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EP1694773A2 - Cross-linkable products based on organosilicon compounds - Google Patents

Cross-linkable products based on organosilicon compounds

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Publication number
EP1694773A2
EP1694773A2 EP04803981A EP04803981A EP1694773A2 EP 1694773 A2 EP1694773 A2 EP 1694773A2 EP 04803981 A EP04803981 A EP 04803981A EP 04803981 A EP04803981 A EP 04803981A EP 1694773 A2 EP1694773 A2 EP 1694773A2
Authority
EP
European Patent Office
Prior art keywords
radical
optionally
radicals
organosilicon compounds
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04803981A
Other languages
German (de)
French (fr)
Inventor
Uwe Scheim
Christian Ochs
Gabriele Dineiger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP1694773A2 publication Critical patent/EP1694773A2/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • 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
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/34—Filling pastes
    • 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
    • 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
    • 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
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition

Definitions

  • the invention relates to crosslinkable compositions based on organosilicon compounds with biostatic properties and to a process for their production and their use.
  • One-component sealing compounds which are storable with the exclusion of water and which vulcanize to elastomers when water is admitted at room temperature are known. These products are used in large quantities, for example in the construction industry. Especially in environments with high air humidity, such as in bathrooms, kitchens, but also tropical regions, for example, the surface of the sealants easily forms an overgrowth with organisms such as fungi or algae. In order to prevent this, biocides such as fungicides have been added to the sealants to prevent fouling.
  • fungicides used in sealing compounds are methylbenzimidazol-2-ylcarbamate (carbendazim), 10, 10'-oxy-bisphenoxarsin, 2- (4-thiazolyl) -benzimidazole, N-octyl-4-isothiazolin-3-one, 4 , 5-dichloro-2-n-octyl-4-isothiazolin-3-one, diiodomethyl-p-tolylsulfone (Amical, cf. e.g. EP 34 877 A), triazolyl compounds such as tebuconazole in combination with silver-containing zeolites (cf.
  • the invention relates to crosslinkable compositions based on organosilicon compounds, characterized in that they contain organosilicon compounds with quaternary ammonium groups.
  • the crosslinkable compositions are preferably crosslinkable compositions by means of a condensation reaction.
  • condensation reaction is also intended to include a possibly preceding hydrolysis step.
  • compositions according to the invention are particularly preferably those comprising (A) organosilicon compound having at least two condensable groups, (B) organosilicon compound having at least one unit of the formula -SiR 2 2 -R 4 -N + R 3 2 -R 4 -SiR 2 2 - • X " (II),
  • R 2 can be the same or different and has a meaning given for R below
  • R 3 can be the same or different and represents a monovalent, optionally substituted hydrocarbon radical or can be part of a bridging alkylene radical
  • X- represents an organic or inorganic anion
  • R 4 represents a divalent, optionally substituted carbonic acid residue which can be interrupted by heteroatoms, and optionally
  • (C) crosslinker (C) crosslinker.
  • condensable radicals should also be understood to mean those radicals which also include a possibly preceding hydrolysis step.
  • the condensable groups which the organosilicon compounds used which are involved in the crosslinking reaction can have can be any groups, such as hydroxyl, acetoxy, oximato and organyloxy groups, in particular alkoxy radicals, such as ethoxy radicals, alkoxyethoxy radicals and methoxy radicals.
  • the organosilicon compounds (B) used according to the invention can be any organosilicon compounds with at least one radical of the formula (II), which are both pure siloxanes, ie ⁇ Si-O-Si ⁇ structures, and silcarbanes, thus ⁇ Si-R'-Si ⁇ structures with R 'can be a divalent, optionally substituted or interrupted by hetero-hydrocarbon radical or any copolymers containing organosilicon groups.
  • formula (II) are both pure siloxanes, ie ⁇ Si-O-Si ⁇ structures, and silcarbanes, thus ⁇ Si-R'-Si ⁇ structures with R 'can be a divalent, optionally substituted or interrupted by hetero-hydrocarbon radical or any copolymers containing organosilicon groups.
  • the organosilicon compounds (A) used according to the invention can be all organosilicon compounds with at least two condensable groups which have also been used to date in compositions which can be crosslinked by the condensation reaction. These can be both pure siloxanes, ie ⁇ Si-O-Si ⁇ structures, and silcarbanes, i.e. ⁇ Si-R '' - Si ⁇ structures with R '' equal to a divalent, optionally substituted or with heteroatoms interrupted hydrocarbon radical or any copolymers having organosilicon groups.
  • the organosilicon compounds (A) used according to the invention are preferably those containing units of the formula
  • R can be the same or different and means optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms,
  • R 1 can be the same or different and means hydrogen atom or monovalent, optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms
  • Y can be the same or different and halogen atom, pseudohalogen radical, Si-N-bonded amine radicals, amide radicals, Oxime radicals, amine oxy radicals and acyloxy radicals means, a is 0, 1, 2 or 3, preferably 1 or 2, b is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0, and c is 0, 1, 2 or 3, preferably 0 or 1, particularly preferably 0, with the proviso that the sum of a + b + c is less than or equal to 4 and at least two condensable radicals (OR 1 ) are present per molecule.
  • the sum a + b + c is preferably less than or equal to 3.
  • the radical R is preferably monovalent hydrocarbon radicals having 1 to 18 carbon atoms, which may optionally contain halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or (poly) glycol residues are substituted, the latter being composed of oxyethylene and / or oxypropylene units, particularly preferably alkyl radicals having 1 to 12 carbon atoms, in particular the methyl radical.
  • the radical R can also be divalent radicals which, for example, connect two silyl groups to one another.
  • radicals R are alkyl radicals, such as the 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 residues, such as the n-heptyl residue; 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 the
  • substituted radicals R are methoxyethyl, ethoxyethyl and the ethoxyethoxyethyl radical.
  • divalent radicals R are polyisobutylene diyl radicals and propanediyl-terminated polypropylene glycol radicals.
  • radicals R 1 are the monovalent radicals indicated for R.
  • the radical R 1 is preferably a hydrogen atom or alkyl radicals having 1 to 12 carbon atoms, particularly preferably a hydrogen atom, methyl or ethyl radical, in particular a hydrogen atom.
  • radical Y examples are acetoxy, dirnethylamino, cyclohexylamino and methylethylketoximo radical, the acetoxy radical being preferred.
  • organosilicon compounds (A) used according to the invention are particularly preferably those of the formula
  • R and R 1 have one of the meanings given above, e is 30 to 3000 and f is 1 or 2.
  • f is 2 if R 1 is hydrogen and f is 1 if R 1 is hydrogen.
  • organosilicon compounds (A) are (MeO) 2 MeSiO [SiMe 2 0] 200 _ 2000 SiMe (OMe) 2 ,
  • the organosilicon compounds (A) used according to the invention have a viscosity of preferably 100 to 10 6 Pas, particularly preferably 10 3 to 350 000 mPas, in each case at 25 ° C.
  • organosilicon compounds (A) are commercially available products or can be prepared by methods customary in silicon chemistry.
  • radicals R 2 are the one-valent examples given for radical R.
  • the radical R 2 is preferably hydrocarbon radicals having 1 to 18 carbon atoms, which are optionally substituted by halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or (poly) glycol radicals, the latter consisting of oxyethylene and / or oxypropyl radicals units are built up, particularly preferably around alkyl radicals with 1 to 12 carbon atoms, in particular around the methyl radical.
  • radicals R 3 are the monovalent examples given for radical R as well as divalent optionally substituted hydrocarbon radicals having 1 to 30 carbon atoms.
  • the radical R 3 is preferably hydrocarbon radicals having 1 to 8 carbon atoms, particularly preferably alkyl radicals having 1 to 6 carbon atoms and benzyl radicals.
  • the radical R 3 can also be a divalent radical derived therefrom, so that for example two radicals R 3 form a ring with the nitrogen atom.
  • anion X examples include organic anions, such as carboxylate ions, enolate ions and sulfonate ions, as well as inorganic anionic such as halide ions such as fluoride ions, chloride ions, bromide ions and iodide ions, and sulfate ions.
  • organic anions such as carboxylate ions, enolate ions and sulfonate ions
  • inorganic anionic such as halide ions such as fluoride ions, chloride ions, bromide ions and iodide ions, and sulfate ions.
  • Anion X ′′ is preferably carboxylate ion and halide ion, particularly preferably chloride ion and acetate ion.
  • radical R 4 are divalent linear, cyclic or branched, saturated or unsaturated hydrocarbon radicals which are interrupted once or several times by oxygen atoms, like all alkylene radicals, arylene radicals,
  • the radical R 4 is preferably alkylene radicals and - (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -, particularly preferably around - (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -.
  • the organosilicon compounds (B) used according to the invention are preferably those of the formula
  • D 1 represents a hydrogen atom, hydroxyl radical, halide radical, a radical -NR * 2 or a monovalent organic radical, where R * can be the same or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical and the radical -NR * 2 also as ammonium - salt may be present, and
  • D 2 is a group of the formula - (OSiR 2 2 ) g -R 4 k -D 1 means with R 2 , R 3 , D 1 , X ⁇ and R 4 equal to one of the meanings given above, the two radicals D 1 in each polymer molecule of formula (III) may be the same or different, and d is an integer from 1 to 200, h is 0 or 1, k is 0 or 1, g is a number from 0 to 1000 and n is an integer Number is from 1 to 50.
  • Examples of D 1 equal to halide are -Cl and -Br and for -NR * 2 the -N (CH 3 ) 2 -rest.
  • the organosilicon compounds (B) used according to the invention are particularly preferably polymers of the formula (III) where R 4 is alkylene radicals having at least 4 carbon atoms and at least one hydroxyl group, - (CH 2 ) 3 OCH 2 -CH (OH) - CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -, particularly preferably around - (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -.
  • Examples of the organosilicon compounds (B) used according to the invention are
  • D 1 Cl
  • D 2 -OSi (CH 3 ) 2 (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N (CH 3 ) 2 and n approx. 20,
  • D 1 (CH 3 ) 2 N-
  • D 2 - (OSi (CH 3 ) 2 ) g (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N (CH 3 ) 2
  • n approx. 20
  • the organosilicon compounds (B) used according to the invention have a viscosity of preferably 10 4 to 10 8 mPas, particularly preferably 10 5 to 5 * 10 7 mPas, in each case at 25 ° C.
  • organosilicon compounds (B) used according to the invention are commercially available products or can be prepared by known processes, for example by reacting the corresponding epoxy-functional silanes and / or siloxanes with dialkylammonium salts such as, for example, dimethylammonium chloride or by reacting the corresponding amino compounds with alkyl halides.
  • crosslinking agents (C) optionally used in the compositions according to the invention can be any, previously known crosslinking agents with at least three condensable radicals, such as, for example, silanes or siloxanes with at least three organyloxy groups.
  • crosslinking agents (C) optionally used in the compositions according to the invention are preferably organosilicon compounds of the formula
  • R 5 can be the same or different and means monovalent, optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms, R 5 can be the same or different and has the meaning given above for R 1 ,
  • Z can be the same or different and has a meaning given for Y, k is 0, 1, 2, 3 or 4, preferably 2 or 3, particularly preferably 3, and
  • the partial hydrolyzates can be partial homohydrolysates, i.e. Partial hydrolyzates of some kind of organosilicon compound of formula (V) as well as partial hydrolyzates, i.e. Partial hydrolysates of at least two different types of organosilicon compounds of the formula (V).
  • crosslinking agents (C) used in the compositions according to the invention are partial hydrolysates of organosilicon compounds of the formula (V), preference is given to those having up to 6 silicon atoms.
  • radical R 5 examples are the examples mentioned above for radical R 1 .
  • the radical R 6 is preferably a hydrogen atom and alkyl radicals, particularly preferably a hydrogen atom and alkyl radicals having 1 to 4 carbon atoms, in particular a hydrogen atom, the methyl and the ethyl radical.
  • radical R 5 are the monovalent examples mentioned above for radical R, hydrocarbon radicals having 1 to 12 carbon atoms being preferred and the methyl and vinyl radicals being particularly preferred.
  • Z are the examples given for Y, preference being given to acetooxy radicals and methylethylketoximo radicals.
  • crosslinking agents (C) optionally used in the compositions according to the invention are particularly preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysimylililililtrilyltrimyloxysilane, phenyltriethoxysimylilililililililililililililililtrilyltrimethoxysilane, phenyltriethoxysimylilililililililililililtrilyltrimethoxysilane, phenyltriethoxysimylilililililililililtrilyltrimethoxysilane, phenyltriethoxysimyliloxililililtrilyltriloxysilane, phenyltri
  • crosslinking agents (C) optionally used in the compositions according to the invention are commercially available products or can be prepared by processes known in silicon chemistry.
