Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
  • C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
  • C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
  • C07C279/12—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
  • C07C279/16—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to carbon atoms of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
  • C07C279/18—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to carbon atoms of six-membered aromatic rings
• • 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
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
• • 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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  • 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
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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  • 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
  • C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the invention relates to id-in or guanidine group-containing silanes and their use as catalysts for the crosslinking of curable compositions.
• Curable compositions play an important role in many technical applications, for example as adhesives, sealants or coatings. Their curing is effected by crosslinking reactions which proceed via free or latent reactive groups such as isocyanate groups, epoxide groups, hydroxyl groups, amino groups or silane groups, which react after mixing, by heating or by contact with moisture with themselves or with each other and so in the Covalently connect the composition contained in the composition to a polymeric network. Catalysts are often used to accelerate such crosslinking reactions. Very often these are toxicologically questionable substances which pose a potential hazard to the processor and the environment, in particular after curing of the composition, when the catalyst or its degradation products are released by outgassing, migration or leaching.
• free or latent reactive groups such as isocyanate groups, epoxide groups, hydroxyl groups, amino groups or silane groups
• Silane-group-containing polymers are in particular polyorganosiloxanes, which are commonly referred to as “SNicone” or “silicone rubbers”, and silane-containing organic polymers, which are also known as “silanfunktionelle polymers", “silane-modified polymers” (SMP) or Their crosslinking proceeds via the condensation of silanol groups to form siloxane bonds and is conventionally catalyzed by means of organotin compounds, in particular di-alkyltin (IV) carboxylates high activity in terms of silanol condensation and are very hydro- lysebestix; However, they are harmful to health and highly hazardous to water. Often they are combined with other catalysts, mainly with basic compounds such as amines in particular, which accelerate the upstream hydrolysis of the silane groups.
• organotin compounds have been described as alternative metal catalysts.
• organotitanates, zirconates and aluminates have been described as alternative metal catalysts.
• these usually have a lower catalytic activity with respect to the silanol condensation and cause significantly slower crosslinking. Because of their lack of hydrolytic stability they can lose a large part of their activity when storing the composition by residual moisture content of the ingredients, whereby the curing slowed down greatly or comes to a standstill.
• organotin compounds are strongly basic nitrogen compounds from the class of amidines and guanidines, which can be used in combination with the mentioned metal catalysts or alone.
• many of the common amidine and guanidine catalysts in particular 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,1,3,3-tetramethylguanidine (TMG)
• DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
• TMG 1,1,3,3-tetramethylguanidine
• DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
• TMG 1,1,3,3-tetramethylguanidine
• the described use of aromatic, solid at room amidines and guanidines remedy this, but requires the use of suitable solvents and brings about losses in the catalytic activity and thus the crosslinking rate.
• a catalyst for the crosslinking of curable compositions in particular silane groups.
• the catalyst should have a low vapor pressure and a high compatibility with the composition, so that it is prone to neither separation or migration nor evaporation, and should be as odorless and less toxic.
• amidine or guanidine group-containing silane according to claim 1 contains at least one alkoxy radical having an aliphatic amidine or guanidine group and exhibits a high catalytic activity, while aromatic amidine or
• Guanidine group-containing compounds are hardly or not catalytically active. Unlike many known in the art
• silanes of claim 1 are typically liquid and low viscosity, which is advantageous for their use and dosage, are catalytically active, especially in silane cross-linking compositions, and can not cause stability problems caused by free hydroxyl groups during storage of such composition.
• the volatile organic compound (alcohol or ketoxime) released in the preparation of the silane according to claim 1 can be selectively removed, which is advantageous when used in curable compositions, since their emission of volatile organic compounds is thus reduced.
• the silane according to claim 1 and / or an amidine or guanidine group-containing reaction product thereof is outstanding. It is suitable for use in silane-containing compositions where, as the sole catalyst or in combination with other catalysts, it enables rapid curing to a mechanically high-grade and durable material without adversely affecting the shelf-life of the uncured composition. It is excellently compatible with the composition both before and after cure, and has no tendency to separate or migrate, unlike many similar compositions with prior art amidine and guanidine catalysts where catalyst-induced migration effects play a strong role play. It enables low-emission and low-odor products, which neither have greasy or sticky surfaces nor cause substrate contamination. Finally, the silane of claim 1 in a surprisingly simple and fast process without additives from commercially available, inexpensive starting materials produced.
• the invention relates to a silane of the formula (I)
• Z is an amidine or guanidine group bonded via a nitrogen atom
• A is a divalent aliphatic or cycloaliphatic or arylaliphatic hydrocarbon radical having 2 to 20 C atoms, which optionally contains ether oxygen or secondary or tertiary amine nitrogen,
• R 6 either represents an alkoxy radical having 1 to 12 C atoms, which optionally contains ether oxygen, or represents a ketoximato radical having 1 to 13 C atoms,
• R 7 is a monovalent hydrocarbon radical having 1 to 12 C atoms
• Y is a monovalent hydrocarbon radical having 1 to 20 C atoms which optionally has a terminal mercapto group, epoxy group, (meth) acrylic group, amidine group, guanidine, urethane or urea group or a terminal amino group of the formula -NHR 8 and which optionally ether Oxygen or secondary amine nitrogen, wherein R 8 is a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 C atoms or a radical
• silane of formula (I) does not contain a nitrogen atom which is directly attached to an aromatic ring or part of a heteroaromatic ring system, such as imidazole or pyrimidine.
• amino group denotes a silyl group bonded to an organic radical or to a polyorganosiloxane radical having one to three, in particular two or three, hydrolyzable substituents on the silicon atom Particularly suitable hydrolyzable substituents are alkoxy radicals.
• silane groups are also referred to as “alkoxysilane groups”. Silane groups may also be present in partially or completely hydrolyzed form.
• hydroxysilane denotes organoalkoxysilanes which have one or more hydroxyl, isocyanato, amino or mercapto groups on the organic radical in addition to the silane group.
• primary amino group or “primary amine nitrogen” denotes an NH 2 group or its nitrogen atom, which is attached to an organic amine. see rest is bound, and as “secondary amino group” or “secondary amine nitrogen” an NH group or its nitrogen atom is called, which is bound to two organic radicals, which may also be part of a ring together , and “tertiary amine” or “tertiary amine nitrogen” is an N-group or its nitrogen atom, the or to three organic radicals, which may also be two or three part of one or more rings, is bound.
• organic polymer encompasses a collective of chemically uniform, but different in terms of degree of polymerization, molecular weight and chain length macromolecules, which was prepared by a polyreaction (polymerization, polyaddition, polycondensation) and having a majority of carbon atoms in the polymer backbone, and reaction products
• polymers having a polyorganosiloxane backbone commonly referred to as "silicones" are not organic polymers within the meaning of the present specification.
• silane-group-containing polyether also encompasses silane-group-containing organic polymers which, in addition to polyether units, may also contain urethane groups, urea groups or thiourethane groups Such silane-group-containing polyethers may also be termed “silane-containing polyurethanes" become.
• molecular weight is meant in this document the molar mass (in grams per mole) of a molecule or part of a molecule, also referred to as “residue”.
• average molecular weight is meant the number average M n of an oligomeric or polymeric mixture of molecules or residues, which is usually determined by gel permeation chromatography (GPC) against polystyrene as a standard.
• a “stable in storage” or “storable” refers to a substance or composition when it can be stored at room temperature in a suitable container for a prolonged period of time, typically at least 3 months to 6 months or more, without being present in its contents - application or service properties, in particular the viscosity and the rate of crosslinking, changed by the storage in a relevant for their use to the extent.
• a dashed line in the formulas in this document in each case represents the bond between a substituent and the associated molecular residue.
