Classifications

• • 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
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • 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
  • C07C279/08—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 singly-bound oxygen atoms
• • 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
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/10—Block or graft copolymers containing polysiloxane sequences
• • 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 room temperature curable compositions based on silane-containing polymers, which are particularly suitable as an adhesive, sealant or coating.
• Silane-group-containing polymers are in particular polyorganosiloxanes, which are commonly referred to as “silicones” or “silicone rubbers”, and silane-containing organic polymers which are also known as “silane-functional polymers", “silane-modified polymers” (SMP) or "silane-terminated Such compositions play an important role in many technical applications, for example as adhesives, sealants or coatings.They are cured by crosslinking reactions of the silane groups, which hydrolyze under the influence of moisture, as silanol groups condense and condense Catalysts are often used to speed up the curing process and are often toxicologically hazardous substances which pose a potential hazard to the user and the environment, especially after curing when the catalysts or their catalysts are used Degradation products are released by outgassing, migration or leaching.
• organotin compounds in particular dialkyltin (IV) carboxylates
• dialkyltin (IV) carboxylates are conventionally used. These are characterized by a good activity with respect to the silanol condensation and are very resistant to hydrolysis; However, they are harmful to health and highly hazardous to water. Often, they are used in combination with other catalysts, mainly basic compounds, especially amines, which, in particular, accelerate the upstream hydrolysis of the silane groups.
• EHS mainly basic compounds, especially amines
• Increased emphasis on the EHS aspects by professional associations and consumers, as well as stricter state regulation has for some time been making more of an effort to substitute organotin compounds for other, less toxic catalysts.
• organotitanates, zirconates and aluminates have been described as alternative metal catalysts.
• 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
• They tend to migrate due to poor compatibility in the composition, thereby causing separation, exudation or substrate contamination.
• 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.
• Object of the present invention is therefore to provide a room-temperature curable composition based on silane-containing polymers, which allows low risk classification, low emissions and low odor, has a good shelf life without Separationsneist, cured by means of moisture crosslinking of the silane groups quickly and thereby forms a mechanically high-quality and durable material, which hardly tends to migration-related errors such as sweating and substrate contamination.
• compositions according to claim 1 comprising a catalyst of the formula (I).
• a catalyst of the formula (I) contains aliphatic amidine or guanidine groups and exhibits high catalytic activity, while aromatic amidines or guanidines are barely or not catalytically active.
• compositions according to the invention have a very rapid curing based on the presence of the catalyst of the formula (I), even if the catalyst of the formula (I) is relatively large and not very mobile. Another surprising feature is the fact that inventive compositions neither before nor after the
• compositions with aliphatic amidine and guanidine catalysts according to the prior art, where catalyst-related migration effects play a strong role. This is surprising, since the catalyst of the formula (I) is free of silane groups and thus is not bound to the polymer during curing.
• the present invention relates to a composition
• a composition comprising
• n is an integer from 2 to 20
• A is an n-valent aliphatic or cycloaliphatic or arylaliphatic hydrocarbon radical having 2 to 100 carbon atoms, which optionally contains unsaturated moieties, optionally contains heteroatoms and optionally has amino groups, and
• Z is a radical of the formula stands, where
• R 1 and R ° independently of one another are each hydrogen or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 C atoms
• R 2 is hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contain heteroatoms and which optionally has terminal primary or secondary amino groups, is,
• R 3 is -NR 4 R 5 or is hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms,
• R 4 and R 5 independently of one another each represent hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains heteroatoms,
• R 1 and R 2 together can also stand for an alkylene radical having 2 to 6 C atoms,
• R 2 and R ° can also stand together for an alkylene radical having 3 to 6 C atoms, which optionally contains heteroatoms,
• 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 for an alkylene radical having 4 to 7 carbon atoms, which optionally contains heteroatoms, may stand, and
• R 2 and R 5 together can also stand for an alkylene radical having 2 to 12 C atoms; wherein the catalyst 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, the hydrolyzable substituents being in particular alkoxy -, acetoxy, ketoximato, amido or enoxy radicals having 1 to 13 carbon atoms, preferably alkoxy or ketoximato radicals, particularly preferably alkoxy radicals; the latter silane groups are referred to hereinafter as "alkoxysilane groups”.
• silane groups furthermore refers to silanol groups which correspond formally partially or completely hydrolyzed silane groups and have one or more hydroxyl radicals on the silicon atom.
• hydroxysilane denotes organoalkoxysilanes which have one or more hydroxyl, isocyanato, amino or mercapto groups on the organic radical in addition to the silane group.
• 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 polydiorganosiloxane 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-containing polyethers may also be referred to as "silane-containing polyurethanes”.
• 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 substance or composition is defined as “shelf-stable” or “storable” if 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 absorbed their 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.
• Room temperature refers to a temperature of about 23 ° C.
• the catalyst of formula (I) can also be present in tautomeric form All possible tautomeric forms of the catalyst of the formula (I) are considered equivalent in the context of the present invention.
• the catalyst of the formula (I) can be present in protonated form.
• the catalyst of the formula (I) can be present in complexed form, in particular with cations of zinc, iron or molybdenum.
• A is preferably an n-valent aliphatic or cycloaliphatic or arylaliphatic hydrocarbon radical having 2 to 50, in particular 2 to 20, carbon atoms, which optionally contains ether oxygen or amine nitrogen, in particular one to three ether oxygens or one to five amine nitrogens.
