WO2012130663A1 - Matières réticulables à base de polymères à terminaison organyloxysilane - Google Patents

Matières réticulables à base de polymères à terminaison organyloxysilane Download PDF

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Publication number
WO2012130663A1
WO2012130663A1 PCT/EP2012/054858 EP2012054858W WO2012130663A1 WO 2012130663 A1 WO2012130663 A1 WO 2012130663A1 EP 2012054858 W EP2012054858 W EP 2012054858W WO 2012130663 A1 WO2012130663 A1 WO 2012130663A1
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formula
different
radicals
possibly
compositions
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PCT/EP2012/054858
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German (de)
English (en)
Inventor
Volker Stanjek
Marko Prasse
Wolfram Schindler
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Wacker Chemie Ag
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Priority to EP12710695.3A priority Critical patent/EP2688937A1/fr
Publication of WO2012130663A1 publication Critical patent/WO2012130663A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33344—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carbamate group
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides

Definitions

  • the invention relates to crosslinkable compositions based on silane-crosslinking prepolymers, processes for their preparation and their use as adhesives, in particular for bonding substrates.
  • Adhesives based on alkoxysilane-crosslinking polymers in the cured state show not only good adhesion properties on some substrates, but also very good mechanical properties, since they can be both tear-resistant and highly elastic.
  • Another key advantage of silane crosslinking systems over many other adhesive and sealant technologies e.g., over isocyanate crosslinking systems is the toxicological safety of the prepolymers.
  • one-component systems (1-component systems) are preferred which cure when exposed to atmospheric moisture.
  • the decisive advantages of single-component systems are, above all, their very easy applicability since no mixing of different adhesive components by the user is required here.
  • the time / labor savings and the safe avoidance of any dosage errors is at 4858
  • einkomonentigen systems also not given the need to process the adhesive / sealant within a usually quite narrow time window, as is the case with multi-component systems after mixing of the two components.
  • the corresponding mixtures therefore typically contain significant amounts of toxicologically harmful tin catalysts.
  • the use of so-called ⁇ -silane-terminated prepolymers is advantageous which have reactive alkoxysilyl groups which are connected by a methylene spacer to an adjacent urethane unit.
  • This class of compounds is highly reactive and requires neither tin catalysts nor strong acids or bases to achieve high cure rates on exposure to air.
  • silane-crosslinking adhesives generally have the disadvantage of not having sufficiently good adhesion on all materials. For example, they often show inadequate adhesion to concrete, especially wet concrete, as well as numerous plastics, especially PVC. The adhesion to wood is not optimal in many cases. This applies in particular to adhesives which have a tensile strength measured after curing according to DIN EN 14293 and / or DIN EN 53504 of at least 1 MPa. In particular, these tear solid adhesives for mechanically stressed adhesive seams high demands on the liability, as they not only do not tear when high tensile forces occur but of course not allowed to detach from the substrate.
  • the invention relates to crosslinkable compositions having a viscosity of at least 20,000 mPas at 25 ° C containing
  • A represents a divalent polyoxyalkylene radical
  • R may be identical or different and represents a monovalent, optionally substituted, Sic-bonded hydrocarbon radical
  • R 1 may be identical or different and is hydrogen or a monovalent, optionally substituted hydrocarbon 12 054858
  • R 2 may be the same or different and represents hydrogenator or a monovalent, optionally substituted hydrocarbon radical
  • a may be the same or different and is 0, 1 or 2, preferably 0 or 1, and
  • b may be identical or different and is an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3, in particular 1,
  • R 3 may be identical or different and denotes a monovalent Sic-bonded hydrocarbon radical having 10 to 40 carbon atoms,
  • R 4 may be identical or different and is hydrogen or optionally substituted hydrocarbon radicals
  • R 5 may be identical or different and is a monovalent, Sic-bonded, hydrocarbon est having 1 or 2 carbon atoms
  • c is 1, 2, 3 or 4, preferably 1, and
  • d is 0, 1, 2 or 3, preferably 2 or 3, more preferably 3
  • radicals R are alkyl radicals such as methyl, ethyl, n ⁇ f propyl iso-propyl, ln-butyl, 2-n-butyl, iso-butyl, tert.