• a "room temperature” is a temperature of about 23 ° C.
• silane of formula (I) may also be present in tautomeric form. All possible tautomeric forms of the silane of the formula (I) are considered equivalent in the context of the present invention.
• silane of formula (I) may be present in protonated form.
• silane of the formula (I) can be present in complexed form, in particular with cations of zinc, iron or molybdenum.
• Z preferably stands for , in which
• R ° is a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 C atoms
• R 1 is a hydrogen radical or an alkyl or cycloalkyl or Aralkyl radical having 1 to 8 carbon atoms or together with R 2 is R 9
• R 2 is a hydrogen radical or an alkyl
• Cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains ether oxygen or tertiary amine nitrogen, or together with R 1 represents R 9
• R 9 is a hydrogen radical or an alkyl or cycloalkyl or Aralkyl radical having 1 to 8 carbon atoms or together with R 2 is R 9
• R 2 is a hydrogen radical or an alkyl
• Cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains ether oxygen or tertiary amine nitrogen, or together with R 1 represents R 9
• R 3 is -NR 4 R 5 or is a hydrogen radical or an alkyl- or cycloalkyl or aralkyl radical having 1 to 12 C atoms,
• R 4 and R 5 independently of one another are each a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains ether oxygen or tertiary amine nitrogen, and R 9 is 1, 2-ethylene or 1, 2-propylene or 1, 3-propylene or 1, 3-butylene or
• R 2 and R ° can also stand together for an alkylene radical having 3 to 6 C atoms, which may contain, if appropriate, ether oxygen or tertiary amine nitrogen,
• R 2 and R 3 together can also stand for an alkylene radical having 3 to 6 C atoms,
• R 4 and R 5 together also represent an alkylene radical having 4 to 7 C atoms, which may contain, if appropriate, ether oxygen or tertiary amine nitrogen, and
• R 2 and R 5 together can also stand for an alkylene radical having 2 to 12 C atoms.
• A is preferably an alkylene radical having 2 to 10, in particular 2 to 6, carbon atoms, which optionally contains one or two ether oxygens.
• A is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,1-dimethyl-1,2-ethylene, 1,5-pentene - ylen, 1, 6-hexylene, (1, 5,5-trimethylcyclohexan-1-yl) methane-1, 3, 3-oxa-1, 5-pentylene and 3,6-dioxa-1, 8-octylene.
• e is 0 or 1.
• F is preferably 0 or 1, in particular 0.
• R 6 is preferably an alkoxy radical having 1 to 4 C atoms, which optionally contains one or two ether oxygens, in particular methoxy or ethoxy.
• R 6 is preferably a ketoximato radical having 1 to 6 C atoms, in particular methylethykeoximato or methylisobutylketoximato.
• R 7 is preferably a monovalent hydrocarbon radical having 1 to 6 C atoms, in particular a methyl radical or a phenyl radical.
• Y is preferably a monovalent hydrocarbon radical having 1 to 8 C atoms which optionally has a terminal mercapto group, epoxy group, (meth) acrylic group, amidine group, guanidine group, urethane group or urea group or a terminal amino group of the formula -NHR 8 , and which optionally contains an ether oxygen or a secondary amine nitrogen.
• Y is selected from the group consisting of methyl, octyl, isooctyl, phenyl, vinyl, 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl, 3-mercaptopropyl, 3-glycidoxypropyl, 3-acryloxypropyl, 3 Methacryloxypropyl and
• R is preferably a hydrogen radical or an alkyl radical having 1 to 4 C atoms, in particular a hydrogen radical.
• R 1 is preferably a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 4 C atoms or together with R 2 is R 9 .
• R 2 is preferably an alkyl, cycloalkyl or aralkyl radical having 1 to 12, in particular 1 to 8, C atoms, which optionally contains ether oxygen or tertiary amine nitrogen, or together with R 1 for R 9 .
• R 3 preferably stands for -NR 4 R 5 or for a hydrogen radical or for an alkyl, cycloalkyl or aralkyl radical having 1 to 8, in particular 1 to 4, C atoms.
• R 4 and R 5 are each, independently of one another, each represent a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms, which optionally contains an ether oxygen or a tertiary amine nitrogen.
• R 4 and R 5 together are preferably an alkylene radical having 4 to 7 C atoms, which optionally contains an ether oxygen or a tertiary amine nitrogen.
• R 4 particularly preferably represents a hydrogen radical.
• Z is an amidine group.
• Such a silane is hereinafter also referred to as "amidinosilane of the formula (I)".
• R 3 is a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical having 1 to 12, preferably 1 to 8, in particular 1 to 4, C-atoms, or together with R 2 is an alkylene Radical having 3 to 6, in particular 3 to 5, carbon atoms.
• R 3 is a hydrogen radical or a methyl radical, in particular a methyl radical.
• An amidinosilane of the formula (I) has the advantage that it has a not so high catalytic activity and can therefore be used in a slightly higher amount, as a result of which it is less susceptible to interferences by other constituents of the composition, in particular the constituents contained therein. contaminants.
• R 3 and R 9 have the meanings mentioned.
• R 3 is a hydrogen radical or a methyl radical.
• R 9 is 1, 3-propylene.
• R 3 is methyl and R 9 is 1, 3-propylene.
• Z is a guanidine group.
• a silane is hereinafter also referred to as "guanidinosilane of the formula (I)".
• R 3 is -NR 4 R 5 .
• R 4 is a hydrogen radical.
• R 5 is an alkyl, cycloalkyl or aralkyl radical having 1 to 18 carbon atoms, which optionally contains heteroatoms.
• a guanidinosilane of the formula (I) has the advantage that it has a particularly high catalytic activity.
• R 2 and R 5 independently of one another each represent an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms, which optionally contains ether oxygen or tertiary amine nitrogen.
• R 2 and R 5 independently of one another are each preferably ethyl, isopropyl, tert-butyl, 3- (dimethylamino) propyl or cyclohexyl, in particular isopropyl or cyclohexyl.
• the preferred silanes of the formula (I) can be easily prepared from commercially available, inexpensive raw materials and show a high catalytic activity and compatibility in curable compositions, especially those based on silane-containing polymers.
• Another object of the invention is a process for the preparation of
• R ° is a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 C atoms and
• R 2 is an alkyl, cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains heteroatoms, or R ° and R 2 together represent an alkylene radical having 3 to 6 C atoms, which optionally contains heteroatoms,
• At least one reagent for the introduction of amidine or guanidine groups at least one reagent for the introduction of amidine or guanidine groups
• At least one alkoxy or ketoximato silane are reacted together.
• R 1 , and R 9 have the meanings already mentioned.
• reaction product from this process can be used without further processing as a catalyst for the crosslinking of a curable composition.
• Suitable as amine of the formula (IIa) or (IIb) are aliphatic or cycloaliphatic or arylaliphatic hydroxylamines, in particular 2-aminoethanol, 2-methylaminoethanol (2-amino-1-propanol), 1-amino-2-propanol, 3 Amino-1-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino 1-heptanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3, 5,5-trimethylcyclohexanol, a primary amino-bearing derivatives of
• the amine of the formula (IIa) or (IIb) is preferably selected from the group consisting of 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4- Amino-1-butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 3-aminomethyl-3,5,5-trimethyl-cyclohexanol, 2- (2-aminoethoxy ) ethanol, 2- (2- (2-aminoethoxy) ethoxy) ethanol, N- (2-aminoethyl) -2-aminoethanol and N- (3-aminopropyl) -2-aminoethanol.
• Suitable as amine of the formula R 2 -NH-R ° are aliphatic, cycloaliphatic or arylaliphatic monoamines, in particular amines of the formula R 2 -NH 2 .