• A is particularly preferably selected from the group consisting of 1, 2-ethylene; 1,3-propylene; 1, 2-propylene; 1, 4-butylene; 1, 3-butylene; 1, 2-butylene; 2,3-butylene; 1, 3-pentylene; 2-methyl-1, 5-pentylene; 1, 6-hexylene; 2,2 (4), 4-trimethyl-1,6-hexamethylene; 1,8-octylene; 1, 10-decylene; 1,12-dodecylene; (1, 5,5-trimethylcyclohexan-1-yl) methane-1, 3; 1,3-cyclohexylene bis (methylene); 1,4-cyclohexylene-bis (methylene); 1, 3-phenylene-bis (methylene); 2- and / or 4-methyl-1,3-cyclohexylene; 4-aza-N-methyl-1, 7-heptylene; 4-aza-N-ethyl-1, 7-heptylene; 3-aza-1, 5-pentylene; 3,6-diaza-1,
• radicals A having 2 to 18 C atoms.
• radicals A having 2 to 12 C atoms, which optionally contain 1 to 3 ether oxygens and optionally 1 to 3 secondary or tertiary amino groups.
• n is preferably an integer from 2 to 10. Particularly preferably, n is 2 or 3, in particular 2.
• R 1 and R ° are each independently of one another in each case hydrogen or an alkyl radical having 1 to 4 C atoms, in particular hydrogen.
• R 2 is preferably hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms, in particular 1 to 8 C atoms, which optionally contains heteroatoms.
• R 3 is preferably -NR 4 R 5 or hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 8 C atoms.
• R 3 is -NR 4 R 5 .
• R 4 and R 5 are each, independently of one another, each hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms, which optionally contains an oxygen atom or a nitrogen atom.
• R 4 and R 5 together are preferably an alkylene radical having 4 to 7 C atoms, which optionally contains an oxygen atom or a nitrogen atom.
• R 1 and R 2 together are preferably an alkylene radical having 2 to 4 C atoms, in particular 2 or 3 C atoms.
• R 2 and R ° together are preferably an alkylene radical having 4 to 6 C atoms, which optionally contains heteroatoms.
• R 2 and R 3 together are preferably an alkylene radical having 3 to 5 C atoms.
• R 2 and R 5 together are preferably an alkylene radical having 2 to 4 C atoms.
• R 4 is hydrogen
• the weight ratio between the silane-group-containing polymer and the catalyst of the formula (I) is preferably at least 10/1, in particular at least 20/1, particularly preferably at least 40/1.
• the weight ratio between the silane-containing polymer and the catalyst of formula (I) is preferably at most 10 ⁇ 00 / 1, in particular at most 2 ⁇ 00 / 1, more preferably at most 1 ⁇ 00 / 1.
• the weight ratio between the silane-group-containing organic polymer and the catalyst of the formula (I) is preferably in the range from 10/1 to 2 ⁇ 00 / 1, particularly preferably 20/1 to 2 ⁇ 00 / 1, in particular 40/1 to 1 ⁇ 00 / 1.
• Such a composition has good shelf life and fast cure.
• R 3 is hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 12, preferably 1 to 8, in particular 1 to 4, C atoms, or R 2 and R 3 are together for an alkylene radical having 3 to 6, in particular 3 to 5, carbon atoms.
• These catalysts of the formula (I) have amidine groups.
• R 3 is hydrogen or methyl, especially methyl.
• R 1 is hydrogen or together with R 2 is 1, 2-ethylene or 1, 3-propylene.
• R 2 is hexyl, cyclohexyl, benzyl, 2-ethylhexyl, octyl, decyl, dodecyl or 2-methoxyethyl, or together with R 1 is 1, 2-ethylene or 1, 3-propylene.
• amidine-containing catalysts of the formula (I) are distinguished by good catalytic activity and excellent compatibility in the composition.
• guanidine-containing catalysts of the formula (I) Compared with guanidine-containing catalysts of the formula (I), they have the advantage that they have a not so high catalytic activity and thus can be used in a slightly higher amount, whereby they are less susceptible to interference with other components of the composition, in particular the contained therein impurities.
• amidyne-containing catalysts of the formula (I) are selected from the group consisting of 1, 2-bis (2-methyl-5,6-dihydro-pyrimidin-1 (4H) -yl) ethane, 1, 2-bis ( 2-methyl-4,5-dihydro-1H-imidazol-1-yl) ethane, bis (2- (2-methyl-4,5-dihydro-1H-imidazol-1-yl) ethyl) amine, N, N "- (2,2 (4), 4-trimethylhexane-1, 6-diyl) bis (N'-hexylacetimidamide), N, N" - (2,2 (4), 4-trimethylhexane) 1,6-diyl) bis (N '- (2- (2-methoxyethyl) acetimidamide), N, N "- (2-methylpentane-1, 5-diyl) bis (N'-hexylacetimidamide), N, N" - (propan
• catalysts having cyclic amidine groups which represent a six-membered ring. These catalysts have a particularly high catalytic activity.
• R 3 is -NR 4 R 5 .
• These catalysts of the formula (I) have guanidine groups. They are characterized by an even higher catalytic activity and excellent compatibility in the composition compared to the amidine-containing catalysts.
• R 4 is preferably hydrogen
• R 2 and R 5 are each, independently of one another, each an alkyl, cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains heteroatoms;
• R 1 is preferably hydrogen.
• the preferred embodiments of the guanidine-containing catalysts of the formula (I) have the formula (Ia).
• Catalysts of the formula (Ia) are particularly easy to prepare and have a particularly high catalytic activity.
• R 2 and R 5 are particularly preferably each independently of one another ethyl, isopropyl, tert-butyl, 3- (dimethylamino) propyl or cyclohexyl, in particular isopropyl or cyclohexyl, most preferably cyclohexyl. These catalysts are particularly accessible.
• A is preferably an n-valent aliphatic or cycloaliphatic or arylaliphatic hydrocarbon radical having 2 to 18 C atoms, which optionally contains heteroatoms and optionally has amino groups.
• N is preferably 2 or 3, in particular 2.
