WO2010004038A1 - Compositions durcissables - Google Patents

Compositions durcissables Download PDF

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Publication number
WO2010004038A1
WO2010004038A1 PCT/EP2009/058851 EP2009058851W WO2010004038A1 WO 2010004038 A1 WO2010004038 A1 WO 2010004038A1 EP 2009058851 W EP2009058851 W EP 2009058851W WO 2010004038 A1 WO2010004038 A1 WO 2010004038A1
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WIPO (PCT)
Prior art keywords
composition according
curable composition
alkoxy
group
bis
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PCT/EP2009/058851
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German (de)
English (en)
Inventor
Thomas Bachon
Lars Zander
Helmut Loth
Jennifer Schmidt
Oliver Schmidt
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Henkel Ag & Co. Kgaa
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Publication of WO2010004038A1 publication Critical patent/WO2010004038A1/fr

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    • 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
    • C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C08G65/04—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 from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2642—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 from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • 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
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the invention relates to curable compositions having a viscosity of less than 60,000 mPas, their preparation and use in adhesives, sealants or coating materials.
  • Polymer systems that possess reactive silyl groups are known. In the presence of atmospheric moisture, polymers which have silyl groups with hydrolyzable substituents are capable, even at room temperature, of condensing with elimination of the hydrolyzed radicals. Depending on the content of silyl groups with hydrolyzable substituents and the structure of these silyl groups, mainly long-chain polymers (thermoplastics), relatively wide-mesh, three-dimensional networks (elastomers) or highly crosslinked systems (thermosets) are formed.
  • the polymers usually have an organic skeleton which z.
  • B. carries alkoxy or Acyloxysilyl phenomenon.
  • the organic skeleton may be, for example, polyurethanes, polyesters, polyethers, etc.
  • fillers are usually added to the polymers. Due to the higher strength of the fillers compared to the polymers, higher bond strengths result. However, it is disadvantageous that the added fillers cause turbidity of the compositions and thus cancel any transparency of the original compositions that may be present. Furthermore, the added fillers cause an increased viscosity, which often comes at the expense of processability and applicability.
  • compositions with good processability and applicability. It is also desired that such compositions have good strength and sufficient bonding to substrates.
  • the invention relates to a transparent, curable composition having a viscosity of less than 60,000 mPas (measured using a Brookfield viscometer type RVDVII +, spindle No. 7, 10 rpm at 23 0 C), which a) a prepolymer component P, comprising a1) a alkoxy- and / or acyloxysilanterminATORs polymer having at least one terminal group of the general formula (I) -A n -R-SiXYZ (I) wherein
  • A is a divalent binding group
  • R is a divalent hydrocarbon radical optionally containing a heteroatom with 1
  • X, Y, Z independently of one another are C 1 -C 8 -alkyl-, C 1 -C 8 -alkoxy- or C 1 -C 8 -acyloxy radicals, where at least one of the radicals is a C 1 -C 8 -alkoxy- or C 1 -C 8 -alkoxy- or C 1 -C 8 -alkoxy radical 1 - C 8 - acyloxy group, and n is 0 or 1; a2) a bonding agent; a3) a catalyst; and a4) a plasticizer; and b) a filler F; includes; and which is characterized in that the prepolymer component P has a refractive index n D 20 (measured with an Abbe refractometer at 2O 0 C), of not more than 0.01 deviates from the refractive index of the filler F.
  • n D 20 measured with an Abbe refractometer at 2O 0 C
  • the curable compositions according to the invention are distinguished, in particular, by being transparent. Furthermore, they have a low yield point and show good processability and applicability. This is particularly advantageous when larger areas are to be treated with adhesives, sealants or coating materials, as is the case for example with surface coatings or large-area adhesions. As an example, the large-area gluing of veneer (wood) is mentioned.
  • the compositions according to the invention can easily pass, so that a large-area application is possible. Due to the running of the compositions, uneven floors can also be leveled very well.
  • the curable compositions are pourable, so that they can be poured from a bottle or an open container, for example, on a bottom surface, so that they can be applied much faster and easier than highly viscous compositions, for example, from a tube be applied.
  • the transparency of the curable composition is retained even after curing. Therefore, it is also very easy to bond transparent workpieces, such as glass or transparent plastics.
  • the transparency of the composition is also advantageous in the processing of non-transparent materials, since, for example, in the case of (unclean) processing, the composition which forms after bleaching does not stand out unpleasantly since it is transparent.
  • curable compositions according to the invention are characterized by good cohesive properties, in particular good strength and good tear strength, as well as good adhesion properties, i. a good and firm bond to different substrates, from.
  • a curable composition is understood to mean a substance or a mixture of several substances which can be hardened by physical or chemical measures. These chemical or physical measures, for example, in the supply of energy in the form of heat, light or other electromagnetic radiation, but also in the most simple contact with atmospheric moisture, water or a reactive component.
  • the prepolymer component P comprises a1) an alkoxy- and / or acyloxysilane-terminated polymer, a2) an adhesion promoter, a3) a catalyst and a4) a plasticizer.
  • a filler F is contained in the curable composition.
  • the silane-terminated polymer P has at least one end group of the general formula I.
  • a divalent or divalent bonding group A is a divalent chemical group which links the polymer skeleton of the alkoxy- and / or acyloxysilane-terminated polymer with the radical R of the end group.
  • the divalent linking group A can be formed, for example, in the preparation of the alkoxy- and / or acyloxysilane-terminated polymer, e.g. as a urethane group by the reaction of a hydroxyl-functionalized polyether with an isocyanatosilane.
  • the divalent binding group of structural features occurring in the underlying polymer skeleton can be both distinguishable and indistinguishable. The latter is, for example, if it is identical to the points of attachment of the repeat units of the polymer backbone.
  • n 0 or 1
  • the radical R is a divalent, optionally containing a heteroatom hydrocarbon radical having 1 to 12 carbon atoms.
  • heteroatom for example, oxygen (O) or nitrogen (N) may be included.
  • the hydrocarbon radical may be, for example, a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical.
  • the hydrocarbon radical may be saturated or unsaturated.
  • X, Y and Z are independently C 1 - C 8 - alkyl radicals, C 1 - C 8 - alkoxy radicals or C 1 - C 8 - Acyloxyreste. At least one of the radicals X, Y, Z must be a hydrolyzable group, ie a C 1 -C 8 -alkoxy group or radical or a C 1 -C 8 -acyloxy radical or radical.
