EP3735447A1 - Mastic silicone ayant une viscosité ajustable - Google Patents

Mastic silicone ayant une viscosité ajustable

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Publication number
EP3735447A1
EP3735447A1 EP18822400.0A EP18822400A EP3735447A1 EP 3735447 A1 EP3735447 A1 EP 3735447A1 EP 18822400 A EP18822400 A EP 18822400A EP 3735447 A1 EP3735447 A1 EP 3735447A1
Authority
EP
European Patent Office
Prior art keywords
organoalkoxysilane
weight
organoalkoxysiloxane
parts
silicone composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18822400.0A
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German (de)
English (en)
Inventor
Manuel Friedel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3735447A1 publication Critical patent/EP3735447A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J183/04—Polysiloxanes
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/068—Containing also other elements than carbon, oxygen or nitrogen in the polymer main chain
    • C09K2200/0685—Containing silicon

Definitions

  • the invention relates to a one-component moisture-curing
  • Silicone composition a method of bonding or grouting with the composition and its use.
  • RTV silicones are also referred to as RTV-1 silicones and RTV-2 silicones, respectively.
  • RTV-1 silicones have long been known. It is also known that such compounds
  • RTV-1 silicones can be formulated with alkoxy group-containing crosslinkers. Cleavage products of the crosslinking are then alcohols whose odor is significantly less unpleasant.
  • the crosslinkers used are monomeric silanes.
  • hydrophilic mostly fumed silica
  • silicone compositions especially at low shear rates until dormant. This effect is especially noticeable when silicone-terminated silicone polymers are used.
  • compositions are desirable where thixotropic behavior prevents sagging of the applied compositions on sloping or vertical surfaces. However, this also causes problems in certain
  • silicone plasticizers may be unreactive, but this increases the risk of emigration or bleeding of the plasticizers, and thus, e.g. promotes the formation of persistent stains in the adhesive substrate.
  • Reactive plasticizers and the above-mentioned short-chain silicone polymers often lead to an increase in the modulus of the compositions and thus embrittlement, which significantly limits the use as a low modulus sealant.
  • Silicone polymers with alkoxysilane end groups as well as from
  • Silicone composition which is suitable as a low modulus sealant and in addition to a silicone polymer with hydroxyl end groups in addition
  • the object of the present invention is therefore to provide a one-component moisture-curing silicone formulation which can be formulated oxime-free with customary silicone polymers having hydroxyl end groups (silanol end groups) and hydrophilic silica fillers without surface modification, and conventional silane or siloxane crosslinkers, but nevertheless has adjustable self-leveling properties, none Has plasticizer emigration and which can be used as a low modulus sealant.
  • silanol endblocked polydiorganosiloxane 5 to 20
  • Tin catalyst the flow properties of the composition can be adjusted and optionally self-leveling properties can be achieved.
  • the composition is free from the highly reactive
  • Organoalkoxysilane or siloxane is or only very small proportions, e.g. to 1 part by weight thereof, the composition is self-leveling. At higher levels, e.g. between 1 and 5 parts by weight, the
  • composition according to the invention can be formulated as a self-leveling or stable composition and has excellent mechanical properties making it suitable as a low-modulus sealant of class 20 (LM or HM, type F or G) according to ISO 1600.
  • LM or HM, type F or G low-modulus sealant of class 20 (LM or HM, type F or G) according to ISO 1600.
  • the present invention relates to a one-component moisture-curing silicone composition
  • a one-component moisture-curing silicone composition comprising
  • Polydiorganosiloxane OH-PDMS with silanol end groups which at 23 ° C has a viscosity of 1 ⁇ 00 to 350 ⁇ 00 mPa ⁇ s, measured according to DIN EN ISO 3219;
  • Organoalkoxysiloxane AS which is at least one
  • Aminoalkyl group having a primary amino group e) 0.1 to 7 parts by weight of at least one tin catalyst K;
  • Organoalkoxysiloxane OS which is at least two
  • silicone composition less than 1.0 wt .-% water, preferably less than 0.5 wt .-% water, in particular less than 0.1 wt .-% water, based on the total composition, with the proviso that the reactivity for the hydrolysis of the Organoalkoxysilane or organoalkoxysiloxane OS is higher than the reactivity for hydrolysis of the organoalkoxysilane or organoalkoxysiloxane crosslinker V.
