Curable organosiloxane-modified reaction resins

Abstract

The invention relates to curable compositions made of reaction resins, comprising polymerizable functional cyanate ester groups and poly(diorgano)siloxanes with phenolic hydroxy groups, to a method for producing same, and to cured materials and composites which can be obtained therefrom and have a low water uptake and 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 poly (diorgano) siloxanes with phenolic hydroxy groups, processes for their preparation, and cured materials and composites obtainable therefrom which have low water absorption and high fracture toughness.

[0003] Epoxy (EP) resins and epoxy resin systems are used in a wide variety of applications and have established themselves as one of the most widely used classes of thermosets in composite materials, for example in combination with glass, carbon (CFRP) or aramid fibers. In addition, organic high-performance reactive resins such as cyanate ester (CE), bismaleimide (BMI), polyimide (PI), benzoxazine or phthalonitrile resins, or reactive resin mixtures such as bis (benzocyclobutenimide) / bismaleimide, cyanate ester / epoxy or bismaleimide / cyanate ester (BT resins) have become increasingly important as matrix resins in fiber composites in industry, the automotive industry and the aerospace sector in recent years.Compared to epoxy resins, for example, CE-, BMI- or PI-based polymer matrix resins 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.

[0004] However, thermoset systems based on CE resins also have disadvantages. During thermal curing, the reactive cyanate ester groups (= "N=CO-") trimerize to form cyclic triazine rings, creating polycyanurate networks with a high crosslinking density. As a result of the highly crosslinked state, the cured cyanate ester resins exhibit high mechanical stability; however, the networks are brittle, i.e., they have low crack and impact strength. Another significant disadvantage of cyanate ester resin systems is the hydrolysis sensitivity of both the non-crosslinked resins and the cured polycyanurates: Water that penetrates the cured thermoset network causes network degradation (hydrolytic degradation), which impairs the material properties. In particular, highly cross-linked and higher polar thermosets based on novolak cyanate esters show comparatively high

[0005] Water absorption and hydrolysis rates on .

[0006] It would therefore be desirable to provide suitable high-temperature stable modifiers for these already commercially available CE reaction resins, which contribute both to a reduction in water absorption and to higher fracture toughness of the cured duromer networks, so that these can be used commercially as matrix resins in demanding composite applications at high temperatures, preferably for the aerospace industry. It is crucial that the modifiers are compatible with the cyanate ester resins, i.e. can be processed into homogeneous mixtures, and that the cured duromer mixtures do not show any signs of demixing, such as oiling or exuding of the siloxane component from the polycyanurate network or sticky surfaces, which is undesirable because demixing changes the material properties on the one hand and impairs the matrix-fiber bond on the other.

[0007] For the possibility of polycyanurate networks with

[0008] Several approaches have been developed to modify poly(diorgano)siloxanes (“silicones”) which have reactive functional groups copolymerizable with cyanate ester resins.

[0009] US5539041 (= equivalent to EP0518654B1) claims compositions of cyanate ester resins and silicones with reactive, copolymerizable functional groups. In the exemplary embodiments, only amine-functionalized linear siloxanes are disclosed as modifiers for cyanate ester resins. The main disadvantage of using amine-functional modifiers is, on the one hand, their strongly accelerating effect on the crosslinking reaction of the cyanate ester groups, so that the curing of cyanate ester resin mixtures with higher proportions of amino-containing modifiers is uncontrollable. On the other hand, amino groups contribute to higher water absorption, which leads to increased polycyanurate network degradation by aminolysis and is therefore noticeable in a higher hydrolysis rate.

[0010] The working examples in JP2014012759A2 and EP4056371A1 describe the preparation of mixtures of cyanate ester resins with at least two cyanate ester groups and incompatible, higher-molecular-weight poly(dimethyl)siloxanes with terminal phenolpropyl groups. To prevent phase separation of the incompatible components, the mixture is thermally pre-crosslinked to form a prepolymer in solution (JP2014012759A2) or without solvent (EP4056371A1) in the presence of a catalyst that accelerates the co-reaction of the cyanate ester with the phenol-OH groups. In this context, "pre-crosslinked prepolymers" are understood to mean the oligomers obtainable by partial trimerization of the cyanate ester groups with inclusion of the functional phenol groups of the siloxanes, i.e.There is a reaction of cyanate ester groups with each other as well as a co-reaction of phenol with cyanate ester groups, which also forms triazine rings.

[0011] The main disadvantages of these procedures include the bonding of the phenol groups to the siloxane via thermally unstable propyl residues; the use of organic solvents (JP2014012759A), which is problematic for reasons of economics, toxicology and disposal; and the production of pre-crosslinked prepolymers, the further processing of which, both without solvent due to the higher viscosity and in a solvent, is not suitable for all processing methods, e.g. infusion processes, and has a lower storage stability.

[0012] Neither document discloses how the modification of cyanate ester resins with phenolpropyl-terminated poly(diorgano)siloxanes affects properties such as water absorption or fracture toughness of the cured mixtures, nor does it disclose the extent to which low-molecular-weight phenol-terminated siloxanes with shorter chain length are compatible with cyanate ester resins without pre-crosslinking.

[0013] The present invention is based on the object of modifying organic resins with reactive cyanate ester groups in such a way that, after the molding and curing process, crosslinked thermosets with a reduced water absorption rate and thus improved hydrolysis resistance and higher fracture toughness (Kj c ), whereby the advantageous properties inherent in cyanate ester resins, such as thermo-oxidative resistance and high mechanical strength, are largely retained even in the thermosets modified in this way.

[0014] This object is achieved according to the invention in that linear poly (diorgano) siloxanes with Si-bonded aromatic radicals containing at least one phenolic hydroxy group are used, which are compatible with the organic cyanate ester resins without pre-crosslinking in the presence of a catalyst, i.e. can be processed to form homogeneous single-phase mixtures, and the cured duromer mixtures do not show any signs of demixing, such as oiling or exudation of the siloxane component from the polycyanurate network or sticky surfaces.Surprisingly, it has been found that with the linear poly(diorgano)siloxanes according to the invention with Si-bonded phenol groups it is possible to modify organic cyanate ester resins in such a way that the cured mixtures combine the properties of reduced water absorption (and thus a reduced hydrolytic network degradation), higher fracture toughness and high thermo-oxidative stability in a more advantageous manner than was previously known in the prior art.

[0015] The invention relates to curable compositions containing

[0016] (A) at least one organic compound (A) free of siloxy (=Si-O-) units having at least two cyanate ester (-O-C=N) groups (also referred to in the present specification as "cyanate ester resin"), wherein the compound (A) is preferably substituted and / or contains at least one heteroatom, and

[0017] (B) at least one poly (diorgano) siloxane of the general formula (I)

[0018] RaR^-aSi -O- (RdR 1 2-dSi -O- ) b-SiR c R 1 3-c ( I ) wherein

[0019] R is the same or different and

[0020] - monovalent, SiC-bonded, optionally ethers (=C-0-

[0021] Aliphatic hydrocarbon radicals containing C=), hydroxy (-OH) and / or epoxide (=CQC=) groups, or

[0022] - monovalent, SiC-bonded, aromatic hydrocarbon radicals free of phenolic OH groups, which may be interrupted by at least one heteroatom,

[0023] R 1is the same or different and denotes monovalent aromatic hydrocarbon radicals which contain at least one phenolic hydroxy group and which may be interrupted by heteroatoms, a is 2 or 3, preferably 2, b is an integer from 1 to 18, preferably 1 to 13, particularly preferably 1 to 8, in particular 1 to 3, c is 2 or 3, preferably 2, d is 1 or 2, preferably 2, with the proviso that per poly(diorgano)siloxane molecule (B) of the general formula

[0024] (I) one or two residues R 1 , preferably two residues R 1 , are present. The composition according to the invention is preferably curable without the addition of a catalyst, in particular a catalyst for pre-crosslinking components (A) and (B).

