Curable organosiloxane-modified reaction resins

Abstract

The invention relates to curable mixtures of reaction resins with polymerisable functional cyanate ester groups and linear poly(bisphenol-diorganosiloxane) copolymers, methods for their production, and cured materials and composites obtainable therefrom, which exhibit high fracture resistance. Note: The invention underlying the present patent application is the result of a project, which is funded by the Federal Ministry of Education and Research under funding code 03XP0170C. Responsibility for the content of this patent application lies with the applicant.

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(bisphenol-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, 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.

[0004] 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, this thermoset class also represents 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.

[0005] However, thermoset systems based on CE resins also have disadvantages. During thermal curing, cyanate ester resins crosslink. The cyanate ester (N=CO-) groups trimerize to form thermally stable cyanurate rings, creating 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, i.e., they exhibit low crack resistance and impact strength.

[0006] It would therefore be desirable to provide suitable high-temperature stable modifiers for these CE reaction resins already on the market, which contribute to a higher fracture toughness of the cured duromer networks so that they can be used commercially as matrix resins in demanding applications, for example for automotive construction, the aerospace industry, as well as for hydrogen storage and transport.

[0007] The present invention is therefore based on the object of modifying organic cyanate ester resins in such a way that the thermosets cured after the shaping and curing process have a higher fracture toughness (Ki c) 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 such modified thermosets.

[0008] 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.

[0009] RU-C 2738712 discloses the modification of bisphenol dicyanate thermosets or prepolymeric bisphenol dicyanate resins with cyanate (-OC=N)-terminated linear bisphenol siloxane copolymers. Upon curing of these mixtures, cyclotrimerization of the cyanate groups of the thermoset and modifier results in a polycyanurate network modified with alternating bisphenol siloxane structural units, which exhibits an adjustable, temperature-dependent shape memory effect; this requires a modifier content of at least 30%. The influence of linear bisphenol siloxane copolymers with other terminal functional groups on the properties of cured cyanate ester resins was not investigated in this document. Surprisingly, it was found that linear

[0010] Poly(bisphenol-diorganosiloxane) copolymers with terminal hydroxy (-OH), alkyl ether, aryl ether or silyloxy groups significantly improve the fracture toughness of cured cyanate ester thermosets.

[0011] The invention relates to curable compositions comprising

[0012] (A) at least one organic compound (A) free of siloxy (=Si-O-) units with at least two cyanate esters

[0013] (-OC=N) groups (also referred to herein as "cyanate ester resin"), wherein compound (A) is preferably substituted and / or contains at least one heteroatom, and

[0014] (B) at least one linear, cyanate ester group-free, poly(bisphenol-diorganosiloxane) copolymer of the general formula (I)

[0015] R 1 [-Z-0 (-R2Si-O) x ] yZR 1 (I) , wherein

[0016] Z is the same or different and represents a divalent, optionally substituted, aromatic

[0017] Hydrocarbon radical which may be interrupted by at least one heteroatom,

[0018] R is the same or different and represents a hydrogen atom or a monovalent, SiC-bonded hydrocarbon radical which may be interrupted by at least one oxygen atom, R 1 is the same or different and is hydrogen atom, hydroxy

[0019] (-OH) radical or a silyloxy radical of the general formula (II) - (O-SiR 2 2) zR 3 (ID , means in which

[0020] R 2 is the same or different and radical R is R 3is the same or different and radical R or a monovalent, Si-O-bonded alkoxy or aryloxy radical having 1 to 18 carbon atoms, preferably aryloxy radical which may be interrupted by at least one heteroatom, x is 1 to 20, preferably 1 to 10, particularly preferably 1 to 5, in particular 1 or 2, y is 1 to 100, preferably 1 to 70, preferably 1 to 50, particularly preferably 1 to 30, in particular 3 to 15, and z is 1 to 20, preferably 1 to 10, particularly preferably 1 to 5, in particular 1 or 2.

[0021] The heteroatoms may be selected from the group consisting of O, S, N, P and Si; preferably O, S and Si; particularly preferably O and S, in particular O.

[0022] In the present invention, the term "component (A)" stands for the totality of the at least one compound (A) and the term "component (B)" stands for the totality of the at least one compound (B).

[0023] 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.

[0024] In order 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.

[0025] Cyanate ester resin (A)

[0026] 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.

[0027] Preferably, the at least one compound (A) is an aromatic hydrocarbon compound which is optionally substituted and / or contains at least one heteroatom, wherein preferably per molecule of the compound (A) the at least two cyanate ester (-OC=N) groups are bonded to aromatic carbon atoms.

[0028] Particularly preferably, at least two optionally substituted and / or at least one heteroatom-containing aromatic hydrocarbon radicals, each having 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 having 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 4 2-

[0029] , -CR 4 =CR 4 -, — C(=CR 4 2)— , -0-, -S-, -N=N-, -CR 4 =N-, -C (=0) - , -C(=0)0-, -0C(=0)0-, -S (=0)-, -S (=0)2-, 0=P(0-)3, =P (=0) , -SiR 42-, 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 , are bonded together.

[0030] The rest R 4 represents in each case independently of one another a hydrogen atom, a halogen atom or a monovalent, optionally substituted and / or interrupted by at least one heteroatom, hydrocarbon radical having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, particularly preferably 1 to 12 carbon atoms, in particular 1 to 6 carbon atoms, which may optionally be substituted either with a substituent or with the other radical R 4 from the bridging unit to form a cyclic unit .

[0031] The rest R 4is selected, for example, from monovalent radicals such as the methyl, ethyl, trifluoromethyl, phenyl and fluorenyl radical; or ring structures of two radicals R 4 , such as the cyclohexane-1,1-diyl-, cyclohexene-1,2-diyl-, 9A-fluorene-9,9-diyl-, N-phenyl-l-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.