  • polymer in the present document comprises on the one hand a
  • the term also encompasses derivatives of such a collective of macromolecules from polyreactions, compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules and which may be chemically uniform or chemically nonuniform.
  • the term also includes so-called prepolymers, that is, reactive oligo mers pre-adducts whose functional groups are involved in the construction of macromolecules.
  • Molecular weight refers to the molar mass (in grams per mole) of a molecule or moiety.
  • average molecular weight refers to the number average molecular weight (M n ) of an oligomeric or poly meric mixture of molecules or molecular residues. It is usually treated by gel permeation chromatography (GPC)
  • viscosity refers to the dynamic viscosity or shear viscosity, which is defined by the ratio between the shear stress and the shear rate (velocity gradient) and determined as described in DIN EN ISO 3219. The measurement can be carried out by means of a cone-plate viscometer MCR101 from Anton Paar, Austria, with a cone type CP 25-1 at 23 ° C. Unless stated otherwise, the viscosity values given refer to a shear rate of 0.5 s -1 .
  • a “storage stable” or “storable” is a substance or a composition tion is called if they at room temperature in a suitable Ge binding for a long time, typically for at least 3 months to 6 months and more, can be stored without them changed in their application or use properties by storage in a relevant for their use to the extent.
  • the terms “mass” and “weight” are used interchangeably throughout this document. Thus, a “weight percent” (% by weight) refers to a percentage by weight which, unless otherwise stated, refers to the mass (weight) of the total composition, or to the context of the entire molecule.
  • room temperature refers to a temperature of 23 ° C.
  • a silane in this document is a silicon compound consisting of a silicon atom and 4 functional groups or atoms attached thereto.
  • a siloxane is a compound that has at least two over one
  • Oxygen atom bridged silicon atoms comprises.
  • Siloxanes are thus condensation products of silanes.
  • An organosilane is a monomeric silicon compound having at least one nonhydrolyzable group linked via a Si-C bond.
  • An organosiloxane is a compound obtainable from the condensation of at least two organosilanes.
  • An alkoxysilane is a monomeric silane having at least one alkoxy group attached to the Si atom.
  • a trialkoxysilane and a tetraalkoxysilane are a monomeric silane having three or four alkoxy groups attached to the Si atom.
  • the alkoxy group may e.g. be a Ci-C6 alkoxy group.
  • An alkoxysiloxane is a compound obtainable from the condensation of at least two alkoxysilanes but still after condensation
  • An organoalkoxysilane is a monomeric silane having at least one
  • An organoalkoxysiloxane is a compound which is obtainable from the condensation of at least two organoalkoxysilanes or at least one alkoxysilane and an organoalkoxysilane but which still has at least one alkoxy group after the condensation.
  • the one-component moisture-curing silicone composition is in particular an RTV-1 silicone.
  • RTV-1 silicones the curing at room temperature by contact with water, generally by contact with the humidity in the air.
  • the one-part moisture-curing silicone composition comprises first one or more crosslinkable polydiorganosiloxanes.
  • crosslinkable polydiorganosiloxanes are well known to those skilled in the art.
  • the crosslinkable polydiorganosiloxanes have silicon-bonded ones
  • silanol groups on which a crosslinking is possible.
  • These silanol groups may be present in a side group or end group of the polydiorganosiloxane, with terminal hydroxyl groups being preferred.
  • Silanol-terminated polydiorganosiloxanes are also referred to as a, w-functional polydiorganosiloxanes.
  • the hydroxyl groups on the polymers can react with the alkoxy groups of the crosslinker or other silanes or siloxanes in the composition to form a bond.
  • This bond is formed in a condensation reaction, whereby by-products such as water or alcohol are usually released. It may be and is even likely that the alkoxysilane first hydrolyzes to a silanol before condensation takes place. These reactions take place preferentially and much more efficiently under the influence of a catalyst, which is also present in the composition according to the invention. This will be described below.
  • the viscosity of the polydiorganosiloxanes may vary depending on the purpose in a wide range.