[0025] In a particular embodiment, the proviso also applies that no pre-crosslinking takes place in the presence of a catalyst of components (A) with (B), and / or without the addition of solvents and in the absence of a catalyst, components (A) and (B) are present in liquid form at a temperature of 100°C as a stable, homogeneous mixture, this stable, homogeneous mixture being characterized in particular in that after storage of the mixture at 100°C for at least 15 minutes, no macroscopic demixing occurs due to the formation of a phase interface that can be seen with the naked eye, i.e. two-phase formation.

[0026] In addition, a further feature of the stability of the mixture according to the invention is that the thermoset mixtures obtained after curing do not exhibit any macroscopic demixing in the form of exudation or oiling of the siloxane component (B) from the polycyanurate network, which can be seen with the naked eye, or sticky surfaces.

[0027] 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.

[0028] In the present invention, "phenolic hydroxy group" means an aromatic hydroxy compound in which the hydroxy group is directly bonded to aromatic carbon atoms. In the present invention, the term "component (A)" refers to the totality of the at least one compound (A) and the term "component (B)" refers to the totality of the at least one compound (B).

[0029] In order to avoid making the number of pages of the description of the present invention too extensive, only the preferred embodiments of the individual features are listed.

[0030] However, the knowledgeable reader should explicitly understand this type of disclosure to mean that every combination of different preference levels is explicitly disclosed and explicitly desired - that is, every combination both within a single compound / characteristic and between different compounds / characteristics.

[0031] Cyanate ester resin (A)

[0032] 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.

[0033] 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.

[0034] Particularly preferably, at least two aromatic hydrocarbon radicals, which may be substituted or contain at least one heteroatom and each have a cyanate ester group bonded to an aromatic carbon atom, are present per molecule of the compound (A); in particular, the aromatic hydrocarbon radicals, which may be substituted or contain at least one heteroatom and each have 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 2 2- , -CR 2 =CR 2 -, - C(=CR 2 2)- , -O-, -S-, -N=N-, -CR 2 =N-, -C(=0)-, -C(=0)0-, -OG (=0)0-, -S (=0)-, -S (=0)2-, 0=P(0- ) 3, -SiR 22-, a divalent aromatic hydrocarbon residue, such as phenylene, toluylene, biphenylene and naphthylene; or a divalent cycloalkanediyl residue, such as tricyclo [ 5.2.1.0 2 ' 6 ] decanediyl and bicyclo [ 2.2.1 ] heptanediyl , are bonded together.

[0035] For rest R 2 are each independently a hydrogen atom, a halogen atom or a monovalent, optionally substituted, hydrocarbon radical having 1 to 30 carbon atoms, which may optionally be substituted either with a substituent or with the other radical R 2 is connected to a cyclic unit.

[0036] Examples of remainder R 2 are monovalent residues, such as the methyl, ethyl, trifluoromethyl, phenyl and fluorenyl residues; ring structures consisting of two residues R 2, such as the 1, 1-cyclohexanediyl, 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.

[0037] The heteroatoms can be selected from the group consisting of O, S, N, P and Si, preferably O and S.

[0038] Examples of component (A) used according to the invention are

[0039] Di- and poly-cyanate esters of monoaromatic hydrocarbons, such as phenylene-1,2-dicyanate, phenylene-1,3-dicyanate (CAS 1129-88-0), phenylene-1,4-dicyanate (CAS 1129-80-2),

[0040] 2,4,5-Trifluorophenylene-1,3-dicyanate, 1,3,5-tricyanatobenzene, methyl (2,4-dicyanatophenyl) ketone and 2,7-dicyanonaphtalene; cyanate esters of bisphenols, such as 2,2-bis(4-cyanatophenyl)butane,

[0041] 2.2-Bis ( 4-cyanatophenyl ) propane (CAS 1156-51-0, Bisphenol A- Cyanatester; Handelsbezeichnungen: AroCy® B10, PRIMASET® BADCy bzw. CYTESTER® TA) 32728-27-1, Bisphenol AF-Cyanatester ),

[0042] 2.2-Bis (3-methyl-4-cyanatophenyl) propane (Bisphenol C-Cyanate ester), 1, IBis (4-cyanatophenyl) ethane (CAS 47073-92-7, Bisphenol E--Cyanate ester; Trade names: AroCy® L-10, PRIMASET® LECy, CYTESTER® P201), 1, 1-Bis (4-cyanatophenyl)-1-phenylethane (Bisphenol AP-Cyanate ester), Bis (4-cyanatophenyl) methane (Bisphenol F-Cyanate ester), Bis (4-cyanato-

[0043] 3,5-dimethylphenyl ) methane (CAS 101657-77-6, Tetramethyl- Bisphenol F-Cyanate Ester), 1 , 3-Bis (2- (4-cyanatophenyl ) propan-2-yl)benzene (CAS 127667-44-1, Bisphenol M-Cyanate Ester; trade names: AroCy® XU 366), Bis (4-cyanatophenyl ) thioether), Bis (4-cyanatophenyl) ether, l,l-Bis (4-cyanatophenyl) -3, 3, 5-trimethyl-cyclohexane, 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 (3A) -isobenzofuranone (CAS 32728-31-7) , 3, 3-Bis (4-cyanatophenyl) -2-benzofuran-l-one, 10, 10-bis (4-cyanatophenyl) anthracen-9 (10A) -one, l-Ethyl-2-methyl-3- (4-cyanatophenyl) -5-cyanatoindan, 1, l-Dimethyl-3- methyl-3-(4-cyanatophenyl) cyanatoindane, 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'-dicyanobiphenyl (CAS 1219-14-3), 2,4'-dicyanobiphenyl and 2,2'-dicyanobiphenyl; 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, for example, by acid- or alkali-catalyzed condensation of phenols, naphthols, naphthalenediols, xylenols or cresols with formaldehyde, such as, for example, 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-dicyanatoperfluorooctane; cyanate esters of naturally occurring polyphenols, such as trans-3, 5, 4'-tricyanatostilbene; 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 end-terminated cyanate ester polymer resins 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; 3 2-, -CR 3 =CR 3 -, -C(=CR 3 2)-, -O-, -S-, -N=N-, -CR 3=N-, -C(=O)-, -C(=O)O-, -OC (=0) 0- , -S (=0)-, -S (=0)2-, 0=P(0-)3, -SiR 3 2- or a divalent cycloalkanediyl radical, such as tricyclo [ 5.2.1.0 2 ' 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 .

[0044] For rest R 3 are each independently the ones for R 2 mentioned residues.

[0045] Component (A) is preferably 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. In particular, component (A) is 1,1-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene and cresol or phenol novolak cyanate esters.

[0046] Only one cyanate ester resin (A) or a mixture of different cyanate ester resins (A) can be used, or 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) can be used.

