Curable organosiloxane-modified reaction resins

Abstract

The invention relates to curable compositions made of reaction resins, comprising polymerizable functional cyanate ester groups and linear poly(imide diorganosiloxane) copolymers, to a method for producing same, and to cured materials and composites which can be obtained therefrom and have a high fracture resistance.

Description

[0001] Curable organosiloxane-modified reactive resins

[0002] The invention relates to curable compositions of reaction resins with polymerizable functional cyanate ester groups and linear poly(imide-diorganosiloxane) copolymers, processes for their preparation, and cured materials and composites obtainable therefrom which have high fracture toughness.

[0003] Due to the constantly increasing demands on materials for high-temperature-resistant composite systems, fast data communications, and new electrical and hydrogen storage technologies, the use of high-performance polymers that combine advantages such as thermal resilience, high mechanical strength, a high glass transition temperature, and chemical resistance with low weight compared to metallic materials is becoming increasingly important. Epoxy (EP) resins and epoxy resin systems are used in a wide variety of applications and have established themselves as one of the most frequently used high-performance polymers in composite materials, for example, in combination with glass, carbon (CFRP), or aramid fibers. In addition, organic high-performance reactive resins such as phenol-formaldehyde resins (PF), cyanate ester (CE), bismaleimide (BMI), polyimide (PI), benzoxazine, and phthalonitrile resins have also gained ground.Reactive resin mixtures, such as bis(benzocyclobutenimide) / bismaleimide, cyanate ester / epoxide, or bismaleimide / cyanate ester (BT resins), have gained increasing importance as matrix resins in fiber composites in industry, automotive engineering, and aerospace in recent years. Compared to epoxy resins, polymer matrix resins based on CE, BMI, or PI, for example, combine high mechanical strength with high glass transition temperatures, high thermal resilience, and long-term stability, which greatly expands the application possibilities of these thermosets, especially in the high-temperature range. Cyanate ester resins, in particular, are characterized by low water absorption and a low dielectric constant in the cured state and by good processability in the uncured state.In terms of toxicological properties as well as flame and smoke characteristics, CE resins represent the best alternative compared to most other resin systems. This unique combination of properties predestines the use of CE resins for a wide range of applications.

[0004] However, thermoset systems based on CE resins also have disadvantages. During thermal curing, cyanate ester resins crosslink through trimerization of the cyanate ester (NsC-O-) groups to form thermally stable cyanurate rings, resulting in polycyanurate networks with a high crosslink density. As a result of the highly crosslinked state, the cured thermosets are characterized by high mechanical stability; however, the networks are brittle, meaning they exhibit low fracture and impact strength.

[0005] It would therefore be desirable to provide suitable high-temperature-stable modifiers for these already commercially available CE reactive resins, which contribute to a higher fracture toughness of the cured thermoset networks so that they can be used commercially as matrix resins in demanding applications, for example, in automotive engineering, the aerospace industry, as well as for hydrogen storage and transport. The present invention is therefore based on the object of modifying organic cyanate ester resins so that the thermosets cured after the molding and curing process have a higher fracture toughness (K lc ) and consequently have improved ageing resistance, whereby the advantageous properties inherent in thermosets, such as thermo-oxidative resistance, high glass transition temperature and high mechanical strength, are largely retained even in thermosets modified in this way.

[0006] It is known that the fracture toughness of cyanate ester resins can be improved by a second organic or inorganic phase; thermoplastics, elastomers, core / shell particles, and block copolymers have proven to be effective modifiers.

[0007] A group of authors demonstrates in RSC Adv., 2016, 6, 49436-49447 (doi.org / 10.1039 / C6RA08229G) the possibility of improving the impact strength of cyanate ester resins by adding a block copolymer with terminal amine groups as a modifier. The polymer backbone of the block copolymer is composed of "rod-shaped" polyimide blocks and "spiral-shaped" poly(dimethylsiloxane) blocks with an average chain length of approximately 15 siloxane units. With increasing proportions of flexible poly(dimethylsiloxane) blocks, the block copolymer modifiers in the cured cyanate resin matrix tend to form larger spherical and additionally "worm-like" micelles; both of these, according to the authors, contribute to an improvement in impact strength properties.However, the disclosed block copolymers also have several disadvantages: Firstly, aromatic diamines are used for the synthesis of the polyimide blocks, which are sometimes classified as CMR substances and thus pose toxicological concerns. A further disadvantage is that the terminal amine groups have a strong accelerating effect on the crosslinking reaction of the cyanate ester groups, so that the curing of cyanate ester resin mixtures becomes more uncontrollable with increasing modifier content, and the storage stability of the mixtures decreases accordingly. Furthermore, the amine groups contribute to higher water absorption and increased polycyanurate network degradation through aminolysis, which manifests itself in a higher hydrolysis rate of the cured resin mixtures.A further limitation is that with increasing poly(dimethylsiloxane) block content, which has a positive effect on toughness, the miscibility with cyanate resins decreases, so that the modifier content in the cyanate resin and thus also the possibility of toughening is limited.

[0008] The above-mentioned problems can be overcome by copolymerizing an aromatic dianhydride with a short-chain siloxane with terminal amine groups and an aromatic monoanhydride or an aromatic monoamine. Surprisingly, it has been found that these polyamide-siloxane copolymers, which do not have a block copolymer structure, are capable of significantly improving the fracture toughness of cured cyanate ester thermosets.

[0009] The invention relates to curable compositions comprising

[0010] (A) at least one organic compound (A) free of siloxy (=Si-O-) units and having at least two cyanate ester (-OC^N) groups (also referred to herein as "cyanate ester resin"), wherein the compound (A) is preferably substituted and / or contains at least one heteroatom, and (B) at least one linear compound free of cyanate ester groups,

[0011] Poly(imide-diorganosiloxane) copolymer of formula (I) wherein

[0012] R is the same or different and represents a methyl, vinyl or phenyl radical,

[0013] R 1 , R 2 , R 3 and R 4 are the same or different and represent a monovalent, optionally substituted hydrocarbon radical,

[0014] R 5is the same or different and is a monovalent, optionally substituted, hydrocarbon radical, Y is the same or different and is a methylene (-CH2-)-, ethylene (- (CH2-)2) _ or propylene (- (CH2-) 3) group, and

[0015] Z is the same or different and represents a covalent bond or a divalent radical selected from the group consisting of -O=O-, -CR 6 =CR 6 -, -CR 6 2-, -0-, -S-, -S (=O)-, -S(=O)2-, -

[0016] C(=O)-, -00 (=O)O-, -C(=O)0-, -O (=O) O- (C6H4) -OC (=O) -, -O- (C6H4)-CR 6 2-(C6H4)-0-, -0-(C6H4)-CR 6 2-(C6H4)-CR 6 2-(C6H4)-0-; or divalent cycloalkanediyl radicals, such as

[0017] Tricyclo [5.2.1.0 2 ' 6 ]decanediyl and bicyclo[2.2.1]heptanediyl, wherein

[0018] R 6is the same or different and is hydrogen atom, halogen atom or a monovalent, optionally substituted, optionally interrupted by at least one heteroatom, hydrocarbon radical having 1 to 30 carbon atoms, which may optionally be substituted either by a substituent or by the other radical R 6 is linked to a cyclic unit, means that m is 1 to 15, preferably 1 to 10, particularly preferably 1 to 5, in particular 1, and n is 1 to 20, preferably 1 to 15, particularly preferably 1 to 10, in particular 1 to 5.

[0019] Examples of remainder R 6 are monovalent residues, such as the methyl, ethyl, trifluoromethyl, phenyl and fluorenyl residues; ring structures consisting of two residues R 6, such as the cyclohexane-1,1-diyl, cyclohexene-1,2-diyl, 9H-fluorene-9,9-diyl, N-phenyl-1-isoindolinone-3,3-diyl, 1(3H)-isobenzofuranone-3,3-diyl, anthracene-9(10H)-one-10,10-diyl, 9,10-dihydroanthracene-9,9-diyl and the 3,3,5-trimethylcyclohexane-1,1-diyl residue.

[0020] The heteroatoms can be selected from the group consisting of O, S, N, P and Si, preferably O and S.

[0021] In the present invention, the term "component (A)" stands for the entirety of the at least one compound (A) and the term "component (B)" stands for the entirety of the at least one compound (B). In the present invention, the term "1-propenyl" stands for the radical "-CH=CH-CH3", "2-propenyl" or "allyl" stands for the radical "-CH2-CH=CH2", and the term "propenyl" stands for the 1- or 2-propenyl radical.

[0022] To limit the number of pages describing the present invention, only the preferred embodiments for the individual features are listed. However, the skilled reader should understand this type of disclosure to explicitly include any combination of different levels of preference—that is, any combination both within a single compound / feature and between different compounds / features.

[0023] Cyanate ester resin (A)

[0024] These are organic compounds free of siloxy (=Si-O-) units and containing at least two cyanate ester (-OC^N) groups per molecule. Compound (A) may be substituted and / or contain at least one heteroatom.

[0025] Preferably, compound (A) is an aromatic hydrocarbon compound which is optionally substituted and / or contains at least one heteroatom, wherein preferably per molecule of compound (A) the at least two cyanate ester (-OC^N) groups are bonded to aromatic carbon atoms.

[0026] Particularly preferably, at least two optionally substituted and / or at least one heteroatom-containing aromatic hydrocarbon radicals, each with a cyanate ester group bonded to an aromatic carbon atom, are present per molecule of the compound (A); in particular, the optionally substituted and / or at least one heteroatom-containing aromatic hydrocarbon radicals, each with a cyanate ester group bonded to an aromatic carbon atom, are linked via a covalent bond or at least one bridging unit selected from the group consisting of -CR 7 2-

[0027] , -CR 7=CR 7 -, -C(=CR 7 2)-, -O-, -S-, -N=N-, -CR 7 =N-, -C (=O)- , -C(=O)0-, -OG (=O)0-, -S(=O)-, -S(=O)2-, 0=P(0-)3, (=O), -SiR 7 2-, a divalent aromatic

[0028] hydrocarbon radical, such as phenylene, toluene, biphenylene and naphthylene; or a divalent cycloalkanediyl radical, such as tricyclo [5.2.1.0 2 ' 6 ]decanediyl and bicyclo[2.2.1]heptanediyl.

