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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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  • 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
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  • 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
  • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
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  • 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
  • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/54—Nitrogen-containing linkages
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  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
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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
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • 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
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  • 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
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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  • 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
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  • 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
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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  • 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
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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  • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/357—Six-membered rings
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/28—Non-macromolecular organic substances
  • C08L2666/36—Nitrogen-containing compounds

Definitions

• the present invention relates to a polymerizable composition which comprises at least one organosilicon compound having at least two hydrosilylation-reactive ⁇ Si-H groups as component A and at least one benzoxazine compound having at least two unsaturated carbon-carbon reactive in the hydrosilylation with component A Bindings as component B includes.
• Further objects of the present invention are adhesives, sealants or coatings containing the polymerizable composition of the invention, as well as the polymerization products of said compositions.
• Epoxy-based resin systems have long been used successfully in the aerospace, automotive, or electrical industries as adhesives, sealants, or for coating surfaces, or as resin systems with a variety of materials used to make composites.
• Benzoxazine-based resin systems generally have a high glass transition temperature and are characterized by their good electrical properties and their positive fire protection behavior.
• Polymers comprising, besides benzoxazine units, at least one further structural unit other than the former are also known.
• Japanese Patent Application JP-A-2007-154018 claims benzoxazine-based resin systems which can be prepared by reacting formaldehyde and diphenols with methyl-substituted hexamethylenediamines. From JP-A 2007-106 benzoxazine-based resin systems are known, in the production of araliphatic diamines are used.
• Japanese Patent Application JP-A-2007-146070 relates to benzoxazine-based resin systems prepared by reacting formaldehyde with diphenols and various polysiloxane diamines. The polymers obtained are distinguished, above all, by their good dielectric and mechanical properties.
• Silsesquioxane-containing benzoxazine compounds are described by F.C. Chang et al. in "Syntheses, thermal properties, and phase morphologies of novel benzoxazines functionalized with polyhedral oligomeric silsesquioxane (POSS) nanocomposites” polymer, Elsevier Science Publishers B.V., Vol. 45, No. 18, 6321-63131 (2004).
• PES polyhedral oligomeric silsesquioxane
• benzoxazine-based resin systems comprising siloxane groups described in the prior art can be polymerized thermally by a self-initiating mechanism or by the addition of cationic initiators.
• An often later desired post-crosslinking which is technically desirable, in particular radical post-crosslinking of the resulting polymers to increase the final strength, is generally not possible.
• Such subsequent post-crosslinking is desirable, for example, in the case of adhesives, coating compositions or sealants.
• the object of the present invention is to provide a benzoxazine-based polymerizable composition which, after polymerization, has advantageous mechanical properties and is accessible to further post-crosslinking, in particular further radical post-crosslinking.
• the said composition is distinguished by a low viscosity and ease of processing before the polymerization reaction.
• the present invention therefore provides a polymerizable composition
• a polymerizable composition comprising at least one silicon-organic compound having at least two hydrosilylation-reactive ⁇ Si-H groups as component A and at least one benzoxazine compound having at least two unsaturated in the hydrosilylation with component A unsaturated Carbon-carbon bonds as component B.
• the polymerizable composition of the present invention is particularly suitable for the preparation of adhesives, sealants or coatings. Therefore, adhesives, sealants or coating compositions comprising the polymerizable composition of the present invention are the subject of the present invention. Further objects of the present invention are the polymerization product of the polymerizable composition according to the invention and a process for its preparation.
• the present invention also provides a curable composition comprising at least one curable resin component and the polymerization product of the polymerizable composition according to the invention, and the cured product of the curable Composition.
• the cured product is preferably obtained by thermal curing of the curable composition.
• Another object of the present invention is a process for producing the cured product, said product repackaging a layer or bundle of fibers, such as carbon fibers, and being particularly suitable as a composite material.
• silicon organic compound for the purposes of the present invention includes organosilicon compounds containing carbon in addition to silicon.
• a ⁇ Si-H group is to be understood as meaning a group in which a tetravalent silicon atom is bonded to one hydrogen atom and three further atoms.
• the polymerizable composition of the present invention may undergo a polymerization reaction in the form of a polyaddition reaction, the polyaddition reaction being particularly based on a hydrosilylation reaction.
• a polymerization reaction in the form of a polyaddition reaction, the polyaddition reaction being particularly based on a hydrosilylation reaction.
• the polymerizable composition of the invention may preferably comprise at least one hydrosilylation catalyst. It is likewise possible to use mixtures of different hydrosilylation catalysts.
• the hydrosilylation catalyst may be provided in an amount of 1 to 100,000 ppm based on the total weight of the polymerizable composition.