[0047] An example of a prepolymer made from a cyanate ester resin (A) is bisphenol A dicyanate homopolymer (CAS 25722-66-1, trade name: Primaset® BA-200).

[0048] Connection (B)

[0049] The compounds (B) used according to the invention are linear poly(diorgano)siloxanes of the general formula (I) as described above.

[0050] Poly(diorgano)siloxanes (B) can be solid or liquid at 23°C and 1013 hPa, with the poly(diorgano)siloxanes (B) preferably being liquid at 23°C and 1013 hPa.

[0051] If the poly(diorgano)siloxanes (B) used according to the invention are liquid, they have a dynamic viscosity of preferably 5 mPa-s to 100,000 mPa-s, particularly preferably 5 mPa-s to 10,000 mPa-s, in particular 10 mPa-s to 1,000 mPa-s, in each case at 23°C.

[0052] For the purposes of the present invention, the dynamic viscosity is determined according to DIN 53019 at a temperature of 23°C, unless otherwise specified, and an air pressure of 1013 hPa. The measurement is performed 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; a cone-and-plate measuring system (Searle system with a CP 50-1 measuring cone) is used for viscosities greater than 200 mPa-s.The shear rate is adapted 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; 200000 to 299999 mPa-s at 2.5 s-1; 300000 to 1000000 mPa • s at 1.5 s-1.

[0053] After the measuring system has been brought to the measuring 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 taken 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.

[0054] The poly(diorgano)siloxanes (B) used according to the invention have a weight-average molecular weight Mw of preferably 300 to 3000 g / mol, more preferably 300 g / mol to 2000 g / mol, particularly preferably 300 g / mol to 1000 g / mol.

[0055] The poly(diorgano)siloxanes (B) used according to the invention have a number-average molar mass Mn of preferably 300 to 2000 g / mol, more preferably 300 g / mol to 1500 g / mol, particularly preferably 300 g / mol to 1000 g / mol. Examples of monovalent, SiC-bonded, optionally ether (C-OC) and / or epoxy (C-OC) groups, aliphatic

[0056] Hydrocarbon radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl radical; hexyl radicals, such as n-hexyl radical; heptyl radicals, such as n-heptyl radical; octyl radicals, such as n-octyl and iso-octyl radicals, such as 2, 4, 4-trimethylpentyl and 2,2,4-trimethylpentyl radicals; nonyl radicals, such as n-nonyl radical; decyl radicals, such as n-decyl radical; dodecyl radicals, such as n-dodecyl radical; Hexadecyl radicals, such as the n-hexadecyl radical; octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl radical and methylcyclohexyl radical; alkenyl radicals, such as the vinyl, allyl, cyclopentenyl and cyclohexenyl radicals; and epoxide radicals, such as the 3-glycidoxypropyl, oxiran-2-yl and 2-(3,4-epoxycyclohexyl)ethyl radical.

[0057] Examples of monovalent, SiC-bonded, aromatic hydrocarbon radicals R which are free of phenolic OH groups and which can be interrupted by at least one heteroatom are aryl radicals, such as the phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as tolyl, xylyl and ethylphenyl radicals; aralkyl radicals, such as the benzyl, cumyl, the α- and the β-phenylethyl radical; alkoxyaryl radicals, such as the methoxyphenyl radical; aryloxyaryl radicals, such as the phenyloxyphenyl radical; haloaryl radicals, such as fluorophenyl, chlorophenyl, bromophenyl and trifluoromethylphenyl radicals; as well as heterocyclic aromatic hydrocarbon residues, such as pyridyl, pyrazinyl, quinolinyl, furyl residues and the (9, 10-dihydro-9-oxa-1 O-phosphaphenanthren-10-oxid-l 0-yl) ethyl residue.The radical R is preferably a monovalent, SiC-bonded alkyl radical having 1 to 8 carbon atoms and / or an aryl radical, particularly preferably the methyl radical and / or the phenyl radical.

[0058] The monovalent aromatic hydrocarbon radicals R containing at least one phenolic hydroxy group 1 , which may be interrupted by heteroatoms, can be described by the formula (II),

[0059] (II) , wherein

[0060] R 4 , R 5 , R 6 , R 7 and R 8 each independently of each other

[0061] hydrogen atom, a hydroxyl group or a hydrocarbon radical having 1 to 18 carbon atoms, optionally containing hydroxyl groups and optionally interrupted by at least one heteroatom, with the proviso that in formula (II) at least one radical R 4 , R 5 , R 6 , R 7or R 8 is or contains a phenolic hydroxy group.

[0062] Although not explicitly expressed in formula (II), as a further embodiment of the invention, two or more radicals R 4 , R 5 , R 6 , R 7 and R 8 are divalent hydrocarbon radicals which may contain hydroxyl groups and may be interrupted by at least one heteroatom and together form one or more ring structures. For example, R 5 and R 6 together form a ring, as in 5, 6,7,8-tetrahydro-l-naphthol or 1-naphthol. Preferably, the radical R 4 , R 5 , R 6 , R 7 and R 8each independently of one another is a hydrogen atom, a hydroxy group or a hydrocarbon radical having 1 to 8 carbon atoms, optionally containing hydroxy groups and optionally bonded via an oxy (-0-) unit.

[0063] Preferably, the residue R 6 a hydroxy group and residue R 4 , R 5 , R 7 and R 8 each independently of one another is a hydrogen atom or a hydrocarbon radical having 1 to 12 carbon atoms, optionally bonded via an oxy (-O-) unit.

[0064] Particularly preferably, the residue R 6 a hydroxy group and residue R 4 , R 5 , R 7 and R 8 each independently of one another is a hydrogen atom or a hydrocarbon radical with 1 to 4 carbon atoms.

[0065] In particular, the rest R 6a hydroxy group and residue R 4 , R 5 , R 7 and R 8 around hydrogen atom.

[0066] Examples of possibly substituted

[0067] Hydrocarbon residues R 1 are hydroxyphenyl [-CeH4 (OH) ] - ,

[0068] Hydroxy (methyl ) phenyl [-CeH3(OH) (CH3) ]-, Hydroxy (dimethyl ) phenyl [-C6H2(OH) (CH3) 2] -, Hydroxy (ethyl) phenyl [-C6H3(OH) (CH2CH3) ] -, Hydroxy (methyl ) (iso-propyl ) phenyl [-CeH3(OH) (CH3) (CH (CH3) 2) ] -,

[0069] Hydroxy (methoxy ) phenyl [-CeH3(OH) (OCH3) ]-,

[0070] Hydroxy (phenyloxy ) phenyl [-CeH3(OH) (OCeHs) ]-, (Hydroxyphenyl) phenyl [-C6H4 (CeH4 (OH) ) ] -, Hydroxynaphthyl [-CioHe (OH) ] -, Hydroxy (phenyl ) phenyl [-CeH3(OH) (CeHs) ]-, Hydroxy (benzyl ) phenyl [-CeH3(OH) (CH2 (CeHs) ) ] - and the (hydroxycumyl) phenyl

[0071] [-C6H3(C (CH3) 2) (C6H4(OH) ) ] -rest. Preferably, the rest R is1 to

[0072] Hydroxyphenyl-, Hydroxy(methyl)phenyl-, Hydroxy(dimethyl)phenyl-

[0073] , hydroxy ( ethyl ) phenyl and hydroxy ( methyl ) ( iso-propyl ) phenyl radical, particularly preferably the hydroxyphenyl radical.

