, olefins, halogenated hydrocarbons, aromatics, esters, ethers or acetals.
  • the components used can be mixed with one another in any order.
  • the mixing according to the invention is preferably carried out at the pressure of the surrounding atmosphere, i.e. approximately 900 to 1100 hPa.
  • the process (2) according to the invention is preferably carried out at temperatures in the range from 50 to 150 ° C.
  • the reaction time is preferably 1 hour to 8 hours.
  • the amount of catalyst, reaction time and reaction temperature are preferably adjusted so that no more crystals precipitate after removal of any solvent used and/or cooling to room temperature.
  • the basic catalyst can be neutralized or removed using customary methods.
  • sulfonic acids such as methanesulfonic acid
  • chlorine compounds which can split off hydrogen chloride during hydrolysis, such as chlorosilanes or acid chlorides.
  • Ion exchangers with sulfonic acid groups are preferably used for separation, such as those available under the trade names Purolite CT269 or Amberlyst 15 or Amberlyst 16.
  • Purolite CT269 or Amberlyst 15 or Amberlyst 16.
  • compositions according to the invention can contain silanes (C) of the formula (R 8 O)4-bSiR 9 b (III) and/or their partial hydrolysates, where b is 0, 1 or 2 , preferably 1, is, Wa12208-S/Bu 12 R 8 can be the same or different and means acyl radicals and R 9 can be the same or different and means monovalent hydrocarbon radicals with 1 to 16 carbon atoms.
  • Examples and preferred radicals for radical R 8 are the examples and preferred radicals given above for R 2 .
  • examples and preferred radicals for radical R 9 are the examples and preferred radicals given above for R 1 .
  • the radicals R 8 within component (C) have an identical meaning, which particularly preferably corresponds to the meaning of R 2 in component (B).
  • the partial hydrolysates (C) which may be used can be partial homohydrolysates, ie partial hydrolysates of one type of silane of the formula (III), as well as partial cohydrolysates, ie partial hydrolysates of at least two different types of silanes of the formula (III ).
  • the term partial hydrolysates means products that are formed by hydrolysis and/or condensation. If the component (C) used in the compositions according to the invention is partial hydrolysates of silanes of the formula (III), then those with up to 10 silicon atoms are preferred.
  • component (C) optionally used according to the invention are methyltriacetoxysilane, ethyltriacetoxysilane, n-propyltriacetoxysilane, iso-octyltriacetoxysilane, vinyltriacetoxysilane and phenyltriacetoxysilane, their partial homohydrolysates Wa12208-S/Bu 13 or partial cohydrolysates and mixtures thereof, with methyltriacetoxysilane, ethyltriacetoxysilane and vinyltriacetoxysilane, their partial homohydrolysates or partial cohydrolysates and mixtures thereof being preferred.
  • Component (C) is a commercially available product or can be produced using methods commonly used in silicon chemistry. If the compositions according to the invention contain component (C), these are amounts of preferably 1 to 20 parts by weight, particularly preferably 2 to 16 parts by weight, in particular 3 to 12 parts by weight, in each case based on 100 parts by weight of component (A).
  • the compositions according to the invention preferably contain component (C).
  • the compositions according to the invention can now contain all substances that have previously been used in compositions that can be crosslinked by a condensation reaction, such as, for example, hardening accelerators (D), plasticizers ( E), fillers (F), adhesion promoters (G) and additives (H).
  • hardening accelerators that have previously been used in masses that can be crosslinked by a condensation reaction can be used as hardening accelerators (D).
  • hardening accelerators (D) are titanium compounds, such as tetrabutyl or tetraisopropyl titanate, or titanium chelates, such as bis(ethylacetoacetato)diisobutoxytitanium, or organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate , di-n-butyltin oxide, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin dineodecanoate, dimethyltin oxide, di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-oc- Wa12208-S/Bu 14 tyltin oxide and reaction products of these compounds with alkoxysilanes
  • compositions according to the invention contain curing accelerators (D), these are amounts of preferably 0.001 to 2 parts by weight, particularly preferably 0.01 to 1 part by weight, based in each case on 100 parts by weight of component (A).
  • the compositions according to the invention preferably contain curing accelerators (D).
  • plasticizers (E) which may be used are polydimethylsiloxanes which are liquid at room temperature and end-blocked by trimethylsiloxy groups, in particular with viscosities at 25° C. in the range between 5 and 1000 mPas, as well as high-boiling hydrocarbons, such as paraffin oils or mineral oils from naphthenic and paraffinic units.
  • compositions according to the invention contain component (E), these are amounts of preferably 1 to 50 parts by weight, preferably 1 to 30 parts by weight, based in each case on 100 parts by weight of siloxanes (A).
  • the compositions according to the invention preferably contain plasticizers (E).