[0029] For rest R 7 These are each independently the values ​​for R 6 mentioned residues.

[0030] Examples of the compound (A) according to the invention are di- and poly-cyanate esters of monoaromatic hydrocarbons, such as phenylene-1,2-dicyanate, phenylene-1,3-dicyanate (GAS 1129-88-0), phenylene-1,4-dicyanate (GAS 1129-80-2), 2,4,5-trifluorophenylene-1,3-dicyanate, 1,3,5-tricyanatobenzene, methyl (2,4-dicyanatophenyl) ketone and 2,7-dicyano-naphthalene; Cyanate esters of bisphenols ("bisphenol dicyanate"), such as 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)propane (GAS 1156-51-0, bisphenol A cyanate ester; trade names: AroCy® BIO, PRIMASET® BADCy orCYTESTER® TA), 2,2-Bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane (GAS 32728-27-1, Bisphenol AF-Cyanatester), 2,2-Bis(3-methyl-4-cyanatophenyl)propane (Bisphenol C-Cyanatester), l,l-Bis(4-cyanatophenyl)ethane (GAS 47073-92-7, Bisphenol E-Cyanatester; Trade names: AroCy® L-10, PRIMASET® LECy, CYTESTER® P201), 1,1-Bis(4-cyanatophenyl)-1-phenylethane (Bisphenol AP-Cyanatester), Bis(4-cyanatophenyl)methane (Bisphenol F-Cyanatester), Bis(4-cyanato-3,5-dimethylphenyl)methane (CAS 101657-77-6, Tetramethyl-Bisphenol F-Cyanatester), 1,3-Bis(2-(4-cyanatophenyl)propan-2-yl)benzol (CAS 127667-44-1, Bisphenol.

[0031] M-cyanate esters; trade names: AroCy® XU 366), bis(4-cyanatophenyl)thioether), bis(4-cyanatophenyl)ether, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-cyanatophenyl)cyclohexane, 9,9-bis(4-cyanatophenyl)fluorene (bisphenol FL cyanate ester), bis(4-cyanatophenyl)sulfone (CAS 2918-28-7;Bisphenol S cyanate ester), bis(4-cyanatophenyl)ketone, bis(4-(4-cyanatophenoxy)phenyl)ketone, bis(4-(4-cyanatophenoxy)phenyl)sulfone, bis(4-cyanatophenoxy)sulfoxide, bis(4-(4-cyanatophenoxy)phenyl)(phenyl)phosphine oxide, bis(4-cyanatophenyl)(methyl)phosphine oxide, 1,l-dibromo-2,2-bis(4-cyanatophenyl)ethylene, 1,l-dichloro-2,2-bis(4-cyanatophenyl)ethylene, 3,3-bis(4-cyanatophenyl)-N-phenylphthalimide, 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone (CAS 32728-31-7), 3,3-Bis(4-cyanatophenyl)-2-benzofuran-l-one, 10,10-bis(4-cyanatophenyl)anthracen-9(10H)-one, l-ethyl-2-methyl-3-(4-cyanatophenyl)-5-cyanatoindan, 1,l-dimethyl-3-methyl-3-(4-cyanatophenyl)cyanatoindan, bis(2-cyanato-3-methoxy-5-methylphenyl)methane and 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane (bisphenol Z cyanate ester);Cyanate esters of propenyl-substituted bisphenols, such as 2,2-bis(3-(2-propenyl)-4-cyanatophenyl)propane, bis{[4-[(3-allyl-4-cyanatophenyl)isopropylidene]phenoxy]phenyl}sulfone and bis{4-[4-cyanato-3-(2-propenyl)phenoxy]phenyl}sulfone; cyanate esters of biphenyl, such as 4,4'-dicyanatobiphenyl (CAS 1219-14-3), 2,4'-dicyanatobiphenyl and 2,2'-dicyanatobiphenyl; phenol-dicyclopentadiene cyanate ester resins, such as dicyclopentadienyl bis(phenol cyanate ester) (CAS 135507-71-0; trade name: AroCy® XU-71787.02); Cyanate esters of phenol-formaldehyde resins, which are produced by acid- or alkali-catalyzed condensation of phenols, naphthols, naphthalenediols, xylenols or cresols with formaldehyde, such as resole cyanate esters or novolak cyanate esters (e.g. CAS 87397-54-4, CAS 153191-90-3, CAS 268734-03-8, CAS 30944-92-4 and CAS 173452-35-2; examples of trade names: Primaset® PT-15, PT-30, PT-60, PT-90 and CT-90, as well as AroCy® XU-371);Cyanate esters of fluoroalkanediols, such as 1,8-dicyano-perfluorooctane; cyanate esters of naturally occurring polyphenols, such as trans-3,5,4'-tricyanostilbene; cyanate esters of bisphenol silanes, such as dimethylbis(4-cyanatophenyl)silane; 1,1,1-tris(4-cyanatophenyl)ethane (CAS 113151-22-7), 1,2,3-tris(4-cyanatophenyl)propane; and polymer resins with terminal cyanate ester groups, which are composed of at least two identical or different repeating units, wherein the backbone of each repeating unit contains at least one divalent aromatic hydrocarbon radical, such as phenylene, biphenylene and naphthylene, or 9H-fluorene-9,9-diyl, and at least one bridging unit selected from the group consisting of -CR; 8 2~, -CR 8 =CR 8 -, -C(=CR 8 2)-, -O-, -S-, -N=N-, -CR 8 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, =P (=O), -SiR 82~ or a divalent cycloalkanediyl radical, such as tricyclo[5.2.1.0® 6 ]decanediyl and bicyclo [2.2.1]heptanediyl. Examples of repeating units in cyanate ester polymer resins are arylene ethers, arylene ether sulfones, or arylene ether ketones.

[0032] For rest R 8 These are each independently the values ​​for R 6 mentioned residues.

[0033] Preferably, compound (A) is 2,2-bis(4-cyanatophenyl)propane, 1,1-bis(4-cyanatophenyl)ethane, bis(4-cyanatophenyl)methane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, 2,2-bis(3-(2-propenyl)-4-cyanatophenyl)propane, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, phenol-dicyclopentadiene cyanate ester resins and cyanate esters of phenol-formaldehyde resins. Component (A) is particularly preferably 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, 1,1-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, phenol-dicyclopentadiene cyanate ester resins, or cyanate esters of phenol-formaldehyde resins. Compound (A) is particularly preferably 1,1-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, cresol, or phenol novolak cyanate esters.

[0034] The compositions according to the invention may contain only one cyanate ester resin (A) or a mixture of different cyanate ester resins (A) or may contain prepolymers of one cyanate ester resin (A) or prepolymers of different cyanate ester resins (A) as well as mixtures of prepolymeric cyanate ester resins or mixtures of prepolymeric cyanate ester resins with one or more cyanate ester resins (A).

[0035] An example of a prepolymer made from a cyanate ester resin (A) is bisphenol A dicyanate homopolymer (CAS 25722-66-1, examples of trade names: Primaset® BA-200).

[0036] Connection (B)

[0037] The at least one compound (B) according to the invention is a linear poly(imide-diorganosiloxane) copolymer (hereinafter also referred to as "copolymer") of the general formulas (I) and / or (II) as described above. Compounds (B) can be solid or liquid at 23°C and 1013 hPa, with the poly(bisphenol-diorganosiloxane) copolymers (B) preferably being solid at 23°C and 1013 hPa.

[0038] The at least one compound (B) according to the invention has a weight-average molar mass Mw of preferably 700 to 20,000 g / mol, preferably 1,000 g / mol to 15,000 g / mol, particularly preferably 1,000 g / mol to 10,000 g / mol, in particular 1,000 g / mol to 8,000 g / mol.

[0039] The at least one compound (B) according to the invention has a number-average molar mass Mn of preferably 500 to 10,000 g / mol, preferably 500 g / mol to 6,000 g / mol, particularly preferably 1,000 g / mol to 5,000 g / mol, in particular 1,000 g / mol to 3,500 g / mol.

[0040] In the context of the present invention, the number-average molar mass Mn and the weight-average molar mass Mw, each in the unit g / mol, rounded to the nearest whole number of ten according to DIN 1333:1992-02 Section 4, are determined by size exclusion chromatography (SEC / GPC) according to DIN 55672-1 / ISO 160414-1 and ISO 160414-3 by calibrating a column set based on polystyrene-co-divinylbenzene as the stationary phase, consisting of three columns with different pore size distributions in the order of 10,000 Å, 500 Å, and 100 Å with an exclusion size of greater than 450,000 g / mol against polystyrene standards. The analysis is carried out using THF as the eluent. The analyses are carried out at a column temperature of 45±1°C and using a refractive index detector.

[0041] Examples of monovalent, optionally substituted hydrocarbon radicals R 1 , R 2 , R 3 and R 4are alkyl radicals, such as the methyl, ethyl, propyl, butyl, pentyl and octyl radicals; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; unsaturated hydrocarbon radicals, such as the vinyl, propenyl, cyclohexenyl, 2-(3-cyclohexenyl)ethyl, bicyclo[2.2.1]hepten-2-yl, dicyclopentenyl, 4-vinylcyclohexyl, norbornenyl, vinylphenyl and propenylphenyl radicals; Aryl radicals such as phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthryl, methoxyphenyl, phenyloxyphenyl, phenylmercaptophenyl, phenylsulfonylphenyl, phenoxycarbonylphenyl, benzoylphenyl, benzoyloxyphenyl, phenyloxycarbonyloxyphenyl and phenanthryl radicals; alkaryl radicals such as tolyl, xylyl, tert-butylphenyl and ethylphenyl radicals; aralkyl radicals such as benzyl, cumyl, α- and β-phenylethyl radicals; and heterocyclic aromatic hydrocarbon radicals such as pyridyl, quinolinyl and furyl radicals.