• the amount of hydrosilylation catalyst preferably depends on the activity of the particular catalyst in the reaction of reacting components A and B.
• amounts of catalyst, based on the total weight of the polymerizable composition of at least 2 ppm, at least 4 ppm, at least 8 ppm, at least 12 ppm, at least 20 ppm and at least 100 ppm preferred.
• catalyst amounts, based on the total weight of the polymerizable composition of at most 10000 ppm, at most 1000 ppm, at most 500 ppm and at most 200 ppm are preferred.
• Hydrosilylation catalysts include metal salts and complexes of transition metals, wherein the transition metal is preferably selected from Pt, Pd, Rh, Ru and Ir. In particular, elements of group VIII of the periodic table are preferred.
• Hydrosilylation catalysts may include, for example, platinum (such as PtCl 2 , dibenzonitrile platinum dichloride, platinum on carbon, dichloro (1, 2-cyclooctadiene) platinum (II) [(COD) PtCl 2 ] available from Strem Chemicals, Inc., New Buryport.
• MA another platinum catalyst which is suitable in terms of reactivity and cost aspects is hexachloroplatinic acid (H 2 PtCl 6 -6H 2 O); Also suitable are divinyl disiloxane platinum complexes, such as the divinyltetramethyl disiloxane platinum complex, available as Hüls America PC075, and the platinum-containing PC072 (a platinum divinyl complex) and PC085, also available from Hüls Amerika.
• Suitable rhodium catalysts are (RhCl (P (C 6 H 5 ) S ) 3 ), [Rh (COD) 2 ] BF 4 and [RhCl (nbd)] 2 , while [Ru (benzene) Cl 2 ], [Ru (p-cymene) Cl 2 ] and [Cp * Ru (MeCN) 3 ] PF 6 are examples of suitable ruthenium catalysts.
• Suitable catalysts are also Lewis acids and peroxides.
• the at least one silicon-organic compound having at least two hydrosilylation-reactive ⁇ Si-H groups is selected from the group consisting of cyclic polysiloxanes, linear polysiloxanes, trisiloxysilanes and tetrasiloxysilanes.
• the trisiloxysilanes and tetrasiloxysilanes mentioned may comprise low molecular weight or oligomeric structures.
• two or more than two of said organosilicon compounds may be used in combination with each other.
• Combinations of at least one tetrasiloxysilane with at least one linear polysiloxane or with at least one cyclic polysiloxane are also preferred, as are combinations of at least one trisiloxysilane with at least one linear polysiloxane or with at least one cyclic polysiloxane.
• ternary combinations are preferred, such as the combination of at least one cyclic polysiloxane or at least one linear polysiloxane with at least one trisiloxysilane and with at least one tetrasiloxysilane.
• Mixtures of at least one linear polysiloxane with at least one cyclic polysiloxane can also be used in the context of the present invention.
• organosilicon compounds having at least two hydrosilylation-reactive ⁇ Si-H groups which have a weight-average molecular weight of 200 to 60,000 g / mol, preferably 600 to 10,000 g / mol, and more preferably 800 to 4,000 g / mol, are preferred exhibit.
• the silicon-organic compound comprises a cyclic polysiloxane of the general formula (I) Formula (I) wherein the radicals R may be the same or different and are each selected from hydrogen, alkyl groups having 1 to 8 carbon atoms, cycloaliphatic groups having 1 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups with 1 to 8 C atoms and aryloxy groups having 6 to 12 C atoms, with the proviso that each R on at least two silicon atoms is hydrogen and n is an integer between 2 and 30.
• R may be the same or different and are each selected from hydrogen, alkyl groups having 1 to 8 carbon atoms, cycloaliphatic groups having 1 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups with 1 to 8 C atoms and aryloxy groups having 6 to 12 C atoms, with the proviso that each R on at least two silicon atoms is hydrogen and n is an
• Preferred cyclic polysiloxanes are, for example, methylhydrocyclosiloxanes (MHCS) and any desired mixtures thereof.
• MHCS methylhydrocyclosiloxanes
• examples include e.g. Tetraoctylcyclotetrasiloxane and hexamethylcyclotetrasiloxane; Tetra- and pentamethylcyclotetrasiloxanes; Tetra-, penta-, hexa- and heptamethylcyclopentasiloxanes; Tetra-, penta- and hexamethylcyclohexasiloxanes, tetraethylcyclotetrasiloxanes and tetraphenylcyclotetrasiloxanes.