  • the polydiorganosiloxane used according to the invention can have, for example, a viscosity of from 1 ⁇ 00 to 350 ⁇ 00 mPa ⁇ s, preferably from 5 ⁇ 00 to 120 ⁇ 00 mPa ⁇ s and particularly preferably from 10 ⁇ 00 to 80 ⁇ 00 mPa ⁇ s, at a temperature of 23 ° C.
  • the polydiorganosiloxane OH-PDMS is a linear one
  • radicals R 1 , R 2 and R 3 are independently linear or branched, monovalent hydrocarbon radicals having 1 to 12 carbon atoms, which optionally one or more heteroatoms, and optionally one or more CC multiple bonds and / or optionally cycloaliphatic and or have aromatic portions;
  • R 4 is a hydroxyl group
  • the index p is a value of 0, 1 or 2;
  • the index m is selected such that the polydiorganosiloxane OH-PDMS has a viscosity of from 1 ⁇ 00 to 350 ⁇ 00 mPa ⁇ s, preferably from 5 ⁇ 00 to 120 ⁇ 00 mPa ⁇ s and particularly preferably from 10 ⁇ 00 to 80 ⁇ 00 mPa ⁇ s, at a temperature of 23 ° C. measured according to DIN 53018.
  • the radicals R 1 and R 2 are each independently preferably selected from alkyl groups having 1 to 5, in particular 1 to 3, carbon atoms, such as propyl, ethyl and methyl, wherein methyl is particularly preferred, optionally a part of the alkyl groups, in particular methyl, may be replaced by other groups such as vinyl, phenyl or 3,3,3-trifluoropropyl.
  • the radical R 3 if present, independently of each other is preferably selected from phenyl, vinyl or methyl groups.
  • the radicals R 1 , R 2 and R 3 in formula (I) are
  • the index m in the formula (I) is selected so that the polydiorganosiloxane has the above viscosity.
  • the subscript m in the formula (I) may be e.g. in the range of 10 to 5000 and preferably 100 to 1500.
  • the crosslinkable polydiorganosiloxane OH-PDMS is preferably one
  • crosslinkable polydimethylsiloxane Preferably used crosslinkable
  • Polydiorganosiloxanes wherein hydroxy-terminated linear polydiorganosiloxanes (a, w-hydroxy-functional polydiorganosiloxanes) are particularly preferred, wherein the polydiorganosiloxane OH-PDMS is preferably a polydimethylsiloxane.
  • the hydroxy-terminated linear polydiorganosiloxanes in particular polydimethylsiloxanes, preferably have a viscosity, measured to DIN 53018, of from 2300 to 35000 mPa ⁇ s, preferably from 5000 to 12000 mPa ⁇ s, more preferably from 10 ⁇ 00 to 80 ⁇ 00 mPa ⁇ s, at 23 ° C. s, up.
  • a viscosity measured to DIN 53018
  • composition according to the invention also contains 5 to 20
  • a hydrophilic silica is a solid which consists predominantly of Si (-0) 4 units but may also have silanol groups on the surface and has a three-dimensional, normally porous structure.
  • the term "hydrophilic” indicates that the silica is not surface treated with hydrophobizing additives.
  • Hydrophilic, ie untreated silicic acids are well known to those skilled in the art as fillers and thickeners. You can, for example, over
  • Precipitation reactions precipitated silica or precipitated silica
  • pyrolysis processes fumed silica
  • Preferred for the invention is fumed silica, as these
  • silicas having a BET surface area of from 50 to 300 m 2 / g, preferably from 100 to 255 m 2 / g.
  • composition of the invention further comprises 1 to 10
  • organoalkoxysilane or organoalkoxysiloxane crosslinker V which contains at least 2 alkoxysilane groups.
  • the crosslinker V has at least 2 alkoxysilane groups, preferably at least 3 or more (only in the case of a siloxane, that is to say an oligomeric silane).
  • Suitable alkoxy groups are, in particular, methoxy, ethoxy, butoxy and propoxy groups. Preference is given to methoxy and ethoxy groups.
  • the crosslinker V furthermore preferably has 1, 2 or more (only in the case of oligomeric siloxanes) non-hydrolyzable functional groups, in particular alkyl groups or alkenyl groups.