[0032] Examples of the at least one compound (A) according to the invention are di- and polycyanate 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), 2,4,5-trifluorophenylene-1,3-dicyanate, 1,3,5-tricyanatobenzene, methyl (2,4-dicyanatophenyl) ketone and 2,7-dicyanatonaphthalene; Cyanate esters of bisphenols ("bisphenol dicyanate"), such as 2, 2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) propane (CAS 1156-51-0, bisphenol A cyanate ester; trade names: AroCy® BIO, PRIMASET® BADCy or CYTESTER® TA), 2, 2-Bis (4-cyanatophenyl) -1, 1, 1, 3, 3, 3-hexaf luoropropane (CAS 32728-27-1, bisphenol AF cyanate ester), 2, 2-Bis (3-methyl-4-cyanatophenyl) propane (bisphenol C cyanate ester), 1, 1-Bis (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-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, 1, 1-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- 1-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 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-dicyanoperfluorooctane; 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 9A-fluorene-9,9-diyl, and at least one bridging unit selected from the group consisting of -CR; 5 2-, -CR 5 =CR 5 -, -C(=CR 5 2)-, -O-, -S-, -N=N-, -CR 5=N-, -C(=O)-, -C(=O)O-, -OC (=0) 0- , -S (=0)-, -S (=0)2-, 0=P(0-)3, =P (=0) , -SiR 5 2- or a divalent cycloalkanediyl radical, such as tricyclo [5.2.1.0 2 ®] decanediyl and bicyclo [ 2.2.1 ] heptanediyl . Examples of repeating units in cyanate ester polymer resins are arylene ethers,

[0033] Arylene ether sulfones, or arylene ether ketones.

[0034] For rest R 5 These are each independently of each other the values ​​for R 4 mentioned residues .

[0035] Preferably, the at least one 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 or cyanate esters of phenol-formaldehyde resins. Particularly preferably, the at least one compound is

[0036] (A) 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 and cyanate esters of phenol-formaldehyde resins. In particular, the at least one compound (A) is l,l-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene and cresol or phenol novolak cyanate esters.

[0037] Only one cyanate ester resin (A) or a mixture of different cyanate ester resins (A) can be used, or prepolymers made from one cyanate ester resin (A) or prepolymers made from 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. 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).

[0038] Connection (B)

[0039] The at least one compound (B) used according to the invention is a linear poly(bisphenol-diorganosiloxane) copolymer (hereinafter also referred to as "copolymer") of the general formula (I) having terminal aromatic hydroxy (-OH), alkyl ether, aryl ether or silyloxy groups of the general formula (II) as described above.

[0040] 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.

[0041] If the compounds (B) according to the invention are liquid, they have a dynamic viscosity of preferably at least 1 mPa-s, particularly preferably 1 mPa-s to 10,000 mPa-s, in particular 5 mPa-s to 1,000 mPa-s, in each case at 80°C.

[0042] In the context of 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 (CC 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 ; 200000 to 299999 mPa-s at 2.5 s -1 ; 300,000 to 1,000,000 mPa-s at 1.5 s -1 .

[0043] 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 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.

[0044] The at least one compound (B) according to the invention has a weight-average molar mass Mw of preferably 1000 to 30000 g / mol, preferably 1500 g / mol to 20000 g / mol, particularly preferably 1500 g / mol to 10000 g / mol, in particular 2000 g / mol to 8000 g / mol.

[0045] The at least one compound (B) according to the invention has a number-average molar mass Mn of preferably 200 to 10,000 g / mol, preferably 200 g / mol to 5,000 g / mol, particularly preferably 200 g / mol to 3,000 g / mol, in particular 500 g / mol to 2,000 g / mol. 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 using size exclusion chromatography (SEC / GPC) according to DIN 55672-1 / ISO 160414-1 and ISO 160414-3. 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, is calibrated against polystyrene standards. The analysis is carried out using THE as the eluent.The analyses are carried out at a column temperature of 45±1°C and using a refractive index detector.

[0046] Examples of monovalent, SiC-bonded, optionally interrupted by at least one oxygen atom, hydrocarbon radicals R are

[0047] Alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, 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, iso-octyl, 2,4,4-trimethylpentyl and 2,2,4-trimethylpentyl radical; 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 and methylcyclohexyl radicals; unsaturated hydrocarbon radicals, such as the vinyl, propenyl, 5-hexenyl, 7-octenyl, 1 O -undecenyl, cyclohexenyl, 2- (3- cyclohexenyl) ethyl, bicyclo[2.2.1] hepten-2-yl, dicyclopentenyl, 4-vinylcyclohexyl, 3-norbornenyl, vinylphenyl, propenylphenyl, ethynyl, propynyl and butynyl radicals; aryl radicals such as the phenyl, biphenyl, cumylphenyl, benzylphenyl, tert-butylphenyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals such as the tolyl, xylyl and ethylphenyl radicals; aralkyl radicals such as the benzyl, cumyl, α- and β-phenylethyl radicals; alkoxyaryl radicals such as the methoxyphenyl radical; aryloxyaryl radicals such as the phenyloxyphenyl radical; and heterocyclic aromatic hydrocarbon radicals such as the furyl radical.

[0048] The radical R is preferably a monovalent, SiC-bonded hydrocarbon radical having 1 to 8 carbon atoms, particularly preferably the methyl or phenyl radical.

[0049] Preferably, the residue R 1 a hydrogen atom, hydroxy (-OH) radical or a silyloxy radical of the formula (II) , where R 2is a methyl or phenyl residue.

[0050] Examples of monovalent, Si-O-bonded, optionally interrupted by at least one heteroatom, alkoxy or aryloxy radicals R 3 are methoxy, ethoxy, phenoxy, 4-phenylphenoxy, 4-(phenyloxy)phenoxy, cumylphenoxy and tert-butylphenoxy residue.

[0051] Preferably, the residue R 3 hydrogen atom, the methyl, phenyl or cumylphenoxy radical.

[0052] The divalent, optionally substituted, optionally interrupted by at least one heteroatom aromatic hydrocarbon radical Z is selected, for example, from monoarylene radicals, such as the 1,3-phenylene, 1,4-phenylene, 6-tert-butyl-1,3-phenylene, 6-methyl-1,3-phenylene, 6-methyl-1,4-phenylene, 2,4-di-tert-butyl-6-methyl-1,3-phenylene and 2,6-dimethyl-1,3-phenylene radicals; and a bisarylene unit, in which two arylene radicals are linked via a covalent bond or at least one bridging unit selected from the group consisting of -CR 6 2-, -CR 6 =CR 6 -, -C(=CR 6 2)-, -O-, -S- , -N=N-, -CR 6 =N-, -C(=O)-, -C(=O)O-, -OC (=0) 0- , -S (=0) - , -S (=0)2-, 0=P(0-)3, =P (=0) , -SiR 6 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 , are linked together.