• the silicon-organic compound comprises a linear polysiloxane of the general formula (II),
• radicals R may be identical or different and are each selected from hydrogen, alkyl groups having 1 to 8 C atoms, cycloaliphatic groups having 1 to 8 C atoms, aryl groups having 6 to 12 C atoms, alkoxy groups having 1 to 8 C, -Atomen and aryloxy groups having 6 to 12 carbon atoms, with the proviso that each R on at least two silicon atoms is hydrogen and m is an integer between 0 and 1000.
• linear polysiloxanes are also linear, short-chain polysiloxanes having ⁇ Si-H end groups with the general formula (11.1) where the radicals R may be identical or different and are each selected from hydrogen, alkyl groups having 1 to 8 C atoms, cycloaliphatic groups having 1 to 8 C atoms, aryl groups having 6 to 12 C atoms, alkoxy groups having 1 to 8 C, -Atomen and aryloxy groups having 6 to 12 carbon atoms and ⁇ f is an integer between 0 and 100.
• linear polysiloxanes which are linear poly (organohydrosiloxanes) of the general formula (II.2),
• radicals R may be identical or different and are each selected from hydrogen, alkyl groups having 1 to 8 C atoms, cycloaliphatic groups having 1 to 8 C atoms, aryl groups having 6 to 12 C atoms, alkoxy groups having 1 to 8 C, -Atomen and aryloxy groups having 6 to 12 carbon atoms, with the proviso that 1 to 50%, preferably 2 to 50% and in particular 5 to 50% of the radicals R are hydrogen and m "is an integer between 2 and 1000
• Exemplary linear poly (organohydrosiloxanes) include trimethylsiloxy-terminated methylhydropolysiloxane, trimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer, dimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer, dimethylsiloxy-terminated polydimethylsiloxane, trimethylsiloxy-terminated methyloctylsiloxane-methylhydrosiloxane copolymer , Dimethylsiloxy-terminated phenylmethylsiloxane-methylhydrosiloxane copolymer, trimethylsiloxy-terminated 2-phenylethylmethylsiloxane-methylhydrosiloxane copolymer, and trimethylsiloxy-terminated 2- (4-methylphenyl) -ethylmethylsiloxane-methylhydrosiloxane copo
• Linear polysiloxanes of the present invention are commercially available at different molecular weights, for example, from Gelest Inc. Morrisville, PA.
• the silicon-organic compound comprises a trisiloxysilane of the general formula (III)
• radicals R may be identical or different and are each selected from hydrogen, alkyl groups having 1 to 8 C atoms, cycloaliphatic groups having 1 to 8 C atoms, aryl groups having 6 to 12 C atoms, alkoxy groups having 1 to 8 C, -Atomen and aryloxy groups having 6 to 12 carbon atoms, with the proviso that each R on at least two silicon atoms is hydrogen and o and q each represents an integer between 0 and 1000 and p is an integer between 1 and 1000 is.
• Trisiloxanes of the present invention are commercially available at different molecular weights, for example, from Gelest Inc. Morrisville, PA.
• the organosilicon compound comprises a tetrasiloxysilane of the general formula (IV)
• radicals R may be identical or different and are each selected from hydrogen, alkyl groups having 1 to 8 C atoms, cycloaliphatic groups having 1 to 8 C atoms, aryl groups having 6 to 12 C atoms, alkoxy groups having 1 to 8 C, -Atomen and aryloxy groups having 6 to 12 carbon atoms, with the proviso that each R on at least two silicon atoms is hydrogen and r and t are each an integer between 0 and 1000 and s is an integer between 1 and 1000 is.
• tetrasiloxanes of the present invention are commercially available at different molecular weights from Gelest Inc. Morrisville, PA.
• the polymerizable composition according to the invention furthermore comprises as additional component at least one benzoxazine compound having at least two unsaturated carbon-carbon bonds which are reactive in the hydrosilylation with component A as component B.
• the benzoxazine compound of the polymerizable composition is preferably a monomer, oligomer or polymer having at least one benzoxazine group and at least two unsaturated carbon-carbon bonds reactive with hydrosilylation with component A.
• Preferred monomers may preferably comprise up to four benzoxazine groups wherein both single monomers and mixtures of two or more monomers may be used as the benzoxazine compound.
• reactive unsaturated carbon-carbon bonds are preferably carbon-carbon double bonds and / or carbon-carbon triple bonds to understand.
• terminal carbon-carbon double bonds are preferred.
• benzoxazine compounds having at least two unsaturated carbon-carbon bonds reactive in the hydrosilylation with component A are preferably selected from the group consisting of N-alkenyl and N-alkynyl-benzoxazine compounds.
• N-alkenyl or N-alkynyl-benzoxazine compounds are preferably understood to mean those compounds which comprise at least two benzoxazine groups and in which at least two N atoms of at least two oxazine rings each have an alkenyl or alkynyl radical wear.