  • compositions according to the invention contain crosslinking agents (C), the amounts are preferably 0.01 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, in particular 1.0 to 5.0 parts by weight, in each case based on 100 parts by weight of organopolysiloxane ( A).
  • compositions according to the invention can now contain all other substances which have also been used in compositions which can be crosslinked by the condensation reaction, such as, for example, gates (D), plasticizers (E), fillers (F), adhesion promoters (G) and additives (H).
  • catalysts (D) are the previously known titanium compounds and organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n-butyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin oxide and reaction products of these compounds with alkoxoxysilanesilane such as tetraoxysilanes , with di-n-butyltin diacetate and dibutyltin oxide in tetraethylsilicate hydrolyzate being preferred and di-n-butyltin oxide in tetraethylsilicate hydrolyzate being particularly preferred.
  • organic tin compounds such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n-butyltin oxide, dioctyltin diacetate
  • compositions according to the invention contain catalyst (D), they are amounts of preferably 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, in each case based on 100 parts by weight of component (A).
  • plasticizers (E) are dimethylpolysiloxanes which are liquid at room temperature and are endblocked by trimethylsiloxy groups, in particular with viscosities at 25 ° C. in the range between 50 and 1000 mPas, and high-boiling hydrocarbons, such as paraffin oils or mineral oils consisting of naphthenic and paraffinic Units.
  • compositions according to the invention contain plasticizers (E) in amounts of preferably 0 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, in particular 20 to 100 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A).
  • fillers (F) are non-reinforcing fillers, ie fillers with a BET surface area of up to 50 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders, 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, ie fillers with a BET surface area of more than 50 m 2 / g, such as pyrogenically prepared silica, precipitated silica, precipitated chalk, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides having a large BET surface area; fibrous fillers such as asbestos and plastic fibers.
  • BET surface area such as quartz, diatomaceous
  • fillers mentioned can be rendered hydrophobic, for example by treatment with organosilanes or organosiloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy groups. If fillers (E) are used, they are preferably hydrophilic fumed silica and precipitated or ground calcium carbonate.
  • compositions according to the invention contain fillers (F) in amounts of preferably 0 to 300 parts by weight, particularly preferably 1 to 200 parts by weight, in particular 5 to 200 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A).
  • adhesion promoters (G) used in the compositions according to the invention are silanes and organopolysiloxanes with functional groups, such as, for example, those with glycidoxypropyl or methacryloxypropyl radicals and tetraalkoxysilanes.
  • compositions according to the invention contain adhesion promoters (G) in amounts of preferably 0 to 50 parts by weight, particularly preferably 1 to 20 parts by weight, in particular 1 to 10 parts by weight parts by weight, each based on 100 parts by weight of organopolysiloxane (A).
  • additives (H) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive carbon black, flame retardants, light stabilizers and agents for prolonging the skin formation time, such as silanes with a SiC-bound mer - captoalkyl radical, cell-producing agents, for example Azodicarbonamide, heat stabilizers and thixotropic agents, such as, for example, phosphoric acid esters, and organic solvents, such as alkylates.
  • additives (H) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive carbon black, flame retardants, light stabilizers and agents for prolonging the skin formation time, such as silanes with a SiC-bound mer - captoalkyl radical, cell-producing agents, for example Azodicarbonamide, heat stabilizers and thixotropic agents, such as, for example, phosphoric acid esters, and organic solvents, such as al
  • compositions according to the invention contain additives (H) in amounts of preferably 0 to 100 parts by weight, particularly preferably 0 to 30 parts by weight, in particular 0 to 10 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A).
  • compositions according to the invention are particularly preferably those which consist of
  • (D) catalyst optionally (E) plasticizer, optionally (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
  • compositions according to the invention all of the constituents can be mixed with one another in any order. This mixing can take place at room temperature and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. If desired, this mixing can also take place at higher temperatures, e.g. at temperatures in the range of 35 ° C to 135 ° C.
  • compositions according to the invention can each be a type of such constituent or a mixture of at least two different types of such constituents.
  • compositions according to the invention are preferably crosslinked at room temperature. If desired, it can also be used at temperatures higher or lower than room temperature, e.g. at -5 ° to 15 ° C or at 30 ° to 50 ° C and / or by means of concentrations of water exceeding 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.
  • the present invention furthermore relates to moldings produced by crosslinking the compositions according to the invention.
  • the compositions according to the invention can be used for all purposes for which compositions which can be stored with the exclusion of water and which crosslink to form elastomers when water is admitted at room temperature can be used.
  • compositions of the invention are therefore extremely suitable, for example, as sealing compounds for joints, including vertical joints, and similar empty spaces, e.g. 10 to 40 mm clear width, e.g. of buildings, land, water and aircraft, or as adhesives or cementing compounds, e.g. in window construction or in the production of aquariums or showcases, as well as e.g. for the production of protective coatings, including those surfaces which are exposed to the constant action of fresh or sea water, or coatings which prevent sliding, or of rubber-elastic molded articles, and for the insulation of electrical or electronic devices.
  • sealing compounds for joints including vertical joints, and similar empty spaces, e.g. 10 to 40 mm clear width, e.g. of buildings, land, water and aircraft, or as adhesives or cementing compounds, e.g. in window construction or in the production of aquariums or showcases, as well as e.g. for the production of protective coatings, including those surfaces which are exposed to the constant action of fresh or sea water, or coatings which prevent sliding, or of
  • compositions of the invention have the advantage that they are easy to manufacture and have a biocidal action over a long period of time.
  • compositions according to the invention have the advantage that the tendency to discolour both the not yet cured composition and the cured molded articles is extremely low due to the biocidal treatment.
  • crosslinkable compositions according to the invention have the advantage that they are distinguished by a very high storage stability and a high crosslinking rate.
  • Test specimens according to DIN EN ISO 846 are produced from the vulcanizate plates thus produced and tested according to method B as described in the standard. The results are shown in Table 1.
  • Test specimens are produced from the mass obtained in this way as described in Example 1 and tested in accordance with DIN EN ISO 846. The results are shown in Table 1.
  • Example 1 The procedure described in Example 1 is repeated with the modification that twice the amount of the polyquaternary polysiloxane has been used.
  • Test specimens are produced from the mass obtained in this way as described in Example 1 and tested in accordance with DIN EN ISO 846. The results are shown in Table 1.
  • Example 4 233 g of dimethylammonium chloride were dissolved in 1700 ml of water. 2238 g of a polysiloxane consisting of (3-glycidoxypropyl) dimethylsiloxy and dimethylsiloxy units with an average of 8 silicon atoms and an epoxy group content of 2.4 mmol / g are added to the solution, and the mixture is heated under reflux with thorough stirring , The reaction mixture was stirred for 6 hours at 105-110 ° C, the reaction mixture changing from colorless cloudy to clear yellow. The solvent was then removed in vacuo at 120 ° C. The reaction product was a dark yellow, highly viscous oil with a viscosity of approx. 6 * 10 6 mPas. The IH-NMR spectroscopic examination confirmed the formation of a polyquaternary polysiloxane with about 30 to 35 repetition units on average according to the formula
  • 35 g of the polyquaternary polysiloxane thus produced 1400 g of an, ⁇ -dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas, 600 g of a polydimethylsiloxane with -OSi (CH 3 ) 3 end groups and a viscosity of 100 mPas, 90 g
  • Ethyltriacetoxysilane and 190 g of a pyrogenic hydrophilic silica with a specific surface area of 150 m 2 / g were mixed homogeneously in vacuo in a planetary mixer. Then 0.5 g of dibutyltin diacetate was added and homogenized again for 5 minutes.
  • Test specimens are produced from the mass obtained in this way as described in Example 1 and tested in accordance with DIN EN ISO 846. The results are shown in Table 1.

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Abstract

The invention relates to cross-linkable products based on organosilicon compounds and exhibiting biostatic properties and to a method for the production and use thereof, wherein the inventive cross-linkable products contain organosilicon compounds of quaternary ammonium groups.

Description

Vernetzbare Massen auf der Basis von OrganosiliciumverbindungenCrosslinkable compositions based on organosilicon compounds
Die Erfindung betrifft vernetzbare Massen auf der Basis von Organosiliciumverbindungen mit biostatischen Eigenschaften sowie ein Verfahren zu deren Herstellung und deren Verwendung.The invention relates to crosslinkable compositions based on organosilicon compounds with biostatic properties and to a process for their production and their use.
Unter Ausschluss von Wasser lagerfähige, bei Zutritt von Wasser bei Raumtemperatur zu Elastomeren vulkanisierende Einkomponen- ten-Dichtmassen sind bekannt. Diese Produkte werden in großen Mengen zum Beispiel in der Bauindustrie eingesetzt. Insbesondere in Umgebungen mit hoher Luftfeuchtigkeit, wie zum Beispiel in Bädern, Küchen, aber beispielsweise auch tropischen Regionen, bildet sich auf der Oberfläche der Dichtmassen leicht ein Bewuchs mit Organismen wie Pilzen oder auch Algen. Um dies zu verhindern werden bisher den Dichtmassen Biozide wie beispielsweise Fungicide zugesetzt, die den Bewuchs verhindern. Beispiele für in Dichtmassen eingesetzte Fungicide sind Methylbenzimi- dazol-2-ylcarbamat (Carbendazim) , 10, 10 ' -Oxy-bisphenoxarsin, 2- (4-Thiazolyl) -benzimidazol, N-Octyl-4-isothiazolin-3-on, 4,5- Dichlor-2-n-octyl-4-isothiazolin-3-on, Diiodmethyl-p-tolylsul- fon (Amical, vgl. z.B. EP 34 877 A) , Triazolyl-Verbindungen wie Tebuconazol in Kombination mit silberhaltigen Zeolithen (vgl. z.B. EP 931 811 A und EP 640 661 A) und Benzothiophen-2-cyclo- hexylcarboxamid-S, S-dioxid. Diese Wirkstoffe haben jedoch be- stimmte Nachteile, wie Gehalt an giftigen Schwermetallen, chemische Unbeständigkeit in manchen Dichtstoffformulierungen oder auch Neigung zur Verfärbung. Die Biozide haben weiterhin den Nachteil, dass sie eine gewisse Wasserlöslichkeit besitzen müssen, um wirksam zu sein. Deshalb ist diese Art der bioziden Ausrüstung nur für eine sehr begrenzte Zeit wirksam. Außerdem gelangen diese Stoffe somit langsam .komplett ins Abwasser. Gegenstand der Erfindung sind vernetzbare Massen auf der Basis von Organosiliciumverbindungen, dadurch gekennzeichnet, dass sie Organosiliciumverbindungen mit quaternären Ammoniumgruppen Gruppen enthalten .One-component sealing compounds which are storable with the exclusion of water and which vulcanize to elastomers when water is admitted at room temperature are known. These products are used in large quantities, for example in the construction industry. Especially in environments with high air humidity, such as in bathrooms, kitchens, but also tropical regions, for example, the surface of the sealants easily forms an overgrowth with organisms such as fungi or algae. In order to prevent this, biocides such as fungicides have been added to the sealants to prevent fouling. Examples of fungicides used in sealing compounds are methylbenzimidazol-2-ylcarbamate (carbendazim), 10, 10'-oxy-bisphenoxarsin, 2- (4-thiazolyl) -benzimidazole, N-octyl-4-isothiazolin-3-one, 4 , 5-dichloro-2-n-octyl-4-isothiazolin-3-one, diiodomethyl-p-tolylsulfone (Amical, cf. e.g. EP 34 877 A), triazolyl compounds such as tebuconazole in combination with silver-containing zeolites (cf. eg EP 931 811 A and EP 640 661 A) and benzothiophene-2-cyclohexylcarboxamide-S, S-dioxide. However, these active ingredients have certain disadvantages, such as the content of toxic heavy metals, chemical instability in some sealant formulations or the tendency to discolour. The biocides also have the disadvantage that they have to have a certain water solubility in order to be effective. Therefore this type of biocidal treatment is only effective for a very limited time. In addition, these substances end up in the sewage slowly. The invention relates to crosslinkable compositions based on organosilicon compounds, characterized in that they contain organosilicon compounds with quaternary ammonium groups.
Bei den vernetzbaren Massen handelt es sich bevorzugt um durch Kondensationsreaktion vernetzbare Massen.The crosslinkable compositions are preferably crosslinkable compositions by means of a condensation reaction.