[0053] For rest R 6 These are each independently the values ​​for R 4 mentioned residues.

[0054] The Z residue is preferably derived from the corresponding bisphenols (CAS numbers in brackets) by substitution of all phenolic hydroxy (-OH) groups by covalent single bonds, such as -C6H4- (GAS 123-31-9, GAS 108-46-3), -C6H3(C(CH3)3)- (GAS 1948-33-0), -C6H3(CH3)- (GAS 95-71-6), -C6H4-C6H4- (GAS 92-88-6, GAS 611-62-1, GAS 1806-29-7), -C6H4-C(CH3)2-C6H4- (GAS 80-05-7), -C6H3(CH2-CH=CH2) -C (CH3) 2-C6H3(CH2-CH=CH2) - (GAS 1745-89-7) , -C6H4-S (=0) 2-C6H4- (GAS 80-09-1) , -C6H4-S (=0) -C6H4- (GAS 1774-34-1) , -C6H4-CH2-C6H4- (GAS 620-92-8, GAS 2467-02-9, GAS 2467-03-0) , -C6H4-C (CPs) 2-C6H4- (GAS 1478-61-1) , -C6H4-C (CH2CH3) (CH3) -C6H4- (GAS 77-40-7) , -C6H2(CH3) 2-C (CH3) 2-C6H2 (CH3) 2- (GAS 5613-46-7) , -C6H4-O- (m-C6H4) -O-C6H4- (GAS 126716-90-3) , -C6H4-O- (p-C6H4) -O-C6H4- (GAS 5085-95-0) , -C6H4(CH3) -S-C6H4(CH3) - (GAS 24197-34-0) , -C6H4-C (CH3) 2- (p-C6H4) -C (CH3) 2-C6H4- (GAS 2167-51-3) ,-C6H4-C (CH3) 2- (m-C6H4) -C (CH3) 2-C6H4- (GAS 13595-25-0) , -C6H3(CH3) -C (CH3) 2-C6H2 (CH3) - (GAS 79-97-0) , -C6H4- (Cyclohexan-1, 1-diyl) -C6H4- (CAS 843-55-0) ,

[0055] -C6H2(CH3)2) -S (=0) 2-C6H2(CH3) 2) - (CAS 13288-70-5) ,

[0056] -C6H4- (9H-Fluoren-9, 9-diyl) -C6H4- (CAS 3236-71-3) ,

[0057] -C6H2(CH3) 2-C (CH3) 2- (p-C6H4) -C (CH3) 2-C6H2(CH3) 2- (CAS 36395-57-0) ,

[0058] -C6H3(CH3) - (9H-Fluoren-9, 9-diyl) -C6H3(CH3) - (CAS 88938-12-9) ,

[0059] -C6H3(C6HS) -C (CH3) 2-C6H3(C6HS) - (CAS 24038-68-4) ,

[0060] -C6H3(CH3) - (Cyclohexan-1, 1-diyl) -C6H3(CH3) - (CAS 2362-14-3) ,

[0061] -C6H4- (9H-Fluoren-9, 9-diyl) -C6H4- (CAS 351521-78-3)

[0062] -C6H4-C (=0) -C6H4- (CAS 611-99-4, CAS 835-11-0) ,

[0063] -C6H4-S-C6H4- (CAS 2664-63-3) ,

[0064] -C6H4-O-C6H4- (CAS 1965-09-9, CAS 15764-52-0) ,

[0065] -C6H4-C (C6HS) 2-C6H4- (CAS 1844-01-5) ,

[0066] -C6H4-C (=CBr2) -C6H4-) ,

[0067] -C6H4-C (=CC12) -C6H4- (CAS 14868-03-2) ,

[0068] -C6H4-C (CH2CH (CH3) 2) (CH3) -C6H4- (CAS 6807-17-6) ,

[0069] -CeHsBr-CeHsBr- (CAS 189039-64-3) ,

[0070] -C6H4-CH (CH3) -C6H4- (CAS 2081-08-5) ,

[0071] -C6H2(C (CH3)3) 2-CH2-C6H2 (C (CH3)3) 2) - (CAS 118-82-1) ,

[0072] -C6H4-C (CH3) (C6HS) -C6H4- (CAS 1571-75-1) ,

[0073] -C6H2(CH3) 2) -CH2-C6H2 (CH3) 2) - (CAS 5384-21-4) ,

[0074] -C6H2Br2-C (CH3) 2-C6H2Br2- (CAS 79-94-7) ,

[0075] -C6H2(CH3) 2-C6H2(CH3) 2- (CAS 2417-04-1) ,

[0076] -C6H3(cycio-CeHu) -C (CH3) 2-C6H3(cycio-CeHu) - (CAS 57100-74-0) ,

[0077] -C6H3(iPr) -C (CH3) 2-C6H3(iPr) - (CAS 127-54-8) ,

[0078] -C3H4- (3, 3, 5-Trimethyl-cyclohexan-l, 1-diyl) -C3H4- (CAS 129188- 99-4) ,

[0079] -C6H4-O-C6H4-C (=0) -C6H4-O-C6H4- ,

[0080] -C6H4-O-C6H4-S (=0) 2-C6H4-O-C6H4- ,

[0081] -CioHe- (CAS 571-60-8, CAS 83-56-7, CAS 575-44-0, CAS 575-38-2,

[0082] CAS 92-44-4, CAS 582-17-2, CAS 581-43-1) ,

[0083] Benzonorbornan-3 , 6-diyl (CAS 16144-91-5) ,

[0084] — C3H4— ( 1 ( 3H) — I sobenzo f ur anon— 3 , 3 — di y 1 ) — C3H4— (CAS 77-09-8) ,

[0085] — C3H4— ( 1 ( 3H) — 2 — Pheny 1 i so indo 1 in— 3 , 3 — di y 1 ) — C3H4— (CAS 77-09-8) , -CeH4- (3, 3, 5-Trimethyl-cyclohexan-l, 1-diyl) -CeH4- (CAS 129188- 99-4) ; Propenyl-substituierte Reste Z, wie

[0086] -C6H3(CH2-CH=CH2) -C (CH3) 2-C6H3(CH2-CH=CH2) - (CAS 1745-89-7) , -C6H3(CH=CH2-CH3) -O-C6H4-C (=0) -C6H4-O-C6H3(CH=CH2-CH3) - (CAS 109423-33-8) ,

[0087] -C6H3(CH2-CH=CH2) -S (=O)2-C6H3(CH2-CH=CH2) - (CAS 41481-66-7) and -C6H3(CH2-CH=CH2) -O-C6H4-S (=O)2-C6H4-O-C6H3(CH2-CH=CH2) - .

