Curable organosiloxane-modified reactive resin

Abstract

The present invention relates to a curable composition comprising a reactive resin having polymerizable cyanate ester functional groups and a linear poly(bisphenol-diorganosiloxane) copolymer, a method for producing the same, and curable materials and composites obtained therefrom that have high fracture toughness.

Description

[Technical Field]

[0001] The present invention relates to a curable composition comprising a reactive resin having polymerizable cyanate ester functional groups and a linear poly(bisphenol-diorganosiloxane) copolymer, a method for producing the same, and curable materials and composites obtained therefrom that have high fracture toughness. [Background technology]

[0002] As the demand for composite materials to meet the needs of high-temperature resistance, high-speed data communication, and new technologies for power and hydrogen storage steadily increases, the use of high-performance polymers is expanding. These polymers are lighter than metallic materials while offering advantages such as heat resistance, high mechanical strength, high glass transition temperature, and chemical resistance. Among these materials, epoxy (EP) resins and epoxy resin systems are used in a wide range of applications and are now established as one of the most commonly used high-performance polymers in composite materials, for example, in combination with glass fibers, carbon fiber reinforced polymers (CFRP), or aramid fibers. Furthermore, high-performance organic reactive resins, such as phenol-formaldehyde (PF) resins, cyanate ester (CE) resins, bismaleimide (BMI) resins, polyimide (PI) resins, benzoxazine resins, or phthalonitrile resins, as well as reactive resin mixtures, such as bis(benzocyclobutenimide)bismaleimide, cyanate ester / epoxide, or bismaleimide / cyanate ester (BT resins), have recently gained increasing importance as matrix resins for fiber composite materials in industrial, automotive, and aerospace fields.

[0003] Compared to epoxy resins, polymer matrix resins based on CE, BMI, or PI offer advantages such as high mechanical strength, high glass transition temperature, high heat resistance, and high long-term stability, significantly expanding the applications of these thermosetting resins, particularly in high-temperature regions.

[0004] Furthermore, cyanate ester resins, in particular, are characterized by low water absorption and low dielectric constant in the cured state, as well as good processability in the uncured state. This group of thermosetting resins also represents the best alternative to most other resin systems in terms of toxicological properties and flame retardancy / smoke emission properties. This unique combination of properties makes CE resins an ideal material for a wide range of applications.

[0005] However, thermosetting resin systems based on CE resin also have drawbacks. During the thermosetting process, cyanate ester resins undergo a crosslinking reaction through the formation of trimers of cyanate ester groups (N≡CO-), creating thermally stable cyanurate rings. This results in the formation of a polycyanurate network with high crosslink density. While this highly crosslinked state gives the cured thermosetting resin high mechanical stability, the network is brittle, meaning it has low fracture toughness or impact strength properties.

[0006] Therefore, it is desirable to provide suitable modifiers that are stable at high temperatures and contribute to improving the fracture toughness of cured thermosetting resin networks, so that these CE-reactive resins already on the market can be commercially used as matrix resins in demanding applications such as automotive structures, the aerospace industry, and hydrogen storage and transportation.

[0007] Therefore, the objective of the present invention is to provide a thermosetting resin that has been cured after the molding and curing process with higher fracture toughness (K Ic The organic cyanate ester resin is modified to have improved aging resistance as a result, while at the same time, the advantageous properties inherent to thermosetting resins, such as thermal oxidation stability, high glass transition temperature, and high mechanical strength, are largely retained even in the thermosetting resin thus modified.

[0008] The fracture toughness of cyanate ester resins is known to be improved by a second organic or inorganic phase. Effective modifiers whose usefulness has been demonstrated include, for example, thermoplastic resins, elastomers, core / shell particles, and block copolymers.

[0009] Russian Patent No. 2738712 discloses the modification of bisphenol-dicyanate thermosetting resins or prepolymeric bisphenol-dicyanate resins having linear bisphenol-siloxane copolymers terminated with cyanate groups (-OC≡N). During the curing of these mixtures, a cyclization-trimmerization reaction of the cyanate groups between the thermosetting resin and the modifier forms a polycyanurate network modified with alternately arranged bisphenol-siloxane structural units, exhibiting a controllable temperature-dependent memory effect. To obtain this effect, a modifier content of at least 30% is required. The effect of linear bisphenol-siloxane copolymers with other terminal functional groups on the properties of cured cyanate ester resins is not discussed herein. [Overview of the Initiative]

[0010] Surprisingly, linear poly(bisphenol diorganosiloxane) copolymers having hydroxyl (-OH), alkyl ether, aryl ether, or silyloxy groups at their terminals have been found to significantly improve the fracture toughness of cured cyanate ester thermosetting resins. The present invention is as follows: (A) At least one organic compound (A) (also referred to herein as "cyanate ester resin") which does not contain siloxy (≡Si-O) units and has at least two cyanate ester (-OC≡N) groups, wherein compound (A) is preferably substituted and / or contains at least one heteroatom, (B) At least one linear poly(bisphenol-diorganosiloxane) copolymer represented by general formula (I) that does not contain a cyanate ester group: [ka] (In the formula, Z represents a divalent aromatic hydrocarbon group that is identical or different and may be optionally substituted, and may be interrupted by at least one heteroatom. R represents a monovalent SiC bonded hydrocarbon group, which may be identical or different and may be interrupted by a hydrogen atom or at least one oxygen atom. R 1 These are identical or different hydrogen atoms, hydroxy(-OH) groups, or silyloxy groups represented by general formula (II): [ka] (In the formula, R 2 They are identical or different, and represent the base R. R 3 (This represents a monovalent Si-O bonded alkoxy or aryloxy group having 1 to 18 carbon atoms, preferably an aryloxy group, which may be identical or different and may be separated by a group R or at least one heteroatom.) This represents, x is 1 to 20, preferably 1 to 10, particularly preferably 1 to 5, and especially preferably 1 or 2. y is 1 to 100, preferably 1 to 70, preferably 1 to 50, particularly preferably 1 to 30, and especially preferably 3 to 15, and z is 1 to 20, preferably 1 to 10, particularly preferably 1 to 5, and especially preferably 1 or 2. The present invention provides a curable composition containing the following:

[0011] The heteroatoms can be selected from the group consisting of O, S, N, P, and Si; preferably O, S, and Si; particularly preferably O and S; and especially preferably O.

[0012] In this invention, the notation "component (A)" refers to the entirety of at least one compound (A), and the notation "component (B)" refers to the entirety of at least one compound (B).

[0013] In the present invention, "1-propenyl" refers to a "-CH=CH-CH3" group, "2-propenyl" or "allyl" refers to a "-CH2-CH=CH2" group, and "propenyl" refers to a 1-propenyl group or a 2-propenyl group.

[0014] To avoid an excessive increase in the number of pages in the description of the present invention, only preferred embodiments of individual features will be described.

[0015] However, readers with expertise should clearly understand that this type of disclosure implies that all combinations of different preferred levels (i.e., combinations within a single compound / feature and combinations between different compounds / features) are also explicitly disclosed and explicitly desired. Specific Description of the Invention

[0016] Cyanate ester resin (A) These are organic compounds that do not contain siloxy (≡Si-O) units and have at least two cyanate ester groups (-OC≡N) per molecule. Compound (A) may be substituted and / or contain at least one heteroatom.

[0017] Preferably, at least one compound (A) is an aromatic hydrocarbon compound that is optionally substituted and / or contains at least one heteroatom. Here, at least two cyanate ester groups (-OC≡N) per molecule of compound (A) are preferably bonded to an aromatic carbon atom.

[0018] Particularly preferably, at least two aromatic hydrocarbon groups are present per molecule of compound (A), each optionally substituted and / or containing at least one heteroatom, and each having a cyanate ester group bonded to an aromatic carbon atom. In particular, the aromatic hydrocarbon groups, each optionally substituted and / or containing at least one heteroatom, and each having a cyanate ester group bonded to an aromatic carbon atom, are bonded covalently or via -CR 4 2-, -CR4 =CR 4 -, -C(=CR 4 2)-, -O-, -S-, -N=N-, -CR 4 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, ≡P(=O), -SiR 4 2-, a divalent aromatic hydrocarbon group (e.g., phenylene, tolylene, biphenylene, and naphthylene, etc.; or a divalent cycloalkanediyl group, e.g., tricyclo[5.2.1.0 2,6 decandiyl and bicyclo[2.2.1]heptanediyl, etc.) selected from the group consisting of at least one crosslinking unit and are bonded to each other via the crosslinking unit.

[0019] Group R 4 independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, particularly preferably 1 to 12 carbon atoms, and most preferably 1 to 6 carbon atoms, optionally substituted and / or interrupted by at least one heteroatom, and optionally bonded to any of the other groups R 4 derived from substituents or crosslinking units to form a cyclic unit.

[0020] Group R 4 is, for example, a monovalent group, such as a methyl group, an ethyl group, a trifluoromethyl group, a phenyl group, and a fluorenyl group, etc.; or a ring structure composed of two groups R 4 such as cyclohexane-1,1-diyl, cyclohexene-1,2-diyl, 9H-fluorene-9,9-diyl, N-phenyl-1-isoindolinone-3,3-diyl, 1(3H)-isobenzofuranone-3,3-diyl, anthracene-9(10H)-one-10,10-diyl, 9,10-dihydroanthracene-9,9-diyl, and 3,3,5-trimethylcyclohexane-1,1-diyl group, etc. selected from.