  • hydrolyzable groups preference is given to alkoxy groups, in particular methoxy, ethoxy, n- or isopropoxy and n- or isobutoxy groups. This is advantageous since no substances irritating the mucous membranes are released during the curing of compositions containing alkoxy groups. The alcohols formed are harmless in the released amounts and evaporate. Therefore, such compositions are particularly suitable for the home improvement sector.
  • acyloxy groups such as an acetoxy group -O-CO-CH 3 can also be used.
  • the prepolymer component P has a refractive index n D 20 which does not deviate more than 0.01 from the refractive index of the filler F. This means that the refractive index of the prepolymer component P is within plus or minus 0.01 of the refractive index of the filler F located. Above a refractive index deviation of 0.01, the compositions begin to become cloudy and do not show the excellent transparency of the composition of the invention.
  • the refractive index and the refractive index or the refractive index be measured with an Abbe refractometer at 2O 0 C. This is done using a Zeiss Abbe Refractometer Type B according to DIN 51423-2, working with the light of the D-line of sodium.
  • To determine the refractive index of the filler F it is introduced into a liquid whose refractive index is systematically varied until it corresponds to the respective refractive index of the filler. Subsequently, the refractive index n D 20 of the liquid can be determined in the manner just described.
  • the refractive index of the prepolymer component P does not deviate from the refractive index of the filler F by more than 0.005.
  • the compositions exhibit crystal clear transparency, are colorless, and thus are eminently suitable for particularly demanding applications.
  • the refractive index of the plasticizer is in the range of 1.39 to 1.55.
  • the values of the usable further constituents of the prepolymer component and of the fillers are preferably also such that transparent systems can be obtained.
  • the range of the refractive index is at the same time large enough to ensure a good variability in the selection of the plasticizers. It is particularly advantageous if the refractive index of the plasticizer is in the range from 1.43 to 1.50. Within these limits, the refractive index corresponds optimally with the values of the other prepolymer constituents and the fillers that can be used, so that compositions with a particularly clear transparency are formed.
  • the refractive index of the prepolymer component P is in the range from 1.43 to 1.48. It has been found that this range leaves enough latitude for both variations in the composition within the prepolymer component and for combination with various fillers and other components in order to produce transparent compositions with outstanding performance characteristics on as broad a basis as possible. Optimal transparency results when the refractive index of the prepolymer component is in the most preferred range of 1.45 to 1.46.
  • the alkoxy- and / or acyloxysilane-terminated polymer has at least two terminal groups of the general formula (I).
  • Each polymer chain thus contains at least two linkage sites at which the condensation of the polymers can take place with elimination of the hydrolyzed radicals in the presence of atmospheric moisture. In this way, a regular and fast crosslinkability is achieved, so that bonds can be obtained with good strength. In addition, can be on the amount and structure of the hydrolyzable groups -.
  • X is an alkyl group and Y and Z are an alkoxy group, or X, Y and Z are an alkoxy group.
  • polymers which contain di- or trialkoxysilyl groups have highly reactive attachment sites which enable rapid curing, high degrees of crosslinking and thus good final strengths.
  • Another advantage of such polymers containing alkoxy groups is the fact that when cured under the influence of moisture alcohols are formed, which are harmless in the released amounts and evaporate. Therefore, such compositions are particularly suitable for the home improvement sector.
  • dialkoxysilyl groups - the first mentioned variant at the beginning of this paragraph - is that the corresponding compositions are more elastic, softer and more flexible after curing than systems containing trialkoxysilyl groups.
  • trialkoxysilyl groups are therefore particularly suitable for use as sealants. In addition, they cease even less alcohol when curing and are therefore of particular interest when the amount of alcohol released is to be reduced. With trialkoxysilyl groups, on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a harder, stronger mass is desired after curing. In addition, trialkoxysilyl groups are more reactive, ie they crosslink faster and thus reduce the required amount of catalyst, and they have advantages in the "cold flow" - the dimensional stability of a corresponding adhesive under the influence of force and possibly temperature.
  • X, Y and Z are each independently a methyl, an ethyl, a methoxy or an ethoxy group.
  • Methoxy and ethoxy groups as relatively small hydrolyzable groups with low steric demand are very reactive and thus allow rapid curing even with low catalyst use. They are therefore particularly interesting for systems in which a rapid curing is desired, such as adhesives, which should have a high initial adhesion.
  • X, Y and Z are a methyl or a methoxy group.
  • compounds having alkoxysilyl groups have different reactivities in chemical reactions.
  • R is a hydrocarbon radical having 1 to 6 C atoms. Over the length of the hydrocarbon radicals, which form the link between the polymer backbone and the silyl radical, the curing rate of the composition can be influenced, which opens up a further design possibility for the composition according to the invention.
  • R is a methylene, ethylene iso-propylene or n-propylene radical.
  • Methylene and 1, 3-propylene or n-propylene radicals are particularly preferably used.
  • Alkoxysilane-terminated compounds having a methylene group as a link to the polymer backbone - so-called ⁇ -silanes - have a particularly high reactivity of the final silyl group, which leads to shortened setting times and thus to a very rapid curing of formulations based on such polymers.
  • an extension of the connecting hydrocarbon chain leads to a reduced reactivity of the polymers.
  • the ⁇ -silanes - they contain the unbranched propylene radical as a link - have a balance between necessary reactivity (acceptable curing times) and delayed curing (open time, possibility of correction after bonding) on.
  • the curing rate of the systems can be influenced as desired.
  • composition according to the invention A is an amide, carbamate, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group or an oxygen or nitrogen atom.
  • the binding group A can in the preparation of the silyl-terminated polymers are formed by reacting the backbone polymer with a reactive compound bearing the -R-SiXYZ sequence.
  • Group A may be both distinguishable and indistinguishable from structural features occurring in the underlying polymer backbone. The latter is, for example, if it is identical to the points of attachment of the repeat units of the polymer backbone. In this case, n would correspond to the value 0. If the binding group A is distinguishable from the linking groups in the polymer backbone, n corresponds to the value 1.
  • urethane and urea groups which can be obtained by reacting certain functional groups of a prepolymer with an organosilane which carries a further functional group.
  • Urethane groups can, for. B. arise when either the polymer backbone contains terminal hydroxyl groups and isocyanatosilanes used as a further component, or conversely, when a polymer having terminal isocyanate groups is reacted with a terminal hydroxy-containing alkoxysilane.
  • urea groups can be obtained when a terminal primary or secondary amino group - either silane or polymer - is used which reacts with a terminal isocyanate group present in each reactant.