[0042] Although not expressed in formula (I), radicals R 1 and R 2 and / or residues R 3 and R 4 form one or more ring structures such as in succinimide, 3-allyl-succinimide, cyclohexane-1,2-dicarboximide, 4-cyclohexene-1,2-dicarboximide, 1,2,3,6-tetrahydrophthalimide, 3,4,5,6-tetrahydrophthalimide, phthalimide, 4-phenoxy-phthalimide, 4-benzoyl-phthalimide, 4-phenylsulfonyl-phthalimide, maleimide, bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, bicyclo[2.2.1]heptane-2,3-dicarboximide, 3,6-epoxy-1,2,3,6-tetrahydrophthalimide, bicyclo[2.2.2]oct-5-ene-2,3-dicarboximide, tetrafluorosuccinimide, tetrafluorophthalimide, 3- Phenyl succinimide and naphthalene-2,3-dicarboximide.

[0043] Preferably, residues R 1 and R 2 and / or residues R 3 and R 4Ring structures such as in phthalimide, succinimide, and bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, particularly preferably as in phthalimide. Examples of monovalent, optionally substituted hydrocarbon radicals R 5 are those for R 1 , R 2 , R 3 and R 4 mentioned residues as well as carbonyl-functional residues, such as the benzoyl and phenoxycarbonyl residue.

[0044] Preferably, the residue R 5 around the phenyl, benzylphenyl, cumylphenyl, tert-butylphenyl, phenoxyphenyl, phenylmercaptophenyl, phenylsulfonylphenyl or benzoylphenyl radical; particularly preferably the phenyl, benzoylphenyl or benzylphenyl radical.

[0045] Preferably, the residue Z is a covalent bond, the residue -O-, -C(=O)-, -C(CF3)2-, -S(=O)2- or -O-(C6H4)-C(CH3)2-(C6H4)-0-.

[0046] Examples of the copolymers (B) used according to the invention are with Mw = 4860 g / mol, Mn = 2350 g / mol; with Mw = 7730 g / mol, Mn = 3410 g / mol; with Mw = 4790 g / mol, Mn = 1950 g / mol; and with Mw = 5170 g / mol, Mn = 2080 g / mol; where x is preferably 3 to 10.

[0047] The compounds (B) according to the invention are preferably those of formula (I). Compounds (B) of formula (I) particularly preferably contain no aliphatic carbon-carbon multiple bonds and no aromatic heteroatoms.

[0048] The compounds (B) used according to the invention can be prepared by processes commonly used in chemistry. Compounds (B) are preferably prepared by first reacting the bisanhydrides and optionally monoanhydrides with the aminoalkyl-functionalized poly(diorgano)siloxanes and optionally the aromatic monoamines in an inert solvent, such as tetrahydrofuran, to form amide functional groups. The ring closure reaction is then carried out by heating the mixture to 150°C to 220°C, preferably 170°C to 190°C, in a vacuum, with elimination of water to form the functional imide groups. The degree of polymerization depends on the ratio of the reagents bisanhydride and aminoalkyl-terminated poly(diorgano)siloxane, as well as monoanhydride and aromatic monoamine.

[0049] For the preparation of compound (B), only one bisanhydride or a mixture of different bisanhydrides can be reacted with one or more different aminoalkyl-terminated poly(diorgano)siloxane(s) and either one or more different monoanhydrides or one or more different aromatic amines. Compound (B) is preferably prepared from a bisanhydride, an aminoalkyl-terminated poly(diorgano)siloxane, and a monoanhydride or an aromatic amine; particularly preferably, compound (B) is prepared from a monoanhydride, a bisanhydride, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane.

[0050] The composition according to the invention may only contain one compound

[0051] (B) or a mixture of different compounds (B), preferably only one compound (B).

[0052] The compositions according to the invention contain the at least one compound (B) in amounts of preferably 1 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, in particular 5 to 35 parts by weight, in each case based on 100 parts by weight of component (A).

[0053] In addition to the at least one compound (A) and (B), the compositions according to the invention may contain further substances which are different from components (A) and (B), such as modifier (C), reactive resin (D), filler (E), curing accelerator (F), solvent (G) and auxiliaries (H).

[0054] In a preferred embodiment, the composition according to the invention further comprises the following compounds:

[0055] (C) at least one modifier (C);

[0056] (D) at least one reactive resin (D);

[0057] (E) at least one filler (E);

[0058] (F) at least one curing accelerator (F);

[0059] (G) at least one solvent (G); and / or

[0060] (H) at least one auxiliary substance (H), wherein the at least one modifier (C), the at least one reactive resin (D), the at least one filler (E), the at least one curing accelerator (F), the at least one solvent (G), and / or the at least one auxiliary substance (H) are different from the at least one compounds (A) and (B).

[0061] The composition according to the invention can

[0062] • comprise only one compound (C) or a mixture of different compounds (C), preferably only one compound (C);

[0063] • comprise only one compound (D) or a mixture of different compounds (D), preferably only one compound (D);

[0064] • comprise only one compound (E) or a mixture of different compounds (E), preferably only one compound (E);

[0065] • comprise only one compound (F) or a mixture of different compounds (F), preferably only one compound (F);

[0066] • comprise only one compound (G) or a mixture of different compounds (G), preferably only one compound (G); and / or

[0067] • comprise only one compound (H) or a mixture of different compounds (H), preferably only one compound (H).

[0068] In the present invention, the term "component (C)" stands for the totality of the at least one compound (C), the term "component (D)" stands for the totality of the at least one compound (D), the term "component (E)" stands for the totality of the at least one compound (E), the term "component (F)" stands for the totality of the at least one compound (F), the term "component

[0069] (G) " for the totality of the at least one compound (G) and the designation "component (H) " for the totality of the at least one compound (H).

[0070] Connection (C)

[0071] The optional at least one modifier (C) is preferably

[0072] Organosilicon compounds (Gl) containing units of the formula

[0073] R 9 h (OR 10 )iSiO (4 -hi) / 2 (III), where

[0074] R 9is the same or different and represents a hydrogen atom or a monovalent, SiC-bonded, optionally substituted, hydrocarbon radical which may be interrupted by at least one heteroatom,

[0075] R 10 is the same or different and is a hydrogen atom or a monovalent, aliphatic hydrocarbon radical having 1 to 12 carbon atoms, h is 0, 1, 2 or 3, preferably 1, 2 or 3, i is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1, in particular 0, with the proviso that in formula (III) the sum h+i is <3, that compound (Gl) contains 2 to 20 units of formula (III) and that

[0076] Compound (Gl) has no imide (-N (-C (=O)-)2) bonds.

[0077] Examples of monovalent, SiC-bonded, optionally substituted, optionally interrupted by at least one heteroatom, hydrocarbon radicals R 9 are those for R 1 , R 2, R 3 and R 4 mentioned radicals; epoxy radicals, such as the 3-glycidoxypropyl, 4-(oxiran-2-yl)phenyl, oxiran-2-yl and 2-(3,4-epoxycyclohexyl)ethyl radical; acrylate and methacrylate radicals, such as the 3-methacryloxypropyl, acryloxymethyl and methacryloxymethyl radical; amine radicals, such as the aminophenyl, 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-phenylaminomethyl radical; hydroxy-substituted radicals, such as the hydroxyphenyl and hydroxypropyl radicals; halogenated radicals, such as the trifluoromethyl, fluorophenyl, chlorophenyl, bromophenyl and trifluoromethylphenyl radicals; as well as the polycaprolactone, polycaprolactam, cyanatophenyl, 3-cyanatopropyl, isocyanatophenyl, and 3-isocyanatopropyl radicals.

[0078] Preferably, the residue R 9 a hydrogen atom, the phenyl or the methyl radical.

[0079] Preferably, the residue R 10an aliphatic hydrocarbon radical having 1 to 8 carbon atoms, particularly preferably the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl or iso-butyl radical, in particular the methyl or ethyl radical.