[0021] Examples of at least one compound (A) according to the present invention include dicyanate esters and polycyanate esters of monocyclic aromatic hydrocarbons, for example, 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-tricyanatebenzene, methyl(2,4-dicyanatephenyl)ketone, and 2,7-dicyanatenaphthalene; cyanate esters of bisphenols ("bisphenol dicyanate"), for example, 2,2-bis(4-cyanatephenyl)butane, 2,2-bis(4-cyanatephenyl)propane (CAS 1156-51-0, Bisphenol A cyanate ester; Trade names: AroCy (registered trademark) B10, PRIMASET (registered trademark) BAD Cy and CYTESTER (registered trademark) TA), 2,2-Bis(4-cyanatephenyl)-1,1,1,3,3,3-hexafluoropropane (CAS 32728-27-1, Bisphenol A cyanate ester), 2,2-Bis(3-methyl-4-cyanatephenyl)propane (Bisphenol C cyanate ester), 1,1-Bis(4-cyanatephenyl)ethane (CAS 47073-92-7, Bisphenol E Cyanate esters; Trade names: AroCy® L-10, PRIMASET® LECy, CYTESTER® P201), 1,1-bis(4-cyanatephenyl)-1-phenylethane (bisphenol AP cyanate ester), bis(4-cyanatephenyl)methane (bisphenol F cyanate ester), bis(4-cyanate-3,5-dimethylphenyl)methane (CAS 101657-77-6, tetramethylbisphenol F cyanate ester), 1,3-bis(2-(4-cyanatephenyl)propan-2-yl)benzene (CAS 127667-44-1, bisphenol M cyanate ester;Product Name: AroCy(Registered Trademark) XU 366), Bis(4-cyanatephenyl)thioether, Bis(4-cyanatephenyl)ether, 1,1-bis(4-cyanatephenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-cyanatephenyl)cyclohexane, 9,9-bis(4-cyanatephenyl)fluorene (bisphenol FL-cyanate ester), Bis(4-cyanatephenyl)sulfone (CAS 2918-28-7; Bisphenol S-cyanate ester), bis(4-cyanatephenyl)ketone, bis(4-(4-cyanatephenoxy)phenyl)ketone, bis(4-(4-cyanatephenoxy)phenyl)sulfone, bis(4-cyanatephenoxy)sulfoxide, bis(4-(4-cyanatephenoxy)phenyl)(phenyl)phosphine oxide, bis(4-cyanatephenyl)(methyl)phosphine oxide, 1,1-dibromo-2,2-bis(4-cyanatephenyl)ethylene, 1,1-dichloro-2,2-bis(4-cyanatephenyl)ethylene, 3,3-bis(4-cyanatephenyl)-N-phenylphthalimide, 3,3-bis(4-cyanatephenyl)-1(3H)-isobenzofuranone (CAS 32728-31-7), 3,3-bis(4-cyanatephenyl)-2-benzofuran-1-one, 10,10-bis(4-cyanatephenyl)anthracene-9(10H)-one, 1-ethyl-2-methyl-3-(4-cyanatephenyl)-5-cyanateindan, 1,1-dimethyl-3-methyl-3-(4-cyanatephenyl)cyanateindan, bis(2-cyanate-3-methoxy-5-methylphenyl)methane, and 1,1-bis(3- Examples include methyl-4-cyanatephenyl)cyclohexane(bisphenol Z-cyanate ester); cyanate esters of propenyl-substituted bisphenols, such as 2,2-bis(3-(2-propenyl)-4-cyanatephenyl)propane, bis{[4-[(3-allyl-4-cyanatephenyl)isopropylidene]phenoxy]phenyl}sulfone, and bis{4-[4-cyanate-3-(2-propenyl)phenoxy]phenyl}sulfone;Cyanate esters of biphenyls, e.g., 4,4'-dicyanate biphenyl (CAS 1219-14-3), 2,4'-dicyanate biphenyl, and 2,2'-dicyanate biphenyl; phenol-dicyclopentadiene cyanate ester resins, e.g., dicyclopentadienylbis(phenol cyanate ester) (CAS 135507-71-0; trade name: AroCy(registered trademark) XU-71787.02); cyanate esters of phenol-formaldehyde resins produced by acid or alkali catalytic concentration of phenols, naphthols, naphthalenediols, xylenols, or cresols with formaldehyde, e.g., resol cyanate esters or novolac 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, and also AroCy® XU-371); Cyanate esters of fluoroalkanediols, e.g., 1,8-disyanate perfluorooctane; Cyanate esters of naturally occurring polyphenols, e.g., trans-3,5,4'-tricyanate stilbene; Cyanate esters of bisphenolsilanes, e.g., dimethylbis(4-cyanatephenyl)silane; 1,1,1-tris(4-cyanatephenyl)ethane (CAS 113151-22-7), 1,2,3-tris(4-cyanatephenyl)propane; and also a polymer resin having a cyanate ester group at the end, comprising at least two identical or different repeating units, wherein the main chain of each repeating unit comprises at least one divalent aromatic hydrocarbon group such as phenylene, biphenylene, and naphthylene, or 9H-fluorene-9,9-diyl, and -CR; 5 2-, -CR 5 =CR 5 -, -C (=CR 5 2) -, -O-, -S-, -N=N-, -CR 5=N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, ≡P(=O), -SiR 5 2-, or divalent cycloalkanediyl group (e.g., tricyclo[5.2.1.0 2,6 Examples of polymer resins include those containing at least one crosslinking unit selected from the group consisting of decanediyl and bicyclo[2.2.1]heptanediyl. Examples of repeating units of cyanate ester polymer resins include arylene ethers, arylene ether sulfones, or arylene ether ketones.

[0022] In each case, base R 5 R is independent of R 4 It represents the base as defined in [the relevant text].

[0023] Preferably, at least one compound (A) is a cyanate ester of 2,2-bis(4-cyanatephenyl)propane, 1,1-bis(4-cyanatephenyl)ethane, bis(4-cyanatephenyl)methane, 1,3-bis(2-(4-cyanatephenyl)propan-2-yl)benzene, 2,2-bis(3-(2-propenyl)-4-cyanatephenyl)propane, bis(4-cyanatephenyl)thioether, bis(4-cyanatephenyl)sulfone, phenol-dicyclopentadiene cyanate ester resin, or phenol-formaldehyde resin. Particularly preferred, at least one compound (A) is a cyanate ester of 2,2-bis(4-cyanatephenyl)propane, bis(4-cyanatephenyl)methane, 1,1-bis(4-cyanatephenyl)ethane, 1,3-bis(2-(4-cyanatephenyl)propan-2-yl)benzene, bis(4-cyanatephenyl)thioether, bis(4-cyanatephenyl)sulfone, phenol-dicyclopentadiene cyanate ester resin, and also phenol-formaldehyde resin. Particularly preferred, at least one compound (A) is 1,1-bis(4-cyanatephenyl)ethane, 1,3-bis(2-(4-cyanatephenyl)propan-2-yl)benzene, and also a novolac cyanate ester of cresol or phenol.

[0024] It is possible to use only one type of cyanate ester resin (A), or to use a mixture of different cyanate ester resins (A), or to use a prepolymer of one type of cyanate ester resin (A), or a mixture of prepolymers of different cyanate ester resins (A) and cyanate ester resin prepolymers, or a mixture of cyanate ester resin prepolymers and one or more types of cyanate ester resins (A).

[0025] An example of a prepolymer of cyanate ester resin (A) is bisphenol A dicyanate homopolymer (CAS 25722-66-1, trade name example: Primaset® BA-200).

[0026] Compound (B) At least one compound (B) used in accordance with the present invention is a poly(bisphenol-diorganosiloxane) copolymer represented by general formula (I) (hereinafter also referred to as "copolymer") having an aromatic hydroxy(-OH) group, an aryl ether group, or a silyloxy group represented by general formula (II) at its terminus.

[0027] Compound (B) may be a solid or liquid at 23°C and 10¹³ hPa, but it is preferable that the poly(bisphenol-diorganosiloxane) copolymer (B) is a solid at 23°C and 10¹³ hPa.

[0028] When compound (B) according to the present invention is a liquid, it has a dynamic viscosity at 80°C, preferably at least 1 mPa·s, particularly preferably 1 mPa·s to 10,000 mPa·s, and especially preferably 5 mPa·s to 1,000 mPa·s.

[0029] In the context of this invention, dynamic viscosity is determined according to DIN 53019 at a temperature of 23°C and an air pressure of 1,013 hPa, unless otherwise specified. Measurements are performed using an Anton Paar "Physica MCR 300" rotary rheometer. For viscosities of 1 to 200 mPa·s, a coaxial cylindrical measuring system (CC 27) with an annular measuring gap of 1.13 mm is used, and for viscosities exceeding 200 mPa·s, a cone-plate measuring system (Searle system with CP 50-1 measuring cone) is used. The shear rate is set according to the polymer viscosity (100 s). -1 1-99 mPa·s; 200s -1 100-999 mPa·s; 120s -11,000-2,999 mPa·s; 80s -1 3,000-4,999 mPa·s; 62s -1 5,000-9,999 mPa·s; 50s -1 10,000~12,499 mPa·s; 38.5s -1 33s -1 16,000-19,999 mPa·s; 25s -1 20,000-24,999 mPa·s; 20s -1 25,000~29,999 mPa·s; 17s -1 30,000-39,999 mPa·s; 10s -1 40,000~59,999 mPa·s; 5s -1 60,000~149,999;3.3s -1 150,000~199,999 mPa·s; 2.5s -1 200,000~299,999 mPa·s; 1.5s -1 (300,000 to 1,000,000 mPa·s).

[0030] Once the system for measuring dynamic viscosity is thermally equilibrated at the measurement temperature, a three-stage measurement program is executed, consisting of a run-in phase, pre-shearing, and viscosity measurement. The run-in phase involves taking measurements and gradually accelerating the shear rate over one minute to the shear rate corresponding to the predicted viscosity. Once this shear rate is reached, pre-shearing is performed at a constant shear rate for 30 seconds, followed by 25 individual measurements of 4.8 seconds each for viscosity measurement, and the results are averaged. The average value corresponds to the dynamic viscosity and is reported in mPa·s.

[0031] The at least one compound (B) according to the present invention has a weight-average molecular weight Mw of preferably 1,000 to 30,000 g / mol, preferably 1,500 g / mol to 20,000 g / mol, particularly preferably 1,500 g / mol to 10,000 g / mol, and especially preferably 2,000 g / mol to 8,000 g / mol.

[0032] The at least one compound (B) according to the present invention has a number-average molecular weight 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, and especially preferably 500 g / mol to 2,000 g / mol.

[0033] In the context of this invention, the number-average molecular weight Mn and weight-average molecular weight Mw are in g / mol units in both cases, rounded to the nearest ten according to Section 4 of DIN 1333:1992-02, and determined by size exclusion chromatography (SEC / GPC) in accordance with DIN 55672-1 / ISO 160414-1 and ISO 160414-3. In this measurement, a column array using polystyrene-kodivinbenzene as the stationary phase is calibrated using a polystyrene standard. The array consists of three columns with different pore size distributions in the order of 10,000 Å, 500 Å, and 100 Å, with a maximum size cutoff of 450,000 g / mol. The analysis is performed using THF as the eluent. The analysis is performed at a column temperature of 45 ± 1 °C using a refractive index detector.