• Particularly preferred guanidine group-containing catalysts of the formula (I) are selected from the group consisting of 1,1'- (1, 2-ethylene) bis (2,3-diisopropylguanidine), 1,1 '- (1,2-ethylene) bis (2,3-dicyclohexylguanidine), 1,1 '- (1,3-propylene) bis (2,3-diisopropylguanidine), 1,1' - (1,3-propylene) bis (2,3-dicyclohexyl) hexylguanidine), 1, 1 '- (1, 2-propylene) bis (2,3-diisopropylguanidine), 1, 1' - (1, 2-propylene) bis (2,3-dicyclohexylguanidine), 1, 1 '- (1,4-Butylene) bis (2,3-diisopropylguanidine), 1,1' - (1,4-Butylene) bis (2,3-dicyclohexylguanidine
• the preferred embodiments of the catalyst of formula (I) can be prepared from commercially available, inexpensive raw materials and have particularly good properties in terms of catalytic activity and compatibility of the catalyst.
• the catalyst of the formula (I) is obtained, in particular, by the reaction of at least one suitable polyamine with at least one reagent.
• a suitable polyamine with at least one reagent.
• an amidine or guanidine group selected from the group consisting of orthoesters, 1, 3-keto esters, 1, 3-ketoamides, nitriles, imidic acid, ImidTexrechlo den, amides, lactams, cyanamide, carbodiimides, ureas, O Alkylisoureas, thioureas, S-alkylisothioureas, Aminoiminonnethansulfonklaren, guanylpyrazoles and guanidines.
• orthoesters 1,3-ketoesters, 1,3-ketamidides, nitriles, imidic acid esters, imidic acid chlorides, amides and lactams are suitable, in particular orthoesters, 1,3-ketoesters and nitriles.
• a catalyst of the formula (I) in which R 3 is hydrogen or an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms at least one suitable polyamine is used reacted with at least one orthoester or at least one 1, 3-ketoester or at least one nitrile. This produces an amidine-containing catalyst of the formula (I).
• Preferred orthoesters are orthoformates, orthoacetates, orthopropionates, orthobutyrates and orthovalerates, in particular trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate.
• Preferred 1,3-keto esters are methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate or tert-butyl acetoacetate, especially ethyl acetoacetate.
• Preferred nitriles are acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile and capronitrile, in particular acetonitrile.
• An amidine group-containing catalyst of the formula (I) is preferably obtained by the reaction of at least one polyamine with at least one orthoester of the formula R 3 -C (OR a ) 3 and optionally at least one monoamine of the formula R 2 -NH-R ° , in particular R 2 -NH 2 , with liberation of alcohol R a OH, wherein R a is in particular an alkyl radical having 1 to 4 C-atoms.
• This reaction is preferably carried out at elevated temperature, in particular at 40 to 160 ° C and more preferably at 60 to 140 ° C, and elevated pressure in the presence of a catalyst.
• a catalyst containing amidine groups of the formula (I) is preferably obtained by the reaction of at least one polyamine with at least one 1, 3-keto ester of the formula R 3 -C (O) CH 2 C (O) OR a .
• This 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.
• Preferred monoamines are n-hexylamine, cyclohexylamine, benzylamine, 2-ethylhexylamine, n-octylamine, n-decylamine, laurylamine and 2-methoxyethylamine.
• the implementation can take place in one or more stages.
• a polyalkylene amine having two primary and at least two secondary amino groups in particular TETA, TEPA or N4-amine
• TETA, TEPA or N4-amine is reacted with the orthoester or 1, 3-ketoester such that at least two moles of orthoester or 1,3 -Ketoester per mole of polyalkyleneamine molecule are present.
• a catalyst of the formula (I) is formed with two amidine groups in which R 1 and R 2 are each together for 1,2-ethylene or 1, 3-propylene.
• a polyamine having two primary amino groups free of secondary amino groups is reacted with the orthoester or 1,3-ketoester such that the polyamine and the orthoester or 1,3-ketoester are in a molar ratio in the Range from 1 .2 to 1 .5 are present.
• Alcohol or ester release produces mixtures which, in addition to a catalyst of the formula (I), also contain oligomeric by-products with a plurality of amidine groups.
• At least one polyamine having two primary amino groups, at least one orthoester or 1,3-ketoester and at least one monoamine of the formula R 2 -NH-R °, in particular of the formula R 2 -NH 2 are reacted in that at least two mol of orthoester or 1, 3-ketoester and at least two mol of monoamine are present per mole of polyamine. If a polyamine having more than two primary amino groups is used, preference is given to using as much orthoester or 1,3-ketoester and as much monoamine that per equivalent of primary amino group one mole of orthoester or 1,3-ketoester and one mole of monoamine amine are present.
• catalysts of the formula (I) which are free of primary amino groups.
• Cyanamides, carbodiimides, ureas, O-alkylisoureas, thioureas, S-alkylisothioureas, aminoimino-methanesulfonic acids, guanylpyrazoles and guanidines are suitable for introducing guanidine groups. Cyanamides and carbodiimides are preferred.
• a guanidine-containing catalyst of the formula (I a) is formed.
• R 1 , R 2 , R 3 , R 4 , R 5 and n have the meanings already described.
• Suitable carbodiimides are typically aliphatic, cycloaliphatic or arylaliphatic carbodiimides, in particular simple, commercially available aliphatic and cycloaliphatic carbodiimides, preferably N, N'-diisopropylpodiimide (DIC), N, N'-di-tert-butylcarbodiimide, N, N '-Dicyclohexylcarbodiimide (DCC) or N-ethyl-N' - (3-dimethylaminopropyl) carbodiimide (EDC), more preferably ⁇ , ⁇ '-diisopropylcarbodiimide (DIC) or N, N'-dicyclohexylcarbodiimide (DCC), especially DCC.
• DIC N'-diisopropylpodiimide
• DCC N, N'-Dicyclohexylcarbodiimide
• EDC N-ethy
• the reaction of the polyamine with the carbodiimide is preferably carried out at elevated temperature, in particular at 40 to 160 ° C and particularly preferably at 60 to 140 ° C.