• the reagent for introducing amidine or guanidine groups is preferably selected from the group consisting of orthoesters, 1, 3-ketoesters, 1, 3-ketoamides, nitriles, imidic acid esters, imidic acid chlorides, amides, lactams, cyanamides, carbodiimides, ureas , O-alkylisoureas, thioureas, S-alkylisothioureas, aminoiminomethanesulfonic acids, guanylpyrazoles and guanidines.
• Suitable for introducing amidine groups are orthoesters, 1,3-keto esters, 1,3-ketoamides, nitriles, imidic acid esters, imidic acid chlorides, amides or lactams. Preference is given to orthoesters, 1,3-keto esters or nitriles.
• Preferred orthoesters are orthoesters of the formula R 3 -C (OR a ) 3, where R 3 has the meanings mentioned and R a is an alkyl radical having 1 to 4 C atoms.
• Particularly suitable is an orthoformate, orthoacetate, orthopropionate, orthobutyrate or orthovalerate, in particular trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate or triethyl orthoacetate.
• Preferred 1, 3-keto esters are 1, 3-keto esters of the formula
• R 3 -C (O) CH 2 C (O) OR a where R 3 and R a have the meanings already mentioned, in particular methyl acetoacetate, ethyl acetoacetate, isopropyl aceto acetate or tert-butyl acetoacetate, particularly preferably ethyl acetoacetate.
• Preferred nitriles are nitriles of the formula R 3 -CN, where R 3 has the abovementioned meanings, in particular acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile or capronitrile, particularly preferably acetonitrile.
• Suitable guanidine groups are cyanan- idides, carbodimides, ureas, O-alkylisoureas, thioureas, S-alkylisothioureas, aminoiminomethanesulfonic acids, guanylpyrazoles or guanidines.
• DIC ⁇ , ⁇ '-diisopropylcarbodiimide
• DCC N-di-tert-butylcarbodiimide
• EDC N-ethyl-N '- (3-dimethylaminopropyl) carbodiimide
• DIC ⁇ , ⁇ '-diisopropylcarbodiimide
• DCC N-ethyl-N
• the reagent for introducing amidine or guanidine groups is preferably selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, acetonitrile, N, N'-diisocyanate.
• silanes with particularly high catalytic activity are obtained in a particularly simple manner.
• Preferred alkoxy- or ketoximato-silanes are orthosilicates, organoalkoxysilanes, organoketoximatosilanes or silanes with alkoxy and ketoximato groups.
• the alkoxy or ketoximato-silane is preferably selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, propytrimethoxysilane, phenyltrimethoxysilane, phenyldimethoxymethylsilane, octyltrimethoxysilane, iso octyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethoxynethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldinnethoxynethylsilane, N- (2-aminoethyl) -3-aminopropyltrinnethoxysilane, N- (2-aminoethyl) -3-aminopropyldime
• the implementation can take place in one or more stages. Preferably, it takes place in two stages.
• a preferred embodiment of the process for preparing the silane of the formula (I) is that
• the amine of formula (IIa) or (IIb) and optionally the amine of formula R 2 -NH-R ° with the reagent for introducing amidine or guanidine groups to a hydroxy-amidine or guanidine of the formula (III) is implemented,
• a and Z have the meanings already mentioned.
• the reaction in the first step of the process described is preferably carried out at elevated temperature, if appropriate under elevated pressure and if appropriate in the presence of a catalyst, where spills released from the reagent for introducing amidine or guanidine groups, such as alcohols, esters or amines during or after implementation. To be removed, in particular by means of distillation, optionally under vacuum.
• the reaction is preferably carried out at a temperature of 40 to 160 ° C., in particular 60 to 140 ° C., the liberated alcohol R a OH is preferably removed by distillation.
• a catalyst is used, in particular an acid.
• the reaction is preferably carried out at a temperature of 20 to 100 ° C, in particular 40 to 80 ° C, wherein the liberated ester CH 3 C (O) OR a is preferably removed by distillation.
• a catalyst in particular an acid, preferably a sulfonic acid.
• a nitrile of the formula R 3 -CN is used as reagent for the introduction of amidine groups, the reaction is preferably carried out at a temperature of 60 to 180 ° C, in particular 80 to 160 ° C, optionally under elevated pressure, the liberated ammonia is preferably removed by distillation.
• a catalyst is preferably used, in particular a Lewis acid, preferably boron trifluoride etherate, lithium perchlorate, zinc chloride, zinc triflate or lanthanum triflate.
• the reaction is preferably carried out at a temperature of 40 to 160 ° C., in particular 60 to 140 ° C.
• a catalyst is used, in particular an acid, preferably a carboxylic acid or a Lewis acid, more preferably boron trifluoride etherate, lithium perchlorate, zinc chloride, zinc triflate or lanthanum triflate.
• the ratio between the amine of formula (IIa) or (IIb) and the reagent for introducing amidine or guanidine groups is selected such that the reagent for introducing amidine or guanidine groups is completely reacted in the reaction becomes.
• the reaction in the second step of the described process is preferably carried out at a temperature in the range of 20 to 160 ° C, wherein the alcohols or ketoximes liberated by transesterification from the alkoxy- or ketoximato-silane are preferably removed from the reaction mixture during or after the reaction, in particular by means of distillation, optionally under reduced pressure. If appropriate, a catalyst is used which accelerates the transesterification reaction of the alkoxy- or ketoximato-silane.
• the ratio between the hydroxy-amidine or guanidine of formula (III) and the alkoxy or ketoximato-silane is selected such that at most one hydroxyl group of the hydroxy-amidine or guanidine is present on an alkoxy or ketoximato group. More preferably, the molar ratio between the hydroxy-amidine or guanidine of formula (III) and the alkoxy or ketoximato-silane is about 1: 1.
• Preferred hydroxy-amidine of the formula (III) are reaction products of an amine of the formula (IIa) or (IIb) and, if appropriate, an amine of the formula R 2 -NH-R ° with an orthoester of the formula R 3 -C (OR a ) 3 or with a 1, 3-keto ester of the formula R 3 -C (O) CH 2 C (O) oR a, or with a nitrile of the formula R 3 is -CN.
• the hydroxy-amidine or guanidine of the formula (III) is particularly preferably selected from the group consisting of 1- (2-hydroxypropyl) -2,3-diisopropylphenylguanidine, 1- (2-hydroxypropyl) -2,3-dicyclohexylguanidine , 1- (3-hydroxypropyl) -2,3-diisopropylguanidine, 1- (3-hydroxypropyl) -2,3-dicyclohexylguanidine, 1- (4-hydroxybutyl) -2,3-diisopropylguanidine, 1- (4- Hydroxybutyl) -2,3-dicyclohexylguanidine, 1- (2-hydroxy-1,1-dimethylethyl) -2,3-diisopropylguanidine, 1- (2-hydroxy-1, 1-dimethylethyl) -2,3 -dicyclohexylguanidine, 1- (5-hydroxypentyl) -2,3
• Another preferred embodiment of the process for preparing the silane of the formula (I) is that
• the amine of the formula (IIa) or (IIb) is reacted with the alkoxy- or ketoximato-silane to form a silane of the formula (IVa) or (IVb),
• Y ' is a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally has a terminal mercapto group, epoxy group, (meth) acrylic group, amidine, guanidine, urethane or urea group or a terminal amino group of the formula -NHR 8 and which optionally ether Contains oxygen or secondary amine nitrogen,
• R 8 is a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 carbon atoms or a radical of the formula
• the silane of formula (IVa) or (IVb) is reacted with the reagent for introducing amidine or guanidine groups to the silane of formula (I).