  • fillers (F) that may be used are non-reinforcing fillers (F), i.e.
  • fillers with a Wa12208-S/Bu 15 BET surface area of up to 20 m 2 /g such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powder, such as aluminum, titanium, iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate , gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powder, such as polyacrylonitrile powder; reinforcing fillers, i.e.
  • the component (F) optionally used according to the invention is preferably non-reinforcing silicate fillers (F), such as quartz, diatomaceous earth or calcium silicate and/or reinforcing silicate fillers, such as fumed silica or precipitated silica , with fumed silicas being particularly preferred.
  • compositions according to the invention contain fillers (F), these are amounts of preferably 10 to 150 parts by weight, particularly preferably 10 to 130 parts by weight, in particular 10 to 100 parts by weight, in each case based on 100 parts by weight of organopolysiloxanes (A).
  • the compositions according to the invention preferably contain filler (F).
  • the adhesion promoters (G) optionally used in the compositions according to the invention are silanes and organopolysiloxanes with functional groups, such as those with glycidoxypropyl, aminopropyl, aminoethylaminepropyl, ureidopropyl, tert-butoxy or methacryloxypropyl radicals .
  • adhesion promoter (G) can be used. Wa12208-S/Bu 16 can be omitted.
  • the component (G) optionally used according to the invention is preferably di-tert-butoxydiacetoxysilane, (3-glycidoxypropyl)trimethoxysilane or (3-glycidoxypropyl)triethoxysilane, their partial homohydrolysates or partial cohydrolysates and mixtures thereof , with di-tert-butoxydiacetoxysilane being particularly preferred.
  • Component (G) is a commercially available product or can be produced using methods common in silicon chemistry.
  • compositions according to the invention contain component (G), these are amounts of preferably 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based in each case on 100 parts by weight of organopolysiloxanes (A).
  • the compositions according to the invention preferably contain component (G).
  • additives (H) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive soot, flame-repellent agents, light stabilizers, biocides such as fungicides, bactericides and acaricides, cell-producing agents, for example azodicar- bonamide, heat stabilizers, co-catalysts, such as Lewis and Brönsted acids, for example sulfonic acids, phosphoric acids, phosphoric acid esters, phosphonic acids and phosphonic acid esters, thixotropic agents, such as polyethylene glycol terminated with OH on one or both sides, agents for further regulating the modulus such as polydimethylsiloxanes an OH end group, as well as any siloxanes that are different from components (A), (B), (C) and (G).
  • additives (H) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive soot
  • compositions according to the invention contain additives (H), these are amounts of preferably 0.1 to 20 parts by weight, particularly preferably 0.1 to 15 parts by weight, in particular 0.1 to 10 parts by weight, in each case based on 100 parts by weight of organopolysiloxanes (A).
  • additives H
  • the compositions according to the invention preferably contain component (H).
  • the individual components of the compositions according to the invention can each be one type of such component or a mixture of at least two different types of such components.
  • compositions according to the invention are preferably those which can be prepared using (A) organopolysiloxanes of the formula (I), (B) siloxanes of the formula (II), optionally (C) silanes of the formula (III) and/or their Partial hydrolysates, optionally (D) hardening accelerators, optionally (E) plasticizers, optionally (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
  • compositions according to the invention are particularly preferably those which can be prepared using (A) organopolysiloxanes of the formula (I), (B) siloxanes of the formula (II), (C) silanes of the formula (III) and/or their partial hydrolysates, optionally (D) hardening accelerators, optionally (E) plasticizers, optionally (F) fillers, optionally (G) adhesion promoters and Wa12208-S/Bu 18 optionally (H) additives.
  • compositions according to the invention are those which can be prepared using (A) organopolysiloxanes of the formula (I), (B) siloxanes of the formula (II) with R 2 equal to acetyl radical, (C) silanes of the formula (III) and/or their partial hydrolysates, (D) hardening accelerators, optionally (E) plasticizers, optionally (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
  • compositions according to the invention are those which can be prepared using (A) organopolysiloxanes of the formula (I), (B) siloxanes of the formula (II) with R 2 equal to an acetyl radical, (C) silanes of the formula ( III) and/or their partial hydrolysates, (D) hardening accelerators, optionally (E) plasticizers, (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
  • the compositions according to the invention are those which can be prepared using (A) organopolysiloxanes of the formula (I), (B) siloxanes of the formula (II) with R 2 equal to acetyl, (C) silanes of Formula (III) and/or their partial hydrolysates, (D) hardening accelerators, (E) plasticizers, Wa12208-S/Bu 19 (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
  • the compositions according to the invention preferably contain no other components apart from components (A) to (H).
  • the compositions according to the invention are preferably viscous to pasty masses.
  • compositions according to the invention can be mixed together in any order.