[0074] Examples of the at least one compound (B) used according to the invention are preferably those of the formulas (III) to (XII)

[0075] (VII) ,

[0076] (XII) , wherein Me is methyl radical, Ph is phenyl radical, m is 1 to 19, n is 1 to 18 and o is 1 to 18, with the proviso that the sum of n + o is 2 to 19. The at least one compound (B) used according to the invention is preferably one of the formulas (III), (VI), (X) and (XI), particularly preferably one of the formulas

[0077] (III) , (X) and (XI) .

[0078] Preferably, in formulas (III) to (XI), m is equal to 1 to 14, particularly preferably 1 to 9, in particular 1 to 4.

[0079] Preferably, in formula (XII) the sum n + o is equal to 1 to

[0080] 14, particularly preferably 1 to 9, in particular 1 to 4.

[0081] The at least one compound (B) used according to the invention is particularly preferably one of the formulas (III), (X) or (XI) where m is 1 to 9.

[0082] In particular, the at least one compound (B) used according to the invention is one of the formulas (III) and (X) where m is 1 to 4.

[0083] Poly(diorgano)siloxanes (B) used according to the invention are commercially available products or can be prepared by processes commonly used in chemistry. For example, a process for preparing bis[1,3-(4-hydroxyphenyl)]tetramethyldisiloxane is described in "ACS Symposium Series, Vol. 729, Silicones and Silicone-Modified Materials, Chapter 9, pp. 164-169 (DOI: 10.1021 / bk-2000-0729.ch009)" and in "ACS Polymer Preprints 1992, 33(1), pp. 988-989." The reaction proceeds via a Grignard reaction of 4-bromophenylpyranyl ether with dimethyldichlorosilane or dimethyldiethoxysilane, followed by hydrolysis and condensation. Similarly, longer-chain siloxanes can be prepared, for example, by Grignard reaction of 4-bromophenylpyranyl ether with a, o-dichloro-poly (diorgano) siloxane [CI (R 9 2SiO) i-i9SiR 9 2Cl], 1-Chloro-o-triorganosilyl-poly(diorgano)siloxane [Eq(SiR 9 2O) i-igSiR 93] or a mono-chloro-substituted poly (diorgano) siloxane with terminal triorganosilyl groups [ ( SiR 9 3O) i- p (ClSiR 9 2O) (SiR 9 3O) i- q ] , where R 9 has the meaning of R and the sum p+q is 19, and subsequent removal of the tetrahydropyranyl protecting group. Other phenol-OH protecting groups can also be used, such as trimethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, methyl, tert-butyl, triphenylmethyl, benzyl, allyl, methoxymethyl, benzoyloxymethyl, or the methoxybenzyl protecting group.

[0084] Only one poly(diorgano)siloxane (B) or a mixture of different poly(diorgano)siloxanes (B) can be used.

[0085] The compositions according to the invention contain a total of poly(diorgano)siloxane (B) in amounts of preferably 1 to 70 parts by weight, particularly preferably 5 to 50 parts by weight, in particular 5 to 30 parts by weight, in each case based on 100 parts by weight of component (A).

[0086] In addition to components (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).

[0087] In a preferred embodiment, the inventive

[0088] Composition also includes the following compounds:

[0089] (C) at least one modifier (C);

[0090] (D) at least one reactive resin (D);

[0091] (E) at least one filler (E);

[0092] (F) at least one curing accelerator (F); (G) at least one solvent (G); and / or

[0093] (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).

[0094] The composition according to the invention can

[0095] • comprise only one compound (C) or a mixture of different compounds (C), preferably only one compound

[0096] (C) ;

[0097] • comprise only one compound (D) or a mixture of different compounds (D), preferably only one compound

[0098] (D) ;

[0099] • comprise only one compound (E) or a mixture of different compounds (E), preferably only one compound

[0100] (E) ;

[0101] • comprise only one compound (F) or a mixture of different compounds (F), preferably only one compound

[0102] (F) ;

[0103] • comprise only one compound (G) or a mixture of different compounds (G), preferably only one compound

[0104] (G) ; and / or

[0105] • comprise only one compound (H) or a mixture of different compounds (H), preferably only one compound

[0106] (H) .

[0107] In the present invention, the designation "component (C)" stands for the entirety of the at least one compound (C), the designation "component (D)" stands for the entirety of the at least one compound (D), the designation "component (E)" stands for the entirety of the at least one compound (E), the designation "component (F)" stands for the entirety of the at least one compound (F), the designation "component (G)" stands for the entirety of the at least one compound (G) and the designation "component (H)" stands for the entirety of the at least one compound (H).

[0108] Connection (C)

[0109] The optional at least one modifier (C) is preferably

[0110] Organosilicon compounds (CI) containing units of the formula

[0111] R 10 i (OR 11 ) : SiO(4-ip / 2 (XIII) , where

[0112] R 10is 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,

[0113] R 11 is the same or different and is a hydrogen atom or a monovalent hydrocarbon radical having 1 to 18 carbon atoms and optionally interrupted by at least one heteroatom, i is 0, 1, 2 or 3, preferably 1, 2 or 3, j is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1, in particular 0, and with the proviso that in formula (XIII) the sum i+j is <3, that compound (CI) contains 2 to 20 units of formula (XIII) and that compound (CI) has no phenolic hydroxy groups.

[0114] Examples of monovalent, SiC-bonded, optionally substituted, optionally interrupted by at least one heteroatom, hydrocarbon radicals R 10are the radicals mentioned for R; unsaturated hydrocarbon radicals, such as vinyl, propenyl, 5-hexenyl, cyclohexenyl, 2- ( 3-cyclohexenyl ) ethyl, bicyclo [ 2.2.1] hepten-2-yl, dicyclopentenyl, 7-octenyl, 10-undecenyl, 4-vinylcyclohexyl, 3-norbornenyl, vinylphenyl, propenylphenyl, ethynyl, propynyl and butynyl, arylethynyl and ethynylphenyl residue; Imido residues, such as the N-(5-ethynylphthalimido)phenyl, N-(5-(phenylethynyl)phthalimido)phenyl, nadimidophenyl, maleimidophenyl and 3-maleimidopropyl residues; Epoxy radicals, such as the 3-glycidoxypropyl, 4-(oxiran-2-yl)phenyl, oxiran-2-yl and 2-(3,4-epoxycyclohexyl)ethyl radical; acrylate radicals, such as the 3-methacryloxypropyl, acryloxymethyl and methacryloxymethyl radical; amine radicals, such as aminophenyl radicals, the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-phenylaminomethyl radical; hydroxyalkyl radicals, such as the hydroxypropyl radical; and the polycaprolactone, polycaprolactam, cyanatophenyl, 3-cyanatopropyl, isocyanatophenyl and 3-isocyanatopropyl radicals.

[0115] Preferably, the residue R 10hydrogen atom, the phenyl, or the methyl residue.

[0116] Preferably, the residue R 11 aliphatic hydrocarbon radicals 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.