  • the non-hydrolyzable functional groups are selected from methyl, ethyl, vinyl, n-propyl, cyclopentyl, phenyl, cyclohexyl, n-octyl, isooctyl and hexadecyl.
  • crosslinker V It is also possible to use tetraalkoxysilanes as crosslinker V,
  • Methylvinyldimethoxysilane or the corresponding compounds in which the methoxy group is replaced by ethoxy or propoxy such as methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane and phenyltripropoxysilane.
  • the oligomeric organoalkoxysiloxane crosslinkers V are condensation products of one or more of such monomeric silane crosslinkers, optionally with the use of further silanes, e.g.
  • Tetraalkoxysilanes Tetraalkoxysilanes.
  • Such oligomeric siloxanes are known and commercially available, for example under the trade name Dynasylan ® 6490 from Evonik Degussa GmbH.
  • the oligomeric siloxane can e.g. are formed from hydrolysis and condensation of one or more identical or different monomeric silanes.
  • An alkoxy-containing siloxane may be linear, cyclic or three-membered branched. It is preferably an oligomeric alkoxy-containing siloxane.
  • Such an oligomeric siloxane contains functional groups derived from the monomeric silanes used in their synthesis. For example, a first condensation of two tetramethoxysilane molecules results in a dimer containing six functional groups; Each of a functional group of each molecule is formed by condensation of the linkage. As already stated, the structure of the oligomers formed can be complicated. The number of functional groups in the oligomer can be determined by the degree of condensation, the type of condensation and monomers used Silanes vary, but is at least 2, but usually larger, for example 4 or more.
  • the degree of condensation of the oligomeric siloxane i. the number of monomeric silanes condensed with each other can vary widely depending on
  • Condensation degree especially at higher degrees of condensation, often only represents an average value.
  • the degree of condensation refers to the number of condensed monomeric alkoxysilanes in the siloxane and can also be referred to as the degree of polymerization.
  • Alkoxylene-containing siloxane is at least 5, more preferably at least 6, and most preferably at least 7.
  • the average degree of condensation of the alkoxylene-containing siloxane can vary widely depending on the application and may preferably be e.g. not more than 15, and more preferably not more than 12. It is understood that the degree of condensation, especially at higher condensation levels, often represents an average value, i. E. As a rule, the siloxane is a mixture of compounds of different degrees of condensation.
  • the average degree of condensation is understood here as the average degree of condensation based on the number average. As is known to those skilled in the art, this can be determined by measuring the siloxane using 29 Si NMR spectroscopy and evaluating the spectrum obtained.
  • Measurement and determination can be carried out as described in J. Zhang et al, J Sol-Gel Sei Technol, 2010, 56, 197-202. respectively.
  • organoalkoxysilane or organoalkoxysiloxane crosslinker V for the silicone composition according to the invention also any mixture of the aforementioned silanes and / or siloxanes can be used.
  • the composition of the invention further comprises 1 to 7
  • organoalkoxysilane or organoalkoxysiloxane AS are essentially the same structures as described above for the crosslinker V, in particular also for the oligomeric siloxanes, with the difference, however, that the organoalkoxysilane or organoalkoxysiloxane AS comprises at least one aminoalkyl group having a primary amino group. monomers
  • Organoalkoxysilanes AS can contain 1 or 2 aminoalkyl groups and 2 or 3 alkoxy groups per silicon atom. Oligomeric organoalkoxysiloxanes AS can also have more or fewer amino groups.
  • organoalkoxysilane or organoalkoxysiloxane AS causes the composition to cure more rapidly, since the amino group acts cocatalytically, on the other hand, it surprisingly leads to the compositions, if all other constituents according to the invention (with restrictions with respect to organoalkoxysilane or
  • Organoalkoxysiloxane OS Organoalkoxysiloxane OS
  • monomeric organoalkoxysilanes AS are 3-aminopropyltrimethoxysilane and 2-aminoethyl-3-aminopropyltrimethoxysilane, as well as the corresponding compounds in which the methoxy group has been replaced by ethoxy or propoxy, for example 3-aminopropyltriethoxysilane.