[0034] Examples of monovalent SiC-bonded hydrocarbon groups R that may be cleaved by at least one oxygen atom include: Alkyl groups, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl group, etc.; Hexyl groups, e.g., n-hexyl group, etc.; Heptyl groups, e.g., n-heptyl group, etc.; Octyl groups, e.g., n-octyl, isooctyl, 2,4,4-trimethylpentyl, and 2,2,4-trimethylpentyl group, etc.; Nonyl groups, e.g., n-nonyl group, etc.; Decyl groups, e.g., n-decyl group, etc.; Dodecyl groups, e.g., n-dodecyl group, etc.; Hexadecyl groups, e.g., n-hexadecyl group, etc.; Octadecyl groups, e.g., n-octadecyl group, etc.; Cycloalkyl groups, e.g., cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl group, etc.; Unsaturated hydrocarbon groups, such as vinyl, propenyl, 5-hexenyl, 7-octenyl, 10-undecenyl, cyclohexenyl, 2-(3-cyclohexenyl)ethyl, bicyclo[2.2.1]hepten-2-yl, dicyclopentenyl, 4-vinylcyclohexyl, 3-norborneyl, vinylphenyl, propenylphenyl, ethynyl, propynyl, and butynyl groups; aryl groups, such as phenyl, biphenyl, cumylphenyl, benzylphenyl, tert-butylphenyl, naphthyl, anthryl, and phenanthryl groups; alkaryl groups, such as tolyl, xylyl, and ethylphenyl groups; aralkyl groups, such as benzyl, cumyl, α- and β-phenylethyl groups; alkoxyaryl groups, such as methoxyphenyl group; aryloxyaryl groups, such as phenyloxyphenyl group; and heterocyclic aromatic hydrocarbon groups, such as furyl groups.

[0035] The group R is preferably a monovalent SiC-bonded hydrocarbon group having 1 to 8 carbon atoms, and is particularly preferably a methyl group or a phenyl group.

[0036] base R 1 R is preferably a hydrogen atom, a hydroxy(-OH) group, or a silyloxy group represented by formula (II), where R 2 This is either a methyl group or a phenyl group.

[0037] A monovalent Si-O bonded alkoxy or aryloxy group R, which may be interrupted by at least one heteroatom. 3 Examples include the methoxy group, ethoxy group, phenoxy group, 4-phenylphenoxy group, 4-(phenyloxy)phenoxy group, cumylphenoxy group, and tert-butylphenoxy group.

[0038] base R 3 It is preferable that this is a hydrogen atom, a methyl group, a phenyl group, or a cumylphenoxy group.

[0039] The divalent, optionally substituted aromatic hydrocarbon group Z, optionally cleaved by at least one heteroatom, is, for example, a monoarylene group, such as 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; as well as two arylene groups bonded covalently or -CR 6 2-, -CR 6 =CR 6 -, -C (=CR 6 2) -, -O-, -S-, -N=N-, -CR 6 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, ≡P(=O), -SiR 6 2-, divalent aromatic hydrocarbon groups, such as phenylene, triylene, biphenylene, and naphthylene; or divalent cycloalkanediyl groups (e.g., tricyclo[5.2.1.0 2,6 Selected from bisarylene units bonded to one another via at least one crosslinking unit selected from the group consisting of decanediyl and bicyclo[2.2.1]heptanediyl, etc.

[0040] In each case, base R 6 R is independent of R 4 It represents the base as defined in [the relevant text].

[0041] Group Z is preferably a group obtained by substituting all phenolic hydroxyl groups (-OH) with a single covalent bond from the corresponding bisphenol (CAS number indicated in parentheses), for example, -C6H4-(CAS 123-31-9, CAS 108-46-3), -C6H3(C(CH3)3)-(CAS 1948-33-0), -C6H3(CH3)-(CAS 95-71-6), -C6H4-C6H4-(CAS 92-88-6、CAS 611-62-1、CAS 1806-29-7)、 -C6H4-C(CH3)2-C6H4-(CAS 80-05-7)、 -C6H3(CH2-CH=CH2)-C(CH3)2-C6H3(CH2-CH=CH2)-(CAS 1745-89-7)、 -C6H4-S(=O)2-C6H4-(CAS 80-09-1)、 -C6H4-S(=O)-C6H4-(CAS 1774-34-1)、 -C6H4-CH2-C6H4-(CAS 620-92-8、CAS 2467-02-9、CAS 2467-03-0)、 -C6H4-C(CF3)2-C6H4-(CAS 1478-61-1)、 -C6H4-C(CH2CH3)(CH3)-C6H4-(CAS 77-40-7)、 -C6H2(CH3)2-C(CH3)2-C6H2(CH3)2-(CAS 5613-46-7)、 -C6H4-O-(m-C6H4)-O-C6H4-(CAS 126716-90-3)、 -C6H4-O-(p-C6H4)-O-C6H4-(CAS 5085-95-0)、 -C6H4(CH3)-S-C6H4(CH3)-(CAS 24197-34-0)、 -C6H4-C(CH3)2-(p-C6H4)-C(CH3)2-C6H4-(CAS 2167-51-3)、 -C6H4-C(CH3)2-(m-C6H4)-C(CH3)2-C6H4-(CAS 13595-25-0)、 -C6H3(CH3)-C(CH3)2-C6H2(CH3)-(CAS 79-97-0)、 -C6H4-(シクロヘキサン-1,1-ジイル)-C6H4-(CAS 843-55-0)、 -C6H2(CH3)2)-S(=O)2-C6H2(CH3)2)-(CAS 13288-70-5)、 -C6H4-(9H-fluorene-9,9-diyl)-C6H4-(CAS 3236-71-3), -C6H2(CH3)2-C(CH3)2-(p-C6H4)-C(CH3)2-C6H2(CH3)2-(CAS 36395-57-0), -C6H3(CH3)-(9H-Fluorene-9,9-Diyl)-C6H3(CH3)-(CAS 88938-12-9), -C6H3(C6H5)-C(CH3)2-C6H3(C6H5)-(CAS 24038-68-4), -C6H3(CH3)-(cyclohexane-1,1-diyl)-C6H3(CH3)-(CAS 2362-14-3), -C6H4-(9H-Fluorene-9,9-Diyl)-C6H4-(CAS 351521-78-3) -C6H4-C(=O)-C6H4-(CAS 611-99-4, CAS 835-11-0), -C6H4-S-C6H4-(CAS 2664-63-3), -C6H4-O-C6H4-(CAS 1965-09-9, CAS 15764-52-0), -C6H4-C(C6H5)2-C6H4-(CAS 1844-01-5), -C6H4-C(=CBr2)-C6H4-), -C6H4-C(=CCl2)-C6H4-(CAS 14868-03-2), -C6H4-C(CH2CH(CH3)2)(CH3)-C6H4-(CAS 6807-17-6), -C6H3Br-C6H3Br-(CAS 189039-64-3), -C6H4-CH(CH3)-C6H4-(CAS 2081-08-5), -C6H2(C(CH3)3)2-CH2-C6H2(C(CH3)3)2)-(CAS 118-82-1), -C6H4-C(CH3)(C6H5)-C6H4-(CAS 1571-75-1), -C6H2(CH3)2)-CH2-C6H2(CH3)2)-(CAS 5384-21-4), -C6H2Br2-C(CH3)2-C6H2Br2-(CAS 79-94-7), -C6H2(CH3)2-C6H2(CH3)2-(CAS 2417-04-1), -C6H3 (Cyclo-C6H 11 )-C(CH3)2-C6H3(Cyclo-C6H 11 )-(CAS 57100-74-0), -C6H3(iPr)-C(CH3)2-C6H3(iPr)-(CAS 127-54-8), -C6H4-(3,3,5-trimethylcyclohexane-1,1-diyl)-C6H4-(CAS 129188-99-4), -C6H4-O-C6H4-C(=O)-C6H4-O-C6H4-, -C6H4-O-C6H4-S(=O)2-C6H4-O-C6H4-, -C 10 H6-(CAS 571-60-8, CAS 83-56-7, CAS 575-44-0, CAS 575-38-2, CAS 92-44-4, CAS 582-17-2, CAS 581-43-1), Benzonorbornane-3,6-diyl (CAS 16144-91-5), -C6H4-(1(3H)-isobenzofuranone-3,3-diyl)-C6H4-(CAS 77-09-8), -C6H4-(1(3H)-2-phenylisoindoline-3,3-diyl)-C6H4-(CAS 77-09-8), -C6H4-(3,3,5-trimethylcyclohexane-1,1-diyl)-C6H4-(CAS 129188-99-4), etc. Propenyl substituent Z, for example. -C6H3(CH2-CH=CH2)-C(CH3)2-C6H3(CH2-CH=CH2)-(CAS 1745-89-7), -C6H3(CH=CH2-CH3)-O-C6H4-C(=O)-C6H4-O-C6H3(CH=CH2-CH3)-(CAS 109423-33-8), -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)- These are some examples.

[0042] The group 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-, -C The compounds are 6H4-S(=O)2-C6H4-, -C6H4-CH2-C6H4-, or -C6H4-C(CH3)2-C6H4-C(CH3)2-C6H4-, and are particularly preferably -C6H4-C(CH3)2-C6H4-, -C6H4-S(=O)2-C6H4-, or -C6H4-S-C6H4-.

[0043] Compound (B) preferably does not contain aliphatic carbon-carbon multiple bonds. It is particularly preferable that compound (B) does not contain aliphatic carbon-carbon multiple bonds and does not contain any heteroatoms other than oxygen and sulfur.

[0044] Examples of copolymers (B) used in accordance with the present invention include: - HO[-C6H4-CMe2-C6H4-O-Me2Si-O] m -C6H4-CMe2-C6H4-OH (In the formula, Mw=9890g / mol, Mn=2440g / mol); - HO[-C6H4-CMe2-C6H4-O-Ph2Si-O] m -C6H4-CMe2-C6H4-OH (In the formula, Mw=6880g / mol, Mn=2230g / mol); - HO[-C6H4-CMe2-C6H4-O(-Me2Si-O)2] m -C6H4-CMe2-C6H4-OH (Where, Mw = 4740 g / mol, Mn = 1900 g / mol); - HO[-C6H4-CMe2-C6H4-O-Ph2MeSi-O] m [-C6H4-CMe2-C6H4-O(-Me2Si-O)2] n -C6H4-CMe2-C6H4-OH (In the formula, Mw = 8360 g / mol, Mn = 2150 g / mol); - PhMe2Si-O[-C6H4-CMe2-C6H4-O(-Me2Si-O)2] m -C6H4-CMe2-C6H4-O-SiPhMe2 (In the formula, Mw = 5570 g / mol, Mn = 1450 g / mol); - H[-C6H4-CMe2-C6H4-O(-Me2Si-O)2] m -C6H4-CMe2-C6H4-H (In the formula, Mw = 2930 g / mol, Mn = 1230 g / mol); - C6H4tBu(-Me2Si-O)2-[C6H4-CMe2-C6H4-O(-Me2Si-O)2] m -C6H4tBu (In the formula, Mw = 5930 g / mol, Mn = 2080 g / mol); - HO[-C6H2Me2-CMe2-C6H2Me2-O(-Me2Si-O)2] m -C6H2Me2-CMe2-C6H2Me2-OH (In the formula, Mw = 3240 g / mol, Mn = 1510 g / mol); - HO[-C6H4-S-C6H4-O-(-Me2Si-O)2] m -C6H4-S-C6H4-OH (In the formula, Mw = 6140 g / mol, Mn = 2470 g / mol); - HO[-C6H4-C(=O)-C6H4-O(-Me2Si-O-Ph2Si-O-Me2Si-O)] m-C6H4-C(=O)-C6H4-OH (In the formula, Mw=8230g / mol, Mn=2370g / mol); These are examples, where Me is a methyl group, Ph is a phenyl group, and tBu is a tert-butyl group, and the sum of m+n in copolymer (B) is on average 3 to 10.