• the reaction can be carried out completely without the use of VOC solvents.
• Catalyst in particular an acid such as a carboxylic acid or carbonic acid, or a Lewis acid such as boron trifluoride etherate, aluminum chloride, aluminum acetylacetonate, iron (III) chloride, lithium perchlorate, zinc chloride, zinc acetate, zinc neodecanoate, zinc acetylacetonate, zinc triflate or lanthanum triflate.
• the implementation can take place in one or more stages.
• the carbodiimide is used stoichiometrically with respect to the primary amino groups of the polyamine.
• the resulting catalyst of formula (I) is substantially free of primary amino groups.
• reaction product from this process is preferably used without workup and / or purification in the composition, except for the removal by distillation of volatile compounds, optionally under vacuum.
• a suitable polyamine for the preparation of a catalyst of the formula (I) is an aliphatic, cycloaliphatic or arylaliphatic polyamine selected from the following group:
• Amino groups and optionally ether groups in particular 4-amino-methyl-1,8-octanediamine, 1,3,5-tris (aminomethyl) -cyclohexane, 1,3,5-tris (aminomethyl) -benzene, tris (2) aminoethyl) amine, polyoxyalkylene triamines having an average molecular weight in the range of 200 to 2 ⁇ 00 g / mol, as (commercially for example under the trade name Jeffamine ® from
• polyetheramines from BASF
• PC amines ® are available from Nitroil (, characterized in that it comprises 2-aminopropyl or 2-amino-butyl end groups bear, especially Jeffamine ® T-403 and Jeffamine ® XTJ-566 (both from Huntsman), as well as analogous types from BASF and Nitroil.
• Polyethyleneimines ie products from the polymerization of branched-structure ethylenimine containing primary, secondary and tertiary amino groups, exemplified below by means of a single molecule. These are mixtures of different molecules with molecular weight distributions, as they typically arise in polymerizations.
• Suitable polyethyleneimines are commercially available under the brand names Lupa- sol ® (BASF) and Epomin ® (from Nippon Shokubai) available. Preferred types are Lupasol ® FG and Lupasol ® G 20 anhydrous, Epomin SP-003 ®, Epomin SP-006 ®, Epomin SP-012 ® and Epomin ® SP-018th
• Polyvinylamines especially those commercially available under the brand name Lup- amine ® types available (from BASF).
• aliphatic, cycloaliphatic or arylaliphatic polyamines having a primary, a secondary and optionally a tertiary amino group, in particular N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl
• aliphatic, cycloaliphatic or arylaliphatic polyamines having two or three secondary amino groups, in particular N, N-dimethyl-1, 2 ethanediamine, N, N-diethyl-1, 2-ethanediamine, N, N-dimethyl-1, 3-propanediamine, N, N-diethyl-1, 3-propanediamine, N 1, N 1 -diethyl-1, 4- pentane diamine, and secondary polyoxyalkylene amines having an average molecular weight in the range of 200 to 2000 g / mol, especially Jeffamine ® SD-231, Jeffamine ® SD-401, Jeffamine ® SD-2001 and Jeffamine ® ST-404 (all available from Huntsman).
• polyamines having at least two primary amino groups are preferred.
• polyamines having 2 to 50, in particular 2 to 20, carbon atoms preference is furthermore given to polyamines having 2 to 50, in particular 2 to 20, carbon atoms.
• polyamines having 2 to 18, in particular 2 to 12, carbon atoms.
• a process for preparing a catalyst of the formula (I) may in particular also be carried out "in situ", ie in the presence of the silane-group-containing polymer, be performed.
• the polyamine and reagent for introducing an amidine or guanidine group are mixed with the silane-containing polymer and reacted at a temperature in the range of 40 to 120 ° C.
• the in situ reaction can also be carried out in particular in the presence of further ingredients, as are typical of compositions based on silane-containing polymers.
• This process is particularly preferred for the preparation of a guanidine-containing catalyst of the formula (I) from the reaction of a polyamine with a carbodiimide.
• the conversion to a catalyst of the formula (I) can also be carried out in a fully formulated sealant or adhesive or a fully formulated coating, ie also in the presence of, for example, drying agents and / or plasticizers and / or fillers and / or rheology modifiers.
• the in-situ preparation of the catalyst of the formula (I) in the composition is particularly advantageous, since the catalyst thus arises only with a certain time delay and thus little disturbs the compounding process.
• This can in practice represent a significant advantage, for example in the case of moist constituents such as fillers, which can be dried in the composition with drying agents and their moisture thus not react with inclusion of the catalyst with silane groups of the silane-containing polymer. Thereby, the viscosity of the composition is not undesirably increased.
• R, R 'and R are each independently a monovalent hydrocarbon radical having 1 to 12 carbon atoms;
• X 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.
• X is preferably a hydroxyl radical or an alkoxy or Ketoximato radical having 1 to 6 C-atoms, in particular a hydroxyl, methoxy, ethoxy, methylethyl ketoximato or methyl isobutylketoximato radical.
• X is a hydroxyl radical.
• a is preferably 0 or 1, in particular 0.
• m is preferably chosen so that the polyorganosiloxane of the formula (III) at room temperature has a viscosity in the range from 100 to 500 ⁇ 00 mPa s, in particular from 1000 to 100 ⁇ 00 mPa s.
• Such polyorganosiloxanes are easy to handle and crosslink with moisture and / or Silanvernetzern to solid silicone polymers having elastic properties.
• the composition preferably comprises a silane crosslinker, in particular a silane of the formula (IV),
• R '" is a monovalent hydrocarbon radical having 1 to 12 C atoms
• X' is a hydroxyl radical or an alkoxy, acetoxy, Ketoximato, amido or enoxy radical having 1 to 13 carbon atoms stands;
• silanes of the formula (IV) are methyltrimethoxysilane, ethyltrimethoxysilane, propytrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltris (methylethylketoximo) silane, vinyltris (methylethylketoximo) silane and methyltris (isobutyl ketoximo) silane.