• N-alkenyl or N-alkynyl-benzoxazine compounds are understood to mean those compounds which comprise at least two benzoxazine groups and in which each N atom of each oxazine ring bears an alkenyl or alkynyl radical.
• Suitable benzoxazine compounds having at least two unsaturated carbon-carbon bonds which are reactive in the hydrosilylation with component A are preferably described by formula (V),
• R 2 is selected from the group consisting of hydrogen and an alkyl group having 1 to 8 C Atoms
• R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent radical which renders the benzoxazine structure a corresponding naphthoxazine structure.
• benzoxazine compounds having at least two unsaturated carbon-carbon bonds which are reactive in the hydrosilylation with component A are furthermore compounds of the general formula (V.4),
• R 2 and R 4 each have the meanings given above.
• u is an integer selected from 1, 2 or third
• benzoxazine compounds having at least two unsaturated carbon-carbon bonds reactive with hydrosilylation with component A have only one benzoxazine group.
• benzoxazine compounds of the general formula (V.5) can be used, wherein R 2 and R 2 and u and u 'may be the same or different and R 2 and R 2 are independently selected from the group consisting of hydrogen and an alkyl group having 1 to 8 carbon atoms and u and u ' respectively are an integer between 1 and 10, in particular 1, 2 or 3.
• the molar ratio of component A to component B in the polymerizable composition of the present invention is in a range of 1:10 to 10: 1, preferably in a range of 1: 5 to 5: 1 and more preferably in a range of 1: 2 to 2: 1.
• component A and component B are in an equimolar ratio to each other in the polymerizable invention.
• the proportion of component A in the total amount of the polymerizable composition according to the invention is between 1 and 80% by weight, preferably between 20 and 60% by weight and in particular between 40 and 60% by weight.
• the proportion of component B in the total amount of the polymerizable composition according to the invention is between 1 and 80% by weight, preferably between 20 and 60% by weight and in particular between 40 and 60% by weight.
• the at least one silicon-organic compound (component A) comprises only two ⁇ Si-H groups reactive in the hydrosilylation and the at least one benzoxazine compound (component B) also only two in the hydrosilylation having component A reactive unsaturated carbon-carbon bonds.
• the at least one organosilicon compound (component A) comprises more than two ⁇ Si-H groups reactive in the hydrosilylation and / or the at least one benzoxazine compound (component B) more than two hydrosilylation with component A reactive carbon-carbon unsaturated bonds.
• Another object of the present invention is the polymerization product of the polymerizable composition according to the invention.
• the said polymerization product it is preferably the polyaddition product of the polyaddition reaction of components A and B.
• a polyaddition reaction is preferably to be understood as meaning a hydrosilylation reaction in which a new Si-carbon bond and a new carbon-hydrogen bond are formed by addition of a ⁇ Si-H group to an unsaturated carbon-carbon bond becomes.
• the said polymerization product is preferably characterized in that it has terminal unsaturated carbon-carbon bonds and / or terminal ⁇ Si-H groups as reactive end groups. These reactive end groups allow later postcrosslinking of the resulting polymerization product, whereby the final strength, such as the impact strength, the fatigue behavior and / or the compressive strength of the polymerization can be increased or improved depending on the application.
• a radical post-crosslinking can be achieved by reacting the resulting polymerization with crosslinking agents, wherein the crosslinking agents can be selected, for example, from the group consisting of polymerizable monomers, oligomers or polymers, provided that they have at least two polymerizable groups per molecule, such as divinylstyrene.
• crosslinking agents can be selected, for example, from the group consisting of polymerizable monomers, oligomers or polymers, provided that they have at least two polymerizable groups per molecule, such as divinylstyrene.
• Particularly suitable crosslinking agents are furthermore di-, tri-, tetra- and / or penta-acrylates, which can be selected, for example, from the group consisting of pentaerythritol tetraacrylate (PETTA), trimethylolpropane triacrylate (TMPTA), di-trimethylolpropane tetraacrylate (DiTMPTTA), dipentaerythritol pentaacrylate (DiPEPA) or Tripropylene glycol diacrylate (TPGDA) or any of their mixtures.
• PETTA pentaerythritol tetraacrylate
• TMPTA trimethylolpropane triacrylate
• DITMPTTA di-trimethylolpropane tetraacrylate
• DiPEPA dipentaerythritol pentaacrylate
• TPGDA Tripropylene glycol diacrylate
• postcrosslinking can also take place in the form of a hydrosilylation reaction in which said polymerization product is preferably reacted with at least one monomeric, oligomeric or polymer having at least two reactive in the hydrosilylation unsaturated carbon-carbon bonds.