[0088] The radical Z is particularly preferably -C6H4-C6H4-, - C6H4-C (CH3)2-C6H4-, -C6H3(CH3) -C (CH3)2-C6H2(CH3) -, -C6H4-S-C6H4-, - C6H4-C (=O) -C6H4-, -C6H2(CH3)2-C (CH3)2-C6H2(CH3)2-, -CeH4-S (=O)2-C6H4-, -C6H4-CH2-C6H4- or -C6H4-C (CH3)2-C6H4-C (CH3)2-C6H4- ; in particular -C6H4-C(CH3)2-C6H4-, -C6H4-S(=O)2-C6H4- or -C6H4-S-C6H4- .

[0089] Compounds (B) preferably do not contain any aliphatic carbon-carbon multiple bonds. Compounds (B) particularly preferably do not contain any aliphatic carbon-carbon multiple bonds and, apart from oxygen and sulfur, no other heteroatoms.

[0090] Examples of the copolymers (B) used according to the invention are

[0091] - HO [-C6H4-CMe2-C6H4-O-Me2Si-O]m-C6H4-CMe2-C6H4-OH with Mw = 9890 g / mol, Mn = 2440 g / mol;

[0092] - HO [-C6H4-CMe2-C6H4-O-Ph2Si-O]m-C6H4-CMe2-C6H4-OH with Mw = 6880 g / mol, Mn = 2230 g / mol;

[0093] - HO [-C6H4-CMe2-C6H4-O (-Me2Si-O)2] m -C6H4-CMe2-C6H4-OH with Mw = 4740 g / mol, Mn = 1900 g / mol;

[0094] - HO [-C6H4-CMe2-C6H4-O-Ph2MeSi-O] m [-C6H4-CMe2-C6H4-O (-Me2Si-

[0095] 0)2] n-C6H4-CMe2-C6H4-OH with Mw = 8360 g / mol, Mn = 2150 g / mol;

[0096] - PhMe2Si-0 [-C6H4-CMe2-C6H4-O (-Me2Si-O)2] m -C6H4-CMe2-C6H4-O- SiPhMe2 with Mw = 5570 g / mol, Mn = 1450 g / mol;

[0097] - H [-C6H4-CMe2-C6H4-O (-Me2Si-O)2] m-C6H4-CMe2-C6H4-H with Mw = 2930 g / mol, Mn = 1230 g / mol;

[0098] - C6H4tBu (-Me2Si-O)2- [C6H4-CMe2-C6H4-O (-Me2Si-O) 2] m-C6H4tBu with Mw = 5930 g / mol, Mn = 2080 g / mol;

[0099] - HO [-C6H2Me2-CMe2-C6H2Me2-O (-Me2Si-O) 2] m-C6H2Me2-CMe2-C6H2Me2-OH with Mw = 3240 g / mol, Mn = 1510 g / mol;

[0100] - HO [-C6H4-S-C6H4-O- (-Me2Si-O)2]m-C6H4-S-C6H4-OH with Mw = 6140 g / mol, Mn = 2470 g / mol;

[0101] - HO [-C6H4-C (=0) -C6H4-O ( -Me2Si-O-Ph2Si-O-Me2Si-O) ] m-C6H4-C (=0) -

[0102] C6H4-OH with Mw = 8230 g / mol, Mn = 2370 g / mol; where Me is methyl radical, Ph is phenyl radical and tBu is tert-butyl radical and the sum of m + n in copolymer (B) is on average 3 to 10.

[0103] Compounds (B) used according to the invention can be prepared by processes commonly used in chemistry, e.g. by the processes mentioned in RU-C 2738712. Another possibility is the Piers-Rubinsztajn reaction, in which bisphenol is reacted with diorganosilane (H-R2S1-H) and / or poly(diorganosiloxane) [H (— R2S1-O) 2 to 20-H] with terminal silicon-bonded hydrogen atoms, in the presence of a boron catalyst.

[0104] (B(CeF5)3) can be copolymerized in an inert solvent such as toluene or hexane; monophenols, triorganoalkoxysilanes or triorganosilanes can be added to regulate the average molecular weight.

[0105] Preference is given to compounds (B) prepared from the corresponding bisphenols and diorganodichlorosilanes (C1-R2S1-Cl) and / or poly(diorganosiloxanes) [Cl (-R2S1-O) X >i-Cl] with terminal silicon-bonded chlorine atoms and optionally an aromatic compound with a phenolic hydroxy (OH) group or a triorganochlorosilane, in the presence of an auxiliary base, such as

[0106] Nitrogen base, preferably pyridine, and in organic

[0107] Solvents such as toluene, ethers such as diethyl ether, anisole or tetrahydrofuran; and acetals such as ethylal.

[0108] For the preparation of compound (B) only one bisphenol or a mixture of different bisphenols and one reactive or several different reactive diorganosilane(s) and / or poly(diorganosiloxane(s) and optionally either one reactive or several reactive triorganosilane(s) or one or several aromatic compound(s) having only one phenolic hydroxyl (OH) group can be used.

[0109] The term "reactive" diorganosilane(s), poly(diorganosiloxane(s)) and triorganosilane(s) means in the context of the present invention in particular that the compounds have functional groups, such as SiH or SiCl, which are capable of reacting with phenolic hydroxy (OH) groups.