[0117] Examples of organosilicon compounds (CI) are 1,3, 5, 7-

[0118] Tetrakis (2-(3,4-epoxycyclohexyl)ethyl)-1, 3, 5, 7-tetramethylcyclotetrasiloxane (CAS 121225-98-7), 2, 4, 6,8-

[0119] Tetramethyl-2, 4, 6, 8-tetrakis [3-

[0120] (glycidoxy)propyl] cyclotetrasiloxane (CAS 257284-60-9), bis[2-(3,4-epoxycyclohex-l-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (GAS 18724-32-8), 1,3-bis(norbornenylethyl)-1,1,3,3,-tetramethyldisiloxane, organopolysiloxane of average composition (PhSiC>3 / 2) 20 (PhSi(OMe)O2 / 2) 66 (PhSi(OMe)2O1 / 2) 14 and a weight average molar mass Mw = 2190 g / mol, organopolysiloxane of average composition (PhSiO5 / 2) 75 (MesSiOi / 2) 25 and a weight average molar mass Mw = 1380 g / mol, Octa (epoxycyclohexyl) -POSS (GAS 187333-74-0), Octaphenyl-POSS (GAS 5256-79-1), Octaphenylcyclotetrasiloxane (GAS 546-56-5), 2,4, 6, 8-Tetramethyl-2, 4, 6, 8-tetraphenylcyclotetrasiloxane (GAS 77-63-4), 1, 1, 3, 3, 5, 7-Hexamethyl-5, 7-diphenylcyclotetrasiloxane,

[0121] 1,1,3, 3-Tetramethyl-5, 5, 7, 7-tetraphenylcyclotetrasiloxane (GAS 1693-47-6), 1, 3, 5-trimethyl-1, 1,3,5, 5-pentaphenyltrisiloxane

[0122] (3390-61-2) , 1, 3, 3, 5-Tetramethyl-l, 1, 5, 5-tetraphenyltrisiloxan

[0123] (3982-82-9) , 1,3,5, 7 -Tetramethyl- 1, 1, 3, 5, 7, 7- hexaphenyltetrasiloxan (GAS 38421-40-8) , und 1 , 9-Dimethoxy- 1, 3, 5, 7, 9-pentamethyl-l , 3,5,7, 9-pentaphenylpentasiloxan .

[0124] The optional at least one modifier (C) is preferably a thermoplastic organic polymer ("thermoplastic") (02) which is free from siloxy (=Si-O-) units and from cyanate ester groups and has 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(amidimide), polyarylate, polyesterimide, polyetherimide, polyaramid, polyacrylate, polyhydantoin, liquid crystal polymer, polycarbonate, polyester carbonate and polyethylene terephthalate; and mixtures or copolymeric compounds thereof. The thermoplastics (C2) have either reactive or chemically inert end groups. Reactive end groups remain from the corresponding reactive groups of the monomers during the polymerization reaction due to the manufacturing process.These are preferably hydroxy, 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, particularly 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, particularly preferably from 2000 to 30,000 g / mol, in particular from 3000 to 20,000 g / mol.

[0125] The optional at least one modifier (C) is preferably an organic, monofunctional cyanate ester (C3) of the general formula (XIV) which is free from siloxy (=Si-O-) units and phenolic hydroxy groups

[0126] R 12 -OCN (XIV) , where R 12means 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.

[0127] 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-chloro-cyanatobenzene, 4-cyanatodiphenylsulfone, 4-cyanatotoluene, 4-cyanatodiphenyl ether, 4-cyanatodiphenyl ketone, 4-(cyanato)methoxybenzene; and propenyl-substituted monofunctional cyanate esters, such as 4-cumyl-2-(propenyl)cyanatobenzene or 2-(propenyl)cyanatobenzene. 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.

[0128] 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.

[0129] The optional aliphatic carbon-carbon multiple bonds in compound (C4) are preferably propenyl groups bonded to aromatic carbon atoms, with compound (C4) particularly preferably having a phenolic hydroxy group and optionally a propenyl group bonded to an aromatic radical.

[0130] 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,a-dimethylbenzyl)phenol, nonylphenol, xylenol or 2,6-dinonylphenol; polyhydric phenols, such as pyrocatechol (benzene-1,2-diol), resorcinol (benzene-1,3-diol), hydroquinone (benzene-1,4-diol), pyrogallol (benzene-1,2,3-triol), phloroglucinol (benzene-1,3,5-triol), dihydroxynaphthalene;aromatic compounds with two (bisphenol) 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), 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.;

[0131] 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 ) f luoren and 4- ( 1- ( 4-hydroxy-3- propenylphenyl ) propyl) -2-propenylphenol .

[0132] Verbindung (C4) ist bevorzugt 4-Phenylphenol , 2-Methoxy-4- (2- propenyl ) -phenol , 4-Cumylphenol , 4-Isopropylphenol, 4-tert- Butylphenol, 2- tert-Butylphenol , Bisphenole, 2 , 2-Bis ( 3- ( 2- propenyl) -4-hydroxyphenyl) propan, 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 oder 2- ( 2-Propenyl ) phenol ; wobei 2-Methoxy-4- (2- propenyl ) -phenol , 4-Cumylphenol , 4- tert-Butylphenol , 2,2-Bis (3- (2-propenyl) -4-hydroxyphenyl ) propan, Bis (3- (2-propenyl) -4- hydroxyphenyl ) sulfon, 4-Cumyl-2- (2-propenyl) phenol, 4-tert- Butyl-2- ( 2-propenyl ) phenol , sowie Bisphenol A, E, F, M und S besonders bevorzugt sind.

[0133] If the compositions according to the invention contain at least one modifier (C), either only one modifier (Gl) to (C4) or several different modifiers (Gl) to (C4) can be contained in a mixture.

[0134] 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).

[0135] Connection (D)

[0136] 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, polymerizable 5-ethynylphthalimido, 5-(phenylethynyl)phthalimido, nadimido, benzocyclobutenephthalimido or maleimido groups bonded to aromatic carbon atoms per molecule;the maleimido, glycidyloxy, glycidylamino, diglycidylamino groups are particularly preferred;

[0137] 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 which contain at least two, optionally substituted, optionally interrupted by at least one heteroatom, aromatic hydrocarbon radicals each having a maleimido, glycidyloxy, glycidylamino or diglycidylamino group bonded to an aromatic carbon atom, which are linked via a covalent bond or a bridging unit selected from the group consisting of -CR 132- , -CR 13 =CR 13 -, =C=CR 13 2, -0-, -S-, -N=N-, -CR 13 =N-, -C (=0) -

[0138] , -C(=0)0-, -OG (=0)0-, -S(=0)2-, 0=P(0-)3, -SiR 13 2-, phenylene, arylene, biphenylene, biarylene, naphthylene or cycloalkanediyl groups, such as tricyclo [ 5.2.1.0 2 ' 6 ] decanediyl or

[0139] Bicyclo [ 2.2.1 ] heptanediyl , are linked together.

[0140] For rest R 13 are each independently the ones for R 2 mentioned residues.

[0141] Reactive resins (D) preferably contain heteroatom-free aromatic ring frameworks.

[0142] Epoxy resins (D1) are preferably copolymerizable with cyanate ester resin (A). Imide resins (D2) are preferably not copolymerizable with cyanate ester resin (A).