Im Rahmen der vorliegenden Erfindung soll die Bezeichnung „Kon- densationsreaktion" auch einen gegebenenfalls vorangehenden Hydrolyseschritt mitumfassen.In the context of the present invention, the term “condensation reaction” is also intended to include a possibly preceding hydrolysis step.
Besonders bevorzugt handelt es sich bei den erfindungsgemäßen Massen um solche enthaltend (A) Organosiliciumverbindung mit mindestens zwei kondensationsfähigen Gruppen, (B) Organosiliciumverbindung mit mindestens einer Einheit der Formel -SiR2 2-R4-N+R3 2-R4-SiR2 2- • X" (II),The compositions according to the invention are particularly preferably those comprising (A) organosilicon compound having at least two condensable groups, (B) organosilicon compound having at least one unit of the formula -SiR 2 2 -R 4 -N + R 3 2 -R 4 -SiR 2 2 - • X " (II),
wobeiin which
R2 gleich oder verschieden sein kann und eine für R unten angegebene Bedeutung hat, R3 gleich oder verschieden sein kann und einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest bedeutet oder Bestandteil eines verbrückenden Alkylenrestes sein kann, X- ein organisches oder anorganisches Anion darstellt, R4 einen zweiwertigen, gegebenenfalls substituierten Kohlen- asserstoffrest darstellt, der mit Heteroatomen unterbrochen sein kann, und gegebenenfallsR 2 can be the same or different and has a meaning given for R below, R 3 can be the same or different and represents a monovalent, optionally substituted hydrocarbon radical or can be part of a bridging alkylene radical, X- represents an organic or inorganic anion, R 4 represents a divalent, optionally substituted carbonic acid residue which can be interrupted by heteroatoms, and optionally
(C) Vernetzer. Im Rahmen der vorliegenden Erfindung sollen unter der Bezeichnung „kondensationsfähige" Reste auch solche Reste verstanden werden, die auch einen gegebenenfalls vorangehenden Hydrolyse- schritt miteinschließen.(C) crosslinker. In the context of the present invention, the term “condensable” radicals should also be understood to mean those radicals which also include a possibly preceding hydrolysis step.
Bei den kondensationsfähigen Gruppen, welche die eingesetzten, an der Vernetzungsreaktion beteiligten Organosiliciumverbindungen aufweisen können, kann es sich um beliebige Gruppen han- dein, wie Hydroxy-, Acetoxy-, Oximato- und Organyloxygruppen, insbesondere Alkoxyreste, wie Ethoxyreste, Alkoxyethoxyreste und Methoxyreste.The condensable groups which the organosilicon compounds used which are involved in the crosslinking reaction can have can be any groups, such as hydroxyl, acetoxy, oximato and organyloxy groups, in particular alkoxy radicals, such as ethoxy radicals, alkoxyethoxy radicals and methoxy radicals.
Bei den erfindungsgemäß eingesetzten Organosiliciumverbindungen (B) kann es sich um beliebige Organosiliciumverbindungen mit mindestens einem Rest der Formel (II) handeln, wobei es sich dabei sowohl um reine Siloxane, also ≡Si-O-Si≡ -Strukturen, als auch um Silcarbane, also ≡Si-R'-Si≡ -Strukturen mit R' gleich einem zweiwertigen, gegebenenfalls substituierten oder mit He- teroatomen unterbrochenen Kohlenwasserstoffrest oder beliebigen Organosiliciumgruppen aufweisende Copolymere handeln kann.The organosilicon compounds (B) used according to the invention can be any organosilicon compounds with at least one radical of the formula (II), which are both pure siloxanes, ie ≡Si-O-Si≡ structures, and silcarbanes, thus ≡Si-R'-Si≡ structures with R 'can be a divalent, optionally substituted or interrupted by hetero-hydrocarbon radical or any copolymers containing organosilicon groups.
Bei den erfindungsgemäß eingesetzten Organosiliciumverbindungen (A) kann es sich um alle Organosiliciumverbindungen mit mindes- tens zwei kondensationsfähigen Gruppen handeln, die auch bisher in durch Kondensationsreaktion vernetzbaren Massen eingesetzt worden sind. Es kann sich dabei sowohl um reine Siloxane, also ≡Si-O-Si≡ -Strukturen, als auch um Silcarbane, also ≡Si-R''-Si≡ -Strukturen mit R' ' gleich einem zweiwertigen, gegebenenfalls substituierten oder mit Heteroatomen unterbrochenen Kohlenwasserstoffrest oder beliebigen Organosiliciumgruppen aufweisende Copolymere handeln. Bevorzugt handelt es sich bei den erfindungsgemäß eingesetzten Organosiliciumverbindungen (A) um solche enthaltend Einheiten der FormelThe organosilicon compounds (A) used according to the invention can be all organosilicon compounds with at least two condensable groups which have also been used to date in compositions which can be crosslinked by the condensation reaction. These can be both pure siloxanes, ie ≡Si-O-Si≡ structures, and silcarbanes, i.e. ≡Si-R '' - Si≡ structures with R '' equal to a divalent, optionally substituted or with heteroatoms interrupted hydrocarbon radical or any copolymers having organosilicon groups. The organosilicon compounds (A) used according to the invention are preferably those containing units of the formula
Ra(OR1)bYcSiO(4-a-b-c)/2 (I),R a (OR 1 ) b Y c SiO ( 4-abc) / 2 (I),
wobeiin which
R gleich oder verschieden sein kann und gegebenenfalls substituierte Kohlenwasserstoffreste, die durch Sauerstoffatome un- terbrochen sein können, bedeutet,R can be the same or different and means optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms,
R1 gleich oder verschieden sein kann und Wassersto fatom oder einwertige, gegebenenfalls substituierte Kohlenwasserstoffres- te, die durch Sauerstoffatome unterbrochen sein können, bedeutet, Y gleich oder verschieden sein kann und Halogenatom, Pseudoha- logenrest, Si-N-gebundene Aminreste, Amidreste, Oximreste, Ami- noxyreste und Acyloxyreste bedeutet, a 0, 1, 2 oder 3, bevorzugt 1 oder 2, ist, b 0, 1, 2 oder 3, bevorzugt 0, 1 oder 2, besonders bevorzugt 0, ist und c 0, 1, 2 oder 3, bevorzugt 0 oder 1, besonders bevorzugt 0, ist, mit der Maßgabe, dass die Summe aus a+b+c kleiner oder gleich 4 ist und pro Molekül mindestens zwei kondensationsfähige Reste (OR1) anwesend sind.R 1 can be the same or different and means hydrogen atom or monovalent, optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms, Y can be the same or different and halogen atom, pseudohalogen radical, Si-N-bonded amine radicals, amide radicals, Oxime radicals, amine oxy radicals and acyloxy radicals means, a is 0, 1, 2 or 3, preferably 1 or 2, b is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0, and c is 0, 1, 2 or 3, preferably 0 or 1, particularly preferably 0, with the proviso that the sum of a + b + c is less than or equal to 4 and at least two condensable radicals (OR 1 ) are present per molecule.
Bevorzugt ist die Summe a+b+c kleiner oder gleich 3.The sum a + b + c is preferably less than or equal to 3.
Bevorzugt handelt es sich bei Rest R um einwertige Kohlenwas- serstoffreste mit 1 bis 18 Kohlenstoffatomen, die gegebenenfalls mit Halogenatomen, Aminogruppen, Ethergruppen, Estergruppen, Epoxygruppen, Mercaptogruppen, Cyanogruppen oder (Poly) - glykolresten substituiert sind, wobei letztere aus Oxyethylen- und/oder Oxypropyleneinheiten aufgebaut sind, besonders bevorzugt um Alkylreste mit 1 bis 12 Kohlenstoffatomen, insbesondere um den Methylrest. Es kann sich bei Rest R aber auch um zweiwertige Reste handeln, die z.B. zwei Silylgruppen miteinander verbinden.The radical R is preferably monovalent hydrocarbon radicals having 1 to 18 carbon atoms, which may optionally contain halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or (poly) glycol residues are substituted, the latter being composed of oxyethylene and / or oxypropylene units, particularly preferably alkyl radicals having 1 to 12 carbon atoms, in particular the methyl radical. However, the radical R can also be divalent radicals which, for example, connect two silyl groups to one another.
Beispiele für Reste R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, 1-n-Butyl-, 2-n-Butyl-, iso-Butyl-, tert . -Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert.-Pen- tylrest; Hexylreste, wie der n-Hexylrest; Heptylreste, wie der n-Heptylrest; Octylreste, wie der n-Octylrest und iso-Octylres- te, wie der 2, 2, 4-Trimethylpentylrest; Nonylreste, wie der n- Nonylrest; Decylreste, wie der n-Decylrest; Dodecylreste, wie der n-Dodecylrest; Octadecylreste, wie der n-Octadecylrest; Cy- cloalkylreste, wie der Cyclopentyl-, Cyclohexyl-, Cycloheptyl- rest und Methylcyclohexylreste; Alkenylreste, wie der Vinyl-, 1-Propenyl- und der 2-Propenylrest; Arylreste, wie der Phenyl-, Naphthyl-, Anthryl- und Phenanthrylrest; Alkarylreste, wie o-, m-, p-Tolylreste; Xylylreste und Ethylphenylreste; und Aralkyl- reste, wie der Benzylrest, der der α- und der ß-Phenylethyl- rest .Examples of radicals R are alkyl radicals, such as the 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 residues, such as the n-heptyl residue; 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 the n-octadecyl radical; Cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl radical and methylcyclohexyl radicals; Alkenyl radicals, such as the vinyl, 1-propenyl and 2-propenyl radicals; Aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl residues and ethylphenyl residues; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.
Beispiele für substituierte Reste R sind Methoxyethyl-, Ethoxy- ethyl- und der Ethoxyethoxyethylrest .Examples of substituted radicals R are methoxyethyl, ethoxyethyl and the ethoxyethoxyethyl radical.
Beispiele für zweiwertige Reste R sind Polyisobutylendiylreste und propandiylterminierte Polypropylenglykolreste .Examples of divalent radicals R are polyisobutylene diyl radicals and propanediyl-terminated polypropylene glycol radicals.
Beispiele für Reste R1 sind die für R angegebenen einwertigen Reste. Bevorzugt handelt es sich bei Rest R1 um Wasserstoffatom oder Alkylreste mit 1 bis 12 Kohlenstoffatomen, besonders bevorzugt um Wasserstoffatom, Methyl- oder Ethylrest, insbesondere um Wasserstoffatom.Examples of radicals R 1 are the monovalent radicals indicated for R. The radical R 1 is preferably a hydrogen atom or alkyl radicals having 1 to 12 carbon atoms, particularly preferably a hydrogen atom, methyl or ethyl radical, in particular a hydrogen atom.
Beispiele für Rest Y sind Acetoxy-, Dirnethylamino-, Cyclohexyl- amino- und Methylethylketoximorest, wobei der Acetoxyrest bevorzugt ist.Examples of radical Y are acetoxy, dirnethylamino, cyclohexylamino and methylethylketoximo radical, the acetoxy radical being preferred.
Besonders bevorzugt handelt es sich bei erfindungsgemäß eingesetzten Organosiliciumverbindungen (A) um solche der FormelThe organosilicon compounds (A) used according to the invention are particularly preferably those of the formula
(OR1) 3-fRfSi- (SiR2-0) e-SiRf (OR1) 3_f (IV) ,(OR 1 ) 3-fRfSi- (SiR 2 -0) e-SiRf (OR 1 ) 3 _ f (IV),
wobeiin which
R und R1 eine der oben angegebenen Bedeutungen haben, e gleich 30 bis 3000 ist und f gleich 1 oder 2 ist.R and R 1 have one of the meanings given above, e is 30 to 3000 and f is 1 or 2.
Vorzugsweise ist f gleich 2, wenn R1 die Bedeutung von Wasserstoffatom hat, und f gleich 1, wenn R1 eine Bedeutung verschieden Wasserstoffatom hat.Preferably f is 2 if R 1 is hydrogen and f is 1 if R 1 is hydrogen.