[0080] Examples of organosilicon compounds (CI) are 1,3,5,7-tetrakis (2-(3,4-epoxycyclohexyl)ethyl)-1,3,5,7-tetramethylcyclotetrasiloxane (CAS 121225-98-7), 2,4,6,8-tetramethyl-2,4,6,8-tetrakis [3-(glycidoxy)propyl]cyclotetrasiloxane (CAS 257284-60-9), bis[2-(3,4-epoxycyclohex-l-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (CAS 18724-32-8), 1,3-bis(norbornenylethyl)-1,1,3,3-tetramethyldisiloxane, organopolysiloxane of medium composition (PhSiO3 / 2)20(PhSi(OMe)O2 / 2)es(PhSi(OMe)2O1 / 2)14 and a weight average molar mass Mw = 2190 g / mol, organopolysiloxane of the average composition (PhSiO3 / 2)75(Me3SiOi / 2)25 and a weight average molar mass Mw = 1380 g / mol, octa(epoxycyclohexyl)-POSS (CAS 187333-74-0), octaphenyl-POSS (CAS 5256-79-1), octaphenylcyclotetrasiloxane (CAS 546-56-5), 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (CAS 77-63-4), 1,1,3,3,5,7- Hexamethyl-5,7-diphenylcyclotetrasiloxane, 1,1,3,3-tetramethyl-5,5,7,7-tetraphenylcyclotetrasiloxane (CAS 1693-47-6), 1,3,5- Trimethyl-1,1,3,5,5-pentaphenyltrisiloxan (3390-61-2), 1,3,3,5- Tetramethyl-1,1,5,5-tetraphenyltrisiloxan (3982-82-9), 1,3,5,7- Tetramethyl-1,1,3,5,7,7-hexaphenyltetrasiloxan (CAS 38421-40- 8), und 1,9-Dimethoxy-l,3,5,7,9-pentamethyl-l,3,5,7,9- pentaphenylpentasiloxan .,

[0081] The optional at least one modifier (C) is a thermoplastic, organic polymer ("thermoplastic") (C2) free of siloxy (=Si-O-) units and cyanate ester groups and having at least two repeating units selected from the group consisting of polyarylene, polyarylene ether, polyarylene sulfide, polysulfone, polyethersulfone, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, polyimide, polybenzimidazole, polyamide, poly(amidoimide), polyarylate, polyesterimide, polyetherimide, polyaramid, polyacrylate, polyhydantoin, liquid crystal polymer, polycarbonate, polyester carbonate and polyethylene terephthalate; as well as mixtures or copolymeric compounds thereof. The thermoplastics (C2) preferably have either reactive or chemically inert end groups. Due to the manufacturing process, reactive end groups remain during the polymerization reaction from the corresponding reactive groups of the polymerizable monomers.These are preferably hydroxyl, amino, carboxyl, and isocyanato groups. Examples of chemically inert end groups are the methyl or phenyl radical. The thermoplastics (C2) have glass transition temperatures above 100°C, preferably from 130°C to 450°C, more preferably from 150°C to 400°C, in particular from 180°C to 350°C; the number-average molar mass Mn of (C2) is preferably from 1100 to 100,000 g / mol, preferably from 2000 to 50,000 g / mol, more preferably from 2000 to 30,000 g / mol, in particular from 3000 to 20,000 g / mol.

[0082] The optional at least one modifier (C) is preferably an organic, monofunctional cyanate ester (C3) of the general formula (IV) which is free from siloxy (=Si-O-) units and phenolic hydroxy groups

[0083] RH-OCN (IV), where R 11means a monovalent, optionally substituted aromatic hydrocarbon radical which may be interrupted by at least one heteroatom, with the proviso that the cyanate ester group is directly bonded to an aromatic carbon atom.

[0084] Examples of compound (C3) are cyanatobenzene (GAS 1122-85-6), l-cyanato-4-cumylbenzene (GAS 110215-65-1), l-cyanato-4-tert-butylbenzene, l-cyanato-2-tert-butylbenzene, 4-cyanatobiphenyl, 1-cyanatonaphthalene, 2-cyanatonaphthalene, 4-cyanatononylbenzene, 4-chlorocyanatobenzene, 4-cyanatodiphenylsulfone, 4-cyanatotoluene, 4-cyanatodiphenyl ether, 4-cyanatodiphenyl ketone, 4-(cyanato)methoxybenzene; as well as propenyl-substituted monofunctional cyanate esters, such as 4-cumyl-2-(propenyl)cyanatobenzene or 2-(propenyl)cyanatobenzene.

[0085] The compound (C3) preferably has a boiling point at 1013 hPa of at least 150 °C, particularly preferably at least 180 °C, in particular at least 220 °C. The optional at least one modifier (C) is preferably a monomeric aromatic hydrocarbon (C4) free of siloxy (=Si-O-) units and of epoxy, imide and cyanate groups and having at least one phenolic hydroxy group and optionally one or more aliphatic carbon-carbon multiple bonds.

[0086] The optional aliphatic carbon-carbon multiple bonds in compound (C4) are preferably propenyl groups bonded to aromatic carbon atoms, wherein in compound (C4) particularly preferably a phenolic hydroxy group and optionally a propenyl group are bonded to an aromatic radical.

[0087] Examples of compounds (C4) without aliphatic carbon-carbon multiple bonds are monovalent, optionally substituted phenols, such as phenol, cresol, naphthol, 4-phenylphenol, thymol, gujacol (2-methoxyphenol), 4-cumylphenol, 4-benzylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-tert-butylphenol, 2,4-di-tert-butylphenol, 2,4-bis(a,adimethylbenzyl)phenol, nonylphenol, xylenol or 2,6-dinonylphenol; polyvalent phenols, such as pyrocatechol (benzene-

[0088] 1,2-diol), resorcinol (benzene-1,3-diol), hydroquinone (benzene-1,4-diol), pyrogallol (benzene-1,2,3-triol), phloroglucin (benzene-

[0089] 1,3,5-triol), dihydroxynaphthalene; aromatic compounds with two (bisphenols) or more hydroxyphenyl residues, such as bis-(2-hydroxyphenyl)methane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E),

[0090] 2,2-bis (4-hydroxyphenyl)propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) butane (bisphenol B), 2,2-bis (4-hydroxyphenyl) hexafluoropropane (bisphenol AF), 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol FL), bis (4-hydroxyphenyl) sulfone (bisphenol S), 1,3-bis (2-(4-hydroxyphenyl)-2-propyl) benzene (bisphenol M), 1,4-bis-[2-(4-hydroxyphenyl)-2-propyl] benzene (bisphenol P), bis (4-hydroxyphenyl) methane (bisphenol F), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) thioether and 1,1,1-tris (4-hydroxyphenyl) ethane.

[0091] Examples of compounds (C4) with propenyl groups are 2,2-bis(3-(2-propenyl)-4-hydroxyphenyl)propane (CAS 1745-89-7), 2-methoxy-4-(2-propenyl)phenol (CAS 97-53-0), 4-(2-propenyl)-2,6-dimethoxyphenol (CAS 6627-88-9), 2-(2-propenyl)-6-methylphenol (CAS 3354-58-3), 2-(2-propenyl)phenol (CAS 1745-81-9), 5,5'-bis(2-propenyl)-2,2'-biphenyldiol (CAS 528-43-8), 3',5-bis(2-propenyl)-2,4'-biphenyldiol (CAS 35354-74-6), bis(3-(2-propenyl)-4-hydroxyphenyl)sulfone (CAS 41481-66-7), 4-cumyl-2-(2-propenyl)phenol, 4-cumyl-2-(2-methyl-2-propenyl)phenol, 4-tert-butyl-2-(2-propenyl)phenol, 4-tert-Butyl-2-(2-methyl-2-propenyl)phenol, 2,2'-bis(3-propenyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2'-bis(3-propenyl-4-hydroxyphenyl)perfluoropropane and 9,9'-bis(3-propenyl-4-hydroxyphenyl)fluorene and 4-(1-(4-Hydroxy-3-propenylphenyl)propyl)-2-propenylphenol.

[0092] Compound (C4) is preferably 4-phenylphenol, 2-methoxy-4-(2-propenyl)phenol, 4-cumylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-tert-butylphenol, bisphenols, 2,2-bis(3-(2-propenyl)-4-hydroxyphenyl)propane, 4-(1-(4-hydroxy-3- propenylphenyl)propyl)-2-propenylphenol, 4-cumyl-2-(2-propenyl)phenol, 4-cumyl-2-(2-methyl-2-propenyl)phenol, 4-tert-butyl-2-(2-propenyl)phenol, 4-tert-butyl-2-(2-methyl-2-propenyl)phenol or 2-(2-propenyl)phenol; wherein 2-methoxy-4-(2-propenyl)phenol, 4-cumylphenol, 4-tert-butylphenol, 2,2-bis(3-(2-propenyl)-4-hydroxyphenyl)propane, bis(3-(2-propenyl)-4-hydroxyphenyl)sulfone, 4-cumyl-2-(2-propenyl)phenol, 4-tert-butyl-2-(2-propenyl)phenol, and bisphenol A, E, F, M or S are particularly preferred.

[0093] If the compositions according to the invention contain at least one modifier (C), either only one modifier (C1) to (C4) or several different

[0094] Modifiers (CI) to (C4) may be included in the mixture.

[0095] If the compositions according to the invention contain at least one modifier (C), the at least one modifier (C) is present in amounts of preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight, in particular 1 to 10 parts by weight, in each case based on 100 parts by weight of the sum of components (A) and (B).

[0096] Connection (D)

[0097] The optional at least one reactive resin (D) is preferably an aromatic hydrocarbon compound which is free from siloxy (=Si-O-) units and from cyanate ester and phenolic hydroxy groups, optionally substituted and optionally interrupted by at least one heteroatom, selected from the group consisting of epoxides (D1) and imides (D2) with the proviso that epoxides (D1) have at least two, preferably at least two, optionally substituted, polymerizable glycidyloxy, glycidyloxycarbonyl, glycidylamino, diglycidylamino or oxiran-2-yl groups bonded to aromatic carbon atoms per molecule; and that imides (D2) have at least two, preferably at least two, optionally substituted, polymerizable 5-ethynylphthalimido, 5-(phenylethynyl)phthalimido, nadimido, benzocyclobutenephthalimido or maleimido groups per molecule bonded to aromatic carbon atoms;the maleimido, glycidyloxy, glycidylamino, diglycidylamino groups being particularly preferred;

[0098] The optional at least one reactive resin (D) preferably contains at least two optionally substituted, optionally interrupted by at least one heteroatom, aromatic hydrocarbon radicals per molecule, each having a maleimido, glycidyloxy, glycidyloxycarbonyl, glycidylamino or diglycidylamino group bonded to an aromatic carbon atom. Particularly preferably, (D) comprises compounds having at least two optionally substituted, optionally containing at least one heteroatom, aromatic hydrocarbon radicals each having a maleimido, glycidyloxy, glycidylamino or diglycidylamino group bonded to an aromatic carbon atom, wherein the optionally substituted, optionally containing at least one heteroatom, aromatic hydrocarbon radicals are linked via a covalent bond or a bridging unit which has at least one functional group selected from the group consisting of -CR12 2~ , -CR 12 =CR 12 -, =C=CR 12 2, -0-, -S-, -N=N-, -CR 12 =N-, -C (=O)- , -C(=O)0-, -OG (=O)0-, -S(=O)2-, 0=P(0-)3, -SiR 12 2-, phenylene, arylene, biphenylene, biarylene, naphthylene or cycloalkanediyl groups, such as tricyclo[5.2.1.0 2 ' 6 ]decanediyl or bicyclo [2.2.1]heptanediyl, are linked together.