• said polymerization product comprises a polymer of the general formula (VI)
• X is selected from the group consisting of alkylene, carbonyl, oxygen, sulfur, sulfoxide, sulfone and a direct, covalent bond
• the radicals R ' may be the same or different and are each selected from hydrogen, alkyl groups having 1 to 8 carbon atoms , cycloaliphatic groups having 1 to 8 C atoms, aryl groups having 6 to 12 C atoms, alkoxy groups having 1 to 8 C atoms, aryloxy groups having 6 to 12 C atoms
• R 2 is selected from the group consisting of hydrogen and a Alkyl groups having 1 to 8 carbon atoms
• R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl
• R 4 is a divalent radical which makes the benzoxazine structure a corresponding naphthoxazine structure
• Y is a is a direct, covalent bond or a divalent group containing at least one siloxane structural element i) of
• the polymerization reaction for producing the polymerization product of the present invention may be carried out under
• solvents are, for example, toluene, tetrahydrofuran and chloroform
• the reaction temperature is essentially dependent on the reactivity of the individual components and, if present, on the reactivity of the at least one hydrosilylation catalyst.
• Preferred reaction temperatures are preferably in a range from 0 0 C to 250 0 C, preferably from 20 to 200 0 C and in particular from 22 ° C to 100 0 C.
• the reaction is usually carried out under normal pressure, but can also be carried out at elevated pressure
• Press such as in the range of about 1.5 to 20 bar, or reduced pressures, e.g. 200 to 600 mbar.
• a reagent that retards the hydrosilylation catalyst catalyzed hydrosilylation reaction such as an amine, such as diethylenetriamine.
• the present invention also provides a process for the preparation of the polymerization product according to the invention comprising the steps: a) providing a polymerizable composition comprising a component A and component B and optionally at least one hydrosilylation catalyst, wherein component A is an organosilicon compound having at least two hydrosilylation reactive ⁇ Si-H groups and component B is at least one benzoxazine compound having at least two in the hydrosilylation with component A reactive unsaturated carbon-carbon bonds; b) Polymerization of the polymerizable composition to produce said polymerization product.
• Said polymerization product of the polymerizable composition of the present invention generally exhibits thermoplastic processability and can be cured by ring-opening the benzoxazine structure into materials having thermosetting properties. Therefore, the polymerization product can be used particularly advantageously in processes based on thermoplastic processability of the respective material, such as injection molding or extrusion processes.
• a further subject of the present invention is therefore the cured polymerization product of the polymerizable composition according to the invention.
• the curing of said polymerization product or the mixture of different polymerization products can be carried out by ring-opening the benzoxazine structure at elevated temperatures according to a self-initiating mechanism (thermal polymerization) or by adding cationic initiators.
• Suitable cationic initiators are, for example, Lewis acids or other cationic initiators, for example metal halides, organometallic reagents, such as metalloporphyrins, methyl tosylates, methyltriflates or trifluorosulphonic acids.
• basic reagents can be used to initiate the polymerization of the polymerizable benzoxazine compound or the mixture of various polymerizable benzoxazine compounds.
• Suitable basic reagents may for example be selected from imidazole or imidazole derivatives.
• the thermal curing of said polymerization product preferably takes place at temperatures of from 150 to 300 ° C., in particular at temperatures of from 160 to 220 ° C.
• the use of the abovementioned initiators and / or other reagents may also lower the curing temperature.
• the cured polymerization products are characterized in particular by their high thermal stability
• Another object of the present invention is an adhesive, sealant or coating composition comprising the polymerizable composition of the invention.
• the adhesives, sealants or coating compositions according to the invention may preferably also be formulated as two-component systems in which, in particular, the two components A and B and optionally the at least one hydrosilylation catalyst are mixed together only shortly before application. As already described, the components A and B react with one another to form a reaction product.
• the resulting reaction product can be cured with ring opening of the benzoxazine structure, preferably thermally cured, preferably thermosetting materials are obtained.
• a method of sealing or gluing which comprises the following steps: a) application of the polymerizable composition according to the invention between a substrate S1 and S2 and b) reaction of said composition to the corresponding polymerization product , wherein the substrates S1 and S2 are the same or different from each other.
• the said polymerization product is preferably the polyaddition product of components A and B.
• At least one of the substrates S1 or S2 is selected from the group consisting of glass, glass ceramic, concrete, mortar, brick, brick, ceramic, gypsum, natural stone, metal or metal alloys, wood, plastics and paints.
• the present invention is the use of the polymerizable composition according to the invention for preparing the reaction product of components A and B.