Beispiele für Organosiliciumverbindungen (A) sind (MeO) 2MeSiO [SiMe20] 200_2000SiMe (OMe) 2,Examples of organosilicon compounds (A) are (MeO) 2 MeSiO [SiMe 2 0] 200 _ 2000 SiMe (OMe) 2 ,
(HO)Me2SiO[SiMe2O]200_2000SiMe2(OH) ,(HO) Me 2 SiO [SiMe 2 O] 200 _ 2000 SiMe 2 (OH),
(EtO) 2MeSiO [SiMe20] 200_2000SiMe (OEt) 2,(EtO) 2 MeSiO [SiMe 2 0] 200 _ 2000 SiMe (OEt) 2 ,
(HO)MeViSiO[SiMe2O]200_2000SiMeVi(OH) ,(HO) MeViSiO [SiMe 2 O] 200 _ 2000 SiMeVi (OH),
(MeO) 2ViSiO [SiMe20] 20o-2ooosivi (OMe) 2 und (EtO)2ViSiO[SiMe2O]200.2000SiVi(OEt)2 , wobei Me Methylrest, Et Ethylrest und Vi Vinylrest bedeutet. Die erfindungsgemäß eingesetzten Organosiliciumverbindungen (A) haben eine Viskosität von bevorzugt 100 bis 106 Pas, besonders bevorzugt von 103 bis 350 000 mPas, jeweils bei 25°C.(MeO) 2 ViSiO [SiMe 2 0] 20 o- 2 ooo sivi (OMe) 2 and (EtO) 2 ViSiO [SiMe 2 O] 200 . 2000 SiVi (OEt) 2 , where Me is methyl, Et is ethyl and Vi is vinyl. The organosilicon compounds (A) used according to the invention have a viscosity of preferably 100 to 10 6 Pas, particularly preferably 10 3 to 350 000 mPas, in each case at 25 ° C.
Bei den Organosiliciumverbindungen (A) handelt es sich um handelsübliche Produkte bzw. können nach in der Siliciumchemie gängigen Methoden hergestellt werden.The organosilicon compounds (A) are commercially available products or can be prepared by methods customary in silicon chemistry.
Beispiele für Reste R2 sind die für Rest R angegebenen einwer- tigen Beispiele.Examples of radicals R 2 are the one-valent examples given for radical R.
Bevorzugt handelt es sich bei Rest R2 um Kohlenwasserstoffreste mit 1 bis 18 Kohlenstoffatomen, die gegebenenfalls mit Halogenatomen, Aminogruppen, Ethergruppen, Estergruppen, Epoxygruppen, Mercaptogruppen, Cyanogruppen oder (Poly) glykolresten substituiert sind, wobei letztere aus Oxyethylen- und/oder Oxypropyle- neinheiten aufgebaut sind, besonders bevorzugt um Alkylreste mit 1 bis 12 Kohlenstoffatomen, insbesondere um den Methylrest.The radical R 2 is preferably hydrocarbon radicals having 1 to 18 carbon atoms, which are optionally substituted by halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or (poly) glycol radicals, the latter consisting of oxyethylene and / or oxypropyl radicals units are built up, particularly preferably around alkyl radicals with 1 to 12 carbon atoms, in particular around the methyl radical.
Beispiele für Reste R3 sind die für Rest R angegebenen einwertigen Beispiele sowie zweiwertige gegebenenfalls substituierte Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen .Examples of radicals R 3 are the monovalent examples given for radical R as well as divalent optionally substituted hydrocarbon radicals having 1 to 30 carbon atoms.
Bevorzugt handelt es sich bei Rest R3 um Kohlenwasserstoffreste mit 1 bis 8 Kohlenstoffatomen, besonders bevorzugt um Alkylreste mit 1 bis 6 Kohlenstoffatomen und Benzylreste. Bei Rest R3 kann es sich aber auch um einen davon abgeleiteten zweiwertigen Rest handeln, so dass beispielsweise zwei Reste R3 mit dem Stickstoffatom einen Ring bilden.The radical R 3 is preferably hydrocarbon radicals having 1 to 8 carbon atoms, particularly preferably alkyl radicals having 1 to 6 carbon atoms and benzyl radicals. The radical R 3 can also be a divalent radical derived therefrom, so that for example two radicals R 3 form a ring with the nitrogen atom.
Beispiele für Anion X sind organische Anionen, wie Carboxylat- ionen, Enolationen und Sulfonationen, sowie anorganische Anio- nen, wie Halogenidionen, wie z.B. Fluoridionen, Chloridionen, Bromidionen und Jodidionen, und Sulfationen.Examples of anion X are organic anions, such as carboxylate ions, enolate ions and sulfonate ions, as well as inorganic anionic such as halide ions such as fluoride ions, chloride ions, bromide ions and iodide ions, and sulfate ions.
Bevorzugt handelt es sich bei Anion X" um Carboxylationen und Halogenidionen, besonders bevorzugt um Chloridionen und Aceta- tionen.Anion X ″ is preferably carboxylate ion and halide ion, particularly preferably chloride ion and acetate ion.
Beispiele für Rest R4 sind zweiwertige lineare, cyclische oder verzweigte, gesättigte oder ungesättigte Kohlenwasserstoffres- te, die von Sauerstoffatomen einfach oder mehrfach unterbrochen sind, wie alle Alkylenreste, Arylenreste,Examples of radical R 4 are divalent linear, cyclic or branched, saturated or unsaturated hydrocarbon radicals which are interrupted once or several times by oxygen atoms, like all alkylene radicals, arylene radicals,
-H2C-CHMe-CH-CH2 — CH- I I CH2-CH2-CMeOH-H 2 C-CHMe-CH-CH 2 - CH- II CH 2 -CH 2 -CMeOH
-H2C-CHMe-CH-CH2-CHOH-CMe--H 2 C-CHMe-CH-CH 2 -CHOH-CMe-
CH2 CH2 CH 2 CH 2
-H2C-CH2-CH-CH2-CHOH-CH- CH2 CH2 -H 2 C-CH 2 -CH-CH 2 -CHOH-CH- CH 2 CH 2
-H2C-CH2-CH-CH2 — CH- I I CH2-CH2-CHOH-H 2 C-CH 2 -CH-CH 2 - CH- II CH 2 -CH 2 -CHOH
-(CH2)3OCH2-CH(OH)-CH2- und - (CH2) 3OCH2-CH [-CH2 (OH) ] -, wobei Me den Methylrest bedeutet.- (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -, where Me is the methyl radical.
Bevorzugt handelt es sich bei Rest R4 um Alkylenreste und -(CH2)3OCH2-CH(OH)-CH2- und - (CH2) 3OCH2-CH [-CH2 (OH) ] -, besonders bevorzugt um - (CH2) 3OCH2-CH (OH) -CH2- und -(CH2)3OCH2-CH[-CH2(OH)]-. Bevorzugt handelt es sich bei den erfindungsgemäß eingesetzten Organosiliciumverbindungen (B) um solche der FormelThe radical R 4 is preferably alkylene radicals and - (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -, particularly preferably around - (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -. The organosilicon compounds (B) used according to the invention are preferably those of the formula
D1-(RSiR2 2)h-[ (OSiR2 2)d-R4-N+R3 2-R4-SiR2 2]n-D2 • nX" (III),D 1 - (RSiR 2 2 ) h - [(OSiR 2 2 ) d -R 4 -N + R 3 2 -R 4 -SiR 2 2 ] n -D 2 • nX " (III),
wobeiin which
D1 ein Wasserstoffatom, Hydroxylrest, Halogenidrest, einen rest -NR*2 oder einen einwertigen organischen Rest bedeutet, wobei R* gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest darstellt und der Rest -NR*2 auch als Ammonium- salz vorliegen kann, undD 1 represents a hydrogen atom, hydroxyl radical, halide radical, a radical -NR * 2 or a monovalent organic radical, where R * can be the same or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical and the radical -NR * 2 also as ammonium - salt may be present, and
D2 eine Gruppe der Formel - (OSiR2 2) g-R4 k-D1 bedeutet mit R2, R3, D1, X~ und R4 gleich einer oben dafür angegebenen Bedeu- tung, wobei die beiden Reste D1 in jedem Polymermolekül der Formel (III) gleich oder unterschiedlich sein können, und d eine ganze Zahl von 1 bis 200 ist, h 0 oder 1 ist, k 0 oder 1 ist, g eine Zahl von 0 bis 1000 ist und n eine ganze Zahl von 1 bis 50 ist.D 2 is a group of the formula - (OSiR 2 2 ) g -R 4 k -D 1 means with R 2 , R 3 , D 1 , X ~ and R 4 equal to one of the meanings given above, the two radicals D 1 in each polymer molecule of formula (III) may be the same or different, and d is an integer from 1 to 200, h is 0 or 1, k is 0 or 1, g is a number from 0 to 1000 and n is an integer Number is from 1 to 50.
Beispiele für D1 gleich Halogenidrest sind -Cl und -Br und für Rest -NR*2 der -N (CH3) 2-Rest .Examples of D 1 equal to halide are -Cl and -Br and for -NR * 2 the -N (CH 3 ) 2 -rest.
Besonders bevorzugt handelt es sich bei den erfindungsgemäß eingesetzten Organosiliciumverbindungen (B) um Polymere der Formel (III) mit R4 gleich Alkylenreste mit mindestens 4 C- Atomen und mindestens einer Hydroxylgruppe, - (CH2) 3OCH2-CH (OH) - CH2- und -(CH2)3OCH2-CH[-CH2(OH) ]-, besonders bevorzugt um -(CH2)3OCH2-CH(OH)-CH2- und - (CH2) 3OCH2-CH [-CH2 (OH) ] - . Beispiele für die erfindungsgemäß eingesetzten Organosiliciumverbindungen (B) sindThe organosilicon compounds (B) used according to the invention are particularly preferably polymers of the formula (III) where R 4 is alkylene radicals having at least 4 carbon atoms and at least one hydroxyl group, - (CH 2 ) 3 OCH 2 -CH (OH) - CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -, particularly preferably around - (CH 2 ) 3 OCH 2 -CH (OH) -CH 2 - and - (CH 2 ) 3 OCH 2 -CH [-CH 2 (OH)] -. Examples of the organosilicon compounds (B) used according to the invention are
D1 [OSi (CH3) 2- (CH2) 3OCH2CH (OH) CH2-N+ (CH3) 2-CH2CH (OH) CH20 (CH2) 3- Si(CH3)2]n-D2-nCl- mit D1 = H, D2 = OH und n= ca. 20,D 1 [OSi (CH 3 ) 2 - (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 - Si (CH 3 ) 2 ] n -D 2 -nCl- with D 1 = H, D 2 = OH and n = approx. 20,
D1 [OSi (CH3) 2- (CH2) 3OCH2CH (OH) CH2-N+ (CH3) 2-CH2CH (OH) CH20 (CH2) 3- Si(CH3)2]n-D2-nCl" mit D1 = H, D2 = OSi(CH3)2-(CH2)3OCH2CH(OH)CH2N(CH3)2 und n= ca. 20,D 1 [OSi (CH 3 ) 2 - (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 - Si (CH 3 ) 2 ] n -D 2 -nCl " with D 1 = H, D 2 = OSi (CH 3 ) 2 - (CH 2 ) 3 OCH 2 CH (OH) CH 2 N (CH 3 ) 2 and n = approx . 20,
n = ca.20 n = approx. 2 0
D1 [ (OSi (CH3) 2) d- (CH2) 3OCH2CH (OH) CH2-N+ (CH3) 2-CH2CH (OH) CH20 (CH2) 3- mit D1 = H, D2 = -(OSi(CH3)2)g-(CH2)3θCH2CH(OH)CH2N(CH3)2, n= ca, 20, d = g = 5-10 oder d = g = 30-60,D 1 [(OSi (CH 3 ) 2 ) d- (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 - with D 1 = H, D 2 = - (OSi (CH 3 ) 2) g- (CH 2 ) 3θCH 2 CH (OH) CH 2 N (CH 3 ) 2, n = approx. 20, d = g = 5 -10 or d = g = 30-60,
d=5-10oderd= 30-60 d = 5-10 or d = 3 0-60
D1-CH2CH (OH) CH20 (CH2) 3Si (CH3) 2- [OSi (CH3) 2- (CH2) 3OCH2CH (OH) CH- N+(CH3)2-CH2CH(OH)CH20(CH2)3-Si(CH3)2]n-D2 • nCl" D 1 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 Si (CH 3 ) 2 - [OSi (CH 3 ) 2 - (CH 2 ) 3 OCH 2 CH (OH) CH- N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 -Si (CH 3 ) 2 ] n -D 2 • nCl "
Mit D1 = Cl, D2 = -OSi(CH3)2(CH2)3OCH2CH(OH)CH2-N(CH3)2 und n ca. 20, With D 1 = Cl, D 2 = -OSi (CH 3 ) 2 (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N (CH 3 ) 2 and n approx. 20,
D1-CH2CH (OH) CH20 (CH2) 3Si (CH3) 2- [ (OSi (CH3) 2) d" (CH2) 3OCH2CH (OH) CH- N+(CH3)2-CH2CH(OH)CH20(CH2)3-Si(CH3)2]n-D2 ' nCl~ D 1 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 Si (CH 3 ) 2 - [(OSi (CH 3 ) 2) d "(CH 2 ) 3 OCH 2 CH (OH) CH- N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 0 (CH 2 ) 3 -Si (CH 3 ) 2 ] n -D 2 'nCl ~
Mit D1 = (CH3)2N-, D2 = - (OSi (CH3) 2) g (CH2) 3OCH2CH (OH) CH2-N (CH3) 2, n = ca. 20 und d = g = 5-10 oder d = g = 30-60,With D 1 = (CH 3 ) 2 N-, D 2 = - (OSi (CH 3 ) 2 ) g (CH 2 ) 3 OCH 2 CH (OH) CH 2 -N (CH 3 ) 2 , n = approx. 20 and d = g = 5-10 or d = g = 30-60,
d=5-10oderd« 30-60 d = 5-10 or d «30-60
n= ca.20 n = approx. 2 0
d=5-10oderd=30-60 d = 5-10 or d = 3 0-60
d = 5-10oderd=30-60 d = 5-10 or d = 3 0-60
wobei der Cl- und -N (CH3) 2-Substituent am Cyclohexylrest unabhängig voneinander nicht nur die 4-Position sondern auch die 3- Position relativ zur -CH2CH2-Gruρpe einnehmen kann und die Angaben für die Indices n und d als mittlere Werte für polymere Verbindungen mit sehr breiter Molmassenverteilung zu verstehen sind.the Cl and -N (CH 3 ) 2 substituent on the cyclohexyl radical independently of one another not only the 4-position but also the 3- Can take position relative to the -CH 2 CH 2 -Gruρpe and the information for the indices n and d are to be understood as mean values for polymeric compounds with a very wide molecular weight distribution.