  • Suitable Oligomers Organoalkoxysiloxanes AS are those commercially available, e.g. under the trade names
  • composition according to the invention comprises up to 5
  • organoalkoxysilane or organoalkoxysiloxane OS The role of organoalkoxysilane or organoalkoxysiloxane OS is to be able to adjust the flow behavior of the composition according to the invention.
  • the composition according to the invention can be formulated entirely without (or with low levels of) organoalkoxysilane or organoalkoxysiloxane OS, and is then present as a completely self-leveling, low-viscosity composition.
  • organoalkoxysilane or organoalkoxysiloxane OS By addition of organoalkoxysilane or
  • Organoalkoxysiloxane OS can then if desired a
  • Organoalkoxysilane or organoalkoxysiloxane OS The bigger the
  • Organoalkoxysilans or organoalkoxysiloxane OS obtained a self-leveling composition, while having a content of 1 to 5
  • Organoalkoxysilans or Organoalkoxysiloxans OS a steadily increasing with increasing proportion of organoalkoxysilane or Organoalkoxysiloxan OS composition is obtained.
  • the expression of this thickening effect, or the amount of organoalkoxysilane or organoalkoxysiloxane OS required for a particular thickening effect of course depends on the nature of the organoalkoxysilane or
  • Thickening effect can be specified. On the other hand it is independent of the Type of Organoalkoxysilans or Organoalkoxysiloxans OS so that a larger amount thereof in the composition of a larger
  • organoalkoxysilane or organoalkoxysiloxane OS are essentially the same structures as described above for the crosslinker V, in particular also for the oligomeric siloxanes.
  • the crosslinker V may have alkoxy groups with a greater alkoxy group than the silane or siloxane OS.
  • methoxysilanes are more reactive than ethoxysilanes, which in turn are more reactive than e.g. Propoxysilanes are.
  • Organoalkoxysilane or organoalkoxysiloxane crosslinker V and in particular also the organoalkoxysilane or organoalkoxysiloxane AS, ethoxy groups, while the organoalkoxysilane or organoalkoxysiloxane OS
  • alpha silanes or siloxanes as organoalkoxysilane or organoalkoxysiloxane OS.
  • a-silanes or siloxanes silanes or siloxanes which have a functional group Si-CH 2 -X, where X is an organic radical which is bonded via an oxygen or nitrogen atom to the methylene group.
  • X is an organic radical which is bonded via an oxygen or nitrogen atom to the methylene group.
  • heteroatom which is bound via a methylene bridge on the silicon atom, electronic effects occur, which significantly increase the reactivity of alkoxy groups on this silicon atom.
  • the effect according to the invention can also be achieved in compositions which use only methoxysilanes and siloxanes or only ethoxysilanes and siloxanes.
  • all the alkoxysilanes and alkoxysiloxanes used are methoxysilanes and
  • Methoxysiloxanes, and the organoalkoxysilane or organoalkoxysiloxane OS has a functional group Si-CH 2 -X, wherein X is an organic radical which is bonded via an oxygen or nitrogen atom to the methylene group. X is particularly preferably a cyclohexylamino radical, an O-methylcarbamate radical or a methacryloxy radical, in particular a methacryloxy radical.
  • Embodiment is particularly reactive and leads to particularly good mechanical properties.
  • Alkoxysiloxanes are ethoxysilanes and ethoxysiloxanes. This embodiment is particularly toxicologically harmless because no methanol is released.
  • a third possibility for achieving the difference in reactivity between crosslinker V and silane or siloxane OS is that silanes or siloxanes OS are higher-functional silanes and / or siloxanes, for example trialkoxysilanes, whereas for crosslinker V
  • all the alkoxysilanes and alkoxysiloxanes used are methoxysilanes
  • Organoalkoxysilane or organoalkoxysiloxane OS predominantly
  • Organoalkoxysiloxane crosslinker V predominantly methyldimethoxysilane has.
  • a fourth way to achieve the difference in reactivity between crosslinker V and silane or siloxane OS is that silanes or siloxanes OS silanes or siloxanes having at least one secondary
  • Amino group can be used in at least one organic radical.