• the silane-containing polymer in a preferred embodiment of the invention 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 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 silane-containing polyolefin or a silane-containing polyester or a silane-containing poly (meth) acrylate or a silane-containing polyether or a mixed form of these polymers. Most preferred is a silane group-containing polyether.
• Preferred silane groups on the organic polymer are alkoxysilane groups, in particular end groups of the formula (V),
• R 7 is a linear or branched, monovalent hydrocarbon radical having 1 to 5 C atoms, in particular methyl, ethyl or isopropyl;
• R 8 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 7 is methyl or ethyl.
• the radical R 7 is preferably an ethyl group, since in this case ecologically and toxicologically harmless ethanol is released during the curing of the composition.
• trimethoxysilane groups dimethoxymethylsilane groups or triethoxysilane groups.
• methoxysilane groups have the advantage that they are particularly reactive, and 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 1000 to 30 ⁇ 00 g / mol, in particular from 2000 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 polyetherpolyols with a superstoichiometric amount of polyisocyanates, with amino silanes, hydroxysilanes or mercaptosilanes.
• Silane-group-containing polyethers from this process are particularly preferred. This method allows the use of a variety 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 weather 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, in particular diisocyanates.
• the reaction between the polyisocyanate and the polyether polyol is preferably carried out with exclusion of moisture at a temperature of 50 ° C. to 160 ° C., if appropriate in the presence of suitable catalysts, the polyisocyanate being metered in such a way that its isocyanate groups are proportionate 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 weight percent %, 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.
• aminosilanes are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3-methyl - butyl-triethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, 4-amino-3,3-dimethylbutyl-triethoxysilane, 2-aminoethyl-trimethoxysilane or 2-aminoethyl-triethoxysilane.
• 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane or 4-amino-3,3-dimethylbutyltriethoxysilane.
• 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, 3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 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 manner 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-triethoxysilylpropyl) -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 Polymer 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 Polymer TM or Silyl TM from Kaneka Corp., especially the types SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951
• Excestar ® Asahi Glass Co.
• Particularly preferred end groups of the formula (V) are end groups of the formula (VI)
• R 9 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;
• Y is a divalent radical selected from -O-, -S-, -N (R 10 ) -,
• R 10 is hydrogen or a linear or branched hydrocarbon radical having 1 to 20 C atoms, which optionally has cyclic moieties, and which optionally has an alkoxysilyl, ether or carboxylic acid ester group;
• R 7 , R 8 and x have the meanings already mentioned.
• R 9 is 1, 3-propylene or 1, 4-butylene, butylene may be substituted with one or two methyl groups. More preferably, R 9 is 1,3-propylene.
• composition according to the invention may contain further catalysts for the crosslinking of the silane groups.
• Particularly suitable as further catalysts are metal catalysts and / or basic nitrogen or phosphorus compounds.
• Possible metal catalysts 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
• Possible basic nitrogen or phosphorus compounds are, in particular, imidazoles, pyridines, phosphazene bases or, preferably, amines, hexahydropriazines or biguanides and amidines or guanidines which do not correspond to the formula (I).
• 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, stea- rylamine, ⁇ , ⁇ -dimethylstearylamine; fatty amines derived from natural fatty acid mixtures, in particular cocoalky
• triazines 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 amidines which do not correspond to the formula (I) 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-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-ene, N, N'-di-n -hexylacetamidine (DHA), 2-methyl-1, 4,5,6-tetrahydropyrimidine, 1, 2-dimethyl-1, 4,5,6-tetrahydropyrimidine, 2,5,5-trimethyl-1, 4,5, 6-tetrahydropyrimidine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole or N- (3-triethoxysilylpropyl) -4,5-dihydro
• Suitable guanidines which do not correspond to the formula (I) are in particular 1-butylguanidine, 1, 1-dimethylguanidine, 1, 3-dimethylguanidine, 1, 1, 3,3-tetramethylguanidine (TMG), 2- (3) (Trimethoxysilyl) propyl) -1,3,3-tetramethylguanidine, 2- (3- (methyldimethoxysilyl) propyl) -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] decane 5-ene, 7-Cyclohexyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1-phenylguanidine, 1 - (o -tolyl) guan
• composition according to the invention 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, neodcanic acid, fatty acid mixtures from the saponification of natural fats and oils or di- and polycarboxylic acids, in particular poly (meth) acrylic acids.
• the composition according to the invention is substantially free of organotin compounds.
• Organotin-free compositions are beneficial in terms of health and environmental protection.
• the tin content of the composition is less than 0.1% by weight, in particular less than 0.05% by weight.
• the composition in addition to the silane-group-containing organic polymer and a catalyst of the formula (I), the composition additionally contains at least one organotitanate.
• a combination of catalyst of the formula (I) and organotitanate has a particularly high catalytic activity. As a result, a rapid curing of the composition is possible with a relatively small amount of the catalyst of the formula (I).
• organotitanates are titanium (IV) complex compounds.
• 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) (commercially available for example as Tyzor ® Ibay of Dorf Ketal) (bis (ethyl acetoacetate) diisopropoxy-titanium (IV) is commercially available for example 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) -ethoxy] -e
• the weight ratio between the silane group-containing polymer and the catalyst of the formula (I) is preferably in the range of 40/1 to 2000/1.
• the weight ratio between the organotitanate and the catalyst of the formula (I) is preferably in the range of 10/1 to 1/10, more preferably 5/1 to 1/5, especially 5/1 to 1/3.