[0099] For rest R 12 are each independently the ones for R 6 mentioned residues.

[0100] Preferably, the at least one reactive resin (D) contains heteroatom-free aromatic ring structures. Epoxy resins (D1) are preferably copolymerizable with cyanate ester resin (A).

[0101] Preferably, imide resins (D2) are not co-polymerizable with cyanate ester resin (A).

[0102] Examples of polymerizable epoxy resins (DI) are glycidyl ethers of phenolic compounds, such as 2,2-bis(4-glycidyloxyphenyl)propane (CAS 1675-54-3), bis(4-glycidyloxyphenyl)methane (CAS 2095-03-6), 1,2-bis(glycidyloxy)benzene (CAS 2851-82-3), 1,3-bis(glycidyloxy)benzene (CAS 101-90-6), 1,4-

[0103] Bis (glycidyloxy)benzol (CAS 129375-41-3), 3,5,3',5'- Tetramethyl-4,4'-diglycidyloxybiphenyl (CAS 85954-11-6), 2,2- Bis (3,5-dibromo-4-glycidyloxyphenyl)propan (CAS 3072-84-2), Tris (4-glycidyloxyphenyl)methan (CAS 66072-38-6), 1,1,2,2- Tetrakis (4-glycidyloxyphenyl)ethan (CAS 7328-97-4), 4,4'- Bis (glycidyloxyphenyl)sulfon (CAS 878-43-1), 9,9-Bis(4- glycidyloxyphenyl)fluoren (CAS 47758-37-2), 1,6- (Diglycidyloxy)naphthalen (CAS 27610-48-6); Glycidylether von Phenol-, Naphthol-, Naphtalendiol-, Bisphenol- oder Cresol- Formaldehyd-Kondensationsprodukten, wie Cresol-Novolak- Glycidylether (CAS 29690-82-2), Phenol-Novolak-Glycidylether (CAS 9003-36-5, CAS 28064-14-4, CAS 158163-01-0) und Bisphenol

[0104] A-epichlorohydrin-formaldehyde copolymer (CAS 28906-96-9); glycidyl ethers of phenol or cresol-dicyclopentadiene condensation products, such as CAS 68610-51-5 and CAS 119345-05-0; glycidyl esters of aromatic carboxylic acids, such as diglycidyl phthalate (CAS 7195-45-1), diglycidyl terephthalate (CAS 7195-44-0), diglycidyl isophthalate (CAS 7195-43-9), triglycidyl 1,2,3-benzenetricarboxylate, triglycidyl 1,2,4-benzenetricarboxylate (CAS 7237-83-4) and triglycidyl 1,3,5-benzenetricarboxylate (CAS 7176-19-4); Glycidyl derivatives of aromatic amines and aminophenols, such as N,N-diglycidyl-4-glycidyloxyaniline (CAS 5026-74-4), 4,4'-methylenebis(N,N-diglycidylaniline) (CAS 28768-32-3), N,N,N ',N '-tetraglycidyl-4,4'-diamino-3,3 '-diethyldiphenylmethane (CAS 130728-76-6) and m-(glycidyloxy)-N,N-diglycidylaniline (CAS 71604-74-5);Glycidyl-terminated thermoplastic polymers, which can be produced, for example, by reacting amino- or hydroxy-terminated thermoplastics (C2) with epichlorohydrin, such as glycidyloxy- or digylcidylamino-terminated polysulfones; homopolymers or copolymers of epoxy resins, such as bisphenol A-epichlorohydrin copolymer (CAS 25036-25-3), 2,2',6,6'-tetrabromobisphenol A-epichlorohydrin copolymer (CAS 40039-93-8) and reaction products of diglycidylbisphenol A with m-phenylenebis(methylamine) (CAS 110839-13-9); as well as mixtures of various epoxy resins (D1).

[0105] Examples of polymerizable maleimide resins (D2) are 4,4'-bis(maleimidophenyl)methane (CAS 13676-54-5), m-xylylenebismaleimide (CAS 13676-53-4), l,l'-(2,2,4-trimethylhexane-1,6-diyl)bis-lH-pyrrole-2,5-dione (CAS 39979-46-9), bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (CAS 105391-33-1), bis(4-maleimido-3-methylphenyl)methane, bis(4-maleimido-3,5-dimethylphenyl)methane, 1,1-bis(4-maleimidophenyl)cyclohexane, 2,4-bismaleimidotoluene (CAS 6422-83-9), N,N '-1,2-Phenylenebismaleimide (CAS 13118-04-2), N,N'-1,3-Phenylenebismaleimide (CAS 3006-93-7), N,N'-1,3-Phenylenebismaleimide (CAS 3278-31-7), copolymers of bismaleimides and aromatic amines, such as 4,4'-

[0106] Bis(maleimidophenyl)methane / 4,4'-bis(aminophenyl)methane copolymer (CAS 26140-67-0); reaction product of a condensation product of formaldehyde and aniline with maleic anhydride (CAS 28630-26-4, CAS 67784-74-1); Bis(4-maleimidophenyl) ether, 2,2-bis[4-(maleimidophenoxy)phenyl]propane (CAS 79922-55-7), bis(4-maleimidophenyl)sulfone (CAS 13102-25-5), bis(4-maleimidophenyl) ketone, 1,1'-(benzene-1,3-diyldimethanediyl)bis(lH-pyrrole-2,5-dione) (CAS 13676-53-4), 4,4'-bis(maleimido)-1,1'-biphenyl (CAS 3278-30-6), 4,4'-bis(3-maleimidophenoxy)diphenylsulfone or maleimide-terminated thermoplastic polymers (D2), which can be prepared, for example, by reacting amino-terminated thermoplastics (C2) with maleic anhydride, such as, for example, maleimide-terminated polysulfone ethers; as well as mixtures of various maleimide resins (D2).

[0107] Preferably, the at least one compound (D) is a monomeric compound without a thermoplastic, homo- or copolymeric polymer component.

[0108] If the compositions according to the invention contain at least one reactive resin (D), the at least one reactive resin is present in amounts of preferably 1 to 40 parts by weight, particularly preferably 1 to 30 parts by weight, in particular 1 to 20 parts by weight, in each case based on 100 parts by weight of the sum of components (A) and (B).

[0109] If the compositions according to the invention contain at least one polymerizable imide (D2), this is preferably present in combination with components that are copolymerizable with both cyanate ester groups and imido groups, preferably maleimido groups. These components are selected from cyanate esters (A), modifiers (C3), or modifiers (C4) that contain propenyl groups bonded to aromatic carbon atoms; or from aromatic hydrocarbon compounds that contain, per molecule, one or two hydroxy groups bonded to aromatic carbon atoms and one or two polymerizable imido groups, preferably maleimido groups, bonded to aromatic carbon atoms, such as, for example, N-(4-hydroxyphenyl)maleimide (GAS 7300-91-6).

[0110] If the compositions according to the invention contain at least one polymerizable imide resin (D2) in combination with the components mentioned in the preceding paragraph, the molar ratio of the sum of the imido groups to the sum of the propenyl groups is in a range of preferably 45:55 to 95:5, particularly preferably 55:45 to 90:10, in particular 65:45 to 80:20.

[0111] Connection (E)

[0112] The at least one filler (E) optionally present in the compositions according to the invention may be any particulate filler known to date.

[0113] The optional at least one filler (E) according to the invention is preferably one which dissolves in toluene at 23 °C and 1000 hPa to a level of less than 1% by weight.

[0114] Examples of fillers are non-reinforcing particulate fillers, i.e. fillers with a BET surface area of ​​preferably up to 50 m 2 / g, for example, made of quartz, glass, cristobalite, diatomaceous earth; water-insoluble silicates, such as calcium silicate, calcium metasilicate, magnesium silicate, zirconium silicate, talc, mica, feldspar, kaolin, zeolites; metal oxides, such as aluminum, titanium, iron, boron or zinc oxides or their mixed oxides; barium sulfate, calcium carbonate, marble powder, gypsum, silicon nitride, silicon carbide, boron nitride, plastic powders, such as polyacrylonitrile or polyetherimide powder; reinforcing fillers, i.e. fillers with a BET surface area of ​​more than 50 m 2 / g, such as pyrogenic silica, precipitated silica, precipitated chalk, carbon black, such as furnace black and acetylene black and silicon-aluminium mixed oxides with a high BET surface area; aluminium trihydroxide, magnesium hydroxide, hollow spherical fillers, such as glass microballoons, glass spheres, phenolic thermal spheres or ceramic microspheres, such as those available under the trade name Zeeospheres™ from 3M Deutschland GmbH in D-Neuss; fibrous fillers, such as wollastonite, montmorillonite, basalt, bentonite and chopped and / or ground fibres made of glass (short glass fibres) or mineral wool; metallic fibres, fibres consisting of metal oxides, glass, ceramic, carbon or plastic; and natural fibres made of cellulose, flax, hemp, wood or sisal.

[0115] The optional at least one filler (E) according to the invention can be contained in the composition according to the invention as a single filler or in any desired mixture of at least two different fillers (E).

[0116] Component (E) is selected from particulate fillers, including fibers up to a length of 5 cm (El) and semi-finished fiber products (E2) containing fibers with a length of more than 5 cm, with semi-finished fiber products (E2) being preferred.