  • the secondary amino group is a reactivity increase of
  • silanes or siloxanes OS are bis (trimethoxysilylpropyl) amine, and N- (n-butyl) -3-aminopropyltrimethoxysilane, as well as their analogues with ethoxysilane groups instead of
  • the organoalkoxysilane or organoalkoxysiloxane OS accordingly has at least one
  • Aminoalkyl radical having a secondary amino group having a secondary amino group.
  • organoalkoxysilane or organoalkoxysiloxane OS must not have any primary amino groups, since otherwise they would belong to the organoalkoxysilane or organoalkoxysiloxane AS.
  • silanes and siloxanes used in the context of this invention are preferably free of oxime groups. Include oxime groups
  • oxime groups are usually in the crosslinker of one-component according to the prior art
  • Crosslinker (as well as other silane-functional constituents) in the presence of moisture or water occurring condensation or crosslinking and / or the previous hydrolysis, in the case of alkoxysilane.
  • the tin catalyst K is, in particular, an organotin compound.
  • Preferred organotin compounds are dialkyltin compounds, e.g. selected from dimethyltin di-2-ethylhexanoate, dimethyltin dilaurate, di-n-butyltin diacetate, di-n-butyltin di-2-ethylhexanoate, di-n-butyltin dicaprylate, di-n-butyltin di-2,2-dimethyloctanoate, di-n-butyltin dilaurate, Di-n-butyltin distearate, di-n-butyltin dimaleinate, di-n-butyltin dioleate, di-n-octyltin di-2-ethylhexanoate, di-n-octyltin di-2,2-dimethyloctanoate, di-n-octyltin dimaleinate, di- n-octyltin di
  • titanates are not or less well suited for the inventive composition. It has also been found that the presence of the organoalkoxysilane or organoalkoxysiloxane AS essential for the invention is indispensable for rapid curing.
  • composition according to the invention may also contain further constituents, as are customary for one-component moisture-curing silicone formulations.
  • additives are e.g. Plasticizers, inorganic and / or organic fillers, odorous substances,
  • wetting aids for pigments, adhesion promoters, processing aids, rheology modifiers, stabilizers, dyes, inhibitors, heat stabilizers, stabilizers, antistatics, flame retardants, biocides, waxes, leveling agents, thixotropic agents and hydroxy-functional polyols.
  • the silicone formulation optionally has one or more additional fillers.
  • the fillers may e.g. affect both the rheological properties of the uncured formulation and the mechanical properties and surface finish of the cured formulation. It may be advantageous to use a mixture of different fillers.
  • suitable fillers are inorganic or organic fillers, such as natural, ground or precipitated calcium carbonates or chalks, which may be surface-treated, e.g. with fatty acids, surface-treated silicic acids, in particular pyrogenic silicic acids, aluminum hydroxides such as aluminum trihydroxide, carbon black, in particular
  • Industrial minerals barium sulphate, dolomite, silica, kaolin, floss, quartz, calcined aluminas, aluminosilicates, magnesium aluminosilicates, zirconium silicates, cristobalite flour, diatomaceous earth, mica, titanium oxides, zirconium oxides, gypsum, graphite, carbon fibers, zeolites, or glass fibers, the surface of which may be combined with a Flydrophobitechnischsstoff is treated.
  • polydimethylsiloxane plasticizers W-PDMS are trialkylsilyl-terminated polydimethylsiloxanes, the trialkylsilyl-terminated polydimethylsiloxanes preferably having a viscosity at 23 ° C. in the range from 1 to 10 ⁇ 00 mPa.s. It may also be e.g.
  • TrimethylsilylterminATOR polydimethylsiloxanes are used in which some of the methyl groups are replaced by other organic groups such as phenyl, vinyl or trifluoropropyl.
  • Polydimethylsiloxane plasticizer W-PDMS may also be monofunctional, i. one end is reactive, e.g. via a hydroxy end group.
  • Hydrocarbons can also be used as plasticizers.
  • the constituents of the composition according to the invention can be mixed with one another in a customary manner, for example with the aid of a suitable mixing unit such as, for example, a forced or planetary mixer.
  • a suitable mixing unit such as, for example, a forced or planetary mixer.