[0110] Preferably, compound (B) is prepared from a bisphenol, a reactive diorganosilane or poly(diorganosiloxane) and optionally an aromatic compound having a phenolic hydroxy (OH) group.

[0111] Particularly preferably, compound (B) is prepared from a bisphenol, a diorganodichlorosilane and / or a tetraorganodisiloxane having terminal silicon-bonded chlorine atoms and optionally an aromatic compound having a phenolic hydroxy (OH) group in the presence of pyridine and in ether. The degree of polymerization depends on the ratio of the reagents bisphenol, reactive diorganosilanes and / or

[0112] Poly(diorganosiloxane) and monophenol or reactive triorganosilane. In this way, the desired copolymer (B) is obtained, preferably with end groups of the formula (I) with R 1 equals hydroxy or hydrogen residue.

[0113] The composition according to the invention may only contain one compound

[0114] (B) or a mixture of different compounds (B), preferably only one compound (B).

[0115] The compositions according to the invention comprise 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).

[0116] 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).

[0117] In a preferred embodiment, the inventive

[0118] Composition also includes the following compounds:

[0119] (C) at least one modifier (C);

[0120] (D) at least one reactive resin (D);

[0121] (E) at least one filler (E);

[0122] (F) at least one curing accelerator (F);

[0123] (G) at least one solvent (G); and / or

[0124] (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).

[0125] The composition according to the invention can

[0126] • comprise only one compound (C) or a mixture of different compounds (C), preferably only one compound (C);

[0127] • comprise only one compound (D) or a mixture of different compounds (D), preferably only one compound (D);

[0128] • comprise only one compound (E) or a mixture of different compounds (E), preferably only one compound (E);

[0129] • comprise only one compound (F) or a mixture of different compounds (F), preferably only one compound (F);

[0130] • comprise only one compound (G) or a mixture of different compounds (G), preferably only one compound (G); and / or

[0131] • comprise only one compound (H) or a mixture of different compounds (H), preferably only one compound (H).

[0132] 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

[0133] (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).

[0134] Connection (C)

[0135] The optional at least one modifier (C) is preferably a

[0136] Organosilicon compound (Gl) containing units of the formula

[0137] R 7 h (OR 8 ) iSiO(4-hi) / 2 (III) , where

[0138] R 7is the same or different and represents a hydrogen atom or a monovalent, SiC-bonded, optionally substituted, optionally interrupted by at least one heteroatom, hydrocarbon radical,

[0139] R 8 is the same or different and denotes a hydrogen atom or a monovalent, optionally interrupted by at least one heteroatom, aliphatic hydrocarbon radical having 1 to 18 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 the formula (III) and that

[0140] Compound (Gl) has no Ar-O-Si bonds.

[0141] The abbreviation "Ar" in the present invention stands for an aromatic hydrocarbon structure.

[0142] Examples of monovalent, SiC-bonded, optionally substituted and / or interrupted by at least one heteroatom, hydrocarbon radicals R 7 are the residues mentioned for R; imido residues, such as N- (5- ethynylphthalimido ) phenyl- , N- (5-

[0143] (Phenyl ethynyl) phthalimido) phenyl, nadimidophenyl, maleimidophenyl and 3-maleimidopropyl radicals; epoxy radicals, such as the 3-glycidoxypropyl, 4-(oxiran-2-yl)phenyl, oxiran-2-yl and 2-(3,4-epoxycyclohexyl)ethyl radicals; acrylate and methacrylate radicals, such as the 3-methacryloxypropyl, acryloxymethyl and methacryloxymethyl radicals; amine radicals, such as the aminophenyl, 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-phenylaminomethyl radicals; hydroxy-substituted radicals, such as the hydroxyphenyl and hydroxypropyl radicals; halogenated radicals, such as trifluoromethyl, fluorophenyl, chlorophenyl, bromophenyl and trifluoromethylphenyl radicals; alkenylaryl radicals, such as vinylphenyl, 2-methyl-2-propen-l-yl ("methallyl") and propenylphenyl radicals; as well as bicyclo [4.2.0] octa-1, 3, 5-trienyl (= benzocyclobutenyl), polycaprolactone, polycaprolactam, cyanatophenyl, 3-cyanatopropyl, isocyanatophenyl, 3-isocyanatopropyl, arylethynyl and ethynylphenyl radicals.

[0144] Preferably, the residue R 7 hydrogen atom, the phenyl or the methyl radical.

[0145] Preferably, the residue R 8 an aliphatic hydrocarbon radical having 1 to 18 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.

[0146] 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, poly (organosiloxane) of average composition (PhSiO3 / 2) 20 (PhSi (OMe) O2 / 2) ee (PhSi (OMe) 2O1 / 2) 14 and a weight average molar mass Mw = 2190 g / mol, poly (organosiloxane) of average composition

[0147] ( PhSiO3 / 2 ) 75 (MeaSiOi / 2 ) 25 und einer Gewichtsmittel-Molmasse Mw = 1380 g / mol, Octa ( epoxycyclohexyl ) -POSS (CAS 187333-74-0) , Octaphenyl-POSS (CAS 5256-79-1) , Octaphenylcyclotetrasiloxan (CAS 546-56-5) , 2 , 4 , 6, 8-Tetramethyl-2 , 4 , 6, 8- tetraphenylcyclotetrasiloxan (CAS 77-63-4) , 1, 1,3, 3,5,7- Hexamethyl-5, 7-diphenylcyclotetrasiloxan, 1,1,3, 3-Tetramethyl- 5, 5, 7 , 7-tetraphenylcyclotetrasiloxan (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 .

[0148] The optional at least one modifier (C) is preferably a thermoplastic organic polymer (“thermoplastics”) (C2) which is free of siloxy (=Si-O-) units and of 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 during the polymerization reaction due to the manufacturing process from the corresponding reactive, polymerizable groups of the 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, 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.

[0149] 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

[0150] R 9 -OCN (IV) , where R 9a 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.

[0151] 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

[0152] Propenyl-substituted monofunctional cyanate esters, such as 4-

[0153] Cumyl-2-(propenyl)cyanatobenzene or 2-(propenyl)cyanatobenzene.

[0154] 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.