• the reaction conditions for the reagents involved in the respective reactions are preferably the same as for the process described via the hydroxy-amidine or guanidine of the formula (III), wherein the alcohols or ketoximes liberated by transesterification from the alkoxy- or ketoximato-silane are preferred also be removed from the reaction mixture during or after the reaction.
• the invention further provides a reaction product containing amidine or guanidine groups which consists of a silane of the formula (I) in which (e + f + g) is 1 or 2 or 3 by condensation with at least one silanol group -containing compound is obtained.
• a reaction product can be used as a catalyst in the same manner as the silane of the formula (I). Preference is given to liquid reaction products at room temperature.
• such a reaction product is obtained solely from the silane of formula (I) wherein (e + f + g) is 1 or 2 or 3 by hydrolysis and subsequent condensation reactions and provides a silanol and / or siloxane groups exhibiting oligomeric secondary product of the silane.
• such a reaction product is obtained from the condensation with at least one silicone oil of the formula
• n is an integer in the range from 3 to 200, preferably 5 to 80, in particular 5 to 20,
• R 10 is a monovalent hydrocarbon radical having 1 to 6 C atoms
• R 11 is a hydroxyl radical or an alkyl or alkoxy or Ketoximato radical having 1 to 12, in particular 1 to 6, carbon atoms.
• the silicone oil has an average molecular weight in the range of 312 to 15 ⁇ 00 g / mol, in particular 460 to 6 ⁇ 00 g / mol.
• silicone oils having an average molecular weight in the range of about 500 to about 1, 500 g / mol.
• the condensation is preferably carried out at a temperature in the range from 20 to 160 ° C, optionally in the presence of suitable catalysts, wherein the liberated releaser HR 6 (an alcohol or ketoxime) can be removed during or after the reaction from the reaction mixture.
• HR 6 an alcohol or ketoxime
• a ratio between the silane of the formula (I) and the silanol groups of the silicone oil of about 1: 1 is preferred.
• Such a reaction product has in particular the formula (Ia)
• R 12 is either a hydroxyl radical or an alkyl or alkoxy or ketoximato radical having 1 to 12, in particular 1 to 6, carbon atoms or for one stands,
• reaction product of the formula (Ia) by first containing the silicone oil with at least one alkoxy or ketoxime is condensed to silane and then the product obtained with at least one hydroxy-amidine or guanidine of the formula (III) in which (e + f + g) is 1 or 2 or 3, is transesterified.
• the silane of the formula (I) and / or an amidine or guanidine group-containing reaction product thereof is notable in that it has an accelerating effect on reactive groups, for example isocyanate groups, epoxide groups, hydroxyl groups, amino groups or silane groups, such as they are contained in curable compositions and are capable of crosslinking reactions with themselves or with each other.
• it has a catalytic activity with respect to the hydrolysis and condensation reaction of silane groups. It is therefore particularly suitable as a catalyst for accelerating the crosslinking of curable compositions, in particular those based on silane-containing polymers.
• the silane of the formula (I) and / or an amidine or guanidine group-containing reaction product thereof furthermore has a low vapor pressure, is preferably liquid, exhibits good compatibility with many silane-containing polymers and does not adversely affect their storage stability, it makes it possible in particular the formulation of particularly low-emission and low-odor products which do not tend to separate or migrate the catalyst.
• the invention also relates to the use of the silane of the formula (I) or an amidine or guanidine group-containing reaction product thereof as a catalyst in curable compositions, in particular silane-containing compositions, where it accelerates the crosslinking or curing of the composition.
• Preferred curable compositions are compositions comprising at least one silane-group-containing polymer, which is in particular selected from the group consisting of polyorganosiloxanes with terminal silane groups and silane group-containing organic polymers, as described in more detail below.
• a silane-terminated polyorganosiloxane has the advantage that in the cured state it is particularly resistant to water and light and allows particularly soft elastic properties.
• a silane-containing organic polymer has the advantage that it has particularly good adhesion properties on a variety of substrates and is particularly cost-effective.
• the silane of formula (I) for this use is prepared separately from the curable composition, that is not generated in situ in the composition of a hydroxy-amidine or guanidine of formula (III).
• the alcohol or the released ketoxime released from the alkoxy- or ketoximato-silane during the transesterification is preferably removed before the silane of the formula (I) is contacted with the curable composition.
• Such a composition has the advantage of being particularly low in volatile organic compounds when in contact with moisture
• this approach has the advantage that the silane of the formula (I) in certain compositions, in particular those of low polarity, is more compatible than the underlying hydroxy-amidine or guanidine of the formula (III). Furthermore, the silane of formula (I) may be condensed with a silicone oil to form a reaction product before contacting with the composition, which may be particularly advantageous in the case of compositions containing silane-terminated polyorganosiloxanes due to even better compatibility.
• Another object of the invention is thus a composition
• a composition comprising at least one silane of the formula (I) and / or at least one amidine or guanidine group-containing reaction product thereof and at least one silane-containing polymer.
• Such a composition typically has good shelf life without separation tendency, permits low hazard classification due to the low toxicity and low volatility of the silane of formula (I), and enables low emission and low odor products which cure rapidly to form a mechanically high quality and durable material , Particularly advantageous is the fact that this material is prone to migration-related defects such as sweating or substrate contamination, in contrast to compositions containing catalysts of the prior art, such as DBU or TMG.
• compositions containing such known from the prior art catalysts are prone to migration effects, which can manifest itself before curing by separation and after curing by sticky and / or greasy surfaces and / or substrate soiling. Especially the latter effects are extremely undesirable, since sticky and greasy surfaces quickly become dirty and poorly paintable, and substrate contamination can lead to permanent discoloration.
• the silane group-containing polymer in a preferred embodiment is a silane-terminated polyorganosiloxane.
• a preferred silane-terminated polyorganosiloxane has the formula (V)
• G is a hydroxyl radical or an alkoxy, acetoxy, ketoximato, amido or enoxy radical having 1 to 13 C atoms;
• a 0, 1 or 2;
• n is an integer in the range of 50 to about 2,500.
• R is preferably methyl, vinyl or phenyl.
• R 'and R are each, independently of one another, each an alkyl radical having 1 to 5, preferably 1 to 3, C atoms, in particular methyl.
• G preferably represents a hydroxyl radical or an alkoxy or ketoxymato radical having 1 to 6 C atoms, in particular a hydroxyl, methoxy, ethoxy, methyl ethyl ketoximato or methyl isobutyl ketoximato radical.
• G is particularly preferably a hydroxyl radical.
• a is preferably 0 or 1, in particular 0.
• m is preferably selected so that the polyorganosiloxane of formula (V) at room temperature has a viscosity in the range of 100 to 500 ⁇ 00 mPa s, in particular from 1000 to 100 ⁇ 00 mPa s.
• Polyorganosiloxanes of the formula (V) are easy to handle and crosslink with moisture and / or silane crosslinkers to form solid silicone polymers having elastic properties.
• Suitable commercially available polyorganosiloxanes of the formula (V) are obtainable, for example, from Wacker, Momentive Performance Material, GE Advanced Materials, Dow Corning, Bayer or Shin Etsu.
• the composition preferably contains a silane crosslinker, in particular a silane crosslinker of the formula (VI),
• R '" is a monovalent hydrocarbon radical having 1 to 12 C atoms
• G' is a hydroxyl radical or an alkoxy, acetoxy, Ketoximato, amido or enoxy radical having 1 to 13 C. Atoms stands;
• q represents a value of 0, 1 or 2, in particular 0 or 1.
• silane crosslinkers of the formula (VI) are methyltrimethoxysilane, ethyltrimethoxysilane, propytrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltris (methylethylketoximato) silane, vinyltris (methylethylketoximato) silane and methyltris (isobutylketoximato ) silane.