Die erfindungsgemäß eingesetzten Organosiliciumverbindungen (B) haben eine Viskosität von bevorzugt 104 bis 108 mPas, besonders bevorzugt 105 bis 5*107 mPas, jeweils bei 25°C.The organosilicon compounds (B) used according to the invention have a viscosity of preferably 10 4 to 10 8 mPas, particularly preferably 10 5 to 5 * 10 7 mPas, in each case at 25 ° C.
Die erfindungsgemäß eingesetzten Organosiliciumverbindungen (B) sind handelsübliche Produkte bzw. können nach bekannten Verfahren hergestellt werden, wie etwa durch Umsetzung der entsprechenden epoxyfunktionellen Silane und/oder Siloxane mit Dialky- lammoniumsalzen wie zum Beispiel Dimethylammoniumchlorid oder durch Umsetzung der entsprechenden Aminoverbindungen mit Alkyl- halogeniden.The organosilicon compounds (B) used according to the invention are commercially available products or can be prepared by known processes, for example by reacting the corresponding epoxy-functional silanes and / or siloxanes with dialkylammonium salts such as, for example, dimethylammonium chloride or by reacting the corresponding amino compounds with alkyl halides.
Bei den in den erfindungsgemäßen Massen gegebenenfalls eingesetzten Vernetzern (C) kann es sich um beliebige, bisher be- kannte Vernetzer mit mindestens drei kondensationsfähigen Resten handeln, wie beispielsweise Silane oder Siloxane mit mindestens drei Organyloxygruppen.The crosslinking agents (C) optionally used in the compositions according to the invention can be any, previously known crosslinking agents with at least three condensable radicals, such as, for example, silanes or siloxanes with at least three organyloxy groups.
Bei den in den erfindungsgemäßen Massen gegebenenfalls einge- setzten Vernetzern (C) handelt es sich vorzugsweise um Organosiliciumverbindungen der FormelThe crosslinking agents (C) optionally used in the compositions according to the invention are preferably organosilicon compounds of the formula
(RδO)kZιSiR5 (4-k-l) (V),(R δ O) k ZιSiR 5 (4-kl) (V),
wobeiin which
R5 gleich oder verschieden sein kann und einwertige, gegebenenfalls substituierte Kohlenwasserstoffreste, die durch Sauerstoffatome unterbrochen sein können, bedeutet, R5 gleich oder verschieden sein kann und eine oben für R1 genannte Bedeutung besitzt,R 5 can be the same or different and means monovalent, optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms, R 5 can be the same or different and has the meaning given above for R 1 ,
Z gleich oder verschieden sein kann und eine für Y angegebene Bedeutung hat, k 0, 1, 2, 3 oder 4, bevorzugt 2 oder 3, besonders bevorzugt 3, ist undZ can be the same or different and has a meaning given for Y, k is 0, 1, 2, 3 or 4, preferably 2 or 3, particularly preferably 3, and
1 0, 1, 2, 3 oder 4, bevorzugt 0 oder 3, besonders bevorzugt 0, ist, mit der Maßgabe, dass die Summe k+1 gleich 3 oder 4 ist, sowie deren Teilhydrolysate .1 is 0, 1, 2, 3 or 4, preferably 0 or 3, particularly preferably 0, with the proviso that the sum k + 1 is 3 or 4, and their partial hydrolyzates.
Bei den Teilhydrolysaten kann es sich dabei um Teilhomohydroly- sate handeln, d.h. Teilhydrolysate von einer Art von Organosiliciumverbindung der Formel (V) , wie auch um Teilcohydrolysate, d.h. Teilhydrolysate von mindestens zwei verschiedenen Arten von Organosiliciumverbindungen der Formel (V) .The partial hydrolyzates can be partial homohydrolysates, i.e. Partial hydrolyzates of some kind of organosilicon compound of formula (V) as well as partial hydrolyzates, i.e. Partial hydrolysates of at least two different types of organosilicon compounds of the formula (V).
Handelt es sich bei den in den erfindungsgemäßen Massen gegebenenfalls eingesetzten Vernetzern (C) um Teilhydrolysate von Or- ganosiliciumverbindungen der Formel (V) , so sind solche mit bis zu 6 Siliciumatomen bevorzugt.If the crosslinking agents (C) used in the compositions according to the invention are partial hydrolysates of organosilicon compounds of the formula (V), preference is given to those having up to 6 silicon atoms.
Beispiele für Rest R5 sind die oben für Rest R1 genannten Beispiele. Bevorzugt handelt es sich bei Rest R6 um Wasserstoff- atom und Alkylreste, besonders bevorzugt um Wasserstoffatom und Alkylreste mit 1 bis 4 Kohlenstoffatomen, insbesondere um Wasserstoffatom, den Methyl- und den Ethylrest.Examples of radical R 5 are the examples mentioned above for radical R 1 . The radical R 6 is preferably a hydrogen atom and alkyl radicals, particularly preferably a hydrogen atom and alkyl radicals having 1 to 4 carbon atoms, in particular a hydrogen atom, the methyl and the ethyl radical.
Beispiele für Rest R5 sind die oben für Rest R genannten ein- wertigen Beispiele, wobei Kohlenwasserstoffreste mit 1 bis 12 Kohlenstoffatomen bevorzugt und der Methyl- und der Vinylrest besonders bevorzugt sind. Beispiele für Z sind die für Y angegebenen Beispiele, wobei A- cetoxyreste und Methylethylketoximoreste bevorzugt sind.Examples of radical R 5 are the monovalent examples mentioned above for radical R, hydrocarbon radicals having 1 to 12 carbon atoms being preferred and the methyl and vinyl radicals being particularly preferred. Examples of Z are the examples given for Y, preference being given to acetooxy radicals and methylethylketoximo radicals.
Besonders bevorzugt handelt es sich bei den in den erfindungs- gemäßen Massen gegebenenfalls eingesetzten Vernetzern (C) um Tetramethoxysilan, Tetraethoxysilan, Tetrapropoxysilan, Tetra- butoxysilan, Methyltrimethoxysilan, Methyltriethoxysilan, Vi- nyltrimethoxysilan, Vinyltriethoxysilan, Phenyltrimethoxysilan, Phenyltriethoxysilan, 3-Cyanopropyltrimethoxysilan, 3-Cyanopro- pyltriethoxysilan, 3- (Glycidoxy)propyltriethoxysilan, 1,2-Bis- (trimethoxysilyl) ethan, 1, 2-Bis (triethoxysilyl) ethan, 3-Amino- propyltrimethoxysilan, 3- (2-Aminoethyl) aminopropyltrimethoxy- silan, 3- (2-Aminoethyl) aminopropylmethyldimethoxysilan, Cyclo- hexylaminomethyltriethoxysilan, Methyltriacetoxysilan, Ethyl- triacetoxysilan, Methyltris (methylethylketoximo) silan, Vinyl- tris (methylethylketoximo) silan sowie Teilhydrolysate der genannten Organosiliciumverbindungen, wie z.B. Hexaethoxydisilo- xan.The crosslinking agents (C) optionally used in the compositions according to the invention are particularly preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysimylililililtrilyltrimyloxysilane, phenyltriethoxysimylilililililililililililililililililililtrilyltrimethoxysilane, phenyltriethoxysimylililililililililililtrilyltrimethoxysilane, phenyltriethoxysimyliloxilililililtrilyltriloxysilane, phenyltriethoxysiloxyliloxilyltriloxyloxysilane, triethoxysiloxyliloxyliloxilyltriloxyloxysilane Cyanopropyltriethoxysilane, 3- (glycidoxy) propyltriethoxysilane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane - (2-Aminoethyl) aminopropylmethyldimethoxysilane, cyclohexylaminomethyltriethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, methyltris (methylethylketoximo) silane, vinyltris (methylethylketoximo) silane and partial hydrolyzates of the organosilicon compounds mentioned, such as, for example, organosilicon compounds Hexaethoxydisiloxane.
Die in den erfindungsgemäßen Massen gegebenenfalls eingesetzten Vernetzer (C) sind handelsübliche Produkte bzw. können nach in der Siliciumchemie bekannten Verfahren hergestellt werden.The crosslinking agents (C) optionally used in the compositions according to the invention are commercially available products or can be prepared by processes known in silicon chemistry.
Falls die erfindungsgemäßen Massen Vernetzer (C) enthalten, handelt es sich um Mengen von vorzugsweise 0,01 bis 20 Gewichtsteilen, besonders bevorzugt 0,5 bis 10 Gewichtsteilen, insbesondere 1,0 bis 5,0 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Organopolysiloxan (A) .If the compositions according to the invention contain crosslinking agents (C), the amounts are preferably 0.01 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, in particular 1.0 to 5.0 parts by weight, in each case based on 100 parts by weight of organopolysiloxane ( A).
Zusätzlich zu den oben beschriebenen Komponenten (A) , (B) und (C) können die erfindungsgemäßen Massen nun alle weiteren Stoffe enthalten, die auch bisher in durch Kondensationsreaktion vernetzbaren Massen eingesetzt worden sind, wie z.B. Katalysa- toren (D) , Weichmacher (E) , Füllstoffe (F) , Haftvermittler (G) und Additive (H) .In addition to components (A), (B) and (C) described above, the compositions according to the invention can now contain all other substances which have also been used in compositions which can be crosslinked by the condensation reaction, such as, for example, gates (D), plasticizers (E), fillers (F), adhesion promoters (G) and additives (H).
Beispiele für Katalysatoren (D) sind die bisher schon bekannten Titanverbindungen und organische Zinnverbindungen, wie Di-n-bu- tylzinndilaurat und Di-n-butylzinndiacetat, Di-n-butylzinnoxid, Dioctylzinndiacetat, Dioctylzinndilaurat, Dioctylzinnoxid sowie Umsetzungsprodukte dieser Verbindungen mit Alkoxysilanen wie Tetraethoxysilan, wobei Di-n-butylzinndiacetat und Dibutylzinn- oxid in Tetraethylsilikat-Hydrolysat bevorzugt sind und Di-n- butylzinnoxid in Tetraethylsilikat-Hydrolysat besonders bevorzugt ist.Examples of catalysts (D) are the previously known titanium compounds and organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n-butyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin oxide and reaction products of these compounds with alkoxoxysilanesilane such as tetraoxysilanes , with di-n-butyltin diacetate and dibutyltin oxide in tetraethylsilicate hydrolyzate being preferred and di-n-butyltin oxide in tetraethylsilicate hydrolyzate being particularly preferred.
Falls die erfindungsgemäßen Massen Katalysator (D) enthalten, handelt es sich um Mengen von vorzugsweise 0,01 bis 3 Gewichtsteilen, bevorzugt 0,05 bis 2 Gewichtteilen, jeweils bezogen auf 100 Gewichtsteile Bestandteil (A) .If the compositions according to the invention contain catalyst (D), they are amounts of preferably 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, in each case based on 100 parts by weight of component (A).