  • Composition additionally one or more of the following components: g) 5 to 40 parts by weight of reactive or non-reactive polydimethylsiloxane plasticizer W-PDMS, and / or
  • Desiccant and / or organic extenders Desiccant and / or organic extenders.
  • composition according to the invention is preferably free from
  • Another object of the invention is the use of up to 5 parts by weight of an organoalkoxysilane or organoalkoxysiloxane OS, which contains at least two alkoxysilane, for adjusting the flow behavior of a one-component moisture-curing
  • Silicone composition comprising
  • Polydiorganosiloxane OH-PDMS with silanol end groups which at 23 ° C has a viscosity of 1 ⁇ 00 to 350 ⁇ 00 mPa ⁇ s, measured according to DIN EN ISO 3219;
  • organoalkoxysilane or organoalkoxysiloxane crosslinker V which contains at least 2 alkoxysilane groups
  • organoalkoxysilane or organoalkoxysiloxane AS which contains at least one
  • Aminoalkyl group having a primary amino group e) 0.1 to 7 parts by weight of at least one tin catalyst K; wherein the silicone composition contains less than 1.0 wt .-% water, based on the total composition, with the
  • composition of the invention may be used as an adhesive, coating or sealant in a process for bonding or grouting
  • the inventive method comprises a) the application of the composition to a substrate and
  • step b) preferably takes place by the action of atmospheric moisture.
  • composition of the invention is placed in an airtight container, e.g. a cartridge, a bag or a hobbock and is thus stable in storage.
  • an airtight container e.g. a cartridge, a bag or a hobbock and is thus stable in storage.
  • Silicone composition according to the invention less than 1.0% by weight
  • Water preferably less than 0.5 wt .-% water, more preferably less than 0.1 wt .-% water, based on the total composition.
  • a low water content can be achieved in particular by the
  • compositions according to the invention are dried in advance. These have heat and / or
  • silicone formulation For application, the container is opened and immediately afterwards
  • composition by hand, e.g. a gun, or by automatic application device on the substrate or in the glue joint up or
  • step a) of the abovementioned process can be carried out in a customary manner, e.g. by hand or in an automated process using robots.
  • the substrate provided with the mixture is contacted with another substrate, optionally under pressure, to obtain an adhesive bond between the substrates.
  • step b) the mixture is allowed to cure, usually at room temperature, to achieve the bonding or disposition of the substrates.
  • the inventive bonded or grouted substrates are obtained with the cured composition as an adhesive or sealing material.
  • the substrates to be bonded, coated, pouring or grouting may be made of the same material or of a different material. All customary materials can be bonded, coated, cast or grouted with the one-component composition according to the invention. Preferred materials for bonding, coating,
  • Potting or grouting are glass, metals, e.g. Aluminum, copper,
  • Lime sandstone, asphalt, bitumen, plastics e.g. Polyolefins, PVC, polyvinyl fluoride, PET, polyamide, polycarbonate, polystyrene or polyacrylate, and composites such as CFRP.
  • plastics e.g. Polyolefins, PVC, polyvinyl fluoride, PET, polyamide, polycarbonate, polystyrene or polyacrylate, and composites such as CFRP.
  • inventive one-component composition can thus be used as an adhesive, coating, potting compound or sealant, for example in the fields of construction, plumbing, automotive, solar technology, wind power, white goods, facade and window construction, electronics and boat and shipbuilding.
  • the Shore A hardness was determined after curing the samples for 7 days at 23 ° C and 50% r.F. on a Shore A tester from Bareiss according to DIN ISO 7619-1. To determine the Shore A hardness, round specimens with a diameter of 42 mm and a thickness of 6 mm were produced.
  • the viscosity was determined in accordance with DIN EN ISO 3219 using a cone-and-plate viscometer MCR101 from Anton Paar, Austria, with cone type CP 25-1 and a distance of 0.049 mm at 23 ° C.
  • the stated viscosity values refer to a shear rate of 0.1 s 1 .