[0045] Compound (B) used in accordance with the present invention can be produced by methods commonly used in the chemical field, for example, by the method described in Russian Patent No. 2738712. Alternatively, bisphenols may be produced in the presence of a boron catalyst (B(C6F5)3) in an inert solvent such as toluene or hexane to form diorganosilanes (H-R2Si-H) and / or poly(diorganosiloxanes)[H(-R2Si-O)] having silicon-bonded hydrogen atoms at the terminals. 2~20 There is a Piers-Rubinsztajn reaction that involves copolymerization with [-H]. The average molar mass can be adjusted by further addition of monophenol, triorganoalkoxysilane, or triorganosilane.

[0046] Compound (B) is dissolved in an organic solvent such as toluene, diethyl ether or other ethers, anisole, or tetrahydrofuran, and acetals such as ethylal, in the presence of an auxiliary base such as a nitrogen base, preferably pyridine, and the corresponding bisphenols, as well as diorganodichlorosilane (Cl-R2Si-Cl) and / or poly(diorganosiloxane) [Cl(-R2Si-O)] having a silicon-bonded chlorine atom at the terminal. x>1 It is preferable to produce it from -Cl, or in some cases from an aromatic compound having a phenolic hydroxyl group (OH) or a triorganochlorosilane.

[0047] In the preparation of compound (B), one bisphenol alone, or a mixture of different bisphenols with one or more diorganodichlorosilanes and / or poly(diorganosiloxanes), may be used, and in some cases, one or more reactive triorganosilanes or one or more aromatic compounds having only one phenolic hydroxyl group (OH) may be used.

[0048] In the context of the present invention, the terms “reactive” diorganosilane, poly(diorganosiloxane), and triorganosilane mean, in particular, compounds having a functional group such as SiH or SiCl that can react with a phenolic hydroxyl group (OH).

[0049] Compound (B) is preferably produced from bisphenol, reactive diorganosilane, or poly(diorganosiloxane), and possibly from an aromatic compound having a phenolic hydroxyl group (OH).

[0050] Compound (B) is particularly preferably prepared in ether in the presence of pyridine from bisphenol, diorganodichlorosilane, and / or tetraorganodisiloxane having a silicon-bonded chlorine atom at its terminus, and possibly from an aromatic compound having a phenolic hydroxyl group (OH).

[0051] The degree of polymerization depends on the ratio of the reactant, bisphenol, reactive diorganosilane, and / or poly(diorganosiloxane), to monophenol or reactive triorganosilane. This preferably yields the desired copolymer (B) having terminal groups represented by formula (I), where R 1 This is a hydroxyl group or a hydrogen group.

[0052] The compositions according to the present invention may contain only one compound (B), or a mixture of different compounds (B), preferably only one compound (B).

[0053] In any case, the composition according to the present invention contains, based on 100 parts by weight of component (A), at least one compound (B) preferably in amounts of 1 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, and especially preferably 5 to 35 parts by weight.

[0054] In addition to at least one compound (A) and compound (B), the composition according to the present invention may include further substances different from components (A) and (B), such as a modifier (C), a reactive resin (D), a filler (E), a curing accelerator (F), a solvent (G), and an auxiliary agent (H).

[0055] In a preferred embodiment, the composition according to the present invention comprises the following compounds: (C) at least one modifier (C); (D) At least one reactive resin (D); (E) at least one type of filler (E); (F) at least one type of curing accelerator (F); (G) at least one solvent (G); and / or (H) at least one auxiliary agent (H); It further includes, Here, at least one modifier (C), at least one reactive resin (D), at least one filler (E), at least one curing accelerator (F), at least one solvent (G), and / or at least one auxiliary agent (H) are different from at least one compound (A) and compound (B).

[0056] Compositions according to the present invention, • Containing only one compound (C) or a mixture of different compounds (C), preferably only one compound (C); • Containing only one compound (D), or a mixture of different compounds (D), preferably only one compound (D); • Consists of only one compound (E), or a mixture of different compounds (E), preferably only one compound (E); • Containing only one compound (F), or a mixture of different compounds (F), preferably only one compound (F); • Consists of only one compound (G), or a mixture of different compounds (G), preferably only one compound (G); and / or • Containing only one compound (H), or a mixture of different compounds (H), preferably only one compound (H).

[0057] In the present invention, the notation "component (C)" refers to the entirety of at least one compound (C), the notation "component (D)" refers to the entirety of at least one compound (D), the notation "component (E)" refers to the entirety of at least one compound (E), the notation "component (F)" refers to the entirety of at least one compound (F), the notation "component (G)" refers to the entirety of at least one compound (G), and the notation "component (H)" refers to the entirety of at least one compound (H).

[0058] Compound (C) Any at least one modifier (C) has units represented by the following formula: [ka] (In the formula, R 7 This represents a SiC-bonded, possibly substituted, monovalent hydrocarbon group that is identical or different and optionally cleaved by a hydrogen atom or at least one heteroatom. R 8 This represents a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, which are identical or different and are separated by a hydrogen atom or optionally at least one heteroatom. 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, especially preferably 0, However, in formula (III), the sum of h+i is 3 or less, compound (C1) contains 2 to 20 units of formula (III), and compound (C1) does not contain the Ar-O-Si moiety. It is preferable that the compound is an organosilicon compound (C1) containing [the specified compound].

[0059] In this invention, the abbreviation "Ar" represents an aromatic hydrocarbon structure.

[0060] A monovalent SiC bonded hydrocarbon group R, optionally substituted and / or cleaved by at least one heteroatom. 7 Examples of R include the following groups: imide groups, e.g., N-(5-ethynylphthalimide)phenyl-, N-(5-(phenylethynyl)phthalimide)phenyl-, nadimidphenyl-, maleimidphenyl, and 3-maleimidpropyl; epoxy groups, e.g., 3-glycidoxypropyl, 4-(oxiran-2-yl)phenyl, oxiran-2-yl, and 2-(3,4-epoxycyclohexyl)ethyl; acrylate and methacrylate groups, e.g., 3-methacrylateoxypropyl, acrylicoxymethyl, and methacrylateoxymethyl; amine groups, e.g., aminophenyl, 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, and N-phenylaminomethyl groups, etc.; hydroxy substituents, e.g., hydroxyphenyl and hydroxypropyl groups, etc.; halogenated groups, e.g., trifluoromethyl, fluorophenyl, chlorophenyl, bromophenyl, and trifluoromethylphenyl groups, etc.; alkenylaryl groups, e.g., vinylphenyl, 2-methyl-2-propen-1-yl ("methallyl"), and propenylphenyl groups, etc.; as well as bicyclo[4.2.0]octa-1,3,5-trienyl (=benzocyclobutenyl), polycaprolactone, polycaprolactam, cyanatephenyl, 3-cyanatetopropyl, isocyanatephenyl, 3-isocyanatetopropyl, arylethynyl, and ethynylphenyl groups.

[0061] base R 7It is preferable that this is a hydrogen atom, a phenyl group, or a methyl group.

[0062] base R 8 The group is preferably an aliphatic hydrocarbon group having 1 to 18 carbon atoms, and is particularly preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, or isobutyl group, with methyl or ethyl group being especially preferred.

[0063] Examples of organosilicon compounds (C1) include 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-epoxycyclohexyl-1-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (CAS 18724-32-8), and 1,3-bis(norbornenylethyl)-1,1,3,3-tetramethyldisiloxane, with an average composition of (PhSiO 3 / 2 ) 20 (PhSi(OMe)O 2 / 2 ) 66 (PhSi(OMe)2O 1 / 2 ) 14 and organopolysiloxanes with a weight-average molecular weight Mw = 2190 g / mol, and an average composition (PhSiO 3 / 2 ) 75 (Me3SiO 1 / 2)25 and organopolysiloxanes with a weight-average molecular weight Mw = 1380 g / mol, octa(epoxycyclohexyl)POSS (CAS 187333-74-0), octaphenylPOSS (CAS 5256-79-1), octaphenylcyclotetrasiloxane (CAS 546-56-5), 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (CAS 77-63-4), 1,1,3,3,5,7-hexamethyl-5,7-diphenylcyclotetrasiloxane, 1,1,3,3-tetramethyl-5,5,7,7-tetraphenylcyclotetrasiloxane (CAS Examples include 1693-47-6), 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane (3390-61-2), 1,3,3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane (3982-82-9), 1,3,5,7-tetramethyl-1,1,3,5,7,7-hexaphenyltetrasiloxane (CAS 38421-40-8), and 1,9-dimethoxy-1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylpentasiloxane.

[0064] At least one modifier (C) is preferably a thermoplastic organic polymer ("thermoplastic resin") (C2) that does not contain siloxy (≡Si-O-) units and cyanate ester groups, and comprises at least two repeating units selected from the group consisting of polyarylene, polyarylene ether, polyarylene sulfide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyetheretherketoneketone, polyimide, polybenzimidazole, polyamide, poly(amideimide), polyarylate, polyesterimide, polyetherimide, polyaramid, polyacrylate, polyhydantoin, liquid crystal polymer, polycarbonate, polyester carbonate, and polyethylene terephthalate; and also comprises at least two repeating units selected from the group consisting of mixtures thereof or copolymerizable compounds. The thermoplastic resin (C2) has either reactive or chemically inert end groups. Reactive end groups are residual as a result of being generated in polymerization reactions from the corresponding reactive polymerizable groups of the monomer. These groups are preferably hydroxyl groups, amino groups, carboxyl groups, and isocyanate groups. Examples of chemically inert terminal groups include methyl groups or phenyl groups. The thermoplastic resin (C2) has a glass transition temperature greater than 100°C, preferably 130°C to 450°C, particularly preferably 150°C to 400°C, and especially preferably 180°C to 350°C. The number-average molecular weight Mn of (C2) is preferably 1100 to 100000 g / mol, more preferably 2000 to 50000 g / mol, particularly preferably 2000 to 30000 g / mol, and especially preferably 3000 to 20000 g / mol.