  • substituted radicals R are haloalkyl radicals, such as the 3, 3, 3-trifluoro-n-propyl radical, the 2, 2, 2, 2 ", 2 ', 2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as o-, m- and p-chlorophenyl radical.
  • Radical R is preferably monovalent hydrocarbon radicals having 1 to 6 carbon atoms which are optionally substituted by halogen atoms, more preferably alkyl radicals having 1 or 2 carbon atoms, in particular the methyl radical.
  • radicals R 1 are hydrogen, the radicals indicated for R and optionally substituted by nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group bonded to the carbon atom, optionally substituted hydrocarbon radicals.
  • Radical R 1 is preferably hydrogen atom and hydrocarbon radicals having 1 to 20 carbon atoms, in particular hydrogen atom.
  • radical R 2 are hydrogen atom or the examples given for radical R.
  • the radicals R 2 are preferably hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms optionally substituted by halogen atoms, more preferably alkyl radicals having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.
  • the polyoxyalkylene radicals A are preferably linear polyoxyalkylene radicals, particularly preferably those of the formula
  • R 8 may be the same or different and is an optionally substituted divalent hydrocarbon radical having 1 to 12 carbon atoms, which may be linear or branched, meaning and
  • e is an integer from 50 to 550.
  • radical R 8 are -CH 2 -, ⁇ CH 2 -CH 2 ⁇ , -CH 2 -CH (CH 3 ) -, -CH 2 - CH 2 -CH 2 ⁇ , -CH 2 -CH (-CH 2 -CH 3 ) ⁇ CH ⁇ CH 3 ) ⁇ CH ⁇ CH 3 ) -, -CH 2 ⁇ CH 2 -CH 2 -CH 2 - and -CH 2 ⁇ C ⁇ CH 3 ) 2 -.
  • Radical R 8 is preferably a divalent hydrocarbon est having 1 to 4 carbon atoms, particularly preferably a divalent hydrocarbon radical having 1 to 4 carbon atoms, very particularly preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 - and -CH 2 -CH ⁇ CH 3 ) -, in particular -CH (CH 3 ) ⁇ CH 2 - and ⁇ CH 2 -CH (CH 3 ) -.
  • the polyoxyalkylene radical A is polyoxyalkylene radicals having 65 to 350 repeat units.
  • the polyoxyalkylene radicals A preferably have average molar masses M n of 4,000 to 30,000 daltons, particularly preferably 8,000 to 20,000 daltons.
  • Component (A) is preferably polypropylene glycols having hindered siloxymethylsilyl, trimethoxysilyl, diethoxymethylsilyl or triethoxysilyl end groups.
  • the viscosity of the compounds (A) is preferably at least 0.2 Pas, preferably at least 1 Pas, more preferably at least 5 Pas, and preferably at most 700 Pas, preferably at most 100 Pas, each measured at 20 ° C.
  • component (A) used according to the invention may contain only one type of compound of the formula (I) as well as mixtures of different types of compounds of the formula (I).
  • component (A) may contain exclusively compounds of the formula (I) in which more than 90%, preferably more than 95% and particularly preferably more than 98% of all silyl groups bound to the radical A are identical.
  • a component (A) which contains, at least in part, compounds of the formula (I) in which different silyl groups are bonded to a radical A.
  • component (A) it is also possible to use mixtures of different compounds of the formula ⁇ 1 ⁇ in which a total of at least 2 different types of silyl groups bonded to radicals A are present, but all silyl groups bound to one radical A are identical.
  • component (A) is a different type of compound of formula (I)
  • compositions of the invention preferably contain compounds (A) in concentrations of at most 60% by weight, more preferably at most 40% by weight and preferably at least 10% by weight, particularly preferably at least 15% by weight.