• the silane-group-containing polymer is a silane-containing organic polymer, in particular a polyolefin, polyester, polyamide, poly (meth) acrylate or polyether, or a mixed form of these polymers which carries one or preferably more than one silane groups.
• the silane groups can be laterally in the chain or terminal and are bound via a carbon atom to the organic polymer.
• the silane-group-containing organic polymer is particularly preferably a polyolefin containing polyol or a silane-containing polyester or a silane-containing poly (meth) acrylate or a silane-containing polyether or a mixed form of these polymers.
• the silane group-containing organic polymer is a silane group-containing polyether.
• the silane-group-containing organic polymer preferably has, as silane groups, alkoxysilane groups, in particular alkoxysilane groups of the formula (VII),
• R 14 is a linear or branched, monovalent hydrocarbon radical having 1 to 5 C atoms, in particular methyl, ethyl or isopropyl;
• R 15 is a linear or branched, monovalent hydrocarbon radical having 1 to 8 C atoms, in particular methyl or ethyl;
• x is a value of 0 or 1 or 2, preferably 0 or 1, in particular 0.
• R 14 is particularly preferably methyl or ethyl.
• the radical R 14 is preferably an ethyl group, since in this case ecologically and toxicologically harmless ethanol is released when the composition is cured. Particular preference is given to trimethoxysilane groups, dimethoxymethylsilane groups or triethoxysilane groups.
• methoxysilane groups have the advantage that they are particularly reactive
• ethoxysilane groups have the advantage that they are toxicologically advantageous and particularly stable on storage.
• the silane group-containing organic polymer has on average preferably 1 .3 to 4, in particular 1 .5 to 3, particularly preferably 1 .7 to 2.8 silane groups per molecule.
• the silane groups are preferably terminal.
• the silane-group-containing organic polymer preferably has an average molecular weight, determined by means of GPC over polystyrene standard, in the range from 1 ⁇ 00 to 30 ⁇ 00 g / mol, in particular from 2 ⁇ 00 to 20 ⁇ 00 g / mol.
• the silane group-containing organic polymer preferably has a silane-equivalent weight of 300 to 25 ⁇ 00 g / Eq, in particular from 500 to 15 ⁇ 00 g / Eq, on.
• the silane group-containing organic polymer may be solid or liquid at room temperature. It is preferably liquid at room temperature.
• the silane-group-containing organic polymer is most preferably a silane-group-containing polyether which is liquid at room temperature, the silane groups being in particular dialkoxysilane groups and / or trialkoxysilane groups, more preferably trimethoxysilane groups or triethoxysilane groups.
• silane-containing polyethers are obtainable from the reaction of allyl-containing polyethers with hydrosilanes, optionally with chain extension with, for example, diisocyanates.
• silane-containing polyethers are obtainable from the copolymerization of alkylene oxides and epoxysilanes, optionally with chain extension with, for example, diisocyanates.
• silane-containing polyethers are obtainable from the reaction of polyether polyols with isocyanatosilanes, optionally with chain extension with diisocyanates.
• silane-containing polyethers are obtainable from the reaction of isocyanate-group-containing polyethers, in particular NCO-terminated urethane polyethers, from the reaction of polyether polyols with a superstoichiometric amount of polyisocyanates, with aminosilanes, hydroxysilanes or mercaptosilanes.
• Silane-group-containing polyethers from this process are particularly preferred. This process makes it possible to use a large number of commercially available, inexpensive starting materials, with which different polymer properties can be obtained, for example a high ductility, a high strength, a low elastic modulus, a low glass transition point or a high weathering resistance.
• the silane-group-containing polyether is particularly preferably obtainable from the reaction of NCO-terminated urethane polyethers with aminosilanes or hydroxysilanes.
• Suitable NCO-terminated urethane polyethers are obtainable from the reaction of polyether polyols, in particular polyoxyalkylene diols or polyoxyalkylene triols, preferably polyoxypropylene diols or polyoxypropylene triols, with a superstoichiometric amount of polyisocyanates, especially diisocyanates.
• the reaction between the polyisocyanate and the polyether polyol is carried out with exclusion of moisture at a temperature of 50 ° C to 160 ° C, optionally in the presence of suitable catalysts, wherein the polyisocyanate is metered so that its isocyanate groups in relation to the hydroxyl groups of the polyol are present in stoichiometric excess.
• the excess of polyisocyanate is chosen so that in the resulting urethane polyether after the reaction of all hydroxyl groups, a content of free isocyanate groups of 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.3 to 3% by weight. %, based on the total polymer, remains.
• HDI 1,6-hexamethylene diisocyanate
• IPDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
• TDI 6-Toluylendiiso- cyanate and any mixtures of these isomers
• MDI 4,4'-, 2,4'- and 2,2'- diphenylmethane diisocyanate
• Particularly suitable polyether polyols are polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation lower than 0.02 meq / g, in particular lower than 0.01 meq / g, and an average molecular weight in the range from 400 to 25,000 g / mol, in particular from 1,000 to 20,000 g / mol.
• polyether polyols In addition to polyether polyols, it is also possible proportionally to use other polyols, in particular polyacrylate polyols, and low molecular weight diols or triols.
• Suitable aminosilanes for the reaction with an NCO-terminated urethane polyether are primary and secondary aminosilanes. Preference is given to 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, adducts of primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and Michael acceptors such as acrylonitrile, (
• Suitable hydroxysilanes for the reaction with an NCO-terminated urethane polyether are obtainable in particular from the addition of aminosilanes to lactones or to cyclic carbonates or to lactides.
• Particularly suitable aminosilanes are 3-aminopropyltrimethoxysilane, 3-aminopropylethethoxysilane, 4-aminobutyl-thmethoxysilane, 4-aminobutyltriethoxysilane, 4-amino-3-methylbutyl-thmethoxysilane, 4-amino-3-methyl - Butyl triethoxysilane, 4-amino-3,3-dinethylbutyl-thnnethoxysilane, 4-amino-3,3-dimethylbutyl-triethoxysilane, 2-aminoethyl-thmethoxysilane or 2-aminoethyl triethoxysilane.
• 3-aminopropyl-thmethoxysilane 3-aminopropyl-thethoxysilane, 4-amino-3,3-dinethylbutyl-trinnethoxysilane or 4-amino-3,3-dimethylbutyl-triethoxysilane.
• Suitable lactones are, in particular, ⁇ -valerolactone, ⁇ -octalactone, ⁇ -decalactone, and ⁇ -decalactone, in particular ⁇ -valerolactone.
• Particularly suitable cyclic carbonates are 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2 on, 4-methyl-1,3-dioxolan-2-one or 4- (phenoxymethyl) -1,3-dioxolan-2-one.
• lactides are 1,4-dioxane-2,5-dione (lactide from 2-hydroxyacetic acid, also called “glycolide”), 3,6-dimethyl-1,4-dioxane-2,5-dione ( Lactide from lactic acid, also called “lactide”) and 3,6-diphenyl-1,4-dioxane-2,5-dione (lactic acid from mandelic acid).
• Preferred hydroxysilanes obtained in this way are N- (3-triethoxysilylpropyl) -2-hydroxypropanamide, N- (3-trimethoxysilylpropyl) -2-hydroxypropanamide, N- (3-triethoxysilylpropyl) -4-hydroxypentanamide, N - (3-triethoxysilylpropyl) -4-hydroxyoctanamide, N- (3-triethoxysilylpropyl) -5-hydroxy-decanamide and N- (3-thethoxysilylpropyl) -2-hydroxypropylcarbamate.
• suitable hydroxysilanes are also obtainable from the addition of aminosilanes to epoxides or from the addition of amines to epoxysilanes.
• Preferred hydroxysilanes obtained in this manner are 2-morpholino-4 (5) - (2-trimethoxysilylethyl) cyclohexan-1-ol, 2-morpholino-4 (5) - (2-triethoxysilylethyl) cyclohexan-1-ol or 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol.