[0065] At least one modifier (C) is an organic monofunctional cyanate ester (C3) represented by general formula (IV) that does not contain siloxyl (≡Si-O) units and phenolic hydroxyl groups: [ka] (In the formula, R 9This represents a potentially substituted monovalent aromatic hydrocarbon group that may be interrupted by at least one heteroatom, except that the cyanate ester group is directly bonded to the aromatic carbon atom. It is preferable.

[0066] Examples of compounds (C3) include cyanatebenzene (CAS 1122-85-6), 1-cyanate-4-cumylbenzene (CAS 110215-65-1), 1-cyanate-4-tert-butylbenzene, 1-cyanate-2-tert-butylbenzene, 4-cyanatebiphenyl, 1-cyanatenaphthalene, 2-cyanatenaphthalene, 4-cyanatenonylbenzene, 4-chlorocyanatebenzene, 4-cyanatediphenylsulfone, 4-cyanatetoluene, 4-cyanatediphenyl ether, 4-cyanatediphenylketone, 4-(cyanate)methoxybenzene; and propenyl-substituted monofunctional cyanate esters, such as 4-cumyl-2-(propenyl)cyanatebenzene or 2-(propenyl)cyanatebenzene.

[0067] The compound (C3) preferably has a boiling point of at least 150°C at 1013 hPa, particularly preferably at least 180°C, and especially preferably at least 220°C.

[0068] Preferably, any at least one modifier (C) is a monomeric aromatic hydrocarbon that does not contain siloxy (≡Si-O) units, does not contain epoxy groups, imide groups, or cyanate groups, has at least one phenolic hydroxyl group (C4), and optionally has one or more aliphatic carbon-carbon multiple bonds.

[0069] Preferably, any aliphatic carbon-carbon multiple bond in compound (C4) is a propenyl group bonded to an aromatic carbon atom, and in compound (C4), it is particularly preferable that one phenolic hydroxyl group and any one propenyl group are bonded to an aromatic group in all cases.

[0070] Examples of compounds (C4) that do not have aliphatic carbon-carbon multiple bonds include monovalent hydroxyl groups, or optionally substituted phenols, such as phenol, cresol, naphthol, 4-phenylphenol, thymol, guaiacol (2-methoxyphenol), 4-cumylphenol, 4-benzylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-tert-butylphenol, 2,4-di-tert-butylphenol, and 2,4-bis(α,α-dimethylbenzyl)pheno Nonylphenol, xylenol, or 2,6-dinonylphenol, etc.; polyhydric phenols, such as catechol (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, etc.; aromatic compounds containing two (bisphenol) or two or more hydroxy(huhydroxy)phenyl groups, For example, 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 (bispheno Examples include 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.

[0071] Examples of compounds (C4) containing a propenyl group include 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), and 3',5-bis(2-propenyl)-2,4'-biphenyldiol (CAS Examples include 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, 9,9'-bis(3-propenyl-4-hydroxyphenyl)fluorene, and 4-(1-(4-hydroxy-3-propenylphenyl)propyl)-2-propenylphenol.

[0072] Compound (C4) includes 4-phenylphenol, 2-methoxy-4-(2-propenyl)-phenol, 4-cumylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-tert-butylphenol, bisphenols, 2,2-bis(3-(2-propenyl)-4-hydroxyphenyl)propane, 4-(1-(4-hydroxy-3-propenylphenyl)propyl)-2-propenylphenol, 4-cumyl-2-(2-propenyl)phenol, 4-cumyl-2-(2-methyl-2-propenyl)phenol, and 4-tert-butyl-2-(2-propenyl)pheno It is preferably 4-tert-butyl-2-(2-methyl-2-propenyl)phenol or 2-(2-propenyl)phenol; it is particularly preferably 2-methoxy-4-(2-propenyl)phenol, 4-cumylphenol, 4-tert-butylphenol, 2,2-bis(3-(2-propenyl)-4-hydroxyphenyl)propane, bis(3-(2-propenyl)-4-hydroxyphenyl)sulfone, 4-cumyl-2-(2-propenyl)phenol, 4-tert-butyl-2-(2-propenyl)phenol, and bisphenol A, E, F, M, or S.

[0073] If the composition according to the present invention contains at least one modifier (C), the composition may contain only one modifier (C1) to (C4), or it may contain two or more different modifiers (C1) to (C4).

[0074] If the composition according to the present invention contains at least one modifier (C), the at least one modifier (C) is present in any case in an amount preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight, and especially preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of components (A) and (B).

[0075] Compound (D) Any at least one reactive resin (D) does not contain siloxy (≡Si-O-) units, nor cyanate ester groups and phenolic hydroxyl groups, and is optionally substituted and / or segmented with at least one heteroatom and is selected from the group consisting of epoxide (D1) and imide (D2), provided that the epoxide (D1) per molecule contains at least two, preferably at least two, polymerizable glycidyloxy groups, glycidyloxycarbonyl groups, glycidylamino groups, diglycidylamino groups, or oxiran-2-yl groups bonded to aromatic carbon atoms, and the imide (D2) per molecule has at least two, preferably at least two, polymerizable 5-ethynylphthalimide groups, 5-(phenylethynyl)phthalimide groups, nadimide groups, benzocyclobutene phthalimide groups, or maleimide groups bonded to aromatic carbon atoms. It is preferably an aromatic hydrocarbon compound under these conditions. Here, maleimide groups, glycidyloxy groups, glycidylamino groups, and diglycidylamino groups are particularly preferred.

[0076] Preferably, any at least one reactive resin (D) per molecule is optionally segmented by at least one heteroatom and contains at least two optionally substituted aromatic hydrocarbon groups each having a maleimide group, glycidyloxy group, glycidyloxycarbonyl group, glycidylamino group, or diglycidylamino group bonded to an aromatic carbon atom. Particularly preferably, (D) is optionally segmented by at least one heteroatom and has a maleimide group, glycidyloxy group, glycidylamino group, or diglycidylamino group bonded to an aromatic carbon atom each, and these are bonded via a covalent bond or -CR 11 2-, -CR 11 =CR 11 -, =C=CR 11 2, -O-, -S-, -N=N-, -CR 11 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)2-, O=P(O-)3, -SiR 112-, phenylene group, allylene group, biphenylene group, bialylene group, naphthylene group, or cycloalkanediyl group, for example, tricyclo[5.2.1.0 2,6 The compound contains at least two optionally substituted aromatic hydrocarbon groups bonded to each other via crosslinking units selected from the group consisting of decanediyl or bicyclo[2.2.1]heptanediyl, etc.

[0077] In each case, base R 11 R is independent of R 4 It represents the base as defined in [the relevant text].

[0078] At least one reactive resin (D) preferably contains an aromatic ring structure that does not contain heteroatoms.

[0079] The epoxy resin (D1) is preferably copolymerizable with the cyanate ester resin (A).

[0080] It is preferable that the imide resin (D2) does not copolymerize with the cyanate ester resin (A).

[0081] Examples of polymerizable epoxy resins (D1) include glycidyl ethers of phenolic compounds, such as 2,2-bis(4-glycidyloxyphenyl)propane (CAS 1675-54-3), bis(4-glycidyloxyphenyl)methane (CAS 2095-03-6), 1,2-bis(glycidyloxy)benzene (CAS 2851-82-3), 1,3-bis(glycidyloxy)benzene (CAS 101-90-6), 1,4-bis(glycidyloxy)benzene (CAS 129375-41-3), 3,5,3',5'-tetramethyl-4,4'-diglycidyloxybiphenyl (CAS 85954-11-6), and 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)fluorene (CAS 47758-37-2), 1,6-(diglycidyloxy)naphthalene (CAS 27610-48-6), etc.; glycidyl ethers of phenols, naphthols, naphthalenediols, bisphenols, or cresol-formaldehyde condensates, e.g., cresol-novolac-glycidyl ether (CAS 29690-82-2), phenol-novolac-glycidyl ether (CAS 29690-82-2) Examples include 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 condensates, e.g., CAS 68610-51-5 and CAS 119345-05-0;Glycidyl esters of aromatic carboxylic acids, e.g., 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), etc.; glycidyl derivatives of aromatic amines and aminophenols, e.g., N,N-diglycidyl-4-glycidyloxyaniline (CAS 5026-74-4), 4,4'-methylenebis(N,N-diglycidylaniline) (CAS Examples include 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 that can be produced by the reaction of an amino-terminated or hydroxy-terminated thermoplastic resin (C2) with epichlorohydrin, such as glycidyloxy or diglycidylamino-terminated polysulfone; epoxy resins of homopolymers or copolymers, such as bisphenol A-epichlorohydrin copolymer (CAS 25036-25-3) and 2,2',6,6'-tetrabromobisphenol A-epichlorohydrin copolymer (CAS 25036-25-3). (40039-93-8), and reaction products of diglycidylbisphenol A and m-phenylenebis(methylamine) (CAS 110839-13-9), as well as mixtures of different epoxy resins (D1).

[0082] Examples of polymerizable maleimide resins (D2) include 4,4'-bis(maleimidophenyl)methane (CAS 13676-54-5), m-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), and 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 bismaleimide and aromatic amines, e.g., 4,4'-bis(maleimidophenyl)methane / 4,4'-bis(aminophenyl)methane copolymer (CAS 26140-67-0), etc.; reaction products of formaldehyde and aniline condensates with maleic anhydride (CAS 28630-26-4, CAS 67784-74-1); bis(4-maleimidophenyl) ether, 2,2-bis[4-(maleimidophenoxy)phenyl]propane (CAS 79922-55-7), bis(4-maleimidophenyl) sulfone (CAS Examples include 13102-25-5), bis(4-maleimidophenyl)ketone, 1,1'-(benzene-1,3-diyldimethanediyl)bis(1H-pyrrole-2,5-dione) (CAS 13676-53-4), 4,4'-bis(maleimide)-1,1'-biphenyl (CAS 3278-30-6), 4,4'-bis(3-maleimidophenoxy)diphenylsulfone, or maleimide-terminated thermoplastic polymers (D2) that can be produced by the reaction of an amino-terminated thermoplastic resin (C2) with maleic anhydride, such as maleimide-terminated polysulfone ethers; and also mixtures of different maleimide resins (D2).

[0083] Preferably, at least one compound (D) is a thermoplastic monomer compound that does not contain homopolymeric or copolymeric polymers.

[0084] If the composition according to the present invention contains at least one reactive resin (D), the at least one reactive resin is present in any case in an amount of preferably 1 to 40 parts by weight, particularly preferably 1 to 30 parts by weight, and especially preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of components (A) and (B).