  • the radicals R 3 are preferably branched, linear or cyclic alkyl radicals having 14 to 40 carbon atoms, particularly preferably branched, linear or cyclic, preferably linear, alkyl radicals having 16 to 30 carbon atoms, the alkyl radicals preferably having an even number of carbon atoms ,
  • radical R 3 examples are the decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl radical.
  • Preferred examples of the radical R 3 are the tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl radical.
  • hexadecyl and octadecyl are. 8th
  • the radicals R 4 are preferably a hydrogen atom and optionally with Halogenatottien substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and Kohlenwasserstof radicals having 1 to 10 carbon atoms, in particular methyl and Et yl radical.
  • R 5 is the methyl radical.
  • silanes (B) used according to the invention are decyltrimethoxysilanes, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane, where the examples mentioned are preferably Alkyl silanes is.
  • the silanes used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • compositions of the invention contain component (B) in amounts of preferably from 1 to 50 parts by weight, more preferably from 2 to 25 parts by weight, based in each case on 100 parts by weight of compound (A).
  • compositions according to the invention preferably contain at least 1% by weight, more preferably at least 2% by weight and less than 10% by weight, more preferably less than 7% by weight, of the component (B), based in each case on the entire composition the crosslinkable formulation. 54858
  • compositions according to the invention may contain all other substances which have hitherto been used in crosslinkable compositions and which are different from components (A) and (B), such as e.g. further silane-trained polymers ( ⁇ '), basic nitrogen-containing organosilicon compound (C), fillers (D), catalyst (E), adhesion promoter (F), water scavenger (G), additives (H) and additives (K).
  • ⁇ ' silane-trained polymers
  • C basic nitrogen-containing organosilicon compound
  • fillers D
  • catalyst catalyst
  • adhesion promoter F
  • water scavenger G
  • additives H
  • additives (K) additives
  • compositions according to the invention preferably contain no component (A ') or these in amounts of preferably at most 15% by weight, preferably at most 10% by weight and particularly preferably at most 5% by weight, based in each case on the total weight of the components (A ) and ⁇ A ').
  • Component (C) is preferably organosilicon compounds containing units of the formula D h Si (OR 7 ) g R 6 fO ( 4 .fgh) / 2 (III), in which
  • R 6 may be the same or different and a monovalent, optionally substituted SiC-bonded, of basic
  • R 7 may be identical or different and is hydrogen or is optionally substituted hydrocarbon radicals
  • D may be identical or different and represents a monovalent, SiC-bonded radical with basic nitrogen
  • f 0, 1, 2 or 3, preferably 1,
  • g is 0, 1, 2 or 3, preferably 1, 2 or 3, more preferably 1 or 3, and
  • h is 0, 1, 2, 3 or 4, preferably 1, 2 054858
  • radical R 6 are the examples given for R.
  • the radicals R s are preferably hydrocarbon radicals having 1 to 18 carbon atoms which are optionally substituted by halogen atoms, more preferably hydrocarbon radicals having 1 to 5 carbon atoms, in particular the methyl radical.
  • the radicals R 7 is preferably a hydrogen atom and an optionally halogen-substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl and ethyl radicals.
  • radicals D are radicals of the formulas H 2 N ⁇ CH 2 ) 3 ⁇ ,
  • radical D is the H 2 N (CH 2 ) 3 -,
  • Silanes of the formula (III) are H 2 N (CH) 3 -Si ⁇ OCH 3 ⁇ 3 ,
  • Phenyl-NH (CH 2 ) -Si (OC 2 H 5 ) 3 phenyl-NH (CH 2 ) -Si (OCH 3 ) 2 CH 3 , phenyl-NH (CH 2 ) -Si (OC 2 H 5 ⁇ 2 CH 3 , phenyl-NH (CH 2 ) -Si (OH) 3 and
  • organosilicon compounds (C) optionally used according to the invention can also assume the function of a curing catalyst or cocatalyst in the compositions according to the invention.
  • organosilicon compounds (C) which may optionally be used according to the invention may act as adhesion promoters and / or as water scavengers.