[0155] The optional at least one modifier (C) is preferably a monomeric aromatic hydrocarbon free from siloxy (=Si-O-) units and from epoxy, imide and cyanate groups and having at least one phenolic hydroxy group (C4) and optionally one or more aliphatic carbon-carbon multiple bonds.

[0156] The optional aliphatic carbon-carbon multiple bonds in compound (C4) are preferably propenyl groups bonded to aromatic carbon atoms, with particular preference in compound (C4) for one phenolic hydroxy group and optionally one propenyl group to be bonded to an aromatic radical.

[0157] 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.;

[0158] Beispiele für Verbindungen (C4) mit Propenyl-Gruppen sind 2,2- Bis ( 3- ( 2-propenyl ) -4-hydroxyphenyl ) propan (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) sulfon (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- diisopropylbenzol , 2, 2 '-Bis (3-propenyl-4- hydroxyphenyl ) perfluorpropan, 9, 9 ' -Bis ( 3-propenyl-4- hydroxyphenyl ) f luoren und 4- ( 1- ( 4-Hydroxy-3- propenylphenyl ) propyl) -2-propenylphenol .

[0159] 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 -propenylpheno 1 , 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-

[0160] ( 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 oder S besonders bevorzugt sind.

[0161] If the compositions according to the invention contain at least one modifier (C), either only one modifier (CI) to (C4) may be present or several different modifiers (CI) to (C4) may be present.

[0162] If the compositions according to the invention contain at least one modifier (C), the at least one modifier is

[0163] (C) 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).

[0164] Connection (D)

[0165] 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 / or 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, 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 being particularly preferred.

[0166] 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 11 2-, — CR 11= CR 11 — , =C=CR 11 2, -0-, -S- , -N=N-, -CR 21=N-, - C(=0)-, -C(=0)0-, -OG (=0)0-, -S (=0)2-, 0=P(0-)3, -SiR 11 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 .

[0167] For rest R 11 are each independently the ones for R 4 The at least one reactive resin (D) preferably contains heteroatom-free aromatic ring frameworks.

[0168] Epoxy resins (Dl) are preferably copolymerizable with cyanate ester resin (A).

[0169] Preferably, imide resins (D2) are not co-polymerizable with cyanate ester resin (A).

[0170] Examples of polymerizable epoxy resins (DI) are glycidyl ethers of phenol 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-

[0171] Bis(glycidyloxy)benzene (CAS 129375-41-3), 3, 5, 3', 5'-Tetramethyl-4, 4'-diglycidyloxybiphenyl (CAS 85954-11-6), 2,2-Bis(3, 5-dibromo-4-glycidyloxyphenyl) propane (CAS 3072-84-2) , Tris (4-glycidyloxyphenyl) methane (CAS 66072-38-6) , 1, 1,2,2-Tetrakis (4-glycidyloxyphenyl) ethane (CAS 7328-97-4) , 4,4'-Bis (glycidyloxyphenyl) sulfone (CAS 878-43-1) , 9.9-Bis (4- glycidyloxyphenyl ) f luoren (CAS 47758-37-2), 1, 6- (diglycidyloxy) naphthalene (CAS 27610-48-6); glycidyl ethers of phenol, naphthol, naphthalenediol, bisphenol or cresol-formaldehyde condensation products, such as cresol novolak glycidyl ether (CAS 29690-82-2), phenol novolak glycidyl ether (CAS 9003-36-5, CAS 28064-14-4, CAS 158163-01-0) and bisphenol 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 prepared, for example, by reaction of 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 (DI).

[0172] 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'-

[0173] 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-

[0174] (maleimidophenoxy)phenyl]propane (CAS 79922-55-7), bis(4-maleimidophenyl)sulfone (CAS 13102-25-5), bis(4-maleimidophenyl)ketone, l,l'-(benzene-l,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 reaction of amino-terminated thermoplastics (C2) with maleic anhydride, such as, for example, maleimide-terminated polysulfone ethers; as well as mixtures of various maleimide resins (D2) .

[0175] Preferably, the at least one compound (D) is a monomeric compound without a thermoplastic, homo- or copolymeric polymer component.

[0176] 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).

[0177] If the compositions according to the invention contain at least one polymerizable imide (D2), this is preferably done 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 (GAS 7300-91-6).

[0178] 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.

[0179] Connection (E)

[0180] The at least one filler (E) optionally present in the compositions according to the invention may be any particulate filler known to date.

[0181] 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.

[0182] 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 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,

[0183] calcium carbonate, marble powder, gypsum, silicon nitride,

[0184] Silicon carbide, boron nitride, plastic powder, such as

[0185] 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-aluminum mixed oxides with a large BET surface area; aluminum 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 fibers made of glass (short glass fibers) or mineral wool; metallic fibers, fibers consisting of metal oxides, glass, ceramic, carbon or plastic; and natural fibers made of cellulose, flax, hemp, wood or sisal.

[0186] 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.

[0187] 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.

[0188] 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; or aromatic polyamide fibers, such as poly(p-phenylene terephthalamide).

[0189] 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.

[0190] 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).

[0191] 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, based in each case on 100 parts by weight of the sum of components (A) and (B). The at least one filler (E2) can be present in the composition according to the invention in various forms, e.g., as continuous ropes each having 1,000 to 400,000 individual filaments, woven fabrics, scrims, knitted fabrics, braids, mats, nonwovens, whiskers, chopped strands, or random fiber felt.

[0192] 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).

[0193] 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.

[0194] The optional fiber fabrics (E2) or fiber scrims (E2) according to the invention are preferably used in multiple layers.

[0195] 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).

[0196] Connection (F)

[0197] 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 or copper(II) acetylacetonate.

[0198] 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.

[0199] 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) particularly preferably being used in amounts of from 0.0001 to 0.02 parts by weight, based on 100 parts by weight of component (A).

[0200] 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 (G1) and imide resin (D2). Preferably, no radical-forming curing accelerators (F2) are used.

[0201] Connection (G)

[0202] 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 are 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; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; acetonitrile; and dimethyl sulfoxide.

[0203] The at least one solvent (G) is preferably an aromatic hydrocarbon or a ketone.

[0204] 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).