[0085] If the composition according to the present invention contains at least one polymerizable imide (D2), it is preferable that this be realized in combination with a component copolymerizable with both a cyanate ester group and an imide group, preferably a maleimide group. These components are selected from a cyanate ester (A), a modifier (C3), or a modifier (C4) having a propenyl group bonded to an aromatic carbon atom, or from an aromatic hydrocarbon compound containing one or two hydroxyl groups per molecule bonded to an aromatic carbon atom and one or two polymerizable imide groups per molecule, preferably maleimide groups, bonded to an aromatic carbon atom, such as N-(4-hydroxyphenyl)maleimide (CAS 7300-91-6).

[0086] When the composition according to the present invention includes at least one polymerizable imide resin (D2) in combination with the components described in the preceding paragraph, the molar ratio of the total number of imide groups to the total number of propenyl groups is preferably in the range of 45:55 to 95:5, particularly preferably in the range of 55:45 to 90:10, and especially preferably in the range of 65:45 to 80:20.

[0087] Compound (E) At least one filler (E) in the composition according to the present invention may be any known granular filler, as desired.

[0088] Preferably, at least one filler (E) according to the present invention dissolves in toluene at 23°C and 1000 hPa in an amount of less than 1% by weight.

[0089] Examples of fillers include unreinforced granular fillers, preferably up to 50 m 2 Fillers having a BET specific surface area of ​​50m / g, e.g., quartz, glass, cristobalite, diatomaceous earth; water-insoluble silicates, e.g., calcium silicate, calcium metasilicate, magnesium silicate, zirconium silicate, talc, mica, feldspar, kaolin, zeolite, etc.; metal oxides, e.g., oxides of aluminum, titanium, iron, boron, or zinc, or mixed oxides thereof; fillers consisting of barium sulfate, calcium carbonate, marble powder, gypsum, silicon nitride, silicon carbide, boron nitride, plastic powders, e.g., polyacrylonitrile powder or polyetherimide powder, etc.; reinforced fillers, i.e., 50m 2 Fillers having a BET specific surface area greater than / g, such as fumed silica, precipitated silica, precipitated chalk, carbon black, such as furnace black, and acetylene black, as well as silicon-aluminum mixed oxides having a high BET specific surface area; fillers such as aluminum trihydrate, magnesium hydroxide, hollow spherical fillers, such as glass microballoons, glass spheres, phenolic thermospheres, or ceramic microspheres, for example, available from 3M Deutschland GmbH (Neuss, Germany) under the trade name Zeeospheres®; fibrous fillers, such as wollastonite, montmorillonite, basalt, bentonite, as well as cut and / or crushed glass fibers (short fiber glass), or mineral wool; fibers composed of metal fibers, metal oxides, glass, ceramics, carbon, or plastics; and natural fibers composed of cellulose, flax, hemp, wood, or sisal.

[0090] Any at least one filler (E) according to the present invention may be present in the composition according to the present invention as a single filler or as any mixture of at least two different fillers.

[0091] Component (E) is selected from granular fillers containing fibers (E1) with a maximum length of 5 cm, and fibrous semi-finished products (E2) containing fibers with a length exceeding 5 cm. In this case, fibrous semi-finished products (E2) are preferred.

[0092] Preferably, any at least one filler (E2) is any of the following: all known fiber-forming materials composed of polypropylene, polyethylene, polytetrafluoroethylene, polyester; metal fibers composed of steel; oxide and non-oxide ceramics, such as silicon carbide, aluminum oxide, silicon dioxide, boron oxide, etc.; 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).

[0093] At least one of the described fillers (E) may be surface-treated, for example, by treatment with organosilane or organosiloxane, stearic acid, or one or more modifiers (C), such as hydrophobization. The filler surface may also be modified, for example, by oxidation or treatment with an acid or base, to enable chemical bonding with the cured resin matrix. At least one filler (E2) is preferably surface-treated.

[0094] When the composition according to the present invention contains at least one filler (E1), the proportion of the at least one filler (E1) is preferably 5 to 900 parts by weight, particularly preferably 10 to 400 parts by weight, and especially preferably 15 to 150 parts by weight, based on 100 parts by weight of the total of components (A) and (B).

[0095] When the composition according to the present 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, and especially preferably 100 to 400 parts by weight, based on 100 parts by weight of the total of component (A) and component (B).

[0096] At least one filler (E2) may be present in the composition according to the present invention in different forms, such as a continuous rope, woven fabric, non-crimped woven fabric, knitted fabric, braid, mat, nonwoven fabric, whisker, chopped short fiber, or random fiber felt, each containing 1,000 to 400,000 individual filaments.

[0097] The compositions according to the present invention preferably contain at least one filler (E), where it is particularly preferable that the at least one filler (E) is mainly, and especially entirely, composed of filler (E2).

[0098] The compositions according to the present invention include, as a filler (E2), ropes, textile fabrics, noncrimp textile fabrics, knitted textiles, or braided textiles, in any case particularly preferably consisting of carbon fibers, aromatic polyamide fibers, ceramic fibers, and / or glass fibers. Here, it is particularly preferable that each fiber, and / or the ropes, textile fabrics, noncrimp textile fabrics, knitted textiles, or braided textiles made from them, be surface-treated. It is especially preferable that each fiber be surface-treated.

[0099] In any case, any textile fabric (E2) or non-crimped textile fabric (E2) according to the present invention is preferably used in multiple layers.

[0100] In a preferred embodiment, component (E2) comprises at least 80% by weight, more preferably at least 90% by weight, of a woven fabric, non-crimped woven fabric, knitted fabric, or braided fabric, based on 100% by weight of component (E2).

[0101] Compound (F) The compositions according to the present invention can be cured in the presence of at least one curing accelerator (F) known from the prior art. Suitable curing accelerators (F1) include, for example, acids and bases, such as hydrochloric acid, phosphinic acid, phosphonic acid, and phosphoric acid; aliphatic and aromatic amines, such as triethylamine, N,N-dimethylaniline, and pyridine; amidine, guanidine, 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 include cobalt(II) naphthenate, nickel(II) naphthenate, iron(III) naphthenate, copper(II) naphthenate, manganese(II) naphthenate, aluminum(III) naphthenate, zinc(II) naphthenate, zinc(II) octanoate, zinc(II) acetylacetone, iron(III) acetylacetone, cobalt(II) acetylacetone, chromium(III) acetylacetone, aluminum(III) acetylacetone, or copper(II) acetylacetone.

[0102] When at least one curing accelerator (F1) is used to cure the composition according to the present invention, it is preferably a combination of an organometallic compound and a co-accelerator having at least one active proton, and is particularly preferably a combination of an organometallic compound and a phenol (C4), such as nonylphenol.

[0103] If the composition according to the present invention contains at least one curing accelerator (F1), its content is preferably 0.00001 to 5 parts by weight based on 100 parts by weight of component (A). Here, it is particularly preferable that the organometallic compound (F1) is used in an amount of 0.0001 to 0.02 parts by weight based on 100 parts by weight of component (A).

[0104] If the composition according to the present invention contains a radical polymerizable functional group such as an aliphatic carbon-carbon multiple bond, an organic peroxide, such as dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, and tert-butyl perbenzoate, or an azo compound, such as azobis(isobutyronitrile), can be used alone or in addition to (F1) as a radical generation curing accelerator (F2). If the composition according to the present invention contains a radical generation curing accelerator (F2), its content is preferably 0.1 to 2 parts by weight based on 100 parts by weight of the total of the imide group-containing modifier (C1) and the imide resin (D2). Preferably, the radical generation curing accelerator (F2) is not used.

[0105] Compound (G) Examples of any at least one solvent (G) include aliphatic monohydric and polyhydric alcohols, e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, polypropylene glycol, polyethylene glycol, butane-1,2-diol, butane-1,3-diol, polybutylene glycol, and glycerol; ethers, e.g., methyl tert-butyl ether, di-tert-butyl ether Ethers, and di-, tri-, or tetraethylene glycol dimethyl ethers; saturated hydrocarbons, such as n-hexane, cyclohexane, n-heptane, n-octane, etc., and isomer octanes, such as 2-ethylhexane, 2,4,4-trimethylpentane, 2,2,4-trimethylpentane, 2-methylheptane, and trichloroethylene, etc., as well as mixtures of saturated hydrocarbons with a boiling point range of 60-300°C, available under trade names such as Exxsol®, Hydroseal®, or Shellsol®. ; Aromatic solvents, e.g., benzene, toluene, styrene, o-, m-, or p-xylene, solvent naphtha, dimethyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, mesitylene, and chlorobenzene; Aldehyde acetals, e.g., methylal, ethylhexylal, butyral, 1,3-dioxolane, and glycerol formal; Carbonate esters, e.g., 1,3-dioxolan-2-one, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, propylene glycol carbonate, ethylene carbonate; Ketones, e.g., acetone, Methyl isobutyl ketone, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, acetone, and cyclohexanone, etc.; esters, such as ethyl acetate, n-butyl acetate, ethylene glycol diacetate, γ-butyrolactone, 2-methoxypropyl acetate (MPA), dipropylene glycol dibenzoate, and ethyl ethoxypropionate, etc.; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone, etc.; acetonitrile;Dimethyl sulfoxide is another example.

[0106] At least one solvent (G) is preferably an aromatic hydrocarbon or a ketone.

[0107] If the composition according to the present invention contains at least one solvent (G), the amount thereof is preferably 10 to 300 parts by weight, particularly preferably 10 to 100 parts by weight, and especially preferably 10 to 50 parts by weight, based on 100 parts by weight of the total of components (A) and (B). It is preferable that the composition according to the present invention does not contain solvent (G).

[0108] Compound (H) The at least one auxiliary agent (H) according to the present invention is preferably a pigment, dye, fragrance, processing aid, such as a substance affecting tackiness, lubricant, mold release agent, antiblocking agent, or dispersant; a stabilizer against hydrolysis, light, oxidation, heat, or discoloration; or a flame retardant or plasticizer.

[0109] If the composition according to the present invention contains at least one auxiliary agent (H), the at least one auxiliary agent (H) is present in any case in an amount of preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, and especially particularly 0.1 to 5 parts by weight, based on 100 parts by weight of the total of components (A) and (B). It is preferable that the composition according to the present invention does not contain auxiliary agent (H).

[0110] Compositions according to the present invention, (A) at least one type of cyanate ester resin, (B) At least one poly(bisphenol-diorganosiloxane) copolymer, Depending on the circumstances, (C) at least one modifier, Depending on the case, (D) at least one reactive resin, (E2) At least one fiber-reinforced filler, Depending on the circumstances, (F) at least one type of curing accelerator, Depending on the circumstances, (G) at least one solvent, and Depending on the case, (H) at least one type of auxiliary agent, It is preferable that it contains [something].