Beispiele für Weichmacher (E) sind bei Raumtemperatur flüssige, durch Trimethylsiloxygruppen endblockierte Dimethylpolysiloxa- ne, insbesondere mit Viskositäten bei 25 °C im Bereich zwischen 50 und 1000 mPas, sowie hochsiedende Kohlenwasserstoffe, wie zum Beispiel Paraffinöle oder Mineralöle bestehend aus naphthe- nischen und paraffinischen Einheiten.Examples of plasticizers (E) are dimethylpolysiloxanes which are liquid at room temperature and are endblocked by trimethylsiloxy groups, in particular with viscosities at 25 ° C. in the range between 50 and 1000 mPas, and high-boiling hydrocarbons, such as paraffin oils or mineral oils consisting of naphthenic and paraffinic Units.
Die erfindungsgemäßen Massen enthalten Weichmacher (E) in Mengen von vorzugsweise 0 bis 300 Gewichtsteilen, besonders bevorzugt 10 bis 200 Gewichtsteilen, insbesondere 20 bis 100 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Organopoly- siloxan (A) .The compositions according to the invention contain plasticizers (E) in amounts of preferably 0 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, in particular 20 to 100 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A).
Beispiele für Füllstoffe (F) sind nicht verstärkende Füllstoffe, also Füllstoffe mit einer BET-Oberfläche von bis zu 50 m2/g, wie Quarz, Diatomeenerde, Calciumsilikat, Zirkoniumsilikat, Ze- olithe, Metalloxidpulver, wie Aluminium-, Titan-, Eisen- oder Zinkoxide bzw. deren Mischoxide, Bariumsulfat, Calciumcarbonat, Gips, Siliciumnitrid, Siliciumcarbid, Bornitrid, Glas- und Kunststoffpulver, wie Polyacrylnitrilpulver; verstärkende Füllstoffe, also Füllstoffe mit einer BET-Oberfläche von mehr als 50 m2/g, wie pyrogen hergestellte Kieselsäure, gefällte Kieselsäure, gefällte Kreide, Ruß, wie Furnace- und Acetylenruß und Silicium-Aluminium-Mischoxide großer BET-Oberfläche; faserför- mige Füllstoffe, wie Asbest sowie Kunststofffasern. Die genannten Füllstoffe können hydrophobiert sein, beispielsweise durch die Behandlung mit Organosilanen bzw. -siloxanen oder mit Stearinsäure oder durch Veretherung von Hydroxylgruppen zu Alkoxy- gruppen. Falls Füllstoffe (E) eingesetzt werden, handelt es sich bevorzugt um hydrophile pyrogene Kieselsäure und gefälltes oder gemahlenes Calciumcarbonat.Examples of fillers (F) are non-reinforcing fillers, ie fillers with a BET surface area of up to 50 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders, 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, ie fillers with a BET surface area of more than 50 m 2 / g, such as pyrogenically prepared silica, precipitated silica, precipitated chalk, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides having a large BET surface area; fibrous fillers such as asbestos and plastic fibers. The fillers mentioned can be rendered hydrophobic, for example by treatment with organosilanes or organosiloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy groups. If fillers (E) are used, they are preferably hydrophilic fumed silica and precipitated or ground calcium carbonate.
Die erfindungsgemäßen Massen enthalten Füllstoffe (F) in Mengen von vorzugsweise 0 bis 300 Gewichtsteilen, besonders bevorzugt 1 bis 200 Gewichtsteilen, insbesondere 5 bis 200 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Organopolysiloxan (A) .The compositions according to the invention contain fillers (F) in amounts of preferably 0 to 300 parts by weight, particularly preferably 1 to 200 parts by weight, in particular 5 to 200 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A).
Beispiele für die in den erfindungsgemäßen Massen eingesetzten Haftvermittler (G) sind Silane und Organopolysiloxane mit funktioneilen Gruppen, wie beispielsweise solche mit Glycidoxypro- pyl- oder Methacryloxypropylresten sowie Tetraalkoxysilane.Examples of the adhesion promoters (G) used in the compositions according to the invention are silanes and organopolysiloxanes with functional groups, such as, for example, those with glycidoxypropyl or methacryloxypropyl radicals and tetraalkoxysilanes.
Falls jedoch bereits eine andere Komponente, wie etwa Siloxan (A) oder Vernetzer (C) , die genannten funktioneilen Gruppen aufweist, kann auf einen Zusatz von Haftvermittler verzichtet werden .However, if another component, such as siloxane (A) or crosslinking agent (C), already has the functional groups mentioned, it is not necessary to add an adhesion promoter.
Die erfindungsgemäßen Massen enthalten Haftvermittler (G) in Mengen von vorzugsweise 0 bis 50 Gewichtsteilen, besonders bevorzugt 1 bis 20 Gewichtsteilen, insbesondere 1 bis 10 Ge- wichtsteilen, jeweils bezogen auf 100 Gewichtsteile Organopoly- siloxan (A) .The compositions according to the invention contain adhesion promoters (G) in amounts of preferably 0 to 50 parts by weight, particularly preferably 1 to 20 parts by weight, in particular 1 to 10 parts by weight parts by weight, each based on 100 parts by weight of organopolysiloxane (A).
Beispiele für Additive (H) sind Pigmente, Farbstoffe, Riech- stoffe, Oxidationsinhibitoren, Mittel zur Beeinflussung der e- lektrischen Eigenschaften, wie leitfähiger Ruß, flammabweisend machende Mittel, Lichtschutzmittel und Mittel zur Verlängerung der Hautbildungszeit, wie Silane mit einem SiC-gebundenen Mer- captoalkylrest, zellenerzeugende Mittel, z.B. Azodicarbonamid, Hitzestabilisatoren und Thixotropiermittel, wie beispielsweise Phosphorsäureester, und organischen Lösungsmittel, wie Alkyla- romaten.Examples of additives (H) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive carbon black, flame retardants, light stabilizers and agents for prolonging the skin formation time, such as silanes with a SiC-bound mer - captoalkyl radical, cell-producing agents, for example Azodicarbonamide, heat stabilizers and thixotropic agents, such as, for example, phosphoric acid esters, and organic solvents, such as alkylates.
Die erfindungsgemäßen Massen enthalten Additive (H) in Mengen von vorzugsweise 0 bis 100 Gewichtsteilen, besonders bevorzugt 0 bis 30 Gewichtsteilen, insbesondere 0 bis 10 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Organopolysiloxan (A) .The compositions according to the invention contain additives (H) in amounts of preferably 0 to 100 parts by weight, particularly preferably 0 to 30 parts by weight, in particular 0 to 10 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A).
Insbesondere bevorzugt handelt es sich bei den erfindungsgemä- ßen Massen um solche, die ausThe compositions according to the invention are particularly preferably those which consist of
(A) Organosiliciumverbindungen enthaltend Einheiten der Formel(A) Organosilicon compounds containing units of the formula
(I),(I)
(B) Organosiliciumverbindung mit mindestens einer Einheit der Formel (II), gegebenenfalls(B) Organosilicon compound with at least one unit of the formula (II), if appropriate
(C) Vernetzer der Formel (V) , gegebenenfalls(C) crosslinking agent of the formula (V), if appropriate
(D) Katalysator, gegebenenfalls (E) Weichmacher, gegebenenfalls (F) Füllstoffe, gegebenenfalls (G) Haftvermittler und gegebenenfalls (H) Additive bestehen.(D) catalyst, optionally (E) plasticizer, optionally (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
Zur Bereitung der erfindungsgemäßen Massen können alle Bestandteile in beliebiger Reihenfolge miteinander vermischt werden. Dieses Vermischen kann bei Raumtemperatur und dem Druck der umgebenden Atmosphäre, also etwa 900 bis 1100 hPa, erfolgen. Falls erwünscht, kann dieses Vermischen aber auch bei höheren Temperaturen erfolgen, z.B. bei Temperaturen im Bereich von 35°C bis 135°C.To prepare the compositions according to the invention, all of the constituents can be mixed with one another in any order. This mixing can take place at room temperature and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. If desired, this mixing can also take place at higher temperatures, e.g. at temperatures in the range of 35 ° C to 135 ° C.
Bei den einzelnen Bestandteilen der erfindungsgemäßen Massen kann es sich jeweils um eine Art eines solchen Bestandteils wie auch um ein Gemisch aus mindestens zwei verschiedenen Arten derartiger Bestandteile handeln.The individual constituents of the compositions according to the invention can each be a type of such constituent or a mixture of at least two different types of such constituents.
Für die Vernetzung der erfindungsgemäßen Massen reicht der üb- liehe Wassergehalt der Luft aus. Die Vernetzung der erfindungsgemäßen Massen erfolgt vorzugsweise bei Raumtemperatur. Sie kann, falls erwünscht, auch bei höheren oder niedrigeren Temperaturen als Raumtemperatur, z.B. bei -5° bis 15°C oder bei 30° bis 50 °C und/oder mittels den normalen Wassergehalt der Luft übersteigenden Konzentrationen von Wasser durchgeführt werden.The usual water content of the air is sufficient for the crosslinking of the compositions according to the invention. The compositions of the invention are preferably crosslinked at room temperature. If desired, it can also be used at temperatures higher or lower than room temperature, e.g. at -5 ° to 15 ° C or at 30 ° to 50 ° C and / or by means of concentrations of water exceeding the normal water content of the air.
Vorzugsweise wird die Vernetzung bei einem Druck von 100 bis 1100 hPa, insbesondere beim Druck der umgebenden Atmosphäre, durchgeführt .The crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Formkörper, hergestellt durch Vernetzung der erfindungsgemäßen Massen. Die erfindungsgemäßen Massen können für alle Verwendungszwecke eingesetzt werden, für die unter Ausschluss von Wasser lagerfähige, bei Zutritt von Wasser bei Raumtemperatur zu Elastomeren vernetzende Massen eingesetzt werden können.The present invention furthermore relates to moldings produced by crosslinking the compositions according to the invention. The compositions according to the invention can be used for all purposes for which compositions which can be stored with the exclusion of water and which crosslink to form elastomers when water is admitted at room temperature can be used.
Die erfindungsgemäßen Massen eignen sich somit ausgezeichnet beispielsweise als Abdichtmassen für Fugen, einschließlich senkrecht verlaufender Fugen, und ähnlichen Leerräumen von z.B. 10 bis 40 mm lichter Weite, z.B. von Gebäuden, Land-, Wasser- und Luftfahrzeugen, oder als Klebstoffe oder Verkittungsmassen, z.B. im Fensterbau oder bei der Herstellung von Aquarien oder Vitrinen, sowie z.B. zur Herstellung von Schutzüberzügen, einschließlich solcher für der ständigen Einwirkung von Süß- oder Meerwasser ausgesetzte Oberflächen, oder das Gleiten verhin- dernden Überzügen, oder von gummielastischen Formkörpern sowie für die Isolierung von elektrischen oder elektronischen Vorrichtungen.The compositions of the invention are therefore extremely suitable, for example, as sealing compounds for joints, including vertical joints, and similar empty spaces, e.g. 10 to 40 mm clear width, e.g. of buildings, land, water and aircraft, or as adhesives or cementing compounds, e.g. in window construction or in the production of aquariums or showcases, as well as e.g. for the production of protective coatings, including those surfaces which are exposed to the constant action of fresh or sea water, or coatings which prevent sliding, or of rubber-elastic molded articles, and for the insulation of electrical or electronic devices.
Die erfindungsgemäßen Massen haben den Vorteil, dass sie leicht herzustellen sind und über einen langen Zeitraum biozide Wirkung zeigen.The compositions of the invention have the advantage that they are easy to manufacture and have a biocidal action over a long period of time.
Des weiteren haben die erfindungsgemäßen Massen den Vorteil, dass durch die biozide Ausrüstung die Neigung zur Verfärbung sowohl der noch nicht ausgehärteten Masse als auch der ausgehärteten Formkörper äußerst gering ist.Furthermore, the compositions according to the invention have the advantage that the tendency to discolour both the not yet cured composition and the cured molded articles is extremely low due to the biocidal treatment.
Die erfindungsgemäßen vernetzbaren Massen haben den Vorteil, dass sie sich durch eine sehr hohe Lagerstabilität und eine ho- he Vernetzungsgeschwindigkeit auszeichnen.The crosslinkable compositions according to the invention have the advantage that they are distinguished by a very high storage stability and a high crosslinking rate.