• silane-group-containing polyethers are products which can be obtained commercially, in particular the following: MS Polymer TM (from Kaneka Corp .; in particular the types S203H, S303H, S227, S810, MA903 and S943); MS Po lymer TM or Silyl TM (from Kaneka Corp., especially the types SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951); Excestar ® (Asahi Glass Co.
• MS Polymer TM from Kaneka Corp .; in particular the types S203H, S303H, S227, S810, MA903 and S943
• MS Po lymer TM or Silyl TM from Kaneka Corp., especially the types SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951
• Excestar ® Asahi Glass Co.
• silane-containing organic polymers have end groups of the formula (VIII)
• R 16 is a linear or branched, divalent hydrocarbon radical having 1 to 12 C atoms, which optionally cyclic and / or aromatic moieties and optionally one or more heteroatoms, in particular one or more nitrogen atoms, is;
• T is a divalent radical selected from -O-, -S-, -N (R 17 ) -,
• R 17 is a hydrogen radical or a linear or branched hydrocarbon radical having 1 to 20 C atoms, which optionally has cyclic moieties, and which optionally has an alkoxysilane, ether or carboxylic acid ester group;
• R 14 , R 15 and x have the meanings already mentioned.
• R 16 is 1, 3-propylene or 1, 4-butylene, where butylene may be substituted with one or two methyl groups.
• R 16 is particularly preferably 1,3-propylene.
• the silane of formula (I) is present in the composition in an amount such that the concentration of amidine or guanidine groups from the silane of formula (I), based on the amount of crosslinkable polymer, ranges from 0.1 to 20 mmol / 100 g of polymer, preferably 0.1 to 15 mmol / 100 g of polymer, in particular 0.1 to 10 mmol / 100 g.
• Such a composition has good shelf life and fast cure.
• the composition may comprise further catalysts, in particular for the crosslinking of silane groups.
• Particularly suitable as further catalysts are metal compounds and / or basic nitrogen or phosphorus compounds.
• Suitable metal compounds are, in particular, compounds of tin, titanium, zirconium, aluminum or zinc, in particular diorganotin (IV) compounds, in particular dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dibutyltin (IV) dineodecanoate or Dibutyltin (IV) bis (acetylacetonate) and dioctyltin (IV) dilaurate, and titanium (IV) - or zirconium (IV) - or aluminum (III) - or zinc (II) complexes with in particular alkoxy, carboxylate , 1, 3-diketonate, 1, 3-ketoesterate or 1, 3-ketoamidate ligands.
• diorganotin (IV) compounds in particular dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dibutyltin (IV) dineodecanoate or Dibuty
• Suitable basic nitrogen or phosphorus compounds are, in particular, imidazoles, pyridines, phosphazene bases or, preferably, amines, hexahydro-triazines, biguanides and also further amidines or guanidines.
• Particularly suitable amines are alkyl, cycloalkyl or aralkylamines such as triethylamine, triisopropylamine, 1-butylamine, 2-butylamine, tert-butylamine, 3-methyl-1-butylamine, 3-methyl-2-butylamine, dibutylamine, tributylamine, hexyl amine, dihexylamine, cyclohexylamine, dicyclohexylamine, dimethylcyclohexylamine, benzylamine, dibenzylamine, dimethylbenzylamine, octylamine, 2-ethylhexylamine, di- (2-ethylhexyl) amine, laurylamine, ⁇ , ⁇ -dimethyl-laurylamine, stearylamine.
• alkyl, cycloalkyl or aralkylamines such as triethylamine, triisopropylamine,
• rylamine ⁇ , ⁇ -dimethylstearylamine; of natural fatty acid mixtures derived fatty amines, in particular Cocoalkylamin, N, N-dimethyl-cocoalkyl amine, Ci-6 -22 Alkylannin, N, N-dimethyl-C-i6-22 alkylamine Soyaalkylamin, N, N-dimethyl-soyaalkylamin , Oleylamine, ⁇ , ⁇ -dimethyl-oleylannin, tallowalkylamine or ⁇ , ⁇ -dimethyl-tallowalkylamine, obtainable, for example, under the trade name Armeen® (from Akzo Nobel) or Rofamin® (from Ecogreen Oleochemicals); aliphatic, cycloaliphatic or araliphatic diamines such as ethylenediamine, butanediamine, hexamethylenediamine, dodecanediamine, neopentanediamine, 2-methylpentamethylened
• aminosilanes in particular 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -N'- [3- (trimethoxysilyl) propyl] ethylene diamine or its analogues with ethoxy instead of the methoxy groups on the silicon.
• Particularly suitable hexahydrotriazines are 1,3,5-hexahydrotriazine or 1,3,5-tris (3- (dimethylamino) propyl) hexahydrotriazine.
• Suitable biguanides are, in particular, biguanide, 1-butylbiguanide, 1,1-dimethylbiguanide, 1-butylbiguanide, 1-phenylbiguanide or 1- (o-tolyl) biguanide (OTBG).
• Suitable further amides are in particular 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 6-dibutylamino-1 , 8-diazabi- cyclo [5.4.0] undec-7-ene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, ⁇ , ⁇ '-di-n-hexylacetamidine (DHA), 2-methyl- 1, 4,5,6-tetrahydropyrinidine, 1, 2-dimethyl-1, 4,5,6-tetrahydropyrinnidine, 2,5,5-thymethyl-1, 4,5,6-tetrahydropyrimidine, N- (3 Trimethoxysilylpropyl) -4,5-dihydroimidazole or N- (3-triethoxysilylpropyl) -4,5-dihydroimid
• Suitable further guanidines are, in particular, 1-butylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,1,3,3-tetramethylguanidine (TMG), 2- (3- (trimethoxysilyl) propyl) -1,1 , 3,3-tetramethylguanidine, 2- (3- (methyldimethoxysilyl) propyl) -1, 1, 3,3-tetramethylguanidine, 2- (3- (triethoxysilyl) propyl) -1, 1, 3,3-tetramethylguanidine , 1, 5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 7-cyclohexyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1-phenylguanidine, 1- (o-tolyl) guanidine (OTG),
• the composition can contain as co-catalyst an acid, in particular a carboxylic acid.
• an acid in particular a carboxylic acid.
• aliphatic carboxylic acids such as formic acid, lauric acid, stearic acid, isostearic acid, oleic acid, 2-ethyl-2,5-dimethylcaproic acid, 2-ethylhexanoic acid, neodecanoic acid, fatty acid mixtures from the saponification of natural fats and oils or di- and polycarboxylic acids, in particular poly (meth ) acrylic acids.
• composition in a preferred embodiment is substantially free of organotin compounds.
• Organotin-free compositions are beneficial in terms of health and environmental protection.
• the tin content of the curable composition is less than 0.1% by weight, in particular less than 0.05% by weight.
• the composition contains a combination of at least silane of the formula (I) and / or an amidine or guanidine group-containing reaction product thereof and at least one organotin compound, in particular a diorganotin (IV) compound such as those above mentioned.
• organotin compound in particular a diorganotin (IV) compound such as those above mentioned.
• the composition contains at least one organotitanate.
• a combination of a silane of the formula (I) and / or an amidine or guanidine group-containing reaction product thereof and an organotitanate has a particularly high catalytic activity. This allows rapid curing of such a composition with a relatively small amount of organotitanate used.
• organotitanates are titanium (IV) complex compounds.