  • organosilicon compounds (C) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • compositions according to the invention comprise component (C), these are amounts of preferably 0.01 to 25 parts by weight, more preferably 0.1 to 10 parts by weight, in particular 0.5 to 5 parts by weight, in each case based on 100 parts by weight of component ( A).
  • the compositions of the invention preferably contain component (C).
  • the fillers (D) optionally used in the compositions according to the invention may be any known fillers known to date.
  • Examples of fillers (D) are non-reinforcing fillers, ie fillers having a BET surface area of preferably up to 50 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powder, such as aluminum, titanium -, iron or zinc oxides or their
  • fillers such as asbestos and plastic fibers.
  • the fillers mentioned may be rendered hydrophobic, for example by treatment with organosilanes or siloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy group.
  • the optional fillers (D) used are preferably calcium carbonate, talc, aluminum trihydroxide and silicic acid.
  • Preferred calcium carbonate types are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or its salts.
  • Preferred silica is preferably fumed silica.
  • Optionally used fillers (D) have a moisture content of preferably less than 1% by weight, more preferably less than 0.5% by weight.
  • compositions according to the invention contain fillers (D), these are amounts of preferably 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, in particular 80 to 300 parts by weight, in each case based on 100 parts by weight of component (A).
  • the compositions of the invention preferably contain fillers (D).
  • the compositions according to the invention as fillers (D) comprise a combination of
  • silica in particular fumed silica
  • compositions according to the invention contain this particularly preferred combination of different fillers (D), they preferably contain from 1 to 80 parts by weight, more preferably from 5 to 40 parts by weight, of silica, in particular pyrogenic, diacid, and preferably from 10 to 500 parts by weight, particularly preferably from 50 to 300 Parts by weight, calcium carbonate, aluminum trihydroxide, talc or mixtures of these materials, each based on 100 parts by weight of component (A).
  • the catalysts (E) which may optionally be used in the compositions according to the invention may be any, hitherto known catalysts for compositions which cure by silane condensation.
  • metal-containing curing catalysts (E) are organic titanium and tin compounds, for example titanic acid esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate; compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, di-butyltin oxides, and corresponding dioctyltin compounds.
  • titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate
  • compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutylt
  • metal-free curing catalysts (E) are basic compounds, such as triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, ⁇ , ⁇ -bis- (N, N-direthyl-2-aminoethyl) -methylamine, N, N-dimethylcyclohexylamine, N, N-dimethylphenylamine, and N- Ethylmorpholinin.
  • basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, ⁇ , ⁇ -bis- (N, N-dire
  • acidic compounds such as phosphoric acid and its esters, toluenesulfonic acid, sulfuric acid, nitric acid or organic carboxylic acids, e.g. Acetic acid and benzoic acid.
  • novel compositions comprise catalysts (E), these are amounts of preferably 0.01 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, based in each case on 100 parts by weight of component ⁇ A).
  • the optionally used catalysts (E) are metal-containing curing catalysts, preferably tin-containing catalysts.
  • This embodiment of the invention is particularly preferred when component (A) is wholly or at least partially, ie at least 90% by weight, preferably at least 95% % By weight of compounds of the formula (I) in which b is not equal to 1.
  • metal-containing catalysts (E) preference may then be given to metal-containing catalysts (E), and in particular to catalysts containing tin, if component (A) is wholly or at least partially, ie at least 10% by weight, preferably at least 20 wt .-%, consists of compounds of formula (I), in which b is 1 and R 1 has the meaning of hydrogen atom.
  • component (A) is wholly or at least partially, ie at least 10% by weight, preferably at least 20 wt .-%, consists of compounds of formula (I), in which b is 1 and R 1 has the meaning of hydrogen atom.
  • This embodiment of the invention without metal and in particular without tin-containing catalysts is particularly preferred.
  • the adhesion promoters (F) optionally used in the compositions according to the invention may be any adhesion promoters hitherto known to cure by silane condensation.