  • This mixing can take place at room temperature and the pressure of the surrounding atmosphere, i.e. around 900 to 1100 hPa. If desired, this mixing can also take place at higher temperatures, for example at temperatures in the range from 35 to 135 ° C. Furthermore, it is possible to mix temporarily or continuously under reduced pressure, such as at 30 to 500 hPa absolute pressure, in order to remove volatile compounds or air.
  • the mixing according to the invention preferably takes place with the greatest possible exclusion of water, ie using raw materials which have a water content of preferably less than 10,000 mg/kg, preferably less than 5,000 mg/kg, in particular less than 1,000 mg/kg. kg.
  • the pastes are filled into commercially available moisture-tight containers, such as cartridges, tubular bags, buckets and barrels. Wa12208-S/Bu 20
  • the components (A), (B), optionally (C) and (E) are first mixed together, then optionally fillers (F) are added and finally, if necessary, further components ( D), (G) and (H) are added, with the temperature before bottling not exceeding 60°C.
  • a further subject of the invention is a process for producing the compositions according to the invention by mixing the individual components.
  • the process according to the invention can be carried out continuously, discontinuously or semi-continuously according to known processes and using known apparatus.
  • the compositions according to the invention or produced according to the invention can be stored in the absence of moisture and can be crosslinked if moisture enters.
  • the usual water content of the air is sufficient for crosslinking the compositions according to the invention.
  • Crosslinking of the compositions according to the invention preferably takes place at room temperature. If desired, it can also be carried out at temperatures higher or lower than room temperature, for example at -5° to 15°C or at 30°C to 50°C and/or using concentrations of water that exceed the normal water content of the air.
  • the crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, i.e. approximately 900 to 1100 hPa.
  • Another subject of the present invention are Wa12208-S/Bu 21 shaped bodies, produced by crosslinking the compositions according to the invention.
  • the shaped bodies according to the invention have a tension at 100% elongation of preferably less than 0.4 MPa.
  • the compositions according to the invention can be used for all purposes for which masses which can be stored in the absence of water and which crosslink to resins or elastomers when water is added at room temperature can be used.
  • compositions according to the invention are therefore excellently suitable, for example, as sealing compounds for joints, including vertical joints and similar empty spaces of, for example, 10 to 40 mm clear width, for example of buildings, land, water and aircraft, or as adhesives or cementing compounds, e.g. in window construction or in the production of showcases, as well as, for example, for the production of protective coatings, including those for surfaces that are constantly exposed to fresh or sea water or coatings that prevent sliding or of rubber-elastic molded bodies.
  • the compositions according to the invention have the advantage that they are easy to prepare and are characterized by very high storage stability. Furthermore, the compositions according to the invention have the advantage that they are very easy to handle in use and have excellent processing properties in a variety of applications.
  • the crosslinkable compositions according to the invention have the advantage that the modulus can be specifically adjusted by the proportion of component (B) without influencing the rheology of the masses.
  • the crosslinkable compositions according to the invention have the advantage that they remain homogeneous during storage, especially at temperatures below 0 ° C, and no components crystallize out.
  • the crosslinkable compositions according to the invention have the advantage that they adhere very well to a variety of substrates.
  • the compositions according to the invention have the advantage that in the cured state they achieve high tear resistance of the cured vulcanizates.
  • the compositions according to the invention have the advantage that in the hardened state, moldings according to ISO 8340 reliably pass the tests according to ISO 11600 in class 25.
  • the crosslinkable compositions according to the invention have the advantage that they are very economical in terms of the materials used.
  • all viscosity information relates to a temperature of 25 ° C. Unless otherwise stated, the examples below are carried out at a pressure of the surrounding atmosphere, i.e. approximately 1000 hPa, and at room temperature, i.e. approximately 23° C., or at a temperature that occurs when the reactants are combined at room temperature. temperature without additional heating or cooling, as well Wa12208-S/Bu 23 was carried out at a relative humidity of around 50%. Furthermore, unless otherwise stated, all parts and percentages refer to weight.
  • the tensile strength, elongation at break and stress at 100% elongation are determined according to ISO 8339 (Method A).
  • the hardness is determined in accordance with ISO 868. Abbreviations are used below: Me for methyl radical, Et for ethyl radical and iOct for 2,2,4-trimethylpentyl radical.
  • Acetoxy crosslinker V1 consists of 3% di-tert-butoxydiacetoxysilane and 97% of an oligomer produced by total hydrolysis and condensation of a mixture of methyltriacetoxysilane and ethyltriacetoxysilane with a molar ratio of methyl to ethyl groups of 3 to 7 and a content of SiO2 of 28.7% by weight.
  • MeSi(OAc)3 methyltriacetoxysilane
  • the composition of the mixture was determined using 29-Si-NMR spectroscopy.