  • the alkoxy and / or acyloxysilane-terminated polymer has a backbone selected from the group consisting of polyurethanes, polyethers, polyesters, polyacrylates, poly (meth) acrylates, polyacrylamides, poly (meth) acrylamides, Polyvinyl esters, polyolefins, alkyd resins, phenolic resins, vinyl polymers, styrene-butadiene copolymers, and copolymers of one or more of the aforementioned basic skeletons.
  • a backbone selected from the group consisting of polyurethanes, polyethers, polyesters, polyacrylates, poly (meth) acrylates, polyacrylamides, poly (meth) acrylamides, Polyvinyl esters, polyolefins, alkyd resins, phenolic resins, vinyl polymers, styrene-butadiene copolymers, and copolymers of one or more of the aforementioned basic
  • polyesters can be decomposed by water and bacteria and are therefore of interest for applications where biodegradability is important.
  • Polymers containing polyether as a backbone have a flexible and elastic structure not only at the end groups but also in the polymer backbone. This can be used to produce compositions which have excellent elastic properties. Polyethers are not only flexible in their backbone but also stable at the same time. For example, they are not attacked or decomposed by water and bacteria.
  • the alkoxy- and / or acyloxysilane-terminated polymer has a molecular weight M n of 4,000 to 100,000, preferably 8,000 to 50,000, particularly preferably 10,000 to 30,000, in particular 15,000 to 25,000 g / mol.
  • the molecular weight M n is understood to mean the number average molecular weight of the polymer. This, as well as the weight-average molecular weight M w , can be determined by gel permeation chromatography (GPC). Such a method is known to the person skilled in the art.
  • the stated molecular weights are particularly advantageous, since the corresponding compositions have a balanced ratio of viscosity (easy processability), strength and elasticity. This combination is very advantageous in a molecular weight range from 12,000 to 20,000, in particular from 14,000 to 18,000, pronounced.
  • the ratio M w / M n is less than 1.5.
  • the ratio M w / M n which is also referred to as polydispersity, indicates the width of the molecular weight distribution and thus of the different degrees of polymerization of the individual chains in the case of polydisperse polymers.
  • the polydispersity has a value of about 2. Strict monodispersity would be given at a value of 1.
  • polydispersity of less than 1, 5 indicates a comparatively narrow molecular weight distribution and thus the specific expression of the molecular weight related properties such. As the viscosity, towards.
  • the alkoxy- and / or acyloxysilane-terminated polymer particularly preferably has a polydispersity (M w / M n ) of less than 1.3.
  • the compositions according to the invention which are suitable as adhesives, sealants or coating materials contain, in addition to the abovementioned silylated polymer compounds, further auxiliaries and additives which give them improved elastic properties, improved resilience, sufficiently long working time, fast curing rate and low residual tack. These auxiliaries and additives include adhesion promoters, catalysts and plasticizers as well as fillers.
  • compositions may contain, as further additives, stabilizers, antioxidants, reactive diluents, drying agents, UV stabilizers, anti-aging agents, rheological aids, color pigments or color pastes, fungicides, flame retardants and / or, to a lesser extent, solvents.
  • a plasticizer a substance which reduces the viscosity of the compositions, thereby facilitating processability and, moreover, improving the flexibility and extensibility of the compositions.
  • the plasticizer is selected from a fatty acid ester, a dicarboxylic acid ester, an ester OH-bearing or epoxidized fatty acids, a fat, a glycolic acid ester, a phthalic acid ester, a benzoic acid ester, a phosphoric acid ester, a sulfonic acid ester, a trimellitic acid ester epoxidized plasticizer, a polyether plasticizer, a polystyrene, a hydrocarbon plasticizer and a chlorinated paraffin, and mixtures of two or more thereof.
  • plasticizers particularly advantageously combine their actual function of facilitating processability, improving the flexibility and stretchability of the compositions, with a suitable index of refraction, in order to satisfy the desire for compositions having excellent transparency.
  • dioctyl phthalate dibutyl phthalate, diisoundecyl phthalate, diisononyl phthalate or butyl benzyl phthalate
  • dioctyl adipate diisodecyl adipate
  • diisodecyl adipate furthermore diisodecyl succinate, dibutyl sebacate or butyl oleate.
  • polyether plasticizers are preferably used end-capped polyethylene glycols, for example, polyethylene or polypropylene glycol di-C ⁇ alkyl ethers, in particular the dimethyl or diethyl ether of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.
  • plasticizers are, for example, esters of abietic acid, butyric acid esters, acetic acid esters, propionic acid esters, thiobutyric acid esters, citric acid esters and esters based on nitrocellulose and polyvinyl acetate, and mixtures of two or more thereof. Also suitable, for example the asymmetric esters of adipic acid monooctyl ester with 2-ethylhexanol (Edenol DOA, Cognis Germany GmbH, Dusseldorf).
  • the pure or mixed ethers of monofunctional, linear or branched C 4 are suitable as plasticizers.
  • plasticizers in the context of the present invention are diurethanes which are suitable, for example, by reaction of diols with
  • OH end groups can be prepared with monofunctional isocyanates by the stoichiometry is chosen so that react substantially all free OH groups.
  • excess isocyanate can then be removed from the reaction mixture, for example, by distillation.
  • Another method for the preparation of diurethanes is the reaction of monofunctional alcohols with diisocyanates, where possible to react off all NCO groups.
  • a viscosity of the adhesive or sealant according to the invention which is too high for certain applications can also be reduced in a simple and expedient manner by using a reactive diluent without there being any demixing phenomena (for example plasticizer migration) in the hardened mass.
  • the reactive diluent has at least one functional group, which after the application z. B. reacts with moisture or atmospheric oxygen.
  • groups are silyl groups, isocyanate groups, vinyl unsaturated groups and polyunsaturated systems.
  • Reactive diluents which can be used are all compounds which are miscible with the composition according to the invention with reduction in viscosity and have at least one group reactive with the binder, alone or as a combination of several compounds.
  • the viscosity of the reactive diluent is preferably less than 20,000 mPas, particularly preferably about 0.1-6,000 mPas, very particularly preferably 1-1,000 mPas (Brookfield RVT, 23 ° C., spindle 7, 10 rpm).
  • a reactive diluent z As a reactive diluent z.
  • the following substances are used: polyalkylene glycols reacted with isocyanatosilanes (for example Synalox 100-50B, DOW), alkyltrimethoxysilane, alkyltriethoxysilane, such as methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane (XL 10, Wacker), phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane,
  • isocyanatosilanes for example Synalox 100-50B, DOW
  • alkyltrimethoxysilane alkyltriethoxysilane, such as methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane (XL 10, Wacker)
  • Vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (IOtrimethoxy), isooctyltriethoxysilane (10-triethoxy, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (XL63, Wacker), N- dimethoxy (methyl) silylmethyl-O-methyl carbamate (XL65, Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-i-propyltriethoxysilane and partial hydrolysates of these compounds.