• Preferred organoititanates are in particular selected from
• Titanium (IV) complex compounds with two 1,3-diketonate ligands, in particular 2,4-pentanedionate ( acetylacetonate), and two alkoxide ligands; Titanium (IV) complex compounds with two 1,3-ketoesterate ligands, in particular ethylacetoacetate, and two alkoxide ligands;
• Titanium (IV) complex compounds with one or more aminoalcoholate ligands in particular triethanolamine or 2- ((2-aminoethyl) amino) ethanol, and one or more alcoholate ligands;
• Titanium (IV) tetrabutoxide also referred to as polybutyl titanate
• Tyzor ® AA GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT or Ibay are (all of Dorf Ketal) ; Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from Borica Company Ltd.) and Ken-React ® KR TTS ®, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S , 138S, 133DS, 158FS or LICA 44 ® (all from Kenrich Petrochemicals).
• Very particularly suitable organo selected from bis (ethyl acetoacetate) diisobutoxy-titanium (IV) (konnnnerziell example, available as Tyzor ® Ibay of Dorf Ketal) (bis (ethyl acetoacetate) diisopropoxy-titanium (IV) konnnnerziell example, available as Tyzor ® DC from Ketal village), bis (acetylacetonato) diisopropoxy-titanium (IV), bis (acetylacetonato) diisobutoxy-titanium (IV), tris (oxyethyl) -amine-isopropoxy-titanium (IV), bis [tris (oxyethyl) amine ] diisopropoxy-titanium (IV), bis (2-ethylhexane-1,3-dioxy) -titanium (IV), tris [2- ((2-aminoethyl) -amino) -
• the composition may contain further constituents thereof, in particular the following auxiliaries and additives:
• Adhesion promoters and / or crosslinkers in particular aminosilanes, in particular 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl -dimethoxymethylsilane, N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediamine or its analogues with ethoxy groups instead of methoxy groups, furthermore N-phenyl-, N-cyclohexyl- or N- Alkylaminosilanes, mercaptosilanes, epoxysilanes, (meth) acrylosilanes, anhydridosilanes, carbamosilanes, alkylsilanes or iminos
• 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-ureidopropyltrimethoxysilane , or oligomeric forms of these silanes; Desiccants, in particular tetraethoxysilane, vinylthymethoxysilane, vinyltriethoxysilane or organoalkoxysilanes which have a functional group in the ⁇ -position to the silane group, in particular N- (methyldimethoxysilylmethyl) -O-methyl-carbannate, (methacryloxymethyl) silanes, me
• Plasticizers in particular trialkylsilyl-terminated polydialkylsiloxanes, preferably trimethylsilyl-terminated polydimethylsiloxanes, in particular having viscosities in the range of 10 to 1 ⁇ 00 mPa s, or corresponding compounds in which some of the methyl groups are replaced by other organic groups, in particular phenyl, vinyl or Trifluoropropyl groups, so-called reactive plasticizers in the form of monofunctional, ie unilaterally reactive, polysiloxanes, carboxylic acid esters such as phthalates, in particular dioctyl phthalate, bis (2-ethylhexyl) phthalate, bis (3-propylheptyl) - phthalate, diisononyl phthalate or diisodecyl phthalate, diesters of ortho-cyclohexanedicarboxylic acid , in particular diisononyl-1, 2-cyclohexandicar- boxylat
• inorganic or organic fillers in particular natural, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearic acid, barite, talc, quartz flour, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminum) Silicate), molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicic acids including highly dispersed silicas from pyrolysis processes, industrially produced carbon black, graphite, Metal powders such as aluminum, copper, iron, silver or steel, PVC powder or hollow spheres;
• Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;
• Pigments in particular titanium dioxide or iron oxides
• Rheology modifiers in particular thickeners, in particular
• Phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers or hydrophobically modified polyoxyethylenes;
• non-reactive polymers in particular homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene,
• Propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates in particular polyethylenes (PE), polypropylenes (PP), polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) or atactic poly- ⁇ -olefins (APAO);
• PE polyethylenes
• PP polypropylenes
• EVA ethylene-vinyl acetate copolymers
• APAO atactic poly- ⁇ -olefins
• Flame retardant substances in particular the already mentioned fillers aluminum hydroxide and magnesium hydroxide, or in particular organic phosphoric acid esters such as in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyldiphenyl phosphate, tris (1,3-dichloro-2-propyl) phosphate, tris (2 -chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) - phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris (isopropylphenyl) phosphates of different isopropylation degree, resorcinol bis (diphenyl phosphate ), Bisphenol A bis (diphenyl phosphate) or ammonium poly
• the composition contains at least one drying agent and at least one adhesion promoter and / or crosslinker.
• the composition does not contain phthalates as a plasticizer.
• Such compositions are toxicologically advantageous and have fewer problems with migration effects.
• the proportion of silane-group-containing polymer in the composition is usually from 10 to 80% by weight, in particular from 15 to 60% by weight, preferably from 15 to 50% by weight, based on the total weight of the composition.
• the composition is preferably made and stored in the absence of moisture. Typically, it is storage stable in a suitable package or assembly, such as, in particular, a bottle, can, bag, bucket, keg, or cartridge, excluding moisture.
• a suitable package or assembly such as, in particular, a bottle, can, bag, bucket, keg, or cartridge, excluding moisture.
• composition can be in the form of a one-component or in the form of a multi-component, in particular two-component, composition.
• one-component in this document refers to a composition in which all constituents of the composition are mixed and stored in the same container and which is curable with moisture Composition in two different components, which are stored in separate containers. Only shortly before or during the application of the composition, the two components are mixed together, whereupon the mixed composition cures, optionally under the action of moisture.
• the composition contains a polyorganosiloxane having terminal silane groups
• a one-component composition also referred to as RTV-1
• a two-component composition also referred to as RTV-2
• the silane-terminated polyorganosiloxane is preferably a constituent of the first component
• a silane crosslinker especially a silane crosslinker of the formula (VI)
• the silane of the formula (I) can be present in the first and / or in the second component.
• the composition contains a silane-containing organic polymer
• the composition is preferably one-component.
• a second or optionally further components is or are mixed with the first component before or during the application, in particular via a static mixer or via a dynamic mixer.
• the composition is in particular ambient warm, preferably in a temperature range between 0 ° C and 45 ° C, in particular 5 ° C to 35 ° C, applied and cures even under these conditions.
• the crosslinking reaction of the silane groups begins, optionally under the influence of moisture.
• Existing silane groups can condense with existing silanol groups to siloxane groups (Si-O-Si groups).
• Existing silane groups can also hydrolyze on contact with moisture to form silanol groups (Si-OH groups) and form siloxane groups (Si-O-Si groups) by subsequent condensation reactions.
• Si-OH groups silanol groups
• Si-O-Si groups siloxane groups
• water may either come from the air (humidity) or the composition may be contacted with a water-containing component, for example by painting, for example with a smoothing agent, or by spray, or it may be added to the composition in the application of water or a water-containing component, for example in the form of a water-containing or water-releasing liquid or paste.
• a paste is particularly suitable for the case in which the composition is present in the form of a paste.
• the composition When cured by atmospheric moisture, the composition cures from the outside in, initially forming a skin on the surface of the composition.
• the so-called skin-forming time represents a measure of the curing rate of the composition.
• the rate of curing is generally determined by various factors, such as the availability of water, the temperature, etc.
• the composition is suitable for a multiplicity of applications, in particular as a paint, lacquer or primer, as a resin for producing fiber composite material, as hard foam, flexible foam, molded part, elastomer, fiber, film or membrane, as potting compound, sealant, Adhesive, coating, coating or coating for building and industrial applications, for example as seam sealing, cavity sealing, electrical insulation compound, filler, joint sealant, welding or flanging sealant, assembly adhesive, car body adhesive, pane adhesive, sandwich element adhesive, laminating adhesive, laminate adhesive, packaging adhesive, wood adhesive, Parquet adhesive, anchoring adhesive, floor covering, floor coating, balcony coating, roof coating, concrete protection coating, parking garage coating, sealing, pipe coating, anti-corrosion coating, textile coating, damping element, sealing element or filler.