  • adhesion promoters are epoxysilanes, such as glycidoxypropyltrimethoxysilanes, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmetyldiethoxysilane, 2- (3-triethoxysilylpropyl) maleic anhydride, N- ⁇ 3-trimethoxysilylpropyl ⁇ urea, (3 Triethoxysilylpropyl) urea, N ⁇ (trimethoxysilylmethyl) urea, N- (methyldimethoxysilymethyl) urea, N- (3-triethoxysilylmethyl) urea, N- (3-triethoxysilylpropyl) urea
  • Methyldiethoxysilylmethyl) harnstof f O ethylcarbamatomethyl- methyldimethoxysilane, O- ethy1carbamatomethy1 -1rimethoxysila, Q-EthyIcarbamatomethy1-methyIdiethoxysilan, O-methyl- Ethylcarbamato- riethoxysilan, 3 -Met acryloxypropyl trimethoxysilane, methacryloxymethyl trimethoxysilane, Methacryloxymethy1-methyldimethoxysilane, methacryloxymethyl triethoxysilane, Methacryloxymethyl-methyldiethoxysilane, 3-acryloxypropyltrimeth- oxysilane, acryloxymethyltrimethoxysilane, acryloxymethylmethyldimethoxysilanes, acryloxymethyltriethoxysilane and acryloxymethyl-methyldiethoxysilane
  • compositions according to the invention comprise adhesion promoters (F), these are amounts of preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • adhesion promoters (F) these are amounts of preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • the water scavengers (G) optionally used in the compositions according to the invention may be any water scavengers described for systems which cure by silane condensation.
  • water scavengers examples include silanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyl-1-trimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, and / or their partial condensates and orthoesters such as 1, 1, 1-trimethoxyethane, 1, 1, 1-triethoxyethane, trimethoxymethane and triethoxymethane.
  • silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyl-1-trimethoxysilane, O-ethylcarbamatomethylmethyldieth
  • compositions according to the invention contain water scavengers (G), they are amounts of preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based in each case on 100 parts by weight of crosslinkable composition.
  • the compositions of the invention preferably contain water scavenger ⁇ G ⁇ .
  • the additives (H) which may be used in the compositions according to the invention may be any desired additives known hitherto for silane-crosslinking systems.
  • the additives (H) optionally used according to the invention are preferably antioxidants, UV stabilizers, such as, for example, HALS compounds, fungicides and pigments. If the compositions according to the invention contain additives (H), these are amounts of preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).
  • the compositions of the invention preferably contain additives (H).
  • the additives ⁇ K) optionally used according to the invention are preferably tetraalkoxysilanes, e.g. Tetraethoxysilane and / or their partial condensates, plasticizers, rheology additives, flame retardants and organic solvents.
  • plasticizers (K) are such as phthalic acid esters (e.g., dioctyl phthalate, diisooctyl phthalate and diundecyl phthalate), perhydrogenated phthalic acid esters ⁇ e.g. 1,2-cyclohexanedicarboxylic acid isoisononyl ester and 1,2-cyclohexanedicarboxylic acid dioctyl ester), adipic acid ester (e.g., dioctyl adipate), benzoic acid ester, glycollene ester, esters of saturated alkanediols ⁇ e.g.
  • phthalic acid esters e.g., dioctyl phthalate, diisooctyl phthalate and diundecyl phthalate
  • perhydrogenated phthalic acid esters ⁇ e.g. 1,2-cyclohexanedicarboxylic acid isoisonony
  • the rheology additives (K) are preferably polyamide waxes, hydrogenated castor oils or stearates.
  • organic solvents (K) are the compounds already mentioned above as solvents, preferably alcohols. Preferably no organic solvents (K) are added to the compositions according to the invention.
  • compositions according to the invention comprise one or more components (K), they are each preferably amounts of from 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, in particular 2 to 70 parts by weight, in each case based on 100 parts by weight of component ( A).
  • compositions of the invention are preferably those containing
  • compositions according to the invention preferably contain no further components apart from the components (A) to ().