[0117] The optional at least one filler (E2) preferably comprises all previously known fiber-forming materials made of polypropylene, polyethylene, polytetrafluoroethylene, polyester; metallic fibers made of steel; oxidic and non-oxidic ceramics, such as silicon carbide, aluminum oxide, silicon dioxide, boron oxide; glass, quartz, carbon, aramid, asbestos, graphite, acrylonitrile, poly(benzothiazole), poly(benzimidazole), poly(benzoxazole), titanium dioxide, boron; and aromatic polyamide fibers, such as poly(p-phenylene terephthalamide).

[0118] The at least one filler (E) mentioned may optionally be surface-treated, e.g., hydrophobicized, for example, by treatment with organosilanes or organosilanes, stearic acid, or with one or more modifiers (C). The filler surfaces may also be modified to enable chemical bonding to the cured resin matrix, e.g., by oxidation or treatment with acids or bases. Preferably, the at least one filler (E2) is surface-treated.

[0119] If the composition according to the invention contains at least one filler (El), the proportion of the at least one filler (El) is preferably 5 to 900 parts by weight, particularly preferably 10 to 400 parts by weight, in particular 15 to 150 parts by weight, in each case based on 100 parts by weight of the sum of components (A) and (B).

[0120] If the composition according to the invention contains at least one filler (E2), the proportion of the at least one filler (E2) is preferably 20 to 900 parts by weight, particularly preferably 60 to 900 parts by weight, in particular 100 to 400 parts by weight, in each case based on 100 parts by weight of the sum of components (A) and (B).

[0121] The at least one filler (E2) can be contained in different forms in the composition according to the invention, e.g. as continuous ropes each having 1000 to 400000 individual filaments, woven fabrics, scrims, knitted fabrics, braids, mats, nonwovens, whiskers, chopped strands or random fiber felt.

[0122] The compositions according to the invention preferably contain at least one filler (E), wherein the at least one filler (E) particularly preferably consists predominantly, in particular completely, of filler (E2).

[0123] The compositions according to the invention preferably contain, as filler (E2), ropes, fiber wovens, fiber scrims, fiber knits, or fiber braids, particularly preferably each consisting of carbon fibers, aromatic polyamide fibers, ceramic and / or glass fibers, wherein either the respective fibers and / or the ropes, fiber wovens, fiber scrims, fiber knits, or fiber braids produced therefrom are, in particular, surface-treated. The respective fibers are very particularly preferably surface-treated.

[0124] The optional fiber fabrics (E2) or fiber scrims (E2) according to the invention are preferably used in multiple layers.

[0125] In a preferred embodiment, component (E2) comprises at least 80% by weight, particularly preferably at least 90% by weight, of fiber fabrics, fiber scrims, fiber knits or fiber braids, based on 100% by weight of component (E2).

[0126] Connection (F)

[0127] The composition according to the invention can be cured in the presence of at least one curing accelerator (F), as is known from the prior art. Suitable curing accelerators (F1) include, for example, acids and bases such as hydrochloric acid, phosphinic acid, phosphonic acid, phosphoric acid; aliphatic and aromatic amines such as triethylamine, N,N-dimethylaniline, and pyridine; amidines, guanidines, and sodium hydroxide; halides such as aluminum chloride, lithium chloride, boron fluoride, iron chloride, zinc chloride, zinc fluoride, tin chloride, cobalt chloride, and titanium chloride; and organometallic compounds such as metal alkoxides, metal carboxylates, or metal chelate complexes of aluminum, copper, zinc, titanium, iron, manganese, cobalt, chromium, or nickel.Examples of organometallic compounds are cobalt(II) naphthenate, nickel(II) naphthenate, iron(III) naphthenate, copper(II) naphthenate, manganese(II) naphthenate, aluminum(III) naphthenate, zinc(II) naphthenate, zinc(II) octoate, zinc(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II) acetylacetonate, chromium(III) acetylacetonate, aluminum(III) acetylacetonate and copper(II) acetylacetonate.

[0128] If at least one curing accelerator (F1) is used for curing the compositions according to the invention, it is preferably a combination of an organometallic compound and a co-accelerator which has at least one active proton, particularly preferably a combination of an organometallic compound and a phenol (C4), such as nonylphenol.

[0129] If the compositions according to the invention contain at least one curing accelerator (F1), the amounts used are preferably from 0.00001 to 5 parts by weight, based on 100 parts by weight of component (A), with organometallic compounds (F1) being used particularly preferably in amounts of from 0.0001 to 0.02 parts by weight, based on 100 parts by weight of component (A). If the compositions according to the invention contain radically polymerizable functional groups, such as aliphatic carbon-carbon multiple bonds, radical-forming curing accelerators (F2), such as organic peroxides, e.g., dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, and tert-butyl perbenzoate; or azo compounds, such as azobis(isobutyronitrile), can be used either alone or in addition to (F1).If the compositions according to the invention contain free-radical curing accelerators (F2), these are preferably present in amounts of 0.1 to 2 parts by weight, based on 100 parts by weight of the sum of imido group-containing modifier (Gl) and imide resin (D2). Preferably, no free-radical curing accelerators (F2) are used.

[0130] Connection (G)

[0131] Examples of the optional at least one solvent (G) are aliphatic mono- and polyhydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polyethylene glycol, 1,2-butanediol, 1,3-butanediol, polybutylene glycol and glycerol; ethers, such as methyl tert-butyl ether, di-tert-butyl ether and di-, tri- or tetraethylene glycol dimethyl ether; saturated hydrocarbons such as n-hexane, cyclohexane, n-heptane, n-octane and isomeric octanes such as 2-ethylhexane, 2,4,4-trimethylpentane, 2,2,4-trimethylpentane, 2-methylheptane and trichloroethylene, as well as mixtures of saturated hydrocarbons with boiling ranges between 60-300°C, as available under the trade names Exxsol™, Hydroseal® or Shellsol®; aromatic solvents such as benzene, toluene, styrene, o-, m- or p-xylene, solvent naphtha, dimethyl phthalate, di-isobutyl phthalate, dicyclohexyl phthalate, mesitylene and chlorobenzene;Aldehyde acetals such as methylal, ethylhexylal, butylal, 1,3-dioxolane and glycerol formal; carbonates such as 1,3-dioxolan-2-one, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, propylene glycol carbonate, ethylene carbonate; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, acetone and cyclohexanone; esters such as ethyl acetate, n-butyl acetate, ethylene glycol diacetate, gamma-butyrolactone, 2-methoxypropyl acetate (MPA), dipropylene glycol dibenzoate and ethyl ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; acetonitrile; and dimethyl sulfoxide.;

[0132] The at least one solvent (G) is preferably an aromatic hydrocarbon or a ketone.

[0133] If the compositions according to the invention contain at least one solvent (G), the amounts are preferably from 10 to 300 parts by weight, particularly preferably from 10 to 100 parts by weight, in particular from 10 to 50 parts by weight, based in each case on 100 parts by weight of the sum of components (A) and (B). The compositions according to the invention preferably do not contain any solvent (G).

[0134] Connection (H)

[0135] The optional at least one auxiliary substance (H) according to the invention preferably comprises pigments, dyes, fragrances, processing aids, such as agents for influencing tackiness, lubricants, mold-release agents, antiblocking agents, or dispersants; stabilizers against hydrolysis, light, oxidation, heat, and discoloration; flame-retardant agents, or plasticizers. If the compositions according to the invention contain at least one auxiliary substance (H), the at least one auxiliary substance (H) is present in amounts of preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, in particular 0.1 to 10 parts by weight, based in each case on 100 parts by weight of the sum of components (A) and (B). The compositions according to the invention preferably contain no further constituents (H).

[0136] The compositions according to the invention are preferably those containing

[0137] (A) at least one cyanate ester resin,

[0138] (B) at least one poly(imide-diorganosiloxane) copolymer, optionally (C) at least one modifier, optionally (D) at least one reactive resin,

[0139] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent and optionally (H) at least one auxiliary substance.

[0140] The compositions according to the invention are preferably those containing

[0141] (A) at least one cyanate ester resin,

[0142] (B) at least one poly(imide-diorganosiloxane) copolymer,

[0143] (C) at least one modifier, optionally (D) at least one reactive resin,

[0144] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent, and optionally (H) at least one auxiliary agent. In a particularly preferred embodiment, the compositions according to the invention are those containing

[0145] (A) at least one cyanate ester resin,

[0146] (B) at least one poly(imide-diorganosiloxane) copolymer, optionally (C) at least one modifier,

[0147] (D2) at least one imide resin,

[0148] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent and optionally (H) at least one auxiliary substance.

[0149] In a further particularly preferred embodiment, the compositions according to the invention are those containing

[0150] (A) at least one cyanate ester resin,

[0151] (B) at least one poly(imide-diorganosiloxane) copolymer, optionally (C) at least one modifier,

[0152] (D2) at least one maleimide resin,

[0153] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent and optionally (H) at least one auxiliary substance, with the proviso that at least one component (A), (C3) or (C4) having propenyl groups bonded to aromatic carbon atoms is present.

[0154] The compositions according to the invention preferably contain, in addition to components (A) and (B), the optional components

[0155] (C) to (H) and, where applicable, raw material-specific

[0156] Impurities, for example catalyst residues such as sodium chloride or potassium chloride, impurities in technical cyanate ester resin monomers and, if applicable, reaction products of the components used which arise during mixing or storage, no other components.

[0157] In the compositions according to the invention, the components described so far can be used individually or in the form of a mixture of at least two of the respective components.

[0158] The compositions according to the invention can be prepared by known methods, such as, for example, by mixing the individual components in any order or in a previously known manner.

[0159] A further object of the present invention is a process for preparing the compositions according to the invention by mixing the individual components in any desired order.