• the said reaction product is preferably the polyaddition product of the polyaddition reaction of components A and B.
• the polymerization product of the polymerizable composition may also be used as an additive in curable resin formulations.
• a further subject of the present invention is therefore a curable composition
• a curable composition comprising a) at least one curable resin component, and b) at least one polymerization product of the polymerizable composition according to the invention.
• a curable resin component is preferably to be understood as meaning a thermally curable resin component.
• the at least one resin component may preferably be selected from the group consisting of benzoxazine resins, epoxy resins, polyurethane resins, polyester resins, polyamide resins or phenolic resins or any of their mixtures.
• a benzoxazine resin is understood as meaning a resin composition which is formed on the basis of benzoxazine compounds and / or benzoxazine-containing compounds.
• Preferred benzoxazine compounds are monomers, oligomers or polymers comprising at least one benzoxazine group.
• Preferred monomers may preferably comprise up to four benzoxazine groups wherein both single monomers and mixtures of two or more monomers may be used as the benzoxazine compound.
• benzoxazine compounds comprising up to four benzoxazine groups.
• R 1 and R 2 are the same or are different and are each selected from the group consisting of hydrogen, alkyl, in particular methyl, ethyl, n-propyl, i-propyl, n-butyl or i-butyl, alkenyl, in particular allyl, and aryl and the substituents R 4 are the same or are different and are each selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or each R 4 is a divalent radical which makes the benzoxazine structure of a corresponding naphthoxazine structure.
• Preferred benzoxazine compounds of the formula (B-II) are, for example, benzoxazines of the formula (B-III) to (B-VI),
• R, R and R are as defined above.
• Preferred benzoxazine compounds are furthermore compounds of the general formula (B-VII),
• p 2 and Y is selected from the group consisting of biphenyl, diphenylmethane, diphenylisopropane, diphenylsulfide, diphenylsulfoxide, diphenylsulfone, diphenyl ketone and R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent The remainder is that makes from the benzoxazine structure a corresponding naphthoxazine structure.
• benzoxazine compounds are furthermore compounds of the general formula (B-VIII) to (BX),
• R 1 , R 2 and R 4 are as defined above and R 3 is defined as R 1 or R 2 .
• Suitable benzoxazine compounds in the context of the present invention are, for example, the following compounds:
• Suitable benzoxazine compounds for the purposes of the present invention are both monofunctional and multifunctional benzoxazine compounds.
• monofunctional benzoxazine compounds are meant those compounds which comprise only one benzoxazine group, whereas multifunctional benzoxazine compounds comprise more than one benzoxazine group and may preferably contain up to four benzoxazine groups.
• R is selected from the group consisting of alkyl, in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, alkenyl, in particular allyl, and aryl, each of said groups being optionally substituted and R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent radical which renders the benzoxazine structure a corresponding naphthoxazine structure.
• Preferred monofunctional benzoxazine compounds are described, for example, by the general formula (B-XX).
• Suitable monofunctional benzoxazine compounds in the context of the present invention are, for example, the following compounds (B-XXI) and (B) XXII)
• Benzoxazine compounds within the meaning of the present invention can be obtained via the above-described sources of supply or by the production methods described above.
• the curable composition according to the invention comprises at least one curable benzoxazine resin or a mixture of different curable benzoxazine resins in amounts of from 50 to 99% by weight, preferably from 70 to 95% by weight and more preferably from 80 to 90% by weight. %, in each case based on the total amount of the curable composition g.
• the curable composition comprises as curable resin component only one or more benzoxazine compounds.
• Both the polymerizable benzoxazine compounds of the curable composition and the polymerizable benzoxazine compounds of the polymerizable composition having at least two unsaturated carbon-carbon bonds reactive with hydrosilylation with component A may also comprise partially opened ring structures, wherein the opened ring structure is preferably defined by the formal Breakage of the covalent bond between A and A ' or between B and B ' is obtained (see formula BO).
• the ring-open structures also apply as benzoxazine compounds, in particular as ring-open benzoxazine compounds.
• Benzoxazine resins are particularly preferred in the context of the present invention as the curable resin component of the curable composition.
• an "epoxy resin” is understood to mean a resin composition which is formed on the basis of epoxide compounds or epoxide-containing compounds
• the epoxide compounds or epoxide-containing compounds of the epoxy resin system of the curable composition may be both oligomeric and polymeric
• suitable epoxy resins in the context of the present invention are preferably selected from bisphenol A type epoxy resins, bisphenol S type epoxy resins, epoxy resins from Bisphenol F type, phenolic novolac type epoxy resins, cresol novolac type epoxy resins, epoxidized products of numerous dicyclopentadiene-modified phenolic resins, obtainable by reaction of dicyclopentadiene with numerous phenols, epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol, aromatic epoxy resins such as epoxy resins with naphthalene skeleton and epoxy resins with fluorene skeleton, ali
• the epoxy resins include, for example, the reaction product of bisphenol A and epichlorohydrin, the reaction product of phenol and formaldehyde (novolak resins) and epichlorohydrin, glycidyl esters, and the reaction product of epichlorohydrin and p-aminophenol.