  • the components used according to the invention may in each case be one type of such a component as well as a mixture of at least two types of a respective component.
  • the compositions according to the invention are preferably viscous to pasty compositions having viscosities of preferably from 25,000 to 1,000,000 mPas, more preferably from 30,000 to 500,000 mPas, in each case at 25 ° C.
  • the preparation of the compositions according to the invention can be carried out in any manner known per se, such as by methods and mixing methods, as are customary for the preparation of moisture-curing compositions. The order in which the various components are mixed together can be varied as desired.
  • Another object of the present invention is a process for preparing the composition according to the invention by mixing the individual components in any order.
  • This mixing can be carried out at room temperature and the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • this mixing can also take place at relatively high temperatures, for example at temperatures in the range from 30 to 130.degree.
  • the mixing according to the invention is preferably carried out with the exclusion of moisture.
  • compositions according to the invention are preferably one-component crosslinkable compositions.
  • the compositions according to the invention can also be part of two-component crosslinking systems in which OH-containing compounds, such as water, are added in a second component.
  • compositions according to the invention can be used for all uses for which materials which are storable with the exclusion of water and can crosslink on admission of water at room temperature to elastomeric materials can be used, in particular as adhesives.
  • Another object of the invention is the use of crosslinkable compositions containing
  • the usual content of water in the air is sufficient.
  • the crosslinking of the compositions of the invention is preferably carried out at room temperature. It may, if desired, even at higher or lower temperatures than room temperature, for example at -5 ° to 15 ° C or at 30 ° , 12 054858
  • the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • Another object of the present invention are molded articles prepared by crosslinking of the inventive masses.
  • the moldings according to the invention preferably have a tensile strength of at least 1 MPa, preferably of at least 1.5 MPa, more preferably of at least 2 MPa, in particular of at least 3 MPa, in each case measured according to DIN EN 53504.
  • the moldings according to the invention may be any shaped articles, such as, for example, gaskets, pressed articles, extruded profiles, coatings, impregnations, potting, lenses, prisms, polygonal structures, laminate or adhesive layers.
  • Another object of the invention is a method for producing composite materials, in which the composition of the invention is applied to at least one substrate and then allowed to crosslink.
  • Composite molded parts is to be understood here as meaning a uniform molded article made of a composite material which is composed of a cross-linked product of the compositions according to the invention and at least two substrates, that there is a strong, permanent connection between the substrates.
  • the composition according to the invention can also be vulcanized between at least two identical or different substrates, such as e.g. for gluing or laminates.
  • substrates which can be bonded according to the invention are plastics including PVC, concrete, wood, mineral substrates, metals, glass, ceramics and painted surfaces.
  • compositions of the invention have the advantage that they are easy to prepare.
  • crosslinkable compositions according to the invention have the advantage that they are distinguished by a very high storage stability and a high crosslinking rate. Furthermore, the crosslinkable compositions according to the invention have the advantage that they have an excellent adhesion profile.
  • crosslinkable compositions according to the invention have the advantage that they are easy to process.
  • all viscosity data refer to a temperature of 25 ° C. Unless otherwise specified, the examples below are at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature resulting from combining the reactants at room temperature without additional heating or cooling, as well performed at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.
  • silane-terminated polypropylene glycol having an average molecular weight (M n ) of 12,000 daltons and end groups of the formula
  • the formulation is filled into 310 ml PE cartridges and stored for 1 day at 25 ° C prior to testing.
  • the other examples are formulated analogously.
  • the corresponding plasticizers are initially introduced together with the silane-terminated polymers.
  • the fumed silica is incorporated after incorporation of the chalks and digested with stirring for one minute at 600 U / min.
  • Plasticizers polypropylene glycol having a M n of 2,000 plasticizer Hexamoll DINCH (BASF)
  • crosslinkable compositions obtained in a 2 mm thick layer applied to PE TM film and stored under standard conditions (23 ° C and 50% relative humidity). During curing, the formation of a skin is tested every 5 min. For this purpose, a dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample sticks to the finger, no skin has formed yet. If no sample sticks to the finger, a skin has formed and the time is noted.