• composition according to the invention may contain further constituents, 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, vinyltrimethoxysilane, vinyltriethoxysilane or organoalkoxysilanes, which have a functional group in the ⁇ -position relative to the silane group, in particular N- (methyldimethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, methoxy methylsilanes, orthoformic acid esters, calcium oxide or molecular sieves, in particular vinyltrimethoxysilane or vinyltriethoxysilane; Plasticizers, in particular trialkylsilyl-terminated polydialkylsiloxanes, in particular trimethylsilyl-terminated polydimethylsiloxanes, in particular having viscosities in the range from 10 to 10000 Pas, or corresponding compounds in which some of the methyl groups have been replaced by other organic groups, especially phenyl, vinyl or trifluoropropyl - Groups, so-called reactive plastic
• 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 blacks, graphite, metal powders such as aluminum, copper, iron, silver or steel, PVC powder or hollow spheres;
• 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
• 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, pyrogenic 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 abovementioned fillers aluminum hydroxide and magnesium hydroxide, or in particular organic phosphoric esters, in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl 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 (isopropyl) phenyl phosphates of varying degrees of isopropylation, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) or ammoni
• Biocides in particular algicides, fungicides or fungal growth inhibiting substances;
• 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.
• composition according to the invention is preferably produced and stored in the absence of moisture.
• the composition is storage stable in a suitable package or assembly, such as, in particular, a bottle, can, pouch, bucket, keg, or cartridge, excluding moisture.
• composition according to the invention can be present in the form of a one-component or in the form of a multicomponent, in particular two-component, composition.
• one-component in the present document is meant a composition in which all constituents of the composition are stored mixed in the same container and which is curable with moisture.
• two-component is referred to in this document a composition in which the components of the composition in two different components are present, 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 silane group-containing polymer composition contains a silane-terminated polyorganosiloxane
• 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 and the silane crosslinker, in particular a silane of the formula (IV), preferably a component of the second component, and the catalyst of the formula (I) may be contained either in the first and / or in the second component.
• the composition contains as a silane-containing polymer, a silane-containing organic polymer, the composition is preferably one-component.
• composition according to the invention is applied in particular in a temperature range between 5 and 45 ° C., preferably at ambient temperature, and cures even under these conditions.
• the silane groups present in the composition come into contact with moisture.
• the silane groups hydrolyze.
• Silanol groups Si-OH groups
• siloxane groups Si-O-Si groups
• existing additional moisture-reactive groups also react with existing moisture.
• the catalyst of the formula (I) accelerates this curing.
• water is needed for the curing, this can either come from the air (humidity), or the composition described above can be brought into contact with a water-containing component, for example by brushing, for example with a smoothing agent, or by Spraying, 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 in the event that the composition itself is in the form of a paste.
• Such a water-containing component is typically added to the composition according to the invention in a weight ratio of compositions according to the invention.
• Composition to water-containing component in the range of 5: 1 to 200: 1, preferably 10: 1 to 100: 1, in particular 10: 1 to 50: 1 added.
• a second or optionally further components is or are mixed with the first component, in particular via a static mixer or via a dynamic mixer.
• 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.
• composition according to the invention has a good shelf life without separation tendency, permits a low hazard classification due to the low toxicity and low volatility of the catalyst of the formula (I) and enables low-emission and low-odor compositions which cure rapidly and thereby a mechanically high-quality and durable material form.
• 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, TMG, DHA or titanium (IV) complexes.
• Compositions containing such catalysts have a tendency to migration effects, which can manifest themselves before curing by separation and after curing by sticky and / or greasy surfaces and / or substrate contaminants. The latter effects are highly undesirable because sticky and greasy surfaces are rapidly soiled and poorly paintable, and substrate contamination can lead to permanent discoloration.
• composition of the invention is suitable for a variety of uses, in particular as a paint, lacquer or primer, as a resin for the production of fiber composite material (composite), as potting compound, Sealant, adhesive, coating, coating or coating for construction 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, window 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, corrosion protection coating, textile coating, damping element, sealing element or filler.
• Sealant adhesive, coating, coating or coating for construction 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, window adhesive, sandwich element adhesive, laminating adhesive, laminate adhesive, packaging adhesive, wood adhesive , Parquet adhesive, anchoring
• composition according to the invention is 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;
• resins for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites and other so-called polymer composites;
• Plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA), polyesters, 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, corona or flame;
• CFRP carbon fiber reinforced plastics
• GRP glass fiber reinforced plastics
• SMC sheet molding compounds
• coated substrates such as powder-coated metals or alloys
• the substrates can be pretreated prior to application of 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.
• composition according to the invention is particularly suitable 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 catalysts of formula (I).
• composition is particularly suitable as an adhesive and / or sealant, in particular for joint sealing and elastic adhesive bonds 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, Baikon, parking decks or concrete pipe.
• the present invention thus also relates to the use of a previously described composition as an adhesive, sealant or coating.
• Such a composition typically contains plasticizers, fillers, adhesion promoters and / or crosslinkers and drying agents and optionally further auxiliaries and additives.
• the proportion of silane-containing polymer in the composition according to the invention is 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 preferably has a pasty consistency with pseudoplastic properties.
• a paste-like sealant or adhesive is applied in particular from commercially available cartridges, which are operated manually, by means of compressed air or battery, or from a barrel or hobbock by means of a feed pump or an extruder, optionally by means of an application robot on a substrate.
• the composition preferably has a consistency that is liquid at room temperature 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 invention relates to a cured composition which is obtainable from a composition, as described above, after its curing. Curing takes place with water, in particular in the form of atmospheric moisture, and / or with a suitable crosslinker.
• the cured composition is characterized by the fact that it has little or no tendency for migration-related defects such as sweating or substrate contamination. This is in contrast to cured compositions based on silane-containing polymers containing amidine or guanidine catalysts, as are known in the art, where catalyst-related migration effects are known.
• the use as adhesive, sealant or coating produces an article which has been adhesively bonded, sealed or coated with the described composition.