• epoxy resins that are commercially available include, in particular, octadecylene oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ethers of bisphenol A (eg, those sold under the trade designations "Epon 828”, “Epon 825”, “Epon 1004" and “Epon 1010" from Hexion Specialty Chemicals Inc., "DER-331”, “DER-332”, “DER-334”, "DER-732” and “DER-736” of the Dow
• novolac resins include Epi-Rez TM 5132 from Hexion Specialty Chemicals Inc., ESCN-001 from Sumitomo Chemical, Quatrex 5010 from Dow Chemical Co., RE 305S from Nippon Kayaku, Epiclon TM N673 from DaiNipon Ink Chemistry or Epicote TM 152 from Hexion Specialty Chemicals Inc ..
• the curable composition according to the invention comprises at least one curable epoxy resin or a mixture of different curable epoxy resins in amounts of from 50 to 99% by weight, preferably from 70 to 95% by weight and more preferably from 80 to 90% by weight. %, in each case based on the total amount of the curable composition.
• the curable composition may comprise a mixture of different curable resin components.
• Particularly preferred mixtures are, for example, mixtures of benzoxazine and epoxy resins and / or mixtures of benzoxazine, epoxy and phenolic resins.
• the proportion of all resin components in the total amount of the curable composition is between 50 and 99% by weight, preferably between 70 and 95% by weight. % and most preferably between 80 and 90% by weight.
• the curable composition comprises at least one polymerization product of the polymerizable composition according to the invention in amounts of from 0.001 to 20% by weight, preferably from 1 to 15% by weight and very preferably from 5 to 10% by weight, in each case based on the total amount of the curable composition.
• the curable compositions of the invention may contain additives such as, preferably, dyes and / or fillers, such as ground or precipitated chalk, carbon black, calcium magnesium carbonates, barite and, in particular, aluminum-magnesium-calcium silicate-type silicatic fillers, e.g. B. wollastonite, chlorite.
• additives such as, preferably, dyes and / or fillers, such as ground or precipitated chalk, carbon black, calcium magnesium carbonates, barite and, in particular, aluminum-magnesium-calcium silicate-type silicatic fillers, e.g. B. wollastonite, chlorite.
• the curable compositions of the invention include other additives, such as adjuvants and additives such.
• plasticizers reactive diluents, toughening agents, rheology aids, wetting agents, aging inhibitors, stabilizers and / or color pigments.
• the curable compositions of the invention are free of plasticizers.
• Preferred curable compositions of the invention comprise, based on the total amount of the curable composition: i) 1 to 20% by weight of at least one polymerization product of the polymerizable composition of the invention, ii) 50 to 99% by weight of at least one curable resin component, for example selected from
• the curing of the curable composition can be carried out, for example, at elevated temperatures by a self-initiating mechanism (thermal polymerization) or by the addition of cationic initiators.
• Suitable cationic initiators are, for example, Lewis acids or other cationic initiators, for example metal halides, organometallic reagents, such as metalloporphyrins, methyl tosylates, methyltriflates or trifluorosulphonic acids.
• basic reagents can be used to initiate the polymerization of the polymerizable benzoxazine compound or the mixture of various polymerizable benzoxazine compounds.
• Suitable basic reagents may for example be selected from imidazole or imidazole derivatives.
• the curing of the curable composition according to the invention in particular a curable composition according to the invention comprising benzoxazine resins as a curable resin component, at temperatures of 150 to 300 0 C, in particular at temperatures of 160 to 220 0 C.
• the polymerization temperature may also be lower.
• Curing of the curable composition according to the invention to the cured product takes place in a curable composition comprising benzoxazine resins as a curable resin component, preferably with ring opening, in particular with thermally induced ring opening of the benzoxazine system.
• Another object of the present invention is the cured product of the curable composition of the invention.
• composition an effective toughening of the cured product can be achieved, said product is further characterized by its low tendency to absorb water.
• K1c Critical Stress Intensity Factor
• G1c Critical Energy Release Rate
• the cured product of the curable composition of the present invention encapsulates a layer or bundle of fibers, the fibers being treated with the curable composition of the present invention before curing.