In den nachstehend beschriebenen Beispielen beziehen sich alle Viskositätsangaben auf eine Temperatur von 25°C. Sofern nicht anders angegeben, werden die nachstehenden Beispiele bei einem Druck der umgebenden Atmosphäre, also etwa bei 1000 hPa, und bei Raumtemperatur, also bei etwa 23°C, bzw. bei einer Temperatur, die sich beim Zusammengeben der Reaktanden bei Raumtemperatur ohne zusätzliche Heizung oder Kühlung einstellt, sowie bei einer relativen Luftfeuchtigkeit von etwa 50 % durchgeführt. Des weiteren beziehen sich alle Angaben von Teilen und Prozentsätzen, soweit nichts anderes angegeben ist, auf das Gewicht.In the examples described below, all viscosity data relate to a temperature of 25 ° C. Unless otherwise stated, the following examples are given at a pressure of the surrounding atmosphere, that is to say at about 1000 hPa, and at room temperature, that is to say at about 23 ° C., or at a temperature which when the reactants are combined at room temperature without additional heating or cooling sets, and carried out at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise stated.
Beispiel 1example 1
Herstellung von eines polyquarternären Polysiloxans : 286,4 g Dimethylammoniumchlorid wurden in 1000 ml Wasser gelöst, 1200 g 1, 3-Bis (3-glycidoxypropyl) -1, 1, 3, 3-tetramethyldi- siloxan zugegeben und das Gemisch unter gutem Rühren unter Rückfluss erwärmt. Das Reaktionsgemisch wurde 2 Stunden bei 105-110°C gerührt, wobei sich der Reaktionsansatz von farblos trüb nach klar gelb ändert. Anschließend wurde das Lösungsmittel im Vakuum bei 120 °C entfernt. Das Reaktionsprodukt war ein dunkelgelbes, hochviskoses Öl mit einer Viskosität von ca.Preparation of a polyquaternary polysiloxane: 286.4 g of dimethylammonium chloride were dissolved in 1000 ml of water, 1200 g of 1, 3-bis (3-glycidoxypropyl) -1, 1, 3, 3-tetramethyldisiloxane were added and the mixture was stirred in thoroughly Reflux heated. The reaction mixture was stirred at 105-110 ° C for 2 hours, the reaction mixture changing from colorless cloudy to clear yellow. The solvent was then removed in vacuo at 120 ° C. The reaction product was a dark yellow, highly viscous oil with a viscosity of approx.
16' 106 mPas . Die 1H-NMR-spektroskopische Untersuchung belegte die Bildung eines polyquarternären Polysiloxans mit etwa durchschnittlich 18 bis 20 Wiederholungseinheiten entsprechend der Formel16 '10 6 mPas. The 1 H-NMR spectroscopic examination confirmed the formation of a polyquaternary polysiloxane with an average of 18 to 20 repetition units according to the formula
In einem Planetenmischer mit Vakuumausrüstung werden unter Was- serausschluss 1400 g eines Polydimethylsiloxans mit -OSi (OCH3) 2 (CH3) -Endgruppen, das eine Viskosität von 80000 mPas besitzt, mit 600 g eines Polydimethylsiloxans mit -OSi(CH3)3- Endgruppen und einer Viskosität von 100 mPas, 12 g des polyquarternären Polysiloxans, dessen Herstellung oben beschrieben ist, 100 g Methyltrimethoxysilan, 2,5 g Octylphosphonsäure und 18 g 3-Aminopropyltrimethoxysilan vermischt. Dann werden 200 g pyrogene hydrophilen Kieselsäure mit einer spezifischen Oberfläche von 150 m2/g eingemischt. Nachdem die Mischung homogen ist und durch Evakuieren von eingeschlossener Luft befreit wurde, werden noch 10 g eines Zinnkatalysators (Umsetzungsprodukt, das aus 4 Teilen Tetraethoxysilan mit 2,2 Teilen Dibutylzinndi- acetat hergestellt wurde) eingemischt. Nach weiterem Homogenisieren im Vakuum wird die Mischung in feuchtigkeitsdichte Ge- binde abgefüllt.1400 g of a polydimethylsiloxane with -OSi (OCH 3 ) 2 (CH 3 ) end groups, which has a viscosity of 80,000 mPas, with 600 g of a polydimethylsiloxane with -OSi (CH 3 ) 3 are in a planetary mixer with vacuum equipment with exclusion of water - End groups and a viscosity of 100 mPas, 12 g of the polyquaternary polysiloxane, the preparation of which is described above is, 100 g of methyltrimethoxysilane, 2.5 g of octylphosphonic acid and 18 g of 3-aminopropyltrimethoxysilane mixed. Then 200 g of pyrogenic hydrophilic silica with a specific surface area of 150 m 2 / g are mixed in. After the mixture is homogeneous and freed of trapped air by evacuation, 10 g of a tin catalyst (reaction product which was prepared from 4 parts of tetraethoxysilane with 2.2 parts of dibutyltin diacetate) are mixed in. After further homogenization in vacuo, the mixture is filled into moisture-tight containers.
Mit der so erhaltenen Masse werden 2 mm dicke Probekörper hergestellt, indem die Masse auf einer Polyethylenunterlage ausgestrichen wird und 14 Tage bei 50% relativer Luftfeuchte und 23°C gelagert wird.With the mass obtained in this way, 2 mm thick test specimens are produced by spreading the mass on a polyethylene base and storing for 14 days at 50% relative atmospheric humidity and 23 ° C.
Aus den so hergestellten Vulkanisatplatten werden Probekörper gemäß DIN EN ISO 846 hergestellt und wie in der Norm beschrieben nach Verfahren B getestet. Die Ergebnisse sind in Tabelle 1 aufgeführt.Test specimens according to DIN EN ISO 846 are produced from the vulcanizate plates thus produced and tested according to method B as described in the standard. The results are shown in Table 1.
Zur Ermittlung der Lagerstabilität wurde eine Probe in einem luftfeuchtigkeitsdichten Gebinde 3 Tage bei 100°C gelagert. Es ergaben sich keine Veränderungen hinsichtlich Aushärteverhalten und Aussehen der Probe, was eine ausgezeichnete Lagerstabilität und Vergilbungsresistenz belegt.To determine the storage stability, a sample was stored in an airtight container for 3 days at 100 ° C. There were no changes in the hardening behavior and appearance of the sample, which demonstrates excellent storage stability and yellowing resistance.
Beispiel 2Example 2
1400 g eines α, ω-Dihydroxypolydimethylsiloxans mit einer Visko- sität von 80 000 mPas, 12 g des polyquarternären Polysiloxans, dessen Herstellung in Beispiel 1 beschrieben ist, 300 g eines Polydimethylsiloxans mit -OSi (CH3) 3-Endgruppen und einer Viskosität von 100 mPas, 300 g eines Kohlenwasserstoffgemisches mit einer kinematischen Viskosität von 6,2 mm2/s (bei 40°C), einer Viskositäts-Dichte-Konstante (VDK) von 0,79 und einem Siedebereich von 300°C bis 370°C (Kohlenstoffverteilung 62 % paraffinische, 38 % naphthenische und 0,03 % aromatische Kohlenstoffatome) , 90 g Ethyltriacetoxysilan und 190 g einer pyrogenen hydrophilen Kieselsäure mit einer spezifischen Oberfläche von 150 m/g wurde in einem Planetenmischer homogen im Vakuum vermischt. Anschließend wurde 0,5 g Dibutylzinndiacetat zugegeben und nochmals 5 Minuten homogenisiert.1400 g of an α, ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas, 12 g of the polyquaternary polysiloxane, the preparation of which is described in Example 1, 300 g of a polydimethylsiloxane with -OSi (CH 3 ) 3 end groups and a viscosity of 100 mPas, 300 g of a hydrocarbon mixture with a kinematic viscosity of 6.2 mm 2 / s (at 40 ° C), a viscosity density constant (VDK) of 0.79 and a boiling range of 300 ° C to 370 ° C (carbon distribution 62% paraffinic, 38% naphthenic and 0.03% aromatic carbon atoms), 90 g of ethyl triacetoxysilane and 190 g of a pyrogenic hydrophilic silica with a specific surface area of 150 m / g were homogeneously mixed in a planetary mixer in a vacuum. Then 0.5 g of dibutyltin diacetate was added and homogenized again for 5 minutes.
Aus der so erhaltenen Masse werden wie in Beispiel 1 beschrieben Probekörper hergestellt und gemäß DIN EN ISO 846 geprüft. Die Ergebnisse sind in Tabelle 1 aufgeführt.Test specimens are produced from the mass obtained in this way as described in Example 1 and tested in accordance with DIN EN ISO 846. The results are shown in Table 1.
Zur Ermittlung der Lagerstabilität wurde eine Probe in einem luftfeuchtigkeitsdichten Gebinde 3 Tage bei 100 °C gelagert. Es ergaben sich keine Veränderungen hinsichtlich Aushärteverhalten und Aussehen der Probe, was eine ausgezeichnete Lagerstabilität und Vergilbungsresistenz belegt.To determine the storage stability, a sample was stored in an airtight container for 3 days at 100 ° C. There were no changes in the hardening behavior and appearance of the sample, which demonstrates excellent storage stability and yellowing resistance.
Beispiel 3Example 3
Die in Beipiel 1 beschriebene Arbeitsweise wird wiederholt mit der Abänderung, dass die doppelte Menge des polyquarternären Polysiloxans eingesetzt wurde.The procedure described in Example 1 is repeated with the modification that twice the amount of the polyquaternary polysiloxane has been used.
Aus der so erhaltenen Masse werden wie bei Beispiel 1 beschrieben, Probekörper hergestellt und gemäß DIN EN ISO 846 geprüft. Die Ergebnisse sind in Tabelle 1 aufgeführt.Test specimens are produced from the mass obtained in this way as described in Example 1 and tested in accordance with DIN EN ISO 846. The results are shown in Table 1.
Zur Ermittlung der Lagerstabilität wurde eine Probe in einem luftfeuchtigkeitsdichten Gebinde 3 Tage bei 100°C gelagert. Es ergaben sich keine Veränderungen hinsichtlich Aushärteverhalten und Aussehen der Probe, was eine ausgezeichnete Lagerstabilität und Vergilbungsresistenz belegt.To determine the storage stability, a sample was stored in an airtight container for 3 days at 100 ° C. There were no changes in curing behavior and the appearance of the sample, which demonstrates excellent storage stability and resistance to yellowing.
Beispiel 4 233 g Dimethylammoniumchlorid wurden in 1700 ml Wasser gelöst. Zur Lösung werden 2238 g eines Polysiloxans, bestehend aus (3- Glycidoxypropyl) -dimethylsiloxy- und Dimethylsiloxyeinheiten mit durchschnittlich 8 Siliciumatomen und einem Epoxygruppenge- halt von 2,4 mmol/g, gegeben, und das Gemisch unter gutem Rüh- ren unter Rückfluss erwärmt. Das Reaktionsgemisch wurde 6 Stunden bei 105-110 °C gerührt, wobei sich der Reaktionsansatz von farblos trüb nach klar gelb ändert. Anschließend wurde das Lösungsmittel im Vakuum bei 120 °C entfernt. Das Reaktionsprodukt war ein dunkelgelbes, hochviskoses Öl mit einer Viskosität von ca. 6*106 mPas . Die IH-NMR-spektroskopische Untersuchung belegte die Bildung eines polyquarternären Polysiloxans mit etwa durchschnittlich 30 bis 35 Wiederholungseinheiten entsprechend der FormelExample 4 233 g of dimethylammonium chloride were dissolved in 1700 ml of water. 2238 g of a polysiloxane consisting of (3-glycidoxypropyl) dimethylsiloxy and dimethylsiloxy units with an average of 8 silicon atoms and an epoxy group content of 2.4 mmol / g are added to the solution, and the mixture is heated under reflux with thorough stirring , The reaction mixture was stirred for 6 hours at 105-110 ° C, the reaction mixture changing from colorless cloudy to clear yellow. The solvent was then removed in vacuo at 120 ° C. The reaction product was a dark yellow, highly viscous oil with a viscosity of approx. 6 * 10 6 mPas. The IH-NMR spectroscopic examination confirmed the formation of a polyquaternary polysiloxane with about 30 to 35 repetition units on average according to the formula
35 g des so hergestellten polyquarternären Polysiloxans, 1400 g eines , ω-Dihydroxypolydimethylsiloxans mit einer Viskosität von 80 000 mPas, 600 g eines Polydimethylsiloxans mit -OSi (CH3) 3-Endgruppen und einer Viskosität von 100 mPas, 90 g35 g of the polyquaternary polysiloxane thus produced, 1400 g of an, ω-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas, 600 g of a polydimethylsiloxane with -OSi (CH 3 ) 3 end groups and a viscosity of 100 mPas, 90 g
Ethyltriacetoxysilan und 190 g einer pyrogenen hydrophilen Kieselsäure mit einer spezifischen Oberfläche von 150 m2/g wurde in einem Planetenmischer homogen im Vakuum vermischt. Anschließend wurden 0,5 g Dibutylzinndiacetat zugegeben und nochmals 5 Minuten homogenisiert.Ethyltriacetoxysilane and 190 g of a pyrogenic hydrophilic silica with a specific surface area of 150 m 2 / g were mixed homogeneously in vacuo in a planetary mixer. Then 0.5 g of dibutyltin diacetate was added and homogenized again for 5 minutes.