• a paint, lacquer or primer as a resin for producing fiber composite material, as hard foam, flexible foam, molded part, elastomer, fiber, film or membrane, as potting compound, sealant, Adhesive, coating, coating or
• the composition is particularly suitable as an adhesive and / or sealant, in particular for joint sealing and elastic adhesive bonding in construction and industrial applications, and as an elastic coating with crack-bridging properties, in particular for protecting and / or sealing, for example, roofs, floors, balconies , Parking decks or concrete pipes.
• the composition thus preferably represents an adhesive or a sealant or a coating.
• Such a composition typically contains plasticizers, fillers, adhesion promoters and / or crosslinkers and drying agents and optionally further auxiliaries and additives.
• the composition preferably has a pasty consistency with pseudoplastic properties.
• a paste-like sealant or adhesive is applied in particular from commercial cartridges which are operated manually, by means of compressed air or battery, or from a drum or hobbock by means of a feed pump or an extruder, optionally by means of an application robot.
• the composition preferably has a liquid at room temperature consistency with self-leveling properties. If necessary, it is slightly thixotropic, so that the coating can be applied to sloping to vertical surfaces without immediately flowing away. It is in particular applied by means of a roller or brush or by pouring and distributing by means of, for example, a roller, a scraper or a dental trowel.
• the composition is preferably applied to at least one substrate.
• Suitable substrates are in particular
• metals and alloys such as aluminum, iron, steel or non-ferrous metals, as well as surface-treated metals or alloys, such as galvanized or chromium-plated metals;
• Plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA), polyester, poly (methyl methacrylate) (PMMA), epoxy resins, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymers (EPM) or ethylene / propylene / diene terpolymers (EPDM), or fiber-reinforced Plastics such as carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GRP) or sheet molding compounds (SMC), wherein the plastics may preferably be surface treated by means of plasma, cor
• coated substrates such as powder-coated metals or alloys
• the substrates can be pretreated before applying the composition, in particular by physical and / or chemical cleaning methods or by the application of an adhesion promoter, a primer solution or a primer.
• compositions for contact with substrates which are particularly sensitive to disturbances by migrating substances, in particular by the formation of discolorations or stains.
• substrates which are particularly sensitive to disturbances by migrating substances, in particular by the formation of discolorations or stains.
• substrates which are particularly sensitive to disturbances by migrating substances, in particular by the formation of discolorations or stains.
• substrates which are particularly sensitive to disturbances by migrating substances, in particular by the formation of discolorations or stains.
• substrates which are particularly sensitive to disturbances by migrating substances, in particular by the formation of discolorations or stains.
• fine-pored substrates such as marble, limestone or other natural stones, gypsum, cement mortar or concrete, but also plastics.
• catalysts such as DBU or TMG strong discoloration is observed, which can not be removed by cleaning. Such effects are not observed with the silane of formula (I).
• a cured composition is obtained.
• the article is in particular a building, in particular a building of civil engineering, an industrially manufactured good or a consumer good, in particular a window, a household machine or a means of transport such as in particular an automobile, a bus, a truck, a Rail vehicle, a ship, an airplane or a helicopter; or the article may be an attachment thereof.
• standard climate refers to a temperature of 23 ⁇ 1 ° C and a relative humidity of 50 ⁇ 5%.
• EW means the epoxide equivalent weight 1 H-NMR spectra were measured on a spectrometer Bruker Ascend 400 at 400.14 MHz;.. The chemical shifts ⁇ are expressed in ppm relative to tetramethylsilane (TMS) coupling constants J are given in Hz. True and pseudo-coupling patterns were not distinguished.
• FT-IR Infrared
• GC Gas chromatograms
• the skin formation time was determined by applying a few grams of the composition to cardboard in a layer thickness of about 2 mm and measuring the time in standard climate until lightly tapping the surface of the composition by means of a pipette made of LDPE for the first time no residues on the pipette left more. The condition of the surface was haptically tested.
• Viscosities were measured on a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-to-plate distance 0.05 mm, shear rate 10 s -1 ).
• FT-IR 3214, 3177, 2996, 2925, 2843, 1630, 1542, 1475, 1438, 1380, 1360, 1322, 1294, 1273, 1204, 1 191, 1 139, 1 1 14, 1095, 1035, 1009, 977, 915, 875, 839, 731.
• used alkoxysilanes 3214, 3177, 2996, 2925, 2843, 1630, 1542, 1475, 1438, 1380, 1360, 1322, 1294, 1273, 1204, 1 191, 1 139, 1 1 14, 1095, 1035, 1009, 977, 915, 875, 839, 731. used alkoxysilanes:
• AMMO 3-aminopropyltrimethoxysilane (Silquest ® A-1 1 10, from Momentive)
• VTMO vinyltrimethoxysilane (Silquest ® A-171, Momentive)
• Silane W1 3-aminopropyl-dimethoxy-2- (2-aminoethoxy) ethoxysilane
• Silane K1 1- (2- (2- (3-aminopropyldimethoxysilyloxy) ethoxy) ethyl) -2,3-diisopropylphenylguanidine
• Silane K2 1 - (2- (2- (Vinyldimethoxysilyloxy) ethoxy) ethyl) -2,3-diisopropylguanidine
• VTMO vinyltrimethoxysilane
• Silane K3 1 - (2- (2- (Vinyldiethoxysilyloxy) ethoxy) ethyl) -2,3-diisopropylguanidine
• VTEO vinyltriethoxysilane
• Silane K4 1- (2- (2- (triethoxysilyloxy) ethoxy) ethyl) -2,3-diisopropylguanidine
• Silane K5 1 - (2- (3-aminopropyldimethoxysilyloxy) ethyl) -2-methyl-1, 4,5,6-tetrahydropyrimidine
• Silane K6 1- (3- (2- (2- (2- (2,3-diisopropylguanidino) ethoxy) ethoxy) dimethoxysilyl) -propyl-2,3-diisopropylguanidine
• a composition of 96.5 g of polymer STP-1, 0.5 g of vinyltrimethoxysilane and 3.0 g of 3-aminopropyltrimethoxysilane was mixed with various catalysts in the stated amount according to Table 1 and the mixture was mixed with viscosity and skin formation time (HBZ) under standard conditions before and after storage , checked.
• the skinning time serves as a measure of the activity of the catalyst with respect to the crosslinking reaction of the silane groups, ie the rate of crosslinking; the change in viscosity and skinning time after storage is a measure of storage stability.
• compositions Z10 to Z14 are Compositions Z10 to Z14:
• composition of 95.9 g of polymer STP-2, 0.4 g of vinyltriethoxysilane and 3.7 g of N- (2-aminoethyl) -3-aminopropyltriethoxysilane was mixed with various catalysts in the stated amount according to Table 3 and the mixture as described for composition Z1 on viscosity, Skin formation time (HBZ), surface texture and mechanical properties tested. The results are shown in Tables 3 and 4.
• n.d. not determined or not measurable.
• compositions Z15 to Z18 are Compositions Z15 to Z18:
• the thixotropic paste was prepared by initially charging 300 g of diisodecyl phthalate (Palatinol® Z, from BASF) and 48 g of 4,4'-methylenediphenyl diisocyanate (Desmodur® 44 MC L, from Bayer) in a vacuum mixer and gently warming it up, followed by vigorous stirring 27 g of n-butylamine were slowly added dropwise. The resulting paste was further stirred under vacuum and cooling for one hour. Table 5:
• compositions Z19 to Z22 are Compositions Z19 to Z22:

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