  • polymers are also available from Kaneka Corp. can be used as reactive diluent: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.
  • polymers which can be prepared from an organic skeleton by grafting with a vinyl silane or by reacting polyol, polyisocyanate and alkoxysilane.
  • a polyol is understood as meaning a compound which contains one or more OH groups in the molecule.
  • the OH groups can be both primary and secondary.
  • Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol and higher glycols, as well as other polyfunctional alcohols.
  • the polyols may additionally contain other functional groups, e.g. Contain esters, carbonates, amides.
  • the corresponding polyol component is reacted in each case with an at least difunctional isocyanate.
  • any isocyanate having at least two isocyanate groups is suitable as the at least difunctional isocyanate, but as a rule they are within the scope of the present invention
  • Invention compounds having two to four isocyanate groups, especially with two isocyanate groups preferred.
  • the di- and trialkoxysilyl groups are preferred.
  • Suitable polyisocyanates for preparing a reactive diluent are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1, 3 and 1, 4-diisocyanate, bis (2-isocyanato-ethyl) fumarate, and mixtures of two or more thereof, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3-or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-di
  • polyisocyanates it is possible to use trihydric or higher isocyanates, as obtainable, for example, by oligomerization of diisocyanates, in particular by oligomerization of the abovementioned isocyanates.
  • trihydric and higher polyisocyanates are the tri-isocyanurates of HDI or IPDI or mixtures thereof or their mixed triisocyanurates and Polyphenylmethylenpolyisocyanat, as it is obtainable by phosgenation of aniline-formaldehyde condensation products.
  • Suitable solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters and ether esters.
  • alcohols are used, since in this case the storage stability increases.
  • C 1 -C 10 -AlkOhOIe, especially methanol, ethanol, i-propanol, isoamyl alcohol and hexanol are particularly preferred.
  • composition of the invention also comprises a coupling agent.
  • An adhesion promoter is understood as meaning a substance which improves the adhesive properties of adhesive layers on surfaces.
  • adhesion promoters Conventional adhesion promoters (tackifiers) known to the person skilled in the art can be used alone or as a combination of several compounds. Suitable examples are resins, terpene oligomers, coumarone / indene resins, aliphatic, petrochemical resins and modified phenolic resins. Hydrocarbon resins, for example, which are obtained by polymerization of terpenes, mainly .alpha. Or .beta.-pinene, dipentene or limonene, are suitable for the purposes of the present invention. The polymerization of these monomers is usually cationic with initiation with Friedel-Crafts catalysts.
  • the terpene resins also include copolymers of terpenes and other monomers, for example styrene, ⁇ -methylstyrene, isoprene and the like.
  • the resins mentioned are used, for example, as adhesion promoters for pressure-sensitive adhesives and coating materials.
  • the terpene-phenolic resins prepared by acid catalyzed addition of phenols to terpene or rosin. Terpene-phenolic resins are soluble in most organic solvents and oils and are miscible with other resins, waxes and rubbers.
  • adhesion promoters in the abovementioned sense are the rosins and their derivatives, for example their esters or alcohols. Silane coupling agents, in particular aminosilanes, are particularly suitable.
  • the prepolymer component P comprises a silane of the general formula (II) R ' FTN-R-SiXYZ (II)
  • R ' and R " independently of one another are hydrogen or C 1 -C 8 -alkyl radicals
  • R is a divalent hydrocarbon radical optionally containing one heteroatom and having 1 to 12 C
  • X, Y, Z independently of one another are C 1 -C 8 -alkyl-, C 1 -C 8 -alkoxy- or C 1 -C 8 -acyloxy radicals, where at least one of the radicals is a C 1 -C 8 -alkoxy- or C 1 -C 8 -alkoxy- or C 1 -C 8 -alkoxy radical 1 - C 8 - acyloxy group.
  • the linking group R may, for example, be a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical.
  • the heteroatom contained therein is nitrogen (N) or oxygen (O).
  • X, Y and / or Z are an acyloxy group, this can be done, for example, by For example, be the acetoxy group -OCO-CH 3 .
  • the prepolymer component P of the curable composition of the invention comprises as a further constituent a catalyst.
  • organometallic compounds such as iron or tin compounds are suitable, in particular the 1, 3-dicarbonyl compounds of iron such.
  • iron (III) acetylacetonate or di- or tetravalent tin such as dibutyltin bisacetylacetonate, the dialkyltin (IV) dicarboxylates -.
  • the composition according to the invention is tin-free. Nevertheless, the compositions according to the invention can be cured well and quickly using alternative catalysts without any loss of quality.
  • Boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide or mixed boron halides can alternatively be used as curing catalysts.
  • Particularly preferred are boron trifluoride complexes such as e.g. Boron trifluoride diethyl etherate (CAS No. [109-63-7]), which are easier to handle as liquids than the gaseous boron halides.
  • 1, 8-diazabicyclo [5.4.0] undec-7-ene is useful as a catalyst for the composition of the present invention.
  • titanium, aluminum and zirconium compounds or mixtures of one or more catalysts of one or more of the groups just mentioned are preferably used as catalysts.
  • the use of tin compounds can be avoided in this way, on the other hand, a better adhesion to normally poorly adhering organic surfaces such. B. reach acrylates.
  • the titanium catalysts are preferably used because they provide the best curing results.
  • Titanium catalysts are compounds which have hydroxyl groups and / or substituted or unsubstituted alkoxy groups, ie titanium alkoxides of the general formula
  • R z is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms and the 4 alkoxy groups -OR Z are the same or different. Further, one or more of the radicals -OR Z by acyloxy groups -OCOR Z can be replaced.
  • titanium catalysts titanium alkoxides in which one or more alkoxy groups are replaced by halogen atoms.