[0205] Connection (H)

[0206] 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.

[0207] 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 5 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 excipient (H).

[0208] The compositions according to the invention are preferably those containing

[0209] (A) at least one cyanate ester resin,

[0210] (B) at least one poly(bisphenol-diorganosiloxane) copolymer, optionally (C) at least one modifier, optionally (D) at least one reactive resin,

[0211] (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.

[0212] The compositions according to the invention are preferably those containing

[0213] (A) at least one cyanate ester resin,

[0214] (B) at least one poly(bisphenol-diorganosiloxane) copolymer,

[0215] (C) at least one modifier, optionally (D) at least one reactive resin,

[0216] (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

[0217] (A) at least one cyanate ester resin,

[0218] (B) at least one poly(bisphenol-diorganosiloxane) copolymer, optionally (C) at least one modifier,

[0219] (D2) at least one imide resin,

[0220] (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.

[0221] In a further particularly preferred embodiment, the compositions according to the invention are those containing

[0222] (A) at least one cyanate ester resin,

[0223] (B) at least one poly(bisphenol-diorganosiloxane) copolymer, optionally (C) at least one modifier,

[0224] (D2) at least one maleimide resin,

[0225] (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 directly bonded to aromatic carbon atoms is present.

[0226] The compositions according to the invention preferably contain no further components apart from components (A) and (B), any components (C) to (H) used and any impurities typical of the raw material, for example catalyst residues such as sodium chloride or potassium chloride, impurities in technical cyanate ester resin monomers and any reaction products of the components used which are formed during mixing or storage.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] The process according to the invention can be carried out continuously, discontinuously or semi-continuously, preferably it is carried out discontinuously.

[0233] 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), winding processes (filament winding), compression molding, pultrusion, fiber spraying and injection processes such as transfer molding (resin transfer molding) or vacuum infusion in a bubble-free manner and processed into molded articles.

[0234] 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.

[0235] 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, and 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.

[0236] 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, are located, wherein degassing preferably takes place simultaneously during the injection process.

[0237] 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 applied to a release paper; subsequently, component (E2), preferably aligned ropes, woven fabrics, scrims, knitted fabrics or braids, is pressed between two coated sheets of paper and passed through a series of heated rollers to ensure complete wetting of component (E2).

[0238] 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.

[0239] 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.

[0240] 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.

[0241] A further subject of the invention are therefore shaped bodies obtainable from the compositions according to the invention by shaping and curing.

[0242] The compositions according to the invention or prepared according to the invention are preferably degassed before curing, particularly preferably after shaping and before curing.

[0243] 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.

[0244] By increasing the temperature, curing can be accelerated so that shaping and curing can be carried out in one step.

[0245] The molded bodies according to the invention are preferably fiber composite materials (or fiber-reinforced plastics "FRP"). A further subject of the invention is therefore the use of the composition according to the invention for producing fiber composite materials.

[0246] Another object of the invention is a process for producing fiber composite materials by shaping the composition according to the invention and subsequent curing.

[0247] A further subject of the invention are therefore fiber composite materials obtainable from the compositions according to the invention by shaping and curing.

[0248] 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.

[0249] 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.

[0250] The quotient of the critical stress intensity factor Ki cof 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 1.6, in particular greater than 1.7, in each case measured at 23°C.

[0251] 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), have a glass transition temperature of preferably greater than 200 ° C, particularly preferably greater than 230 ° C, in particular greater than 260 ° C.

[0252] 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 200 hours of storage at 240 ° C, have a weight loss which is preferably at most 100%, preferably at most 80%, particularly preferably at most 60%, in particular at most 40%, higher in comparison with the corresponding unmodified cyanate ester resins (A).

[0253] The compositions according to the invention have the advantage that cyanate ester resin (A) is miscible with poly(bisphenol-diorganosiloxane) copolymer (B) without the addition of further solvent and copolymer (B) does not exude from the duromer network during curing.

[0254] The compositions according to the invention have the advantage that they have a high glass transition temperature and a high fracture toughness (Ki c) compared to the corresponding non-modified cyanate ester resins.

[0255] The compositions according to the invention also have the advantage that they have a high thermo-oxidative stability in the cured state.

[0256] 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 readily available raw materials and in a simple manner.

[0257] 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.

[0258] Examples of implementation

[0259] 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 established 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.

[0260] Production of the test specimens

[0261] First, the cyanate ester resin (A) was heated to 80 ° C while mixing to improve processability. Then

[0262] Copolymer (B) was added, the mixture was homogenized on a Rotavapor for one hour at 110 ° C, then degassed for one hour at 110 ° C and a pressure of 5 mbar and, after breaking the vacuum with nitrogen, immediately hot-filled into a 2-part screwable aluminum casting 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 the fracture toughness, the thermo-oxidative stability and for carrying out the dynamic mechanical analysis (DMA). To prevent sticking and leakage, the mold cavity surface on the inside of the casting mold was treated 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:.

[0263] 1) 18 hours curing at 180°C

[0264] 2) Temperature increase to 200°C within 30 minutes

[0265] 3) 3 hours curing at 200°C

[0266] 4) Temperature increase within 30 minutes to 240°C

[0267] 5) 2 hours curing at 240°C.

[0268] 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 had been 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 corresponding dimensions (length x width).

[0269] Fracture toughness Ki c

[0270] The measurement of the fracture toughness or the critical stress intensity factor Ki c 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 Ki given in Table 1c in MN xm -3 / 2 was rounded to two decimal places according to DIN 1333:1992-02 Section 4. Dynamic mechanical analysis (DMA)

[0271] Measurement conditions:

[0272] • Measuring device: ARES rheometer (TA Instruments)

[0273] • Temperature range: -100°C - 400°C

[0274] • Heating rate: 4 K / min with nitrogen purge

[0275] • Frequency: 1 Hz

[0276] • Strain: Initial 0.03%, automatically increased if measurement signal falls below threshold

[0277] 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.

[0278] In the present invention, the glass transition temperature TG corresponds to 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 .

[0279] 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.

[0280] Thermo-oxidative stability

[0281] 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.

[0282] Value for weight loss given in % and rounded to two decimal places according to DIN 1333:1992-02 Section 4.