[0143] Examples of polymerizable epoxy resins (DI) are glycidyl ethers of phenol compounds, such as 2,2-bis(4-glycidyloxyphenyl)propane (GAS 1675-54-3), bis(4-glycidyloxyphenyl)methane (GAS 2095-03-6), 1,2-bis(glycidyloxy)benzene (GAS 2851-82-3), 1,3-bis(glycidyloxy)benzene (GAS 101-90-6), 1,4-bis(glycidyloxy)benzene (GAS 129375-41-3), 3,5,3',5'-tetramethyl-4,4'-diglycidyloxybiphenyl (GAS 85954-11-6) , 2,2-Bis (3,5-dibromo-4-glycidyloxyphenyl) propane (GAS 3072-84-2) , Tris (4-glycidyloxyphenyl) methane (GAS 66072-38-6) , 1 , 1 , 2 , 2-Tetrakis (4-glycidyloxyphenyl) ethane (GAS 7328-97-4);Glycidyl ethers of phenol, naphthol, naphthalenediol, bisphenol or cresol-formaldehyde condensation products, such as cresol novolak glycidyl ether (GAS 29690-82-2), phenol novolak glycidyl ether (GAS 9003-36-5, GAS 28064-14-4, GAS 158163-01-0) and bisphenol A-epichlorohydrin-formaldehyde copolymer (GAS 28906-96-9); Glycidyl ethers of phenol or cresol-dicyclopentadiene condensation products, such as GAS 68610-51-5 and GAS 119345-05-0; Glycidyl esters of aromatic carboxylic acids, such as diglycidyl phthalate (GAS 7195-45-1), diglycidyl terephthalate (GAS 7195-44-0), diglycidyl isophthalate (GAS 7195-43-9), triglycidyl-1,2,3-benzenetricarboxylate, triglycidyl-1,2,4-benzenetricarboxylate (GAS 7237-83-4) and triglycidyl-1,3,5-benzenetricarboxylate (GAS 7176-19-4);Glycidyl derivatives of aromatic amines and aminophenols, such as N,N-diglycidyl-4-glycidyloxyaniline (GAS 5026-74-4), 4,4'-methylenebis(N,N-diglycidylaniline) (GAS 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).

[0144] Examples of polymerizable maleimide resins (D2) are 4,4'- bis (maleimidophenyl ) methane (CAS 13676-54-5), m-

[0145] Xylylenebismaleimide (CAS 13676-53-4), 1,1'-(2,2,4-Trimethylhexane-1,6-diyl)bis-1H-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-

[0146] Phenylenebismaleimide (CAS 13118-04-2), N,N'-1,3-

[0147] Phenylenebismaleimide (CAS 3006-93-7) , N,N'-1,3-

[0148] Phenylenebismaleimide (CAS 3278-31-7), copolymers of bismaleimides and aromatic amines, such as 4,4'-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-

[0149] (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) (GAS 13676-53-4), 4,4'-bis(maleimido)-1,1'-biphenyl (GAS 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) .

[0150] Preferably, the at least one compound (D) is a monomeric compound without a thermoplastic, homo- or copolymeric polymer component.

[0151] 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).

[0152] If the compositions according to the invention contain at least one polymerizable imide (D2), this is preferably present in combination with components which are copolymerizable with both cyanate ester groups and imido groups, preferably maleimido groups. These components are selected from those cyanate esters (A), modifiers (C3) or modifiers (C4) which have propenyl groups bonded to aromatic carbon atoms; or from aromatic hydrocarbon compounds which have, 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 (CAS 7300-91-6).

[0153] 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.

[0154] Connection (E)

[0155] The at least one filler (E) optionally present in the compositions according to the invention may be any particulate filler known to date.

[0156] 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.

[0157] Examples of fillers are non-reinforcing particulate fillers, i.e. fillers with a BET surface area of ​​preferably up to 50 m2 / 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 large 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 cut 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.

[0158] 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).

[0159] 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.

[0160] 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).

[0161] 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.

[0162] 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).

[0163] 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).

[0164] The at least one filler (E2) can be present 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

[0165] Fiber felt. 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 entirely, of filler (E2).

[0166] 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.

[0167] The optional fiber fabrics (E2) or fiber scrims (E2) according to the invention are preferably used in multiple layers.

[0168] 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).

[0169] Connection (F)

[0170] 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 alcoholates, 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.

[0171] 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.

[0172] 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 particularly preferably used in amounts of from 0.0001 to 0.02 parts by weight, based on 100 parts by weight of component (A).

[0173] 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 radical-forming curing accelerators (F2), the amounts involved are preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the sum of imido group-containing modifier (CI) and imide resin (D2). Preferably, no radical-forming curing accelerators (F2) are used.

[0174] Connection (G)

[0175] 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-iso-butyl 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 iso-butyl ketone, methyl ethyl ketone, methyl iso-amyl ketone, di-iso-butyl 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;

[0176] amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; acetonitrile; and dimethyl sulfoxide.

[0177] The at least one solvent (G) is preferably an aromatic hydrocarbon or a ketone.

[0178] 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).

[0179] Connection (H)

[0180] 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, discoloration; flame-retardant agents or plasticizers.

[0181] If the compositions according to the invention contain at least one excipient (H), the at least one excipient (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, in each case based on 100 parts by weight of the sum of components (A) and (B). The compositions according to the invention preferably contain no excipient (H). The compositions according to the invention are preferably those containing

[0182] (A) at least one cyanate ester resin,

[0183] (B) at least one poly(diorgano)siloxane, optionally (C) at least one modifier, optionally (D) at least one reactive resin,

[0184] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent and optionally (H) further components.

[0185] The compositions according to the invention are preferably those containing

[0186] (A) at least one cyanate ester resin,

[0187] (B) at least one poly(diorgano)siloxane,

[0188] (C) at least one modifier, optionally (D) at least one reactive resin,

[0189] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent and optionally (H) further components.

[0190] In a particularly preferred embodiment, the compositions according to the invention are those containing

[0191] (A) at least one cyanate ester resin,

[0192] (B) at least one poly(diorgano)siloxane, optionally (C) at least one modifier, (Dl) at least one epoxy resin,

[0193] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent, and optionally (H) further components. In a further particularly preferred embodiment, the compositions according to the invention are those containing

[0194] (A) at least one cyanate ester resin,

[0195] (B) at least one poly(diorgano)siloxane, optionally (C) at least one modifier selected from the group (Gl) to (C4),

[0196] (D2) at least one maleimide resin,

[0197] (E2) at least one fiber-reinforcing filler, optionally (F) at least one curing accelerator, optionally (G) at least one solvent and optionally (H) further components, with the proviso that at least one component (A), (C3) or

[0198] (C4) with propenyl groups directly bonded to aromatic carbon atoms.

[0199] The compositions according to the invention preferably contain no further components apart from components (A) and (B), the optional components (C) to (H) and any impurities typical of the raw material, for example catalyst residues such as sodium chloride, potassium chloride, impurities in technical cyanate ester resin monomers and any reaction products of the components used which are formed during mixing or storage.

[0200] 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.

[0201] The compositions according to the invention can be prepared by known processes, such as, for example, by mixing the individual components in any order or in a previously known manner.

[0202] 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.

[0203] 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. Very particular preference is given to mixing 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, it being possible to heat or cool as required.

[0204] Mixing can take place at the pressure of the surrounding atmosphere, i.e. approximately 900 to 1100 hPa. It is also possible to mix temporarily or continuously under reduced pressure, such as 30 to 500 hPa absolute pressure, in order to remove volatile compounds and / or air, or to work at excess pressure, such as pressures between 1100 hPa and 3000 hPa absolute pressure, particularly in continuous operation, when, 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.