[0160] In the process according to the invention, mixing can take place at temperatures in the range of preferably 20 to 150 °C, particularly preferably in the range of 50 to 130 °C, in particular at temperatures of 60 to 120 °C. Mixing is most preferably carried out at the temperature which, when mixing at ambient temperature, results from the temperature of the raw materials plus the temperature increase due to the energy input during mixing, whereby heating or cooling can be used as required.

[0161] Mixing can take place at ambient atmospheric pressure, i.e., approximately 900 to 1100 hPa. Furthermore, it is possible to mix temporarily or continuously under reduced pressure, such as 30 to 500 hPa absolute pressure, to remove volatile compounds and / or air, or to work at overpressure, such as between 1100 hPa and 3000 hPa absolute pressure, particularly in continuous operation, where, for example, these pressures arise in closed systems from the pressure during pumping and from the vapor pressure of the materials used at elevated temperatures.

[0162] The process according to the invention can be carried out continuously, discontinuously or semi-continuously, preferably it is carried out discontinuously.

[0163] In a preferred embodiment of the process according to the invention for producing the compositions according to the invention, the individual components except for component (E) are premixed in any desired order, then filler (E2) is impregnated with the premix by known processing techniques such as prepregging (from the melt, solution or suspension), sheet molding compound (SMC), filament winding, compression molding, pultrusion, fiber spraying and injection processes such as resin transfer molding or vacuum infusion and processed into molded articles.

[0164] The compositions according to the invention can be used for all purposes for which organic reactive resin systems or their prepolymers have previously been used for subsequent curing to thermosets.

[0165] In a variant of the process according to the invention, components (A) and (B) and the optional components (C), (D), (G), and (H) are preferably first mixed in any desired order to form a premix. Then, component (E2), preferably ropes, woven fabrics, non-crimp fabrics, knitted fabrics, or braids, is impregnated with the premix, optionally under pressure, and optionally degassed. In the case of multi-layer woven fabrics or non-crimp fabrics (E2), each layer can be impregnated and degassed individually or all layers together.

[0166] In a further preferred variant of the process according to the invention, components (A) and (B) and the optional components (C), (D), (G) and (H) are first mixed in any desired order to form a premix and then injected into a mold cavity in which component (E2), preferably ropes, woven fabrics, scrims, knitted fabrics or braids, is located, wherein degassing preferably takes place simultaneously during the injection process.

[0167] In a further preferred variant of the process according to the invention, components (A) and (B) and the optional components (C), (D), (G), and (H) are first mixed in any order to form a premix and then applied to a release paper; subsequently, component (E2), preferably aligned ropes, woven fabrics, scrims, knitted fabrics or braids, is pressed between two coated paper sheets and passed through a series of heated rollers to effect complete wetting of component (E2).

[0168] The compositions according to the invention can be formed into any desired shape by mechanical pressure at ambient temperature or, if appropriate, at elevated temperature.

[0169] The compositions according to the invention are preferably moldable and are particularly preferably modeled and cured in a mold cavity or around a molding template. The invention therefore further relates to the use of the composition according to the invention for producing molded articles.

[0170] A further subject of the invention is therefore a process for producing shaped bodies by shaping the composition according to the invention and subsequent curing.

[0171] A further subject of the invention are therefore shaped bodies obtainable from the compositions according to the invention by shaping and curing.

[0172] The compositions according to the invention or prepared according to the invention are preferably degassed before curing, particularly preferably after shaping and before curing.

[0173] The curing according to the invention preferably takes place at temperatures in the range from 50 to 350 °C, particularly preferably from 100 to 300 °C, in particular from 120 to 270 °C. Most preferably, the curing according to the invention takes place stepwise at temperatures from 120 to 270 °C.

[0174] By increasing the temperature, curing can be accelerated so that shaping and curing can be carried out in one step.

[0175] The molded bodies according to the invention are preferably fiber composite materials (or fiber-reinforced plastics "FRP").

[0176] The invention therefore further relates to the use of the composition according to the invention for producing fiber composite materials. The invention further relates to a process for producing fiber composite materials by molding the composition according to the invention and subsequent curing.

[0177] A further subject of the invention are therefore fiber composite materials obtainable from the compositions according to the invention by shaping and curing.

[0178] The compositions according to the invention can be solid or liquid at a temperature of 100°C and an air pressure of 1013 hPa, and are preferably liquid at 100°C and 1013 hPa.

[0179] If the compositions according to the invention are liquid at 100°C and 1013 hPa, they have a dynamic viscosity of preferably 1 to 5000 mPa-s, preferably 1 to 2000 mPa-s, particularly preferably 1 to 1000 mPa-s, in particular 1 to 500 mPa-s, in each case at 100°C and 1013 hPa.

[0180] In the present invention, the dynamic viscosity is determined according to DIN 53019 at a temperature of 23°C, unless otherwise stated, and an air pressure of 1013 hPa. The measurement is carried out using a "Physica MCR 300" rotational rheometer from Anton Paar. A coaxial cylinder measuring system (CG 27) with a ring measuring gap of 1.13 mm is used for viscosities from 1 to 200 mPa-s, and a cone-and-plate measuring system (Searle system with measuring cone CP 50-1) is used for viscosities greater than 200 mPa-s. The shear rate is adjusted to the polymer viscosity (1 to 99 mPa-s at 100 s). -1 ; 100 to 999 mPa-s at 200 s -1 ; 1000 to 2999 mPa-s at 120 s -1 ; 3000 to 4999 mPa-s at 80 s -1 ; 5000 to 9999 mPa-s at 62 s -1 ; 10000 to 12499 mPa-s at 50 s -1 ; 12500 to 15999 mPa-s at 38.5 s' 1 ; 16000 to 19999 mPa-s at 33 s -1 ; 20000 to 24999 mPa-s at 25 s -1; 25000 to 29999 mPa-s at 20 s -1 ; 30000 to 39999 mPa-s at 17 s -1 ; 40000 to 59999 mPa-s at 10 s -1 ; 60000 to 149999 at 5 s -1 ; 150000 to 199999 mPa-s at 3.3 s -1 ; 200,000 to 299,999 mPa-s at 2.5 s~ 300,000 to 1,000,000 mPa-s at 1.5 s -1 .

[0181] After the dynamic viscosity measurement system has been brought to the measurement temperature, a three-stage measurement program is applied, consisting of a run-in phase, a pre-shear phase, and a viscosity measurement. The run-in phase involves gradually increasing the shear rate within one minute to the shear rate specified above, which is dependent on the expected viscosity, at which the measurement is to be taken. Once this rate is reached, pre-shearing is carried out for 30 seconds at a constant shear rate. Subsequently, 25 individual measurements of 4.8 seconds each are performed to determine the viscosity, from which the average value is determined. The average value corresponds to the dynamic viscosity, which is expressed in mPa-s.

[0182] The quotient of the critical stress intensity factor K lcof the cured compositions according to the invention comprising 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B), to the respective cured, unmodified cyanate ester resin (A) is preferably greater than 1.4, particularly preferably greater than 1.5, in particular greater than 1.6, in each case measured at 23°C.

[0183] The cured compositions according to the invention, for example, consisting of 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B), have a glass transition temperature of preferably greater than 200°C, particularly preferably greater than 230°C, in particular greater than 260°C. The cured compositions according to the invention, for example, consisting of 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B), exhibit a weight loss after 200 hours of storage at 240°C that is preferably at most 80%, preferably at most 60%, particularly preferably at most 40%, in particular at most 20%, higher compared to the corresponding unmodified cyanate ester resins (A).

[0184] The compositions according to the invention have the advantage that copolymer (B) is miscible with cyanate ester resin (A) without the addition of further solvent and copolymer (B) does not exude from the thermoset network during curing.

[0185] The compositions according to the invention have the advantage that they have a high glass transition temperature and a high fracture toughness (K lc ) compared to the corresponding unmodified cyanate ester resins.

[0186] The compositions according to the invention also have the advantage that they have a high thermo-oxidative stability in the cured state.

[0187] The molded bodies according to the invention have the advantage that they are heat-stable and have a reduced fire load compared to composite materials made of purely organic cyanate ester resin systems.

[0188] The compositions according to the invention have the advantage that they can be produced from readily available raw materials and in a simple manner. The compositions according to the invention have the advantage that no harmful emissions are generated during processing to the extent that typically occur with organic cyanate ester resins used in the prior art.

[0189] Examples of implementation

[0190] The following examples were carried out at a pressure of the ambient atmosphere, i.e. at about 1013 hPa, and at room temperature, i.e. about 23°C or a temperature which is reached when the reactants come together at room temperature without additional heating or cooling, and describe the basic feasibility of the present invention, without, however, limiting it to the contents disclosed therein.

[0191] Production of the test specimens

[0192] First, the cyanate ester resin (A) was heated to 80°C while thoroughly mixing to improve processability. Copolymer (B) was then added, and the mixture was homogenized for one hour at 110°C using a Rotavapor, then degassed for one hour at 110°C and a pressure of 5 mbar. After breaking the vacuum with nitrogen, the mixture was immediately poured hot into a two-part, screw-on aluminum mold preheated to 160°C. The mold cavity dimensions were 200 mm x 100 mm x 6.5 mm (length x width x height) for the production of test specimens for determining fracture toughness, thermo-oxidative stability, and for conducting dynamic mechanical analysis (DMA). To prevent sticking and leakage, the cavity surface on the inside of the mold was coated with a mold release agent (LOCTITE FREKOTE HMT-2; commercially available from Henkel AG & Co.KGaA, DE-Düsseldorf) and a 2 mm thick round cord made of fluororubber with a hardness of 75 Shore A was placed around the mold cavity. For curing, the filled molds were stored in a circulating air oven according to the following temperature program:.