  • the mixture contained 2.0% by weight of Me2Si(OAc)2 and 98% by weight of an oligomer mixture with the average composition of [MeSi(OAc)2O1/2]0.02MeSi(OAc)O2/2]0.14[ MeSiO3/2]0.10 [Me2SiO2/2]0.39[Me2Si(OAc)O1/2]0.35.
  • EtSi(OAc)3 ethyltriacetoxysilane
  • the composition of the mixture was determined using 29-Si-NMR spectroscopy.
  • the mixture contained 7% by weight of (Me2SiO)3 and 93% by weight of an oligomer mixture with the average composition of [EtSi(OAc)2O1/2]0.13EtSi(OAc)O2/2]0.15[Me2SiO2/2 ]0.44- [Me 2 Si(OAc)O 1/2 ] 0.28 .
  • the mixture contained 1.5% by weight of (Me 2 SiO) 4 , 0.5% by weight of Me 2 Si(OAc) 2 and 98% by weight of an oligomer mixture with the average composition of [Me2SiO2/2]0, 76[Me2Si(OAc)O1/2]0.24.
  • V2 Production of an oligomer mixture B5 110 g (1.5 mol D units) of a double-sided hydroxy-terminated polydimethylsiloxane with a visco
  • Comparative Example 3 1400 g of a linear polydimethylsiloxane with hydroxydimethylsilyl end groups and a viscosity of 80,000 mPa s, 600 g of a trimethylsilyl-terminated linear polydimethylsiloxane on both sides with a viscosity of 1000 mPa s were mixed with 104 g of acetoxy crosslinker V1 mixed together in a planetary mixer and stirred for 5 minutes.
  • the approach is then homogeneously mixed in with 240 g of pyrogenic hydrophilic silica with a specific surface area of 150 m2/g, 1.3 g of a tin catalyst, which is prepared by mixing 0.26 kg of di-n-butyltin diacetate with 32 kg of a trimethylsilyl-terminated linear polydimethylsiloxane on both sides with a viscosity of 100 mPa s, and 5 g of 3-glycidoxypropyltrimethoxysilane and stirred for a further 5 minutes under a reduced pressure of 200 mbar. The resulting mixture was then filled into moisture-tight containers.
  • a tin catalyst which is prepared by mixing 0.26 kg of di-n-butyltin diacetate with 32 kg of a trimethylsilyl-terminated linear polydimethylsiloxane on both sides with a viscosity of 100 mPa s, and 5 g of 3-glycidoxypropyltri
  • Comparative Example 4 (V4) The procedure described in Comparative Example 3 was repeated with the modification that 20 g of oligomer mixture B4 was added together with the acetoxy crosslinker V120. The resulting mixture was processed as described in Comparative Example 3. The results can be found in Table 1. Table 1:

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Abstract

L'invention concerne des compositions réticulables à base de composés organosiliciés pouvant être produits en utilisant (A) des composés organosiliciés ayant au moins deux groupes OH et (B) des siloxanes de formule (II), les radicaux et les indices ayant les significations indiquées dans la revendication 1. L'invention concerne également leur procédé de production et leur utilisation.
PCT/EP2022/058266 2022-03-29 2022-03-29 Compositions réticulables à base de composés organosiliciés WO2023186269A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1218446B (de) * 1963-08-07 1966-06-08 Union Carbide Corp Verfahren zur Herstellung von Organosiloxanen mit endstaendigen Acyloxygruppen
DE102004014216A1 (de) 2004-03-23 2005-10-13 Wacker-Chemie Gmbh Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
EP1640416A1 (fr) * 2004-09-23 2006-03-29 Wacker Chemie AG Masses réticulables a base des composés d'organosilicium
DE102012203273A1 (de) * 2012-03-01 2013-09-05 Wacker Chemie Ag Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
WO2016120106A1 (fr) * 2015-01-28 2016-08-04 Wacker Chemie Ag Matières à base d'organopolysiloxane réticulables par réaction de condensation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1218446B (de) * 1963-08-07 1966-06-08 Union Carbide Corp Verfahren zur Herstellung von Organosiloxanen mit endstaendigen Acyloxygruppen
DE102004014216A1 (de) 2004-03-23 2005-10-13 Wacker-Chemie Gmbh Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
EP1640416A1 (fr) * 2004-09-23 2006-03-29 Wacker Chemie AG Masses réticulables a base des composés d'organosilicium
DE102004046179A1 (de) 2004-09-23 2006-03-30 Wacker Chemie Ag Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
DE102012203273A1 (de) * 2012-03-01 2013-09-05 Wacker Chemie Ag Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
WO2016120106A1 (fr) * 2015-01-28 2016-08-04 Wacker Chemie Ag Matières à base d'organopolysiloxane réticulables par réaction de condensation

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