[0205] The process according to the invention can be carried out continuously, discontinuously or semi-continuously, preferably it is carried out discontinuously. 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 transfer molding (resin transfer molding) or vacuum infusion and processed into molded articles.

[0206] 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.

[0207] 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 firstly mixed in any desired

[0208] The components (E2) are mixed in the following order to form a premix, and then component (E2), preferably ropes, woven fabrics, non-crimp fabrics, knitted fabrics, or braids, is impregnated with the premix, if necessary under pressure, and degassed if necessary. 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.

[0209] 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.

[0210] 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 firstly mixed in any desired

[0211] 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 ensure complete wetting of component (E2).

[0212] The compositions according to the invention can be brought into any desired shape by mechanical pressure at ambient temperature or, if appropriate, at elevated temperature.

[0213] The compositions according to the invention are preferably moldable and are particularly preferably modeled and cured in a mold cavity or around a mold template.

[0214] A further object of the invention is therefore the use of the composition according to the invention for the production of shaped bodies or fiber composite materials.

[0215] A further subject of the invention is therefore a process for producing shaped bodies by shaping the composition and subsequent curing.

[0216] The invention therefore further relates to molded articles obtainable from the compositions according to the invention by shaping and curing. The compositions according to the invention or those produced according to the invention are preferably degassed before curing, particularly preferably after shaping and before curing.

[0217] The crosslinking 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 crosslinking according to the invention takes place stepwise at temperatures from 120 to 270 ° C.

[0218] By increasing the temperature, crosslinking can be accelerated so that shaping and crosslinking can be carried out in one step.

[0219] The molded bodies according to the invention are preferably fiber composite materials (or fiber-reinforced plastics

[0220] FVK" ).

[0221] Another object of the invention is a process for producing fiber composite materials, characterized in that the compositions according to the invention are shaped and cured.

[0222] A further subject of the invention are therefore fiber composite materials obtainable from the compositions according to the invention by shaping and curing.

[0223] 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. 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.

[0224] The quotient of the critical stress intensity factor Kj c of the cured compositions according to the invention, for example from 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of poly(diorgano)siloxane (B), to the respective cured, unmodified cyanate ester resin (A) is preferably greater than 1.0, particularly preferably greater than 1.1, in particular greater than 1.2, in each case measured at 23°C.

[0225] The cured compositions according to the invention, for example from 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B), after 1600 hours of water storage at 70°C, have a water absorption reduced by preferably at least 20%, preferably at least 30%, particularly preferably at least 40%, in particular at least 50%, compared to the corresponding unmodified cyanate ester resin (A).

[0226] The cured compositions according to the invention, for example from 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of the poly(diorgano)siloxane (B), have a glass transition temperature of preferably greater than 170°C, particularly preferably greater than 200°C, in particular greater than 230°C.

[0227] The cured compositions according to the invention, for example from 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of poly(diorgano)siloxane (B), after 200 hours of storage at 240°C, have a weight loss which is preferably at most 300%, preferably at most 200%, particularly preferably at most 100%, in particular at most 80%, higher compared to the corresponding unmodified cyanate ester resins (A).

[0228] The compositions according to the invention have the advantage that cyanate ester resin (A) is miscible with poly(diorgano)siloxane (B) without the addition of further solvent and without pre-crosslinking in the presence of a catalyst, and the cured duromer mixtures of components (A) and (B) do not exhibit any macroscopic demixing in the form of exudation or oiling of the siloxane component from the polycyanurate network or sticky surfaces.

[0229] The compositions according to the invention have the advantage that cyanate ester resin (A) is miscible with poly (diorgano) siloxane (B) without the addition of further solvent and poly (diorgano) siloxane (B) does not exude from the duromer network during or after curing.

[0230] The compositions according to the invention have the advantage that in the cured state they have a reduced water absorption and thus a better hydrolysis resistance compared to the corresponding non-modified cyanate ester resins.

[0231] The compositions according to the invention also have the advantage that they have a high thermo-oxidative stability in the cured state.

[0232] The molded articles according to the invention have the advantage that they are heat-stable and have a reduced fire load compared to composite materials made from purely organic cyanate ester resin systems. The compositions according to the invention have the advantage that they can be produced from accessible raw materials and in a simple manner.

[0233] The compositions according to the invention have the advantage that no harmful emissions are produced during processing to the extent that usually occur with organic cyanate ester resins used according to the prior art.

[0234] Examples of implementation

[0235] 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, restricting it to the contents disclosed therein.

[0236] Molar masses

[0237] In the context of the present invention, the weight-average molar mass Mw and the number-average molar mass Mn, each in the unit g / mol, rounded to whole tens in accordance with DIN 1333: 1992-02 Section 4, are determined by size exclusion chromatography (SEC / GPC) in accordance with DIN 55672-1 / ISO 16014-1 and ISO 16014-3 with tetrahydrofuran (THE) as eluent 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 10000 Å, 500 Å and 100 Å with an exclusion size of greater than 450000 g / mol against polystyrene standards. The analyses are carried out at a column temperature of 4511 °C and using a refractive index detector. Preparation of the test specimens

[0238] First, the cyanate ester resin (A) was heated to 80°C with thorough mixing to improve processability. Poly(diorgano)siloxane (B) was then added, the mixture was homogenized at 110°C for one hour, then degassed at 110°C and a pressure of 10 mbar for one hour and, after breaking the vacuum with nitrogen, immediately hot-filled into a two-part, screw-together 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 producing the test specimens for determining fracture toughness, water absorption, thermo-oxidative stability and for carrying out the 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:.

[0239] 1) 18 hours curing at 180°C

[0240] 2) Temperature increase to 200°C within 30 minutes

[0241] 3) 3 hours curing at 200°C

[0242] 4) Temperature increase within 30 minutes to 240°C

[0243] 5) 2 hours curing at 240°C.

[0244] The specimen was then allowed to cool to ambient temperature in the mold before being demolded. For further use, the top 10 mm of the cured specimen side, which was open and facing air during curing in the mold, was cut off and discarded. The test specimens for measuring fracture toughness, water absorption, thermo-oxidative stability, and DMA were then cut out of the large, 6.5 mm high, cured specimen plate in the corresponding dimensions length x width using a diamond cut-off saw. The 2.00 mm thick test specimens for measuring water absorption were cut out of the pre-sawn piece using an internal hole diamond saw from the inner part, so that all six surfaces of these test specimens were sawn.

[0245] Fracture toughness Ki c

[0246] The measurement of the fracture toughness or the critical stress intensity factor Kj cwas 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 Kj given in Table 1 c in MN x in 3 / 2 was rounded to two decimal places according to DIN 1333:1992-02 Section 4.

[0247] Dynamic Mechanical Analysis (DMA)

[0248] Measurement conditions:

[0249] • Measuring device: ARES rheometer (TA Instruments)

[0250] • Temperature range: -100°C - 300°C

[0251] • Heating rate: 4 K / min with nitrogen purge

[0252] • Frequency: 1 Hz

[0253] • Strain: Initial 0.03%, automatically increased when

[0254] Measurement signal below threshold

[0255] For the investigations, 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.

[0256] In the present invention, the glass transition temperature TG corresponds to the maximum value of the tangent delta curve (= tan deltamax), ie the measuring temperature at which the ratio of loss modulus G' to storage modulus G' is greatest.