• Another object of the present invention is a process for producing the cured product of the curable composition of the present invention wherein the cured composition trans-beds a layer or bundle of fibers.
• the method according to the invention comprises the steps: a) providing at least one layer or at least one bundle of fibers; b) providing a curable composition of the invention; c) producing a composite system by treating at least one layer or at least one bundle of fibers with the curable composition; d) Optionally, removing an excess amount of the curable composition from the composite system, wherein the cured product is obtained by exposing the composite system to elevated temperature and pressure.
• the fibers mentioned are preferably selected from glass fibers, carbon fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers. Two or more of these fibers may be used as a mixture. To produce a product of lower weight and higher durability, the use of carbon fibers is particularly preferred.
• the layer or bundle of fibers are not defined in the context of the present invention to a specific shape or arrangement, and so z.
• long fibers laid in parallel in one direction tows, fabrics, mats, knit fabrics, borders are used.
• the composite systems in the form of fiber-reinforced composite materials, in particular in the form of prepregs or towpregs, which are produced according to the above-mentioned method can be used, for example, in aircraft construction or in the automotive industry because of their low weight and high structural strength.
• the following examples serve to illustrate the invention.
• Table 1 shows the yields of the individual polymerization products as a function of the reaction time
• Table 1 Yield as a function of the reaction time
• TMS implemented as an internal standard.
• FIG. 1 shows FT-IR absorption spectra at different reaction times.
• FIG. 1 (a) shows the output spectrum of the pure benzoxazine compound (B-ala), while FIG. 1 (b) or FIG. 1 (c) document the progress of the reaction and FIG. 1 (d) shows the FT-IR spectrum of the finished polymerization product represents.
• FIG. 2 shows 1 H-NMR spectra at different reaction times.
• FIG. 2 (1) represents the output spectrum of the pure benzoxazine compound (B-ala), while FIG. 2 (2) and FIG. 2 (3) document the progress of the reaction, and FIG. 2 (4) shows the 1 H-NMR spectrum of FIG finished polymerization product represents.
• Figure 1 (a) shows the characteristic absorption band of the benzoxazine group at 1226 cm “1, 1321 cm” 1 and 921 and 1496 cm '1.
• the absorption band of the allyl group is at 3076 cm “1 and 1642 cm' 1.
• FIG. 2 (1) shows characteristic multiplets for the allyl group at 5.2-5.3 ppm and 5.6-5.9 ppm, respectively.
• the -CH 2 - signals of the allyl group are visible as doublets at 3.4 ppm.
• Figure 2 (4) demonstrates the substantial disappearance of the allyl double bond with simultaneous detection of characteristic Si-alkyl proton signals between 0 and 2.7 ppm.
• FIG. 1 and FIG. 2 illustrate that the respective polymerization products are formed in a hydrosilylation reaction with the reaction of the benzoxazine allyl group.
• the characteristic signals of the allyl group which can furthermore be detected in the polymerization product show that the resulting polymerization products have terminal allyl groups.
• the polymerization products (polymer 1, polymer 2, polymer 3) of the reaction described can furthermore be thermally cured by ring-opening the benzoxazine structure.
• thermo-polymer 1, therm-polymer 2 and therm-polymer 3 have a high thermal stability.
• the thermal curing of said polymerization is preferably carried out in a closed form within 1 to 6 h in a convection oven at temperatures of 150 to 300 0 C, in particular at temperatures of 160 to 220 0 C. Subsequently, the polymerization of the form are dissolved and on Room temperature cooled.
• Table 2 shows the curing temperatures determined by DSC (Differential Scanning Calorimetry)
• T Onset is the release temperature of the thermal cure, which is obtained by the intersection of the tangent of the point of inflection of a respective peak with the temperature axis.
• T max is the temperature at which a peak maximum is observed in the DSC diagram for the respective substance.
• thermal stability of the thermal curing products therm-polymer 1, therm-polymer 2 and therm-polymer 3 was determined by means of TGA (thermogravimetric analysis). It was found that the mentioned curing products have an increased thermal stability compared to the thermal curing product thermo- (B-ala) of the benzoxazine compound (B-ala).
• T 5% is the temperature at which the total weight of the respective sample has decreased by 5% compared to the total starting weight of the respective sample.
• T 10% is the temperature at which the total weight of the respective sample has decreased by 10% compared to the total starting weight of the respective sample.
• Y c is the so-called char yield, ie the proportion of carbonized residue (charring at 800 ° C.) of a particular sample in the original total amount of the sample.
• Thermogravimetric analysis was performed under nitrogen flow with a Perkin-Elmer Diamond TA / TGA at a heating rate of 10 ° C / min.

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