  • titanium catalysts z. B the following mixed or non-mixed-substituted titanium alkoxides are used:
  • Tetraethoxy titanium Tetrabenzoxytitanium, tetraoctoxytitanium, tetrakis (2-ethylhexoxy) -titanium, tetradecoxytitanium, tetradodecoxytitanium, tetrastearoxytitanium, tetrabutoxytitanium dimer, tetrakis (8-hydroxyoctoxy) titanium, titanium diisopropoxy-bis (2-ethyl-1,3-hexanediolate), titanium bis ( 2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolate), tetrakis (2-chloroethoxy) titanium, tetrakis (2-bromoethoxy) titanium, tetrakis (2-methoxyethoxy) titanium, tetrakis (2-ethoxyethoxy) titanium, butoxy Trimethoxy titanium, di
  • titanium acylates can be used: triisopropoxytitanium, triisopropoxytitanium methacrylate, diisopropoxytitanium dimethacrylate, isopropoxytitanium trimethacrylate, triisopropoxytitanium hexanoate, triisopropoxytitanium stearate and the like.
  • halogenated titanium catalysts for example, the following compounds can be used: triisopropoxytitanium chloride, diisopropoxytitanium dichloride, isopropoxytitanium trichloride, triisopropoxytitanium bromide, triisopropoxytitanium fluoride, triethoxytitanium chloride, tributoxytitanium chloride.
  • titanium chelate complexes can be used: dimethoxytitanium bis (ethylacetoacetate), dimethoxytitanium bis (acetylacetonate), diethoxytitanium bis (ethylacetoacetate), diethoxytitanium bis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (methylacetoacetate), diisopropoxytitanium bis (t-butylacetoacetate), diisopropoxytitanium bis (methyl-3-oxo 4,4-dimethylhexanoate), diisopropoxy titanium bis (ethyl 3-oxo-4,4,4-trifluorobutanoate), diisopropoxy titanium bis (acetylacetonate), diisopropoxy titanium bis (2, 2,6,6-tetramethyl-3,5-heptanedionate), Di (n-butoxy) titanium bis (ethy
  • Triisopropoxytitanium (methacryloxyethylacetoacetate), 1,2-dioxyethanitanebis (ethylacetoacetate), 1,3-dioxpropane titanium bis (ethylacetoacetate), 2,4-dioxypentanetitanium bis (ethylacetoacetate), 2,4-dimethyl-2,4-dioxypentanetitanium bis (ethylacetoacetate), diisopropoxy titanium bis (triethanolaminate) ), Tetrakis (ethylacetoacetato) titanium, tetrakis (acetylacetonato) titanium, bis (trimethylsiloxy) titanium bis (ethylacetoacetate), bis (trimethylsiloxy) titanium bis (acetylacetonate).
  • titanium chelate complexes are preferably used, since they are commercially available and have a high catalytic activity:
  • Diisopropoxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (acetylacetonate),
  • diethoxytitanium bis ethylacetoacetate
  • diisopropoxytitanium ethylacetoacetate
  • Dibutoxytitanbis (ethylacetoacetate), most preferably Diisopropoxytitanbis (ethylacetoacetate).
  • titanium catalysts can also be used: isopropoxytitanium tris (dioctyl phosphate), isopropoxytitanium tris (dodecylbenzylsulfonate), dihydroxytitanium bislactate.
  • Aluminum catalysts can also be used as curing catalysts, e.g. aluminum alkoxides
  • R z is an organic group, preferably a substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and the three radicals R z are identical or different.
  • R z is an organic group, preferably a substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and the three radicals R z are identical or different.
  • one or more of the alkoxy radicals may be replaced by acyloxy radicals -OC (O) R 2 .
  • aluminum alkoxides can be used in which one or more alkoxy radicals are replaced by halogen atoms.
  • the pure aluminum alcoholates are preferred in view of their stability to moisture and the hardenability of the mixtures to which they are added.
  • aluminum chelate complexes are preferred.
  • the following compounds can be used: trimethoxyaluminum, triethoxyaluminum, triallyloxyaluminum, tri (n-propoxy) aluminum, triisopropoxyaluminum, tri (n-butoxy) aluminum, triisobutoxyaluminum, tri (sec-butoxy) aluminum, tri (t-butoxy) aluminum , Tri (n-pentoxy) aluminum, tricyclopentoxyaluminum, trihexoxyaluminum, tricyclohexoxyaluminum, tribenzoxyaluminum, trioctoxyaluminum, tris (2-ethylhexoxy) aluminum, tridecoxyaluminum, tridodecoxyaluminum, tristearoxyaluminum, dimeric tributoxyaluminum, tris (8-hydroxyoctoxy) aluminum, isopropoxyaluminum bis (2-ethyl) 1, 3-hexanediolate), diisopropoxyaluminum, trimethoxy
  • aluminum acylates may also be used: diisopropoxyaluminum acrylate, diisopropoxyaluminum methacrylate, isopropoxyaluminum dimethacrylate, diisopropoxaluminum hexanoate, diisopropoxyaluminum stearate.
  • aluminum halide compounds can be used, e.g. Diisopropoxyaluminum chloride, isopropoxyaluminum dichloride, diisopropoxyaluminum bromide, diisopropoxyaluminum fluoride, diethoxyaluminum chloride, dibutoxyaluminum chloride.
  • aluminum chelate complexes can be used as catalysts, for example, methoxyaluminum bis (ethylacetoacetate), methoxyaluminum bis (acetylacetonate), ethoxyaluminum bis (ethylacetoacetate), ethoxyaluminum bis (acetylacetonate), isopropoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (methylacetoacetate), isopropoxyaluminum bis (t-butylacetoacetate), dimethoxyaluminum ( ethylacetoacetate), dimethoxyaluminum (acetylacetonate), diethoxyaluminum (ethylacetoacetate), diethoxyaluminum (acetylacetonate), diisopropoxyaluminum (ethylacetoacetate), diisopropoxyaluminum (methylacetoacetate), diisopropoxyaluminum (t-
  • the following aluminum chelate complexes are preferably used as catalysts since they are commercially available and have high catalytic activities: ethoxyaluminum bis (ethylacetoacetate), ethoxyaluminum bis (acetylacetonate), isopropoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (acetylacetonate), butoxyaluminum bis (ethylacetoacetate), butoxyaluminum bis (acetylacetonate) , Dimethoxyaluminum ethylacetoacetate, dimethoxyaluminum acetylacetonate, diethoxyaluminum ethylacetoacetate, di-ethoxyal um umacety lacetonat, diisopropoxyal um in iu methylacetoacetat, Diisopropoxyaluminiummethylacetoacetat and Diisopropoxyaluminium (t-butylacetoa
  • ethoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (ethylacetoacetate), butoxyaluminum bis (ethylacetoacetate), dimethoxyaluminum ethylacetoacetate, diethoxyaluminum ethylacetoacetate and diisopropoxyaluminum ethylacetoacetate.