[0257] The value for the glass transition temperature TG given in Table 1 was rounded to whole numbers, according to DIN 1333:1992-02 Section 4.

[0258] What would take

[0259] In the present invention, water absorption was determined gravimetrically after storage of the test specimens in tempered water. Cuboid-shaped test specimens with the dimensions length x width x thickness = 30.00 mm x 17.00 mm x 2.00 mm were used; the accuracy of the weight determination was 0.01 mg. The test specimens were first dried to constant weight in a vacuum oven at 70°C and 30 mbar, with the weight being determined at 24-hour intervals. The test specimens were considered "dry" if no further weight loss was measured over a period of 48 hours. One dry test specimen was then immersed in 45 ml of deionized water in a suitable sealable container. The sealed container was then placed in a convection oven preheated to 70°C and maintained at this temperature throughout the test period.After 1600 hours, the test specimens were removed, cooled to ambient temperature, and the surfaces wiped dry with a cloth. The weight of the test specimens was then determined again. The water absorption (or weight gain) was calculated according to the formula shown in Table 1.

[0260] Value for water absorption given in % and rounded to two decimal places according to DIN 1333:1992-02 Section 4.

[0261] Thermo-oxidative stability 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 Table 1. The value for weight loss is given in % and rounded to two decimal places according to DIN 1333:1992-02 Section 4.

[0262] compatibility

[0263] The compatibility of compound (B) with cyanate ester resins

[0264] (A) was visually assessed using the criteria given in Table 1 :

[0265] Before curing after storing the mixture for 15 minutes at 100°C:

[0266] "+", meaning mixture is single-phase and , meaning mixture is two-phase;

[0267] After curing:

[0268] "+" = good compatibility, ie no interference with the mere

[0269] Eye visible oiling or sweating of the connection

[0270] (B) from the cured mixture, and = poor compatibility, ie visible oiling or

[0271] Exudation of component (B) from the hardened

[0272] Mixture. Furthermore, the stickiness or oiliness of the air-side surface was determined using an LDPE film (CAS: 9002-88-4) and a filter paper (Whatman™ filter paper grade 589 / 2) by pressing the film or filter paper onto the surface and then peeling it off. As indicated in Table 1, the surface stickiness / oiliness was differentiated into "+" (test specimen surface dry, non-sticky, and non-oily (dry filter paper)) and "-" (test specimen surface soft, sticky, and / or oily (moist filter paper)).

[0273] Preparation of bis [1,3- (4-hydroxyphenyl) ] -1, 1,3,3-tetramethyl di siloxane (CAS 24602-62-8, hereinafter referred to as modifier "MI")

[0274] The siloxane was prepared according to the synthesis instructions in “ACS Polymer Preprints 1992, 33(1) , 988-989”.

[0275] Example Bl

[0276] As described in the section "Preparation of the test specimens", 85 g of 2,2-bis(4-cyanatophenyl)propane (CAS 1156-51-0; commercially available under the trade name Primaset® BADCy from Arxada Ltd., CH-4002 Basel) as component (A) are mixed with 15 g of the previously prepared modifier "MI" as component (B) and then processed.

[0277] The results can be found in Table 1.

[0278] Example B2

[0279] Example B1 is repeated except that a polyphenol cyanate resin (CAS 87397-54-4; commercially available under the trade name Primaset® PT-15 from Arxada Ltd., CH-4002 Basel) is used instead of 2,2-bis(4-cyanatophenyl)propane. The results are shown in Table 1.

[0280] Comparison example VI

[0281] The procedure described in Example B1 was repeated with the modification that no component (B) was added to component (A).

[0282] The results can be found in Table 1. Comparative example V2

[0283] The procedure described in Example B2 was repeated except that no component (B) was added to component (A). The results are shown in Table 1.

[0284] 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 (-O- C=N) groups; and (B) at least one poly(diorgano)siloxane of the general formula (I) RaR^-aSi-O- (RdR 1 2-dSi-O- ) b-SiR c R 1 3-c (I) wherein R is the same or different and is monovalent, SiC-bonded, aliphatic Hydrocarbon residues; or - monovalent, SiC-bonded, aromatic hydrocarbon residues free of phenolic OH groups, R 1 is the same or different and denotes monovalent aromatic hydrocarbon radicals containing at least one phenolic hydroxy group, a is 2 or 3, b is an integer from 1 to 18, c is 2 or 3, and d is 1 or 2, with the proviso that per poly(diorgano)siloxane molecule (B) of the general formula (I) one or two radicals R 1 are present.

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 per molecule of compound (A) there are at least two aromatic hydrocarbon radicals each having a cyanate ester group bonded to an aromatic carbon atom.

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 2 2- , -CR 2 =CR 2 -, - C(=CR 2 2)- , -O-, -S-, -N=N-, -CR 2 =N-, -C(=0) - , -C(=0)0-, -OG (=0)0-, -S(=0) -, -S (=0)2-, 0=P(0-)3, -SiR 2 2-, a divalent aromatic hydrocarbon residue, such as phenylene, toluylene, biphenylene and naphthylene; or a divalent cycloalkanediyl residue, such as tricyclo [ 5.2.1.0 2 ' 6 ] decanediyl and bicyclo [ 2.2.1 ] heptanediyl , are bonded together, wherein R 2 each independently represents a hydrogen atom, halogen atom or a monovalent hydrocarbon radical having 1 to 30 carbon atoms.

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 300 to 3000 g / mol; and / or a number-average molar mass Mn of 300 to 2000 g / mol.

6. Curable composition according to one of the preceding claims, wherein the monovalent, SiC-bonded, aliphatic hydrocarbon radicals R are selected from alkyl radicals, cycloalkyl radicals, and epoxy radicals; and / or the monovalent, SiC-bonded, aromatic hydrocarbon radicals R free of phenolic OH groups are selected from aryl radicals, alkaryl radicals, aralkyl radicals, alkoxyaryl radicals, aryloxyaryl radicals, haloaryl radicals, and heterocyclic aromatic hydrocarbon radicals.

7. A curable composition according to any one of the preceding claims, wherein R 1 represents the units according to the following formula (II), (II) , wherein R 4 , R 5 , R 6 , R 7 and R 8each independently of one another denotes a hydrogen atom, a hydroxy group or a hydrocarbon radical having 1 to 18 carbon atoms, with the proviso that in formula (II) at least one radical R 4 , R 5 , R 6 , R 7 or R 8 is or contains a phenolic hydroxy group.

8. A curable composition according to claim 7, wherein R 6 a hydroxy group and residue R 4 , R 5 , R 7 and R 8 each independently represents a hydrogen atom or a hydrocarbon radical having 1 to 4 carbon atoms.

9. Curable composition according to any one of the preceding Claims, wherein the at least one compound (B) consists of a Compound is selected which corresponds to one of the formulas (III) to (XII): (VIII) (XII) , wherein Me equals methyl residue, Ph is phenyl radical, m is 1 to 19, n is 1 to 18, and o is 1 to 18, with the proviso that the sum of n + o is 2 to 19.

10. Curable composition according to one of the preceding Claims comprising the at least one compound (B) in amounts from 1 to 70 parts by weight based on 100 parts by weight of Totality of at least one compound (A).

11. 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).

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 shaped bodies or fiber composite materials by shaping the curable composition according to any one of claims 1-11 and then curing.

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

15. Shaped body or fiber composite material obtainable from the process according to claim 13.

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