[0111] Compositions according to the present invention, (A) at least one type of cyanate ester resin, (B) At least one poly(bisphenol-diorganosiloxane) copolymer, (C) at least one modifier, Depending on the case, (D) at least one reactive resin, (E2) At least one fiber-reinforced filler, Depending on the circumstances, (F) at least one type of curing accelerator, Depending on the circumstances, (G) at least one solvent, and Depending on the case, (H) at least one type of auxiliary agent, It is preferable that it contains [something].

[0112] In a particularly preferred embodiment, the composition according to the present invention is (A) at least one type of cyanate ester resin, (B) At least poly(bisphenol-diorganosiloxane) copolymer, Depending on the circumstances, (C) at least one modifier, (D2) At least one type of imide resin, (E2) At least one fiber-reinforced filler, Depending on the circumstances, (F) at least one type of curing accelerator, Depending on the circumstances, (G) at least one solvent, and Depending on the case, (H) at least one type of auxiliary agent, It is preferable that it contains [something].

[0113] In a particularly preferred embodiment, the composition according to the present invention is (A) at least one type of cyanate ester resin, (B) At least one poly(bisphenol-diorganosiloxane) copolymer, Depending on the circumstances, (C) at least one modifier, (D2) At least one maleimide resin, (E2) At least one fiber-reinforced filler, Depending on the circumstances, (F) at least one type of curing accelerator, Depending on the circumstances, (G) at least one solvent, and Depending on the case, (H) at least one type of auxiliary agent, It is preferable that it contains, However, this is conditional on the presence of at least one component (A), component (C3), or component (C4) in which a propenyl group is directly bonded to an aromatic carbon atom.

[0114] Preferably, the composition according to the present invention contains no further components in addition to components (A) and (B), optionally used components (C) to (H), and optionally raw material-specific impurities, such as catalyst residues like sodium chloride or potassium chloride, impurities in industrial-grade cyanate ester resin monomers, and reaction products of the components used that may be formed during mixing or storage.

[0115] In the composition according to the present invention, the above-mentioned components may be used individually or in a form in which at least two of the components are mixed.

[0116] The compositions according to the present invention can be produced by known methods, for example, by mixing the individual components in any desired order, or by conventionally known methods.

[0117] The present invention further provides a method for producing a composition according to the present invention by mixing the individual components in any desired order.

[0118] In the method according to the present invention, mixing can be carried out at a temperature preferably in the range of 20°C to 150°C, particularly preferably in the range of 50°C to 130°C, and especially preferably in the range of 60°C to 120°C. Most preferably, mixing is carried out at a temperature obtained as a result of mixing at an ambient temperature which is the temperature of the raw materials plus the temperature rise due to the energy input during mixing. Here, heating or cooling is carried out as necessary.

[0119] Mixing can be carried out under ambient atmospheric pressure, i.e., a pressure of approximately 900–1100 hPa. Mixing can also be carried out intermittently or continuously under reduced pressure, for example, at an absolute pressure of 30–500 hPa, in order to remove volatile substances and / or air. Alternatively, it is possible to operate under positive pressure, such as an absolute pressure of 1100–3000 hPa, which is possible, in particular, in continuous processing modes, for example, when these pressures are established within a closed system as a result of the pressure during pump operation and the vapor pressure of materials used at high temperatures.

[0120] The method according to the present invention can be carried out continuously, discontinuously, or semi-continuously. Discontinuous implementation is preferred.

[0121] In a preferred embodiment of the method of the present invention for producing the composition according to the present invention, the individual components, excluding component (E), are pre-mixed in any desired order, and then the filler (E2) is impregnated with a bubble-free premix by known processing techniques, such as prepregs (from melts, solutions, or suspensions), sheet molding compounds (SMCs), filament winding, compression molding, pultrusion, fiber spraying, and injection molding methods such as resin transfer molding or vacuum injection, and processed into a molded article.

[0122] The compositions according to the present invention can be used in all applications where organic reactive resin systems or their prepolymers have been conventionally used for the purpose of curing them as thermosetting resins.

[0123] In one modification of the method according to the present invention, components (A) and (B), and optionally components (C), (D), (G), and (H) are mixed in any desired order to form a premix, and then component (E2), preferably a rope, fabric, non-crimped fabric, knitted fabric, or braid, is impregnated with the premix, while optionally pressurized and degassed. In the case of multilayer fabrics or non-crimped fabrics (E2), impregnation and degassing may be carried out individually for each layer or for all layers together.

[0124] In a more preferred modification of the method according to the present invention, components (A) and (B), and optionally components (C), (D), (G), and (H) are mixed in any desired order to form a premix, which is then injected into a mold cavity containing component (E2), preferably a rope, fabric, non-crimped fabric, knitted fabric, or braid. Here, degassing is preferably performed simultaneously during the injection process.

[0125] In a more preferred variation of the method according to the present invention, components (A) and (B), and optionally components (C), (D), (G), and (H), are first mixed in any desired order to form a premix, which is then applied to a release paper. Subsequently, component (E2), preferably an oriented rope, fabric, non-crimped fabric, knitted fabric, or braid, is sandwiched between two sheets of covering paper and passed through a series of heated rollers to obtain complete wettability of component (E2).

[0126] The compositions according to the present invention can be molded into any desired shape by applying mechanical pressure at ambient temperature, or optionally at high temperatures.

[0127] The compositions according to the present invention are preferably moldable, and are particularly preferably molded and cured in a mold cavity or around a molding template.

[0128] Therefore, the present invention further provides the use of the composition according to the present invention for the manufacture of molded articles.

[0129] Therefore, the present invention further provides a method for producing a molded article by molding and then curing a composition according to the present invention.

[0130] The present invention further provides molded articles that can be obtained from compositions according to the present invention by molding and curing.

[0131] The composition according to the present invention, or a composition manufactured in accordance with the present invention, is preferably degassed before curing, and particularly preferably degassed after molding and before curing.

[0132] The curing according to the present invention is preferably carried out at a temperature in the range of 50°C to 350°C, particularly preferably in the range of 100°C to 300°C, and especially preferably in the range of 120°C to 270°C. The curing according to the present invention is most preferably carried out in steps within the temperature range of 120°C to 270°C.

[0133] By increasing the temperature, curing can be accelerated, and as a result, it is also possible to perform molding and curing in a single process.

[0134] The molded article according to the present invention is preferably made of a fiber composite material (or fiber-reinforced plastic "FRP").

[0135] Therefore, the present invention further provides the use of the compositions according to the present invention for manufacturing fiber composite materials.

[0136] The present invention further provides a method for producing a fiber composite material by molding and then curing the composition of the present invention.

[0137] Therefore, the present invention further provides a fiber composite material that can be obtained from a composition according to the present invention by molding and curing.

[0138] The composition according to the present invention can be solid or liquid at a temperature of 100 °C and an air pressure of 1013 hPa, where it is preferably liquid at 100 °C and 1013 hPa.

[0139] When the composition according to the present invention is liquid at 100 °C and 1013 hPa, in any case at 100 °C and 1013 hPa, it preferably has a dynamic viscosity of 1 to 5000 mPa·s, preferably 1 to 2000 mPa·s, particularly preferably 1 to 1000 mPa·s, and most preferably 1 to 500 mPa·s.

[0140] The critical stress intensity factor K of the cured composition according to the present invention composed of 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B), and the respective cured unmodified cyanate ester resin (A) Ic The ratio is preferably greater than 1.4, particularly preferably greater than 1.6, and most preferably greater than 1.7 in any case measured at 23 °C.

[0141] For example, the cured composition according to the present invention composed of 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B) preferably has a glass transition temperature exceeding 200 °C, particularly preferably exceeding at 230 °C, and most preferably exceeding 260 °C.

[0142] After storage at 240 °C for 200 hours, the cured composition according to the present invention composed of, for example, 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B) shows a weight loss that is higher than that of the corresponding unmodified cyanate ester resin (A), preferably 100% or less, preferably 80% or less, more preferably 60% or less, and particularly 40% or less.

[0143] The composition according to the present invention has the advantage that the cyanate ester resin (A) is miscible with the poly(bisphenol-diorganosiloxane) copolymer (B) without the addition of further solvents, and that the copolymer (B) does not leach out of the thermosetting resin network during curing.

[0144] The composition according to the present invention exhibits a higher glass transition temperature and higher fracture toughness (K) in the cured state compared to the corresponding unmodified cyanate ester resin. Ic It has the advantage of possessing the following characteristics.

[0145] Furthermore, the composition according to the present invention has the advantage of having high thermal oxidation stability in the cured state.

[0146] The molded article according to the present invention has the advantages of being thermally stable and having a reduced fire load compared to composite materials composed of pure organic cyanate ester resins.

[0147] The composition according to the present invention has the advantage of being easily manufactured from readily available raw materials.

[0148] The composition according to the present invention has the advantage that its processing does not produce health-hazardous emissions to the extent typically observed with organic cyanate ester resins used in the prior art. [Examples]

[0149] Exemplary Embodiments The following examples were carried out at atmospheric pressure, i.e., about 1013 hPa, and room temperature, i.e., about 23°C, or at the temperature at which the reactants were mixed at room temperature without further heating or cooling. While the present invention may be carried out in principle, the disclosure is not limited to that.

[0150] Specimen generation Cyanate ester resin (A) was heated to 80°C while being mixed to improve processability. Next, copolymer (B) was added, and the mixture was homogenized on a rotary evaporator at 110°C for 1 hour. Then, it was degassed at 110°C for 1 hour under a pressure of 5 mbar, and after releasing the vacuum with nitrogen, it was immediately poured while still hot into a two-part aluminum mold with a screw-top lid that had been preheated to 160°C. The dimensions of the mold cavity were set to 200 mm × 100 mm × 6.5 mm (length × width × height) to produce test specimens for determining fracture toughness and thermal oxidation stability, and for performing dynamic mechanical analysis (DMA). To prevent adhesion and leakage, the inner surface of the mold cavity was treated with a release agent (LOCTITE FREKOTE HMT-2; available from Henkel AG & Co. KGaA, Düsseldorf, Germany), and a 2 mm thick round cord of fluororubber with a Shore A hardness of 75 was placed around the mold cavity. To allow curing, the filled molds were stored in a convection oven according to the following temperature program: (1) Curing at 180°C for 18 hours (2) Heat up to 200°C over 30 minutes (3) Curing at 200°C for 3 hours (4) Heat up to 240°C over 30 minutes (5) Curing at 240°C for 2 hours.

[0151] Next, the test specimens were cooled to ambient temperature in the mold and then removed from the mold. Furthermore, the top 10 mm of the hardened side of the test specimens, which had been open and exposed to air during hardening in the mold, was cut off and discarded before use. Subsequently, test specimens for measuring fracture toughness and thermal oxidation stability, as well as test specimens for DMA, were cut from a large 6.5 mm high hardened test specimen slab to the appropriate length × width dimensions using a diamond saw.