  • Mechanical properties obtained in a 2 mm thick layer applied to PE TM film and stored under standard conditions (23 ° C and 50% relative humidity).
  • compositions were each spread on afterfrrittten Teflon plates with 2 mm depth and 2 weeks at 23 ° C, 50 rel. Humidity cured. Shore A hardness is determined according to DIN 53505.
  • Tensile strength is determined according to DIN 5350 -Sl.
  • Elongation at break is determined according to DIN 53504-S1. Liability profile:
  • a 5-7 cm thick bead is applied to the substrate and stored for 7 days at room temperature.
  • Storage B A 5-7 cm thick bead is applied to the substrate and stored in water at room temperature for 7 days and also at room temperature for 2 weeks
  • a peel test is performed in which the caterpillar is cut at one end with a sharp knife over a length of about 2 cm from the substrate. Subsequently, starting from this cut, the remainder of the bead is torn from the substrate and the nature of the resulting crack (cohesive and / or adhesive) is assessed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des matières réticulables ayant une viscosité d'au moins 20 000 mPas à 25° C, contenant (A) des composés de la formule A- [-0-C(=0) -NH- (CR1 2) b-SiRa (OR2) 3-a] 2 (I) et (B) des silanes de la formule R3 cSi(OR4)dR5 4-c-d (II), ainsi que leurs hydrolysats partiels, dans laquelle les restes et indices ont la signification indiquée dans la revendication 1, leur procédé de production et leur utilisation comme adhésifs, en particulier pour le collage de substrats.
PCT/EP2012/054858 2011-03-25 2012-03-20 Matières réticulables à base de polymères à terminaison organyloxysilane WO2012130663A1 (fr)

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DE201110006128 DE102011006128A1 (de) 2011-03-25 2011-03-25 Vernetzbare Massen auf Basis von Organyloxysilanterminierten Polymeren

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170058165A1 (en) * 2013-12-30 2017-03-02 Bostik Sa Self-adhesive article with foam support
CN109996826A (zh) * 2016-09-05 2019-07-09 默兹奔特利股份公司 有机基碳酸酯改性的预聚物作为用于制备不含异氰酸酯和不含异硫氰酸酯的烷氧基硅烷聚合物的反应物的用途

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2872541B1 (fr) 2012-07-13 2017-08-02 Sika Technology AG Composition à haute teneur en charge à base de polymères à terminaison silane
DE102013216852A1 (de) 2013-08-23 2015-02-26 Wacker Chemie Ag Vernetzbare Massen auf Basis von organyloxysilanterminierten Polymeren
WO2017176709A1 (fr) 2016-04-05 2017-10-12 Slips Technologies, Inc. Compositions de polysiloxane durcissables ainsi que matériaux et revêtements glissants et articles fabriqués a partir de ceux-ci

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1179571A1 (fr) 1999-03-23 2002-02-13 Kaneka Corporation Compositions de resine durcissable
EP1724321A1 (fr) 2005-05-17 2006-11-22 Den Braven Sealants bv Agents adhésif et d'étancheité ne contenant pas de solvent
EP1535940B1 (fr) 2003-11-27 2007-06-13 Wacker Chemie AG Procédé pour la préparation de polymères ayant comme groups terminaux organyloxysilyle.