• the article is a building, in particular a civil engineering works, designed to manufactured goods 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.
• the present invention relates to the use of a catalyst of the formula (I) as described above as crosslinking catalyst for curable compositions, in particular for silane-containing curable compositions, in particular as described above.
• the moisture-curing composition is substantially free of organotin compounds.
• the tin content of the composition is less than 0.06 wt .-%, in particular less than 0.01 wt .-%.
• Another object of the present invention is a catalyst of the formula (Ia '
• n ' is 2 or 3, in particular 2;
• a ' is an n'-valent aliphatic or cycloaliphatic or arylaliphatic hydrocarbon radical having 2 to 18 C atoms, which optionally contains heteroatoms and optionally has amino groups; and R 2 and R 5 are each independently an alkyl, cycloalkyl or aralkyl radical having 1 to 18 C atoms, which optionally contains heteroatoms stand.
• the catalyst of the formula (I a ') corresponds to the already described catalyst of the formula (I a) with preferred definitions for n, A, R 2 and R 5 .
• A is preferably an n-valent aliphatic or cycloaliphatic or arylaliphatic hydrocarbon radical having 2 to 12 C atoms, which optionally contains 1 to 3 ether oxygens and optionally 1 to 3 secondary or tertiary amino groups.
• R 2 and R 5 are each, independently of one another, each an alkyl, cycloalkyl or aralkyl radical having 1 to 12 C atoms, in particular 1 to 8 C atoms, which optionally contains heteroatoms, in particular a nitrogen atom.
• R 2 and R 5 are each independently ethyl, isopropyl, tert-butyl, 3- (dimethylamino) propyl or cyclohexyl, especially each isopropyl or cyclohexyl, most preferably each cyclohexyl.
• a catalyst of the formula (I a ') is odorless and thus particularly advantageous. It is particularly easy to prepare and has a particularly high catalytic activity and good selectivity with respect to the hydrolysis and condensation reaction of silane groups. Thus, it enables silane-crosslinking compositions with good shelf life and rapid cure to form mechanically high-quality and durable materials after application, and, as part of a curable composition, does not tend to migration-related defects such as separation, exudation, and substrate contamination either before or after curing.
• the preferred embodiments are particularly easy to prepare and catalytically particularly active.
• the catalyst of the formula (I a ') can be advantageously used in a curable composition, in particular in a silane-containing composition.
• a "standard climate” means a temperature of 23 ⁇ 1 ° C and a relative humidity of 50 ⁇ 5% referred to 1 H-NMR spectra were measured on a spectrometer Bruker Ascend 400 at 400.14 MHz and the chemical shifts ⁇ are indicated in ppm relative to tetramethylsilane (TMS). True and pseudo-coupling patterns were not differentiated.
• FT-IR Infrared spectra
• 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 ).
• the skin formation time was determined by applying a few grams of the composition in a layer thickness of about 2 mm on cardboard and in the standard climate, the time was measured until the slightest tapping the surface of the composition by means of a pipette of LDPE for the first time no residues left more on the pipette. The condition of the surface was haptically tested.
• the Shore A hardness was determined according to DIN 53505 on test specimens cured for 7 days under standard conditions.
• Catalyst K-1 1, 1 '- (2,2 (4), 4-trimethyl-1,6-hexamethylene) bis (2,3-diisoproparguanidine)
• Catalyst K-2 1, 1 '- (4-aza-N-methyl-1, 7-heptylene) bis (2,3-diisopropylguanidin)
• Catalyst K-3 1, 1 '- (2,2 (4), 4-trimethyl-1,6-hexamethylene) bis (2,3-dicyclohexylguanidine)
• Catalyst K-5 1, 1 '- (3,6-dioxa-1,8-octylene) bis (2,3-dicyclohexylguanidine)
• 2,3-dicyclohexylguanidine 2,3-dicyclohexylguanidine
• Catalyst K-6 1, 1 '- (a, co-polyoxypropylene) bis (2,3-dicyclohexylguanidine) having a molecular weight of about 840 g / mol
• Catalyst K-7 1, 1 '- (a, co-polyoxypropylene) bis (2,3-diisopropylguanidine) having a molecular weight of about 680 g / mol
• Catalyst K-8 1, 1 '- (4-aza-N-methyl-1, 7-heptylene) bis (2,3-dicyclohexylguanidine)
• Catalyst K-9 1, 1 '- (3,6-Diaza-1, 8-octylene) bis (2,3-dicyclohexylguanidine) 1.86 g of triethylenetetramine (technical grade, amine content about 25.7 mmol of N / g) and 5.20 g of ⁇ , ⁇ '-dicyclohexylcarbodiimide and the mixture is heated to 120 ° C with stirring. At regular intervals, the reaction mixture was analyzed by FT-IR spectroscopy. After 6 hours, the carbodiimide band was at about 2120 cm "1 completely disappeared.
• Catalyst K-10 1, 1 '- (3,6,9-triaza-1,1,1-undecylene) bis (2,3-dicyclohexyl-guanidine)
• Catalyst K-13 1,2-Bis (2-methyl-5,6-dihydropyrimidin-1 (4H) -yl) ethane
• N4- Amine N4- Amine
• III lanthanum trifluoromethanesulfonate
• Catalyst K-14 Bis (2- (2-methyl-4,5-dihydro-1H-imidazol-1-yl) ethyl) amine
• tetraethylenepentamine Epikure TM Curing Agent 927, from Momentive
• lanthanum (III) trifluoromethanesulfonate a light yellow, low-odor oil
• Catalyst K-15 N, N "- (2,2 (4), 4-trimethylhexane-1, 6-diyl) bis (N'-hexylacetimidamide)
• Catalyst K-16 N, N "- (2,2 (4), 4-trimethylhexane-1, 6-diyl) bis (N '- (2-methoxyethyl) acetimidamide)
• Vestamine ® TMD were (from Evonik), 1 .71 g of 2- methoxyethylamine, 2.86 g of trimethyl orthoacetate to 0.07 g of lanthanum (III) -trifluor- methanesulfonate and mixed in a microwave oven at a maximum pressure of 150 Heated to 180 ° C with stirring for 30 minutes. Then the reaction mixture was transferred to a round bottomed flask and freed from the volatiles. This gave 3.92 g of a slightly cloudy, low-odor oil.