  • Suitable zirconium catalysts are:
  • Preferred diethoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (ethylacetoacetate), dibutoxyzirconium bis (ethylacetoacetate), triispropoxyzirconium (ethylacetoacetate), tris (n-butoxy) zirconium (ethylacetoacetate), isopropoxyzircontris (ethylacetoacetate), n-butoxyzircontris (ethylacetoacetate) and n-butoxyzirconium (acetylacetonate) bis (ethylacetoacetate).
  • diisopropoxyzirconium bis (ethylacetoacetate)
  • zirconacylates may be used: triisopropoxyzirconium, triisopropoxyzirconium methacrylate, diisopropoxyzirconium dimethacrylate, isopropoxyzircontrimethacrylate, triisopropoxyzirconium hexanoate, triisopropoxyzirconstearate and the like.
  • halogenated zirconium catalysts the following compounds can be used: triisopropoxyzirconium chloride, diisopropoxyzirconium dichloride, isopropoxyzirconium trichloride, triisopropoxyzirconium bromide, triisopropoxyzirconium fluoride, triethoxyzirconium chloride, tributoxyzirconium chloride.
  • zirconium chelate complexes dimethoxyzirconium bis (ethylacetoacetate), dimethoxyzirconium bis (acetylacetonate), diethoxyzirconium bis (ethylacetoacetate), diethoxyzirconium bis (acetylacetonate), diisopropoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (methylacetoacetate), diisopropoxyzirconium bis (t-butylacetoacetate), diisopropoxyzirconbis (methyl-3-ol) oxo-4,4-dimethylhexanoate), diisopropoxyzirconium bis (ethyl-3-oxo-4,4,4-trifluorobutanoate), diisopropoxyzirconium bis (acetylacetonate), diisopropoxyzirconium bis (2,2,6,6-tetramethyl-3,5-hept
  • Triisopropoxyzirconium (methacryloxyethylacetoacetate), 1, 2-dioxyethanzirkonbis (ethylacetoacetate), 1, 3-dioxypropanzirkonbis (ethylacetoacetate), 2,4-Dioxypentanzirkonbis (ethylacetoacetate), 2,4-dimethyl-2,4-Dioxypentanzirkonbis (ethylacetoacetate), Diisopropoxyzirkonbis (triethanolaminat ) Tetrakis (ethylacetoacetato) zirconium, tetrakis (acetylacetonato) zirconium, bis (trimethylsiloxy) zirconium bis (ethylacetoacetate), bis (trimethylsiloxy) zirconium bis (acetylacetonate).
  • zirconium chelate complexes are preferably used since they are commercially available and have a high catalytic activity:
  • Diethoxyzirconium bis (ethylacetoacetate), diethoxyzirconium bis (acetylacetonate), diisopropoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (acetylacetonate), dibutoxyzirconium bis (ethylacetoacetate), and dibutoxyzirconic bis (acetylacetonate)
  • diethoxyzirconium bis ethylacetoacetate
  • diisopropoxyzirconium ethylacetoacetate
  • dibutoxyzirconium bis ethylacetoacetate
  • diisopropoxyzirconium bis ethylacetoacetate
  • zirconium catalysts isopropoxyzircontris (dioctyl phosphate), isopropoxyzircontris (dodecylbenzylsulfonate), dihydroxyzirconium bislactate.
  • the hardening catalysts used can be carboxylic acid salts of metals or else a mixture of several such salts, these being selected from the carboxylates of the following metals: calcium, vanadium, iron, titanium, potassium, barium, manganese, nickel, cobalt and / or
  • carboxylates are the calcium, vanadium, iron, titanium, potassium, barium, manganese and
  • Zirkoniumcarboxylate preferred because they have a high activity.
  • the calcium carboxylates, vanadium carboxylates, iron carboxylates, titanium carboxylates, potassium carboxylates, barium carboxylates, manganese carboxylates, nickel carboxylates, cobalt carboxylates and zirconium carboxylates may be used singly or as a mixture of several catalysts from one or more of the mentioned groups.
  • these metal carboxylates can be used in conjunction with tin carboxylates, lead carboxylates, bismuth carboxylates and cercarboxylates.
  • the catalyst is used in an amount of from 0.01 to about 10% by weight, based on the total weight of the composition.
  • Suitable fillers for the composition according to the invention are, for example, chalk, limestone, precipitated and / or fumed silica, zeolites, bentonites, magnesium carbonate, kieselguhr, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals.
  • organic fillers can be used, in particular carbon black, graphite, wood fibers, wood flour, sawdust, pulp, cotton, pulp, wood chips, chaff, chaff, ground walnut shells and other fiber short cuts.
  • short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber or even polyethylene fibers can be added.
  • Aluminum powder is also suitable as a filler.
  • suitable fillers are hollow spheres with a mineral shell or a plastic shell. These may be, for example, glass bubbles, which are commercially available under the trade names Glass Bubbles®.
  • Plastic-based hollow spheres e.g. Expancel® or Dualite® are described, for example, in EP 0 520 426 B1. These are composed of inorganic or organic substances, each having a diameter of 1 mm or less, preferably 500 ⁇ m or less.
  • fillers are preferred which impart thixotropy to the formulations.
  • Such fillers are also described as rheological aids, eg. As hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC. So that they can be pressed out well from a suitable metering device (eg tube), such preparations have a viscosity of 3,000 to 15,000, preferably 4,000 to 8,000 mPas or even 5,000 to 6,000 mPas.
  • the fillers are preferably used in an amount of 1 to 80 wt .-%, based on the total weight of the composition. A single filler or a combination of multiple fillers may be used.
  • the filler is a highly disperse silica having a BET surface area of from 10 to 90 m 2 / g, in particular from 35 to 65 m 2 / g.
  • a silica does not significantly increase the viscosity of the composition of the present invention, but does contribute to enhancing the cured formulation.
  • a highly disperse silica having a BET surface area of 45 to 55 m 2 / g, in particular having a BET surface area of about 50 m 2 / g.
  • Such silicas have the additional advantage of a 30 to 50% shortened incorporation time compared to silicic acids with a higher BET surface area.
  • a further advantage lies in the fact that said highly-dispersed silicic acid can be incorporated into silane-terminated adhesives, sealants or coating materials in a considerably higher concentration without the transparency and the flow properties of the adhesives, sealants or coating materials being impaired.
  • the filler is a finely divided silica having a mean particle size d 50 of less than 25 ⁇ m, measured by laser diffraction according to ISO 13320-1 using a Horiba Type 950 V2 laser scattered light spectrometer. preferably from 5 to 20 microns, is.