[0283] compatibility

[0284] 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.

[0285] Poly (bisphenol-diorganosiloxane) copolymer 1

[0286] Under a nitrogen atmosphere, a mixture of 12.8 g of 1,3-dichloro-1,1,3,3-tetramethyl-disiloxane (CAS 2401-73-2; available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen), 15.8 g of dichlorodiphenylsilane (CAS 80-10-4; available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) and 20.8 g of pyridine anhydrous (CAS 110-86-1; (available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) in 50 ml of diethyl ether was added dropwise over a period of 1 hour while cooling to ice. After the addition, stirring was continued for 30 minutes at 23°C, then for 5 hours at 40°C, and finally overnight at 23°C.For workup, the mixture is filtered, and 1 g of a weakly basic anion resin based on polystyrene-divinylbenzene copolymer (Purolite® AlOSSPlus; commercially available from Purolite GmbH, D-40880 Ratingen) is added to the filtrate. The mixture is stirred for 30 minutes at 23°C, then filtered, and the filtrate is concentrated in a rotary evaporator. To remove the volatile components, the residue is mixed for 1 hour at 110°C and a pressure of 5 mbar in a rotary evaporator. Copolymer 1 has a weight-average molar mass Mw of 8350 g / mol and a number-average molar mass Mn of 2150 g / mol.

[0287] Poly (bisphenol-diorganosiloxane) copolymer 2

[0288] Under a nitrogen atmosphere, 30.0 g of 1,1,3,3-tetramethyldisiloxane (CAS 3277-26-7; available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) and 0.01 g of tris(pentafluorophenyl)borane (CAS 1109-15-5; available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) are mixed in 200 ml of anhydrous toluene (available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen) and stirred for 15 minutes. The reaction flask is cooled in an ice bath; then, 50 g of bisphenol A is added over a period of 30 minutes, while the reaction flask is cooled in an ice bath. After the addition, the mixture is stirred for 10 minutes at 23°C and then for 1.5 hours at 100°C. After the mixture has cooled to 23°C, 1 g of Purolite® A103SPlus is added and stirred for 15 minutes. The mixture is then filtered, and the filtrate is concentrated using a rotary evaporator.To remove the volatile components, the residue is mixed for 1 hour at 110°C and a pressure of 5 mbar in a rotary evaporator. Copolymer 2 has a weight-average molar mass (Mw) of 3485 g / mol and a number-average molar mass (Mn) of 1390 g / mol.

[0289] Example Bl

[0290] 85 g of 2,2-bis(4-cyanatophenyl)propane (CAS 1156-51-0; commercially available from TCI Deutschland GmbH, D-65760 Eschborn) as component (A) are mixed with 15 g of poly(bisphenol-diorganosiloxane) copolymer 1 as component (B) and then processed as described under “Preparation of the test specimens”.

[0291] The results can be found in Table 1 .

[0292] Example B2

[0293] Experiment Bl was repeated with the change that copolymer 2 was used instead of poly(bisphenol-diorganosiloxane) copolymer 1.

[0294] The results can be found in Table 1 .

[0295] Comparison example VI

[0296] The procedure described in Example B1 was repeated with the modification that no component (B) was added to component (A).

[0297] The results can be found in Table 1.

[0298] Table 1 not assessed.

Claims

Claims 1. A curable composition comprising (A) at least one organic compound (A) free of siloxy (=Si-O-) units with at least two cyanate esters (-OC=N) groups; and (B) at least one linear, cyanate ester group-free, poly(bisphenol-diorganosiloxane) copolymer (B) of the general formula (I) R 1 [-Z-0 (-R2Si-O) x ] yZR 1 (I) wherein Z is the same or different and represents a divalent, optionally substituted, aromatic hydrocarbon radical; R is the same or different and represents a hydrogen atom or a monovalent, SiC-bonded hydrocarbon radical; R 1 is the same or different and is hydrogen atom, hydroxy (-OH) radical or a silyloxy radical of the general formula (II) - (O-SiR 2 2) zR 3 (II) means wherein R 2 is the same or different and radical R represents R 3 is the same or different and radical R is or a monovalent, Si-O-bonded alkoxy or aryloxy radical having 1 to 18 carbon atoms; x is 1 to 20; y is 1 to 100; and z is 1 to 20.

2. 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) at least two aromatic hydrocarbon radicals, each with one bonded to an aromatic Carbon atom bound cyanate ester group are present.

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 4 2- , -CR 4 =CR 4 -, — C(=CR 4 2)— , -0-, -S-, -N=N-, -CR 4 =N-, -C (=0) - , -C(=0)0-, -OG (=0)0-, -S (=0)-, -S (=0)2-, 0=P(0-)3, =P (=0) , -SiR 4 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 , where R 4 each independently represents a hydrogen atom, a 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 1000 to 30,000 g / mol; and / or a number-average molar mass Mn of 200 to 10,000 g / mol.

6. Curable composition according to any one of the preceding Claims, wherein R is a monovalent, SiC-bonded hydrocarbon radical having 1 to 8 carbon atoms; and / or wherein R 1 a hydrogen atom, hydroxy (-OH) radical or a silyloxy radical of formula (II), where R 2 is a methyl or phenyl radical; and / or wherein R 3 a hydrogen atom, a methyl, phenyl or cumylphenoxy radical; and / or wherein Z is selected from monoarylene radical or a bisarylene unit in which two arylene radicals are linked via a covalent bond or at least one bridging unit selected from the group consisting of -CR 6 2- , -CR 6 =CR 6 -, - C(=CR 62)- , -O-, -S-, -N=N-, -CR 6 =N-, -C (=0) - , -C(=O)O-, -OG (=0)0-, -S (=O)-, -S (=O)2-, O=P(O-)3, =P (=0) , -SiR 6 2-, a divalent aromatic hydrocarbon radical, such as phenylene, toluylene, biphenylene and naphthylene; or a divalent cycloalkanediyl radical, such as Tricyclo [5.2.1.0 2 ' 6 ] decanediyl and bicyclo [ 2.2.1 ] heptanediyl , where R 6 each independently of each other for R 4 mentioned residues.

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 13.

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