• Catalyst K-17 N, N '- (2-methylpentane-1, 5-diyl) bis (N'-hexylacetimidannid)
• a test tube were 1 .34 g of 1, 5-diamino-2-methylpentane (Dytek ® A, by Invista), 2.38 g of n-hexylamine, 2.96 g of trimethyl orthoacetate and 0.06 g of lanthanum (III) trifluoromethanesulfonate and heated in a microwave oven at a maximum pressure of 150 Pa with stirring for 30 minutes at 160 ° C. The reaction mixture was transferred to a round bottom flask and freed from the volatiles in vacuo to give 3.95 g of a slightly cloudy, low-odor oil.
• Catalyst K-18 N, N "- (Prc> pan-1, 3-diyl) bis (N'-hexylacetimidamide)
• Catalyst K-20 N, N "- (3,6-dioxaoctan-1,8-diyl) bis (N'-hexylacetimidamide)
• N N "- (3,6-dioxaoctan-1,8-diyl) bis (N'-hexylacetimidamide)
• a test tube 1.63 g of 3,6-dioxaoctan-1,8-diamine (cf.
• Catalyst K-21 N, N "- (2,2 (4), 4-trimethylhexane-1, 6-diyl) bis (N '- (2-methoxyethyl) acetimidannide)
• compositions based on silane-containing polymers Compositions based on silane-containing polymers:
• compositions Z1 to Z63 are examples according to the invention, the compositions V1 to V16 are comparative examples.
• compositions Z1 to Z11 and Comparisons V1 to V2 are Compositions Z1 to Z11 and Comparisons V1 to V2:
• 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 tested for viscosity and skin formation time (HBZ) under standard conditions, before and after storage ,
• 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.
• composition 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 3 and the mixture as described for composition Z1 on viscosity, skinning time (HBZ), surface finish and mechanical properties tested. The results are shown in Tables 3 and 4. "Supplement” stands for "composition”.
• compositions Z22 to Z31 and comparisons V5 to V6 are Compositions Z22 to Z31 and comparisons V5 to V6:
• composition of 95.9 g of polymer STP-2, 0.4 g of vinyltriethoxysilane and 3.7 g of 3-aminopropyltriethoxysilane was mixed with various catalysts in the stated amount according to Table 5 and the mixture as described for composition Z1 on viscosity, skinning time (HBZ), surface finish and mechanical Properties tested. The results are given in Tables 5 and 6. "Supplement” stands for "composition”.
• the Thixotroping Paste was prepared by mixing in a vacuum mixer, 300 g of diisodecyl phthalate (Palatinol ® Z, from BASF) and 48 g of 4,4'-methylenediphenyl diisocyanate (Desmodur ® 44 MC L, Bayer) were charged and gently heated with vigorous stirring and then 27 g of n-butylamine were slowly added dropwise. The resulting paste was further stirred under vacuum and cooling for one hour.
• diisodecyl phthalate Palatinol ® Z, from BASF
• Desmodur ® 44 MC L 4,4'-methylenediphenyl diisocyanate
• compositions Z47 to Z55 and Comparison V8 are Compositions Z47 to Z55 and Comparison V8:
• compositions Z56 to Z57 and Comparison V9 to V12 are Compositions Z56 to Z57 and Comparison V9 to V12:
• TEGOPAC® Bond 150 from Evonik
• 0.5 g vinyltnethoxysilane and 3.0 g 3-aminopropyltriethoxysilane were mixed with various catalysts in the stated amount according to Table 9 and the mixture was tested for skinning time (HBZ) and surface quality after 7 days under standard conditions , The results are shown in Table 9.
• "Supplement” stands for "composition”.
• compositions Z58 to Z59 and comparisons V13 to V14 are Compositions Z58 to Z59 and comparisons V13 to V14:
• a plastic cup 20.2 g of a first component consisting of 99 parts by weight (GT) of an OH-terminated linear polydimethylsiloxane with a viscosity of about 50 ⁇ 00 mPas at 23 ° C (Wacker ® Silicone Rubber Polymer FD 50, by Wacker) and 1 GT Wacker ® e 2 silicone oil emulsifier sion (nonionic in water emulsified medium viscosity OH-terminated linear polydimethylsiloxane, from Wacker, solids content 37-40%) with a second component consisting of 0.80 g of vinyltrimethoxysilane (VTMO) and a catalyst in the in the Table 10 intimately mixed and the mixture as described for skinning time (HBZ) and surface texture tested. Furthermore, the applied mixture was tested for 7 days in standard climate to Shore A hardness. The results are shown in Table 10. "Supplement” stands for "composition”. Table 10:
• composition Z60 (in situ preparation of the catalyst):
• a composition of 30.0 g of polymer STP-1, 0.15 g of vinyltrimethoxysilane and 1 .2 g of 3-glycidoxypropyltrimethoxysilane was added under exclusion of moisture with 0.8 g of polyoxypropylenediamine having a mean molecular weight of about 430 g / mol (Jeffamine® D-400 of Huntsman, amine content about 4.4 meq / g) and 0.4 g of ⁇ , ⁇ '-diisopropylcarbodiimide mixed, the mixture filled into an internally painted aluminum tube and heated in the oven to 80 ° C.
• compositions Z62 to Z63 and Comparisons V15 and V16 are Compositions Z62 to Z63 and Comparisons V15 and V16:

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