  • compositions to a vertically mounted cardboard substrate from a 300 ml PE cartridge with hand gun at 23 ° C / 50% RH. In each case about 20 ml were applied on a base area of about 3 cm 2 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de silicone monocomposant durcissant à l'humidité comprenant 100 parties en poids d'au moins un polydiorganosiloxane réticulable OH-PDMS avec des groupes terminaux silanol, 5 à 20 parties en poids d'au moins un acide silicique hydrophile KS, 1 à 10 parties en poids d'au moins un agent de réticulation V organoalcoxysilane ou organoalcoxysiloxane, qui contient au moins 2 groupes alcoxysilane, 1 à 7 parties en poids d'un organoalcoxysilane ou d'un organoalcoxysiloxane AS, qui contient au moins un groupe aminoalkyle avec un groupe amino primaire, 0,1 à 7 parties en poids d'au moins un catalyseur à base d'étain K, jusqu'à 5 parties en poids d'un organoalcoxysilane ou d'un organoalcoxysiloxane OS, qui contient au moins deux groupes alcoxysilane, la composition de silicone contenant moins de 1,0 % en poids d'eau rapporté à la composition totale, à condition que la réactivité pour l'hydrolyse de l'organoalcoxysilane ou l'organoalcoxysiloxane OS soit supérieure à la réactivité pour l'hydrolyse de l'agent de réticulation V organoalcoxysilane ou organoalcoxysiloxane. La composition monocomposant convient en tant qu'adhésif ou mastic à faible module ainsi que comme revêtement ou scellement et peut être formulée au choix comme composition autonivelante ou stable.
EP18822400.0A 2018-01-03 2018-12-21 Mastic silicone ayant une viscosité ajustable Pending EP3735447A1 (fr)

Applications Claiming Priority (2)

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EP18150164 2018-01-03
PCT/EP2018/086619 WO2019134863A1 (fr) 2018-01-03 2018-12-21 Mastic silicone ayant une viscosité ajustable

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EP3763795A1 (fr) 2019-07-08 2021-01-13 tesa SE Matière polymère à stabilité dimensionnelle, réticulable à l'humidité
FR3101079B1 (fr) * 2019-09-19 2022-01-21 Bostik Sa Composition de mastic reticulable a l'humidite pour exposition du joint a temperature elevee
CN115305049B (zh) * 2022-09-16 2023-05-12 成都高新区今天硅材料有限公司 一种高稳定性脱甲醇型硅酮密封胶及其制备方法

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US4499234A (en) * 1983-10-14 1985-02-12 General Electric Company Non-corrosive silicone RTV compositions
CA1333307C (fr) 1988-04-15 1994-11-29 John Earl Dietlein Composition d'etancheite pour joints de dilatation de routes bitumees
US6737494B2 (en) * 2001-11-09 2004-05-18 General Electric Company Synthesis and use of alkylalkoxyacyloxysilanes and blends thereof for use as a crosslinking agent in moisture curing RTV'S
DE10319303A1 (de) * 2003-04-29 2004-12-09 Wacker-Chemie Gmbh Verfahren zur Herstellung von vernetzbaren Massen auf der Basis von Organosiliciumverbindungen
US8124690B2 (en) * 2006-09-13 2012-02-28 Kaneka Corporation Moisture curable polymer having SiF group, and curable composition containing the same
WO2009047580A1 (fr) * 2007-10-11 2009-04-16 Amber Chemical Company Ltd. Compositions d'organopolysiloxane durcissables à température ambiante, thixotropes/sans affaissement
US9145486B2 (en) 2011-08-05 2015-09-29 Dow Corning Corporation Filled silicone compositions, preparations and uses thereof
DE102012208864A1 (de) * 2012-05-25 2013-11-28 Wacker Chemie Ag Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
EP2851395A1 (fr) * 2013-09-20 2015-03-25 Sika Technology AG Combinaison d'une formule de silicone RTV-1 et accélérateur doté d'une caractéristique de durcissement améliorée
CN106190012B (zh) * 2016-08-08 2019-02-05 广州机械科学研究院有限公司 一种透明的高强度自流平脱甲醇型单组份有机硅胶及其制备方法
JP2020509101A (ja) * 2017-02-28 2020-03-26 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ エラストマーを得るための架橋性組成物の製造方法

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CN111770977A (zh) 2020-10-13
CN111770977B (zh) 2022-09-13
US20210062001A1 (en) 2021-03-04

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