Aus der so erhaltenen Masse werden wie in Beispiel 1 beschrieben Probekörper hergestellt und gemäß DIN EN ISO 846 geprüft. Die Ergebnisse sind in Tabelle 1 aufgeführt.Test specimens are produced from the mass obtained in this way as described in Example 1 and tested in accordance with DIN EN ISO 846. The results are shown in Table 1.
Zur Ermittlung der Lagerstabilität wurde eine Probe in einem luftfeuchtigkeitsdichten Gebinde 3 Tage bei 100°C gelagert. Es ergaben sich keine Veränderungen hinsichtlich Aushärteverhalten und Aussehen der Probe, was eine ausgezeichnete Lagerstabilität und Vergilbungsresistenz belegt.To determine the storage stability, a sample was stored in an airtight container for 3 days at 100 ° C. There were no changes in the hardening behavior and appearance of the sample, which demonstrates excellent storage stability and yellowing resistance.
Tabelle 1:Table 1:
A = Aspergillus niger B = Penicillium funiculosum C = Paecillomyces variotiiA = Aspergillus niger B = Penicillium funiculosum C = Paecillomyces variotii
D = Gliocladium virensD = Gliocladium virens
E = Chaetomium globosumE = Chaetomium globosum
00 kein Wachstum bei mikroskopischer Betrachtung erkennbar, Bildung einer Hemmzone um den Prüfkörper 0 kein Wachstum bei mikroskopischer Betrachtung erkennbar 1 kein Wachstum mit bloßem Auge, aber unter dem Mikroskop klar erkennbar 2 Wachstum mit bloßem Auge erkennbar, bis zu 25% der Probenoberfläche bewachsen 3 Wachstum mit bloßem Auge erkennbar, bis zu 50% der Proben- Oberfläche bewachsen 4 beträchtliches Wachstum, über 50% der Probenoberfläche bewachsen 5 starkes Wachstum, ganze Probenoberfläche bewachsen. 00 no growth visible when viewed microscopically, formation of an inhibition zone around the test specimen 0 no growth visible when viewed microscopically 1 no growth visible to the naked eye, but clearly visible under the microscope 2 growth visible to the naked eye, up to 25% of the sample surface overgrown 3 growth Visible to the naked eye, up to 50% of the sample surface covered with 4 considerable growth, over 50% of the sample surface covered with 5 strong growth, entire sample surface covered.

Claims

Patentansprüche claims
1. Vernetzbare Massen auf der Basis von Organosiliciumverbindungen, dadurch gekennzeichnet, dass sie Organosiliciumverbin- düngen mit quaternären Ammoniumgruppen enthalten.1. Crosslinkable compositions based on organosilicon compounds, characterized in that they contain organosilicon compounds with quaternary ammonium groups.
2. Vernetzbare Massen gemäß Anspruch 1, dadurch gekennzeichnet, dass es sich um solche handelt, die (A) Organosiliciumverbindung mit mindestens zwei kondensations- fähigen Gruppen, (B) Organosiliciumverbindung mit mindestens einer Einheit der Formel2. Crosslinkable compositions according to claim 1, characterized in that they are (A) organosilicon compounds with at least two condensable groups, (B) organosilicon compounds with at least one unit of the formula
-SiR 2-R -N+RVR4 •SiR 2- X" (II)-SiR 2-R -N + RVR 4 • SiR 2 - X " (II)
wobeiin which
R2 gleich oder verschieden sein kann und eine für R unten angegebene Bedeutung hat, R3 gleich oder verschieden sein kann und einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest bedeutet oder Bestandteil eines verbrückenden Alkylenrestes sein kann, X~ ein organisches oder anorganisches Anion darstellt, R4 einen zweiwertigen, gegebenenfalls substituierten Kohlen- wasserstoffrest darstellt, der mit Heteroatomen unterbrochen sein kann, und gegebenenfalls (C) Vernetzer enthalten .R 2 can be the same or different and has a meaning given for R below, R 3 can be the same or different and represents a monovalent, optionally substituted hydrocarbon radical or can be part of a bridging alkylene radical, X ~ represents an organic or inorganic anion, R 4 represents a divalent, optionally substituted hydrocarbon radical which can be interrupted by heteroatoms and optionally contain (C) crosslinking agents.
3. Vernetzbare Massen gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass als Organosiliciumverbindungen (A) solche enthaltend Einheiten der Formel3. Crosslinkable compositions according to claim 1 or 2, characterized in that as organosilicon compounds (A) contain units of the formula
Ra(OR1)bYcSiO(4-a-b-c)/2 (I), wobeiRa (OR 1 ) b Y c SiO (4 - a - b - c ) / 2 (I), in which
R gleich oder verschieden sein kann und gegebenenfalls substituierte Kohlenwasserstoffreste, die durch Sauerstoffatome un- terbrochen sein können, bedeutet,R can be the same or different and means optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms,
R1 gleich oder verschieden sein kann und Wasserstoffatom oder einwertige, gegebenenfalls substituierte Kohlenwasserstoffreste, die durch Sauerstoffatome unterbrochen sein können, bedeutet, Y gleich oder verschieden sein kann und Halogenatom, Pseudoha- logenrest, Si-N-gebundene Aminreste, Amidreste, Oximreste, Ami- noxyreste und Acyloxyreste bedeutet, a 0, 1, 2 oder 3 ist, b 0, 1, 2 oder 3 ist und c 0, 1, 2 oder 3 ist, mit der Maßgabe, dass die Summe aus a+b+c kleiner oder gleich 4 ist und pro Molekül mindestens zwei kondensationsfähige Reste (OR1) anwesend sind, eingesetzt werden.R 1 can be the same or different and means hydrogen atom or monovalent, optionally substituted hydrocarbon radicals which can be interrupted by oxygen atoms, Y can be the same or different and halogen atom, pseudohalogen radical, Si-N-bonded amine radicals, amide radicals, oxime radicals, ami - noxy and acyloxy means a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and c is 0, 1, 2 or 3, with the proviso that the sum of a + b + c is smaller or is 4 and at least two condensable radicals (OR 1 ) are present per molecule.
4. Vernetzbare Massen gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass als Organosiliciumverbindungen (B) solche der Formel4. Crosslinkable compositions according to one or more of claims 1 to 3, characterized in that the organosilicon compounds (B) are those of the formula
D1-(RSiR2 2)h-[ (OSiR2 2)d-R-N+R32-R4-SiR2 2]n-D2 • nX~ (III),D 1 - (RSiR 2 2 ) h - [(OSiR 2 2 ) dRN + R 3 2-R 4 -SiR 2 2 ] nD 2 • nX ~ (III),
wobeiin which
D1 ein Wasserstoffatom, Hydroxylrest, Halogenidrest, einen rest -NR*2 oder einen einwertigen organischen Rest bedeutet, wobei R* gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest darstellt und der Rest -NR*2 auch als Ammoniumsalz vorliegen kann, und D2 eine Gruppe der Formel - (OSiR2 2) g-Rk~D1 bedeutet mit R2, R3, D1, X~ und R4 gleich einer oben dafür angegebenen Bedeutung, wobei die beiden Reste D1 in jedem Polymermolekül der Formel (III) gleich oder unterschiedlich sein können, und d eine ganze Zahl von 1 bis 200 ist, h 0 oder 1 ist, k 0 oder 1 ist, g eine Zahl von 0 bis 1000 ist und n eine ganze Zahl von 1 bis 50 ist, eingesetzt werden.D 1 represents a hydrogen atom, hydroxyl radical, halide radical, a radical -NR * 2 or a monovalent organic radical, where R * can be the same or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical and the radical -NR * 2 also as the ammonium salt can be present, and D 2 is a group of the formula - (OSiR 2 2 ) g -R k ~ D 1 means with R 2 , R 3 , D 1 , X ~ and R 4 equal to one of the meanings given above, the two radicals D 1 in each Polymer molecule of formula (III) may be the same or different, and d is an integer from 1 to 200, h is 0 or 1, k is 0 or 1, g is a number from 0 to 1000 and n is an integer from 1 up to 50 is used.
5. Vernetzbare Massen gemäß einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Organosiliciumverbindungen (B) eine Viskosität von 104 bis 108 mPas bei 25°C haben.5. Crosslinkable compositions according to one or more of claims 1 to 4, characterized in that organosilicon compounds (B) have a viscosity of 10 4 to 10 8 mPas at 25 ° C.
6. Vernetzbare Massen gemäß einem oder mehreren der Ansprüche6. Crosslinkable compositions according to one or more of the claims
1 bis 5, dadurch gekennzeichnet, dass als Organosiliciumverbindungen (A) solche der Formel1 to 5, characterized in that as organosilicon compounds (A) those of the formula
(OR1)3-fRfSi-(SiR2-0)e-SiRf(OR1)3-f (IV)(OR 1 ) 3 - f R f Si- (SiR 2 -0) e -SiR f (OR 1 ) 3 - f (IV)
eingesetzt werden, wobeiare used, whereby
R und R1 eine der oben angegebenen Bedeutungen haben, e gleich 30 bis 3000 ist und f gleich 1 oder 2 ist.R and R 1 have one of the meanings given above, e is 30 to 3000 and f is 1 or 2.
7. Vernetzbare Massen gemäß einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es sich bei den erfindungsgemäßen Massen um solche handelt, die aus (A) Organosiliciumverbindungen enthaltend Einheiten der Formel7. Crosslinkable compositions according to one or more of claims 1 to 6, characterized in that the compositions according to the invention are those which consist of (A) organosilicon compounds containing units of the formula
(I),(I)
(B) Organosiliciumverbindung mit mindestens einer Einheit der(B) Organosilicon compound with at least one unit of
Formel (II) , gegebenenfalls (C) Vernetzer der Formel (V) , gegebenenfalls (D) Katalysator, gegebenenfalls (E) Weichmacher, gegebenenfalls (F) Füllstoffe, gegebenenfalls (G) Haftvermittler und gegebenenfalls (H) Additive bestehen.Formula (II), optionally (C) crosslinking agents of formula (V), optionally (D) catalyst, optionally (E) plasticizers, optionally (F) fillers, optionally (G) adhesion promoters and optionally (H) additives.
8. Vernetzbare Massen gemäß einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es sich bei den erfindungsgemäßen Massen um solche handelt, die aus (A) Organosiliciumverbindungen der Formel (IV) , (B) Organosiliciumverbindung der Formel (III) , gegebenenfalls (C) Vernetzer der Formel (V) , gegebenenfalls (D) Katalysator, gegebenenfalls (E) Weichmacher, gegebenenfalls (F) Füllstoffe, gegebenenfalls8. Crosslinkable compositions according to one or more of claims 1 to 7, characterized in that the compositions according to the invention are those which consist of (A) organosilicon compounds of the formula (IV), (B) organosilicon compounds of the formula (III), optionally (C) crosslinking agent of formula (V), optionally (D) catalyst, optionally (E) plasticizer, optionally (F) fillers, optionally
(G) Haftvermittler und gegebenenfalls(G) adhesion promoter and, if applicable
(H) Additive bestehen. (H) additives exist.
9. Formkörper, hergestellt durch Vernetzung der vernetzbaren Massen gemäß einem oder mehreren der Ansprüche 1 bis 8. 9. Shaped body, produced by crosslinking the crosslinkable compositions according to one or more of claims 1 to 8.
EP04803981A 2003-12-22 2004-12-16 Cross-linkable products based on organosilicon compounds Withdrawn EP1694773A2 (en)

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DE10360469A DE10360469A1 (en) 2003-12-22 2003-12-22 Crosslinkable compositions based on organosilicon compounds
PCT/EP2004/014370 WO2005063872A2 (en) 2003-12-22 2004-12-16 Cross-linkable products based on organosilicon compounds

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CN1898332A (en) 2007-01-17
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WO2005063872A2 (en) 2005-07-14

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