DE102006003821A1 (de) * 2006-01-26 2007-08-02 Wacker Chemie Ag Alkoxysilanterminierte Polymere enthaltende Polymerabmischungen
EP1967550A1 (fr) * 2005-12-02 2008-09-10 Momentive Performance Materials Japan LLC Composition polymerique durcissable a temperature ambiante contenant des groupements a base de silicium
EP1975910A2 (fr) 2007-03-26 2008-10-01 Samsung SDI Co., Ltd. Affichage à plasma et procédé de commande associé
EP1896523B1 (fr) 2005-06-23 2010-10-27 Wacker Chemie AG Transformation continue de polymeres analogues de monomeres de silane reactifs avec des polymeres fonctionnalises
WO2010126937A1 (fr) 2009-05-01 2010-11-04 Momentive Performance Materials Inc. Compositions polymères silylées durcissables à l'humidité contenant des modificateurs réactifs
DE102009027817A1 (de) * 2009-07-17 2011-01-20 Wacker Chemie Ag Vernetzbare Zusammensetzungen auf der Basis von Organosiliciumverbindungen
WO2011131506A1 (fr) * 2010-04-23 2011-10-27 Wacker Chemie Ag Composition de revêtement pour l'étanchéisation de surfaces

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10201703A1 (de) * 2002-01-17 2003-08-07 Consortium Elektrochem Ind Alkoxysilanterminierte Polymere enthaltende vernetzbare Polymerabmischungen
DE102006022095A1 (de) * 2006-05-11 2007-11-15 Wacker Chemie Ag Alkoxysilanterminierte Polymere enthaltende transparente Polymerabmischungen
DE102006022834A1 (de) * 2006-05-16 2007-11-22 Wacker Chemie Ag Verbesserung der elastischen Rückstellung bei alkoxysilanvernetzten Polymeren
DE602007004228D1 (de) * 2007-11-02 2010-02-25 Drywood Coatings B V Verfahren zum Fügen von Holzelementen unter Verwendung eines feuchtigkeitsabdichtenden Klebstoffs
DE102009027357A1 (de) * 2009-06-30 2011-01-05 Wacker Chemie Ag Alkoxysilanterminierte Polymere enthaltende Kleb- oder Dichtstoffmassen
DE102009029200A1 (de) * 2009-09-04 2011-03-17 Wacker Chemie Ag Isocyanatfreie silanvernetzende Zusammensetzungen

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1179571A1 (fr) 1999-03-23 2002-02-13 Kaneka Corporation Compositions de resine durcissable
EP1535940B1 (fr) 2003-11-27 2007-06-13 Wacker Chemie AG Procédé pour la préparation de polymères ayant comme groups terminaux organyloxysilyle.
EP1724321A1 (fr) 2005-05-17 2006-11-22 Den Braven Sealants bv Agents adhésif et d'étancheité ne contenant pas de solvent
EP1896523B1 (fr) 2005-06-23 2010-10-27 Wacker Chemie AG Transformation continue de polymeres analogues de monomeres de silane reactifs avec des polymeres fonctionnalises
EP1967550A1 (fr) * 2005-12-02 2008-09-10 Momentive Performance Materials Japan LLC Composition polymerique durcissable a temperature ambiante contenant des groupements a base de silicium
DE102006003821A1 (de) * 2006-01-26 2007-08-02 Wacker Chemie Ag Alkoxysilanterminierte Polymere enthaltende Polymerabmischungen
EP1975910A2 (fr) 2007-03-26 2008-10-01 Samsung SDI Co., Ltd. Affichage à plasma et procédé de commande associé
WO2010126937A1 (fr) 2009-05-01 2010-11-04 Momentive Performance Materials Inc. Compositions polymères silylées durcissables à l'humidité contenant des modificateurs réactifs
DE102009027817A1 (de) * 2009-07-17 2011-01-20 Wacker Chemie Ag Vernetzbare Zusammensetzungen auf der Basis von Organosiliciumverbindungen
WO2011131506A1 (fr) * 2010-04-23 2011-10-27 Wacker Chemie Ag Composition de revêtement pour l'étanchéisation de surfaces

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170058165A1 (en) * 2013-12-30 2017-03-02 Bostik Sa Self-adhesive article with foam support
US9873822B2 (en) * 2013-12-30 2018-01-23 Bostik Sa Self-adhesive article with foam support
CN109996826A (zh) * 2016-09-05 2019-07-09 默兹奔特利股份公司 有机基碳酸酯改性的预聚物作为用于制备不含异氰酸酯和不含异硫氰酸酯的烷氧基硅烷聚合物的反应物的用途

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EP2688937A1 (fr) 2014-01-29

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