[0152] Fracture toughness K Ic Fracture toughness or critical stress intensity factor K Ic Measurement is 、The test was conducted under conditions of 23°C and 50% relative humidity, as described in the reference "Reactive and Functional Polymers 142 (2019) 159-182". The specimen thickness was 6.5 mm. Fracture toughness K is shown in Table 1. Ic SGMN×m -3 / 2 The result was rounded to two decimal places according to item 4 of DIN 1333:1992-02.

[0153] Dynamic mechanical analysis (DMA) Measurement conditions: • Measuring device: ARES rheometer (TA Instruments) Temperature range: -100℃ to 400℃ • Heating rate: 4K / min under nitrogen purge • Frequency: 1Hz • Strain: Initial value 0.03%, automatically increases if a signal below the threshold is detected.

[0154] The test was conducted using a rectangular parallelepiped specimen with dimensions of length × width × height = 40 mm × 6 mm × 3 mm. The result showed that the fixed length was 25 mm.

[0155] In the present invention, the glass transition temperature T G This is the maximum value of the tangent delta curve (=tan delta max This corresponds to the measurement temperature at which the ratio of the loss modulus G'' to the storage modulus G' is maximized.

[0156] Glass transition temperature T listed in Table 1 G The value was rounded to an integer according to item 4 of DIN 1333:1992-02.

[0157] thermal oxidative stability In this invention, thermal oxidation stability was determined by gravimetric measurement after storing the test specimens at 240°C. A rectangular parallelepiped test specimen with dimensions of length × width × thickness = 12.00 mm × 6.50 mm × 6.50 mm was used. The accuracy of the gravimetric measurement was ±0.1 mg. The test specimens were first dried in a vacuum oven at 70°C and 30 mbar, with their weight measured every 24 hours until a constant weight was reached. The test specimens were considered "dried" when no further weight loss was detected within 48 hours. Subsequently, the test specimens were stored in a circulating oven at 240°C. After 200 hours, the test specimen was removed and its weight was measured again. The weight reduction rates are as follows:

number

[0158] Compatibility The compatibility between compound (B) and cyanate ester resin (A) was evaluated immediately after curing, based on the prepared test specimens. In Table 1, compatibility is reported as follows: "+" = good compatibility, i.e., no visible seepage or leaching of component (B) from the cured mixture; and "-" = poor compatibility, i.e., visible seepage or leaching of the siloxane component from the cured mixture, and the surface of the test specimen being oily and / or sticky.

[0159] Poly(bisphenol-diorganosiloxane) copolymer 1 A mixture of 12.8 g of 1,3-dichloro-1,1,3,3-tetramethyldisiloxane (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 anhydrous pyridine (CAS 110-86-1; available from Sigma-Aldrich Chemie GmbH (D-82024 Taufkirchen)) in 50 mL of diethyl ether is mixed with 30.0 g of bisphenol A (CAS 80-05-7; available from Sigma-Aldrich Chemie GmbH (D-82024 Taufkirchen)) in 200 mL of anhydrous diethyl ether (available from Sigma-Aldrich Chemie GmbH, D-82024 Taufkirchen). The mixture (available from GmbH (D-82024 Taufkirchen)) is added dropwise over 1 hour under a nitrogen atmosphere while being cooled with ice. After the addition is complete, the mixture is stirred further at 23°C for 30 minutes, then at 40°C for 5 hours, and then at 23°C overnight. As a workup, the mixture is filtered and 1 g of a weakly basic anionic resin based on polystyrene-divinylbenzene copolymer (Purolite® A103SPlus; available from Purolite GmbH, D-40880 Ratingen) is added to the filtrate. The mixture is stirred at 23°C for 30 minutes, then filtered, and the filtrate is concentrated in a rotary evaporator. To remove volatile components, the residue is mixed on the rotary evaporator at 110°C and a pressure of 5 mbar for 1 hour. Copolymer 1 has a weight-average molecular weight Mw of 8350 g / mol and a number-average molecular weight Mn of 2150 g / mol.

[0160] Poly(bisphenol-diorganosiloxane) copolymer 2 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 with 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 30 minutes while the reaction flask is cooled in an ice bath.

[0161] After addition, the mixture is stirred at 23°C for 10 minutes, followed by stirring at 100°C for 1.5 hours. Once the mixture has cooled to 23°C, 1 g of Purolite® A103SPlus is added, and the mixture is stirred for 15 minutes. The mixture is then filtered, and the filtrate is concentrated in a rotary evaporator. To remove volatile components, the residue is mixed on the rotary evaporator at 110°C and a pressure of 5 mbar for 1 hour. Copolymer 2 has a weight-average molecular weight Mw of 3485 g / mol and a number-average molecular weight Mn of 1390 g / mol.

[0162] Example B1 85 g of 2,2-bis(4-cyanatephenyl)propane (CAS 1156-51-0; available from TCI Deutschland GmbH (65760 Eschborn, Germany)) as component (A) was mixed with 15 g of c-poly(bisphenol-diorganosiloxane) copolymer 1 as component (B), and then processed as described in "Preparation of Test Specimens". The results are shown in Table 1.

[0163] Example B2 Experiment B1 was repeated with the modification of using copolymer 2 instead of poly(bisphenol-diorganosiloxane) copolymer 1. The results are shown in Table 1.

[0164] Comparative Example V1 The procedure described in Example B1 was repeated with the modification of not adding component (B) to component (A). The results are shown in Table 1.

[0165] [Table 1]

Claims

1. (A) At least one organic compound (A) that does not contain a siloxy (≡Si-O-) unit and has at least two cyanate ester (-O-C≡N) groups, (B) At least one linear poly(bisphenol-diorganosiloxane) copolymer (B) that does not contain cyanate ester groups and is represented by general formula (I): 【Chemistry 1】 (In the ceremony Z represents a divalent aromatic hydrocarbon group that is identical or different and may be optionally substituted, and may be interrupted by at least one heteroatom; R represents a monovalent SiC bonded hydrocarbon group, which may be identical or different and may be interrupted by a hydrogen atom or at least one oxygen atom; R １ These are identical or different hydrogen atoms, hydroxy (-OH) groups, or silyloxy groups represented by general formula (II): 【Chemistry 2】 (In the ceremony R ２ These are identical or different, representing the base R. R ３ (This represents a monovalent Si-O bonded alkoxy or aryloxy group having 1 to 18 carbon atoms, which may be identical or different and may be separated by a group R or at least one heteroatom.) It represents; x is between 1 and 20; y is between 1 and 100; and z is between 1 and 20. A curable composition comprising the above.

2. The curable composition according to claim 1, wherein the at least one compound (A) is an aromatic hydrocarbon compound that is optionally substituted and / or contains at least one heteroatom.

3. The curable composition according to claim 1 or 2, wherein at least two aromatic hydrocarbon groups are present per molecule of compound (A), each of which is optionally substituted and / or contains at least one heteroatom and each has a cyanate ester group bonded to an aromatic carbon atom.

4. which may be substituted and / or contain at least one heteroatom, and an aromatic hydrocarbon group having a cyanate ester group bonded to each aromatic carbon atom is bonded to each other via a covalent bond or -CR ４ ２ -, -CR ４ =CR ４ -, -C(=CR ４ ２ ), -, -O-, -S-, -N=N-, -CR ４ =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O) ２ -, O=P(O-) ３ , ≡P(=O), -SiR ４ ２ -, a divalent aromatic hydrocarbon group (e.g., phenylene, tolylene, biphenylene, and naphthylene); or a divalent cycloalkanediyl group (e.g., tricyclo[5.2.1.0 ２，６ decandiyl and bicyclo[2.2.1]heptanediyl) and are bonded to each other via at least one crosslinking unit selected from the group consisting of Here, R ４ However, independently, it represents a monovalent hydrocarbon group having 1 to 30 carbon atoms that are substituted and / or separated by a hydrogen atom, a halogen atom, or optionally substituted and / or separated by at least one heteroatom. The curable composition according to claim 3.

5. The above-mentioned at least one compound (B) Weight-average molecular weight Mw of 1,000 to 30,000 g / mol; and / or Number average molecular weight Mn 200–10,000 g / mol A curable composition according to any one of claims 1 to 4, having the following characteristics.

6. R is a monovalent SiC-bonded hydrocarbon group having 1 to 8 carbon atoms; and / or R １ However, R is a hydrogen atom, a hydroxy (-OH) group, or a silyloxy group represented by formula (II), ２ but is a methyl group or a phenyl group; and / or R ３ but is a hydrogen atom, a methyl group, a phenyl group, or a cumylphenoxy group; and / or Z is selected from a monoarylene group or a bisarylene unit, where two arylene groups are bonded covalently or -CR ６ ２ -, -CR ６ =CR ６ -, -C (=CR ６ ２ )-, -O-, -S-, -N=N-, -CR ６ =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O) ２ -, O = P(O-) ３ , ≡P(=O), -SiR ６ ２ -, divalent aromatic hydrocarbon groups (e.g., phenylene, triylene, biphenylene, and naphthylene); or divalent cycloalkanediyl groups (e.g., tricyclo[5.2.1.0 ２，６ They are linked to each other via at least one crosslinking unit selected from the group consisting of ]decanediyl and bicyclo[2.2.1]heptanediyl, In each case, R ６ However, R ４ Representing the aforementioned base as defined in, A curable composition according to any one of claims 1 to 5.

7. The curable composition according to any one of claims 1 to 6, comprising 1 to 100 parts by weight of the at least one compound (B) based on a total amount of 100 parts by weight of the at least one compound (A).

8. The following compounds: (C) at least one modifier (C); (D) at least one reactive resin (D); (E) at least one type of filler (E); (F) at least one type of curing accelerator (F); (G) at least one solvent (G); and / or (H) at least one type of adjuvant (H); It further includes, 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 agent (H) are different from the at least one compound (A) and compound (B). A curable composition according to any one of claims 1 to 7.

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

10. (C) at least one modifier (C); and (E2) At least one fiber-reinforced filler A curable composition according to any one of claims 1 to 7, further comprising:

11. (D2) at least one imide resin; and (E2) At least one fiber-reinforced filler A curable composition according to any one of claims 1 to 7, further comprising:

12. A method for producing the curable composition according to any one of claims 1 to 11 by mixing the individual components in any order.

13. A method for producing a molded article or fiber composite material by molding a curable composition according to any one of claims 1 to 11 and then curing it.

14. Use of the curable composition according to any one of claims 1 to 11 for manufacturing a molded article or a fiber composite material.

15. A molded article or fiber composite material obtained by the method described in claim 13.

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