  • a filler is particularly well suited when highly transparent, clear compositions are needed for particularly demanding applications.
  • composition of the invention may contain antioxidants.
  • the proportion of antioxidants in the composition according to the invention is preferably up to about 7% by weight, in particular up to about 5% by weight.
  • the composition of the invention may further contain UV stabilizers.
  • the proportion of UV stabilizers in the composition according to the invention is preferably up to about 2% by weight, in particular about 1% by weight.
  • Particularly suitable UV stabilizers are the so-called hindered amine light stabilizers (HALS). It is preferred in the context of the present invention, when a UV stabilizer is used, which carries a silyl group and is incorporated in the final product during curing or curing.
  • Particularly suitable for this purpose are the products Lowilite 75, Lowilite 77 (Great Lakes, USA). It is also possible to add benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus and / or sulfur.
  • compositions according to the invention against penetrating moisture, in order to increase shelf life even more.
  • Such an improvement in shelf life can be achieved, for example, by the use of desiccants.
  • Suitable drying agents are all compounds which react with water to form an inert group with respect to the reactive groups present in the composition, and thereby undergo the smallest possible changes in their molecular weight.
  • the reactivity of the desiccants to moisture penetrated into the composition must be higher than the reactivity of the end groups of the present invention silyl group-bearing polymer.
  • Suitable drying agents are, for example, isocyanates.
  • Silanes are also advantageously used as desiccants, for example vinyl silanes such as 3-vinylpropyltriethoxysilane, oxime silanes such as methyl-O, O ' , O " -butan-2-one-thoximosilane or 0.0 ' , 0 " , 0 " -butan-2-one. ontetraoximosilane (CAS Nos. 022984-54-9 and 034206-40-1) or benzamidosilanes such as bis (N-methylbenzamido) methylethoxysilane (CAS No.
  • carbamatosilanes such as carbamatomethyltrimethoxysilane, but also the use of methyl, Ethyl- or vinyltrimethoxysilane, tetramethyl- or -ethylethoxysilane is possible, Vinyltrimethoxysilane and tetraethoxysilane being particularly preferred in terms of efficiency and cost.
  • a desiccant are the abovementioned reactive diluents, provided that they have a molecular weight (M n ) of less than about 5,000 g / mol and have end groups whose reactivity to moisture penetration is at least as great, preferably greater, than the reactivity of the reactive Groups of the silyl group-carrying polymer according to the invention.
  • M n molecular weight
  • alkyl orthoformates or orthoacetates as desiccants, for example methyl or ethyl orthoformate, methyl or ethyl orthoacetate,
  • composition of the invention typically contains from about 0.01 to about 10 weight percent desiccant. In a further preferred embodiment of the composition according to the invention contains these
  • additives such as pigments, stabilizers, UV absorbers, anti-aging agents,
  • Fungicides and flame retardants are Fungicides and flame retardants.
  • compositions based on these proportions open up the possibility of obtaining readily processable adhesives, sealants or coating materials which have good strength and adhesion.
  • properties of the composition can be determined by a specific
  • Weighting of the shares to be precisely matched to the particular field of application.
  • the viscosity of the composition from 5000 to 55,000 mPas (measured with a Brookfield viscometer type RVDVII +, spindle no. 7, 10 rpm at 23 0 C).
  • the viscosity of the composition according to the invention is less than 50,000 mPas.
  • the viscosity of the composition is 9,000 to 40,000 mPas.
  • the viscosity is 10,000 to 30,000, in particular 12,000 to 22,000 mPas.
  • the invention further provides a process for preparing a transparent, curable composition according to the invention, which comprises a) a prepolymer component P comprising a1) an alkoxy- and / or acyloxysilane-terminated polymer having at least one end group of the general formula (I)
  • A is a divalent binding group
  • R is a divalent hydrocarbon radical optionally containing a heteroatom with 1
  • X, Y, Z are each independently C 1 - C 8 - alkyl, C 1 - C 8 - alkoxy or C 1 - C 8 -
  • Acyloxyreste are, wherein at least one of the radicals a C 1 - C 8 - alkoxy or C 1 - C 8 -
  • n is 0 or 1; and a2) an adhesion promoter; a3) a catalyst; and a4) a plasticizer; and b) a filler F are mixed together.
  • the individual components are defined as listed above.
  • the radical R may, for example, be a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical which optionally contains oxygen (O) or nitrogen (N) as heteroatom. If X, Y and / or Z are an acyloxy group, this can be done, for example, by B. be the acetoxy group.
  • plasticizer is added to the curable composition until the prepolymer component P has a refractive index (measured with an Abbe refractometer at 20 ° C.) of not more than 0.01, in particular not more than 0.005 differs from the refractive index of the filler F.
  • the process of the invention can also be carried out by adding plasticizer to the curable composition until the curable composition becomes transparent. Regardless of which criterion is used, in this process, with careful metering of the plasticizer, exactly that amount is used which is necessary in order to impart to the curable composition in addition to the outstanding performance properties also a consumer perceived as extremely advantageous transparency.
  • Another object of the invention is the use of a curable composition or a composition according to the invention prepared by the method according to the invention described above as adhesive, sealing or Besen ichtungsstoff.
  • Preference is given to the use as an adhesive for bonding plastics, metals, glass, ceramics, wood, wood-based materials, paper, paper materials, rubber and textiles.
  • the composition of the invention can be well processed and applied due to its low viscosity and allows good adhesion and strength after curing.
  • As a special application advantage is the transparency - even after curing - to call, which allows an application for their part transparent materials such as glass or transparent plastics and thereby causes no aesthetic disadvantages.
  • joints o. ⁇ .
  • Bonding area was 2.5 cm x 2.0 cm.
  • the adhesive was applied on one side. Using a toothed spatula, excess adhesive was removed. After 7 days, the tensile shear strength was determined by means of material testing equipment from Zwick (type
  • compositions as adhesives which have good strength and good adhesion.
  • the viscosities were determined using a Brookfield viscometer type RVDVII +, spindle no. 7, 10 rpm at 23 0 C.
  • the compositions of Comparative Examples 1 to 3 show high viscosities and no longer meet the requirement that they can be processed and applied well.
  • the refractive index of the polymer component P was determined with a Zeiss Abbe refractometer type B according to DIN 51423-2 at 20 0 C using the light of the D line of sodium.