[0193] 1) 18 hours curing at 180°C

[0194] 2) Temperature increase to 200°C within 30 minutes

[0195] 3) 3 hours curing at 200°C

[0196] 4) Temperature increase within 30 minutes to 240°C

[0197] 5) 2 hours curing at 240°C.

[0198] The specimen was then allowed to cool to ambient temperature in the mold before being removed from the mold. For further use, the top 10 mm of the cured specimen side, which was open and exposed to air during curing in the mold, was cut off and discarded. The test specimens for fracture toughness, thermo-oxidative stability, and DMA were then cut out of the large, 6.5 mm high, cured specimen plate using a diamond saw in the appropriate dimensions (length x width).

[0199] Fracture toughness Ki c

[0200] The measurement of the fracture toughness or the critical stress intensity factor K lc was carried out as described in the publication "Reactive and Functional Polymers 142 (2019) 159-182" at 23°C and 50% relative humidity; the thickness of the specimens was 6.5 mm. The value for the fracture toughness K given in Table 1 lcin MN xm -3 / 2 was rounded to two decimal places according to DIN 1333:1992-02 Section 4.

[0201] Dynamic Mechanical Analysis (DMA)

[0202] Measurement conditions: Measuring instrument: ARES rheometer (TA-Instruments)

[0203] • Temperature range: -100°C - 400°C

[0204] • Heating rate: 4 K / min with nitrogen purge

[0205] • Frequency: 1 Hz

[0206] • Strain: Initial 0.03%, automatically increased if measurement signal falls below threshold

[0207] For the tests, cuboid-shaped test specimens with the dimensions length x width x height = 40 mm x 6 mm x 3 mm were used; the resulting clamping length was 25 mm. In the present invention, the glass transition temperature T G the maximum value of the tangent delta curve (= tan delta max ), ie the measuring temperature at which the ratio of loss modulus G' to storage modulus G' is greatest.

[0208] The value for the glass transition temperature T given in Table 1 G was rounded to whole numbers, according to DIN 1333:1992-02 Section 4.

[0209] Thermo-oxidative stability

[0210] In the present invention, the thermo-oxidative stability was determined gravimetrically after storage of the test specimens at 240°C. Cuboid-shaped test specimens with the dimensions length x width x thickness = 12.00 mm x 6.50 mm x 6.50 mm were used; the accuracy of the weight determination was ±0.1 mg. The test specimens were first dried in a vacuum oven at 70°C and 30 mbar until constant weight was reached, with the weight being determined at intervals of 24 hours. The test specimens were considered "dry" if no further weight loss was measured over a period of 48 hours. The test specimens were then stored in a circulating air oven at 240°C. After 200 hours, the test specimens were removed and the weight of the test specimens was determined again. The weight loss was calculated according to the formula given in Table 1.

[0211] Value for weight loss given in % and divided into two

[0212] Decimal places rounded according to DIN 1333:1992-02

[0213] Section 4.

[0214] compatibility

[0215] The compatibility of compound (B) with cyanate ester resins (A) was assessed using the test specimens prepared directly after curing. In Table 1, compatibility is indicated as "+" = good compatibility, i.e., no visible oiling or bleeding of component (B) from the cured mixture, and = poor compatibility, i.e., visible oiling or bleeding of the siloxane component from the cured mixture, as well as an oily and / or sticky test specimen surface.

[0216] Poly (imide-diorganosiloxane) copolymer 1

[0217] 40.0 g (129 mmol) of 4,4'-oxydiphthalic anhydride (GAS 1823-59-2, commercially available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) and 13.3 g (90 mmol) of phthalic anhydride (GAS 85-44-9, commercially available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) are mixed in 150 ml of anhydrous tetrahydrofuran (commercially available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen); Subsequently, a solution of 43.2 g (347 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (CAS 2469-55-8, commercially available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) in 50 ml of anhydrous tetrahydrofuran is added dropwise. The mixture is stirred for 1 h at 40°C, then the solvent is distilled off using a rotary evaporator, and the residue is evaporated, first for 1 hour at 150°C and ambient pressure and then for 2 hours at 180°C and a pressure of 5 mbar with continuous mixing. Copolymer 1 has a weight-average molar mass Mw of 4600 g / mol and a

[0218] Number average molar mass Mn of 2020 g / mol

[0219] Example Bl 85 g of 2,2-bis(4-cyanatophenyl)propane (GAS 1156-51-0; commercially available from TCI Deutschland GmbH, D-65760 Eschborn) as component (A) were mixed with 15 g of poly(imide-diorganosiloxane) copolymer 1 as component (B) and then processed as described under "Preparation of the test specimens".

[0220] The results can be found in Table 1.

[0221] Comparative example VI

[0222] The procedure described in Example Bl was repeated with the modification that no component (B) was added to component (A).

[0223] Table 1 not assessed.

Claims

Patent claims 1. A curable composition comprising (A) at least one organic compound (A) free of siloxy (=Si-O-) units and having at least two cyanate ester (-OC^N) groups; and (B) at least one linear, cyanate ester group-free, Poly (imide-diorganosiloxane) copolymer of general Formula (I) and / or the general formula (II) wherein R is the same or different and represents a methyl, vinyl or phenyl radical; R 1 , R 2 , R 3 and R 4 are the same or different and represent a monovalent hydrocarbon radical, R 5 is the same or different and represents a monovalent hydrocarbon radical; Y is the same or different and is a methylene (-CH2-)-, ethylene (-(CH2-)2) _ or propylene (-(CH2-)3) group; Z is the same or different and represents a covalent bond or a divalent radical selected from the group consisting of -C=C-, -CR 6 =CR 6 -, -CR 6 2-, -0- , -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -OG (=O)0-, -C(=O)0- , -c (=O)0-(C6H4)-oc (=O)-, -0-(C6H4)-CR 6 2-(C6H4)-0-, -0-(CgH4)-CR 6 2-(CgH4)-CR 6 2-(CgH4)-0-; or divalent cycloalkanediyl residues, such as tricyclo[5.2.1.0 2 ' 6 ]decanediyl and bicyclo[2.2.1]heptanediyl, wherein R 6 is the same or different and represents a hydrogen atom, a halogen atom or a monovalent hydrocarbon radical having 1 to 30 carbon atoms; m is 1 to 15; and n is 1 to 20.

2. The curable composition according to claim 1, wherein the at least one compound (A) is an aromatic hydrocarbon compound.

3. Curable composition according to claim 1 or 2, wherein at least two aromatic hydrocarbon radicals, each having a cyanate ester group bonded to an aromatic carbon atom, are present per molecule of compound (A).

4. Curable composition according to claim 3, wherein the aromatic hydrocarbon radicals are each bonded to an aromatic carbon atom with a cyanate ester group via a covalent bond or at least one bridging unit selected from the group consisting of -CR 7 2- , -CR 7 =CR 7 -, -C(=CR 7 2)-, -O-, -S-, -N=N-, -CR 7 =N-, -0 (=O)- , -C(=O)0-, -00 (=O)0-, -S(=O)-, -S(=O)2-, 0=P(0-)3, (=O), -SiR 7 2-, a divalent aromatic hydrocarbon radical, such as phenylene, toluene, biphenylene and naphthylene; or a divalent cycloalkanediyl radical, such as tricyclo [5.2.1.0 2 ' 6]decanediyl and bicyclo[2.2.1]heptanediyl, wherein R 7 each independently of each other for R 6 mentioned residues.

5. Curable composition according to one of the preceding claims, wherein the at least one compound (B) has a weight-average molar mass Mw of 700 to 20,000 g / mol; and / or a number-average molar mass Mn of 500 to 10,000 g / mol.

6. Curable composition according to any one of the preceding claims, where residues R 1 and R 2 and / or residues R 3 and R 4form one or more ring structures, such as in succinimide, 3-allyl-succinimide, cyclohexane-1,2-dicarboximide, 4-cyclohexene-1,2-dicarboximide, 1,2,3,6-tetrahydrophthalimide, 3,4,5,6-tetrahydrophthalimide, phthalimide, 4-phenoxy-phthalimide, 4-benzoyl-phthalimide, 4-phenylsulfonyl-phthalimide, maleimide, bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, bicyclo[2.2.1]heptane-2,3-dicarboximide, 3,6-epoxy-1,2,3,6-tetrahydrophthalimide, bicyclo[2.2.2]oct-5-ene-2,3-dicarboximide, tetrafluorosuccinimide, tetrafluorophthalimide, 3-phenyl succinimide and naphthalene-2,3-dicarboximide.

7. Curable composition according to one of the preceding claims, comprising the at least one compound (B) in amounts of 1-100 parts by weight based on 100 parts by weight of the total of the at least one compound (A).

8. A curable composition according to any one of the preceding claims, further comprising the compounds: (C) at least one modifier (C); (D) at least one reactive resin (D); (E) at least one filler (E); (F) at least one curing accelerator (F); (G) at least one solvent (G); and / or (H) at least one auxiliary substance (H), wherein the at least one modifier (C), the at least one reactive resin (D), the at least one filler (E), the at least one curing accelerator (F), the at least one solvent (G), and / or the at least one auxiliary substance (H) are different from the at least one compounds (A) and (B).

9. Curable composition according to any one of claims 1-7, further comprising (E2) at least one fiber-reinforcing filler.

10. Curable composition according to any one of claims 1-7, further comprising (C) at least one modifier; and (E2) at least one fiber-reinforcing filler.

11. Curable composition according to any one of claims 1-7, further comprising (D2) at least one imide resin; and (E2) at least one fiber-reinforcing filler.

12. A process for preparing the curable composition according to any one of the preceding claims by mixing the individual components in any order.

13. A process for producing molded articles or fiber composite materials by molding the curable composition according to any one of claims 1-11 and subsequently curing it.

14. Use of the curable composition according to any one of claims 1-11 for producing molded articles or fiber composite materials.

15. Shaped body or fiber composite material obtainable from the process according to claim 12.

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