  • the refractive index of the filler was determined according to the procedure described above

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Abstract

L'invention concerne une composition durcissable transparente d'une viscosité inférieure à 60 000 mPas (mesurée avec un viscosimètre Brookfield de type RVDVII +, mobile n° 7, 10 t/m à 23° C), comprenant un composant prépolymère P a) comprenant a1) un polymère à terminaison alcoxy et/ou acyloxysilane avec au moins un groupe terminal de la formule générale (I) -An-R-SiXYZ (I), dans laquelle A représente un groupe de liaison bivalent, R un reste hydrocarbure bivalent contenant éventuellement un hétéroatome avec 1 - 12 atomes de carbones, et X, Y, Z représentent indépendamment les uns des autres des restes alkyle C1-C8, alcoxy C1-C8 ou acyloxy C1-C8, au moins un des restes étant un groupe alcoxy C1-C8 ou acyloxy C1-C8 et n étant 0 ou 1; a2) un agent adhésif; a3) un catalyseur; et a4) un plastifiant; et b) une matière de remplissage F; et qui est caractérisée en ce que le composant prépolymère P présente un indice de réfraction nD 20 (mesuré avec un réfractomètre Abbe à 20° C) qui ne s'écarte pas de plus de 0,01 de l'indice de réfraction de la matière de remplissage F.
PCT/EP2009/058851 2008-07-11 2009-07-10 Compositions durcissables WO2010004038A1 (fr)

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WO2011051056A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Adhésif pour stratifiés contenant une réticulation silane
JP2013518954A (ja) * 2010-02-02 2013-05-23 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ポリエーテルブロックコポリマーおよびそれから得られる組成物
WO2014170072A2 (fr) 2013-04-17 2014-10-23 Evonik Industries Ag Matières adhésives et d'étanchéité alcoxysilylées à viscosité intrinsèquement réduire
DE102013208356A1 (de) 2013-05-07 2014-11-13 Evonik Industries Ag Vernetzung von IPMS Addukten mit Aminosilanen
DE102013224708A1 (de) 2013-12-03 2015-06-03 Evonik Industries Ag Alkoxysilylhaltige Klebdichtstoffe mit intrinsisch reduzierter Viskosität
EP2812387B1 (fr) 2012-02-06 2016-05-04 Wacker Chemie AG Matières à base de polymères à terminaison organyloxysilane
EP3050910A1 (fr) 2015-01-28 2016-08-03 Evonik Degussa GmbH Produit d'alcoxylation modifié comportant au moins un groupe alcoxysilane non terminal, doté d'une stabilité au stockage accrue et d'une dilatation améliorée du polymère fabriqué en utilisant celui-ci
EP3202816A1 (fr) 2016-02-04 2017-08-09 Evonik Degussa GmbH Colle d'etancheite contenant des alkoxysilyles et ayant une resistance amelioree a l'allongement d'une dechirure amorcee
US10100148B2 (en) 2013-11-18 2018-10-16 Evonik Degussa Gmbh Use of guanidine reaction products in the production of polyurethane systems

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DE102010062186A1 (de) * 2010-11-30 2012-05-31 Henkel Ag & Co. Kgaa Zweikomponentige härtbare Zusammensetzung
DE102011006366A1 (de) 2011-03-29 2012-10-04 Evonik Goldschmidt Gmbh Alkoxysilylhaltige Klebdichtstoffe mit erhöhter Bruchspannung
MX2018011655A (es) 2016-06-13 2019-01-10 Henkel Ag & Co Kgaa Composicion curable de alto modulo.
US11359100B2 (en) * 2018-09-10 2022-06-14 Evonik Operations Gmbh Tin-free catalysis of silane-functional polyurethane crosslinkers

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JP2013509463A (ja) * 2009-10-30 2013-03-14 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン シラン架橋を有する貼合わせ用接着剤
WO2011051056A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Adhésif pour stratifiés contenant une réticulation silane
JP2013518954A (ja) * 2010-02-02 2013-05-23 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ポリエーテルブロックコポリマーおよびそれから得られる組成物
EP2812387B1 (fr) 2012-02-06 2016-05-04 Wacker Chemie AG Matières à base de polymères à terminaison organyloxysilane
EP2812387B2 (fr) † 2012-02-06 2019-03-06 Wacker Chemie AG Matières à base de polymères à terminaison organyloxysilane
US10077386B2 (en) 2012-02-06 2018-09-18 Wacker Chemie Ag Compositions on the basis of organyloxysilane-terminated polymers
WO2014170072A2 (fr) 2013-04-17 2014-10-23 Evonik Industries Ag Matières adhésives et d'étanchéité alcoxysilylées à viscosité intrinsèquement réduire
DE102013206883A1 (de) 2013-04-17 2014-10-23 Evonik Industries Ag Alkoxysilylhaltige Klebdichtstoffe mit intrinsisch reduzierter Viskosität
US9550928B2 (en) 2013-04-17 2017-01-24 Evonik Degussa Gmbh Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity
JP2016522852A (ja) * 2013-05-07 2016-08-04 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ Ｉｐｍｓ付加物とアミノシランとの架橋
CN105164176A (zh) * 2013-05-07 2015-12-16 赢创德固赛有限公司 Ipms加合物与氨基硅烷的交联
WO2014180623A1 (fr) 2013-05-07 2014-11-13 Evonik Industries Ag Réticulation d'adduits d'ipms avec des aminosilanes
DE102013208356A1 (de) 2013-05-07 2014-11-13 Evonik Industries Ag Vernetzung von IPMS Addukten mit Aminosilanen
US10626291B2 (en) 2013-05-07 2020-04-21 Evonik Operations, GmbH Crosslinking of IPMS adducts with aminosilanes
US10100148B2 (en) 2013-11-18 2018-10-16 Evonik Degussa Gmbh Use of guanidine reaction products in the production of polyurethane systems
WO2015082264A1 (fr) 2013-12-03 2015-06-11 Evonik Industries Ag Matières adhésives et d'étanchéité alcoxysilylées à viscosité intrinsèquement réduite
DE102013224708A1 (de) 2013-12-03 2015-06-03 Evonik Industries Ag Alkoxysilylhaltige Klebdichtstoffe mit intrinsisch reduzierter Viskosität
EP3050910A1 (fr) 2015-01-28 2016-08-03 Evonik Degussa GmbH Produit d'alcoxylation modifié comportant au moins un groupe alcoxysilane non terminal, doté d'une stabilité au stockage accrue et d'une dilatation améliorée du polymère fabriqué en utilisant celui-ci
EP3202816A1 (fr) 2016-02-04 2017-08-09 Evonik Degussa GmbH Colle d'etancheite contenant des alkoxysilyles et ayant une resistance amelioree a l'allongement d'une dechirure amorcee

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